Bacillus coagulans tolerance to 1-ethyl-3-methylimidazolium-based ionic liquids in aqueous and solid-state thermophilic culture.

PubMed

Simmons, Christopher W; Reddy, Amitha P; Vandergheynst, Jean S; Simmons, Blake A; Singer, Steven W

2014-01-01

The use of ionic liquids (ILs) to disrupt the recalcitrant structure of lignocellulose and make polysaccharides accessible to hydrolytic enzymes is an emerging technology for biomass pretreatment in lignocellulosic biofuel production. Despite efforts to reclaim and recycle IL from pretreated biomass, residual IL can be inhibitory to microorganisms used for downstream fermentation. As a result, pathways for IL tolerance are needed to improve the activity of fermentative organisms in the presence of IL. In this study, microbial communities from compost were cultured under high-solids and thermophilic conditions in the presence of 1-ethyl-3-methylimidazolium-based ILs to enrich for IL-tolerant microorganisms. A strain of Bacillus coagulans isolated from an IL-tolerant community was grown in liquid and solid-state culture in the presence of the ILs 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) or 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) to gauge IL tolerance. Viability and respiration varied with the concentration of IL applied and the type of IL used. B. coagulans maintained growth and respiration in the presence of 4 wt% IL, a concentration similar to that present on IL-pretreated biomass. In the presence of both [C2mim][OAc] and [C2mim][Cl] in liquid culture, B. coagulans grew at a rate approximately half that observed in the absence of IL. However, in solid-state culture, the bacteria were significantly more tolerant to [C2mim][Cl] compared with [C2mim][OAc]. B. coagulans tolerance to IL under industrially relevant conditions makes it a promising bacterium for understanding mechanisms of IL tolerance and discovering IL tolerance pathways for use in other microorganisms, particularly those used in bioconversion of IL-pretreated plant biomass. © 2013 American Institute of Chemical Engineers.

CNT/conductive polymer composites for low-voltage driven EAP actuators

NASA Astrophysics Data System (ADS)

Sugino, Takushi; Shibata, Yoshiyuki; Kiyohara, Kenji; Asaka, Kinji

2012-04-01

We investigated the effects of additives incorporated into the electrode layer in order to improve the actuation performance of dry-type carbon nanotube (CNT) actuators. Especially, the addition of conductive nano-particles such as polyaniline (PANI) and polypyrrole (PPy) improves actuation performance very much rather than the addition of nonconductive nano-particles such as mesoprous silica (MCM-41 type). In this paper, we studied on the influences of applied voltage, species of ionic liquid (IL), amounts of IL, thickness of actuator to optimize actuation performance. Imidazolium type ionic liquids with three different anions, that is, 1-ethyl-3-methylimidazolium (EMI) as a cation and tetrafluoroborate (BF4), trifluoromethanesulfonate (OTf), and bis(trifluoromethanesulfonyl)imide (TFSI) as anions were chosen in this study. EMIBF4 is the most suitable IL for our CNT actuator including PANI in the electrode layer. We tuned the amount of IL and the thickness of actuator. As a result, the strain was improved to be 2.2% at 0.1 Hz by applying the voltage of 2.5 V. This improved value is almost 2 times larger than our previous results. We also show the potential of improved CNT actuators for a thin and light Braille display.

Solvent effects on the polar network of ionic liquid solutions

NASA Astrophysics Data System (ADS)

Bernardes, Carlos E. S.; Shimizu, Karina; Canongia Lopes, José N.

2015-05-01

Molecular dynamics simulations were used to probe mixtures of ionic liquids (ILs) with common molecular solvents. Four types of systems were considered: (i) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide plus benzene, hexafluorobenzene or 1,2-difluorobenzene mixtures; (ii) choline-based ILs plus ether mixtures (iii) choline-based ILs plus n-alkanol mixtures; and (iv) 1-butyl-3-methylimidazolium nitrate and 1-ethyl-3-methylimidazolium ethyl sulfate aqueous mixtures. The results produced a wealth of structural and aggregation information that highlight the resilience of the polar network of the ILs (formed by clusters of alternating ions and counter-ions) to the addition of different types of molecular solvent. The analysis of the MD data also shows that the intricate balance between different types of interaction (electrostatic, van der Waals, H-bond-like) between the different species present in the mixtures has a profound effect on the morphology of the mixtures at a mesoscopic scale. In the case of the IL aqueous solutions, the present results suggest an alternative interpretation for very recently published x-ray and neutron diffraction data on similar systems.

Thermal Decomposition Mechanism of 1-ethyl-3-methylimidazolium Bromide Ionic Liquid (Preprint)

DTIC Science & Technology

2011-09-14

TetraethylammoniumTrifluoromentanesulfonate Ionic Liquid and Neutralized Nafion 117 for High-Temperature Fuel Cells J. Am. Chem. Soc. 2010, 132, 2183-2195. (7) Kim, S. Y.; Kim, S...bromide 5b. GRANT NUMBER ionic liquid (Preprint) 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Steven D. Chambreau, Jerry A. Boatz, Ghanshyam L. Vaaghjiani...In order to better understand the volatilization process for ionic liquids , the vapor evolved from heating the ionic liquid 1-ethyl-3

Ionic liquids as novel solvents for ionic polymer transducers

NASA Astrophysics Data System (ADS)

Bennett, Matthew D.; Leo, Donald J.

2004-07-01

The use of ionic liquids as solvents for ionic polymer (specifically, Nafion) transducers is demonstrated. Ionic liquids are attractive for this application because of their high inherent stability. Ionic liquids are salts that exist as liquids at room temperature and have no measureable vapor pressure. Therefore, the use of ionic liquids as solvents for ionic polymer transducers can eliminate the traditional problem of water evaporation in these devices. Another benefit of the use of ionic liquids in this way is the reduction or elimination of the characteristic back-relaxation common in water-solvated ionic polymer actuators. The results demonstrate that the viscosity of the ionic liquid and the degree to which the ionic liquid swells the membrane are the important physical parameters to consider. Five ionic liquids were studied, based on substituted pyrrolidinium, phosphonium, or imidazolium cations and fluoroanions. Of these five ionic liquids, transduction is demonstrated in three of them and the best results are obtained with 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid. This substance has an electrochemical stability window of 4.1 V, a melting point of -10 °C, and a viscosity of 35-45 cP [19]. Results demonstrate that platinum-plated Nafion transducers solvated with this ionic liquid exhibit sensing and actuation responses and that these transducers are stable in air. Endurance testing of this sample reveals a decrease in the free strain of only 25 % after 250,000 actuation cycles in air.

Temperature-programed time-of-flight secondary ion mass spectrometry study of 1-butyl-3-methylimidazolium trifluoromethanesulfonate during glass-liquid transition, crystallization, melting, and solvation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Souda, Ryutaro; Guenster, Jens; CiC Ceramic Institute Clausthal GmbH, D-38678 Clausthal-Zellerfeld

2008-09-07

For this study, time-of-flight secondary ion mass spectrometry was used to analyze the molecular orientation of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]) and its interaction with the adsorbed Na and LiI species at temperatures of 150-300 K. A glassy [bmim][OTf] film crystallizes at around 230 K, as observed from the increase in the [bmim]{sup +} yield. LiI and Na adsorbed on the glassy film are solvated, whereas they tend to form islands on a crystalline film. The crystalline surface inertness is ascribable to the termination with the CF{sub 3} and C{sub 4}H{sub 9} groups, whereas the exposure of polar SO{sub 3} and imidazolemore » groups at the glassy film results in the solvation. Surface layering occurs during solvation of LiI on the glassy film in such a way that the [bmim]{sup +} ([OTf]{sup -}) moiety is exposed to the vacuum (oriented to the bulk). The LiI adsorbed on the glassy film is incorporated into the bulk at temperatures higher than 200 K because of the glass-liquid transition. No further uptake of LiI is observed during crystallization, providing a contrast to the results of normal molecular solids such as water and ethanol. The surface layers of the crystal melt at temperatures below the bulk melting point, as confirmed from the dissolution of adsorbed LiI, but the melting layer retains a short-range order similar to the crystal. The [bmim][OTf] can be regarded as a strongly correlated liquid with the combined liquid property and crystal-type local structure. The origin of this behavior is discussed.« less

Helium Nanodroplet Isolation and Infrared Spectroscopy of the Isolated Ion-Pair 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

DTIC Science & Technology

2013-09-01

Use in Lithium Metal-Polymer Electrolyte Batteries. J. Electrochem. Soc. 2005, 152, A978-A983.     4. Henderson, W. A.; Shin, J. H.; Passerini, S...Chen, L. Q.; Hu, Y. S.; Li, H.; Huang, X. J. Novel Room Temperature Molten Salt Electrolyte Based on Litfsi and Acetamide for Lithium Batteries...the Structure of Ionic Liquid 1-Ethyl-3- Methylimidazolium Hexafluorophosphate . Chinese J. Struc. Chem. 2005, 24, 576-580.     37. Liu, K. H.; Pu, M

1-Ethyl-3-methylimidazolium acetate as a highly efficient organocatalyst for cyanosilylation of carbonyl compounds with trimethylsilyl cyanide

PubMed Central

Ullah, Bakhtar; Chen, Jingwen; Zhang, Zhiguo; Xing, Huabin; Yang, Qiwei; Bao, Zongbi; Ren, Qilong

2017-01-01

1-Ethyl-3-methylimidazolium acetate is introduced as a robust organocatalyst for solvent-free cyanosilylation of carbonyl compounds with trimethylsilyl cyanide (TMSCN). The catalyst loading can be reduced to as low as 0.1–0.0001 mol % under mild reaction conditions, giving considerably high TOF values from 10,843 h−1 to 10,602,410 h−1 in the field of organocatalyzed transformations. The present protocol not only tolerates with extensive carbonyl compounds but also provides somewhat insight into the mechanism of ionic liquids (ILs)-catalyzed reactions. PMID:28198462

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE PAGES

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian; ...

2018-10-02

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Rotational dynamics of imidazolium-based ionic liquids: do the nature of the anion and the length of the alkyl chain influence the dynamics?

PubMed

Prabhu, Sugosh R; Dutt, G B

2014-11-20

The rotational dynamics of 1-alkyl-3-methylimidazolium-based ionic liquids has been investigated by monitoring their inherent fluorescence with the intent to unravel the characteristics of the emitting species. For this purpose, temperature-dependent fluorescence anisotropies of 1-alkyl-3-methylimidazolium (alkyl = ethyl and hexyl) ionic liquids with anions such as tris(pentafluoroethyl)trifluorophosphate ([FAP]), bis(trifluoromethylsulfonyl)imide ([Tf2N]), tetrafluoroborate ([BF4]), and hexafluorophosphate ([PF6]) have been measured. It has been observed that the reorientation times (τr) of the ionic liquids with an ethyl chain scale linearly with viscosity and were found to be independent of the nature of the anion. The experimentally measured τr values are a factor of 3 longer than the ones calculated for 1-ethyl-3-methylimidazolium cation using the Stokes-Einstein-Debye (SED) hydrodynamic theory with stick boundary condition, which suggests that the emitting species is not the imidazolium moiety but some kind of associated species. The reorientation times of ionic liquids with a hexyl chain, in contrast, follow the trend τr([FAP]) > τr([Tf2N]) = τr([BF4]) > τr([PF6]) at a given viscosity (η) and temperature (T). The ability of the ionic liquids with longer alkyl chains to form the organized structure appears to be responsible for the observed behavior considering the fact that significant deviations from linearity have been noticed in the τr versus η/T plots for strongly associating anions [BF4] and [PF6], especially at ambient temperatures.

Surface polymerization of (3,4-ethylenedioxythiophene) probed by in situ scanning tunneling microscopy on Au(111) in ionic liquids

NASA Astrophysics Data System (ADS)

Ahmad, Shahzada; Carstens, Timo; Berger, Rüdiger; Butt, Hans-Jürgen; Endres, Frank

2011-01-01

The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situscanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situSTM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situmicroscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM).The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situscanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situSTM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situmicroscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM). Electronic supplementary information (ESI) available: In situ image of PEDOT in [HMIm]FAP and in situ studies of PEDOT grown in [EMIm]TFSA and redox behavior of PEDOT. See DOI: 10.1039/c0nr00579g

Enrichment, isolation and characterization of fungi tolerant to 1-ethyl-3-methylimidazolium acetate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singer, S.W.; Reddy, A. P.; Gladden, J. M.

2010-12-15

This work aims to characterize microbial tolerance to 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]), ionic liquid that has emerged as a novel biomass pretreatment for lignocellulosic biomass. Enrichment experiments performed using inocula treated with [C2mim][OAc] under solid and liquid cultivation yielded fungal populationsdominated by Aspergilli. Ionic liquid-tolerant Aspergillus isolates from these enrichments were capable of growing in a radial plate growth assay in the presence of 10% [C2mim][OAc]. When a [C2mim][OAc]-tolerant Aspergillus fumigatus strain was grown in the presence of switchgrass, endoglucanases and xylanases were secreted that retained residual enzymatic activity in the presence of 20% [C2mim][OAc]. The results of the study suggestmore » tolerance to ionic liquids is a general property of Aspergilli. Tolerance to an industrially important ionic liquid was discovered in a fungal genera that is widely used in biotechnology, including biomass deconstruction.« less

Global transcriptome response to ionic liquid by a tropical rain forest soil bacterium, Enterobacter lignolyticus.

PubMed

Khudyakov, Jane I; D'haeseleer, Patrik; Borglin, Sharon E; Deangelis, Kristen M; Woo, Hannah; Lindquist, Erika A; Hazen, Terry C; Simmons, Blake A; Thelen, Michael P

2012-08-07

To process plant-based renewable biofuels, pretreatment of plant feedstock with ionic liquids has significant advantages over current methods for deconstruction of lignocellulosic feedstocks. However, ionic liquids are often toxic to the microorganisms used subsequently for biomass saccharification and fermentation. We previously isolated Enterobacter lignolyticus strain SCF1, a lignocellulolytic bacterium from tropical rain forest soil, and report here that it can grow in the presence of 0.5 M 1-ethyl-3-methylimidazolium chloride, a commonly used ionic liquid. We investigated molecular mechanisms of SCF1 ionic liquid tolerance using a combination of phenotypic growth assays, phospholipid fatty acid analysis, and RNA sequencing technologies. Potential modes of resistance to 1-ethyl-3-methylimidazolium chloride include an increase in cyclopropane fatty acids in the cell membrane, scavenging of compatible solutes, up-regulation of osmoprotectant transporters and drug efflux pumps, and down-regulation of membrane porins. These findings represent an important first step in understanding mechanisms of ionic liquid resistance in bacteria and provide a basis for engineering microbial tolerance.

Isolation and Characterisation of 1-Alkyl-3-Methylimidazolium Chloride Ionic Liquid-Tolerant and Biodegrading Marine Bacteria

PubMed Central

Megaw, Julianne; Busetti, Alessandro; Gilmore, Brendan F.

2013-01-01

The aim of this study was to isolate and identify marine-derived bacteria which exhibited high tolerance to, and an ability to biodegrade, 1-alkyl-3-methylimidazolium chloride ionic liquids. The salinity and hydrocarbon load of some marine environments may induce selective pressures which enhance the ability of microbes to grow in the presence of these liquid salts. The isolates obtained in this study generally showed a greater ability to grow in the presence of the selected ionic liquids compared to microorganisms described previously, with two marine-derived bacteria, Rhodococcus erythropolis and Brevibacterium sanguinis growing in concentrations exceeding 1 M 1-ethyl-3-methylimidazolium chloride. The ability of these bacteria to degrade the selected ionic liquids was assessed using High Performance Liquid Chromatography (HPLC), and three were shown to degrade the selected ionic liquids by up to 59% over a 63-day test period. These bacterial isolates represent excellent candidates for further potential applications in the bioremediation of ionic liquid-containing waste or following accidental environmental exposure. PMID:23560109

Effect of the physicochemical properties of binary ionic liquids on lipase activity and stability.

PubMed

Yao, Peipei; Yu, Xinxin; Huang, Xirong

2015-01-01

In the present study, the lipase-catalyzed hydrolysis of p-nitrophenyl butyrate is used as a model reaction to determine the activity and stability of Candida rugosa lipase in binary ionic liquids (ILs). The binary ILs consist of hydrophobic 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF6) and a small amount of hydrophilic 1-butyl-3-methylimidazolium nitrate ([Bmim]NO3) or 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([Bmim]CF3SO3) or 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF4). The activity and the stability of lipase are first correlated with the physicochemical properties of the binary ILs. In the three binary IL systems, both the hydrophilicity and the polarity of the systems increase with the increase of the content of hydrophilic ILs (HILs). At a fixed concentration of HIL, they vary in a descending order of [Bmim]PF6/[Bmim]NO3>[Bmim]PF6/[Bmim]CF3SO3>[Bmim]PF6/[Bmim]BF4. This order is in contrast with the order of the lipase conformation stability, i.e., the higher the polarity of ILs, the more unstable the lipase conformation. However, both the activity and the stability of lipase depend on the type and the content of the HIL in binary ILs, showing a complex dependency. Analysis shows that the catalytic performance of lipase in the binary ILs is affected not only by the direct influence of the ILs on lipase conformation, but also through their indirect influence on the physicochemical properties of water. The present study helps to explore binary IL mixtures suitable for lipase-based biocatalysis. Copyright © 2015 Elsevier B.V. All rights reserved.

Probing the interaction of 1-ethyl-3-methylimidazolium ethyl sulfate ([Emim][EtSO4]) with alcohols and water by solvent and rotational relaxation.

PubMed

Sarkar, Souravi; Pramanik, Rajib; Ghatak, Chiranjib; Setua, Palash; Sarkar, Nilmoni

2010-03-04

The effect of the addition of cosolvents in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium ethyl sulfate ([Emim][EtSO(4)]) was probed by the solvent and rotational relaxation studies of coumarin 153 in neat ionic liquid [Emim][EtSO(4)] and [Emim][EtSO(4)]-cosolvent mixtures by using steady-state and time-resolved fluorescence spectroscopy. With gradual addition of cosolvents in the RTIL, both the average solvation time and rotational relaxation times gradually decrease. Addition of cosolvents in the IL decreases the viscosity of the medium. We have optimized the geometry of [Emim][EtSO(4)] and [Emim][EtSO(4)]-cosolvent mixtures by using quantum chemical calculations using density functional theory methods, which show the formation of hydrogen bond between cosolvents with [Emim][EtSO(4)]. With addition of the same amount of alcohols in neat [Emim][EtSO(4)], the rotational relaxation time decreases more compared to the addition of the same amount of water.

Thermochemical Properties of the 1-Ethyl-3-Methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid under Conditions of Equilibrium with Atmospheric Moisture

NASA Astrophysics Data System (ADS)

Ramenskaya, L. M.; Grishina, E. P.; Kudryakova, N. O.

2018-01-01

Thermochemical properties of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ionic liquid [EMim]NTf2 containing moisture absorbed from the atmosphere (0.242 wt %) are investigated. The phase behavior and thermal stability relative to salt dried in vacuum are studied by means of thermogravimetry and differential scanning calorimetry at different heating and cooling rates. The glass transition, crystallization, and melting temperatures, the enthalpies of phase transitions, and the changes in heat capacity during the formation of glass are determined. It is established that the absorbed water crystallizes at a temperature of around -40.6°C and has virtually no effect on the thermal stability and phase behavior of the salt. Rapid cooling results in the ionic liquid transitioning into the glass state at -91.7 °C and the formation of three mesophases with different melting temperatures; one crystalline modification that melts at a temperature of -19.3°C forms upon slow cooling.

Vaporisation of an ionic liquid near room temperature.

PubMed

Lovelock, Kevin R J; Deyko, Alexey; Licence, Peter; Jones, Robert G

2010-08-21

The temperature at which the vapour phase of the ionic liquids (ILs) 1-ethyl-3-methylimidazolium bis[(trifluoromethane)sulfonyl]imide, [C(2)C(1)Im][Tf(2)N], and 1-ethyl-3-methylimidazolium ethylsulfate, [C(2)C(1)Im][EtOSO(3)], can be detected was investigated using line-of-sight mass spectrometry (LOSMS). By optimising the detection system used in previous experiments, the lowest temperature for which vapour was detected for [C(2)C(1)Im][Tf(2)N] was approximately 340 K, whereas for [C(2)C(1)Im][EtOSO(3)] it was approximately 390 K. Initial investigations also show that the temperature at which measurements are made affects the enthalpy of vaporisation at 298 K, Delta(vap)H(298). The reasons for these differences in Delta(vap)H(298) with respect to temperature are discussed. The vapour pressure of both ILs is estimated at far lower temperatures than previously achieved and extrapolations to room temperature are given.

Direct Electrodeposition of UO2 from Uranyl Bis(trifluoromethanesulfonyl)imide Dissolved in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Room Temperature Ionic Liquid System

DOE PAGES

Freiderich, John W.; Wanigasekara, Eranda P.; Sun, Xiao-Guang; ...

2013-11-11

Our study demonstrates a direct electrodeposition of UO 2 at a Pt cathode from a solution of uranyl bis(trifluoromethanesulfonyl)imide [UO 2(NTf 2) 2)] in a bulk room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM +NTf 2 –). Cyclic voltammetry (CV) studies revealed two reduction waves corresponding to the conversion of uranium(VI) to uranium(IV), and a mechanism for the overall electroreduction is proposed. A controlled-potential experiment was performed, holding the reduction potential at–1.0 V for 24 h to obtain a brown-black deposit of UO 2 on the Pt cathode. The Faradaic efficiency of the reduction process was determined to be >80%. Themore » UO 2deposit was characterized by powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).« less

Thermal decomposition mechanism of 1-ethyl-3-methylimidazolium bromide ionic liquid.

PubMed

Chambreau, Steven D; Boatz, Jerry A; Vaghjiani, Ghanshyam L; Koh, Christine; Kostko, Oleg; Golan, Amir; Leone, Stephen R

2012-06-21

In order to better understand the volatilization process for ionic liquids, the vapor evolved from heating the ionic liquid 1-ethyl-3-methylimidazolium bromide (EMIM(+)Br(-)) was analyzed via tunable vacuum ultraviolet photoionization time-of-flight mass spectrometry (VUV-PI-TOFMS) and thermogravimetric analysis mass spectrometry (TGA-MS). For this ionic liquid, the experimental results indicate that vaporization takes place via the evolution of alkyl bromides and alkylimidazoles, presumably through alkyl abstraction via an S(N)2 type mechanism, and that vaporization of intact ion pairs or the formation of carbenes is negligible. Activation enthalpies for the formation of the methyl and ethyl bromides were evaluated experimentally, ΔH(‡)(CH(3)Br) = 116.1 ± 6.6 kJ/mol and ΔH(‡)(CH(3)CH(2)Br) = 122.9 ± 7.2 kJ/mol, and the results are found to be in agreement with calculated values for the S(N)2 reactions. Comparisons of product photoionization efficiency (PIE) curves with literature data are in good agreement, and ab initio thermodynamics calculations are presented as further evidence for the proposed thermal decomposition mechanism. Estimates for the enthalpy of vaporization of EMIM(+)Br(-) and, by comparison, 1-butyl-3-methylimidazolium bromide (BMIM(+)Br(-)) from molecular dynamics calculations and their gas phase enthalpies of formation obtained by G4 calculations yield estimates for the ionic liquids' enthalpies of formation in the liquid phase: ΔH(vap)(298 K) (EMIM(+)Br(-)) = 168 ± 20 kJ/mol, ΔH(f, gas)(298 K) (EMIM(+)Br(-)) = 38.4 ± 10 kJ/mol, ΔH(f, liq)(298 K) (EMIM(+)Br(-)) = -130 ± 22 kJ/mol, ΔH(f, gas)(298 K) (BMIM(+)Br(-)) = -5.6 ± 10 kJ/mol, and ΔH(f, liq)(298 K) (BMIM(+)Br(-)) = -180 ± 20 kJ/mol.

Multi-Scale Simulation of High Energy Density Ionic Liquids

DTIC Science & Technology

2007-06-19

and simulation of ionic liquids (ILs). A polarizable model was developed to simulate ILs more accurately at the atomistic level. A multiscale coarse...propellant, 1- hydroxyethyl-4-amino-1, 2, 4-triazolium nitrate (HEATN), were studied with the all-atom polarizable model. The mechanism suggested for HEATN...with this AFOSR-supported project, a polarizable forcefield for the ionic liquids such as 1-ethyl-3-methylimidazolium nitrate (EMIM*/NO3-) was

Free volume dependence of an ionic molecular rotor in Fluoroalkylphosphate (FAP) based ionic liquids

NASA Astrophysics Data System (ADS)

Singh, Prabhat K.; Mora, Aruna K.; Nath, Sukhendu

2016-01-01

The emission properties of Thioflavin-T (ThT), a cationic molecular rotor, have been investigated in two fluoroalkylphosphate ([FAP]) anion based ionic liquids, namely, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate and 1-(2-hydroxyethyl)-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, over a wide temperature range. The micro-viscosities of ionic liquids around ThT, measured from the emission quantum yield, are found to be quite different from their bulk viscosities. The temperature dependence of the viscosity and the emission quantum yield reveals that, despite the very low shear viscosity of these ILs, the non-radiative torsional relaxation has a strong dependence on the free volume of these [FAP] anion based ILs.

Physical properties and solubility parameters of 1-ethyl-3-methylimidazolium based ionic liquids/DMSO mixtures at 298.15 K

NASA Astrophysics Data System (ADS)

Saba, H.; Yumei, Z.; Huaping, W.

2015-12-01

Densities, refractive indices, conductivities and viscosities of binary mixtures of 1-ethyl-3-methylimidazolium-based ionic liquids (ILs) with dimethyl sulfoxide at 298.15 K are reported. Excess molar volumes have been calculated from experimental data and were fitted with Redlich-Kister equation. The density and refractive index were found to increase with increasing concentration in all cases except [EMIM]COOH. The free mobility of ions has found to enhance conductivity and decrease viscosity to varying extent in all mixtures being studied. It has been observed that solubility parameters, dielectric constants and nature of anions of ILs being used play a vital role in determining the subsequent characteristics. As DMSO has high dielectric constant therefore, it was able to form interactions with most of ILs except with [EMIM]COOH due to anomalous nature of anion.

ForConX: A forcefield conversion tool based on XML.

PubMed

Lesch, Volker; Diddens, Diddo; Bernardes, Carlos E S; Golub, Benjamin; Dequidt, Alain; Zeindlhofer, Veronika; Sega, Marcello; Schröder, Christian

2017-04-05

The force field conversion from one MD program to another one is exhausting and error-prone. Although single conversion tools from one MD program to another exist not every combination and both directions of conversion are available for the favorite MD programs Amber, Charmm, Dl-Poly, Gromacs, and Lammps. We present here a general tool for the force field conversion on the basis of an XML document. The force field is converted to and from this XML structure facilitating the implementation of new MD programs for the conversion. Furthermore, the XML structure is human readable and can be manipulated before continuing the conversion. We report, as testcases, the conversions of topologies for acetonitrile, dimethylformamide, and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate comprising also Urey-Bradley and Ryckaert-Bellemans potentials. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osti, Naresh C.; Gallegos, Alejandro; Dyatkin, Boris

Well-tailored mixtures of distinct ionic liquids can act as optimal electrolytes that extend the operating electrochemical window and improve charge storage density in supercapacitors. Here, we explore two room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF 4). We study their electric double-layer behavior in the neat state and as binary mixtures on the external surfaces of onion-like carbon electrodes using quasielastic neutron scattering (QENS) and classical density functional theory techniques. Computational results reveal that a mixture with 4:1 EmimTFSI/EmimBF 4 volume ratio displaces the larger [TFSI –] anions with smaller [BF 4 –] ions, leading to an excessmore » adsorption of [Emim +] cations near the electrode surface. These findings are corroborated by the manifestation of nonuniform ion diffusivity change, complementing the description of structural modifications with changing composition, from QENS measurements. In conclusion, molecular-level understanding of ion packing near electrodes provides insight for design of ionic liquid formulations that enhance the performance of electrochemical energy storage devices.« less

Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors

DOE PAGES

Osti, Naresh C.; Gallegos, Alejandro; Dyatkin, Boris; ...

2018-04-19

Well-tailored mixtures of distinct ionic liquids can act as optimal electrolytes that extend the operating electrochemical window and improve charge storage density in supercapacitors. Here, we explore two room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF 4). We study their electric double-layer behavior in the neat state and as binary mixtures on the external surfaces of onion-like carbon electrodes using quasielastic neutron scattering (QENS) and classical density functional theory techniques. Computational results reveal that a mixture with 4:1 EmimTFSI/EmimBF 4 volume ratio displaces the larger [TFSI –] anions with smaller [BF 4 –] ions, leading to an excessmore » adsorption of [Emim +] cations near the electrode surface. These findings are corroborated by the manifestation of nonuniform ion diffusivity change, complementing the description of structural modifications with changing composition, from QENS measurements. In conclusion, molecular-level understanding of ion packing near electrodes provides insight for design of ionic liquid formulations that enhance the performance of electrochemical energy storage devices.« less

Development of a united-atom force field for 1-ethyl-3-methylimidazolium tetracyanoborate ionic liquid

NASA Astrophysics Data System (ADS)

Koller, Thomas; Ramos, Javier; Garrido, Nuno M.; Fröba, Andreas P.; Economou, Ioannis G.

2012-06-01

Three united-atom (UA) force fields are presented for the ionic liquid 1-ethyl-3-methylimidazolium tetracyanoborate, abbreviated as [EMIM]+[B(CN)4]-. The atomistic charges were calculated based on the restrained electrostatic potential (RESP) of the isolated ions (abbreviated as force field 1, FF-1) and the ensemble averaged RESP (EA-RESP) method from the most stable ion pair configurations obtained by MP2/6-31G*+ calculations (abbreviated as FF-2 and FF-3). Non-electrostatic parameters for both ions were taken from the literature and Lennard-Jones parameters for the [B(CN)4]- anion were fitted in two different ways to reproduce the experimental liquid density. Molecular dynamics (MD) simulations were performed over a wide temperature range to identify the effect of the electrostatic and non-electrostatic potential on the liquid density and on transport properties such as self-diffusion coefficient and viscosity. Predicted liquid densities for the three parameter sets deviate less than 0.5% from experimental data. The molecular mobility with FF-2 and FF-3 using reduced charge sets is appreciably faster than that obtained with FF-1. FF-3 presents a refined non-electrostatic potential that leads to a notable improvement in both transport properties when compared to experimental data.

Biodegradation of imidazolium ionic liquids by activated sludge microorganisms.

PubMed

Liwarska-Bizukojc, Ewa; Maton, Cedric; Stevens, Christian V

2015-11-01

Biological properties of ionic liquids (ILs) have been usually tested with the help of standard biodegradation or ecotoxicity tests. So far, several articles on the identification of intermediate metabolites of microbiological decay of ILs have been published. Simultaneously, the number of novel ILs with unrecognized characteristics regarding biodegradability and effect on organisms and environment is still increasing. In this work, seven imidazolium ionic liquids of different chemical structure were studied. Three of them are 1-alkyl-3-methyl-imidazolium bromides, while the other four are tetra- or completely substituted imidazolium iodides. This study focused on the identification of intermediate metabolites of the aforementioned ionic liquids subjected to biodegradation in a laboratory activated sludge system. Both fully substituted ionic liquids and 1-ethyl-3-methyl-imidazolium bromide were barely biodegradable. In the case of two of them, no biotransformation products were detected. The elongation of the alkyl side chain made the IL more susceptible for microbiological decomposition. 1-Decyl-3-methyl-imidazolium bromide was biotransformed most easily. Its primary biodegradation up to 100 % could be achieved. Nevertheless, the cleavage of the imidazolium ring has not been observed.

Structure and lifetimes in ionic liquids and their mixtures.

PubMed

Gehrke, Sascha; von Domaros, Michael; Clark, Ryan; Hollóczki, Oldamur; Brehm, Martin; Welton, Tom; Luzar, Alenka; Kirchner, Barbara

2018-01-01

With the aid of molecular dynamics simulations, we study the structure and dynamics of different ionic liquid systems, with focus on hydrogen bond, ion pair and ion cage formation. To do so, we report radial distribution functions, their number integrals, and various time-correlation functions, from which we extract well-defined lifetimes by means of the reactive flux formalism. We explore the influence of polarizable force fields vs. non-polarizable ones with downscaled charges (±0.8) for the example of 1-butyl-3-methylimidazolium bromide. Furthermore, we use 1-butyl-3-methylimidazolium trifluoromethanesulfonate to investigate the impact of temperature and mixing with water as well as with the chloride ionic liquid. Smaller coordination numbers, larger distances, and tremendously accelerated dynamics are observed when the polarizable force field is applied. The same trends are found with increasing temperature. Adding water decreases the ion-ion coordination numbers whereas the water-ion and water-water coordination is enhanced. A domain analysis reveals that the nonpolar parts of the ions are dispersed and when more water is added the water clusters increase in size. The dynamics accelerate in general upon addition of water. In the ionic liquid mixture, the coordination number around the cation changes between the two anions, but the number integrals of the cation around the anions remain constant and the dynamics slow down with increasing content of the chloride ionic liquid.

Physico-Chemical Properties and Phase Behaviour of Pyrrolidinium-Based Ionic Liquids

PubMed Central

Domańska, Urszula

2010-01-01

A review of the relevant literature on 1-alkyl-1-methylpyrrolidinium-based ionic liquids has been presented. The phase diagrams for the binary systems of {1-ethyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate) [EMPYR][CF3SO3] + water, or + 1-butanol} and for the binary systems of {1-propyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate) [PMPYR][CF3SO3] + water, or + an alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol)} have been determined at atmospheric pressure using a dynamic method. The influence of alcohol chain length was discussed for the [PMPYR][CF3SO3]. A systematic decrease in the solubility was observed with an increase of the alkyl chain length of an alcohol. (Solid + liquid) phase equilibria with complete miscibility in the liquid phase region were observed for the systems involving water and alcohols. The solubility of the ionic liquid increases as the alkyl chain length on the pyrrolidinium cation increases. The correlation of the experimental data has been carried out using the Wilson, UNIQUAC and the NRTL equations. The phase diagrams reported here have been compared to the systems published earlier with the 1-alkyl-1-methylpyrrolidinium-based ionic liquids. The influence of the cation and anion on the phase behaviour has been discussed. The basic thermal properties of pure ILs, i.e., melting temperature and the enthalpy of fusion, the solid-solid phase transition temperature and enthalpy have been measured using a differential scanning microcalorimetry technique. PMID:20480044

Surface polymerization of (3,4-ethylenedioxythiophene) probed by in situ scanning tunneling microscopy on Au(111) in ionic liquids.

PubMed

Ahmad, Shahzada; Carstens, Timo; Berger, Rüdiger; Butt, Hans-Jürgen; Endres, Frank

2011-01-01

The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situ scanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situ STM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situ microscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM).

Development of Formaldehyde Biosensor for Determination of Formalin in Fish Samples; Malabar Red Snapper (Lutjanus malabaricus) and Longtail Tuna (Thunnus tonggol)

PubMed Central

Noor Aini, Bohari; Siddiquee, Shafiquzzaman; Ampon, Kamaruzaman

2016-01-01

Electrochemical biosensors are widely recognized in biosensing devices due to the fact that gives a direct, reliable, and reproducible measurement within a short period. During bio-interaction process and the generation of electrons, it produces electrochemical signals which can be measured using an electrochemical detector. A formaldehyde biosensor was successfully developed by depositing an ionic liquid (IL) (e.g., 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM][Otf])), gold nanoparticles (AuNPs), and chitosan (CHIT), onto a glassy carbon electrode (GCE). The developed formaldehyde biosensor was analyzed for sensitivity, reproducibility, storage stability, and detection limits. Methylene blue was used as a redox indicator for increasing the electron transfer in the electrochemical cell. The developed biosensor measured the NADH electron from the NAD+ reduction at a potential of 0.4 V. Under optimal conditions, the differential pulse voltammetry (DPV) method detected a wider linear range of formaldehyde concentrations from 0.01 to 10 ppm within 5 s, with a detection limit of 0.1 ppm. The proposed method was successfully detected with the presence of formalin in fish samples, Lutjanus malabaricus and Thunnus Tonggol. The proposed method is a simple, rapid, and highly accurate, compared to the existing technique. PMID:27376338

Rheological properties of concentrated solutions of gelatin in an ionic liquid 1-ethyl-3-methylimidazolium dimethyl phosphate.

PubMed

Horinaka, Jun-Ichi; Okamoto, Arisa; Takigawa, Toshikazu

2016-10-01

Rheological properties of gelatin solutions were examined in concentrated regions. Gelatin species from porcine skin and from bovine bone were dissolved in an ionic liquid 1-ethyl-3-methylimidazolium dimethyl phosphate. The dynamic viscoelasticity data for the solutions exhibited rubbery plateaus, indicating the existence of entanglement coupling between gelatin chains in the solutions. From the analogy with rubber elasticity, assuming that the molecular weight between entanglements (Me) is the average mesh size of the entanglement network, Me for gelatin in the solutions were determined from the heights of the rubbery plateaus. Then the value of Me in the molten state (Me,melt), a material constant reflecting the chemical structure of polymer species, for gelatin was estimated to be 8.7×10(3). Compared to synthetic polyamides whose Me,melt were known, Me,melt for gelatin was significantly larger, which could be explained by the densely repeating amide bonds composing gelatin. Copyright © 2016 Elsevier B.V. All rights reserved.

Ideal gas solubilities and solubility selectivities in a binary mixture of room-temperature ionic liquids.

PubMed

Finotello, Alexia; Bara, Jason E; Narayan, Suguna; Camper, Dean; Noble, Richard D

2008-02-28

This study focuses on the solubility behaviors of CO2, CH4, and N2 gases in binary mixtures of imidazolium-based room-temperature ionic liquids (RTILs) using 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][Tf2N]) and 1-ethyl-3-methylimidazolium tetrafluoroborate ([C2mim][BF4]) at 40 degrees C and low pressures (approximately 1 atm). The mixtures tested were 0, 25, 50, 75, 90, 95, and 100 mol % [C2mim][BF4] in [C2mim][Tf2N]. Results show that regular solution theory (RST) can be used to describe the gas solubility and selectivity behaviors in RTIL mixtures using an average mixture solubility parameter or an average measured mixture molar volume. Interestingly, the solubility selectivity, defined as the ratio of gas mole fractions in the RTIL mixture, of CO2 with N2 or CH4 in pure [C2mim][BF4] can be enhanced by adding 5 mol % [C2mim][Tf2N].

Elucidation of the effect of ionic liquid pretreatment on rice husk via structural analyses

PubMed Central

2012-01-01

Background In the present study, three ionic liquids, namely 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc), and 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIM]DEP), were used to partially dissolve rice husk, after which the cellulose were regenerated by the addition of water. The aim of the investigation is to examine the implications of the ionic liquid pretreatments on rice husk composition and structure. Results From the attenuated total reflectance Fourier transform-infrared (ATR FT-IR) spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM) results, the regenerated cellulose were more amorphous, less crystalline, and possessed higher structural disruption compared with untreated rice husk. The major component of regenerated cellulose from [BMIM]Cl and [EMIM]DEP pretreatments was cellulose-rich material, while cellulose regenerated from [EMIM]OAc was a matrix of cellulose and lignin. Cellulose regenerated from ionic pretreatments could be saccharified via enzymatic hydrolysis, and resulted in relatively high reducing sugars yields, whereas enzymatic hydrolysis of untreated rice husk did not yield reducing sugars. Rice husk residues generated from the ionic liquid pretreatments had similar chemical composition and amorphousity to that of untreated rice husk, but with varying extent of surface disruption and swelling. Conclusions The structural architecture of the regenerated cellulose and rice husk residues showed that they could be used for subsequent fermentation or derivation of cellulosic compounds. Therefore, ionic liquid pretreatment is an alternative in the pretreatment of lignocellulosic biomass in addition to the conventional chemical pretreatments. PMID:22958710

Rotational dynamics of coumarin-153 and 4-aminophthalimide in 1-ethyl-3-methylimidazolium alkylsulfate ionic liquids: effect of alkyl chain length on the rotational dynamics.

PubMed

Das, Sudhir Kumar; Sarkar, Moloy

2012-01-12

Rotational dynamics of two neutral organic solutes, coumarin-153 (C-153) and 4-aminophthalimide (AP), with only the latter having hydrogen-bond-donating ability, has been investigated in a series of 1-ethyl-3-methylimidazolium alkyl sulfate ionic liquids as a function of temperature. The ionic liquids differ only in the length of the linear alkyl side chain (alkyl = ethyl, butyl, hexyl, and octyl) on the anionic moiety. The present study has been undertaken to examine the role of alkyl side chains on the rotational dynamics of the two solutes in these ionic liquids. Analysis of the results using Stokes-Einstein-Debye hydrodynamic theory indicates that the rotational dynamics of C-153 lies between the stick and slip boundary condition in the ethyl analogue and finally reaches subslip condition as in case of the octyl substituent. The observed rotational behavior of C-153 has been explained on the basis of an increase in the size of the solvent, which offers lower friction for solute rotation. On the other hand, AP shows superstick behavior in the ethyl system and exceeds the stick limit in the octyl derivative. Superstick behavior of AP has been attributed to the specific hydrogen-bonding interaction between AP and the sulfate moiety. Proton NMR investigation confirms the hydrogen-bonding interaction between the N-H hydrogen of AP and the ionic liquid. The decrease in rotational coupling constant values for AP with increasing length of alkyl side chains has been attributed to the decrease in the solute-solvent-specific interaction with an increase in the alkyl side chain length on the sulfate moiety.

A recyclable and base-free method for the synthesis of 3-iodothiophenes by the iodoheterocyclisation of 1-mercapto-3-alkyn-2-ols in ionic liquids.

PubMed

Mancuso, Raffaella; Pomelli, Christian S; Chiappe, Cinzia; Larock, Richard C; Gabriele, Bartolo

2014-01-28

The first example of an iodocyclisation reaction made recyclable by the use of an ionic liquid as the reaction medium is reported. Readily available 1-mercapto-3-alkyn-2-ols were smoothly converted into the corresponding 3-iodothiophenes (50-81% yields, 10 examples) when allowed to react with iodine (1-2 equiv.) in a proper ionic liquid, such as 1-ethyl-3-methylimidazolium ethyl sulfate (EmimEtSO4), as the solvent under mild reaction conditions (25 °C) and in the absence of an external base. The reaction medium can be recycled several times without significantly affecting the reaction outcome. Theoretical calculations have also been performed to investigate the role of the ionic liquid anion in the reaction.

Enhancing the Capacitive Performance of Electric Double-Layer Capacitors with Ionic Liquid Mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lian, C.; Liu, K.; Van Aken, Katherine L.

Formulating room-temperature ionic liquid (RTIL) mixed electrolytes was recently proposed as an effective and convenient strategy to increase the capacitive performance of electrochemical capacitors. In this paper, we investigate the electrical double-layer (EDL) structure and the capacitance of two RTILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF 4), and their mixtures with onion-like carbon electrodes using experiment and classical density functional theory. The principal difference between these ionic liquids is the smaller diameter of the BF 4 – anion relative to the TFSI – anion and the EMI + cation. A volcano-shaped trend is identified for the capacitance versus themore » composition of the RTIL mixture. The mixture effect, which makes more counterions pack on and more co-ions leave from the electrode surface, leads to an increase of the counterion density within the EDL and thus a larger capacitance. Finally, these theoretical predictions are in good agreement with our experimental observations and offer guidance for designing RTIL mixtures for EDL supercapacitors.« less

Enhancing the Capacitive Performance of Electric Double-Layer Capacitors with Ionic Liquid Mixtures

DOE PAGES

Lian, C.; Liu, K.; Van Aken, Katherine L.; ...

2016-04-18

Formulating room-temperature ionic liquid (RTIL) mixed electrolytes was recently proposed as an effective and convenient strategy to increase the capacitive performance of electrochemical capacitors. In this paper, we investigate the electrical double-layer (EDL) structure and the capacitance of two RTILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF 4), and their mixtures with onion-like carbon electrodes using experiment and classical density functional theory. The principal difference between these ionic liquids is the smaller diameter of the BF 4 – anion relative to the TFSI – anion and the EMI + cation. A volcano-shaped trend is identified for the capacitance versus themore » composition of the RTIL mixture. The mixture effect, which makes more counterions pack on and more co-ions leave from the electrode surface, leads to an increase of the counterion density within the EDL and thus a larger capacitance. Finally, these theoretical predictions are in good agreement with our experimental observations and offer guidance for designing RTIL mixtures for EDL supercapacitors.« less

Characterization of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][Tf2N])∕TX-100∕cyclohexane ternary microemulsion: investigation of photoinduced electron transfer in this RTIL containing microemulsion.

PubMed

Sarkar, Souravi; Pramanik, Rajib; Ghatak, Chiranjib; Rao, Vishal Govind; Sarkar, Nilmoni

2011-02-21

In this study we have characterized a ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethyl- sulfonyl)imide containing ternary nonaqueous microemulsion ([Emim][Tf(2)N]∕∕TX-100∕cyclo- hexane). The phase behavior and dynamic light scattering study show that the [Emim][Tf(2)N]∕TX-100∕cyclohexane three component system can form microemulsion with [Emim][Tf(2)N] as polar core at suitable condition. We have investigated photoinduced electron transfer (PET) using dimethyl aniline as electron donor and several Coumarin dyes as electron acceptor molecules at two different R values (R = [ionic liquid]∕[surfactant]) to observe how the dynamics of the PET rate is affected in this type of confined microenvironment compared to that of the PET dynamics in neat ionic liquid and other pure solvent media. The plot of observed k(q) values with the free energy change (ΔG(0)) for electron transfer reaction shows an apparent inversion in the observed rate as predicted by the Marcus theory.

Extensional ionomeric polymer conductor composite actuators with ionic liquids

NASA Astrophysics Data System (ADS)

Liu, Sheng; Lin, Minren; Zhang, Qiming

2008-03-01

Although the Ionic Polymer-Metal Composite (IPMC) actuators developed up to date are in the form of bending actuators, development of extensional actuators based on IMPC is highly desirable from practical applications and fundamental understanding points of view. This talk presents the design, fabrication and characterization of a recent work on an extensional Ionic Polymer-Metal Composite actuator. The extensional actuator consists of the Nafion ionomer as the matrix and the sub-micron size RuO II particles as the conductive filler for the conductor/ionomr composites. In this investigation, several ionic liquids (IL) were investigated. For a Nafion/RuO II composite with 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate (EMI-Tf) IL, it was found that as the ions are driven into the ionomer/RuO II composite (the composite under negative voltage), an extensional strain of 0.9% was observed; while as the ions were expelled from the ionomer/RuO II composite (under positive voltage), a contraction of -1.2% was observed. The results indicate that multiple ions are participating in charge transport and actuation process. In this paper, we also discuss several design considerations for future extensional actuators with fast response, much improved strain and stress level. Especially an actuator based on multilayer configuration can significantly increase the electric field level in the actuator and consequently significantly improve the actuator speed. The extensional actuator investigated here provides a unique platform to investigate various phenomena related to ion transport and their interaction with the ionomer/conductor matrix to realize high electromechanical performance.

Impact of two ionic liquids, 1-ethyl-3-methylimidazolium acetate and 1-ethyl-3-methylimidazolium methylphosphonate, on Saccharomyces cerevisiae: metabolic, physiologic, and morphological investigations.

PubMed

Mehmood, Nasir; Husson, Eric; Jacquard, Cédric; Wewetzer, Sandra; Büchs, Jochen; Sarazin, Catherine; Gosselin, Isabelle

2015-01-01

Ionic liquids (ILs) are considered as suitable candidates for lignocellulosic biomass pretreatment prior enzymatic saccharification and, obviously, for second-generation bioethanol production. However, several reports showed toxic or inhibitory effects of residual ILs on microorganisms, plants, and animal cells which could affect a subsequent enzymatic saccharification and fermentation process. In this context, the impact of two hydrophilic imidazolium-based ILs already used in lignocellulosic biomass pretreatment was investigated: 1-ethyl-3-methylimidazolium acetate [Emim][OAc] and 1-ethyl-3-methylimidazolium methylphosphonate [Emim][MeO(H)PO2]. Their effects were assessed on the model yeast for ethanolic fermentation, Saccharomyces cerevisiae, grown in a culture medium containing glucose as carbon source and various IL concentrations. Classical fermentation parameters were followed: growth, glucose consumption and ethanol production, and two original factors: the respiratory status with the oxygen transfer rate (OTR) and carbon dioxide transfer rate (CTR) of yeasts which were monitored online by respiratory activity monitoring systems (RAMOS). In addition, yeast morphology was characterized by environmental scanning electron microscope (ESEM). The addition of ILs to the growth medium inhibited the OTR and switched the metabolism from respiration (conversion of glucose into biomass) to fermentation (conversion of glucose to ethanol). This behavior could be observed at low IL concentrations (≤5% IL) while above there is no significant growth or ethanol production. The presence of IL in the growth medium also induced changes of yeast morphology, which exhibited wrinkled, softened, and holed shapes. Both ILs showed the same effects, but [Emim][MeO(H)PO2] was more biocompatible than [Emim][OAc] and could be better tolerated by S. cerevisiae. These two imidazolium-derived ILs were appropriate candidates for useful pretreatment of lignocellulosic biomass in the context of second-generation bioethanol production. This fundamental study provides additional information about the toxic effects of ILs. Indeed, the investigations highlighted the better tolerance by S. cerevisiae of [Emim][MeO(H)PO2] than [Emim][OAc].

Physical Properties of Substituted Imidazolium Based Ionic Liquids Gel Electrolytes

NASA Astrophysics Data System (ADS)

Sutto, Thomas E.; De Long, Hugh C.; Trulove, Paul C.

2002-11-01

The physical properties of solid gel electrolytes of either polyvinylidene diflurohexafluoropropylene or a combination of polyvinylidene hexafluoropropylene and polyacrylic acid, and the molten salts 1-ethyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-3-n-propylimidazolium tetrafluoroborate, and the new molten salts 1,2-dimethyl-3-n-butylimidazolium tetrafluoroborate, and 1,2-dimethyl-3-n-butylimidazolium hexafluorophosphate were characterized by temperature dependent ionic conductivity measurements for both the pure molten salt and of the molten salt with 0.5 M Li+ present. Ionic conductivity data indicate that for each of the molten salts, the highest concentration of molten salt allowable in a single component polymer gel was 85%, while gels composed of 90%molten salt were possible when using both polyvinylidene hexafluorophosphate and polyacrylic acid. For polymer gel composites prepared using lithium containing ionic liquids, the optimum polymer gel composite consisted of 85% of the 0.5 M Li+/ionic liquid, 12.75% polyvinylidene hexafluoropropylene, and 2.25% poly (1-carboxyethylene). The highest ionic conductivity observed was for the gel containing 90%1-ethyl-3-methyl-imidazolium tetrafluoroborate, 9.08 mS/cm. For the lithium containing ionic liquid gels, their ionic conductivity ranged from 1.45 to 0.05 mS/cm, which is comparable to the value of 0.91 mS/cm, observed for polymer composite gels containing 0.5 M LiBF4 in propylene carbonate.

Influences of porous reservoir Laplace pressure on emissions from passively fed ionic liquid electrospray sources

DOE Office of Scientific and Technical Information (OSTI.GOV)

Courtney, Daniel G., E-mail: dcourtney@alum.mit.edu; Shea, Herbert

2015-09-07

Passively fed ionic liquid electrospray sources are capable of efficiently emitting a variety of ion beams with promising applications to spacecraft propulsion and as focused ion beams. Practical devices will require integrated or coupled ionic liquid reservoirs; the effects of which have not been explored in detail. Porous reservoirs are a simple, scalable solution. However, we have shown that their pore size can dramatically alter the beam composition. Emitting the ionic liquid 1-ethyl-3-methylimidazolium bis(triflouromethylsulfonyl)amide, the same device was shown to yield either an ion or droplet dominated beam when using reservoirs of small or large pore size, respectively; with themore » latter having a mass flow in excess of 15 times larger than the former at negative polarity. Another source, emitting nearly purely ionic beams of 1-ethyl-3-methylimidazolium tetrafluoroborate, was similarly shown to emit a significant droplet population when coupled to reservoirs of large (>100 μm) pores; constituting a reduction in propulsive efficiency from greater than 70% to less than 30%. Furthermore, we show that reservoir selection can alter the voltage required to obtain and sustain emission, increasing with smaller pore size.« less

Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1-Butyl-3-Methylimidazolium Ionic Liquids and Propylene Carbonate.

PubMed

Schütte, Kai; Barthel, Juri; Endres, Manuel; Siebels, Marvin; Smarsly, Bernd M; Yue, Junpei; Janiak, Christoph

2017-02-01

Decomposition of transition-metal amidinates [M{MeC(N i Pr) 2 } n ] [M(AMD) n ; M=Mn II , Fe II , Co II , Ni II , n= 2; Cu I , n= 1) induced by microwave heating in the ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF 4 ]), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF 6 ]), 1-butyl-3-methylimidazolium trifluoromethanesulfonate (triflate) ([BMIm][TfO]), and 1-butyl-3-methylimidazolium tosylate ([BMIm][Tos]) or in propylene carbonate (PC) gives transition-metal nanoparticles (M-NPs) in non-fluorous media (e.g. [BMIm][Tos] and PC) or metal fluoride nanoparticles (MF 2 -NPs) for M=Mn, Fe, and Co in [BMIm][BF 4 ]. FeF 2 -NPs can be prepared upon Fe(AMD) 2 decomposition in [BMIm][BF 4 ], [BMIm][PF 6 ], and [BMIm][TfO]. The nanoparticles are stable in the absence of capping ligands (surfactants) for more than 6 weeks. The crystalline phases of the metal or metal fluoride synthesized in [BMIm][BF 4 ] were identified by powder X-ray diffraction (PXRD) to exclusively Ni- and Cu-NPs or to solely MF 2 -NPs for M=Mn, Fe, and Co. The size and size dispersion of the nanoparticles were determined by transmission electron microscopy (TEM) to an average diameter of 2(±2) to 14(±4) nm for the M-NPs, except for the Cu-NPs in PC, which were 51(±8) nm. The MF 2 -NPs from [BMIm][BF 4 ] were 15(±4) to 65(±18) nm. The average diameter from TEM is in fair agreement with the size evaluated from PXRD with the Scherrer equation. The characterization was complemented by energy-dispersive X-ray spectroscopy (EDX). Electrochemical investigations of the CoF 2 -NPs as cathode materials for lithium-ion batteries were simply evaluated by galvanostatic charge/discharge profiles, and the results indicated that the reversible capacity of the CoF 2 -NPs was much lower than the theoretical value, which may have originated from the complex conversion reaction mechanism and residue on the surface of the nanoparticles.

Comparative study of bending characteristics of ionic polymer actuators containing ionic liquids for modeling actuation

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Sakamoto, Takumi; Tsuchitani, Shigeki; Asaka, Kinji

2011-04-01

Ionic polymer metal composites (IPMCs) that can operate in air have recently been developed by incorporating an ionic liquid in ionic polymers. To understand transduction in these composites, it is important to determine the role of the ionic liquid in the ionic polymer (Nafion®), to identify the counter cation, and to investigate the interaction of IPMCs with water vapor in the air. We used Fourier-transform infrared spectroscopy to analyze three Nafion® membranes, which were soaked in mixtures of water and an ionic liquid (1-ethyl-3-methyl-imidazolium tetrafluoroborate (EMIBF4), 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6)). The results demonstrate that only cations (EMI+ and BMI+) in the ionic liquids are taken into the Nafion® membranes as counter ions and that the water content of the membranes in air is less than ˜4% that of Nafion® swollen with water. Based on the experimental results, a transduction model is proposed for an IPMC with an ionic liquid. In this model, bending is caused by local swelling due to the volume effect of the bulky counter cations. This model can explain 30-50% of the experimentally observed bending curvature.

Surface segregation in a binary mixture of ionic liquids: Comparison between high-resolution RBS measurements and moleculardynamics simulations.

PubMed

Nakajima, Kaoru; Nakanishi, Shunto; Chval, Zdeněk; Lísal, Martin; Kimura, Kenji

2016-11-14

Surface structure of equimolar mixture of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C 2 C 1 Im][Tf 2 N]) and 1-ethyl-3-methylimidazolium tetrafluoroborate ([C 2 C 1 Im][BF 4 ]) is studied using high-resolution Rutherford backscattering spectroscopy (HRBS) and molecular dynamics (MD) simulations. Both HRBS and MD simulations show enrichment of [Tf 2 N] in the first molecular layer although the degree of enrichment observed by HRBS is more pronounced than that predicted by the MD simulation. In the subsurface region, MD simulation shows a small depletion of [Tf 2 N] while HRBS shows a small enrichment here. This discrepancy is partially attributed to the artifact of the MD simulations. Since the number of each ion is fixed in a finite-size simulation box, surface enrichment of particular ion results in its artificial depletion in the subsurface region.

Surface segregation in a binary mixture of ionic liquids: Comparison between high-resolution RBS measurements and molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Nakajima, Kaoru; Nakanishi, Shunto; Chval, Zdeněk; Lísal, Martin; Kimura, Kenji

2016-11-01

Surface structure of equimolar mixture of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C2C1Im][Tf2N]) and 1-ethyl-3-methylimidazolium tetrafluoroborate ([C2C1Im][BF4]) is studied using high-resolution Rutherford backscattering spectroscopy (HRBS) and molecular dynamics (MD) simulations. Both HRBS and MD simulations show enrichment of [Tf2N] in the first molecular layer although the degree of enrichment observed by HRBS is more pronounced than that predicted by the MD simulation. In the subsurface region, MD simulation shows a small depletion of [Tf2N] while HRBS shows a small enrichment here. This discrepancy is partially attributed to the artifact of the MD simulations. Since the number of each ion is fixed in a finite-size simulation box, surface enrichment of particular ion results in its artificial depletion in the subsurface region.

Dissolving process of a cellulose bunch in ionic liquids: a molecular dynamics study.

PubMed

Li, Yao; Liu, Xiaomin; Zhang, Suojiang; Yao, Yingying; Yao, Xiaoqian; Xu, Junli; Lu, Xingmei

2015-07-21

In recent years, a variety of ionic liquids (ILs) were found to be capable of dissolving cellulose and mechanistic studies were also reported. However, there is still a lack of detailed information at the molecular level. Here, long time molecular dynamics simulations of cellulose bunch in 1-ethyl-3-methylimidazolium acetate (EmimAc), 1-ethyl-3-methylimidazolium chloride (EmimCl), 1-butyl-3-methylimidazolium chloride (BmimCl) and water were performed to analyze the inherent interaction and dissolving mechanism. Complete dissolution of the cellulose bunch was observed in EmimAc, while little change took place in EmimCl and BmimCl, and nothing significant happened in water. The deconstruction of the hydrogen bond (H-bond) network in cellulose was found and analyzed quantitatively. The synergistic effect of cations and anions was revealed by analyzing the whole dissolving process. Initially, cations bind to the side face of the cellulose bunch and anions insert into the cellulose strands to form H-bonds with hydroxyl groups. Then cations start to intercalate into cellulose chains due to their strong electrostatic interaction with the entered anions. The H-bonds formed by Cl(-) cannot effectively separate the cellulose chain and that is the reason why EmimCl and BmimCl dissolve cellulose more slowly. These findings deepen people's understanding on how ILs dissolve cellulose and would be helpful for designing new efficient ILs to dissolve cellulose.

Genome Sequence of Halomonas sp. Strain KO116, an Ionic Liquid- Tolerant Marine Bacterium Isolated from a Lignin-Enriched Seawater Microcosm

DOE PAGES

O'Dell, Kaela; Woo, Hannah L.; Utturkar, Sagar M.; ...

2015-05-07

Halomonas sp. strain KO116 was isolated from Nile Delta Mediterranean Sea surface water enriched with insoluble organosolv lignin. It was further screened for growth on alkali lignin minimal salts medium agar. The strain tolerates the ionic liquid 1-ethyl-3-methylimidazolium acetate. Its complete genome sequence is presented in this report.

Soft shape-adaptive gripping device made from artificial muscle

NASA Astrophysics Data System (ADS)

Hamburg, E.; Vunder, V.; Johanson, U.; Kaasik, F.; Aabloo, A.

2016-04-01

We report on a multifunctional four-finger gripper for soft robotics, suitable for performing delicate manipulation tasks. The gripping device is comprised of separately driven gripping and lifting mechanisms, both made from a separate single piece of smart material - ionic capacitive laminate (ICL) also known as artificial muscle. Compared to other similar devices the relatively high force output of the ICL material allows one to construct a device able to grab and lift objects exceeding multiple times its own weight. Due to flexible design of ICL grips, the device is able to adapt the complex shapes of different objects and allows grasping single or multiple objects simultaneously without damage. The performance of the gripper is evaluated in two different configurations: a) the ultimate grasping strength of the gripping hand; and b) the maximum lifting force of the lifting actuator. The ICL is composed of three main layers: a porous membrane consisting of non-ionic polymer poly(vinylidene fluoride-co-hexafluoropropene) (PVdF-HFP), ionic liquid 1-ethyl-3-methylimidazolium trifluoromethane-sulfonate (EMITFS), and a reinforcing layer of woven fiberglass cloth. Both sides of the membrane are coated with a carbonaceous electrode. The electrodes are additionally covered with thin gold layers, serving as current collectors. Device made of this material operates silently, requires low driving voltage (<3 V), and is suitable for performing tasks in open air environment.

Extraction of Proanthocyanidins and Anthocyanins from Grape Skin by Using Ionic Liquids

PubMed Central

2017-01-01

Summary In this study, eight different types of imidazolium-based ionic liquids (ILs) were applied as new solvents in the extraction of flavonoids from grape skin, and compared to the conventional organic solvent extraction that was not reported earlier. The structure of anions, cations and concentration of ILs significantly affected extraction yields. The highest mass fractions of proanthocyanidins and anthocyanins were obtained with 2.5 mol/L of 1-butyl-3-methylimidazolium bromide [C4mim][Br] and 2.5 mol/L of 1-ethyl-3-methylimidazolium bromide [C2mim][Br], respectively. The studied ILs provided an excellent preliminary result in the extraction of anthocyanins. Significantly higher mass fractions of total and all free anthocyanins were extracted with 2.5 mol/L of [C2mim][Br] and 2.5 mol/L of 1-methylimidazolium hydrogen sulfate [mim][HSO4] than with conventional solvent with the exception of anthocyanin-3-O-acetylmonoglucosides in the latter. On the other hand, 2.5 mol/L of [C4mim][Br] and 2.5 mol/L of 1-(4-sulfobutyl)-3-methylimidazolium hydrogen sulfate [sC4mim][HSO4] showed significantly higher selectivity towards anthocyanin-3-O-acetylmonoglucosides and anthocyanin-3-(6-O-p-coumaroyl)monoglucosides. PMID:29089857

Vapor-Liquid Equilibria of Imidazolium Ionic Liquids with Cyano Containing Anions with Water and Ethanol.

PubMed

Khan, Imran; Batista, Marta L S; Carvalho, Pedro J; Santos, Luís M N B F; Gomes, José R B; Coutinho, João A P

2015-08-13

Isobaric vapor-liquid equilibria of 1-butyl-3-methylimidazolium thiocyanate ([C4C1im][SCN]), 1-butyl-3-methylimidazolium dicyanamide ([C4C1im][N(CN)2]), 1-butyl-3-methylimidazolium tricyanomethanide ([C4C1im][C(CN)3]), and 1-ethyl-3-methylimidazolium tetracyanoborate ([C2C1im][B(CN)4]), with water and ethanol were measured over the whole concentration range at 0.1, 0.07, and 0.05 MPa. Activity coefficients were estimated from the boiling temperatures of the binary systems, and the data were used to evaluate the ability of COSMO-RS for describing these molecular systems. Aiming at further understanding the molecular interactions on these systems, molecular dynamics (MD) simulations were performed. On the basis of the interpretation of the radial and spatial distribution functions along with coordination numbers obtained through MD simulations, the effect of the increase of CN-groups in the IL anion in its capability to establish hydrogen bonds with water and ethanol was evaluated. The results obtained suggest that, for both water and ethanol systems, the anion [N(CN)2](-) presents the higher ability to establish favorable interactions due to its charge, and that the ability of the anions to interact with the solvent, decreases with further increasing of the number of cyano groups in the anion. The ordering of the partial charges in the nitrogen atoms from the CN-groups in the anions agrees with the ordering obtained for VLE and activity coefficient data.

Experimental and computational study on the properties of pure and water mixed 1-ethyl-3-methylimidazolium L-(+)-lactate ionic liquid.

PubMed

Aparicio, Santiago; Alcalde, Rafael; Atilhan, Mert

2010-05-06

Ionic liquids have attracted great attention, from both industry and academe, as alternative fluids for a large collection of applications. Although the term green is used frequently to describe ionic liquids in general, it is obvious that it cannot be applied to the huge quantity of possible ionic liquids, and thus, those with adequate environmental and technological profiles must be selected for further and deeper studies, from both basic science and applied approaches. In this work, 1-ethyl-3-methylimidazolium L-(+)-lactate ionic liquid is studied, because of its remarkable properties, through a wide-ranging approach considering thermophysical, spectroscopic, and computational tools, to gain a deeper insight into its complex liquid structure, both pure and mixed with water, thus implying the main factors that would control the technological applications that could be designed using this fluid. The reported results shows a strongly structured pure ionic liquid, in which hydrogen bonding, because of the hydroxyl group of the lactate anion, develops a remarkable role, together with Coulombic forces to determine the fluid's behavior. Upon mixing with water, the ionic liquid retains its structure up to very high dilution levels, with the effect of the ionic liquid on the water structure being very large, even for very low ionic liquid mole fractions. Thus, in water solution, the studied ionic liquid evolves from noninteracting ions solvated by water molecules toward large interacting structures with increasing ionic liquid content.

Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids

DOE PAGES

Wu, Boning; Liang, Min; Maroncelli, Mark; ...

2015-10-26

Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyano-borate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients andmore » time-integrated spectra. Finally, application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V 0, where D is the relative diffusion coefficient between donor and acceptor and V 0 is the value of the electronic coupling at donor-acceptor contact.« less

Glass dynamics and anomalous aging in a family of ionic liquids above the glass transition temperature.

PubMed

Shamim, Nabila; McKenna, Gregory B

2010-12-09

The present paper reports the results of a systematic rheological study of the dynamic moduli of 1-butyl 3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]), 1-butyl 3-methylimidazolium hexafluorophosphate ([Bmim][PF(6)]), and 1-ethyl 3-methylimidazolium ethylsulfate ([Emim][EtSO(4)]) in the vicinity of their respective glass transition temperatures. The results show an anomalous aging in that the dynamic and the low shear rate viscosities decrease with time at temperatures near to, but above, the glass transition temperature, and this is described. The samples that are aged into equilibrium obey the time-temperature superposition principle, and the shift factors and the viscosities follow classic super-Arrhenius behaviors with intermediate fragility values as the glass transition is approached. Similar experiments using a high-purity [Bmim][BF(4)] show that using a higher purity of the ionic liquid, while changing absolute values of the properties, does not eliminate the anomalous aging response. The data are also analyzed in a fashion similar to that used for polymer melts, and we find that these ionic liquids do not follow, for example, the Cox-Merz relationship between the steady shear viscosity and the dynamic viscosity.

Hormetic effect of ionic liquid 1-ethyl-3-methylimidazolium acetate on bacteria

DOE PAGES

Nancharaiah, Y. V.; Francis, A. J.

2015-02-19

The biological effect of ionic liquids (ILs) is one of the highly debated topics as they are being contemplated for various industrial applications. 1-ethyl-2-methylimidazolium acetate ([EMIM][Ac]) showed remarkable hormesis on anaerobic Clostridium sp. and aerobic Psueudomonas putida. Bacterial growth was stimulated at up to 2.5 g L -1 and inhibited at > 2.5 g L -1 of ([EMIM][Ac]). The growth of Clostridium sp. and P. putida were higher by 0.4 and 4-fold respectively, in the presense of 0.5 g L -1 of ([EMIM][Ac]). Assessment of the effect of [EMIM][Ac] under different growth conditions showed that the hormesis of [EMIM][Ac] wasmore » mediated via regulation of medium pH. Hormetic effect of [EMIM][Ac] was evident only in medium with poor buffering capacity and in the presence of a fermentable substrate as the carbon source. The hormetic effect of [EMIM][Ac] on bacterial growth is most likely associated with the buffering capacity of acetate anion. These observations have implications in ILs toxicity studies and ecological risk assessment.« less

Polymer gel electrolytes for application in aluminum deposition and rechargeable aluminum ion batteries

DOE PAGES

Sun, Xiao -Guang; Fang, Youxing; Jiang, Xueguang; ...

2015-10-22

Polymer gel electrolyte using AlCl3 complexed acrylamide as functional monomer and ionic liquids based on acidic mixture of 1-ethyl-3-methylimidazolium chloride (EMImCl) and AlCl 3 as plasticizer has been successfully prepared for the first time by free radical polymerization. Aluminum deposition is successfully obtained with a polymer gel membrane contianing 80 wt% ionic liquid. As a result, the polymer gel membranes are also good candidates for rechargeable aluminum ion batteries.

Ion Conduction in Perfectly Aligned Block Copolymer-Ionic Liquid Mixtures

NASA Astrophysics Data System (ADS)

Choi, Jae-Hong; Elabd, Yossef A.; Winey, Karen I.

2011-03-01

Our earlier work to correlate the transport measurements in diblock copolymer-ionic liquid mixtures was limited by our bulk samples that have only partial alignment. Here, thin films with perfect alignment of lamellar microdomains from mixtures of a poly(methyl methacrylate- b -styrene) diblock copolymer and an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, have been studied. The morphologies will be characterized by cross-sectional transmission electron microscopy. Ion conduction will be presented within and through the thin film.

The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes

PubMed Central

Akhmetshina, Alsu A.; Davletbaeva, Ilsiya M.; Grebenschikova, Ekaterina S.; Sazanova, Tatyana S.; Petukhov, Anton N.; Atlaskin, Artem A.; Razov, Evgeny N.; Zaripov, Ilnaz I.; Martins, Carla F.; Neves, Luísa A.; Vorotyntsev, Ilya V.

2015-01-01

Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N2, NH3, H2S, and CO2 gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF6] and [emim][Tf2N]. The modification of SILMs by nanosize silica particles leads to an increase of NH3 separation relatively to CO2 or H2S. PMID:26729177

Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1‐Butyl‐3‐Methylimidazolium Ionic Liquids and Propylene Carbonate

PubMed Central

Schütte, Kai; Barthel, Juri; Endres, Manuel; Siebels, Marvin; Smarsly, Bernd M.; Yue, Junpei

2016-01-01

Abstract Decomposition of transition‐metal amidinates [M{MeC(NiPr)2}n] [M(AMD)n; M=MnII, FeII, CoII, NiII, n=2; CuI, n=1) induced by microwave heating in the ionic liquids (ILs) 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIm][BF4]), 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([BMIm][PF6]), 1‐butyl‐3‐methylimidazolium trifluoromethanesulfonate (triflate) ([BMIm][TfO]), and 1‐butyl‐3‐methylimidazolium tosylate ([BMIm][Tos]) or in propylene carbonate (PC) gives transition‐metal nanoparticles (M‐NPs) in non‐fluorous media (e.g. [BMIm][Tos] and PC) or metal fluoride nanoparticles (MF2‐NPs) for M=Mn, Fe, and Co in [BMIm][BF4]. FeF2‐NPs can be prepared upon Fe(AMD)2 decomposition in [BMIm][BF4], [BMIm][PF6], and [BMIm][TfO]. The nanoparticles are stable in the absence of capping ligands (surfactants) for more than 6 weeks. The crystalline phases of the metal or metal fluoride synthesized in [BMIm][BF4] were identified by powder X‐ray diffraction (PXRD) to exclusively Ni‐ and Cu‐NPs or to solely MF2‐NPs for M=Mn, Fe, and Co. The size and size dispersion of the nanoparticles were determined by transmission electron microscopy (TEM) to an average diameter of 2(±2) to 14(±4) nm for the M‐NPs, except for the Cu‐NPs in PC, which were 51(±8) nm. The MF2‐NPs from [BMIm][BF4] were 15(±4) to 65(±18) nm. The average diameter from TEM is in fair agreement with the size evaluated from PXRD with the Scherrer equation. The characterization was complemented by energy‐dispersive X‐ray spectroscopy (EDX). Electrochemical investigations of the CoF2‐NPs as cathode materials for lithium‐ion batteries were simply evaluated by galvanostatic charge/discharge profiles, and the results indicated that the reversible capacity of the CoF2‐NPs was much lower than the theoretical value, which may have originated from the complex conversion reaction mechanism and residue on the surface of the nanoparticles. PMID:28168159

The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes.

PubMed

Akhmetshina, Alsu A; Davletbaeva, Ilsiya M; Grebenschikova, Ekaterina S; Sazanova, Tatyana S; Petukhov, Anton N; Atlaskin, Artem A; Razov, Evgeny N; Zaripov, Ilnaz I; Martins, Carla F; Neves, Luísa A; Vorotyntsev, Ilya V

2015-12-30

Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf₂N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N₂, NH₃, H₂S, and CO₂ gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF₆] and [emim][Tf₂N]. The modification of SILMs by nanosize silica particles leads to an increase of NH₃ separation relatively to CO₂ or H₂S.

Volatilization Mechanism of 1-Ethyl-3-methylimidazolium Bromide Ionic Liquid (Briefing Charts)

DTIC Science & Technology

2012-04-01

bromides and alkylimidazoles, presumably through alkyl abstraction via an SN2 type mechanism, and that vaporization of intact ion pairs or the formation...116.1±6.6 kJ/mol and H.‡(CH3CH2Br) = 122.9±7.2 kJ/mol, and the results are found to be in agreement with calculated values for the SN2 reactions

[CuCl(n)](2-n) ion-pair species in 1-ethyl-3-methylimidazolium chloride ionic liquid-water mixtures: ultraviolet-visible, X-ray absorption fine structure, and density functional theory characterization.

PubMed

Li, Guosheng; Camaioni, Donald M; Amonette, James E; Zhang, Z Conrad; Johnson, Timothy J; Fulton, John L

2010-10-07

We studied the coordination environment about Cu(II) in a pure ionic liquid, 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl), and in binary mixtures of this compound with water across the entire range of compositions, using a combination of X-ray absorption fine structure (XAFS), ultraviolet-visible (UV-vis) spectroscopy, and electronic structure calculations. Our results show a series of stages in the ion pairing of the divalent cation, Cu(II), including the contact ion pairing of Cu(2+) with multiple Cl(-) ligands to form various CuCl(n)((2-n)) polyanions, as well as the subsequent solvation and ion pairing of the polychlorometallate anion with the EMIM(+) cation. Ion-pair formation is strongly promoted in [EMIM]Cl by the low dielectric constant and by the extensive breakdown of the water hydrogen-bond network in [EMIM]Cl-water mixtures. The CuCl(4)(2-) species dominates in the [EMIM]Cl solvent, and calculations along with spectroscopy show that its geometry distorts to C(2) symmetry compared to D(2d) in the gas phase. These results are important in understanding catalysis and separation processes involving transition metals in ionic liquid systems.

The Influence of Anion Shape on the Electrical Double Layer Microstructure and Capacitance of Ionic Liquids-Based Supercapacitors by Molecular Simulations.

PubMed

Chen, Ming; Li, Song; Feng, Guang

2017-02-16

Room-temperature ionic liquids (RTILs) are an emerging class of electrolytes for supercapacitors. In this work, we investigate the effects of different supercapacitor models and anion shape on the electrical double layers (EDLs) of two different RTILs: 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Emim][Tf₂N]) and 1-ethyl-3-methylimidazolium 2-(cyano)pyrrolide ([Emim][CNPyr]) by molecular dynamics (MD) simulation. The EDL microstructure is represented by number densities of cations and anions, and the potential drop near neutral and charged electrodes reveal that the supercapacitor model with a single electrode has the same EDL structure as the model with two opposite electrodes. Nevertheless, the employment of the one-electrode model without tuning the bulk density of RTILs is more time-saving in contrast to the two-electrode one. With the one-electrode model, our simulation demonstrated that the shapes of anions significantly imposed effects on the microstructure of EDLs. The EDL differential capacitance vs. potential (C-V) curves of [Emim][CNPyr] electrolyte exhibit higher differential capacitance at positive potentials. The modeling study provides microscopic insight into the EDLs structure of RTILs with different anion shapes.

Study of the mechanism for electrodeposition of dendrite-free zinc in an alkaline electrolyte modified with 1-ethyl-3-methylimidazolium dicyanamide

NASA Astrophysics Data System (ADS)

Xu, M.; Ivey, D. G.; Qu, W.; Xie, Z.

2015-01-01

Electrodeposition of Zn was conducted in a new electrolyte system composed of an alkaline solution (9 M KOH + 5 wt% ZnO) modified with a small amount (0.5 wt%) of room temperature ionic liquid 1-ethyl-3-methylimidazolium dicyanamide (EMI-DCA). At a high deposition current density of 80 mA cm-2, a porous, dendrite-free Zn film characterized by clusters of small Zn particles was obtained. The mechanism for the modified Zn morphology in the EMI-DCA containing electrolyte was studied by cyclic voltammetry, chronoamperometry, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy. It was found that the addition of EMI-DCA changed the Zn nucleation process and reduced the potential variation during electrodeposition, which suppressed the uneven growth of Zn deposits and the formation of Zn dendrites. EIS results indicated that there was adsorption of EMI+ cations at the Zn film/electrolyte interface, which may have contributed to suppressed dendritic Zn growth.

Relationship between lignocellulosic biomass dissolution and physicochemical properties of ionic liquids composed of 3-methylimidazolium cations and carboxylate anions.

PubMed

Moyer, Preenaa; Smith, Micholas Dean; Abdoulmoumine, Nourredine; Chmely, Stephen C; Smith, Jeremy C; Petridis, Loukas; Labbé, Nicole

2018-01-24

The ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([EMIM]Acetate) has been widely used for biomass processing, i.e., to pretreat, activate, or fractionate lignocellulosic biomass to produce soluble sugars and lignin. However, this IL does not achieve high biomass solubility, therefore minimizing the efficiency of biomass processing. In this study, [EMIM]Acetate and three other ILs composed of different 3-methylimidazolium cations and carboxylate anions ([EMIM]Formate, 1-allyl-3-methylimidazolium ([AMIM]) formate, and [AMIM]Acetate) were analyzed to relate their physicochemical properties to their biomass solubility performance. While all four ILs are able to dissolve hybrid poplar under fairly mild process conditions (80 °C and 100 RPM stirring), [AMIM]Formate and [AMIM]Acetate have particularly increased biomass solubility of 40 and 32%, respectively, relative to [EMIM]Acetate. Molecular dynamics simulations suggest that strong interactions between IL and specific plant biopolymers may contribute to this enhanced solubilization, as the calculated second virial coefficients between ILs and hemicellullose are most favorable for [AMIM]Formate, matching the trend of the experimental solubility measurements. The simulations also reveal that the interactions between the ILs and hemicellulose are an important factor in determining the overall biomass solubility, whereas lignin-IL interactions were not found to vary significantly, consistent with literature. The combined experimental and simulation studies identify [AMIM]Formate as an efficient biomass solvent and explain its efficacy, suggesting a new approach to rationally select ionic liquid solvents for lignocellulosic deconstruction.

The 1-ethyl-3-methylimidazolium bis(trifluoro-methylsulfonyl)-imide ionic liquid nanodroplets on solid surfaces and in electric field: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Dong, Dengpan; Vatamanu, Jenel P.; Wei, Xiaoyu; Bedrov, Dmitry

2018-05-01

Atomistic molecular dynamics simulations were conducted to study the wetting states of 1-ethyl-3-methylimidazolium bis(trifluoro-methylsulfonyl)-imide ionic liquid (IL) nanodroplets on surfaces with different strengths of van der Waals (VDW) interactions and in the presence of an electric field. By adjusting the depth of Lennard-Jones potential, the van der Waals interaction between the solid surface and ionic liquid was systematically varied. The shape of the droplets was analyzed to extract the corresponding contact angle utilized to characterize wetting states of the nanodroplets. The explored range of surface-IL interactions allowed contact angles ranging from complete IL spreading on the surface to poor wettability. The effect of the external electrical field was explored by adding point charges to the surface atoms. Systems with two charge densities (±0.002 e/atom and ±0.004 e/atom) that correspond to 1.36 V/nm and 2.72 V/nm electric fields were investigated. Asymmetrical wetting states were observed for both cases. At 1.36 V/nm electric field, contributions of IL-surface VDW interactions and Coulombic interactions to the wetting state were competitive. At 2.72 V/nm field, electrostatic interactions dominate the interaction between the nanodroplet and surface, leading to enhanced wettability on all surfaces.

Influence of alkyl chain length and anion species on ionic liquid structure at the graphite interface as a function of applied potential

NASA Astrophysics Data System (ADS)

Li, Hua; Wood, Ross J.; Endres, Frank; Atkin, Rob

2014-07-01

Atomic force microscopy (AFM) force measurements elucidate the effect of cation alkyl chain length and the anion species on ionic liquid (IL) interfacial structure at highly ordered pyrolytic graphite (HOPG) surfaces as a function of potential. Three ILs are examined: 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM] FAP), 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIM] FAP), and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM] TFSA). The step-wise force-distance profiles indicate the ILs adopt a multilayered morphology near the surface. When the surface is biased positively or negatively versus Pt quasireference electrode, both the number of steps, and the force required to rupture each step increase, indicating stronger interfacial structure. At all potentials, push-through forces for [HMIM] FAP are the highest, because the long alkyl chain results in strong cohesive interactions between cations, leading to well-formed layers that resist the AFM tip. The most layers are observed for [EMIM] FAP, because the C2 chains are relatively rigid and the dimensions of the cation and anion are similar, facilitating neat packing. [EMIM] TFSA has the smallest push-through forces and fewest layers, and thus the weakest interfacial structure. Surface-tip attractive forces are measured for all ILs. At the same potential, the attractions are the strongest for [EMIM] TFSA and the weakest for [HMIM] FAP because the interfacial layers are better formed for the longer alkyl chain cation. This means interfacial forces are stronger, which masks the weak attractive forces.

Tandem dissolution of UO 3 in amide-based acidic ionic liquid and in situ electrodeposition of UO 2 with regeneration of the ionic liquid: a closed cycle

DOE PAGES

Wanigasekara, Eranda; Freiderich, John W.; Sun, Xiao-Guang; ...

2016-05-19

A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO 3 to UO 2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO 2) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.

Tandem dissolution of UO 3 in amide-based acidic ionic liquid and in situ electrodeposition of UO 2 with regeneration of the ionic liquid: a closed cycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wanigasekara, Eranda; Freiderich, John W.; Sun, Xiao-Guang

A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO 3 to UO 2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO 2) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.

High-resolution mapping of molecules in an ionic liquid via scanning transmission electron microscopy.

PubMed

Miyata, Tomohiro; Mizoguchi, Teruyasu

2018-03-01

Understanding structures and spatial distributions of molecules in liquid phases is crucial for the control of liquid properties and to develop efficient liquid-phase processes. Here, real-space mapping of molecular distributions in a liquid was performed. Specifically, the ionic liquid 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (C2mimTFSI) was imaged using atomic-resolution scanning transmission electron microscopy. Simulations revealed network-like bright regions in the images that were attributed to the TFSI- anion, with minimal contributions from the C2mim+ cation. Simple visualization of the TFSI- distribution in the liquid sample was achieved by binarizing the experimental image.

Electrochemical Behavior of PEDOT/Lignin in Ionic Liquid Electrolytes: Suitable Cathode/Electrolyte System for Sodium Batteries.

PubMed

Casado, Nerea; Hilder, Matthias; Pozo-Gonzalo, Cristina; Forsyth, Maria; Mecerreyes, David

2017-04-22

Biomass-derived polymers, such as lignin, contain quinone/ hydroquinone redox moieties that can be used to store charge. Composites based on the biopolymer lignin and several conjugated polymers have shown good charge-storage properties. However, their performance has been only studied in acidic aqueous media limiting their applications mainly to supercapacitors. Here, we show that PEDOT/lignin (PEDOT: poly(3,4-ethylenedioxythiophene)) biopolymers are electroactive in aprotic ionic liquids (ILs) and we move a step further by assembling sodium full cell batteries using PEDOT/lignin as electrode material and IL electrolytes. Thus, the electrochemical activity and cycling of PEDOT/lignin electrodes was investigated in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPyrTFSI), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (BMPyrFSI), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI) and 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMImFSI) IL electrolytes. The effects of water and sodium salt addition to the ILs were investigated to obtain optimum electrolyte systems for sodium batteries. Finally, sodium batteries based on PEDOT/lignin cathode with imidazolium-based IL electrolyte showed higher capacity values than pyrrolidinium ones, reaching 70 mAhg -1 . Our results demonstrate that PEDOT/lignin composites can serve as low cost and sustainable cathode materials for sodium batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mixtures of the 1-ethyl-3-methylimidazolium acetate ionic liquid with different inorganic salts: insights into their interactions.

PubMed

Oliveira, Filipe S; Cabrita, Eurico J; Todorovic, Smilja; Bernardes, Carlos E S; Lopes, José N Canongia; Hodgson, Jennifer L; MacFarlane, Douglas R; Rebelo, Luís P N; Marrucho, Isabel M

2016-01-28

In this work, we explore the interactions between the ionic liquid 1-ethyl-3-methylimidazolim acetate and different inorganic salts belonging to two different cation families, those based on ammonium and others based on sodium. NMR and Raman spectroscopy are used to screen for changes in the molecular environment of the ions in the ionic liquid + inorganic salt mixtures as compared to pure ionic liquid. The ion self-diffusion coefficients are determined from NMR data, allowing the discussion of the ionicity values of the ionic liquid + inorganic salt mixtures calculated using different methods. Our data reveal that preferential interactions are established between the ionic liquid and ammonium-based salts, as opposed to sodium-based salts. Computational calculations show the formation of aggregates between the ionic liquid and the inorganic salt, which is consistent with the spectroscopic data, and indicate that the acetate anion of the ionic liquid establishes preferential interactions with the ammonium cation of the inorganic salts, leaving the imidazolium cation less engaged in the media.

Comprehensive Computational and Experimental Analysis of Biomaterial toward the Behavior of Imidazolium-Based Ionic Liquids: An Interplay between Hydrophilic and Hydrophobic Interactions.

PubMed

Umapathi, Reddicherla; Vepuri, Suresh B; Venkatesu, Pannuru; Soliman, Mahmoud E

2017-05-11

To provide insights into the aggregation behavior, hydration tendency and variation in phase transition temperature produced by the addition of ionic liquids (ILs) to poly(N-isopropylacrylamide) (PNIPAM) aqueous solution, systematic physicochemical studies, and molecular dynamic simulations were carried out. The influence of ILs possessing the same [Cl] - anion and a set of cations [C n mim] + with increasing alkyl chain length such as 1-ethyl-3-methylimidazolium ([Emim] + ), 1-allyl-3-methylimidazolium ([Amim] + ), 1-butyl-3-methylimidazolium ([Bmim] + ), 1-hexyl-3-methylimidazolium ([Hmim] + ), 1-benzyl-3-methylimidazolium ([Bzmim] + ), and 1-decyl-3-methylimidazolium ([Dmim] + ) on the phase transition of PNIPAM was monitored by the aid of UV-visible absorption spectra, fluorescence intensity spectra, viscosity (η), dynamic light scattering (DLS), and Fourier transform infrared (FTIR) spectroscopy. Furthermore, to interpret the direct images and surface morphologies of the PNIPAM-IL aggregates, we performed field emission scanning electron microscopy (FESEM). The overall specific ranking of ILs in preserving the hydration layer around the PNIPAM aqueous solution was [Emim][Cl] > [Amim][Cl] > [Bmim][Cl] > [Hmim][Cl] > [Bzmim][Cl] > [Dmim][Cl]. Moreover, to investigate the molecular mechanism behind the change in the lower critical solution temperature (LCST) of the polymer in the presence of the ILs, a molecular dynamics (MD) study was performed. The MD simulation has clearly shown the reduction in hydration shell of the polymer after interacting with the ILs at their respective LCST. MD study revealed significant changes in polymer conformation because of IL interactions and strongly supports the experimental observation of polymer phase transition at a temperature lower than typical LCST for all the studied ILs. The driving force for concomitant sharp configurational transition has been attributed to the displacement of water molecules on the polymer surface by the ILs because of their hydrophobic interaction with the polymer.

Studies on the solvation dynamics of coumarin 153 in 1-ethyl-3-methylimidazolium alkylsulfate ionic liquids: dependence on alkyl chain length.

PubMed

Das, Sudhir Kumar; Sarkar, Moloy

2012-08-06

Steady-state and time-resolved fluorescence behavior of coumarin 153 (C153) is investigated in a series of 1-ethyl-3-methylimidazolium alkylsulfate ([C(2)mim][C(n)OSO(3)]) ionic liquids differing only in the length of the linear alkyl chain (n = 4, 6, and 8) in the anion. The aim of the present study is to understand the role of alkyl chain length in solute rotation and solvation dynamics of C153 in these ionic liquids. The blueshift observed in the steady-state absorption and emission maxima of C153 on going from the C(4)OSO(3) to the C(8)OSO(3) system indicates increasing nonpolar character of the microenvironment of the solute with increasing length of the alkyl side chain of the anion of the ionic liquids. The average solvation time is also found to increase on changing the substituent from butyl to octyl, and this is attributed to the increase in the bulk viscosity of the ILs. A steady blueshift of the time-zero maximum of the fluorescence spectrum with increasing alkyl chain length also indicates that the probe molecule experiences a less polar environment in the early part of the dynamics. Rotational dynamics of C153 are also analyzed by using the Stokes-Einstein-Debye (SED), Gierer-Wirtz (GW), and Dote-Kivelson-Schwartz (DKS) theories. Analyses of the results seem to suggest decoupling of the rotational motion of the probe from solvent viscosity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A molecular dynamics computer simulation study of room-temperature ionic liquids. II. Equilibrium and nonequilibrium solvation dynamics.

PubMed

Shim, Y; Choi, M Y; Kim, Hyung J

2005-01-22

The molecular dynamics (MD) simulation study of solvation structure and free energetics in 1-ethyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium hexafluorophosphate using a probe solute in the preceding article [Y. Shim, M. Y. Choi and H. J. Kim, J. Chem. Phys. 122, 044510 (2005)] is extended to investigate dynamic properties of these liquids. Solvent fluctuation dynamics near equilibrium are studied via MD and associated time-dependent friction is analyzed via the generalized Langevin equation. Nonequilibrium solvent relaxation following an instantaneous change in the solute charge distribution and accompanying solvent structure reorganization are also investigated. Both equilibrium and nonequilibrium solvation dynamics are characterized by at least two vastly different time scales--a subpicosecond inertial regime followed by a slow diffusive regime. Solvent regions contributing to the subpicosecond nonequilibrium relaxation are found to vary significantly with initial solvation configurations, especially near the solute. If the solvent density near the solute is sufficiently high at the outset of the relaxation, subpicosecond dynamics are mainly governed by the motions of a few ions close to the solute. By contrast, in the case of a low local density, solvent ions located not only close to but also relatively far from the solute participate in the subpicosecond relaxation. Despite this difference, linear response holds reasonably well in both ionic liquids. (c) 2005 American Institute of Physics.

Relationship between lignocellulosic biomass dissolution and physicochemical properties of ionic liquids composed of 3-methylimidazolium cations and carboxylate anions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moyer, Preenaa; Smith, Micholas Dean; Abdoulmoumine, Nourredine

The ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([EMIM]Acetate) has been widely used for biomass processing, i.e., to pretreat, activate, or fractionate lignocellulosic biomass to produce soluble sugars and lignin. However, this IL does not achieve high biomass solubility, therefore minimizing the efficiency of biomass processing. In this paper, [EMIM]Acetate and three other ILs composed of different 3-methylimidazolium cations and carboxylate anions ([EMIM]Formate, 1-allyl-3-methylimidazolium ([AMIM]) formate, and [AMIM]Acetate) were analyzed to relate their physicochemical properties to their biomass solubility performance. While all four ILs are able to dissolve hybrid poplar under fairly mild process conditions (80 °C and 100 RPM stirring), [AMIM]Formatemore » and [AMIM]Acetate have particularly increased biomass solubility of 40 and 32%, respectively, relative to [EMIM]Acetate. Molecular dynamics simulations suggest that strong interactions between IL and specific plant biopolymers may contribute to this enhanced solubilization, as the calculated second virial coefficients between ILs and hemicellullose are most favorable for [AMIM]Formate, matching the trend of the experimental solubility measurements. The simulations also reveal that the interactions between the ILs and hemicellulose are an important factor in determining the overall biomass solubility, whereas lignin–IL interactions were not found to vary significantly, consistent with literature. Finally, the combined experimental and simulation studies identify [AMIM]Formate as an efficient biomass solvent and explain its efficacy, suggesting a new approach to rationally select ionic liquid solvents for lignocellulosic deconstruction.« less

Temperature-triggered micellization of block copolymers on an ionic liquid surface.

PubMed

Lu, Haiyun; Akgun, Bulent; Wei, Xinyu; Li, Le; Satija, Sushil K; Russell, Thomas P

2011-10-18

In situ neutron reflectivity was used to study thermally induced structural changes of the lamellae-forming polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer thin films floating on the surface of an ionic liquid (IL). The IL, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, is a nonsolvent for PS and a temperature-tunable solvent for P2VP, and, as such, micellization can be induced at the air-IL interface by changing the temperature. Transmission electron microscopy and scanning force microscopy were used to investigate the resultant morphologies of the micellar films. It was found that highly ordered nanostructures consisting of spherical micelles with a PS core surrounded by a P2VP corona were produced. In addition, bilayer films of PS homopolymer on top of a PS-b-P2VP layer also underwent micellization with increasing temperature but the micellization was strongly dependent on the thickness of the PS and PS-b-P2VP layers. © 2011 American Chemical Society

Temperature tunable micellization of polystyrene-block-poly(2-vinylpyridine) at Si-ionic liquid interface.

PubMed

Lu, Haiyun; Lee, Dong Hyun; Russell, Thomas P

2010-11-16

Highly ordered and stable micelles formed from both symmetric and asymmetric block copolymers of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) at the Si-ionic liquid (IL) interface have been investigated by scanning force microscopy (SFM) and transmission electron microscopy (TEM). The 1-butyl-3-methylimidazolium trifluoromethanesulfonate IL, a selective and temperature-tunable solvent for the P2VP block, was used and gave rise to block copolymer micelles having different morphologies that strongly depended on the annealing temperature. The effects of film thickness, molecular weight of block copolymers, and experimental conditions, such as preannealing, rinsing, and substrate properties, on the morphologies of block copolymer micelles were also studied. In addition, spherical micelles consisting of PS core and P2VP shell could also be obtained by core-corona inversion by annealing the as-coated micellar film in the IL at high temperatures. The possible mechanism for micelle formation is discussed.

Modular microfluidic valve structures based on reversible thermoresponsive ionogel actuators.

PubMed

Benito-Lopez, Fernando; Antoñana-Díez, Marta; Curto, Vincenzo F; Diamond, Dermot; Castro-López, Vanessa

2014-09-21

This paper reports for the first time the use of a cross-linked poly(N-isopropylacrylamide) ionogel encapsulating the ionic liquid 1-ethyl-3-methylimidazolium ethyl sulphate as a thermoresponsive and modular microfluidic valve. The ionogel presents superior actuation behaviour to its equivalent hydrogel. Ionogel swelling and shrinking mechanisms and kinetics are investigated as well as the performance of the ionogel when integrated as a valve in a microfluidic device. The modular microfluidic valve demonstrates fully a reversible on-off behaviour without failure for up to eight actuation cycles and a pressure resistance of 1100 mbar.

Synthesis of Highly Polymerized Water-soluble Cellulose Acetate by the Side Reaction in Carboxylate Ionic Liquid 1-ethyl-3-methylimidazolium Acetate

NASA Astrophysics Data System (ADS)

Pang, Jinhui; Liu, Xin; Yang, Jun; Lu, Fachuang; Wang, Bo; Xu, Feng; Ma, Mingguo; Zhang, Xueming

2016-09-01

In the present study, we describe a novel one-step method to prepare water-soluble cellulose acetate (WSCA) with higher degree of polymerization values (DP = 650-680) by in situ activation of carboxyl group in ionic liquid. First of all, cellulose was dissolved in 1-ethyl-3-methylimidazolium acetate (EmimAc) and reacted with dichloroacetyl chloride (Cl2AcCl) in order to make cellulose dichloroacetate. Under various conditions, a series of water soluble products were produced. Elemental analysis and NMR results confirmed that they were cellulose acetate with DS (degree of substitution) values in the range from 0.30 to 0.63. NMR studies demonstrated that Cl2AcCl reacted with acetate anion of EmimAc producing a mixed anhydride that acetylated cellulose. Other acylating reagents such as benzoyl chloride, chloroacetyl chloride can also work similarly. 2D NMR characterization suggested that 6-mono-O-acetyl moiety, 3,6-di-O-acetylcellulose and 2,6-di-O-acetyl cellulose were all synthesized and the reactivity of hydroxyl groups in anhydro-glucose units was in the order C-6>C-3>C-2. This work provides an alternative way to make WSCA, meanwhile, also services as a reminder that the activity of EmimAc toward carbohydrate as acylating reagents could be a problem, because the expected acylated products may not be resulted and recycling of this ionic liquid could also be difficult.

Effect of cation on diffusion coefficient of ionic liquids at onion-like carbon electrodes.

PubMed

Van Aken, Katherine L; McDonough, John K; Li, Song; Feng, Guang; Chathoth, Suresh M; Mamontov, Eugene; Fulvio, Pasquale F; Cummings, Peter T; Dai, Sheng; Gogotsi, Yury

2014-07-16

While most supercapacitors are limited in their performance by the stability of the electrolyte, using neat ionic liquids (ILs) as the electrolyte can expand the voltage window and temperature range of operation. In this study, ILs with bis(trifluoromethylsulfonyl)imide (Tf2N) as the anion were investigated as the electrolyte in onion-like carbon-based electrochemical capacitors. To probe the influence of cations on the electrochemical performance of supercapacitors, three different cations were used: 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium and 1,6-bis(3-methylimidazolium-1-yl). A series of electrochemical characterization tests was performed using cyclic voltammetry (CV), galvanostatic cycling and electrochemical impedance spectroscopy (EIS). Diffusion coefficients were measured using EIS and correlated with quasielastic neutron scattering and molecular dynamics simulation. These three techniques were used in parallel to confirm a consistent trend between the three ILs. It was found that the IL with the smaller sized cation had a larger diffusion coefficient, leading to a higher capacitance at faster charge-discharge rates. Furthermore, the IL electrolyte performance was correlated with increasing temperature, which limited the voltage stability window and led to the formation of a solid electrolyte interphase on the carbon electrode surface, evident in both the CV and EIS experiments.

A high performance hybrid battery based on aluminum anode and LiFePO4 cathode.

PubMed

Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; Fang, Youxing; Bridges, Craig A; Paranthaman, M Parans; Dai, Sheng; Brown, Gilbert M

2016-01-28

A novel hybrid battery utilizing an aluminum anode, a LiFePO4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl3) (EMImCl-AlCl3, 1-1.1 in molar ratio) with or without LiAlCl4 is proposed. The hybrid ion battery delivers an initial high capacity of 160 mA h g(-1) at a current rate of C/5. It also shows good rate capability and cycling performance.

A high performance hybrid battery based on aluminum anode and LiFePO 4 cathode

DOE PAGES

Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; ...

2015-12-07

A unique battery hybrid utilizes an aluminum anode, a LiFePO 4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl 3) (EMImCl-AlCl 3, 1-1.1 in molar ratio) with or without LiAlCl 4 is proposed. This hybrid ion battery delivers an initial high capacity of 160 mAh g -1 at a current rate of C/5. It also shows good rate capability and cycling performance.

Highly Safe Ionic Liquid Electrolytes for Sodium-Ion Battery: Wide Electrochemical Window and Good Thermal Stability.

PubMed

Wu, Feng; Zhu, Na; Bai, Ying; Liu, Libin; Zhou, Hang; Wu, Chuan

2016-08-24

Novel ionic liquid (IL) electrolytes are prepared by mixing 1-ethyl-3-methylimidazolium-bis-tetrafluoroborate (EMIBF4) with different concentrations of sodium salt (NaBF4). The as-prepared IL electrolytes display wide electrochemical windows of ∼4 V (1-5 V), which are consistent with the quantum chemical theoretical calculation. The IL electrolyte with 0.1 M NaBF4 shows excellent ionic conductivity, namely, 9.833 × 10(-3) S cm(-1) at 20 °C. In addition, nonflammability and good thermal stability are exhibited by combustion test and thermogravimetric analysis (TGA), which indicate the high safety of the IL electrolyte.

Ionic-liquid-induced changes in the properties of aqueous zwitterionic surfactant solution: solvent and rotational relaxation studies.

PubMed

Rao, Vishal Govind; Ghatak, Chiranjib; Ghosh, Surajit; Mandal, Sarthak; Sarkar, Nilmoni

2012-03-29

In the recent past, the chameleon-like nature of zwitterionic micelles has been utilized for performing electrophilic, nucleophilic, base, and acid catalyzed reactions. But the use of simple salts to induce the zwitterionic character limits the variation to inorganic cations and anions only. To overcome this problem, we have used room temperature ionic liquids (RTILs), which can be tailored according to need. More precisely, we have shown the effect of added RTILs on the nature of water molecules in the palisade layer of a zwitterionic (N-hexadecyl-N,N-dimethylammonio-1-propanesulfonate (SB-16)) micelle using solvation and rotational relaxation studies of C-153 dye. We have carried out a comparative study of changes in the solvent and rotational relaxation parameters of C-153 in an aqueous solution of SB-16 upon addition of three different ionic liquids (ILs): 1-ethyl-3-methylimidazolium ethyl sulfate [C(2)mim][C(2)SO(4)], 1-ethyl-3-methylimidazolium n-butyl sulfate [C(2)mim][C(4)SO(4)], and 1-ethyl-3-methylimidazolium n-hexyl sulfate [C(2)mim][C(6)SO(4)]. It has been observed that in the presence of added RTILs the solvation dynamics become faster and the change in solvation dynamics is more pronounced in the case of [C(2)mim][C(6)SO(4)] compared to that for [C(2)mim][C(4)SO(4)] and [C(2)mim][C(2)SO(4)]. This can be accounted for by considering the increased water penetration (increased microfluidity) with the addition of ILs. In accordance with solvation dynamics results, fluorescence anisotropy studies also indicate an increase in microfluidity of the palisade layer of the SB-16 micelle with the added RTILs. The average rotational relaxation time in 28 mM SB-16 was found to be 1.12 ns. With the addition of 800 mM [C(2)mim][C(2)SO(4)], the average rotational relaxation time remains the same (1.12 ns), whereas with the addition of 800 mM [C(2)mim][C(6)SO(4)] it decreases to 0.40 ns. This observation is in agreement with our earlier report on the microfluidity of SB-16 solution with the addition of [C(2)mim][C(2)SO(4)] and [C(2)mim][C(6)SO(4)] (Rao, V. G.; Ghatak, C.; Ghosh, S.; Mandal, S.; Sarkar, N. Chem. Phys. Chem. DOI: 10.1002/cphc.201100866).

Self-aggregation of bio-surfactants within ionic liquid 1-ethyl-3-methylimidazolium bromide: A comparative study and potential application in antidepressants drug aggregation

NASA Astrophysics Data System (ADS)

Banjare, Manoj Kumar; Behera, Kamalakanta; Kurrey, Ramsingh; Banjare, Ramesh Kumar; Satnami, Manmohan L.; Pandey, Siddharth; Ghosh, Kallol K.

2018-06-01

Aggregation behavior of bio-surfactants (BS) sodium cholate (NaC) and sodium deoxycholate (NaDC) within aqueous solution of ionic liquid (IL) 1-ethyl-3-methylimidazolium bromide [Emim][Br] has been investigated using surface tension, conductivity, steady state fluorescence, FT-IR and dynamic light scattering (DLS) techniques. Various interfacial and thermodynamic parameters are determined in the presence of different wt% of IL [Emim][Br]. Information regarding the local microenvironment and size of the aggregates is obtained from fluorescence and DLS, respectively. FT-IR spectral response is used to reveal the interactions taking place within aqueous NaC/NaDC micellar solutions. It is noteworthy to mention that increasing wt% of [Emim][Br] results in an increase in the spontaneity of micelle formation and the hydrophilic IL shows more affinity for NaC as compared to NaDC. Further, the micellar solutions of BS-[Emim][Br] are utilized for studying the aggregation of antidepressants drug promazine hydrochloride (pH). UV-vis spectroscopic investigation reveals interesting outcomes and the results show changes in spectral absorbance of PH drug on the addition of micellar solution (BS-[Emim][Br]). Highest binding affinity and most promising activity are shown for NaC as compared to NaDC.

Matrix effects on secondary ion emission from a room-temperature ionic liquid, 1-ethyl-3-methylimidazolium bis[trifluoromethanesulfonyl]imide

NASA Astrophysics Data System (ADS)

Souda, Ryutaro

2009-06-01

The ionization mechanism of room-temperature ionic liquids has been investigated using time-of-flight secondary ion mass spectrometry in the temperature range of 15-300 K. Analyses of 1-ethyl-3-methylimidazolium bis[trifluoromethanesulfonyl]imide ([emim][Tf2N]) deposited on a Ni(111) substrate revealed that the [emim]+ and [Tf2N]- yields increase together with the Ni+ yield at monolayer coverage; no such increase was observed for the films deposited on a D2O spacer layer. Results indicated that the [emim][Tf2N] molecule is not perfectly ionized; the Ni(111) surface accepts (for [emim]+) or donates (for [Tf2N]-) an electron with higher efficiency than the counterion because of the metal band effect. This phenomenon might be induced by electrostatic interactions between the separated cation and anion during sputtering. It is also suggested that the sputtered Ni atom can be ionized nonadiabatically by the formation of a quasimolecule with adspecies. The multilayer of [emim][Tf2N] deposited at 15 K has a porous structure, resembling that of polar molecules, because of nonionic intermolecular interactions. The phase transition is identifiable, together with the morphological change in the crystalline film, from temperature evolutions of the secondary ion yields.

Density, refractive index, interfacial tension, and viscosity of ionic liquids [EMIM][EtSO4], [EMIM][NTf2], [EMIM][N(CN)2], and [OMA][NTf2] in dependence on temperature at atmospheric pressure.

PubMed

Fröba, Andreas P; Kremer, Heiko; Leipertz, Alfred

2008-10-02

The density, refractive index, interfacial tension, and viscosity of ionic liquids (ILs) [EMIM][EtSO 4] (1-ethyl-3-methylimidazolium ethylsulfate), [EMIM][NTf 2] (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), [EMIM][N(CN) 2] (1-ethyl-3-methylimidazolium dicyanimide), and [OMA][NTf 2] (trioctylmethylammonium bis(trifluoromethylsulfonyl)imide) were studied in dependence on temperature at atmospheric pressure both by conventional techniques and by surface light scattering (SLS). A vibrating tube densimeter was used for the measurement of density at temperatures from (273.15 to 363.15) K and the results have an expanded uncertainty ( k = 2) of +/-0.02%. Using an Abbe refractometer, the refractive index was measured for temperatures between (283.15 and 313.15) K with an expanded uncertainty ( k = 2) of about +/-0.0005. The interfacial tension was obtained from the pendant drop technique at a temperature of 293.15 K with an expanded uncertainty ( k = 2) of +/-1%. For higher and lower temperatures, the interfacial tension was estimated by an adequate prediction scheme based on the datum at 293.15 K and the temperature dependence of density. For the ILs studied within this work, at a first order approximation, the quantity directly accessible by the SLS technique was the ratio of surface tension to dynamic viscosity. By combining the experimental results of the SLS technique with density and interfacial tension from conventional techniques, the dynamic viscosity could be obtained for temperatures between (273.15 and 333.15) K with an estimated expanded uncertainty ( k = 2) of less than +/-3%. The measured density, refractive index, and viscosity are represented by interpolating expressions with differences between the experimental and calculated values that are comparable with but always smaller than the expanded uncertainties ( k = 2). Besides a comparison with the literature, the influence of structural variations on the thermophysical properties of the ILs is discussed in detail. The viscosities mostly agree with values reported in the literature within the combined estimated expanded uncertainties ( k = 2) of the measurements while our density and interfacial tension data differ by more than +/-1% and +/-5%.

Imidazolium-Based Ionic Liquids in Water: Assessment of Photocatalytic and Photochemical Transformation.

PubMed

Calza, Paola; Vione, Davide; Fabbri, Debora; Aigotti, Riccardo; Medana, Claudio

2015-09-15

The photoinduced transformation of two ionic liquids, 1-methylimidazolium hydrogensulfate (HMIM) and 1-ethyl-3-methylimidazolium hydrogensulfate (EMIM), was investigated under photocatalytic conditions in the presence of irradiated TiO2. We monitored substrate disappearance, transformation products (TPs), degree of mineralization, and toxicity of the irradiated systems. Acute toxicity measures suggested in both cases the occurrence of more toxic TPs than the parent molecules. A total of five TPs were detected by HPLC-HRMS from HMIM and nine from EMIM. Complete mineralization and stoichiometric release of nitrogen was achieved for both compounds within 4 h of irradiation. The photochemical transformation kinetics and pathways in surface waters (direct photolysis and indirect photoreactions) were studied for EMIM, to assess its persistence in sunlit water bodies such as rivers or lakes. Environmental phototransformation would be dominated by direct photolysis, with half-life times of up to one month under fine-weather conditions.

Three dimensional ink-jet printing of biomaterials using ionic liquids and co-solvents.

PubMed

Gunasekera, Deshani H A T; Kuek, SzeLee; Hasanaj, Denis; He, Yinfeng; Tuck, Christopher; Croft, Anna K; Wildman, Ricky D

2016-08-15

1-Ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) and 1-butyl-3-methylimidazolium acetate ([C4C1Im][OAc]) have been used as solvents for the dissolution and ink-jet printing of cellulose from 1.0 to 4.8 wt%, mixed with the co-solvents 1-butanol and DMSO. 1-Butanol and DMSO were used as rheological modifiers to ensure consistent printing, with DMSO in the range of 41-47 wt% producing samples within the printable range of a DIMATIX print-head used (printability parameter < 10) at 55 °C, whilst maintaining cellulose solubility. Regeneration of cellulose from printed samples using water was demonstrated, with the resulting structural changes to the cellulose sample assessed by scanning electron microscopy (SEM) and white light interferometry (WLI). These results indicate the potential of biorenewable materials to be used in the 3D additive manufacture process to generate single-component and composite materials.

Quasi-Chemical PC-SAFT: An Extended Perturbed Chain-Statistical Associating Fluid Theory for Lattice-Fluid Mixtures.

PubMed

Parvaneh, Khalil; Shariati, Alireza

2017-09-07

In this study, a new modification of the perturbed chain-statistical associating fluid theory (PC-SAFT) has been proposed by incorporating the lattice fluid theory of Guggenheim as an additional term to the original PC-SAFT terms. As the proposed model has one more term than the PC-SAFT, a new mixing rule has been developed especially for the new additional term, while for the conventional terms of the PC-SAFT, the one-fluid mixing rule is used. In order to evaluate the proposed model, the vapor-liquid equilibria were estimated for binary CO 2 mixtures with 16 different ionic liquids (ILs) of the 1-alkyl-3-methylimidazolium family with various anions consisting of bis(trifluoromethylsulfonyl) imide, hexafluorophosphate, tetrafluoroborate, and trifluoromethanesulfonate. For a comprehensive comparison, three different modes (different adjustable parameters) of the proposed model were compared with the conventional PC-SAFT. Results indicate that the proposed modification of the PC-SAFT EoS is generally more reliable with respect to the conventional PC-SAFT in all the three proposed modes of vapor-liquid equilibria, giving good agreement with literature data.

Photoinduced electron transfer in an imidazolium ionic liquid and in its binary mixtures with water, methanol, and 2-propanol: appearance of Marcus-type of inversion.

PubMed

Sarkar, Souravi; Mandal, Sarthak; Ghatak, Chiranjib; Rao, Vishal Govind; Ghosh, Surajit; Sarkar, Nilmoni

2012-02-02

The photoinduced electron transfer (PET) reaction has been investigated in a room temperature imidazolium ionic liquid (RTIL), 1-ethyl-3-methylimidazolium ethyl sulfate ([Emim][EtSO(4)]) and also in [Emim][EtSO(4)]-co-solvents mixtures from N,N-dimethyl aniline (DMA) to different Coumarin dyes using steady state and time-resolved fluorescence quenching measurements. We have used water and methanol and 2-propanol as the cosolvents of RTILs for the PET study. On going from neat ionic liquid to the RTIL-co-solvents mixtures the electron transfer rate has been largely enhanced. In neat RTIL as well as in [Emim][EtSO(4)]-co-solvents mixtures, a Marcus type of inversion in the PET rate have been observed.

NafionxAE-based polymer actuators with ionic liquids as solvent incorporated at room temperature

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Tsuchitani, Shigeki

2009-09-01

Nafion®-based ionic polymer-metal composites (IPMCs), with ionic liquids as solvent, were fabricated by exchanging counterions to ionic liquids at room temperature. Ion exchange is performed by only immersing IPMC in a mixture of de-ionized water and ionic liquids at room temperature for 48 h. The fabricated IPMCs exhibited a bending curvature the same as or larger than that of conventional IPMCs with ionic liquids, formed by ion exchange to ionic liquids at an elevated temperature up to about 100 °C, and also had long-term stability in operation in air, with a fluctuation smaller than 21% in bending curvature during a 180 min operation. The effective ion exchange to ionic liquids in the present method is probably due to an increase in diffusion speed of ionic liquids into IPMC by adsorption of water in a Nafion® membrane. It is a surprise that among IPMCs with ionic liquids 1-ethyl-3-methyl-imidazolium tetrafluoroborate, 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6), IPMC with water-insoluble BMIPF6 exhibited a larger bending curvature than that IPMC with water-miscible BMIBF4. This might be due to effective incorporation of BMIPF6 into IPMC, since BMIPF6 has a higher affinity with IPMC than with water in the mixture of water and BMIPF6. From measurements of complex impedance and step voltage response of the driving current of IPMCs with ionic liquid, they are expressed by an equivalent circuit of a parallel combination of a serial circuit of membrane resistance of Nafion® and electric double layer capacitance at metal electrodes, with membrane capacitance of Nafion®, in a frequency range higher than about 0.1 Hz. The difference in magnitude of bending curvature in three kinds of IPMCs with ionic liquids is mainly due to the difference in bending response speed coming from the difference in the membrane resistance.

Electronic structure and normal vibrations of the 1-ethyl-3-methylimidazolium ethyl sulfate ion pair.

PubMed

Dhumal, Nilesh R; Kim, Hyung J; Kiefer, Johannes

2011-04-21

Electronic and structural properties of the ion pair 1-ethyl-3-methylimidazolium ethyl sulfate are studied using density functional methods. Three locally stable conformers of the ion pair complex are considered to analyze molecular interactions between its cation and anion. Manifestations of these interactions in the vibrational spectra are discussed and compared with experimental IR and Raman spectroscopy data. NBO analysis and difference electron density coupled with molecular electron density topography are used to interpret the frequency shifts of the normal vibrations of the ion pair, compared to the free anion and cation. Excitation energies of low-lying singlet excited states of the conformers are also studied. The density functional theory results are found to be in a reasonable agreement with experimental UV/vis absorption spectra.

SO2 Solvation in the 1-Ethyl-3-Methylimidazolium Thiocyanate Ionic Liquid by Incorporation into the Extended Cation-Anion Network.

PubMed

Firaha, Dzmitry S; Kavalchuk, Mikhail; Kirchner, Barbara

We have carried out an ab initio molecular dynamics study on the sulfur dioxide (SO 2 ) solvation in 1-ethyl-3-methylimidazolium thiocyanate for which we have observed that both cations and anions play an essential role in the solvation of SO 2 . Whereas, the anions tend to form a thiocyanate- and much less often an isothiocyanate-SO 2 adduct, the cations create a "cage" around SO 2 with those groups of atoms that donate weak interactions like the alkyl hydrogen atoms as well as the heavy atoms of the [Formula: see text]-system. Despite these similarities between the solvation of SO 2 and CO 2 in ionic liquids, an essential difference was observed with respect to the acidic protons. Whereas CO 2 avoids accepting hydrogen bonds form the acidic hydrogen atoms of the cations, SO 2 can from O(SO 2 )-H(cation) hydrogen bonds and thus together with the strong anion-adduct it actively integrates in the hydrogen bond network of this particular ionic liquid. The fact that SO 2 acts in this way was termed a linker effect by us, because the SO 2 can be situated between cation and anion operating as a linker between them. The particular contacts are the H(cation)[Formula: see text]O(SO 2 ) hydrogen bond and a S(anion)-S(SO 2 ) sulfur bridge. Clearly, this observation provides a possible explanation for the question of why the SO 2 solubility in these ionic liquids is so high.

Ultrasonic irradiation-assisted synthesis of Bi2S3 nanoparticles in aqueous ionic liquid at ambient condition.

PubMed

de la Parra-Arciniega, Salomé M; Garcia-Gomez, Nora A; Garza-Tovar, Lorena L; García-Gutiérrez, Domingo I; Sánchez, Eduardo M

2017-05-01

In this work, an easy, fast and environmentally friendly method to obtain Bi 2 S 3 nanostructures with sphere-like morphology is introduced. The promising material was successfully synthesized by a sonochemical route in 20% 1-ethyl-3-methylimidazolium ethyl sulfate [EMIM][EtSO 4 ] ionic liquid solution (IL). Morphological studies by electron microscopy (SEM and TEM) show that the use of IL in the synthesis of Bi 2 S 3 favors the formation of nanocrystals non-agglomerated. Micro Raman and energy dispersive X-ray spectroscopy (EDXS) were used to determine the composition and purity of the synthesized material. X-ray powder diffraction (XRD) and selective area electron diffraction (SAED) revealed that ultrasonic radiation accelerated the crystallization of Bi 2 S 3 into orthorhombic bismuthinite structure. The band gap calculated from the diffuse reflectance spectra (DRS) was found to be 1.5eV. Copyright © 2016 Elsevier B.V. All rights reserved.

On the Formation of Lightweight Nanocrystalline Aluminum Alloys by Electrodeposition

DOE PAGES

Hilty, Robert D.; Masur, Lawrence J.

2017-08-08

New nanocrystalline aluminum alloys have been fabricated by electrodeposition. These are thermodynamically stable alloys of Al-Mn and Al-Zr with grain sizes < 100nm. Al-Mn and Al-Zr alloys are characterized here showing high strength (up to 1350 MPa) and hardness (up to 450 HVN) while maintaining the specific gravity of Al. Smooth and dense deposits plated from ionic liquids, such as EMIM:Cl (1-Ethyl-3-methylimidazolium chloride), can develop to thicknesses of 1mm or more.

High power density supercapacitors based on the carbon dioxide activated D-glucose derived carbon electrodes and 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid

NASA Astrophysics Data System (ADS)

Tooming, T.; Thomberg, T.; Kurig, H.; Jänes, A.; Lust, E.

2015-04-01

The electrochemical impedance spectroscopy, cyclic voltammetry, constant current charge/discharge and the constant power discharge methods have been applied to establish the electrochemical characteristics of the electrical double-layer capacitor (EDLC) consisting of the 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) ionic liquid and microporous carbon electrodes. Microporous carbon material used for preparation of electrodes (GDAC - glucose derived activated carbon), has been synthesised from D-(+)-glucose by the hydrothermal carbonization method, including subsequent pyrolysis, carbon dioxide activation and surface cleaning step with hydrogen. The Brunauer-Emmett-Teller specific surface area (SBET = 1540 m2 g-1), specific surface area calculated using the non-local density functional theory in conjunction with stable adsorption integral equation using splines (SAIEUS) model SSAIEUS = 1820 m2 g-1, micropore surface area (Smicro = 1535 m2 g-1), total pore volume (Vtot = 0.695 cm3 g-1) and the pore size distribution were obtained from the N2 sorption data. The SBET, Smicro and Vtot values have been correlated with the electrochemical characteristics strongly dependent on the carbon activation conditions applied for EDLCs. Wide region of ideal polarizability (ΔV ≤ 3.2 V), very short charging/discharging time constant (2.7 s), and high specific series capacitance (158 F g-1) have been calculated for the optimized carbon material GDAC-10h (activation of GDAC with CO2 during 10 h) in EMImBF4 demonstrating that this system can be used for completing the EDLC with high energy- and power densities.

Molecular structure and interactions in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

PubMed

Dhumal, Nilesh R; Noack, Kristina; Kiefer, Johannes; Kim, Hyung J

2014-04-03

Electronic structure theory (density functional and Møller-Plesset perturbation theory) and vibrational spectroscopy (FT-IR and Raman) are employed to study molecular interactions in the room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Different conformers of a cation-anion pair based on their molecular interactions are simulated in the gas phase and in a dielectric continuum solvent environment. Although the ordering of conformers in energy varies with theoretical methods, their predictions for three lowest energy conformers in the gas phase are similar. Strong C-H---N interactions between the acidic hydrogen atom of the cation imidazole ring and the nitrogen atom of the anion are predicted for either the lowest or second lowest energy conformer. In a continuum solvent, different theoretical methods yield the same ion-pair conformation for the lowest energy state. In both phases, the density functional method predicts that the anion is in a trans conformation in the lowest energy ion pair state. The theoretical results are compared with experimental observations from Raman scattering and IR absorption spectroscopies and manifestations of the molecular interactions in the vibrational spectra are discussed. The directions of the frequency shifts of the characteristic vibrations relative to the free anion and cation are explained by calculating the difference electron density coupled with electron density topography.

Self-aggregation of bio-surfactants within ionic liquid 1-ethyl-3-methylimidazolium bromide: A comparative study and potential application in antidepressants drug aggregation.

PubMed

Banjare, Manoj Kumar; Behera, Kamalakanta; Kurrey, Ramsingh; Banjare, Ramesh Kumar; Satnami, Manmohan L; Pandey, Siddharth; Ghosh, Kallol K

2018-06-15

Aggregation behavior of bio-surfactants (BS) sodium cholate (NaC) and sodium deoxycholate (NaDC) within aqueous solution of ionic liquid (IL) 1-ethyl-3-methylimidazolium bromide [Emim][Br] has been investigated using surface tension, conductivity, steady state fluorescence, FT-IR and dynamic light scattering (DLS) techniques. Various interfacial and thermodynamic parameters are determined in the presence of different wt% of IL [Emim][Br]. Information regarding the local microenvironment and size of the aggregates is obtained from fluorescence and DLS, respectively. FT-IR spectral response is used to reveal the interactions taking place within aqueous NaC/NaDC micellar solutions. It is noteworthy to mention that increasing wt% of [Emim][Br] results in an increase in the spontaneity of micelle formation and the hydrophilic IL shows more affinity for NaC as compared to NaDC. Further, the micellar solutions of BS-[Emim][Br] are utilized for studying the aggregation of antidepressants drug promazine hydrochloride (pH). UV-vis spectroscopic investigation reveals interesting outcomes and the results show changes in spectral absorbance of PH drug on the addition of micellar solution (BS-[Emim][Br]). Highest binding affinity and most promising activity are shown for NaC as compared to NaDC. Copyright © 2018 Elsevier B.V. All rights reserved.

Solubility of sugars and sugar alcohols in ionic liquids: measurement and PC-SAFT modeling.

PubMed

Carneiro, Aristides P; Held, Christoph; Rodríguez, Oscar; Sadowski, Gabriele; Macedo, Eugénia A

2013-08-29

Biorefining processes using ionic liquids (ILs) require proper solubility data of biomass-based compounds in ILs, as well as an appropriate thermodynamic approach for the modeling of such data. Carbohydrates and their derivatives such as sugar alcohols represent a class of compounds that could play an important role in biorefining. Thus, in this work, the pure IL density and solubility of xylitol and sorbitol in five different ILs were measured between 288 and 339 K. The ILs under consideration were 1-ethyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium dicyanamide ([bmim][DCA]), Aliquat dicyanamide, trihexyltetradecylphosphonium dicyanamide, and 1-ethyl-3-methylimidazolium trifluoroacetate. Comparison with the literature data was performed, showing good agreement. With the exception of [bmim][DCA], the solubility of these sugar alcohols in the other ILs is presented for the first time. The measured data as well as previously published solubility data of glucose and fructose in these ILs were modeled by means of PC-SAFT using a molecular-based associative approach for ILs. PC-SAFT was used in this work as it has shown to be applicable to model the solubility of xylitol and sorbitol in ILs (Paduszyński; et al. J. Phys. Chem. B 2013, 117, 7034-7046). For this purpose, three pure IL parameters were fitted to pure IL densities, activity coefficients of 1-propanol at infinite dilution in ILs, and/or xylitol solubility in ILs. This approach allows accurate modeling of the pure IL data and the mixture data with only one binary interaction parameter k(ij) between sugar and the IL or sugar alcohol and the IL. In cases where only the pure IL density and activity coefficients of 1-propanol at infinite dilution in ILs were used for the IL parameter estimation, the solubility of the sugars and sugar alcohols in the ILs could be predicted (k(ij) = 0 between sugar and the IL or sugar alcohol and the IL) with reasonable accuracy.

Molecular dynamics investigation of the ionic liquid/enzyme interface: application to engineering enzyme surface charge.

PubMed

Burney, Patrick R; Nordwald, Erik M; Hickman, Katie; Kaar, Joel L; Pfaendtner, Jim

2015-04-01

Molecular simulations of the enzymes Candida rugosa lipase and Bos taurus α-chymotrypsin in aqueous ionic liquids 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium ethyl sulfate were used to study the change in enzyme-solvent interactions induced by modification of the enzyme surface charge. The enzymes were altered by randomly mutating lysine surface residues to glutamate, effectively decreasing the net surface charge by two for each mutation. These mutations resemble succinylation of the enzyme by chemical modification, which has been shown to enhance the stability of both enzymes in ILs. After establishing that the enzymes were stable on the simulated time scales, we focused the analysis on the organization of the ionic liquid substituents about the enzyme surface. Calculated solvent charge densities show that for both enzymes and in both solvents that changing positively charged residues to negative charge does indeed increase the charge density of the solvent near the enzyme surface. The radial distribution of IL constituents with respect to the enzyme reveals decreased interactions with the anion are prevalent in the modified systems when compared to the wild type, which is largely accompanied by an increase in cation contact. Additionally, the radial dependence of the charge density and ion distribution indicates that the effect of altering enzyme charge is confined to short range (≤1 nm) ordering of the IL. Ultimately, these results, which are consistent with that from prior experiments, provide molecular insight into the effect of enzyme surface charge on enzyme stability in ILs. © 2015 Wiley Periodicals, Inc.

Thermo-responsive triblock copolymer phase transition behaviour in imidazolium-based ionic liquids: Role of the effect of alkyl chain length of cations.

PubMed

Umapathi, Reddicherla; Venkatesu, Pannuru

2017-01-01

Different biophysical techniques such as fluorescence spectroscopy, dynamic light scattering (DLS), viscosity (η) and Fourier transform infrared (FTIR) spectroscopy have been carried out to characterize the effect of imidazolium-based ionic liquids (ILs) on the thermo-responsive triblock copolymer, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly-(ethylene glycol) (PEG-PPG-PEG). In addition, to demonstrate the distinct morphological changes of various self-assembled morphologies, we further employed field emission scanning electron microscope (FESEM). To investigate the effect of alkyl chain length of the cation, concentration of the ILs and the related Hofmeister series on the phase behaviour of PEG-PPG-PEG, we used a series of ILs possessing same Cl - anion and a set of cation [C n mim] + with increasing alkyl chain length of cation such as 1-ethyl-3-methylimidazolium chloride ([Emim][Cl]), 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]), 1-hexyl-3-methylimidazolium chloride ([Hmim][Cl]) and 1-decyl-3-methylimidazolium chloride ([Dmim][Cl]). The critical micellization temperature (CMT) of the copolymer in the presence of well hydrated cations is directly correlated to their hydration. The overall specific ranking of ILs in decreasing the CMT of PEG-PPG-PEG in aqueous solution was [Emim][Cl]>[Bmim][Cl]>[Hmim][Cl]>[Dmim][Cl]. The trend of these ILs followed the well-known Hofmeister series of cations of ILs. The present study provides important information about the solution properties that can be helpful to tune the IL or temperature-sensitive copolymer CMT and micelle shapes which are crucial for understanding the drug delivery mechanisms. Copyright © 2016 Elsevier Inc. All rights reserved.

Physical Properties and CO2 Reaction Pathway of 1-Ethyl-3-Methylimidazolium Ionic Liquids with Aprotic Heterocyclic Anions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seo, S; DeSilva, MA; Brennecke, JF

2014-12-25

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 processmore » 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 H-1 and C-13 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 degrees 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.« less

Molecular dynamics investigation of water-exchange reactions on lanthanide ions in water/1-ethyl-3-methylimidazolium trifluoromethylsufate ([EMIm][OTf])

NASA Astrophysics Data System (ADS)

Tu, Yi-Jung; Lin, Zhijin; Allen, Matthew J.; Cisneros, G. Andrés

2018-01-01

We report a kinetic study of the water exchange on lanthanide ions in water/[1-ethyl-3-methylimidazolium][trifluoromethylsufate] (water/[EMIm][OTf]). The results from 17O-NMR measurements show that the water-exchange rates in water/[EMIm][OTf] increase with decreasing size of the lanthanide ions. This trend for water-exchange is similar to the previously reported trend in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO4]) but opposite to that in water. To gain atomic-level insight into these water-exchange reactions, molecular dynamics simulations for lanthanide ions in water/[EMIm][OTf] have been performed using the atomic-multipole-optimized-energetics-for-biomolecular-application polarizable force field. Our molecular dynamics simulations reproduce the experimental water-exchange rates in terms of the trend and provide possible explanations for the observed experimental behavior. The smaller lanthanide ions in water/[EMIm][OTf] undergo faster water exchange because the smaller lanthanide ions coordinate to the first shell [OTf]- anions more tightly, resulting in a stronger screening effect for the second-shell water. The screening effect weakens the interaction of the lanthanide ions with the second-shell water molecules, facilitating the dissociation of water from the second-shell and subsequent association of water molecules from the outer solvation shells.

Molecular dynamics investigation of water-exchange reactions on lanthanide ions in water/1-ethyl-3-methylimidazolium trifluoromethylsufate ([EMIm][OTf]).

PubMed

Tu, Yi-Jung; Lin, Zhijin; Allen, Matthew J; Cisneros, G Andrés

2018-01-14

We report a kinetic study of the water exchange on lanthanide ions in water/[1-ethyl-3-methylimidazolium][trifluoromethylsufate] (water/[EMIm][OTf]). The results from 17 O-NMR measurements show that the water-exchange rates in water/[EMIm][OTf] increase with decreasing size of the lanthanide ions. This trend for water-exchange is similar to the previously reported trend in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO 4 ]) but opposite to that in water. To gain atomic-level insight into these water-exchange reactions, molecular dynamics simulations for lanthanide ions in water/[EMIm][OTf] have been performed using the atomic-multipole-optimized-energetics-for-biomolecular-application polarizable force field. Our molecular dynamics simulations reproduce the experimental water-exchange rates in terms of the trend and provide possible explanations for the observed experimental behavior. The smaller lanthanide ions in water/[EMIm][OTf] undergo faster water exchange because the smaller lanthanide ions coordinate to the first shell [OTf] - anions more tightly, resulting in a stronger screening effect for the second-shell water. The screening effect weakens the interaction of the lanthanide ions with the second-shell water molecules, facilitating the dissociation of water from the second-shell and subsequent association of water molecules from the outer solvation shells.

Mixture cytotoxicity assessment of ionic liquids and heavy metals in MCF-7 cells using mixtox.

PubMed

Zhu, Xiang-Wei; Ge, Hui-Lin; Cao, Yu-Bin

2016-11-01

Ionic liquids (ILs) are widely used as extractants for heavy metals. However, the effect of mixtures of ILs and heavy metals is rarely understood. In this study, we tested the cytotoxicity of four ILs, four heavy metals and their mixtures on human MCF-7 cells in 96-well microplates. The toxicity of single compounds in MCF-7 cells ranges from 3.07 × 10(-6) M for Cu(II) to 2.20 × 10(-3) M for 1-ethyl-3-methylimidazolium tetrafluoroborate. The toxicity of heavy metals in MCF-7 is generally higher than the toxicity of ILs. A uniform experimental design was used to simulate environmentally realistic mixtures. Two classical reference models (concentration addition and independent action) were used to predict their mixture. The experiments to evaluate the toxicity of the mixture revealed antagonism among four ILs and four heavy metals in MCF-7 cells. Pearson correlation analysis showed that Ni(II) and 1-dodecyl-3-methylimidazolium chloride are positively correlated with the extent of antagonism, while 1-hexyl-3-methylimidazolium tetrafluoroborate showed a negative correlation. Data analysis was conducted in the R package mixtox, which integrates features such as curve fitting, experimental design, and mixture toxicity prediction. The international community of toxicologists is welcome to use this package and provide feedback as suggestions and comments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Corrosion Inhibition of Cast Iron in Arabian Gulf Seawater by Two Different Ionic Liquids

PubMed Central

Sherif, El-Sayed M.; Abdo, Hany S.; Zein El Abedin, Sherif

2015-01-01

In this paper we report on the corrosion inhibition of cast iron in Arabian Gulf seawater by two different ionic liquids namely, 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) and 1-butyl-1-methylpyrrolidinium chloride ([Py1,4]Cl). The inhibiting influence of the employed ionic liquids was investigated by weight loss, open circuit potential electrochemical impedance spectroscopy, and cyclic potentiodynamic polarization. The results show the corrosion inhibition impact of the employed ionic liquids (ILs). Compared with [Py1,4]Cl, [EMIm]Cl shows a higher inhibition efficiency at a short immersion time, for the examined ILs concentrations. However, [Py1,4]Cl exhibits a higher efficiency upon increasing the immersion time indicating the persistence of the inhibiting influence. The corrosion inhibition of the employed ionic liquids is attributed to the adsorption of the cations of the ionic liquids onto the surface of cast iron forming a corrosion barrier. PMID:28793413

Decomposition of Imidazolium-Based Ionic Liquids in Contact with Lithium Metal.

PubMed

Schmitz, Paulo; Jakelski, Rene; Pyschik, Marcelina; Jalkanen, Kirsi; Nowak, Sascha; Winter, Martin; Bieker, Peter

2017-03-09

Ionic liquids (ILs) are considered to be suitable electrolyte components for lithium-metal batteries. Imidazolium cation based ILs were previously found to be applicable for battery systems with a lithium-metal negative electrode. However, herein it is shown that, in contrast to the well-known IL N-butyl-N-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide ([Pyr 14 ][TFSI]), 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C2MIm][TFSI]) and 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C4MIm][TFSI]) are chemically unstable versus metallic lithium. A lithium-metal sheet was immersed in pure imidazolium-based IL samples and aged at 60 °C for 28 days. Afterwards, the aged IL samples were investigated to deduce possible decomposition products of the imidazolium cation. The chemical instability of the ILs in contact with lithium metal and a possible decomposition starting point are shown for the first time. Furthermore, the investigated imidazolium-based ILs can be utilized for lithium-metal batteries through the addition of the solid-electrolyte interphase (SEI) film-forming additive fluoroethylene carbonate. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lyotropic Phase Behavior of Polybutadiene-Poly(ethylene oxide) Diblock Copolymers in Ionic Liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simone, Peter M.; Lodge, Timothy P.

2008-08-26

The lyotropic phase behavior of three poly(1,2-butadiene-b-ethylene oxide) diblock copolymers (PB-PEO) with different monomer volume fractions has been studied in two different ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF{sub 6}]), across the complete concentration range. The ordered microstructures present in the solutions were characterized via small-angle X-ray scattering (SAXS). The phase diagrams for the PB-PEO/ionic liquid solutions include regions corresponding to the classical copolymer microstructures: body-centered-cubic lattices of spheres, hexagonally ordered cylinders, and lamellae. Additionally, the phase diagrams also include wide regions of coexisting microstructures and regions apparently corresponding to a disordered network microstructure. The phase behavior ofmore » the PB-PEO copolymers in both ionic liquids was comparable to their previously reported aqueous solution behavior. The temperature dependence of the phase diagrams was very modest, indicative of a highly segregated system. The level of solvent selectivity was also investigated via cryogenic transmission electron microscopy (cryo-TEM) on dilute solutions. On the basis of the morphology of the dilute solution copolymer aggregate structures in the ionic liquid solvents, and on the structural length scales of the concentrated solutions, it was concluded that for PB-PEO [BMI][PF{sub 6}] behaves as a more selective solvent than [EMI][TFSI].« less

Electrodeposition and characterisation of Al-W alloy films from ionic liquid

NASA Astrophysics Data System (ADS)

Höhlich, D.; Wachner, D.; Müller, M.; Scharf, I.; Lampke, T.

2018-06-01

Al–W alloy films were prepared by electrodeposition using anhydrous 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic-liquid solution with aluminium chloride in a ratio of 1:1.5. As a commercially available tungsten precursor, tungsten hexachloride was used. The metal is dissolved in the ionic liquid at concentrations up to 0.06 mol/l. The deposition took place outside the glove box with a continuous argon stream over the electrolyte at a temperature of 60 °C with a current density of 1 A/m2. Resulting alloys show a tungsten content higher than 20 wt% (3.5 at%). The phase composition of Al-W alloys was observed by X-ray diffraction (XRD), and the chemical composition was characterised by scanning electron microscopy (SEM) and inductively-coupled plasma optical emission spectroscopy (ICP-OES).

Ionic liquid as an electrolyte additive for high performance lead-acid batteries

NASA Astrophysics Data System (ADS)

Deyab, M. A.

2018-06-01

The performance of lead-acid battery is improved in this work by inhibiting the corrosion of negative battery electrode (lead) and hydrogen gas evolution using ionic liquid (1-ethyl-3-methylimidazolium diethyl phosphate). The results display that the addition of ionic liquid to battery electrolyte (5.0 M H2SO4 solution) suppresses the hydrogen gas evolution to very low rate 0.049 ml min-1 cm-2 at 80 ppm. Electrochemical studies show that the adsorption of ionic liquid molecules on the lead electrode surface leads to the increase in the charge transfer resistance and the decrease in the double layer capacitance. I also notice a noteworthy improvement of battery capacity from 45 mAh g-1 to 83 mAh g-1 in the presence of ionic liquid compound. Scanning electron microscopy and energy dispersive X-ray analysis confirm the adsorption of ionic liquid molecules on the battery electrode surface.

Vaporization behavior of tetraoctylphosphonium bis(2-ethylhexyl)phosphate ionic liquid

DOE PAGES

McMurray, J. W.; Zhou, Y.; Luo, H. M.; ...

2016-11-18

We determined the equilibrium vapor pressures, p e, of the ionic liquid tetraoctylphosphonium bis(2-ethylhexyl)phosphate ([P 8888][DEHP]) over the temperature range 409–495 K using mass loss Knudsen effusion. The p e versus temperature relationship compares well to 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide ([C 8mim][NTf 2]) but is lower than that of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C 2mim][NTf 2]) when measured using the same technique. Here, we determined the discrepancies between the p e for [C 8mim][NTf 2] and [C 2mim][NTf 2] with previous studies is discussed. Finally, the enthalpy and entropy of vaporization for all three fluids are estimated from the Clasius-Clapeyron relation.

Vaporization behavior of tetraoctylphosphonium bis(2-ethylhexyl)phosphate ionic liquid

NASA Astrophysics Data System (ADS)

McMurray, J. W.; Zhou, Y.; Luo, H. M.; Qu, J.

2017-01-01

The equilibrium vapor pressures, pe, of the ionic liquid tetraoctylphosphonium bis(2-ethylhexyl)phosphate ([P8888][DEHP]) over the temperature range 409-495 K were determined for the first time using mass loss Knudsen effusion. The pe versus temperature relationship compares well to 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide ([C8mim][NTf2]) but is lower than that of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) when measured using the same technique. The discrepancies between the pe determined in this work for [C8mim][NTf2] and [C2mim][NTf2] with previous studies is discussed. The enthalpy and entropy of vaporization for all three fluids are estimated from the Clasius-Clapeyron relation.

Auto-Tandem Catalysis in Ionic Liquids: Synthesis of 2-Oxazolidinones by Palladium-Catalyzed Oxidative Carbonylation of Propargylic Amines in EmimEtSO₄.

PubMed

Mancuso, Raffaella; Maner, Asif; Ziccarelli, Ida; Pomelli, Christian; Chiappe, Cinzia; Della Ca', Nicola; Veltri, Lucia; Gabriele, Bartolo

2016-07-08

A convenient carbonylative approach to 2-oxazolidinone derivatives carried out using an ionic liquid (1-ethyl-3-methylimidazolium ethyl sulfate, EmimEtSO₄) as the solvent is presented. It is based on the sequential concatenation of two catalytic cycles, both catalyzed by the same metal species (auto-tandem catalysis): the first cycle corresponds to the oxidative monoaminocarbonylation of the triple bond of propargylic amines to give the corresponding 2-ynamide intermediates, while the second one involves the cyclocarbonylation of the latter to yield 2-(2-oxooxazolidin-5-ylidene)-acetamides. Reactions are carried out using a simple catalytic system consisting of PdI₂ in conjunction with an excess of KI, and the catalyst/solvent system could be recycled several times without appreciable loss of activity after extraction of the organic product with Et₂O.

The gaseous enthalpy of formation of the ionic liquid 1-butyl-3-methylimidazolium dicyanamide from combustion calorimetry, vapor pressure measurements, and ab initio calculations.

PubMed

Emel'yanenko, Vladimir N; Verevkin, Sergey P; Heintz, Andreas

2007-04-04

Ionic liquids are attracting growing interest as alternatives to conventional molecular solvents. Experimental values of vapor pressure, enthalpy of vaporization, and enthalpy of formation of ionic liquids are the key thermodynamic quantities, which are required for the validation and development of the molecular modeling and ab initio methods toward this new class of solvents. In this work, the molar enthalpy of formation of the liquid 1-butyl-3-methylimidazolium dicyanamide, 206.2 +/- 2.5 kJ.mol-1, was measured by means of combustion calorimetry. The molar enthalpy of vaporization of 1-butyl-3-methylimidazolium dicyanamide, 157.2 +/- 1.1 kJ.mol-1, was obtained from the temperature dependence of the vapor pressure measured using the transpiration method. The latter method has been checked with measurements of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, where data are available from the effusion technique. The first experimental determination of the gaseous enthalpy of formation of the ionic liquid 1-butyl-3-methylimidazolium dicyanamide, 363.4 +/- 2.7 kJ.mol-1, from thermochemical measurements (combustion and transpiration) is presented. Ab initio calculations of the enthalpy of formation in the gaseous phase have been performed for 1-butyl-3-methylimidazolium dicyanamide using the G3MP2 theory. Excellent agreement with experimental results has been observed. The method developed opens a new way to obtain thermodynamic properties of ionic liquids which have not been available so far.

Computer Simulation Study of Graphene Oxide Supercapacitors: Charge Screening Mechanism.

PubMed

Park, Sang-Won; DeYoung, Andrew D; Dhumal, Nilesh R; Shim, Youngseon; Kim, Hyung J; Jung, YounJoon

2016-04-07

Graphene oxide supercapacitors in the parallel plate configuration are studied via molecular dynamics (MD) simulations. The full range of electrode oxidation from 0 to 100% is examined by oxidizing the graphene surface with hydroxyl groups. Two different electrolytes, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI(+)BF4(-)) as an ionic liquid and its 1.3 M solution in acetonitrile as an organic electrolyte, are considered. While the area-specific capacitance tends to decrease with increasing electrode oxidation for both electrolytes, its details show interesting differences between the organic electrolyte and ionic liquid, including the extent of decrease. For detailed insight into these differences, the screening mechanisms of electrode charges by electrolytes and their variations with electrode oxidation are analyzed with special attention paid to the aspects shared by and the contrasts between the organic electrolyte and ionic liquid.

High-performance supercapacitors based on poly(ionic liquid)-modified graphene electrodes.

PubMed

Kim, Tae Young; Lee, Hyun Wook; Stoller, Meryl; Dreyer, Daniel R; Bielawski, Christopher W; Ruoff, Rodney S; Suh, Kwang S

2011-01-25

We report a high-performance supercapacitor incorporating a poly(ionic liquid)-modified reduced graphene oxide (PIL:RG-O) electrode and an ionic liquid (IL) electrolyte (specifically, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide or EMIM-NTf(2)). PIL:RG-O provides enhanced compatibility with the IL electrolyte, thereby increasing the effective electrode surface area accessible to electrolyte ions. The supercapacitor assembled with PIL:RG-O electrode and EMIM-NTf(2) electrolyte showed a stable electrochemical response up to 3.5 V operating voltage and was capable of yielding a maximum energy density of 6.5 W·h/kg with a power density of 2.4 kW/kg. These results demonstrate the potential of the PIL:RG-O material as an electrode in high-performance supercapacitors.

Pesticide Removal from Aqueous Solutions by Adding Salting Out Agents

PubMed Central

Moscoso, Fátima; Deive, Francisco J.; Esperança, José M. S. S.; Rodríguez, Ana

2013-01-01

Phase segregation in aqueous biphasic systems (ABS) composed of four hydrophilic ionic liquids (ILs): 1-butyl-3-methylimidazolium methylsulfate and 1-ethyl-3-methylimidazolium methylsulfate (CnC1im C1SO4, n = 2 and 4), tributylmethyl phosphonium methylsulfate (P4441 C1SO4) and methylpyridinium methylsulfate (C1Py C1SO4) and two high charge density potassium inorganic salts (K2CO3 and K2HPO4) were determined by the cloud point method at 298.15 K. The influence of the addition of the selected inorganic salts to aqueous mixtures of ILs was discussed in the light of the Hofmeister series and in terms of molar Gibbs free energy of hydration. The effect of the alkyl chain length of the cation on the methylsulfate-based ILs has been investigated. All the solubility data were satisfactorily correlated to several empirical equations. A pesticide (pentachlorophenol, PCP) extraction process based on the inorganic salt providing a greater salting out effect was tackled. The viability of the proposed process was analyzed in terms of partition coefficients and extraction efficiencies. PMID:24145747

Pretreatment of corn straw using the alkaline solution of ionic liquids.

PubMed

Liu, Zhen; Li, Longfei; Liu, Cheng; Xu, Airong

2018-07-01

In the present work, the pretreatment of corn stalk with the solution of 1-ethyl-3-methylimidazolium acetate ([Emim]Ac) ionic liquid containing NaOH was explored for its lignin removal. The effects of reaction temperature, reaction time, and solid-liquid ratio on the lignin removal efficiency were determined by the response surface methodology (RSM). The pretreatment conditions were optimized by the Box-Behnken design and the comparative study of the composition and structure of corn straw before and after the pretreatment to be: reaction temperature 98.5 °C, reaction time 1.31 h, and solid-liquid ratio 1:8.7. Under the optimized conditions, the cellulose and hemicellulose contents of the corn straw were increased to 85.69% and 9.1%, respectively, and the lignin content was reduced to 2.27% with the lignin removal efficiency up to 87.4%. Copyright © 2018 Elsevier Ltd. All rights reserved.

Divergent syntheses of iodinated isobenzofuranones and isochromenones by iodolactonization of 2-alkynylbenzoic acids in ionic liquids.

PubMed

Mancuso, Raffaella; Pomelli, Christian C; Malafronte, Francesco; Maner, Asif; Marino, Nadia; Chiappe, Cinzia; Gabriele, Bartolo

2017-06-07

The regiochemical outcome of the iodolactonization of 2-alkynylbenzoic acids, carried out at 100 °C in ionic liquids (ILs) as unconventional solvents and with molecular iodine as the iodine source, in the absence of external bases, was found to be strongly dependent on the nature of the IL medium. In particular, while the use of N-ethyl-N-methylmorpholinium dicyanamide (Mor 1,2 N(CN) 2 ) promoted the stereoselective formation of (E)-3-(iodomethylene)isobenzofuran-1(3H)-ones, through an anti-5-exo-dig cyclization route, the use of 1-ethyl-3-methylimidazolium ethyl sulfate (EmimEtSO 4 ) tended to favor the 6-endo-dig cyclization mode, with preferential or selective formation of 4-iodo-1H-isochromen-1-ones. In any case, the IL solvent could be easily recycled after extraction of the product from the reaction mixture with diethyl ether. DFT calculations have been carried out to clarify the role of the IL's nature in favoring either the anti-5-exo-dig cyclization route or the 6-endo-dig mode. In the case of iodocyclization of 2-ethynylbenzoic acid, only the 5-exo-dig mode was observed in both EmimEtSO 4 and Mor 1,2 N(CN) 2 solvents. The structures of two representative products have been confirmed by X-ray diffraction analysis.

Electrocapillarity and zero-frequency differential capacitance at the interface between mercury and ionic liquids measured using the pendant drop method.

PubMed

Nishi, Naoya; Hashimoto, Atsunori; Minami, Eiji; Sakka, Tetsuo

2015-02-21

The structure of ionic liquids (ILs) at the electrochemical IL|Hg interface has been studied using the pendant drop method. From the electrocapillarity (potential dependence of interfacial tension) differential capacitance (Cd) at zero frequency (in other words, static differential capacitance or differential capacitance in equilibrium) has been evaluated. The potential dependence of zero-frequency Cd at the IL|Hg interface exhibits one or two local maxima near the potential of zero charge (Epzc), depending on the cation of the ILs. For 1-ethyl-3-methylimidazolium tetrafluoroborate, an IL with the cation having a short alkyl chain, the Cdvs. potential curve has one local maximum whereas another IL, 1-octyl-3-methylimidazolium tetrafluoroborate, with the cation having a long alkyl chain, shows two maxima. These behaviors of zero-frequency Cd agree with prediction by recent theoretical and simulation studies for the electrical double layer in ILs. At negative and positive potentials far from Epzc, the zero-frequency Cd increases for both the ILs studied. The increase in zero-frequency Cd is attributable to the densification of ionic layers in the electrical double layer.

Ionic-liquid-induced ferroelectric polarization in poly(vinylidene fluoride) thin films

NASA Astrophysics Data System (ADS)

Wang, Feipeng; Lack, Alexander; Xie, Zailai; Frübing, Peter; Taubert, Andreas; Gerhard, Reimund

2012-02-01

Thin films of ferroelectric β-phase poly(vinylidene fluoride) (PVDF) were spin-coated from a solution that contained small amounts of the ionic liquid (IL) 1-ethyl-3-methylimidazolium nitrate. A remanent polarization of 60 mC/m2 and a quasi-static pyroelectric coefficient of 19 μC/m2K at 30 °C were observed in the films. It is suggested that the IL promotes the formation of the β phase through dipolar interactions between PVDF chain-molecules and the IL. The dipolar interactions are identified as Coulomb attraction between hydrogen atoms in PVDF chains and anions in IL. The strong crystallinity increase is probably caused by the same dipolar interaction as well.

Solubility of alkali metal halides in the ionic liquid [C4C1im][OTf].

PubMed

Kuzmina, O; Bordes, E; Schmauck, J; Hunt, P A; Hallett, J P; Welton, T

2016-06-28

The solubilities of the metal halides LiF, LiCl, LiBr, LiI, NaF, NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbCl, CsCl, CsI, were measured at temperatures ranging from 298.15 to 378.15 K in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4C1im][OTf]). Li(+), Na(+) and K(+) salts with anions matching the ionic liquid have also been investigated to determine how well these cations dissolve in [C4C1im][OTf]. This study compares the influence of metal cation and halide anion on the solubility of salts within this ionic liquid. The highest solubility found was for iodide salts, and the lowest solubility for the three fluoride salts. There is no outstanding difference in the solubility of salts with matching anions in comparison to halide salts. The experimental data were correlated employing several phase equilibria models, including ideal mixtures, van't Hoff, the λh (Buchowski) equation, the modified Apelblat equation, and the non-random two-liquid model (NRTL). It was found that the van't Hoff model gave the best correlation results. On the basis of the experimental data the thermodynamic dissolution parameters (ΔH, ΔS, and ΔG) were determined for the studied systems together with computed gas phase metathesis parameters. Dissolution depends on the energy difference between enthalpies of fusion and dissolution of the solute salt. This demonstrates that overcoming the lattice energy of the solid matrix is the key to the solubility of inorganic salts in ionic liquids.

Corrosion inhibition performance of imidazolium ionic liquids and their influence on surface ferrous carbonate layer formation

NASA Astrophysics Data System (ADS)

Yang, Dongrui

Corrosion inhibitors as effective anti-corrosion applications were widely studied and drawn much attention in both academe and industrial area. In this work, a systematic work, including inhibitors selection, anti-corrosion property and characterization, influence on scale formation, testing system design and so on, were reported. The corrosion inhibition performance of four imidazolium ionic liquids in carbon dioxide saturated NaCl solution was investigated by using electrochemical and surface analysis technologies. The four compounds are 1-ethyl-3-methylimidazolium chloride (a), 1-butyl-3-methylimidazolium chloride (b), 1-hexyl-3-methylimidazolium chloride (c), 1-decyl-3-methylimidazolium chloride (d). Under the testing conditions, compound d showed the highest inhibition efficiency and selected as the main object of further study. As a selected representative formula, 1-decyl-3-methylimidazolium chloride was studied in detail about its corrosion inhibition performance on mild steel in carbon dioxide saturated NaCl brine at pH 3.8 and 6.8. Electrochemical and surface analysis techniques were used to characterize the specimen corrosion process during the immersion in the blank and inhibiting solutions. The precorrosion of specimen surface showed significant and different influences on the anti-corrosion property of DMICL at pH 3.8 and 6.8. The corrosion inhibition efficiency (IE) was calculated based on parameters obtained from electrochemical techniques; the achieved IE was higher than 98% at the 25th hour for the steel with a well-polished surface at pH 3.8. The fitting parameters obtained from electrochemical data helped to account for the interfacial changes. As proved in previous research, 1-decyl-3-methylimidazolium chloride could be used as good corrosion inhibitors under certain conditions. However, under other conditions, such chemicals, as well as other species in oil transporting system, could be a factor influencing the evolution of protective surface inorganic layer. In this part, the FeCO3 layer evolution process for API 5L X52 carbon steel in CO2-saturated NaCl brine in the absence and in the presence of 1-decyl-3-methylimidazolium chloride ionic liquid was characterized using electrochemical techniques. Two models were developed to account for the interfacial evolution: the first model considered the balance of positive and negative charges at the interface of the metal and electrolyte in blank solution, while the second one considered the layer coverage and evolution with the imidazolium compound. The corrosion testing system is scientifically and practically critical for corrosion testing and simulations. In this part, a flowing fluid loop cell (FFLC) system was constructed to simulate the corrosion environment in the pipeline. Main content of this work include the construction of the flowing fluid cell loop (FFLC) system, as well as FFLC-based corrosion/anticorrosion tests under simulated acid conditions. Electrochemical Impedance Spectroscopy (EIS) and Linear Polarization Resistance (LPR) were used as prime techniques to quantify and characterize the corrosion behaviors of carbon steel specimen. The Eff vs. Reynolds number (Re) plots for the specimen located in the chamber and in the loop branch were provided.

Simulating structure and dynamics in small droplets of 1-ethyl-3-methylimidazolium acetate

NASA Astrophysics Data System (ADS)

Brehm, Martin; Sebastiani, Daniel

2018-05-01

To investigate the structure and dynamics of small ionic liquid droplets in gas phase, we performed a DFT-based ab initio molecular dynamics study of several 1-ethyl-3-methylimidazolium acetate clusters in vacuum as well as a bulk phase simulation. We introduce an unbiased criterion for average droplet diameter and density. By extrapolation of the droplet densities, we predict the experimental bulk phase density with a deviation of only a few percent. The hydrogen bond geometry between cations and anions is very similar in droplets and bulk, but the hydrogen bond dynamics is significantly slower in the droplets, becoming slower with increasing system size, with hydrogen bond lifetimes up to 2000 ps. From a normal mode analysis of the trajectories, we identify the modes of the ring proton C-H stretching, which are strongly affected by hydrogen bonding. From analyzing these, we find that the hydrogen bond becomes weaker with increasing system size. The cations possess an increased concentration inside the clusters, whereas the anions show an excess concentration on the outside. Almost all anions point towards the droplet center with their carboxylic groups. Ring stacking is found to be a very important structural motif in the droplets (as in the bulk), but side chain interactions are only of minor importance. By using Voronoi tessellation, we define the exposed droplet surface and find that it consists mainly of hydrogen atoms from the cation's and anion's methyl and ethyl groups. Polar atoms are rarely found on the surface, such that the droplets appear completely hydrophobic on the outside.

Electrodeposition of Al in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ionic liquids: in situ STM and EQCM studies.

PubMed

Moustafa, E M; El Abedin, S Zein; Shkurankov, A; Zschippang, E; Saad, A Y; Bund, A; Endres, F

2007-05-10

In the present paper, the electrodeposition of Al on flame-annealed Au(111) and polycrystalline Au substrates in two air- and water-stable ionic liquids namely, 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide, [Py(1,4)]Tf(2)N, and 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)amide, [EMIm]Tf(2)N, has been investigated by in situ scanning tunneling microscopy (STM), electrochemical quartz crystal microbalance (EQCM), and cyclic voltammetry. The cyclic voltammogram of aluminum deposition and stripping on Au(111) in the upper phase of the biphasic mixture of AlCl(3)/[EMIm]Tf(2)N at room temperature (25 degrees C) shows that the electrodeposition process is completely reversible as also evidenced by in situ STM and EQCM studies. Additionally, a cathodic peak at an electrode potential of about 0.55 V vs Al/Al(III) is correlated to the aluminum UPD process that was evidenced by in situ STM. A surface alloying of Al with Au at the early stage of deposition occurs. It has been found that the Au(111) surface is subject to a restructuring/reconstruction in the upper phase of the biphasic mixture of AlCl(3)/[Py(1,4)]Tf(2)N at room temperature (25 degrees C) and that the deposition is not fully reversible. Furthermore, the underpotential deposition of Al in [Py(1,4)]Tf(2)N is not as clear as in [EMIm]Tf(2)N. The frequency shift in the EQCM experiments in [Py(1,4)]Tf(2)N shows a surprising result as an increase in frequency and a decrease in damping with bulk aluminum deposition at potentials more negative than -1.8 V was observed at room temperature. However, at 100 degrees C there is a frequency decrease with ongoing Al deposition. At -2.0 V vs Al/Al(III), a bulk aluminum deposition sets in.

Flexible thin-film battery based on solid-like ionic liquid-polymer electrolyte

NASA Astrophysics Data System (ADS)

Li, Qin; Ardebili, Haleh

2016-01-01

The development of high-performance flexible batteries is imperative for several contemporary applications including flexible electronics, wearable sensors and implantable medical devices. However, traditional organic liquid-based electrolytes are not ideal for flexible batteries due to their inherent safety and stability issues. In this study, a non-volatile, non-flammable and safe ionic liquid (IL)-based polymer electrolyte film with solid-like feature is fabricated and incorporated in a flexible lithium ion battery. The ionic liquid is 1-Ethyl-3-methylimidazolium dicyanamide (EMIMDCA) and the polymer is composed of poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP). The electrolyte exhibits good thermal stability (i.e. no weight loss up to 300 °C) and relatively high ionic conductivity (6 × 10-4 S cm-1). The flexible thin-film lithium ion battery based on solid-like electrolyte film is encapsulated using a thermal-lamination process and demonstrates excellent electrochemical performance, in both flat and bent configurations.

A novel ionic liquid-tolerant Fusarium oxysporum BN secreting ionic liquid-stable cellulase: consolidated bioprocessing of pretreated lignocellulose containing residual ionic liquid.

PubMed

Xu, Jiaxing; Wang, Xinfeng; Hu, Lei; Xia, Jun; Wu, Zhen; Xu, Ning; Dai, Benlin; Wu, Bin

2015-04-01

In this study, microbial communities from chemicals polluted microhabitats were cultured with the addition of imidazolium-based ionic liquid (IL) to enrich for IL-tolerant microbes. A strain of Fusarium oxysporum BN producing cellulase from these enrichments was capable of growing in 10% (w/v) 1-ethyl-3-methylimidazolium phosphinate, much higher than the normal IL concentrations in the lignocellulose regenerated from ILs. Cellulase secreted by the strain showed high resistance to ILs based on phosphate and sulfate radicals, evidencing of a high conformational stability in relevant media. Gratifyingly, F. oxysporum BN can directly convert IL-pretreated rice straw to bioethanol via consolidated bioprocessing (I-CBP). At optimum fermentation condition, a maximum ethanol yield of 0.125 g ethanol g(-1) of rice straw was finally obtained, corresponding to 64.2% of the theoretical yield. Copyright © 2015 Elsevier Ltd. All rights reserved.

Molecular dynamics simulation and pulsed-field gradient NMR studies of bis(fluorosulfonyl)imide (FSI) and bis[(trifluoromethyl)sulfonyl]imide (TFSI)-based ionic liquids.

PubMed

Borodin, Oleg; Gorecki, W; Smith, Grant D; Armand, Michel

2010-05-27

The pulsed-field-gradient spin-echo NMR measurements have been performed on 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide ([emim][FSI]) and 1-ethyl-3-methylimidazolium [bis[(trifluoromethyl)sulfonyl]imide] ([emim][TFSI]) over a wide temperature range from 233 to 400 K. Molecular dynamics (MD) simulations have been performed on [emim][FSI], [emim][TFSI], [N-methyl-N-propylpyrrolidinium][FSI] ([pyr(13)][FSI]), and [pyr(13)][TFSI] utilizing a many-body polarizable force field. An excellent agreement between the ion self-diffusion coefficients from MD simulations and pfg-NMR experiments has been observed for [emim][FSI] and [emim][TFSI] ILs. The structure factor of [pyr(13)][FSI], [pyr(14)][TFSI], and [emim][TFSI] agreed well with the previously reported X-ray diffraction data performed by Umebayashi group. Ion packing in the liquid state is compared with packing in the corresponding ionic crystal. Faster transport found in the FSI-based ILs compared to that in TFSI-based ILs is associated with the smaller size of FSI(-) anion and lower cation-anion binding energies. A significant artificial increase of the barriers (by 3 kcal/mol) for the FSI(-) anion conformational transitions did not result in slowing down of ion transport, indicating that the ion dynamics is insensitive to the FSI(-) anion torsional energetic, while the same increase of the TFSI(-) anion barriers in [emim][TFSI] and [pyr(13)][TFSI] ILs resulted in slowing down of the cation and anion transport by 40-50%. Details of ion rotational and translational motion, coupling of the rotational and translational relaxation are also discussed.

Ionic liquids at the surface of graphite: Wettability and structure

NASA Astrophysics Data System (ADS)

Bordes, Emilie; Douce, Laurent; Quitevis, Edward L.; Pádua, Agílio A. H.; Costa Gomes, Margarida

2018-05-01

The aim of this work is to provide a better understanding of the interface between graphite and different molecular and ionic liquids. Experimental measurements of the liquid surface tension and of the graphite-liquid contact angle for sixteen ionic liquids and three molecular liquids are reported. These experimental values allowed the calculation of the solid/liquid interfacial energy that varies, for the ionic liquids studied, between 14.5 mN m-1 for 1-ethyl-3-methylimidazolium dicyanamide and 37.8 mN m-1 for 3-dodecyl-1-(naphthalen-1-yl)-1H-imidazol-3-ium tetrafluoroborate. Imidazolium-based ionic liquids with large alkyl side-chains or functionalized with benzyl groups seem to interact more favourably with freshly peeled graphite surfaces. Even if the interfacial energy seems a good descriptor to assess the affinity of a liquid for a carbon-based solid material, we conclude that both the surface tension of the liquid and the contact angle between the liquid and the solid can be significant. Molecular dynamics simulations were used to investigate the ordering of the ions near the graphite surface. We conclude that the presence of large alkyl side-chains in the cations increases the ordering of ions at the graphite surface. Benzyl functional groups in the cations lead to a large affinity towards the graphite surface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

McMurray, J. W.; Zhou, Y.; Luo, H. M.

We determined the equilibrium vapor pressures, p e, of the ionic liquid tetraoctylphosphonium bis(2-ethylhexyl)phosphate ([P 8888][DEHP]) over the temperature range 409–495 K using mass loss Knudsen effusion. The p e versus temperature relationship compares well to 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide ([C 8mim][NTf 2]) but is lower than that of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C 2mim][NTf 2]) when measured using the same technique. Here, we determined the discrepancies between the p e for [C 8mim][NTf 2] and [C 2mim][NTf 2] with previous studies is discussed. Finally, the enthalpy and entropy of vaporization for all three fluids are estimated from the Clasius-Clapeyron relation.

Direct electroplating of copper on tantalum from ionic liquids in high vacuum: origin of the tantalum oxide layer.

PubMed

Schaltin, Stijn; D'Urzo, Lucia; Zhao, Qiang; Vantomme, André; Plank, Harald; Kothleitner, Gerald; Gspan, Christian; Binnemans, Koen; Fransaer, Jan

2012-10-21

In this paper, it is shown that high vacuum conditions are not sufficient to completely remove water and oxygen from the ionic liquid 1-ethyl-3-methylimidazolium chloride. Complete removal of water demands heating above 150 °C under reduced pressure, as proven by Nuclear Reaction Analysis (NRA). Dissolved oxygen gas can only be removed by the use of an oxygen scavenger such as hydroquinone, despite the fact that calculations show that oxygen should be removed completely by the applied vacuum conditions. After applying a strict drying procedure and scavenging of molecular oxygen, it was possible to deposit copper directly on tantalum without the presence of an intervening oxide layer.

On the dielectric conductivity of molecular ionic liquids.

PubMed

Schröder, Christian; Steinhauser, Othmar

2009-09-21

The contribution of the conductivity to the spectrum of the generalized dielectric constant or susceptibility of molecular ionic liquids is analyzed, both in theoretical terms and computationally by means of molecular dynamics simulation of the concrete system 1-ethyl-3-methyl-imidazolium dicyanoamide at 300 K. As a central quantity the simulated current autocorrelation function is modeled by a carefully designed fit function. This not only gives a satisfactory numerical representation but yields the correct conductivity upon integration. In addition the fit function can be Fourier-Laplace transformed analytically. Both, the real and imaginary parts of the transform show expected behavior, in particular, the right limits for zero frequency. This altogether demonstrates that the components of the fit function are of physical relevance.

Addition of ammonia and/or oxygen to an ionic liquid for delignification of miscanthus.

PubMed

Rodríguez, Héctor; Padmanabhan, Sasisanker; Poon, Geoffrey; Prausnitz, John M

2011-09-01

Ammonia and/or oxygen were used to enhance the delignification of miscanthus dissolved in 1-ethyl-3-methylimidazolium acetate at 140°C. After dissolution of the gas at 9 bar, water was added as antisolvent to regenerate the dissolved biomass. In a next step, an acetone/water mixture was used to remove carbohydrate-free lignin from the regenerated biomass. The lignin content in the final product was around 10%, much lower than the ca. 23% lignin content of the raw dry miscanthus. This lignin reduction is achieved without diminution of cellulose or of total carbohydrates recovered, relative to the recovery achieved with the ionic liquid pretreatment in contact with air or nitrogen. Copyright © 2011 Elsevier Ltd. All rights reserved.

Effect of ionic liquid treatment on the ultrastructural and topochemical features of compression wood in Japanese cedar (Cryptomeria japonica).

PubMed

Kanbayashi, Toru; Miyafuji, Hisashi

2016-07-18

The morphological and topochemical changes in wood tissues in compression wood of Japanese cedar (Cryptomeria japonica) upon treated with two types of ionic liquids, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) and 1-ethylpyridinium bromide ([EtPy][Br]) were investigated. Compression wood tracheids were swollen by both ionic liquids but their swelling behaviors were different in the types of ionic liquids used. Under the polarized light, we confirmed that crystalline cellulose in compression wood is amorphized by [C2mim][Cl] treatment whereas it changes slightly by [EtPy][Br] treatment. Raman microscopic analyses revealed that [C2mim][Cl] can preferentially liquefy polysaccharides in compression wood whereas [EtPy][Br] liquefy lignin. In addition, the interaction of compression wood with ionic liquids is different for the morphological regions. These results will assist in the use of ionic liquid treatment of woody biomass to produce valuable chemicals, bio-fuels, bio-based composites and other products.

Effect of ionic liquid treatment on the ultrastructural and topochemical features of compression wood in Japanese cedar (Cryptomeria japonica)

PubMed Central

Kanbayashi, Toru; Miyafuji, Hisashi

2016-01-01

The morphological and topochemical changes in wood tissues in compression wood of Japanese cedar (Cryptomeria japonica) upon treated with two types of ionic liquids, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) and 1-ethylpyridinium bromide ([EtPy][Br]) were investigated. Compression wood tracheids were swollen by both ionic liquids but their swelling behaviors were different in the types of ionic liquids used. Under the polarized light, we confirmed that crystalline cellulose in compression wood is amorphized by [C2mim][Cl] treatment whereas it changes slightly by [EtPy][Br] treatment. Raman microscopic analyses revealed that [C2mim][Cl] can preferentially liquefy polysaccharides in compression wood whereas [EtPy][Br] liquefy lignin. In addition, the interaction of compression wood with ionic liquids is different for the morphological regions. These results will assist in the use of ionic liquid treatment of woody biomass to produce valuable chemicals, bio-fuels, bio-based composites and other products. PMID:27426470

Improved in situ saccharification of cellulose pretreated by dimethyl sulfoxide/ionic liquid using cellulase from a newly isolated Paenibacillus sp. LLZ1.

PubMed

Hu, Dongxue; Ju, Xin; Li, Liangzhi; Hu, Cuiying; Yan, Lishi; Wu, Tianyun; Fu, Jiaolong; Qin, Ming

2016-02-01

A cellulase producing strain was newly isolated from soil samples and identified as Paenibacillus sp. LLZ1. A novel aqueous-dimethyl sulfoxide (DMSO)/1-ethyl-3-methylimidazolium diethyl phosphate ([Emin]DEP)-cellulase system was designed and optimized. In the pretreatment, DMSO was found to be a low-cost substitute of up to 70% ionic liquid to enhance the cellulose dissolution. In the enzymatic saccharification, the optimum pH and temperature of the Paenibacillus sp. LLZ1 cellulase were identified as 6.0 and 40°C, respectively. Under the optimized reaction condition, the conversion of microcrystalline cellulose and bagasse cellulose increased by 39.3% and 37.6%, compared with unpretreated cellulose. Compared to current methods of saccharification, this new approach has several advantages including lower operating temperature, milder pH, and less usage of ionic liquid, indicating a marked progress in environmental friendly hydrolysis of biomass-based materials. Copyright © 2015 Elsevier Ltd. All rights reserved.

Cellulose Crystal Dissolution in Imidazolium-Based Ionic Liquids: A Theoretical Study.

PubMed

Uto, Takuya; Yamamoto, Kazuya; Kadokawa, Jun-Ichi

2018-01-11

The highly crystalline nature of cellulose results in poor processability and solubility, necessitating the search for solvents that can efficiently dissolve this material. Thus, ionic liquids (ILs) have recently been shown to be well suited for this purpose, although the corresponding dissolution mechanism has not been studied in detail. Herein, we adopt a molecular dynamics (MD) approach to study the dissolution of model cellulose crystal structures in imidazolium-based ILs and gain deep mechanistic insights, demonstrating that dissolution involves IL penetration-induced cleavage of hydrogen bonds between cellulose molecular chains. Moreover, we reveal that in ILs with high cellulose dissolving power (powerful solvents, such as 1-allyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium chloride), the above molecular chains are peeled from the crystal phase and subsequently dispersed in the solvent, whereas no significant structural changes are observed in poor-dissolving-power solvents. Finally, we utilize MD trajectory analysis to show that the solubility of microcrystalline cellulose is well correlated with the number of intermolecular hydrogen bonds in cellulose crystals. The obtained results allow us to conclude that both anions and cations of high-dissolving-power ILs contribute to the stepwise breakage of hydrogen bonds between cellulose chains, whereas this breakage does not occur to a sufficient extent in poorly solubilizing ILs.

Efficient biomass pretreatment using ionic liquids derived from lignin and hemicellulose

PubMed Central

Socha, Aaron M.; Parthasarathi, Ramakrishnan; Shi, Jian; Pattathil, Sivakumar; Whyte, Dorian; Bergeron, Maxime; George, Anthe; Tran, Kim; Stavila, Vitalie; Venkatachalam, Sivasankari; Hahn, Michael G.; Simmons, Blake A.; Singh, Seema

2014-01-01

Ionic liquids (ILs), solvents composed entirely of paired ions, have been used in a variety of process chemistry and renewable energy applications. Imidazolium-based ILs effectively dissolve biomass and represent a remarkable platform for biomass pretreatment. Although efficient, imidazolium cations are expensive and thus limited in their large-scale industrial deployment. To replace imidazolium-based ILs with those derived from renewable sources, we synthesized a series of tertiary amine-based ILs from aromatic aldehydes derived from lignin and hemicellulose, the major by-products of lignocellulosic biofuel production. Compositional analysis of switchgrass pretreated with ILs derived from vanillin, p-anisaldehyde, and furfural confirmed their efficacy. Enzymatic hydrolysis of pretreated switchgrass allowed for direct comparison of sugar yields and lignin removal between biomass-derived ILs and 1-ethyl-3-methylimidazolium acetate. Although the rate of cellulose hydrolysis for switchgrass pretreated with biomass-derived ILs was slightly slower than that of 1-ethyl-3-methylimidazolium acetate, 90–95% glucose and 70–75% xylose yields were obtained for these samples after 72-h incubation. Molecular modeling was used to compare IL solvent parameters with experimentally obtained compositional analysis data. Effective pretreatment of lignocellulose was further investigated by powder X-ray diffraction and glycome profiling of switchgrass cell walls. These studies showed different cellulose structural changes and differences in hemicellulose epitopes between switchgrass pretreatments with the aforementioned ILs. Our concept of deriving ILs from lignocellulosic biomass shows significant potential for the realization of a “closed-loop” process for future lignocellulosic biorefineries and has far-reaching economic impacts for other IL-based process technology currently using ILs synthesized from petroleum sources. PMID:25136131

Gaining insight in the behaviour of imidazolium-based ionic liquids as additives in reversed-phase liquid chromatography for the analysis of basic compounds.

PubMed

Ubeda-Torres, M T; Ortiz-Bolsico, C; García-Alvarez-Coque, M C; Ruiz-Angel, M J

2015-02-06

In reversed-phase liquid chromatography in the absence of additives, cationic basic compounds give rise to broad and asymmetrical peaks as a result of ionic interactions with residual free silanols on silica-based stationary phases. Ionic liquids (ILs), added to the mobile phase, have been suggested as alternatives to amines to block the activity of silanols. However, the dual character of ILs should be considered: both cation and anion may be adsorbed on the stationary phase, thereby creating a double asymmetrical layer positively or negatively charged, depending on the relative adsorption of both ions. In this work, a study of the performance of six imidazolium-based ILs (the chlorides and tetrafluoroborates of 1-ethyl-, 1-butyl- and 1-hexyl-3-methylimidazolium) as modifiers of the chromatographic behaviour of a group of 10 β-blockers is performed, and compared with triethylamine and dimethyloctylamine. In order to gain more insight in the behaviour of ILs in RPLC, the changes in the nature of the chromatographic system, at increasing concentration of the additives, were followed based on retention and peak shape modelling. The multiple interactions that amines and ILs experience inside the chromatographic system suggest that the suppressing potency should be measured based on the shape of chromatographic peaks and not on the changes in retention. The ILs 1-hexyl-3-methyl-imidazolium chloride and tetrafluoroborate offered the most interesting features for the separation of the basic drugs. Copyright © 2014 Elsevier B.V. All rights reserved.

Extraction and Chromatographic Determination of Shikimic Acid in Chinese Conifer Needles with 1-Benzyl-3-methylimidazolium Bromide Ionic Liquid Aqueous Solutions

PubMed Central

Chen, Fengli; Hou, Kexin; Li, Shuangyang; Zu, Yuangang; Yang, Lei

2014-01-01

An ionic liquids-based ultrasound-assisted extraction (ILUAE) method was successfully developed for extracting shikimic acid from conifer needles. Eleven 1-alkyl-3-methylimidazolium ionic liquids with different cations and anions were investigated and 1-benzyl-3-methylimidazolium bromide solution was selected as the solvent. The conditions for ILUAE, including the ionic liquid concentration, ultrasound power, ultrasound time, and liquid-solid ratio, were optimized. The proposed method had good recovery (99.37%–100.11%) and reproducibility (RSD, n = 6; 3.6%). ILUAE was an efficient, rapid, and simple sample preparation technique that showed high reproducibility. Based on the results, a number of plant species, namely, Picea koraiensis, Picea meyeri, Pinus elliottii, and Pinus banksiana, were identified as among the best resources of shikimic acid. PMID:24782942

Reactions of Starch in Ionic Liquids

USDA-ARS?s Scientific Manuscript database

We found that starches are found to be soluble at 80 ºC in ionic liquids such as 1-butyl-3-methylimidazolium chloride (BMIMCl) and 1-butyl-3-methylimidazolium dicyanamide (BMIMdca) in concentration up to 10% (w/w). Higher concentrations of biopolymers in these novel solvents resulted in solutions w...

Anisotropic thermal expansion in a metal-organic framework.

PubMed

Madsen, Solveig Røgild; Lock, Nina; Overgaard, Jacob; Iversen, Bo Brummerstedt

2014-06-01

Ionothermal reaction between Mn(II)(acetate)2·4H2O and 1,3,5-benzenetricarboxylic acid (H3BTC) in either of the two ionic liquids 1-ethyl-3-methylimidazolium bromide (EMIMBr) and 1-ethyl-3-methylimidazolium tosylate (EMIMOTs) resulted in the formation of the new metal-organic framework (MOF) EMIM[Mn(II)BTC] (BTC = 1,3,5-benzenetricarboxylate). The compound crystallizes in the orthorhombic space group Pbca with unit-cell parameters of a = 14.66658 (12), b = 12.39497 (9), c = 16.63509 (14) Å at 100 K. Multi-temperature single-crystal (15-340 K) and powder X-ray diffraction studies (100-400 K) reveal strongly anisotropic thermal expansion properties. The linear thermal expansion coefficients, αL(l), attain maximum values at 400 K along the a- and b-axis, with αL(a) = 115 × 10(-6) K(-1) and αL(b) = 75 × 10(-6) K(-1). At 400 K a negative thermal expansion coefficient of -40 × 10(-6) K(-1) is observed along the c-axis. The thermal expansion is coupled to a continuous deformation of the framework, which causes the structure to expand in two directions. Due to the rigidity of the linker, the expansion in the ab plane causes the network to contract along the c-axis. Hirshfeld surface analysis has been used to describe the interaction between the framework structure and the EMIM cation that resides within the channel. This reveals a number of rather weak interactions and one governing hydrogen-bonding interactions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pasaribu, Marvin H., E-mail: marvin-shady88@yahoo.com; Arcana, I Made, E-mail: arcana@chem.itb.ac.id; Wahyuningrum, Deana, E-mail: deana@chem.itb.ac.id

Lithium ion battery has been currently developed and produced because it has a longer life time, high energycapacity, and the efficient use of lithium ion battery that is suitable for storing electrical energy. However, this battery has some drawbacks such as use liquid electrolytes that are prone to leakage and flammability during the battery charging process in high temperature. In this study, an ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) containing Li{sup +} ions was synthesized and combined with chitosan polymer host as a polymer electrolyte membrane for lithium-ion batteries to solve this problems. This ionic liquid was obtained from the anionmore » metathesis reaction between EMImBr and LiBF4 salt, while EMImBr was synthesized from the reaction between 1-methylimidazole and ethyl bromide utilizing Microwave Assisted Organic Synthesis (MAOS) method. The ionic liquid obtained was characterized by microstructure analysis with using NMR and FTIR spectroscopy. The polymer electrolyte membrane was characterized by analysis functional groups (FTIR), ionic conductivity (EIS), and surface morphology (SEM). The analysis results of ion conductivity by the EIS method showed the increase the ionic conductivity value of membranes from 1.30 × 10{sup −2} S cm{sup −1} for chitosan to 1.30 × 10{sup −2} S cm{sup −1} for chitosan with EMImBF4/Li{sup +}, and this result was supported by analysis the surface morphology (SEM)« less

Investigation of Ternary Mixtures Containing 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)azanide, Ethylene Carbonate and Lithium Bis(trifluoromethanesulfonyl)azanide

PubMed Central

Hofmann, Andreas; Migeot, Matthias; Arens, Lukas; Hanemann, Thomas

2016-01-01

Temperature-dependent viscosity, conductivity and density data of ternary mixtures containing 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)azanide (EMIM-TFSA), ethylene carbonate (EC), and lithium bis(trifluoromethanesulfonyl)azanide (Li-TFSA) were determined at atmospheric pressure in the temperature range of 20 to 80 °C. Differential scanning calorimetry (DSC) measurements were performed to characterize phase conditions of the mixtures in a temperature range of −120 to +100 °C. The viscosity data were fitted according to the Vogel-Fulcher-Tammann-Hesse (VFTH) equation and analyzed with the help of the fractional Walden rule. In this study, fundamental physicochemical data about the mixtures are provided and discussed as a basis for structure-property relationship calculations and for potential use of those mixtures as electrolytes for various applications. PMID:27153066

Microscopic characterization of tension wood cell walls of Japanese beech (Fagus crenata) treated with ionic liquids.

PubMed

Kanbayashi, Toru; Miyafuji, Hisashi

2016-09-01

Tension wood that is an abnormal part formed in angiosperms has been barely used for wood industry. In this study, to utilize the tension wood effectively by means of liquefaction using ionic liquid, we performed morphological and topochemical determination of the changes in tension wood of Japanese beech (Fagus crenata) during ionic liquid treatment at the cellular level using light microscopy, scanning electron microscopy and confocal Raman microscopy. Ionic liquid treatment induced cell wall swelling in tension wood. Changes in the tissue morphology treated with ionic liquids were different between normal wood and tension wood, moreover the types of ionic liquids. The ionic liquid 1-ethyl-3-methylimidazolium chloride liquefied gelatinous layers rapidly, whereas 1-ethylpyridinium bromide liquefied slowly but delignified selectively. These novel insights into the deconstruction behavior of tension wood cell walls during ionic liquid treatment provide better understanding of the liquefaction mechanism. The obtained knowledge will contribute to development of an effective chemical processing of tension wood using ionic liquids and lead to efficient use of wood resources. Copyright © 2016 Elsevier Ltd. All rights reserved.

Promoting Effect of Layered Titanium Phosphate on the Electrochemical and Photovoltaic Performance of Dye-Sensitized Solar Cells

PubMed Central

2010-01-01

We reported a composite electrolyte prepared by incorporating layered α-titanium phosphate (α-TiP) into an iodide-based electrolyte using 1-ethyl-3-methylimidazolium tetrafluoroborate(EmimBF4) ionic liquid as solvent. The obtained composite electrolyte exhibited excellent electrochemical and photovoltaic properties compared to pure ionic liquid electrolyte. Both the diffusion coefficient of triiodide (I3−) in the electrolyte and the charge-transfer reaction at the electrode/electrolyte interface were improved markedly. The mechanism for the enhanced electrochemical properties of the composite electrolyte was discussed. The highest conversion efficiency of dye-sensitized solar cell (DSSC) was obtained for the composite electrolyte containing 1wt% α-TiP, with an improvement of 58% in the conversion efficiency than the blank one, which offered a broad prospect for the fabrication of stable DSSCs with a high conversion efficiency. PMID:20676195

Evaporation Study of an Ionic Liquid with a Double-Charged Cation.

PubMed

Chilingarov, Norbert S; Zhirov, Maksim S; Shmykova, Anna M; Martynova, Ekaterina A; Glukhov, Lev M; Chernikova, Elena A; Kustov, Leonid M; Markov, Vitaliy Yu; Ioutsi, Vitaliy A; Sidorov, Lev N

2018-05-07

The evaporation of a dicationic ionic liquid, 1,3-bis(3-methylimidazolium-1-yl)propane bis(trifluoromethanesulfonyl)amide ([C 3 (MIm) 2 2+ ][Tf 2 N - ] 2 ), was studied by Knudsen effusion mass spectrometry. Its evaporation is accompanied by a partial thermal decomposition producing monocationic ionic liquids, 1,3-dimethylimidazolium and 1-(2-propenyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)amides, as volatile products. This decomposition does not affect the vaporization characteristics of [C 3 (MIm) 2 2+ ][Tf 2 N - ] 2 , which were established to be as follows. The vaporization enthalpy (550 K) is equal to (155.5 ± 3.2) kJ·mol -1 ; the saturated vapor pressure is described by the equation ln( p/Pa) = -(18699 ± 381)/( T/K) + (30.21 ± 0.82) in the range of 508-583 K. 1,3-Bis(3-methylimidazolium-1-yl)propane bis(trifluoromethanesulfonyl)amide is the first dicationic ionic liquid, the vaporization characteristics of which were determined with an acceptable accuracy.

Microwave-assisted synthesis of gold, silver, platinum and palladium nanostructures and their use in electrocatalytic applications.

PubMed

Safavi, Afsaneh; Tohidi, Maryam

2014-09-01

Microwave-assisted ionic liquid method was used for synthesis of various noble metals, such as gold, silver, platinum and palladium nanomaterials. This route does not employ any template agent, surface capping agents or reducing agents. The process is fast, simple and of high yield. Different metal precursors in various ionic liquids media (1-butyl-3-methylimidazolium tetrafluoroborate, octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate) were applied to produce metal nanomaterials. Silver, platinium and palladium nanoparticles exhibit spherical morphology while nanosheets with high aspect ratio were obtained for gold. These metal nanostructures were incorporated into a carbon ionic liquid electrode to investigate their electrocatalytic properties. It was found that synthesis in different ionic liquids result in different activity. Excellent electrocatalytic effects toward adenine, hydrazine, formaldehyde and ethanol were observed for the modified electrodes with different nanoparticles synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate. The high conductivity, large surface-to-volume ratio and active sites of nanosized metal particles are responsible for their electrocatalytic activity. In contrast, the carbon ionic liquid electrode modified with synthesized metal nanoparticles in octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate showed negligible activity for detection of these probes.

Effect of degree of crosslinking and polymerization of 3D printable polymer/ionic liquid composites on performance of stretchable piezoresistive sensors

NASA Astrophysics Data System (ADS)

Lee, Jeongwoo; Faruk Emon, Md Omar; Vatani, Morteza; Choi, Jae-Won

2017-03-01

Ionic liquid (IL)/polymer composites (1-ethyl-3-methyl-imidazolium tetrafluoroborate (EMIMBF4)/2-[[(butylamino)carbonyl]oxy]ethyl acrylate (BACOEA)) were fabricated to use as sensing materials for stretchable piezoresistive tactile sensors. The detectability of the IL/polymer composites was enhanced because the ionic transport properties of EMIMBF4 in the composites were improved by the synergic actions between the coordinate sites generated by the local motion of BACOEA chain segments under enough activation energy. The performance of the piezoresistive sensors was investigated with the degree of crosslinking and polymerization of the IL/polymer composites. As the compressive strain was increased, the distance between two electrodes decreased, and the motion of polymer chains and IL occurred, resulting in a decrease in the electrical resistance of the sensors. We have confirmed that the sensitivity of the sensors are affected by the degree of crosslink and polymerization of the IL/polymer composites. In addition, all of the materials (skins, sensing material, and electrode) used in this study are photo-curable, and thus the stretchable piezoresistive tactile sensors can be successfully fabricated by 3D printing.

Impact of Mixed Feedstocks and Feedstock Densification on Ionic Liquid Pretreatment Efficiency

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jian Shi; Vicki S. Thompson; Neal A. Yancey

2013-01-01

Background: Lignocellulosic biorefineries must be able to efficiently process the regional feedstocks that are available at cost-competitive prices year round. These feedstocks typically have low energy densities and vary significantly in composition. One potential solution to these issues is blending and/or densifying the feedstocks in order to create a uniform feedstock. Results/discussion: We have mixed four feedstocks - switchgrass, lodgepole pine, corn stover, and eucalyptus - in flour and pellet form and processed them using the ionic liquid 1-ethyl-3-methylimidazolium acetate. Sugar yields from both the mixed flour and pelletized feedstocks reach 90% within 24 hours of saccharification. Conclusions: Mixed feedstocks,more » in either flour or pellet form, are efficiently processed using this pretreatment process, and demonstrate that this approach has significant potential.« less

Development of regenerated cellulose/halloysites nanocomposites via ionic liquids.

PubMed

Hanid, Nurbaiti Abdul; Wahit, Mat Uzir; Guo, Qipeng; Mahmoodian, Shaya; Soheilmoghaddam, Mohammad

2014-01-01

In this study, regenerated cellulose/halloysites (RC/HNT) nanocomposites with different nanofillers loading were fabricated by dissolving the cellulose in 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic liquid. The films were prepared via solution casting method and were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The mechanical properties were investigated by tensile testing. It clearly displayed a good enhancement of both tensile strength and Young's modulus with HNT loading up to 5 wt%. As the HNT loadings increased to 5 wt%, the thermal behaviour and water resistance rate was also increased. The TEM and SEM images also depicted even dispersion of the HNT and a good intertubular interaction between the HNT and the cellulose matrix. Copyright © 2013 Elsevier Ltd. All rights reserved.

Structure of cyano-anion ionic liquids: X-ray scattering and simulations.

PubMed

Dhungana, Kamal B; Faria, Luiz F O; Wu, Boning; Liang, Min; Ribeiro, Mauro C C; Margulis, Claudio J; Castner, Edward W

2016-07-14

Ionic liquids with cyano anions have long been used because of their unique combination of low-melting temperatures, reduced viscosities, and increased conductivities. Recently we have shown that cyano anions in ionic liquids are particularly interesting for their potential use as electron donors to excited state photo-acceptors [B. Wu et al., J. Phys. Chem. B 119, 14790-14799 (2015)]. Here we report on bulk structural and quantum mechanical results for a series of ionic liquids based on the 1-ethyl-3-methylimidazolium cation, paired with the following five cyano anions: SeCN(-), SCN(-), N(CN)2 (-), C(CN)3 (-), and B(CN)4 (-). By combining molecular dynamics simulations, high-energy X-ray scattering measurements, and periodic boundary condition DFT calculations, we are able to obtain a comprehensive description of the liquid landscape as well as the nature of the HOMO-LUMO states for these ionic liquids in the condensed phase. Features in the structure functions for these ionic liquids are somewhat different than the commonly observed adjacency, charge-charge, and polarity peaks, especially for the bulkiest B(CN)4 (-) anion. While the other four cyano-anion ionic liquids present an anionic HOMO, the one for Im2,1 (+)/B(CN)4 (-) is cationic.

Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Boning; Liang, Min; Zmich, Nicole

Recently, we have reported a systematic study of photoinduced electron-transfer reactions in ionic liquid solvents using neutral and anionic electron donors and a series of cyano-substituted anthracene acceptors [Wu, B.; Maroncelli, M.; Castner, E. W., Jr.Photoinduced Bimolecular Electron Transfer in Ionic Liquids. J. Am. Chem. Soc.139, 2017, 14568]. In this paper, we report complementary results for a cationic class of 1-alkyl-4-dimethylaminopyridinium electron donors. Reductive quenching of cyano-substituted anthracene fluorophores by these cationic quenchers is studied in solutions of acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Varying the length of the alkyl chain permits tuning of the quencher diffusivities in solution.more » The observed quenching kinetics are interpreted using a diffusion-reaction analysis. Finally, together with results from the prior study, these results show that the intrinsic electron-transfer rate constant does not depend on the quencher charge in this family of reactions.« less

Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

DOE PAGES

Wu, Boning; Liang, Min; Zmich, Nicole; ...

2018-01-29

Recently, we have reported a systematic study of photoinduced electron-transfer reactions in ionic liquid solvents using neutral and anionic electron donors and a series of cyano-substituted anthracene acceptors [Wu, B.; Maroncelli, M.; Castner, E. W., Jr.Photoinduced Bimolecular Electron Transfer in Ionic Liquids. J. Am. Chem. Soc.139, 2017, 14568]. In this paper, we report complementary results for a cationic class of 1-alkyl-4-dimethylaminopyridinium electron donors. Reductive quenching of cyano-substituted anthracene fluorophores by these cationic quenchers is studied in solutions of acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Varying the length of the alkyl chain permits tuning of the quencher diffusivities in solution.more » The observed quenching kinetics are interpreted using a diffusion-reaction analysis. Finally, together with results from the prior study, these results show that the intrinsic electron-transfer rate constant does not depend on the quencher charge in this family of reactions.« less

Development and Characterization of Poly(1-vinylpyrrolidone-co-vinyl acetate) Copolymer Based Polymer Electrolytes

PubMed Central

Sa'adun, Nurul Nadiah; Subramaniam, Ramesh; Kasi, Ramesh

2014-01-01

Gel polymer electrolytes (GPEs) are developed using poly(1-vinylpyrrolidone-co-vinyl acetate) [P(VP-co-VAc)] as the host polymer, lithium bis(trifluoromethane) sulfonimide [LiTFSI] as the lithium salt and ionic liquid, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [EMImTFSI] by using solution casting technique. The effect of ionic liquid on ionic conductivity is studied and the optimum ionic conductivity at room temperature is found to be 2.14 × 10−6 S cm−1 for sample containing 25 wt% of EMImTFSI. The temperature dependence of ionic conductivity from 303 K to 353 K exhibits Arrhenius plot behaviour. The thermal stability of the polymer electrolyte system is studied by using thermogravimetric analysis (TGA) while the structural and morphological properties of the polymer electrolyte is studied by using Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction analysis (XRD), respectively. PMID:25431781

Insights on the solubility of CO2 in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide from the microscopic point of view.

PubMed

Lourenço, Tuanan C; Coelho, Mariny F C; Ramalho, Teodorico C; van der Spoel, David; Costa, Luciano T

2013-07-02

Emissions of greenhouse gases due to human activities have been well documented as well as the effects on global warming resulting from it. Efforts to reduce greenhouse gases at the source are crucial to curb climate change, but due to insignificant economic incentives to reduce usage of fossil fuels, not a lot of progress has been made by this route. This necessitates additional measures to reduce the occurrence of greenhouse gases in the atmosphere. Here we used theoretical methods to study the solubility of carbon dioxide in ionic liquids (ILs) since sequestration of CO2 in ILs has been proposed as a possible technology for reducing the emissions of CO2 to the atmosphere. Ionic liquids form a class of solvents with melting temperatures below 100 °C and, due to very low vapor pressures, which are not volatile. We have performed molecular dynamics (MD) simulations of 1-ethyl-3-methylimidazolium (C2mim) bis(trifluoromethylsulfonyl)imide (Tf2N) and its mixtures with carbon dioxide in order to investigate the CO2 concentration effect on the CO2-cation and CO2-anion interactions. A systematic investigation of CO2 concentration effects on resulting equilibrium liquid structure, and the local environment of the ions is provided. The Quantum Theory of Atoms in Molecules (QTAIM) was used to determine the interaction energy for CO2-cation and CO2-anion complexes from uncorrelated structures derived from MD simulations. A spatial distribution function analysis demonstrates the specific interactions between CO2 and the ionic liquid. Our findings indicate that the total volume of the system increases with the CO2 concentration, with a molar volume of CO2 of about 0.038 L/mol, corresponding to liquid CO2 under a pressure of 100 bar. In other words, the IL effectively pressurizes the CO2 inside its matrix. The thermodynamics of CO2 solvation in C2 min-Tf2N were computed using free energy techniques, and the solubility of CO2 is found to be higher in this IL (-3.7 ± 1 kcal/mol) than in water (+0.2 kJ/mol), predominantly due to anion-CO2 interactions.

Determination of triazine herbicides in juice samples by microwave-assisted ionic liquid/ionic liquid dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography.

PubMed

Su, Rui; Li, Dan; Wu, Lijie; Han, Jing; Lian, Wenhui; Wang, Keren; Yang, Hongmei

2017-07-01

A novel microextraction method, termed microwave-assisted ionic liquid/ionic liquid dispersive liquid-liquid microextraction, has been developed for the rapid enrichment and analysis of triazine herbicides in fruit juice samples by high-performance liquid chromatography. Instead of using hazardous organic solvents, two kinds of ionic liquids, a hydrophobic ionic liquid (1-hexyl-3-methylimidazolium hexafluorophosphate) and a hydrophilic ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate), were used as the extraction solvent and dispersion agent, respectively, in this method. The extraction procedure was induced by the formation of cloudy solution, which was composed of fine drops of 1-hexyl-3-methylimidazolium hexafluorophosphate dispersed entirely into sample solution with the help of 1-butyl-3-methylimidazolium tetrafluoroborate. In addition, an ion-pairing agent (NH 4 PF 6 ) was introduced to improve recoveries of the ionic liquid phase. Several experimental parameters that might affect the extraction efficiency were investigated. Under the optimum experimental conditions, the linearity for determining the analytes was in the range of 5.00-250.00 μg/L, with the correlation coefficients of 0.9982-0.9997. The practical application of this effective and green method is demonstrated by the successful analysis of triazine herbicides in four juice samples, with satisfactory recoveries (76.7-105.7%) and relative standard deviations (lower than 6.6%). In general, this method is fast, effective, and robust to determine triazine herbicides in juice samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application and recovery of ionic liquids in the preparative separation of four flavonoids from Rhodiola rosea by on-line three-dimensional liquid chromatography.

PubMed

Ma, Shufeng; Hu, Liming; Ma, Chaoyang; Lv, Wenping; Wang, Hongxin

2014-09-01

A novel on-line three-dimensional liquid chromatography method was developed to separate four main flavonoids from Rhodiola rosea. Ethyl acetate/0.5 mol/L ionic liquid 1-butyl-3-methylimidazolium chloride aqueous solution was selected as the solvent system. In the first-dimension separation, the target flavonoids were entrapped and subsequently desorbed into the second-dimension high-speed countercurrent chromatographic column for separation. In the third-dimension chromatography, the residual ionic liquid in the four separated flavonoids was removed and the used ionic liquid was recovered. As a result, 35.1 mg of compound 1, 20.4 mg of compound 2, 8.5 mg of compound 3, and 10.6 mg of compound 4 were obtained from 1.53 g R. rosea extract. They were identified as rhodiosin, rhodionin, herbacetin, and kaempferol, respectively. The recovery of ionic liquid reached 99.1% of the initial amount. The results showed that this method is a powerful technology for the separation of R. rosea flavonoids and that the ionic-liquid-based solvent system has advantages over traditional solvent systems in renewable and environmentally friendly properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crosslinking of polysaccharides in room temperature ionic liquids by ionizing radiation

NASA Astrophysics Data System (ADS)

Kimura, Atsushi; Nagasawa, Naotsugu; Shimada, Akihiko; Taguchi, Mitsumasa

2016-07-01

Crosslinking of polysaccharides in room temperature ionic liquids (RTILs) by ionizing radiation were investigated by the scavenging method, fluorescent and X-ray photoelectron spectroscopy (XPS) analysis. Radiation chemical yields of hydroxyl radicals inducing the crosslinking of cellulose were estimated with phenol as a scavenger, and increased with water content in 1-ethyl-3-methylimidazolium acetate (EMI-acetate). Cellulose gel was also produced in fluorescent carboxylate-based RTILs, 1,3-dibutylimidazolium acetate (DBI-acetate). Light emission from DBI-acetate in cellulose gel was observed and 20-nm red shifted at a maximum wavelength of 415 nm when excited at 323 nm. Expected elements of carbon and oxygen were detected in neat cellulose by XPS, while additional nitrogen was detected in radiation-crosslinked cellulose gel produced in EMI-acetate. These results indicate that RTILs is incorporated in the cellulose gel. Chitin gel was first obtained in 1-butyl-3-methyimidazolium chloride by γ-ray irradiations, and its gel fraction increased with the dose and reached 86% at 60 kGy.

The vapour of imidazolium-based ionic liquids: a mass spectrometry study.

PubMed

Deyko, A; Lovelock, K R J; Licence, P; Jones, R G

2011-10-06

Eight common dialkylimidazolium-based ionic liquids have been successfully evaporated in ultra-high vacuum and their vapours analysed by line of sight mass spectrometry using electron ionisation. The ionic liquids investigated were 1-alkyl-3-methylimidazolium bis[(trifluoromethane)sulfonyl]imide, [C(n)C(1)Im][Tf(2)N] (where n = 2, 4, 6, 8), 1-alkyl-3-methylimidazolium tetrafluoroborate, [C(n)C(1)Im][BF(4)] (where n = 4, 8), 1-butyl-3-methylimidazolium octylsulfate, [C(4)C(1)Im][C(8)OSO(3)] and 1-butyl-3-methylimidazolium tetrachloroferrate, [C(4)C(1)Im][FeCl(4)]. All ionic liquids studied here evaporated as neutral ion pairs; no evidence of decomposition products in the vapour phase were observed. Key fragment cations of the ionised vapour of the ionic liquids are identified. The appearance energies, E(app), of the parent cation were measured and used to estimate the ionisation energies, E(i), for the vapour phase neutral ion pairs. Measured ionisation energies ranged from 10.5 eV to 13.0 eV. Using both the identity and E(app) values, the fragmentation pathways for a number of fragment cations are postulated. It will be shown that the enthalpy of vaporisation, Δ(vap)H, can successfully be measured using more than one fragment cation, although caution is required as many fragment cations can also be formed by ionisation of decomposition products.

Study of fluorescence resonance energy transfer in zwitterionic micelle: ionic-liquid-induced changes in FRET parameters.

PubMed

Rao, Vishal Govind; Mandal, Sarthak; Ghosh, Surajit; Banerjee, Chiranjib; Sarkar, Nilmoni

2012-10-04

The fluorescence resonance energy transfer (FRET) using Coumarin-153 (C-153) as the donor and Rhodamine 6G (R6G) as the acceptor is studied in an aqueous solution of N-hexadecyl-N,N-dimethylammonio-1-propanesulfonate (SB-16) micelles by steady-state and picosecond time-resolved fluorescence spectroscopy. We have determined the rate of FRET (k(FRET)) from the rise of the acceptor (R6G) emission. In the absence of donor (C-153), the acceptor (R6G) displays a single-exponential decay with average lifetime of 4.77 ns, whereas in presence of donor (C-153), the acceptor (R6G) exhibits a biexponential fluorescence transient having a distinct rise component of 0.94 ns and decay component of 5.16 ns. We have carried out a comparative study of changes in FRET parameters upon addition of three different ionic liquids (ILs), 1-ethyl-3-methylimidazolium ethylsulfate [C(2)mim][C(2)SO(4)], 1-ethyl-3-methylimidazolium n-butylsulfate [C(2)mim][C(4)SO(4)], and 1-ethyl-3-methylimidazolium n-hexylsulfate [C(2)mim][C(6)SO(4)], where each ionic liquid bears the same cationic part and the anionic parts differ in the alkyl chain length only. It has been observed that with gradual addition of the ILs [C(2)mim][C(2)SO(4)], [C(2)mim][C(4)SO(4)], and [C(2)mim][C(6)SO(4)], the rise component gradually decreases and the rate of FRET (k(FRET)) gradually increases. The k(FRET) was found to be 1.06 × 10(9) s(-1) in 28 mM aqueous SB-16 micelles. With the addition of 100 mM [C(2)mim][C(2)SO(4)], the k(FRET) increases by a factor of 1.33 (1.41 × 10(9) s(-1)), whereas with the addition of 100 mM [C(2)mim][C(6)SO(4)] it increases by a factor of 3.25 (3.45 × 10(9) s(-1)). This rapid increase in k(FRET) in the case of [C(2)mim][C(6)SO(4)] can be explained by our earlier observation ( Rao, V. G.; Ghatak, C.; Ghosh, S.; Mandal, S.; Sarkar, N. J. Phys. Chem. B2012, 116, 3690-3698 ), where we have shown that with the addition of [C(2)mim][C(6)SO(4)], C-153 moves toward the outer surface of the micelle. This movement of C-153 causes reduction in donor-acceptor distance and enhancement in FRET rate (k(FRET)). This is well-supported by the reduced donor-acceptor distance (R(DA)) observed with the addition of [C(2)mim][C(6)SO(4)]. The R(DA) was found to be 29.1 Å in 28 mM aqueous SB-16 micelles. With the addition of 100 mM [C(2)mim][C(6)SO(4)], the R(DA) decreases to 24.8 Å. With further increase in the concentration of [C(2)mim][C(6)SO(4)], the R(DA) decreases, but the time constant for the rise of acceptor emission decreases to such an extent that we are unable to observe it by our instrumental setup.

All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes.

PubMed

Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

2012-02-17

All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf(2)]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g(-1) at a current density of 2 A g(-1), when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg(-1) and 41 Wh kg(-1), respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes

NASA Astrophysics Data System (ADS)

Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

2012-02-01

All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf2]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g-1 at a current density of 2 A g-1, when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg-1 and 41 Wh kg-1, respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

Developing Ionic Liquid Know-How for the Design of Modular Functionality, Versatile Platforms, and New Synthetic Methodologies for Energetic Materials

DTIC Science & Technology

2013-12-05

Protocol for the Synthesis of Alkylated Imidazolium Salt Derivatives 1,3-Dimethylimidazolium chloride (1,3-diMe-IM][Cl]) (19c) and 1,2,3...C5’). A8. Hypergolic Ionic Liquids to Mill, Suspend, and Ignite Boron Nanoparticles Synthesis of 1-Butyl-3-methylimidazolium chloride ([1-Bu...3-methylimidazolium chloride , 5[Cl] D5. Zinc-assisted synthesis of imidazolium-tetrazolate bi-heterocyclic zwitterions with variable alkyl

Capacitance of Ti 3C 2T x MXene in Ionic Liquid Electrolyte

DOE PAGES

Lin, Zifeng; Barbara, Daffos; Taberna, Pierre-Louis; ...

2016-04-14

Ti 3C 2T x MXene, a two-dimensional (2D) early transition metal carbide, has shown an extremely high volumetric capacitance in aqueous electrolytes, but in a narrow voltage window (less than 1.23 V). The utilization of MXene materials in ionic liquid electrolytes with a large voltage window has never been addressed. Here, we report the preparation of the Ti 3C 2T x MXene ionogel film by vacuum filtration for use as supercapacitor electrodes operating in 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI) neat ionic liquid electrolyte. Due to the disordered structure of the Ti 3C 2T x hydrogel film and a stable spacing after vacuummore » drying, achieved through ionic liquid electrolyte immersion of the Ti 3C 2T x hydrogel film, the Ti 3C 2T x surface became accessible to EMI + and TFSI - ions. A capacitance of 70 F g -1 together with a large voltage window of 3 V was obtained at a scan rate of 20 mV s -1 in neat EMI-TFSI electrolyte. The electrochemical signature indicates a capacitive behavior even at a high scan rate (500 mV s -1) and a high power performance. This work opens up the possibilities of using MXene materials with various ionic liquid electrolytes.« less

Effect of alkyl chain length on the rotational diffusion of nonpolar and ionic solutes in 1-alkyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imides.

PubMed

Gangamallaiah, V; Dutt, G B

2013-10-10

Rotational diffusion of a nonpolar solute 9-phenylanthracene (9-PA) and a cationic solute rhodamine 110 (R110) has been examined in a series of 1-alkyl-3-methylimidazolium (alkyl = octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl) bis(trifluoromethylsulfonyl)imides to understand the influence of alkyl chain length on solute rotation. In this study, reorientation times (τr) have been measured as a function of viscosity (η) by varying the temperature (T) of the solvents. These results have been analyzed using the Stokes-Einstein-Debye (SED) hydrodynamic theory along with the ones obtained for the same solutes in 1-alkyl-3-methylimidazolium (alkyl = methyl, ethyl, propyl, butyl, and hexyl) bis(trifluoromethylsulfonyl)imides (Gangamallaiah and Dutt, J. Phys. Chem. B 2012, 116, 12819-12825). It has been noticed that the data for 9-PA and R110 follows the relation τr = A(η/T)(n) with A being the ratio of hydrodynamic volume of the solute to the Boltzmann constant and n = 1 as envisaged by the SED theory. However, upon increasing the alkyl chain length from methyl to octadecyl significant deviations from the SED theory have been observed especially from the octyl derivative onward. From methyl to octadecyl derivatives, the value of A decreases by a factor of 3 for both the solutes and n by a factor of 1.4 and 1.6 for 9-PA and R110, respectively. These observations have been rationalized by taking into consideration the organized structure of the ionic liquids, whose influence appears to be pronounced when the number of carbon atoms in the alkyl chain attached to the imidazolium cation exceeds eight.

Parametric study for the optimization of ionic liquid pretreatment of corn stover

DOE Office of Scientific and Technical Information (OSTI.GOV)

Papa, Gabriella; Feldman, Taya; Sale, Kenneth L.

A parametric study of the efficacy of the ionic liquid (IL) pretreatment (PT) of corn stover (CS) using 1-ethyl-3-methylimidazolium acetate ([C 2C 1Im][OAc] ) and cholinium lysinate ([Ch][Lys] ) was conducted. The impact of 50% and 15% biomass loading for milled and non-milled CS on IL-PT was evaluated, as well the impact of 20 and 5 mg enzyme/g glucan on saccharification efficiency. The glucose and xylose released were generated from 32 conditions – 2 ionic liquids (ILs), 2 temperatures, 2 particle sizes (S), 2 solid loadings, and 2 enzyme loadings. Statistical analysis indicates that sugar yields were correlated with lignin andmore » xylan removal and depends on the factors, where S did not explain variation in sugar yields. Both ILs were effective in pretreating large particle sized CS, without compromising sugar yields. The knowledge from material and energy balances is an essential step in directing optimization of sugar recovery at desirable process conditions.« less

Computational analysis of the solvation of coffee ingredients in aqueous ionic liquid mixtures.

PubMed

Zeindlhofer, Veronika; Khlan, Diana; Bica, Katharina; Schröder, Christian

2017-01-13

In this paper, we investigate the solvation of coffee ingredients including caffeine, gallic acid as representative for phenolic compounds and quercetin as representative for flavonoids in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate [C 2 mim][OAc] at various concentrations. Due to the anisotropy of the solutes we show that classical Kirkwood-Buff theory is not appropriate to study solvation effects with increasing ionic liquid content. However, excess coordination numbers as well as the mean residence time of solvent molecules at the surface of the solutes can be determined by Voronoi tessellation. Since the volume of the hydration shells is also available by this method, solvation free energies will be discussed as a function of the ionic liquid concentration to yield a physical meaningful picture of solvation for the anisotropic solutes. Hydrogen bonding capabilities of the solutes and their relevance for experimental extraction yields from spent coffee grounds are also discussed.

Interactions in the ionic liquid [EMIM][FAP]: a coupled experimental and computational analysis.

PubMed

Voroshylova, Iuliia V; Teixeira, Filipe; Costa, Renata; Pereira, Carlos M; Cordeiro, M Natália D S

2016-01-28

Gas-phase electronic and structural properties of the room temperature ionic liquid 1-ethyl-3-methylimidazolium tris(perfluoroethyl)trifluorophosphate ([EMIM][FAP]) were studied using density functional theory, and confirmed with results from infrared spectroscopy. A conformational analysis allowed the identification of several plausible conformers of the ion pairs. For the detected conformers, the infrared spectra were predicted and their thermodynamic properties were evaluated. The topology of the electronic density of the most stable conformers of [EMIM][FAP] ion pairs were characterised using the quantum theory of atoms in molecules. A number of possible hydrogen bonds between the cations and anions of the ionic liquid were identified. Excellent correspondence was found between the predicted spectra of gas-phase [EMIM][FAP] conformers and the experimental infrared spectrum, which in turn allowed a clear attribution of the vibration modes of [EMIM][FAP]. Finally, the contribution of the various conformers of both isomers of the [FAP](-) anion to the ionic liquid macro-properties is shown.

Why are ionic liquid ions mainly associated in water? A Car-Parrinello study of 1-ethyl-3-methyl-imidazolium chloride water mixture

NASA Astrophysics Data System (ADS)

Spickermann, C.; Thar, J.; Lehmann, S. B. C.; Zahn, S.; Hunger, J.; Buchner, R.; Hunt, P. A.; Welton, T.; Kirchner, B.

2008-09-01

In this study we present the results of a first principles molecular dynamics simulation of a single 1-ethyl-3-methyl-imidazolium chloride [C2C1im][Cl] ion pair dissolved in 60 water molecules. We observe a preference of the in plane chloride coordination with respect to the cation ring plane as compared to the energetic slightly more demanding on top coordination. Evaluation of the different radial distribution functions demonstrates that the structure of the hydration shell around the ion pair differs significantly from bulk water and that no true ion pair dissociation in terms of completely autonomous solvation shells takes place on the timescale of the simulation. In addition, dipole moment distributions of the solvent in distinct solvation shells around different functional parts of the [C2C1im][Cl] ion pair are calculated from maximally localized Wannier functions. The analysis of these distributions gives evidence for a depolarization of water molecules close to the hydrophobic parts of the cation as well as close to the anion. Examination of the angular distribution of different OH(H2O )-X angles in turn shows a linear coordination of chloride accompanied by a tangential orientation of water molecules around the hydrophobic groups, being a typical feature of hydrophobic hydration. Based on these orientational aspects, a structural model for the obvious preference of ion pair association is developed, which justifies the associating behavior of solvated [C2C1im][Cl] ions in terms of an energetically favorable interface between the solvation shells of the anion and the hydrophobic parts of the cation.

Why are ionic liquid ions mainly associated in water? A Car-Parrinello study of 1-ethyl-3-methyl-imidazolium chloride water mixture.

PubMed

Spickermann, C; Thar, J; Lehmann, S B C; Zahn, S; Hunger, J; Buchner, R; Hunt, P A; Welton, T; Kirchner, B

2008-09-14

In this study we present the results of a first principles molecular dynamics simulation of a single 1-ethyl-3-methyl-imidazolium chloride [C(2)C(1)im][Cl] ion pair dissolved in 60 water molecules. We observe a preference of the in plane chloride coordination with respect to the cation ring plane as compared to the energetic slightly more demanding on top coordination. Evaluation of the different radial distribution functions demonstrates that the structure of the hydration shell around the ion pair differs significantly from bulk water and that no true ion pair dissociation in terms of completely autonomous solvation shells takes place on the timescale of the simulation. In addition, dipole moment distributions of the solvent in distinct solvation shells around different functional parts of the [C(2)C(1)im][Cl] ion pair are calculated from maximally localized Wannier functions. The analysis of these distributions gives evidence for a depolarization of water molecules close to the hydrophobic parts of the cation as well as close to the anion. Examination of the angular distribution of different OH(H(2)O)-X angles in turn shows a linear coordination of chloride accompanied by a tangential orientation of water molecules around the hydrophobic groups, being a typical feature of hydrophobic hydration. Based on these orientational aspects, a structural model for the obvious preference of ion pair association is developed, which justifies the associating behavior of solvated [C(2)C(1)im][Cl] ions in terms of an energetically favorable interface between the solvation shells of the anion and the hydrophobic parts of the cation.

Effect of the structure of imidazolium cations in [BF4](-)-type ionic liquids on direct electrochemistry and electrocatalysis of horseradish peroxidase in Nafion films.

PubMed

Lu, Lu; Huang, Xirong; Qu, Yinbo

2011-10-01

The direct electrochemistry and bioelectrocatalysis of horseradish peroxidase (HRP) in Nafion films at glassy carbon electrode (GCE) was investigated in three [BF(4)](-)-type room-temperature ionic liquids (ILs) to understand the structural effect of imidazolium cations. The three ILs are 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim][BF(4)]), 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]) and 1-hexyl-3-methylimidazolium tetrafluoroborate ([Hmim][BF(4)]). A small amount of water in the three ILs is indispensable for maintaining the electrochemical activity of HRP in Nafion films, and the optimum water contents decrease with the increase of alkyl chain length on imidazole ring. Analysis shows that the optimum water contents are primarily determined by the hydrophilicity of ILs used. In contrast to aqueous medium, ILs media facilitate the direct electron transfer of HRP, and the electrochemical parameters obtained in different ILs are obviously related to the nature of ILs. The direct electron transfer between HRP and GCE is a surface-confined quasi-reversible single electron transfer process. The apparent heterogeneous electron transfer rate constant decreases gradually with the increase of alkyl chain length on imidazole ring, but the changing extent is relatively small. The electrocatalytic reduction current of H(2)O(2) at the present electrode decreases obviously with the increase of alkyl chain length, and the mass transfer of H(2)O(2) via diffusion in ILs should be responsible for the change. In addition, the modified electrode has good stability and reproducibility; the ability to tolerate high levels of F(-) has been greatly enhanced due to the use of Nafion film. When an appropriate mediator is included in the sensing layer, a sensitive nonaqueous biosensor could be fabricated. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of Brönsted acidic ionic liquid 1-(1-propylsulfonic)-3-methylimidazolium chloride on growth and co-fermentation of glucose, xylose and arabinose by Zymomonas mobilis AX101.

PubMed

Gyamerah, M; Ampaw-Asiedu, M; Mackey, J; Menezes, B; Woldesenbet, S

2018-06-01

The potential of large-scale lignocellulosic biomass hydrolysis to fermentable sugars using ionic liquids has increased interest in this green chemistry route to fermentation for fuel-ethanol production. The ionic liquid 1-(1-propylsulfonic)-3-methylimidazolium chloride compared to other reported ionic liquids has the advantage of hydrolysing lignocellulosic biomass to reducing sugars at catalytic concentrations (≤0·032 mol l -1 ) in a single step. However, effects of this ionic liquid on co-fermentation of glucose, xylose and arabinose to ethanol by recombinant Zymomonas mobilisAX101 has not been studied. Authentic glucose, xylose and arabinose were used to formulate fermentation media at varying catalytic 1-(1-propylsulfonic)-3-methylimidazolium chloride concentrations for batch co-fermentation of the sugars using Z. mobilisAX101. The results showed that at 0·008, 0·016 and 0·032 mol l -1 ionic liquid in the culture medium, cell growth decreased by 10, 27 and 67% respectively compared to the control. Ethanol yields were 62·6, 61·8, 50·5 and 23·1% for the control, 0·008, 0·016 and 0·032 mol l -1 ionic liquid respectively. The results indicate that lignocellulosic biomass hydrolysed using 0·008 mol l -1 of 1-(1-propylsulfonic)-3-methylimidazolium chloride would eliminate an additional separation step and provide a ready to use fermentation substrate. This is the first reported study of the effect of the Brönsted acidic ionic liquid 1-(1-propylsulfonic)-3-methylimidazolium chloride on growth and co-fermentation of glucose, xylose and arabinose by Zymomonas mobilisAX101 in batch culture. Growth on and co-fermentation of the sugars by Z. mobilisAX 101 with no significant inhibition by the ionic liquid at the same catalytic amounts of 0·008 mol l -1 used to hydrolyse lignocellulosic biomass to reducing sugars overcome two major hurdles that adversely affect the process economics of large-scale industrial cellulosic fuel ethanol production; the energy-intensive hydrolysis and ionic liquid separation steps. © 2018 The Society for Applied Microbiology.

Dynamics Simulations and Statistical Modeling of Thermal Decomposition of 1-Ethyl-3-methylimidazolium Dicyanamide and 1-Ethyl-2,3-dimethylimidazolium Dicyanamide

DTIC Science & Technology

2014-10-02

SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT 18 . NUMBER OF PAGES 19a. NAME OF RESPONSIBLE PERSON G. Vaghjiani c...Evib of EMIM +DCA− (eV) 0.33 1.66 2.67 3.78 18.34 Evib of EMMIM +DCA− (eV) 0.37 1.88 3.02 4.28 20.80 Erot (eV) 0.04 0.1 0.13 0.16 0.52 The Journal of...Intramolecular and Nonlinear Dynamics; JAI: Greenwich, U.K., 1998. ( 18 ) Sun, L.; Song, K.; Hase, W. L. A Sn2 Reaction That Avoids Its Deep Potential

Optimization of oligomeric enzyme activity in ionic liquids using Rhodotorula glutinis yeast phenylalanine ammonia lyase.

PubMed

Barron, Christiaan C; Sponagle, Brandon J D; Arivalagan, Pugazhendhi; D'Cunha, Godwin B

2017-01-01

Phenylalanine ammonia lyase (E.C.4.3.1.24, PAL) activity of Rhodotorula glutinis yeast has been demonstrated in four commonly used ionic liquids. PAL forward reaction was carried out in 1-butyl-3-methylimidazolium methyl sulfate ([BMIM][MeSO 4 ]), 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF 4 ]), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF 6 ]) and 1-butyl-3-methylimidazolium lactate ([BMIM][lactate]). Our experiments have revealed that PAL is catalytically active in ionic liquids and the enzyme activity in ([BMIM][PF 6 ]) is comparable to that obtained in aqueous buffer medium. Different conditions were optimized for maximal PAL forward activity including time of incubation (30.0min) L -phenylalanine substrate concentration (30.0mM), nature of buffer (50.0mM Tris-HCl), pH (9.0), temperature (37°C), and speed of agitation (100 rev min -1 ). Under these optimized conditions, about 83% conversion of substrate to product was obtained for the PAL forward reaction that was determined using UV spectroscopy at 290nm. PAL reverse reaction in ([BMIM][PF 6 ]) was determined spectrophotometrically at 520nm; and about 59% substrate conversion was obtained. This data provides further knowledge in enzyme biocatalysis in non-aqueous media, and may be of importance when studying the function of other oligomeric/multimeric proteins and enzymes in ionic liquids. Copyright © 2016 Elsevier Inc. All rights reserved.

Structure of cyano-anion ionic liquids: X-ray scattering and simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhungana, Kamal B.; Faria, Luiz F. O.; Wu, Boning

2016-07-14

Ionic liquids with cyano anions have long been used because of their unique combination of low-melting temperatures, reduced viscosities, and increased conductivities. Recently we have shown that cyano anions in ionic liquids are particularly interesting for their potential use as electron donors to excited state photo-acceptors [B. Wu et al., J. Phys. Chem. B 119, 14790–14799 (2015)]. Here we report on bulk structural and quantum mechanical results for a series of ionic liquids based on the 1-ethyl-3-methylimidazolium cation, paired with the following five cyano anions: SeCN-, SCN-, N(CN)-2N(CN)2-, C(CN)-3C(CN)3-, and B(CN)-4B(CN)4-. By combining molecular dynamics simulations, high-energy X-ray scattering measurements,more » and periodic boundary condition DFT calculations, we are able to obtain a comprehensive description of the liquid landscape as well as the nature of the HOMO-LUMO states for these ionic liquids in the condensed phase. Features in the structure functions for these ionic liquids are somewhat different than the commonly observed adjacency, charge-charge, and polarity peaks, especially for the bulkiest B(CN)-4B(CN)4- anion. While the other four cyano-anion ionic liquids present an anionic HOMO, the one for Im+2,1Im2,1+/B(CN)-4B(CN)4- is cationic.« less

Scaling-Up Ionic Liquid-Based Technologies: How Much Do We Care About Their Toxicity? Prima Facie Information on 1-Ethyl-3-Methylimidazolium Acetate.

PubMed

Ostadjoo, Shaghayegh; Berton, Paula; Shamshina, Julia L; Rogers, Robin D

2018-02-01

The potential of the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) to dissolve a variety of biopolymers such as cellulose and chitin, makes it an attractive candidate for scaled-up industrial utilization. In fact, the first steps towards its use at industrial scale have been taken. This increases the urgency to fill the knowledge gaps in its toxicity and environmental impact in order to predict and control its environmental fate. In this mini-review, we discuss the available literature surrounding this key IL. The literature (through the analysis of toxicity of the anion and the cation separately) suggests that [C2mim][OAc] is a relatively safe choice for industrial applications. However, because the IL should be considered as a compound, with unique properties arising from the interactions between the ions, comprehensive toxicity information for this particular IL is still required. To decide, prima facie, if this IL is toxic or not, evaluation of its influence on human health and ecotoxicity is needed prior to its large scale utilization. We chose in this mini-review to focus on toxicity surrounding this IL and evaluate what is known and what is not. Here with all the information in hand, we hope that the urgent need for [C2mim][OAc] toxicological assessment before it can be used in numerous technologies is highlighted. In the near future, we expect that the assessment of toxicity and environmental fate and impact can be integrated directly into any research into the industrial utilization of this IL and any others contemplated for industrial application. © The Author 2017. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Nonaqueous electrolyte for electrical storage devices

DOEpatents

McEwen, Alan B.; Yair, Ein-Eli

1999-01-01

Improved nonaqueous electrolytes for application in electrical storage devices such as electrochemical capacitors or batteries are disclosed. The electrolytes of the invention contain salts consisting of alkyl substituted, cyclic delocalized aromatic cations, and their perfluoro derivatives, and certain polyatomic anions having a van der Waals volume less than or equal to 100 .ANG..sup.3, preferably inorganic perfluoride anions and most preferably PF.sub.6.sup.-, the salts being dissolved in organic liquids, and preferably alkyl carbonate solvents, or liquid sulfur dioxide or combinations thereof, at a concentration of greater than 0.5M and preferably greater than 1.0M. Exemplary electrolytes comprise 1-ethyl-3-methylimidazolium hexafluorophosphate dissolved in a cyclic or acylic alkyl carbonate, or methyl formate, or a combination therof. These improved electrolytes have useful characteristics such as higher conductivity, higher concentration, higher energy storage capabilities, and higher power characteristics compared to prior art electrolytes. Stacked capacitor cells using electrolytes of the invention permit high energy, high voltage storage.

Pretreatment of Oil Palm Frond (OPF) with Ionic Liquid

NASA Astrophysics Data System (ADS)

Azmi, I. S.; Azizan, A.; Salleh, R. Mohd

2018-05-01

Pretreatment is the key to unlock the recalcitrance of lignocellulose for cellulosic biofuel production. Increasing attention has been drawn to ionic liquids (ILs) for pretreatment of lignocellulosic biomass because this approach was considered as a green engineering method over other conventional methods. In this work, Oil palm frond (OPF) was pretreated by using the ionic liquid 1-ethyl-3-methylimidazolium acetate [EMIM] Ac at the temperature of 99˚C for 3 hours. The characterization of the untreated and pretreated OPF was conducted by using different techniques which are Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The pretreatment of OPF with [EMIM] Ac was demonstrated to be effective evidenced by the significant reduction of Lateral Order Index (LOI) from FTIR, reduction of Crystallinity Index (CI) based on XRD and the significant morphology changes indicated by SEM. The CI value for the pretreated OPF decreased from 0.47 (untreated sample) to 0.28 while the LOI value decreased from 1.10 to 0.24 after pretreatment with [EMIM]Ac and the SEM morphology showed that the pretreated OPF becomes distorted and disordered.

Characterization of cellulose II nanoparticles regenerated from ionic liquid, 1-butyl-3-methylimidazolium chloride

USDA-ARS?s Scientific Manuscript database

Regenerated cellulose nanoparticles (RCNs) including both elongated fiber and spherical structures were prepared from microcrystalline cellulose (MCC)and cotton using 1-butyl-3-methylimidazolium chloride followed by high-pressure homogenization. The crystalline structure of RCNs was cellulose II in ...

Dispersion polymerization of L-lactide utilizing ionic liquids as reaction medium

NASA Astrophysics Data System (ADS)

Fahmiati, Sri; Minami, Hideto; Haryono, Agus; Adilina, Indri B.

2017-11-01

Dispersion polymerization of L-lactide was proceeded in various ionic liquids. Ionic liquids as 1-Hexyl-3-methylimidazolium bis (trifluormethylsulfonyl) imide, [HMIM] [TFSI], 1-Butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, [BMP] [TFSI], and N,N,N-Trimethyl-N-Propylammonium Bis (trifloromethanesulfonyl) imide, [TMPA] [TFSI], were employed as reaction medium that dissolved both of lactide and stabilizer (polyvinylprrolidone). Sn-supported on bentonite was used as a ring opening catalyst of L-lactide. Gel Permeation Chromatography result showed that poly-(L-lactic acid) were formed in ionic liquids [HMIM] [TFSI] and [BMP] [TFSI] with molecular weight as 19390 and 20844, respectively.

Atomistic polarizable force field for molecular dynamics simulations of azide anion containing ionic liquids and crystals.

NASA Astrophysics Data System (ADS)

Starovoytov, Oleg; Hooper, Justin; Borodin, Oleg; Smith, Grant

2010-03-01

Atomistic polarizable force field has been developed for a number of azide anion containing ionic liquids and crystals. Hybrid Molecular Dynamics/Monte Carlo (MD/MC) simulations were performed on methylguanazinium azide and 1-(2-butynyl)-3-methyl-imidazolium azide crystals, while 1-butyl-2,3-dimethylimidazolium azide and 1-amino-3-methyl-1,2,3-triazolium azide ionic liquids were investigated using MD simulations. Crystal cell parameters and crystal structures of 1-(2-butynyl)-3-methyl-imidazolium azide were found in good agreement with X-ray experimental data. Density and ion transport of 1-butyl-2,3-dimethylimidazolium azide predicted from MD simulations were in good agreement with experiments. Details of the ionic liquid structure and relaxation mechanism will be discussed.

A roadmap to uranium ionic liquids: anti-crystal engineering.

PubMed

Yaprak, Damla; Spielberg, Eike T; Bäcker, Tobias; Richter, Mark; Mallick, Bert; Klein, Axel; Mudring, Anja-Verena

2014-05-19

In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C4mim) cation. As dithiocarbamate ligands binding to the UO2(2+) unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim to establish structure-property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. These materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A roadmap to uranium ionic liquids: Anti-crystal engineering

DOE PAGES

Yaprak, Damla; Spielberg, Eike T.; Bäcker, Tobias; ...

2014-04-15

In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C 4mim) cation. As dithiocarbamate ligands binding to the UO 2 2+ unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand withmore » the aim to establish structure–property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. As a result, these materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery.« less

Molecular dynamics simulations of pyrrolidinium and imidazolium ionic liquids at graphene interfaces.

PubMed

Begić, Srđan; Jónsson, Erlendur; Chen, Fangfang; Forsyth, Maria

2017-11-15

Understanding the electrode-electrolyte interface is essential in the battery research as the ion transport and ion structures at the interface most likely affect the performance of a battery. Here we investigate interfacial structures of three ionic liquids: 1-ethyl-3-methylimidazolium dicyanamide ([C 2 mim][dca]), 1-butyl-3-methylimidazolium dicyanamide ([C 4 mim][dca]) and N-butyl-N-methylpyrrolidinium dicyanamide ([C 4 myr][dca]) at a charged and uncharged graphene interface using molecular dynamics simulations. We find that these ionic liquids (ILs) behave differently both in the bulk phase and near a graphene interface and we find that this difference is apparent in all types of analyses performed here. First, a partial density analysis in the direction perpendicular to the surface of the electrodes, which, in the cases near a negatively charged graphene, reveals that the pyrrolidinium system is generally more layered than the imidazolium systems. Second, a 2D topographic structure analysis of the IL species in the inner layer near a negatively charged graphene surface, which reveals that the pyrrolidinium system exhibits a quasi-hexagonal surface configuration of the cations, while the imidazolium systems show linearly arranged groups of cations. Third, a 3D orientation-preference analysis of cation rings near the negative graphene electrode, which shows that the pyrrolidinium rings prefer to lie parallel to the electrode surface while the imidazolium rings prefer to stand on the electrode surface at high tilt angles. Extending the imidazolium alkyl chain was found to reduce the number of imidazoliums that can link up into linearly arranged groups in the inner layer 2D structures. Our results support earlier experimental findings and indicate that the interfacial nanostructures may have a significant influence on the electrochemical performance of IL-based batteries.

Enzymatic hydrolysis of cellulose pretreated with ionic liquids and N-methyl Morpholine N-Oxide

NASA Astrophysics Data System (ADS)

Yau Li, Elizabeth

The effect of N-methyl Morpholine N-Oxide (NMMO), 1-ethyl-3-methyl-imidazolium acetate ([Emim]Ac) and 1-ethyl-3-methyl-imidazolium diethyl phosphate ([Emim]DEP) on pretreatment and enzymatic hydrolysis of dissolving pulp was studied. X-ray diffraction measurements of regenerated cellulose from these solvents showed that solvent pretreatment reduces the crystallinity of cellulose. However, crystallinity might not be a major factor affecting the in-situ enzymatic hydrolysis of cellulose in these solvents. Although regenerated cellulose from [Emim]DEP showed the lowest crystallinity index (˜15%), in-situ enzymatic hydrolysis of cellulose dissolved in NMMO showed the highest cellulose conversion (68% compared to 65% for [Emim]Ac and 37% for [Emim]DEP at enzyme loading of 122 FPU/g). Moreover, results showed that enzymes could tolerate up to NMMO concentration of 100 g/L and still yield full conversion of cellulose. Since it is not necessary to remove all the NMMO, less amount of water will be required for the washing step and thus the process will be more economical. The HCH-1 model was used in an attempt to model the enzymatic hydrolysis of cellulose in NMMO. With the incorporation of NMMO inhibition and a factor to account for unreacted cellulose, the model was able to correlate the experimental data of the enzymatic hydrolysis of cellulose (6.68 g/L) at various NMMO concentrations (0, 50, 100, 150 and 250 g/L). However, the experimental results also suggest that NMMO might be deactivating the enzymes rather than inhibiting them. More studies need to be done at varying cellulose, NMMO and enzyme concentrations to find the exact nature of this deactivation of NMMO.

Anodic behavior of uranium in AlCl3-1-ethyl-3-methyl-imidazolium chloride ionic liquid

NASA Astrophysics Data System (ADS)

Jiang, Yidong; Luo, Lizhu; Wang, Shaofei; Bin, Ren; Zhang, Guikai; Wang, Xiaolin

2018-01-01

The oxidation state of metals unambiguously affects its anodic behavior in ionic liquid. We systematically investigated the anodic behavior of uranium with different surface oxidation states by electrochemical measurements, spectroscopic methods and surface analysis techniques. In the anodic process, metal uranium can be oxidized to U3+. The corresponding products accumulated on the metal/ILs interface will form a viscous layer. The anodic behavior of uranium is also strongly dependent upon the surface oxide states including thickness and homogeneity of the oxide film. With an increase in the thickness of oxide film, it will be breached at potentials in excess of a critical value. A uniform oxide on uranium surface can be breached evenly, and then the underlying metal starts to dissolve forming a viscous layer which can facilitate uniformly stripping of oxide, thus giving an oxide-free surface. Otherwise, a nonuniform oxide can result in a severe pitted surface with residue oxygen.

Cycling performance of lithium metal polymer cells assembled with ionic liquid and poly(3-methyl thiophene)/carbon nanotube composite cathode

NASA Astrophysics Data System (ADS)

Kim, Dong-Won; Sivakkumar, S. R.; MacFarlane, Douglas R.; Forsyth, Maria; Sun, Yang-Kook

A poly(3-methylthiophene) (PMT)/multi-walled carbon nanotube (CNT) composite is synthesized by in situ chemical polymerization. The PMT/CNT composite is used as an active cathode material in lithium metal polymer cells assembled with ionic liquid (IL) electrolytes. The IL electrolyte consists of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4) and LiBF 4. A small amount of vinylene carbonate is added to the IL electrolyte to prevent the reductive decomposition of the imidazolium cation in EMIBF 4. A porous poly(vinylidene fluoride- co-hexafluoropropylene) (P(VdF- co-HFP)) film is used as a polymer membrane for assembling the cells. Electrochemical properties of the PMT/CNT composite electrode in the IL electrolyte are evaluated and the effect of vinylene carbonate on the cycling performance of the lithium metal polymer cells is investigated. The cells assembled with a non-flammable IL electrolyte and a PMT/CNT composite cathode are promising candidates for high-voltage-power sources with enhanced safety.

Scattering Studies on Poly(3,4-ethylenedioxythiophene)- Polystyrenesulfonate in the Presence of Ionic Liquids

DOE PAGES

Murphy, Ryan J.; Weigandt, Katie M.; Uhrig, David; ...

2015-11-30

The demand for lower cost and flexible electronics has driven industry to develop alternative transparent electrode (TE) materials to replace indium tin oxide (ITO). ITO is the benchmark TE on the market, but its high cost and low flexibility limit it for use in future technologies. Recent work has shown the combination of the conducting polymer poly(3,4-ethylenedioxythiophene)–polystyrenesulfonate (PEDOT:PSS) with the ionic liquid 1-ethyl-3-methylimidazolium tetracyanoborate (EMIM:TCB) is a viable ITO replacement. This study investigates the nature of the interaction between PEDOT:PSS and EMIM:TCB in the solution state. A combination of scattering methods is used to illustrate a novel, multilength scale modelmore » of this system. At length scales larger than 300nm PEODT:PSS adopts a microgel-like structure, and below ~300nm the system adopts an entangled polyelectrolyte mesh structure. As EMIM:TCB is added, the microgel interior adopts a more neutral polymer mesh structure as EMIM:TCB concentration is increased.« less

Sugarcane bagasse pretreatment using three imidazolium-based ionic liquids; mass balances and enzyme kinetics

PubMed Central

2012-01-01

Background Effective pretreatment is key to achieving high enzymatic saccharification efficiency in processing lignocellulosic biomass to fermentable sugars, biofuels and value-added products. Ionic liquids (ILs), still relatively new class of solvents, are attractive for biomass pretreatment because some demonstrate the rare ability to dissolve all components of lignocellulosic biomass including highly ordered (crystalline) cellulose. In the present study, three ILs, 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), 1-ethyl-3-methylimidazolium chloride ([C2mim]Cl), 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc) are used to dissolve/pretreat and fractionate sugarcane bagasse. In these IL-based pretreatments the biomass is completely or partially dissolved in ILs at temperatures greater than 130°C and then precipitated by the addition of an antisolvent to the IL biomass mixture. For the first time mass balances of IL-based pretreatments are reported. Such mass balances, along with kinetics data, can be used in process modelling and design. Results Lignin removals of 10% mass of lignin in bagasse with [C4mim]Cl, 50% mass with [C2mim]Cl and 60% mass with [C2mim]OAc, are achieved by limiting the amount of water added as antisolvent to 0.5 water:IL mass ratio thus minimising lignin precipitation. Enzyme saccharification (24 h, 15FPU) yields (% cellulose mass in starting bagasse) from the recovered solids rank as: [C2mim]OAc(83%) > >[C2mim]Cl(53%) = [C4mim]Cl(53%). Composition of [C2mim]OAc-treated solids such as low lignin, low acetyl group content and preservation of arabinosyl groups are characteristic of aqueous alkali pretreatments while those of chloride IL-treated solids resemble aqueous acid pretreatments. All ILs are fully recovered after use (100% mass as determined by ion chromatography). Conclusions In all three ILs regulated addition of water as an antisolvent effected a polysaccharide enriched precipitate since some of the lignin remained dissolved in the aqueous IL solution. Of the three IL studied [C2mim]OAc gave the best saccharification yield, material recovery and delignification. The effects of [C2mim]OAc pretreatment resemble those of aqueous alkali pretreatments while those of [C2mim]Cl and [C4mim]Cl resemble aqueous acid pretreatments. The use of imidazolium IL solvents with shorter alkyl chains results in accelerated dissolution, pretreatment and degradation. PMID:22920045

Perfect Composition Depth Profiling of Ionic Liquid Surfaces Using High-resolution RBS/ERDA.

PubMed

Nakajima, Kaoru; Zolboo, Enkhbayar; Ohashi, Tomohiro; Lísal, Martin; Kimura, Kenji

2016-01-01

In order to reveal the surface structures of large molecular ionic liquids (ILs), the near-surface elemental depth distributions of 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C n C 1 Im][Tf 2 N], n = 2, 6, 10) were studied using high-resolution Rutherford backscattering spectroscopy (HRBS) in combination with high-resolution elastic recoil detection analysis (HR-ERDA). The elemental depth profiles of all constituent elements, including hydrogen, were derived from HR-ERDA/HRBS measurements, so that the profiles would reproduce both HR-ERDA and HRBS spectra simultaneously. The derived elemental depth profiles agree with state-of-the-art molecular dynamics simulations, indicating the feasibility of this method. A controversy concerning the preferential orientation of [C 2 C 1 Im] at the surface has been resolved by this new combination analysis; namely, the [C 2 C 1 Im] cation has a preferential orientation with the ethyl chain pointing towards the vacuum in the topmost molecular layer.

Ultrasound assisted lipase catalyzed synthesis of poly-6-hydroxyhexanoate.

PubMed

Gumel, A M; Annuar, M S M; Chisti, Y; Heidelberg, T

2012-05-01

Ultrasonic irradiation greatly improved the Candida antarctica lipase B mediated ring opening polymerization of ε-caprolactone to poly-6-hydroxyhexanoate in the ionic liquid 1-ethyl-3-methylimidazolium tetraflouroborate. Compared to the conventional nonsonicated reaction, sonication improved the monomer conversion by 63% and afforded a polymer product of a narrower molecular weight distribution and a higher degree of crystallinity. Under sonication, the polydispersity index of the product was ~1.44 compared to a value of ~2.55 for the product of the conventional reaction. With sonication, nearly 75% of the monomer was converted to product, but the conversion was only ~16% for the reaction carried out conventionally. Compared to conventional operation, sonication enhanced the rate of polymer propagation by >2-fold and the turnover number of the lipase by >3-fold. Copyright © 2011 Elsevier B.V. All rights reserved.

A shell-resolved analysis of preferential solvation of coffee ingredients in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate

NASA Astrophysics Data System (ADS)

Zeindlhofer, Veronika; Berger, Magdalena; Steinhauser, Othmar; Schröder, Christian

2018-05-01

Ionic liquids increase the solubility of various coffee ingredients in aqueous solution but little is known about the underlying mechanism. Kirkwood-Buff integrals as well as the potential of mean force indicate that the imidazolium cations are accumulated at the surface of the solutes, removing water molecules from the solute surface. Although hydrogen bonding of the anions to hydroxy groups of the solutes can be detected, their concentration at the surface is less enhanced compared to the cations. The decomposition into solvation shells by Voronoi tessellation reveals that structural features are only observed in the first solvation shell. Nevertheless, the depletion of water and the excess concentration of the ions and, in particular, of the cations are visible in the next solvation shells as well. Therefore, classical arguments of hydrotropic theory fail to explain this behavior.

Bionanocomposites of regenerated cellulose/zeolite prepared using environmentally benign ionic liquid solvent.

PubMed

Soheilmoghaddam, Mohammad; Wahit, Mat Uzir; Tuck Whye, Wong; Ibrahim Akos, Noel; Heidar Pour, Raheleh; Ali Yussuf, Abdirahman

2014-06-15

Bionanocomposite films based on regenerated cellulose (RC) and incorporated with zeolite at different concentrations were fabricated by dissolving cellulose in 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic liquid using a simple green method. The interactions between the zeolite and the cellulose matrix were confirmed by Fourier transform infrared spectra. Mechanical properties of the nanocomposite films significantly improved as compared with the pure regenerated cellulose film, without the loss of extensibility. Zeolite incorporation enhanced the thermal stability and char yield of the nanocomposites. The scanning electron microscopy and transmission electron microscopy showed that zeolite was uniformly dispersed in the regenerated cellulose matrix. In vitro cytotoxicity test demonstrated that both RC and RC/zeolite nanocomposite films are cytocompatible. These results indicate that the prepared nanocomposites have potential applications in biodegradable packaging, membranes and biomedical areas. Copyright © 2014 Elsevier Ltd. All rights reserved.

The properties of residual water molecules in ionic liquids: a comparison between direct and inverse Kirkwood-Buff approaches.

PubMed

Kobayashi, Takeshi; Reid, Joshua E S J; Shimizu, Seishi; Fyta, Maria; Smiatek, Jens

2017-07-26

We study the properties of residual water molecules at different mole fractions in dialkylimidazolium based ionic liquids (ILs), namely 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM/BF 4 ) and 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM/BF 4 ) by means of atomistic molecular dynamics (MD) simulations. The corresponding Kirkwood-Buff (KB) integrals for the water-ion and ion-ion correlation behavior are calculated by a direct evaluation of the radial distribution functions. The outcomes are compared to the corresponding KB integrals derived by an inverse approach based on experimental data. Our results reveal a quantitative agreement between both approaches, which paves a way towards a more reliable comparison between simulation and experimental results. The simulation outcomes further highlight that water even at intermediate mole fractions has a negligible influence on the ion distribution in the solution. More detailed analysis on the local/bulk partition coefficients and the partial structure factors reveal that water molecules at low mole fractions mainly remain in the monomeric state. A non-linear increase of higher order water clusters can be found at larger water concentrations. For both ILs, a more pronounced water coordination around the cations when compared to the anions can be observed, which points out that the IL cations are mainly responsible for water pairing mechanisms. Our simulations thus provide detailed insights in the properties of dialkylimidazolium based ILs and their effects on water binding.

Enhancing thermoelectrochemical properties by tethering ferrocene to the anion or cation of ionic liquids: altered thermodynamics and solubility.

PubMed

Aldous, Leigh; Black, Jeffrey J; Elias, Maximo C; Gélinas, Bruno; Rochefort, Dominic

2017-09-13

Entropic changes inherent within a redox process typically result in significant temperature sensitivity. This can be utilised positively or can be a detrimental process. This study has investigated the thermoelectrochemical properties (temperature-dependant electrochemistry) of the ferrocenium|ferrocene redox couple in an ionic liquid, and in particular the effect of covalently tethering this redox couple to fixed positive or negative charges. As such, the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was employed to dissolve ferrocene, as well as cationic-tethered ferrocene (the 1-ethyl-3-(methylferrocenyl)imidazolium cation) and anionic-tethered ferrocene (the ferrocenylsulfonyl(trifluoromethylsulfonyl)imide anion). These systems were characterised in terms of their voltammetry (apparent formal potentials, diffusion coefficients and electron transfer rate constants) and thermoelectrochemistry (temperature coefficients of the cell potential or 'Seebeck coefficients', short circuit current densities and power density outputs). The oxidised cationic species behaved like a dicationic species and was thus 6-fold more effective at converting waste thermal energy to electrical power within a thermoelectrochemical cell than unmodified ferrocene. This was almost exclusively due to a significant boost in the Seebeck coefficient of this redox couple. Conversely, the oxidised anionic species was formally a zwitterion, but this zwitterionic species behaved thermodynamically like a neutral species. The inverted entropic change upon going from ferrocene to anion-tethered ferrocene allowed development of a largely temperature-insensitive reference potential based upon a mixture of acetylferrocene and ferricenyl(iii)sulfonyl(trifluoromethylsulfonyl)imide.

Multi-heteroatom doped carbon coated Na3V2(PO4)3 derived from ionic liquids.

PubMed

Zhang, Lu-Lu; Zhou, Ying-Xian; Li, Tao; Ma, Di; Yang, Xue-Lin

2018-03-28

Multi-heteroatom (N, S and F) doped carbon coated Na 3 V 2 (PO 4 ) 3 (labeled as NVP/C-ILs) derived from an ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM]TF2N) has been successfully fabricated. The as-prepared Na 3 V 2 (PO 4 ) 3 particles are well dispersed and closely coated with a multi-heteroatom (N, S and F) doped carbon layer. As a cathode for sodium-ion batteries, the NVP/C-ILs electrode exhibits high reversible specific capacity (117.5 mA h g -1 at 1C), superior rate performance (93.4 mA h g -1 at 10C) and excellent cycling stability (∼95% capacity retention ratio at 10C over 1000 cycles). The impressive electrochemical performance of NVP/C-ILs can be attributed to effectively conductive networks for electrons and Na + ions induced by a joint effect of N, S and F doping on carbon. The use of multi-heteroatom doped carbon coated Na 3 V 2 (PO 4 ) 3 provides a facile and effective strategy for the fabrication of high performance electrode materials with low intrinsic electrical conductivity.

Separation of 1,3-substituted imidazoles for quality control of a Lewis acidic ionic liquid for aluminum electroplating.

PubMed

Kosmus, Patrick; Steiner, Oliver; Goessler, Walter; Gollas, Bernhard

2014-05-01

Ionic liquids (ILs) are already used or have great potential in many industrial applications. Knowledge about their unique physicochemical characteristics makes ILs suitable for the electrodeposition of metals with very low negative potentials. Aluminum with its good corrosion protection behavior has great capability to be electroplated from IL electrolytes on steel substrates. The stability of the chosen electrolyte is very important to ensure industrial applicability. In this study, temperature and electrochemical long-term stability from electrolytes based on a Lewis acidic mixture of AlCl3 and 1-ethyl-3-methylimidazolium chloride are investigated. A published method was modified to identify possible degradation products using mass spectrometric detection. The optimized method used an Agilent Zorbax SB-Phenyl column (2.0 × 150 mm, 5 μm particles) with a 20 mmol TFA and 5% ACN mobile phase. This method allowed the quantification of several imidazoles from 0.1 to 100 mg/L. When analyzing the long-term stressed electrolytes, no significant changes in electrolyte composition could be observed. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Capillary evaporation of the ionic liquid [EMIM][BF4] in nanoscale solvophobic confinement

NASA Astrophysics Data System (ADS)

Shrivastav, Gourav; Remsing, Richard C.; Kashyap, Hemant K.

2018-05-01

Solvent density fluctuations play a crucial role in liquid-vapor transitions in solvophobic confinement and can also be important for understanding solvation of polar and apolar solutes. In the case of ionic liquids (ILs), density fluctuations can be used to understand important processes in the context of nanoscale aggregation and colloidal self-assemblies. In this article, we explore the nature of density fluctuations associated with capillary evaporation of the IL 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) in the confined region of model solvophobic nanoscale sheets by using molecular dynamics simulations combined with non-Boltzmann sampling techniques. We demonstrate that density fluctuations of the confined IL play an important role in capillary evaporation, suggesting analogies to dewetting transitions involving water. Significant changes in the interfacial structure of the IL are also detailed and suggested to underlie a non-classical (non-parabolic) dependence of the free energy barrier to evaporation on the degree of confinement.

Polarizability effects on the structure and dynamics of ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cavalcante, Ary de Oliveira, E-mail: arycavalcante@ufam.edu.br; Departamento de Química, Universidade Federal do Amazonas, Av. Rodrigo Octávio, 6200, Coroado, Manaus, AM; Ribeiro, Mauro C. C.

2014-04-14

Polarization effects on the structure and dynamics of ionic liquids are investigated using molecular dynamics simulations. Four different ionic liquids were simulated, formed by the anions Cl{sup −} and PF{sub 6}{sup −}, treated as single fixed charge sites, and the 1-n-alkyl-3-methylimidazolium cations (1-ethyl and 1-butyl-), which are polarizable. The partial charge fluctuation of the cations is provided by the electronegativity equalization model (EEM) and a complete parameter set for the cations electronegativity (χ) and hardness (J) is presented. Results obtained from a non-polarizable model for the cations are also reported for comparison. Relative to the fixed charged model, the equilibriummore » structure of the first solvation shell around the imidazolium cations shows that inclusion of EEM polarization forces brings cations closer to each other and that anions are preferentially distributed above and below the plane of the imidazolium ring. The polarizable model yields faster translational and reorientational dynamics than the fixed charges model in the rotational-diffusion regime. In this sense, the polarizable model dynamics is in better agreement with the experimental data.« less

A new method for the determination of vaporization enthalpies of ionic liquids at low temperatures.

PubMed

Verevkin, Sergey P; Zaitsau, Dzmitry H; Emelyanenko, Vladimir N; Heintz, Andreas

2011-11-10

A new method for the determination of vaporization enthalpies of extremely low volatile ILs has been developed using a newly constructed quartz crystal microbalance (QCM) vacuum setup. Because of the very high sensitivity of the QCM it has been possible to reduce the average temperature of the vaporization studies by approximately 100 K in comparison to other conventional techniques. The physical basis of the evaluation procedure has been developed and test measurements have been performed with the common ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C(2)mim][NTf(2)] extending the range of measuring vaporization enthalpies down to 363 K. The results obtained for [C(2)mim][NTf(2)] have been tested for thermodynamic consistency by comparison with data already available at higher temperatures. Comparison of the temperature-dependent vaporization enthalpy data taken from the literature show only acceptable agreement with the heat capacity difference of -40 J K(-1) mol(-1). The method developed in this work opens also a new way to obtain reliable values of vaporization enthalpies of thermally unstable ionic liquids.

Finding the best density functional approximation to describe interaction energies and structures of ionic liquids in molecular dynamics studies

NASA Astrophysics Data System (ADS)

Perlt, Eva; Ray, Promit; Hansen, Andreas; Malberg, Friedrich; Grimme, Stefan; Kirchner, Barbara

2018-05-01

Ionic liquids raise interesting but complicated questions for theoretical investigations due to the fact that a number of different inter-molecular interactions, e.g., hydrogen bonding, long-range Coulomb interactions, and dispersion interactions, need to be described properly. Here, we present a detailed study on the ionic liquids ethylammonium nitrate and 1-ethyl-3-methylimidazolium acetate, in which we compare different dispersion corrected density functional approximations to accurate local coupled cluster data in static calculations on ionic liquid clusters. The efficient new composite method B97-3c is tested and has been implemented in CP2K for future studies. Furthermore, tight-binding based approaches which may be used in large scale simulations are assessed. Subsequently, ab initio as well as classical molecular dynamics simulations are conducted and structural analyses are presented in order to shed light on the different short- and long-range structural patterns depending on the method and the system size considered in the simulation. Our results indicate the presence of strong hydrogen bonds in ionic liquids as well as the aggregation of alkyl side chains due to dispersion interactions.

Hydrogen-bond rich ionic liquids with hydroxyl cationic tails

NASA Astrophysics Data System (ADS)

Deng, Li; Shi, Rui; Wang, Yanting; Ou-Yang, Zhong-Can

2013-02-01

To investigate if the amphiphilic feature exhibited in ionic liquids (ILs) with nonpolar cationic tails still exists in ILs with polar tails, by performing molecular dynamics simulations for 1-(8-hydroxyoctyl)-3-methyl-imidazolium nitrate (COH) and 1-octyl-3-methyl-imidazolium nitrate (C8), we found that, in COH, cationic tail groups can no longer aggregate to form separated nonpolar tail domains, instead hydroxyl groups form a rich number of hydrogen bonds with other groups, indicating that the hydroxyl substituent changes the IL system from an amphiphilic liquid to a polar liquid. Due to the large amount of hydrogen bonds, COH has slower dynamics than C8.

Different characteristic effects of ageing on starch-based films plasticised by 1-ethyl-3-methylimidazolium acetate and by glycerol.

PubMed

Zhang, Binjia; Xie, Fengwei; Zhang, Tianlong; Chen, Ling; Li, Xiaoxi; Truss, Rowan W; Halley, Peter J; Shamshina, Julia L; McNally, Tony; Rogers, Robin D

2016-08-01

The focus of this study was on the effects of plasticisers (the ionic liquid 1-ethyl-3-methylimidazolium acetate, or [Emim][OAc]; and glycerol) on the changes of starch structure on multiple length scales, and the variation in properties of plasticised starch-based films, during ageing. The films were prepared by a simple melt compression moulding process, followed by storage at different relative humidity (RH) environments. Compared with glycerol, [Emim][OAc] could result in greater homogeneity in [Emim][OAc]-plasticised starch-based films (no gel-like aggregates and less molecular order (crystallites) on the nano-scale). Besides, much weaker starch-starch interactions but stronger starch-[Emim][OAc] interactions at the molecular level led to reduced strength and stiffness but increased flexibility of the films. More importantly, [Emim][OAc] (especially at high content) was revealed to more effectively maintain the plasticised state during ageing than glycerol: the densification (especially in the amorphous regions) was suppressed; and the structural characteristics especially on the nano-scale were stabilised (especially at a high RH), presumably due to the suppressed starch molecular interactions by [Emim][OAc] as confirmed by Raman spectroscopy. Such behaviour contributed to stabilised mechanical properties. Nonetheless, the crystallinity and thermal stability of starch-based films with both plasticisers were much less affected by ageing and moisture uptake during storage (42 days), but mostly depended on the plasticiser type and content. As starch is a typical semi-crystalline bio-polymer containing abundant hydroxyl groups and strong hydrogen bonding, the findings here could also be significant in creating materials from other similar biopolymers with tailored sensitivity and properties to the environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rotational diffusion of nonpolar and ionic solutes in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides: is solute rotation always influenced by the length of the alkyl chain on the imidazolium cation?

PubMed

Gangamallaiah, V; Dutt, G B

2012-10-25

In an attempt to find out whether the length of the alkyl chain on the imidazolium cation has a bearing on solute rotation, temperature-dependent fluorescence anisotropies of three structurally similar solutes have been measured in a series of 1-alkyl-3-methylimidazolium (alkyl = methyl, ethyl, propyl, butyl, and hexyl) bis(trifluoromethylsulfonyl)imides. Solute-solvent coupling constants obtained from the experimentally measured reorientation times with the aid of Stokes-Einstein-Debye hydrodynamic theory indicate that there is no influence of the length of the alkyl chain on the rotation of nonpolar, anionic, and cationic solutes 9-phenylanthracene (9-PA), fluorescein (FL), and rhodamine 110 (R110), respectively. It has also been noticed that the rotational diffusion of 9-PA is closer to the predictions of slip hydrodynamics, whereas the rotation of negatively charged FL and positively charged R110 is almost identical and follows stick hydrodynamics in these ionic liquids. Despite having similar shape and size, ionic solutes rotate slower by a factor of 3-4 compared to the nonpolar solute. Interplay of specific and electrostatic interactions between FL and the imidazolium cation of the ionic liquids, and between R110 and the bis(trifluoromethylsulfonyl)imide anion, appear to be responsible for the observed behavior. These results are an indication that the length of the alkyl chain on the imidazolium cation does not alter their physical properties in a manner that has an effect on solute rotation.

Prediction of the vapor pressure and vaporization enthalpy of 1-n-alkyl-3-methylimidazolium-bis-(trifluoromethanesulfonyl) amide ionic liquids.

PubMed

Diedenhofen, Michael; Klamt, Andreas; Marsh, Kenneth; Schäfer, Ansgar

2007-09-07

The vapor pressures and vaporization enthalpies of a series of 1-n-alkyl-3-methylimidazolium-bis-(trifluoromethanesulfonyl) amide ionic liquids have been predicted with two different approaches using the COSMO-RS method and quantum chemical gas phase calculations. While the calculated enthalpies are in good agreement with the experimental data, COSMO-RS seems to underestimate the vapor pressures by roughly 0.5-4 log units dependent on the IL and approach used.

An aluminum - ionic liquid interface sustaining a durable Al-air battery

NASA Astrophysics Data System (ADS)

Gelman, Danny; Shvartsev, Boris; Wallwater, Itamar; Kozokaro, Shahaf; Fidelsky, Vicky; Sagy, Adi; Oz, Alon; Baltianski, Sioma; Tsur, Yoed; Ein-Eli, Yair

2017-10-01

A thorough study of a unique aluminum (Al)-air battery utilizing a pure Al anode, an air cathode, and hydrophilic room temperature ionic liquid electrolyte 1-ethyl-3-methylimidazolium oligofluorohydrogenate [EMIm(HF)2.3F] is reported. The effects of various operation conditions, both at open circuit potential and under discharge modes, on the battery components were discussed. A variety of techniques were utilized to investigate and study the interfaces and processes involved, including electrochemical studies, electron microscopy, spectroscopy and diffraction. As a result of this intensive study, the upon-operation voltage drop (;dip;) obstacle, occurring in the initial stages of the Al-air battery discharge, has been resolved. In addition, the interaction of the Al anode with oligofluorohydrogenate electrolyte forms an Al-O-F layer on the Al surface, which allows both activation and low corrosion rates of the Al anode. The evolution of this layer has been studied via impedance spectroscopy genetic programming enabling a unique model of the Al-air battery.

Characterization of white poplar and eucalyptus after ionic liquid pretreatment as a function of biomass loading using X-ray diffraction and small angle neutron scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Xueming; Duan, Yonghao; He, Lilin

A systematic study was done to understand interactions among biomass loading during ionic liquid (IL) pretreatment, biomass type and biomass structures. White poplar and eucalyptus samples were pretreated using 1-ethyl-3-methylimidazolium acetate (EmimOAc) at 110 °C for 3 h at biomass loadings of 5, 10, 15, 20 and 25 wt%. All of the samples were chemically characterized and tested for enzymatic hydrolysis. Physical structures including biomass crystallinity and porosity were measured by X-ray diffraction (XRD) and small angle neutron scattering (SANS), respectively. SANS detected pores of radii ranging from ~25 to 625 Å, enabling assessment of contributions of pores with different sizes to increased porositymore » after pretreatment. Contrasting dependences of sugar conversion on white poplar and eucalyptus as a function of biomass loading were observed and cellulose crystalline structure was found to play an important role.« less

Characterization of white poplar and eucalyptus after ionic liquid pretreatment as a function of biomass loading using X-ray diffraction and small angle neutron scattering.

PubMed

Yuan, Xueming; Duan, Yonghao; He, Lilin; Singh, Seema; Simmons, Blake; Cheng, Gang

2017-05-01

A systematic study was performed to understand interactions among biomass loading during ionic liquid (IL) pretreatment, biomass type and biomass structures. White poplar and eucalyptus samples were pretreated using 1-ethyl-3-methylimidazolium acetate (EmimOAc) at 110°C for 3h at biomass loadings of 5, 10, 15, 20 and 25wt%. All of the samples were chemically characterized and tested for enzymatic hydrolysis. Physical structures including biomass crystallinity and porosity were measured by X-ray diffraction (XRD) and small angle neutron scattering (SANS), respectively. SANS detected pores of radii ranging from ∼25 to 625Å, enabling assessment of contributions of pores with different sizes to increased porosity after pretreatment. Contrasting dependences of sugar conversion on white poplar and eucalyptus as a function of biomass loading were observed and cellulose crystalline structure was found to play an important role. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of pH on ionic liquid mediated synthesis of gold nanoparticle using elaiseguineensis (palm oil) kernel extract

NASA Astrophysics Data System (ADS)

Irfan, Muhammad; Ahmad, Tausif; Moniruzzaman, Muhammad; Abdullah, Bawadi

2017-05-01

This study was conducted for microwave assisted synthesis of stable gold nanoparticles (AuNPs) by reduction of chloroauric acid with Elaeis Guineensis (palm oil) kernel (POK) extract which was prepared in aqueous solution of ionic liquid, [EMIM][OAc], 1-Ethyl-3-methylimidazolium acetate. Effect of initial pH of reaction mixture (3.5 - 8.5) was observed on SPR absorbance, maximum wavelength (λmax ) and size distribution of AuNPs. Change of pH of reaction mixture from acidic to basic region resulted in appearance of strong SPR absorption peaks and blue shifting of λmax from 533 nm to 522 nm. TEM analysis revealed the formation of predominantly spherical AuNPs with mean diameter of 8.51 nm. Presence of reducing moieties such as flavonoids, phenolic and carboxylic groups in POK extract was confirmed by FTIR analysis. Colloidal solution of AuNPs was remained stable at room temperature and insignificant difference in zeta value was recorded within experimental tenure of 4 months.

Computational analysis of the solvation of coffee ingredients in aqueous ionic liquid mixtures† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra24736a Click here for additional data file.

PubMed Central

Zeindlhofer, Veronika; Khlan, Diana; Bica, Katharina

2017-01-01

In this paper, we investigate the solvation of coffee ingredients including caffeine, gallic acid as representative for phenolic compounds and quercetin as representative for flavonoids in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate [C2mim][OAc] at various concentrations. Due to the anisotropy of the solutes we show that classical Kirkwood–Buff theory is not appropriate to study solvation effects with increasing ionic liquid content. However, excess coordination numbers as well as the mean residence time of solvent molecules at the surface of the solutes can be determined by Voronoi tessellation. Since the volume of the hydration shells is also available by this method, solvation free energies will be discussed as a function of the ionic liquid concentration to yield a physical meaningful picture of solvation for the anisotropic solutes. Hydrogen bonding capabilities of the solutes and their relevance for experimental extraction yields from spent coffee grounds are also discussed. PMID:28496974

Synthesis and characterization of ionic polymer networks in a room-temperature ionic liquid.

PubMed

Stanzione, Joseph F; Jensen, Robert E; Costanzo, Philip J; Palmese, Giuseppe R

2012-11-01

Ionic liquid gels (ILGs) for potential use in ion transport and separation applications were generated via a free radical copolymerization of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and N,N'-methylene(bis)acrylamide (MBA) using 1-ethyl-3-methylimidazolium ethylsulfate (IL) as a room temperature ionic liquid solvent medium. The AMPS and MBA monomer solubility window in the IL in the temperature range of 25 to 65 °C was determined. In situ ATR-FTIR showed near complete conversion of monomers to a cross-linked polymer network. ILGs with glass transition temperatures (T(g)s) near -50 °C were generated with T(g) decreasing with increasing IL content. The elastic moduli in compression (200 to 6600 kPa) decreased with increasing IL content and increasing AMPS content while the conductivities (0.35 to 2.14 mS cm⁻¹) increased with increasing IL content and decreasing MBA content. The polymer-IL interaction parameter (χ) (0.48 to 0.55) was determined via a modified version of the Bray and Merrill equation.

Preparation and characterization of nonaqueous proton-conducting membranes with protic ionic liquids.

PubMed

Lu, Fei; Gao, Xinpei; Yan, Xiaojun; Gao, Hejun; Shi, Lijuan; Jia, Han; Zheng, Liqiang

2013-08-14

Hybrid Nafion membranes were successfully fabricated by incorporating with protic imidazolium ionic liquids 1-(2-aminoethyl)-3-methylimidazolium chloride ([MimAE]Cl), 1-(2-hydroxylethyl)-3-methylimidazolium chloride ([MimHE]Cl), and 1-carboxylmethyl-3-methylimidazolium chloride ([MimCM]Cl) for high-temperature fuel cells. The composite membranes were characterized by impedance spectroscopy, small-angle X-ray scattering (SAXS), scanning electronic microscopy (SEM), and thermogravimetric analysis (TGA). The incorporated protic ionic liquids enhance the doping of phosphoric acid (PA) and result in a relatively high ionic conductivity. The Nafion/10 wt % [MimAE]Cl/PA composite membrane exhibits an ionic conductivity of 6.0 mS/cm at 130 °C without humidification. [MimAE]Cl can swell the Nafion matrix more homogeneously than [MimHE]Cl or [MimCM]Cl, which results in a better ionic conductivity. It is notable that the composite Nafion/IL/PA membranes have a better thermal stability than the pristine Nafion membranes.

Synthesis, Characterization and Application of 1-Butyl-3 Methylimidazolium Chloride as Green Material for Extractive Desulfurization of Liquid Fuel

PubMed Central

Dharaskar, Swapnil A.; Varma, Mahesh N.; Shende, Diwakar Z.; Yoo, Chang Kyoo; Wasewar, Kailas L.

2013-01-01

The possible application of imidazolium ionic liquids as energy-efficient green material for extractive deep desulfurization of liquid fuel has been investigated. 1-Butyl-3-methylimidazolium chloride [BMIM]Cl was synthesized by nucleophilic substitution reaction of n-methylimidazolium and 1-chlorobutane. Molecular structures of the ILs were confirmed by FTIR, 1H-NMR, and 13C-NMR. The thermal properties, conductivity, solubility, water content and viscosity analysis of [BMIM]Cl were carried out. The effects of reaction time, reaction temperature, sulfur compounds, and recycling of IL without regeneration on dibenzothiophene removal of liquid fuel were presented. In the extractive desulfurization process, the removal of dibenzothiophene in n-dodecane using [BMIM]Cl was 81% with mass ratio of 1 : 1, in 30 min at 30°C under the mild reaction conditions. Also, desulfurization of real fuels with IL and multistage extraction were studied. The results of this work might offer significant insights in the perceptive use of imidazoled ILs as energy-efficient green material for extractive deep desulfurization of liquid fuels as it can be reused without regeneration with considerable extraction efficiency. PMID:24307868

Femtosecond Raman-Induced Kerr Effect Study of Temperature-Dependent Intermolecular Dynamics in Imidazolium-Based Ionic Liquids: Effects of Anion Species and Cation Alkyl Groups.

PubMed

Kakinuma, Shohei; Ishida, Tateki; Shirota, Hideaki

2017-01-12

The temperature dependence of the intermolecular vibrational dynamics in imidazolium-based ionic liquids (ILs) with 10 different anions was studied by femtosecond Raman-induced Kerr effect spectroscopy. For all ILs investigated in this study, the intensity in the low-frequency region below 50 cm -1 increases, and the spectral density in the high-frequency region above 80 cm -1 decreases (and shows a redshift) with increasing temperature. The first phenomenon would be attributed to the activation of the translational vibrational motions, whereas the second one is ascribed to the slowing librational motion of the imidazolium ring with increasing temperature. Calculated spectra of the density of states for the intermolecular vibrations of 1-butyl-3-methylimidazolium hexafluorophosphate, which is one of the experiment samples studied here, obtained by molecular dynamics simulation agreed well with the experimental results and confirmed the spectral assignments. When we compared the difference spectra between spectra measured at various temperatures and the spectrum measured at 293 K, a clear difference was found in the ∼50 cm -1 region of the Kerr spectra of 1-butyl-3-methylimidazolium thiocyanate and 1-butyl-3-methylimidazolium dicyanamide from those of the other ILs. The difference might have originated from the librational motions of the corresponding anions. We also compared the temperature-dependent Kerr spectra of hexafluorophosphate salts of 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, and 1-heptyl-3-methylimidazolium cations. These ILs showed a similar temperature dependence, which was not affected by the alkyl group length. The temperature-dependent viscosities and glass transition temperatures of the ILs were also estimated to determine their fragilities.

Tracking Ionic Rearrangements and Interpreting Dynamic Volumetric Changes in Two-Dimensional Metal Carbide Supercapacitors: A Molecular Dynamics Simulation Study.

PubMed

Xu, Kui; Lin, Zifeng; Merlet, Céline; Taberna, Pierre-Louis; Miao, Ling; Jiang, Jianjun; Simon, Patrice

2017-12-06

We present a molecular dynamics simulation study achieved on two-dimensional (2D) Ti 3 C 2 T x MXenes in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM] + [TFSI] - ) electrolyte. Our simulations reproduce the different patterns of volumetric change observed experimentally for both the negative and positive electrodes. The analysis of ionic fluxes and structure rearrangements in the 2D material provide an atomic scale insight into the charge and discharge processes in the layer pore and confirm the existence of two different charge-storage mechanisms at the negative and positive electrodes. The ionic number variation and the structure rearrangement contribute to the dynamic volumetric changes of both electrodes: negative electrode expansion and positive electrode contraction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Suitability of 1-hexyl-3-methylimidazolium ionic liquids for the analysis of pharmaceutical formulations containing tricyclic antidepressants.

PubMed

Calabuig-Hernández, S; Peris-García, E; García-Alvarez-Coque, M C; Ruiz-Angel, M J

2018-07-20

The reversed-phase chromatographic behaviour of six tricyclic antidepressants (amitryptiline, clomipramine, doxepin, imipramine, nortryptiline and maprotiline) was examined in this work with acetonitrile-water mobile phases, in the absence and presence of the ionic liquids 1-hexyl-3-methylimidazolium chloride and 1-hexyl-3-methylimidazolium tetrafluoroborate, which have interesting features for the separation of basic compounds, in terms of peak shape combined with reduced retention. Tricyclic antidepressants are low polarity drugs that strongly associate to the alkyl chains of conventional stationary phases. They are also positively charged in the usual working pH range (2-8) in reversed-phase liquid chromatography, due to their strong basic character. In consequence, they may interact with the residual ionised silanols present in conventional silica-based stationary phases, which is translated in stronger retention, and tailed and broad peaks. A simple chromatographic procedure for the control of tricyclic antidepressants in pharmaceutical formulations was developed using a C8 column and a mobile phase containing 30% acetonitrile/10 mM 1-hexyl-3-methylimidazolium chloride at pH 3, with UV detection. Intra- and inter-day precisions were usually below +1.0%, and intra- and inter-day bias (trueness) ranged between ‒2.1% and +2.4%, and between ‒3.0% and +2.3%, respectively. Sample preparation was simple and only required solubilisation and filtration previous to injection. Copyright © 2017 Elsevier B.V. All rights reserved.

Study of the Imidazolium-Based Ionic Liquid - ag Electrified Interface on the CO_{2} Electroreduction by Sum Frequency Spectroscopy.

NASA Astrophysics Data System (ADS)

Garcia Rey, Natalia; Dlott, Dana

2017-06-01

Imidazolium based ionic liquids (ILs) have been used as a promising system to improve the CO_{2} electroreduction at lower overpotential than other organic or aqueous electrolytes^{1}. Although the detailed mechanism of the CO_{2} electroreduction on Ag has not been elucidated yet, we have developed a methodology to study the electrified interface during the CO_{2} electroreduction using sum frequency generation (SFG) spectroscopy in combination with cyclic voltammetry^{2}. In this work, we tuned the composition of imidazolium-based ILs by exchanging the anion or the functional groups of the imidazolium. We use the nonresonant SFG (NR-SFG) to study the IL-Ag interface and resonant SFG (RES-SFG) to identify the CO adsorbed on the electrode and monitor the Stark shift as a function of cell potential. In previous studies on CO_{2} electroreduction in the IL: 1-ethyl-3-methylimidazolium tetrafluorborate (EMIM-BF_{4}) on Ag, we showed three events occurred at the same potential (-1.33 V vs. Ag/AgCl): the current associated with CO_{2} electroreduction increased, the Stark shift of the adsorbed atop CO doubled in magnitude and the EMIM-BF_{4} underwent a structural transition^{3}. In addition, we also observed how the structural transition of the EMIM-BF_{4} electrolyte shift to lower potentials when the IL is mixed with water. It is known that water enhances the CO_{2} electroreduction producing more CO^{4}. Moreover, the CO is adsorbed in multi-bonded and in atop sites when more water is present in the electrolyte. ^{1}Lau, G. P. S.; Schreier, M.; Vasilyev, D.; Scopelliti, R.; Grätzel, M.; Dyson, P. J., New Insights into the Role of Imidazolium-Based Promoters for the Electroreduction of CO_{2} on a Silver Electrode. J. Am. Chem. Soc. 2016, 138, 7820-7823. ^{2}Garcia Rey, N.; Dlott, D. D., Studies of Electrochemical Interfaces by Broadband Sum Frequency Generation. J. Electroanal. Chem. 2016. DOI:10.1016/j.jelechem.2016.12.023. ^{3}Garcia Rey, N.; Dlott, D. D., Structural Transition in an Ionic Liquid Controls CO_{2} Electrochemical Reduction. J. Phys. Chem. C 2015, 119, 20892-20899. ^{4}Rosen, B. A.; Zhu, W.; Kaul, G.; Salehi-Khojin, A.; Masel, R. I., Water Enhancement of CO_{2} Conversion on Silver in 1-Ethyl-3-Methylimidazolium Tetrafluoroborate. J. Electrochem. Soc. 2013, 160, H138-H141.

Low-temperature heat capacities of 1-alkyl-3-methylimidazolium bis(oxalato)borate ionic liquids and the influence of anion structural characteristics on thermodynamic properties.

PubMed

Yang, Miao; Zhao, Jun-Ning; Liu, Qing-Shan; Sun, Li-Xian; Yan, Pei-Fang; Tan, Zhi-Cheng; Welz-Biermann, Urs

2011-01-07

Two chelated orthoborate ionic liquids (ILs), 1-butyl-3-methylimidazolium bis(oxalato)borate ([Bmim][BOB]) and 1-hexyl-3-methylimidazolium bis(oxalato)borate ([Hmim][BOB]), were prepared and characterized. Their thermodynamic properties were studied using adiabatic calorimetry and differential scanning calorimetry (DSC). The thermodynamic properties of the two ILs were evaluated and compared with each other, and then with those of other [Bmim] type ILs. The results clearly indicate that for a given cation (or anion) and at a certain temperature, the more atoms in the anion (or cation), the higher the heat capacity; the higher glass-transition temperatures of [BOB] type ILs than others are mainly caused by the higher symmetry of the orthoborate anion structure. It is suggested that a high content of strong electronegative atoms and C(n) or C(nv) (n = 1,2,3,…,∞) point group symmetry in the anion are favorable for the design and synthesis of room temperature ILs with a wide liquid range.

Nitrogen and sulfur co-doped porous graphene aerogel as an efficient electrode material for high performance supercapacitor in ionic liquid electrolyte

NASA Astrophysics Data System (ADS)

Chen, Yujuan; Liu, Zhaoen; Sun, Li; Lu, Zhiwei; Zhuo, Kelei

2018-06-01

Nitrogen and sulfur co-doped graphene aerogel (NS-GA) is prepared by one-pot process. The as-prepared materials are investigated as supercapacitors electrodes in an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, EMIMBF4) electrolyte. The NS-GA is characterized using X-ray diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy scanning electron microscopy. The results show that the NS-GA has hierarchical porous structure. Electrochemical performance is investigated by cycle voltammetry and galvanostatic charge-discharge. Notably, the supercapacitor based on the NS-GA-5 possesses a maximum energy density of 100.7 Wh kg-1 at power density of 0.94 kW kg-1. The electrode materials also offer a large specific capacitance of 203.2 F g-1 at a current density of 1 A g-1 and the capacitance retention of NS-GA-5 is 90% after 3000 cycles at a scan rate of 2 A g-1. The NS-GA-5 with numerous advantages including low cost and remarkable electrochemical behaviors can be a promising electrode material for the application of supercapacitors.

Polyurethane-Based Ionogels Exhibiting Durable Thermoresponsive Optical Behavior Under High-Temperature Conditions.

PubMed

Sato, Tomoya; England, Matt W; Wang, Liming; Urata, Chihiro; Kakiuchida, Hiroshi; Hozumi, Atsushi

2018-01-01

Polyurethane (PU)-based transparent and flexible ionogels, showing unusual thermo-responsive optical properties, were successfully prepared by mixing PU-precursor and a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM-TFSI). Although the initial ionogels were transparent at room temperature, significant increases in opacity were observed with increasing temperature up to 120°C, because of macroscopic phase separation of the PU-matrix and hydrophobic EMIM-TFSI. In addition, the optical transition temperature could be arbitrarily controlled simply by varying the mixing ratio of EMIM-TFSI within the PU-matrix. As confirmed by UV-Vis spectra acquired at different temperatures, this thermo-responsive optical behavior was found to be reversible, repeatable and durable even after 30 cycles of a thermal-stress testing between 30 and 100°C.

Short time ionic liquids pretreatment on lignocellulosic biomass to enhance enzymatic saccharification.

PubMed

Uju; Shoda, Yasuhiro; Nakamoto, Aya; Goto, Masahiro; Tokuhara, Wataru; Noritake, Yoshiyuki; Katahira, Satoshi; Ishida, Nobuhiro; Nakashima, Kazunori; Ogino, Chiaki; Kamiya, Noriho

2012-01-01

The potential of 1-buthyl-3-methylpyridinium chloride, [Bmpy][Cl], as a pretreatment solvent for lignocellulosic biomasses, Bagasse and Eucalyptus, was investigated. The yields of regenerated biomasses ranged between 35% and 96%, and varied according to the pretreatment time, type of ionic liquid (IL) and biomass. The pretreatment of the biomass with [Bmpy][Cl] resulted in up to 8-fold increase in the cellulose conversion when compared with the untreated biomass. For a short pretreatment period (i.e., 10 min), [Bmpy][Cl] showed better performance than 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) with respect to the initial enzymatic saccharification rates. The increase in the reaction rates with [Emim][OAc] treatment was because of a reduction in the cellulose crystallinity. In contrast, a decrease in the crystallinity index was not clearly observed for the biomass pretreated with [Bmpy][Cl], and the enhancement of the enzymatic saccharification rates using this IL is presumably due to a reduction in the degree of polymerization of cellulose in the biomass. Copyright © 2011. Published by Elsevier Ltd.

Adsorption of gentian violet dyes in aqueous solution on microporous AlPOs molecular sieves synthesized by ionothermal method

NASA Astrophysics Data System (ADS)

Fortas, W.; Djelad, A.; Hasnaoui, M. A.; Sassi, M.; Bengueddach, A.

2018-02-01

In this work, AlPO-34, like-chabazite (CHA) zeolite, was ionothermally prepared using the ionic liquid (IL), 1-ethyl-3-methylimidazolium chloride [EMIMCl], as solvent. The solids obtained were characterized by x-ray powder diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FTIR), thermal analysis (TG) and nitrogen adsorption/desorption at 77.3 K. The results show that the ionic liquid is occluded in the AlPO-34 framework and consequently it acts also as a structure-directing agent. The variation of chemical composition led to AlPO-34 materials with different crystal sizes and morphologies. The well crystallized AlPO-34 material was used as adsorbent for Crystal Violet (CV) dye removal from aqueous solutions. The effect of adsorption parameters such as pH and initial concentration were investigated. It was found that adsorption dyes is favorable at pH = 6. The adsorption isotherm data follow the Langmuir equation in which parameters are calculated. The selected AlPO-34 sample exhibited a high crystal violet dye removal of 46.08 mg g-1 at pH = 6.

Adsorption of malachite green from aqueous solution by using novel chitosan ionic liquid beads.

PubMed

Naseeruteen, Faizah; Hamid, Nur Shahirah Abdul; Suah, Faiz Bukhari Mohd; Ngah, Wan Saime Wan; Mehamod, Faizatul Shimal

2018-02-01

Chitosan ionic liquid beads were prepared from chitosan and 1-butyl-3-methylimidazolium based ionic liquids to remove Malachite Green (MG) from aqueous solutions. Batch adsorption experiments were carried out as a function of initial pH, adsorbent dosage, agitation time and initial MG concentration. The optimum conditions were obtained at pH 4.0, 0.008g of adsorbent dosage and 20min of agitation time were utilized in the kinetic and isotherm studies. Three kinetic models were applied to analyze the kinetic data and pseudo-second order was found to be the best fitted model with R 2 >0.999. In order to determine the adsorption capacity, the sorption data were analyzed using the linear form of Langmuir, Freundlich and Temkin equations. The isotherm was best fitted by Langmuir isotherm model. The maximum adsorption capacity (q max ) obtained from Langmuir isotherm for two chitosan beads 1-butyl-3-methylimidazolium acetate A and 1-butyl-3-methylimidazolium B are 8.07mgg -1 and 0.24mgg -1 respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

Engineering ionic liquid-tolerant cellulases for biofuels production.

PubMed

Wolski, Paul W; Dana, Craig M; Clark, Douglas S; Blanch, Harvey W

2016-04-01

Dissolution of lignocellulosic biomass in certain ionic liquids (ILs) can provide an effective pretreatment prior to enzymatic saccharification of cellulose for biofuels production. Toward the goal of combining pretreatment and enzymatic hydrolysis, we evolved enzyme variants of Talaromyces emersonii Cel7A to be more active and stable than wild-type T. emersonii Cel7A or Trichoderma reesei Cel7A in aqueous-IL solutions (up to 43% (w/w) 1,3-dimethylimdazolium dimethylphosphate and 20% (w/w) 1-ethyl-3-methylimidazolium acetate). In general, greater enzyme stability in buffer at elevated temperature corresponded to greater stability in aqueous-ILs. Post-translational modification of the N-terminal glutamine residue to pyroglutamate via glutaminyl cyclase enhanced the stability of T. emersonii Cel7A and variants. Differential scanning calorimetry revealed an increase in melting temperature of 1.9-3.9°C for the variant 1M10 over the wild-type T. emersonii Cel7A in aqueous buffer and in an IL-aqueous mixture. We observed this increase both with and without glutaminyl cyclase treatment of the enzymes. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

High-Performance Aluminum-Ion Battery with CuS@C Microsphere Composite Cathode.

PubMed

Wang, Shuai; Jiao, Shuqiang; Wang, Junxiang; Chen, Hao-Sen; Tian, Donghua; Lei, Haiping; Fang, Dai-Ning

2017-01-24

On the basis of low-cost, rich resources, and safety performance, aluminum-ion batteries have been regarded as a promising candidate for next-generation energy storage batteries in large-scale energy applications. A rechargeable aluminum-ion battery has been fabricated based on a 3D hierarchical copper sulfide (CuS) microsphere composed of nanoflakes as cathode material and room-temperature ionic liquid containing AlCl 3 and 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) as electrolyte. The aluminum-ion battery with a microsphere electrode exhibits a high average discharge voltage of ∼1.0 V vs Al/AlCl 4 - , reversible specific capacity of about 90 mA h g -1 at 20 mA g -1 , and good cyclability of nearly 100% Coulombic efficiency after 100 cycles. Such remarkable electrochemical performance is attributed to the well-defined nanostructure of the cathode material facilitating the electron and ion transfer, especially for chloroaluminate ions with large size, which is desirable for aluminum-ion battery applications.

The physicochemical properties of the low-temperature ionic liquid silver bromide-1-butyl-3-methylimidazolium bromide

NASA Astrophysics Data System (ADS)

Grishina, E. P.; Ramenskaya, L. M.; Pimenova, A. M.

2009-11-01

The physicochemical properties of the low-temperature ionic liquid based on 1-butyl-3-methylimidazolium bromide (BMImBr) and silver bromide were studied. Differential scanning calorimetry, Fourier transform IR spectroscopy, densimetry, viscometry, and conductometry measurements were performed to determine the dependences of the parameters under study on the concentration of AgBr. It was shown that the temperature and concentration behavior of the physicochemical properties of BMImBr-AgBr melts characterized the interaction between the system components with the formation of complex particles.

Iron species determination by task-specific ionic liquid-based in situ solvent formation dispersive liquid-liquid microextraction combined with flame atomic absorption spectrometry.

PubMed

Sadeghi, Susan; Ashoori, Vahid

2017-10-01

The task-specific ionic liquid (TSIL) of 1-ethyl-3-methylimidazolium bromide functionalized with 8-hydroxyquinoline was used as a chelating agent and extracting solvent for dispersive liquid-liquid microextraction and subsequent determination of Fe(III) by flame atomic absorption spectrometry. The in situ solvent formation of TSIL using KPF 6 provided the desired water-immiscible ionic liquid. The total Fe concentration could be determined after pre-oxidation of Fe(II) to Fe(III). Various factors affecting the proposed extraction procedure were optimized. The proposed analytical conditions were: sample pH 5, TSIL amount 0.3% (w/v), KPF 6 amount 0.15% (w/v), anti-sticking 0.1% (w/v) and salt concentration 5% (w/v). Under optimal conditions, the linear dynamic ranges for Fe(III) and total Fe were 20-80 and 20-110 ng mL -1 , respectively, with a detection limit of 6.9 ng mL -1 for Fe(III) and relative standard deviation of 2.2%. The proposed method was successfully applied to the determination of trace Fe(III) in water (underground, tap, refined water and artificial sea water) and beverage (apple, tomato, and tea) samples. The developed method offers advantages such as simplicity, ease of operation, and extraction of Fe(III) from aqueous solutions without the use of organic solvent. It was successfully applied for iron speciation in different real samples. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

How Does the Addition of a Third Ion Affect the Molecular Interactions and the Thermodynamic Properties of Acetate-Based Ionic Liquids?

PubMed

Otero, I; Lepre, L F; Dequidt, A; Husson, P; Costa Gomes, M F

2017-10-19

The effect of the addition of a third ion to the ionic liquid 1-butyl-3-methylimidazolium acetate [C 4 C 1 Im][OAc] was studied through the measurement of the enthalpy of mixing and of the excess molar volume of its mixtures with 1-butyl-3-methylimidazolium trifluoroacetate [C 4 C 1 Im][CF 3 CO 2 ], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C 4 C 1 Im][NTf 2 ], and tetrabutylphosphonium acetate [P 4444 ][OAc]. Negative enthalpies of mixing (Δ mix H < 0) and positive excess molar volumes (V E > 0) were observed in all cases. The infrared and NMR studies of the pure ionic liquids and their mixtures show that the presence of a third ion with a weaker affinity with the common counterion contributes to prevailing the more favorable hydrogen-bond, herein always between the imidazolium cation and the acetate anion. Both radial and spatial distribution functions calculated by molecular simulation confirm this behavior. The remarkable enhancement of the viscosities of the [C 4 C 1 Im][OAc] + [P 4444 ][OAc] mixtures could be discussed in light of the calculated friction coefficients.

Hypostatic instability of aluminum anode in acidic ionic liquid for aluminum-ion battery.

PubMed

Lee, Danbi; Lee, Gibaek; Tak, Yongsug

2018-06-19

Aluminum-ion batteries are considered to be a promising post lithium-ion battery system in energy storage devices because aluminum is earth-abundant, has a high theoretical capacity, and is of low cost. We report on the chemical activities and stabilities of chloroaluminate anions [Al n Cl n+1 ] - with aluminum metal using a different mole ratio of AlCl 3 and 1-ethyl-3-methylimidazolium chloride. The morphological changes in the Al metal surface are investigated as a function of dipping time in electrolyte, revealing that the Al metal surface is locally attacked by chloroaluminate anions followed by the formation of a new Al oxide layer with a specific lattice plane and a craterlike surface around the cracking site. The aluminum-ion battery exhibits outstanding cycle life and capacity even at the high C-rate of 3 A g -1 , with a high energy efficiency of 98%, regardless of the differences in the size of chloroaluminate anions.

Dissolution of cellulose in ionic liquid: A review

NASA Astrophysics Data System (ADS)

Mohd, N.; Draman, S. F. S.; Salleh, M. S. N.; Yusof, N. B.

2017-02-01

Dissolution of cellulose with ionic liquids (IL) and deep eutectic solvent (DES) lets the comprehensive dissolution of cellulose. Basically, cellulose can be dissolved, in some hydrophilic ionic liquids, such as 1-butyl-3-methylimidazolium chloride (BMIMCl) and 1-allyl-3-methylimidazolium chloride (AMIMCl). Chloride based ionic liquids are suitable solvents for cellulose dissolution. Although the ILs is very useful in fine chemical industry, its application in the pharmaceutical and food industry have been very limited due to issues with toxicity, purity, and high cost. Seeing to these limitations, new green alternative solvent which is DES was used. This green solvents, may be definitely treated as the next-generation reagents for more sustainable industrial development. Thus, this review aims to discuss the dissolution of cellulose either with ionic liquids or DES and its application.

Multi-scale processes of beech wood disintegration and pretreatment with 1-ethyl-3-methylimidazolium acetate/water mixtures.

PubMed

Viell, Jörn; Inouye, Hideyo; Szekely, Noemi K; Frielinghaus, Henrich; Marks, Caroline; Wang, Yumei; Anders, Nico; Spiess, Antje C; Makowski, Lee

2016-01-01

The valorization of biomass for chemicals and fuels requires efficient pretreatment. One effective strategy involves the pretreatment with ionic liquids which enables enzymatic saccharification of wood within a few hours under mild conditions. This pretreatment strategy is, however, limited by water and the ionic liquids are rather expensive. The scarce understanding of the involved effects, however, challenges the design of alternative pretreatment concepts. This work investigates the multi length-scale effects of pretreatment of wood in 1-ethyl-3-methylimidazolium acetate (EMIMAc) in mixtures with water using spectroscopy, X-ray and neutron scattering. The structure of beech wood is disintegrated in EMIMAc/water mixtures with a water content up to 8.6 wt%. Above 10.7 wt%, the pretreated wood is not disintegrated, but still much better digested enzymatically compared to native wood. In both regimes, component analysis of the solid after pretreatment shows an extraction of few percent of lignin and hemicellulose. In concentrated EMIMAc, xylan is extracted more efficiently and lignin is defunctionalized. Corresponding to the disintegration at macroscopic scale, SANS and XRD show isotropy and a loss of crystallinity in the pretreated wood, but without distinct reflections of type II cellulose. Hence, the microfibril assembly is decrystallized into rather amorphous cellulose within the cell wall. The molecular and structural changes elucidate the processes of wood pretreatment in EMIMAc/water mixtures. In the aqueous regime with >10.7 wt% water in EMIMAc, xyloglucan and lignin moieties are extracted, which leads to coalescence of fibrillary cellulose structures. Dilute EMIMAc/water mixtures thus resemble established aqueous pretreatment concepts. In concentrated EMIMAc, the swelling due to decrystallinization of cellulose, dissolution of cross-linking xylan, and defunctionalization of lignin releases the mechanical stress to result in macroscopic disintegration of cells. The remaining cell wall constituents of lignin and hemicellulose, however, limit a recrystallization of the solvated cellulose. These pretreatment mechanisms are beyond common pretreatment concepts and pave the way for a formulation of mechanistic requirements of pretreatment with simpler pretreatment liquors.

Sensitive, label-free protein assay using 1-ethyl-3-methylimidazolium tetrafluoroborate-supported microchip electrophoresis with laser-induced fluorescence detection.

PubMed

Xu, Yuanhong; Li, Jing; Wang, Erkang

2008-05-01

Based on the dimer-monomer equilibrium movement of the fluorescent dye Pyronin Y (PY), a rapid, simple, highly sensitive, label-free method for protein detection was developed by microchip electrophoresis with LIF detection. PY formed a nonfluorescent dimer induced by the premicellar aggregation of an anionic surfactant, SDS, however, the fluorescence intensity of the system increased dramatically when proteins such as BSA, bovine hemoglobin, cytochrome c, and trypsin were added to the solution due to the transition of dimer to fluorescent monomer. Furthermore, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) instead of PBS was applied as running buffers in microchip electrophoresis. Due to the excellent properties of EMImBF4, not only nonspecific protein adsorption was more efficiently suppressed, but also approximately ten-fold higher fluorescence intensity enhancement was obtained than that using PBS. Under the optimal conditions, detection limits for BSA, bovine hemoglobin, cytochrome c, and trypsin were 1.00x10(-6), 2x10(-6), 7x10(-7), and 5x10(-7) mg/mL, respectively. Thus, without covalent modification of the protein, a protein assay method with high sensitivity was achieved on microchips.

Comparison of physical properties of regenerated cellulose films fabricated with different cellulose feedstocks in ionic liquid.

PubMed

Pang, JinHui; Wu, Miao; Zhang, QiaoHui; Tan, Xin; Xu, Feng; Zhang, XueMing; Sun, RunCang

2015-05-05

With the serious "white pollution" resulted from the non-biodegradable plastic films, considerable attention has been directed toward the development of renewable and biodegradable cellulose-based film materials as substitutes of petroleum-derived materials. In this study, environmentally friendly cellulose films were successfully prepared using different celluloses (pine, cotton, bamboo, MCC) as raw materials and ionic liquid 1-ethyl-3-methylimidazolium acetate as a solvent. The SEM and AFM indicated that all cellulose films displayed a homogeneous and smooth surface. In addition, the FT-IR and XRD analysis showed the transition from cellulose I to II was occurred after the dissolution and regeneration process. Furthermore, the cellulose films prepared by cotton linters and pine possessed the most excellent thermal stability and mechanical properties, which were suggested by the highest onset temperature (285°C) and tensile stress (120 MPa), respectively. Their excellent properties of regenerated cellulose films are promising for applications in food packaging and medical materials. Copyright © 2014 Elsevier Ltd. All rights reserved.

Anomalous piezoelectric properties of poly(vinylidene fluoride-trifluoroethylene)/ionic liquid gels

NASA Astrophysics Data System (ADS)

Fukagawa, Miki; Koshiba, Yasuko; Fukushima, Tatsuya; Morimoto, Masahiro; Ishida, Kenji

2018-04-01

Piezoelectric gels were prepared from low-volatile ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][TFSI]) gels, and their structural, ferroelectric, and piezoelectric properties were investigated. Poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE)/IL gels were formed using thermally reversible physical gels. The structural characterization indicated that the P(VDF-TrFE) molecules in the gels predominantly formed a ferroelectric phase (Form I) of P(VDF-TrFE). Polarization switching peaks were clearly observed using a three-layer stacked device structure. The coercive field of the P(VDF-TrFE)/IL gels substantially decreased to 4-9 MV/m, and their remnant polarizations were maintained at 63-71 mC/m2, which is similar to that for typical solid-state P(VDF-TrFE). Finally, the P(VDF-TrFE)/IL gel films exhibited a piezoelectric response, and the highest piezoelectric coefficient was ˜300 pm/V at an applied voltage frequency of 4 kHz.

Synthesis and Characterisation of ETS-10/Acetate-based Ionic Liquid/Chitosan Mixed Matrix Membranes for CO2/N2 Permeation.

PubMed

Casado-Coterillo, Clara; Del Mar López-Guerrero, María; Irabien, Angel

2014-06-19

Mixed matrix membranes (MMMs) were prepared by incorporating organic surfactant-free hydrothermally synthesised ETS-10 and 1-ethyl-3-methylimidazolium acetate ionic liquid (IL) to chitosan (CS) polymer matrix. The membrane material characteristics and permselectivity performance of the two-component membranes were compared with the three-component membrane and the pure CS membrane. The addition of IL increased CO2 solubility of the polymer, and, thus, the CO2 affinity was maintained for the MMMs, which can be correlated with the crystallinity, measured by FT-IR, and void fraction calculations from differences between theoretical and experimental densities. The mechanical resistance was enhanced by the ETS-10 nanoparticles, and flexibility decreased in the two-component ETS-10/CS MMMs, but the flexibility imparted by the IL remained in three-component ETS-10/IL/CS MMMs. The results of this work provide insight into another way of facing the adhesion challenge in MMMs and obtain CO2 selective MMMs from renewable or green chemistry materials.

Cellulose amorphization by swelling in ionic liquid/water mixtures: a combined macroscopic and second-harmonic microscopy study.

PubMed

Glas, Daan; Paesen, Rik; Depuydt, Daphne; Binnemans, Koen; Ameloot, Marcel; De Vos, Dirk E; Ameloot, Rob

2015-01-01

Amorphization of cellulose by swelling in ionic liquid (IL)/water mixtures at room temperature is a suitable alternative to the dissolution-precipitation pretreatment known to facilitate enzymatic digestion. When soaking microcrystalline cellulose in the IL 1-ethyl-3-methylimidazolium acetate containing 20 wt % water, the crystallinity of the cellulose sample is strongly reduced. As less than 4 % of the cellulose dissolves in this mixture, this swelling method makes a precipitation step and subsequent energy-intensive IL purification redundant. Second-harmonic generation (SHG) microscopy is used as a structure-sensitive technique for in situ monitoring of the changes in cellulose crystallinity. Combined optical and SHG observations confirm that in the pure IL complete dissolution takes place, while swelling without dissolution in the optimal IL/water mixture yields a solid cellulose with a significantly reduced crystallinity in a single step. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Immobilization induced molecular compression of ionic liquid in ordered mesoporous matrix

NASA Astrophysics Data System (ADS)

Tripathi, Alok Kumar; Singh, Rajendra Kumar

2018-02-01

In this work, ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide ([EMIM][FSI]) has been immobilized into ordered mesoporous silica MCM-41 by a physical imbibition process. Transmission electron microscopy confirms the filling of mesopores of MCM-41. The effect of IL content in MCM-41 was probed in terms of thermal stability, chemical interactions, and dielectric properties. N2-sorption results indicate the compression of the IL in the nanopores of MCM-41, which contributes to an increase of the melting point probed by differential scanning calorimetry. The quantum chemical calculations confirmed that the ion-ion interaction in ion-pairs of IL were preferred over the hydrogen bonding interaction in the presence of SiO2 molecules, and these interactions probably compress the molecular size in the nanopores of MCM-41. Strong interactions between IL and porous MCM-41 were suggested as the mechanism of this immobilization, which was characterized by FTIR and dielectric spectroscopy.

Structural Effects of Gating Poly(3-hexylthiophene) through an Ionic Liquid

DOE PAGES

Guardado, Jesus O.; Salleo, Alberto

2017-07-17

Ionic liquids are increasingly employed as dielectrics to generate high charge densities and enable low-voltage operation with organic semiconductors. But, effects on structure and morphology of the active material are not fully known, particularly for permeable semiconductors such as conjugated polymers, in which ions from the ionic liquid can enter and electrochemically dope the semicrystalline film. In order to understand when ions enter, where they go, and how they affect the film, thin films of the archetypal semiconducting polymer, poly(3-hexylthiophene), are electrochemically doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, the archetypal ionic liquid. High-resolution, ex situ X-ray diffraction measurements and complete pole figuresmore » reveal changes with applied voltage, cycling, and frequency in lattice spacing, crystallite orientation, and crystallinity in the bulk and at the buried interface. Dopant ions penetrate the film and enter the crystallites at sufficiently high voltages and low frequencies. Upon infiltrating crystallites, ions permanently expand lamellar stacking and contract pi-stacking. Cycling amplifies these effects, but higher frequencies mitigate the expansion of bulk crystallites as ions are hindered from entering crystallites. Furthermore, this mechanistic understanding of the structural effects of ion penetration will help develop models of the frequency and voltage impedance response of electrochemically doped conjugated polymers and advance electronic applications.« less

Structural Effects of Gating Poly(3-hexylthiophene) through an Ionic Liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guardado, Jesus O.; Salleo, Alberto

Ionic liquids are increasingly employed as dielectrics to generate high charge densities and enable low-voltage operation with organic semiconductors. But, effects on structure and morphology of the active material are not fully known, particularly for permeable semiconductors such as conjugated polymers, in which ions from the ionic liquid can enter and electrochemically dope the semicrystalline film. In order to understand when ions enter, where they go, and how they affect the film, thin films of the archetypal semiconducting polymer, poly(3-hexylthiophene), are electrochemically doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, the archetypal ionic liquid. High-resolution, ex situ X-ray diffraction measurements and complete pole figuresmore » reveal changes with applied voltage, cycling, and frequency in lattice spacing, crystallite orientation, and crystallinity in the bulk and at the buried interface. Dopant ions penetrate the film and enter the crystallites at sufficiently high voltages and low frequencies. Upon infiltrating crystallites, ions permanently expand lamellar stacking and contract pi-stacking. Cycling amplifies these effects, but higher frequencies mitigate the expansion of bulk crystallites as ions are hindered from entering crystallites. Furthermore, this mechanistic understanding of the structural effects of ion penetration will help develop models of the frequency and voltage impedance response of electrochemically doped conjugated polymers and advance electronic applications.« less

Charge Density Dependent Hole Mobility and Density of States Throughout the Entire Finite Potential Window of Conductivity in Ionic Liquid Gated Poly(3-hexylthiophene)

NASA Astrophysics Data System (ADS)

Paulsen, Bryan D.; Frisbie, C. Daniel

2012-02-01

Ionic liquids, used in place of traditional gate dielectric materials, allow for the accumulation of very high 2D and 3D charge densities (>10^14 #/cm^2 and >10^21 #/cm^3 respectively) at low voltage (<5 V). Here we study the electrochemical gating of the benchmark semiconducting polymer poly(3-hexylthiophene) (P3HT) with the ionic liquid 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMI][FAP]). The electrochemical stability of [EMI][FAP] allowed the reproducible accumulation of 2 x 10^21 hole/cm^3, or one hole (and stabilizing anion dopant) per every two thiophene rings. A finite potential/charge density window of high electrical conductivity was observed with hole mobility reaching a maximum of 0.86 cm^2/V s at 0.12 holes per thiophene ring. Displacement current measurements, collected versus a calibrated reference electrode, allowed the mapping of the highly structured and extremely broad density of states of the P3HT/[EMI][FAP] doped composite. Variable temperature and charge density hole transport measurements revealed hole transport to be thermally activated and non-monotonic, displaying a activation energy minimum of ˜20 meV in the region of maximum conductivity and hole mobility. To show the generality of this result, the study was extended to an additional four ionic liquids and three semiconducting polymers.

Do TFSA anions slither? Pressure exposes the role of TFSA conformational exchange in self-diffusion

DOE PAGES

Suarez, Sophia N.; Wishart, James F.; Rua, Armando; ...

2015-10-28

Multi-nuclear ( 1H, 2H, and 19F) magnetic resonance spectroscopy techniques as functions of temperature and pressure were applied to the study of selectively deuterated 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMIM TFSA) ionic liquid isotopologues and related ionic liquids. For EMIM TFSA, temperature-dependent 2H T 1 data indicate stronger electric field gradients in the alkyl chain region compared to the imidazolium ring. Most significantly, the pressure dependences of the EMIM and TFSA self-diffusion coefficients revealed that the displacements of the cations and anions are independent, with diffusion of the TFSA anions being slowed much more by increasing pressure than for the EMIM cations, asmore » shown by their respective activation volumes (28.8 ± 2.5 cm³/mol for TFSA vs. 14.6 ± 1.3 cm³/mol for EMIM). Increasing pressure may lower the mobility of the TFSA anion by hindering its interconversion between trans and cis conformers, a process that is coupled to diffusion according to published molecular dynamics simulations. Measured activation volumes (ΔV ‡) for ion self-diffusion in EMIM bis(fluoromethylsulfonyl)amide and EMIM tetrafluoroborate support this hypothesis.« less

Do TFSA anions slither? Pressure exposes the role of TFSA conformational exchange in self-diffusion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suarez, Sophia N.; Wishart, James F.; Rua, Armando

Multi-nuclear ( 1H, 2H, and 19F) magnetic resonance spectroscopy techniques as functions of temperature and pressure were applied to the study of selectively deuterated 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMIM TFSA) ionic liquid isotopologues and related ionic liquids. For EMIM TFSA, temperature-dependent 2H T 1 data indicate stronger electric field gradients in the alkyl chain region compared to the imidazolium ring. Most significantly, the pressure dependences of the EMIM and TFSA self-diffusion coefficients revealed that the displacements of the cations and anions are independent, with diffusion of the TFSA anions being slowed much more by increasing pressure than for the EMIM cations, asmore » shown by their respective activation volumes (28.8 ± 2.5 cm³/mol for TFSA vs. 14.6 ± 1.3 cm³/mol for EMIM). Increasing pressure may lower the mobility of the TFSA anion by hindering its interconversion between trans and cis conformers, a process that is coupled to diffusion according to published molecular dynamics simulations. Measured activation volumes (ΔV ‡) for ion self-diffusion in EMIM bis(fluoromethylsulfonyl)amide and EMIM tetrafluoroborate support this hypothesis.« less

Temperature Dependence of Low-Frequency Spectra in Molten Bis(trifluoromethylsulfonyl)amide Salts of Imidazolium Cations Studied by Femtosecond Raman-Induced Kerr Effect Spectroscopy.

PubMed

Shirota, Hideaki; Kakinuma, Shohei

2015-07-30

In this study, the temperature dependence of the low-frequency spectra of liquid bis(trifluoromethylsulfonyl)amide salts of the monocations 1-methyl-3-propylimidazolium and 1-hexyl-3-methylimidazolium and the dications 1,6-bis(3-methylimidazolium-1-yl)hexane and 1,12-bis(3-methylimidazolium-1-yl)dodecane has been investigated by means of femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The intensity in the low-frequency region below 20 cm(-1) in the spectra of the four ionic liquids increases with rising temperature. From a line-shape analysis of the broadened low-frequency spectra of the ionic liquids, it is clear that the lowest-frequency component, which peaks at approximately 5 cm(-1), contributes to the temperature dependence of the spectra. This implies that the activity of the intermolecular translational vibrational motion is increasing with rising temperature. It is also possible that decoupling in the crossover process between intermolecular vibrational motion and structural relaxation occurs as a result of a deterioration of the non-Markovian feature or the loss of memory caused by the higher temperature. The peak of the highest-frequency component, which is due mainly to the imidazolium ring libration, shifts to lower frequency with increasing temperature. This is attributed to weaker interactions of the ionic liquids at higher temperatures. Temperature-dependent viscosities from 293 to 353 K of the four ionic liquids have also been characterized.

Fundamental Insights into the Dissolution and Precipitation of Cellulosic Biomass from Ionic Liquid Mixtures

NASA Astrophysics Data System (ADS)

Minnick, David L.

Lignocellulose is the most abundant biopolymer on earth making it a promising feedstock for the production of renewable chemicals and fuels. However, utilization of biomass remains a challenge as recalcitrance of cellulose and hemicellulose hinder separation and conversion of these carbohydrates. For instance, the complex inter- and intra- molecular hydrogen bonding network of cellulose renders it insoluble in nearly all aqueous and organic solvents. Alternatively, select ionic liquids (ILs) dissolve significant quantities. Through an ionic liquid mediated dissolution and precipitation process cellulose crystallinity is significantly reduced consequently enhancing subsequent chemical and biochemical reaction processes. Therefore, understanding the thermodynamics of ionic liquid - cellulose mixtures is imperative to developing an IL based biomass processing system. This dissertation illustrates solid-liquid phase equilibrium results for the dissolution and precipitation of cellulose in various IL/cosolvent, IL/antisolvent, and IL/mixed solvent systems with the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIm][DEP]). Molecular interactions between the ionic liquid, organic solvents, and cellulose are assessed by spectroscopic techniques including Kamlet-Taft solvatochromic analysis, FTIR, and NMR. Additionally, this dissertation discusses how preferential solvation of the IL cation and anion by co- and anti-solvents impact the ability of IL ions to interact with cellulose thus affecting the cellulose dissolution capacity of the various IL-solvent mixtures.

High rate capacitive performance of single-walled carbon nanotube aerogels

DOE PAGES

Van Aken, Katherine L.; Pérez, Carlos R.; Oh, Youngseok; ...

2015-05-30

Single-walled carbon nanotube (SWCNT) aerogels produced by critical-point-drying of wet-gel precursors exhibit unique properties, such as high surface-area-to-volume and strength-to-weight ratios. They are free-standing, are binder-free, and can be scaled to thicknesses of more than 1 mm. In this paper, we examine the electric double layer capacitive behavior of these materials using a common room temperature ionic liquid electrolyte, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI). Electrochemical performance is assessed through galvanostatic cycling, cyclic voltammetry and impedance spectroscopy. Results indicate stable capacitive performance over 10,000 cycles as well as an impressive performance at high charge and discharge rates, due to accessible pore networks andmore » enhanced electronic and ionic conductivities of SWCNT aerogels. Finally, these materials can find applications in mechanically compressible and flexible supercapacitor devices with high power requirements.« less

Electrodeposition of Amorphous Molybdenum Chalcogenides from Ionic Liquids and Their Activity for the Hydrogen Evolution Reaction.

PubMed

Redman, Daniel W; Rose, Michael J; Stevenson, Keith J

2017-09-19

This work reports on the general electrodeposition mechanism of tetrachalcogenmetallates from 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Both tetrathio- and tetraselenomolybdate underwent anodic electrodeposition and cathodic corrosion reactions as determined by UV-vis spectroelectrochemistry. Electrodeposition was carried out by cycling the potential between the anodic and cathodic regimes. This resulted in a film of densely packed nanoparticles of amorphous MoS x or MoSe x as determined by SEM, Raman, and XPS. The films were shown to have high activity for the hydrogen evolution reaction. The onset potential (J = 1 mA/cm 2 ) of the MoS x film was E = -0.208 V vs RHE, and that of MoSe x was E = -0.230 V vs RHE. The Tafel slope of MoS x was 42 mV/decade, and that of MoSe x was 59 mV/decade.

Ionic liquid-based microwave-assisted extraction of flavonoids from Bauhinia championii (Benth.) Benth.

PubMed

Xu, Wei; Chu, Kedan; Li, Huang; Zhang, Yuqin; Zheng, Haiyin; Chen, Ruilan; Chen, Lidian

2012-12-03

An ionic liquids (IL)-based microwave-assisted approach for extraction and determination of flavonoids from Bauhinia championii (Benth.) Benth. was proposed for the first time. Several ILs with different cations and anions and the microwave-assisted extraction (MAE) conditions, including sample particle size, extraction time and liquid-solid ratio, were investigated. Two M 1-butyl-3-methylimidazolium bromide ([bmim] Br) solution with 0.80 M HCl was selected as the optimal solvent. Meanwhile the optimized conditions a ratio of liquid to material of 30:1, and the extraction for 10 min at 70 °C. Compared with conventional heat-reflux extraction (CHRE) and the regular MAE, IL-MAE exhibited a higher extraction yield and shorter extraction time (from 1.5 h to 10 min). The optimized extraction samples were analysed by LC-MS/MS. IL extracts of Bauhinia championii (Benth.)Benth consisted mainly of flavonoids, among which myricetin, quercetin and kaempferol, β-sitosterol, triacontane and hexacontane were identified. The study indicated that IL-MAE was an efficient and rapid method with simple sample preparation. LC-MS/MS was also used to determine the chemical composition of the ethyl acetate/MAE extract of Bauhinia championii (Benth.) Benth, and it maybe become a rapid method to determine the composition of new plant extracts.

Performance of solid state supercapacitors based on polymer electrolytes containing different ionic liquids

NASA Astrophysics Data System (ADS)

Tiruye, Girum Ayalneh; Muñoz-Torrero, David; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

2016-09-01

Four Ionic Liquid based Polymer Electrolytes (IL-b-PE) were prepared by blending a Polymeric Ionic Liquid, Poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PILTFSI), with four different ionic liquids: 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) (IL-b-PE1), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14FSI) (IL-b-PE2), 1-(2-hydroxy ethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HEMimTFSI) (IL-b-PE3), and 1-Butyl-1-methylpyrrolidinium dicyanamide, (PYR14DCA) (IL-b-PE4). Physicochemical properties of IL-b-PE such as ionic conductivity, thermal and electrochemical stability were found to be dependent on the IL properties. For instance, ionic conductivity was significantly higher for IL-b-PE2 and IL-b-PE4 containing IL with small size anions (FSI and DCA) than IL-b-PE1 and IL-b-PE3 bearing IL with bigger anion (TFSI). On the other hand, wider electrochemical stability window (ESW) was found for IL-b-PE1 and IL-b-PE2 having ILs with electrochemically stable pyrrolidinium cation and FSI and TFSI anions. Solid state Supercapacitors (SCs) were assembled with activated carbon electrodes and their electrochemical performance was correlated with the polymer electrolyte properties. Best performance was obtained with SC having IL-b-PE2 that exhibited a good compromise between ionic conductivity and electrochemical window. Specific capacitance (Cam), real energy (Ereal) & real power densities (Preal) as high as 150 F g-1, 36 Wh kg-1 & 1170 W kg-1 were found at operating voltage of 3.5 V.

A simple recovery process for biodegradable plastics accumulated in cyanobacteria treated with ionic liquids.

PubMed

Kobayashi, Daigo; Fujita, Kyoko; Nakamura, Nobuhumi; Ohno, Hiroyuki

2015-02-01

Here, we proposed a simple recovery process for poly(3-hydroxybutyrate) (PHB) accumulated in cyanobacteria by using ionic liquids (ILs), which dissolve cyanobacteria but not PHB. First, we investigated the effects of IL polarity on hydrogen-bonding receipt ability (β value) and hydrogen-bonding donating ability (α value) and evaluated the subsequent dissolution of cyanobacteria. We found that ILs having α values higher than approximately 0.4 and β values of approximately 0.9 were suitable for dissolution of cyanobacteria. In particular, 1-ethyl-3-methylimidazolium methylphosphonate ([C2mim][MeO(H)PO2]) was found to dissolve cyanobacteria components, but not PHB. Thus, we verified that PHB produced in cyanobacteria could be separated and recovered by simple filtering after dissolution of cyanobacteria in [C2mim][MeO(H)PO2]. Using this technique, more than 98 % of PHB was obtained on the filter as residues separated from cyanobacteria. Furthermore, [C2mim][MeO(H)PO2] maintained the ability to dissolve cyanobacteria after a simple recycling procedure.

An Electrochemical NO2 Sensor Based on Ionic Liquid: Influence of the Morphology of the Polymer Electrolyte on Sensor Sensitivity

PubMed Central

Kuberský, Petr; Altšmíd, Jakub; Hamáček, Aleš; Nešpůrek, Stanislav; Zmeškal, Oldřich

2015-01-01

A systematic study was carried out to investigate the effect of ionic liquid in solid polymer electrolyte (SPE) and its layer morphology on the characteristics of an electrochemical amperometric nitrogen dioxide sensor. Five different ionic liquids were immobilized into a solid polymer electrolyte and key sensor parameters (sensitivity, response/recovery times, hysteresis and limit of detection) were characterized. The study revealed that the sensor based on 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][N(Tf)2]) showed the best sensitivity, fast response/recovery times, and low sensor response hysteresis. The working electrode, deposited from water-based carbon nanotube ink, was prepared by aerosol-jet printing technology. It was observed that the thermal treatment and crystallinity of poly(vinylidene fluoride) (PVDF) in the solid polymer electrolyte influenced the sensitivity. Picture analysis of the morphology of the SPE layer based on [EMIM][N(Tf)2] ionic liquid treated under different conditions suggests that the sensor sensitivity strongly depends on the fractal dimension of PVDF spherical objects in SPE. Their deformation, e.g., due to crowding, leads to a decrease in sensor sensitivity. PMID:26569248

Ultraslow Phase Transitions in an Anion-Anion Hydrogen-Bonded Ionic Liquid.

PubMed

Faria, Luiz F O; Lima, Thamires A; Ferreira, Fabio F; Ribeiro, Mauro C C

2018-02-15

A Raman spectroscopy study of 1-ethyl-3-methylimidazolium hydrogen sulfate, [C 2 C 1 im][HSO 4 ], as a function of temperature, has been performed to reveal the role played by anion-anion hydrogen bond on the phase transitions of this ionic liquid. Anion-anion hydrogen bonding implies high viscosity, good glass-forming ability, and also moderate fragility of [C 2 C 1 im][HSO 4 ] in comparison with other ionic liquids. Heating [C 2 C 1 im][HSO 4 ] from the glassy phase results in cold crystallization at ∼245 K. A solid-solid transition (crystal I → crystal II) is barely discernible in calorimetric measurements at typical heating rates, but it is clearly revealed by Raman spectroscopy and X-ray diffraction. Raman spectroscopy indicates that crystal I has extended ([HSO 4 ] - ) n chains of hydrogen-bonded anions but crystal II has not. Raman spectra recorded at isothermal condition show the ultraslow dynamics of cold crystallization, solid-solid transition, and continuous melting of [C 2 C 1 im][HSO 4 ]. A brief comparison is also provided between [C 2 C 1 im][HSO 4 ] and [C 4 C 1 im][HSO 4 ], as Raman spectroscopy shows that the latter does not form the crystalline phase with extended anion-anion chains.

Solvent extraction separation of Th-227 and Ac-225 in room temperature ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bell, Jason R; Boll, Rose Ann; Dai, Sheng

2012-01-01

The solvent extractions of Th-227 and Ac-225 from the aqueous phase into ionic liquids (ILs) were investigated by using N,N,N ,N - tetraoctyldiglycolamide (TODGA) or di(2-ethylhexyl)phosphoric acid (HDEHP) as an extractant. Four ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]), 1-butyl-3-methylimidazolium bis(perfluoroethanesulfonyl)imide ([C4mim][BETI]), 1-butyl-2,3-trimethyleneimidazolium (trifluoromethanesulfonyl)imide [BuI5][NTf2], and 1-benzyl pyridinium bis(trifluoromethanesulfonyl)imide ([PhCH2Py][NTf2]) were used as extraction solvents for separation of Th-227 and Ac-225 in this study. Excellent extraction efficiencies and selectivities were found for Th-227/Ac-225 when HDEHP was used as an extractant in these ionic liquids. The effects of different extractant concentrations in ionic liquids and acidities of the aqueous phase on extraction efficienciesmore » and selectivities of Th-227/Ac-225 are also presented in this article.« less

Protein destabilisation in ionic liquids: the role of preferential interactions in denaturation.

PubMed

Figueiredo, Angelo Miguel; Sardinha, Joao; Moore, Geoffrey R; Cabrita, Eurico J

2013-12-07

The preferential binding of anions and cations in aqueous solutions of the ionic liquids (ILs) 1-butyl-3-methylimidazolium ([C4mim](+)) and 1-ethyl-3-methylimidazolium ([C2mim](+)) chloride and dicyanamide (dca(-)) with the small alpha-helical protein Im7 was investigated using a combination of differential scanning calorimetry, NMR spectroscopy and molecular dynamics (MD) simulations. Our results show that direct ion interactions are crucial to understand the effects of ILs on the stability of proteins and that an anion effect is dominant. We show that the binding of weakly hydrated anions to positively charged or polar residues leads to the partial dehydration of the backbone groups, and is critical to control stability, explaining why dca(-) is more denaturing than Cl(-). Direct cation-protein interactions also mediate stability; cation size and hydrophobicity are relevant to account for destabilisation as shown by the effect of [C4mim](+) compared to [C2mim](+). The specificity in the interaction of IL ions with protein residues established by weak favourable interactions is confirmed by NMR chemical shift perturbation, amide hydrogen exchange data and MD simulations. Differences in specificity are due to the balance of interaction established between ion pairs and ion-solvent that determine the type of residues affected. When the interaction of both cation and anion with the protein is strong the net result is similar to a non-specific interaction, leading ultimately to unfolding. Since the nature of the ions is a determinant of the level of interaction with the protein towards denaturation or stabilisation, ILs offer a unique possibility to modulate protein stabilisation or even folding events.

The role of the anion in the toxicity of imidazolium ionic liquids.

PubMed

Biczak, Robert; Pawłowska, Barbara; Bałczewski, Piotr; Rychter, Piotr

2014-06-15

From the environmental protection point of view, the growing interest of ionic liquids in various industrial branches has raised concerns for the toxicity assessment of these compounds. The paper discusses the effect of salts containing the shared 1-ethyl-3-methylimidazolium [EMIM] cation as coupled with five different anions: bromide [Br], nitrate [NO3], p-toluenesulfonate (tosylate) [Ts], dimethylphosphate [dMP] and methanesulfonate [MS] on the growth and development of higher land plants - spring barley and common radish. The experiment was done according to the ISO Standard 11269-2:1995 and the OECD/OCDE Guide 208/2006. As the indications of phytotoxicity, the percentage of sprouts and the level of dry and fresh plant mass were used; in addition, the visual assessment of any signs of damage to the examined plant species, such as growth inhibition and chlorotic changes, was also made. Results of our study has proved the negative impact of ILs on the tested plants and the toxic effect of imidazolium salts was dependent primarily on the applied ionic liquids concentration. The common radish revealed the higher tolerance to the imidazolium as compared to spring barley. The anion type of ionic liquid was crucial for the toxicity against common radish. Copyright © 2014 Elsevier B.V. All rights reserved.

Outstanding features of alginate-based gel electrolyte with ionic liquid for electric double layer capacitors

NASA Astrophysics Data System (ADS)

Soeda, Kazunari; Yamagata, Masaki; Ishikawa, Masashi

2015-04-01

An alginate-based gel electrolyte with an ionic liquid (Alg/IL) is investigated for electric double-layer capacitors (EDLCs) by using physicochemical and electrochemical measurements. The Alg/EMImBF4 (EMImBF4 = 1-ethyl-3-methylimidazolium tetrafluoroborate) gel electrolyte is thermally stable up to 280 °C, where EMImBF4 decomposes. Furthermore, the EDLC with the gel electrolyte can be operated even at high temperature. The cell containing Alg/EMImBF4 is also electrochemically stable even under high voltage (∼3.5 V) operation. Thus, the alginate is a suitable host polymer for the gel electrolyte for EDLCs. According to the result of charge-discharge characteristics, the voltage drop in the charge-discharge curve for the cell with Alg/EMImBF4 gel electrolyte is considerably smaller than that with liquid-phase EMImBF4 electrolyte. To clarify the effect of Alg in contact with the activated carbon electrode, we also prepared an Alg-containing ACFC electrode (Alg + ACFC), and evaluated its EDLC characteristics in liquid EMImBF4. The results prove that the presence of Alg close to the active materials significantly reduces the internal resistance of the EDLC cell, which may be attributed to the high affinity of Alg to activated carbon.

Ultrasound-assisted temperature-controlled ionic liquid emulsification microextraction coupled with capillary electrophoresis for the determination of parabens in personal care products.

PubMed

Ma, Teng; Li, Zheng; Jia, Qiong; Zhou, Weihong

2016-07-01

We developed a CE and ultrasound-assisted temperature-controlled ionic liquid emulsification microextraction method for the determination of four parabens (methyl paraben, ethyl paraben, propyl paraben, and butyl paraben) in personal care products including mouthwash and toning lotion. In the proposed extraction procedure, ionic liquid (IL, 1-octyl-3-methylimidazolium hexafluorophosphate) was used as extraction solvent, moreover, no disperser solvent was needed. Parameters affecting the extraction efficiency including volume of IL, heating temperature, ultrasonic time, extraction time, sample pH, ionic strength, and centrifugation time were optimized. Under the optimized conditions, the method was found to be linear over the range of 3-500 ng/mL with coefficient of determination (R(2) ) in the range of 0.9990-0.9998. The LODs and LOQs for the four parabens were 0.45-0.72 ng/mL and 1.50-2.40 ng/mL, respectively. Intraday and interday precisions (RSDs, n = 5) were in the range of 5.4-6.8% and 7.0-8.7%, respectively. The recoveries of parabens at different spiked levels ranged from 71.9 to 119.2% with RSDs less than 9.5%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquid pretreatment of poplar wood at room temperature: swelling and incorporation of nanoparticles.

PubMed

Lucas, Marcel; Macdonald, Brian A; Wagner, Gregory L; Joyce, Stephen A; Rector, Kirk D

2010-08-01

Lignocellulosic biomass offers economic and environmental advantages over corn starch for biofuels production. However, its fractionation currently requires energy-intensive pretreatments, due to the lignin chemical resistance and complex cell wall structure. Recently, ionic liquids have been used to dissolve biomass at high temperatures. In this study, thin sections of poplar wood were swollen by ionic liquid (1-ethyl-3-methylimidazolium acetate) pretreatment at room temperature. The samples contract when rinsed with deionized water. The controlled expansion and contraction of the wood structure can be used to incorporate enzymes and catalysts deep into the wood structure for improved pretreatments and accelerated cellulose hydrolysis. As a proof of concept, silver and gold nanoparticles of diameters ranging from 20 to 100 nm were incorporated at depths up to 4 mum. Confocal surface-enhanced Raman images at different depths show that a significant number of nanoparticles were incorporated into the pretreated sample, and they remained on the samples after rinsing. Quantitative X-ray fluorescence microanalyses indicate that the majority of nanoparticle incorporation occurs after an ionic liquid pretreatment of less than 1 h. In addition to improved pretreatments, the incorporation of materials and chemicals into wood and paper products enables isotope tracing, development of new sensing, and imaging capabilities.

Comparison of Three Ionic Liquid-Tolerant Cellulases by Molecular Dynamics

PubMed Central

Jaeger, Vance; Burney, Patrick; Pfaendtner, Jim

2015-01-01

We have employed molecular dynamics to investigate the differences in ionic liquid tolerance among three distinct family 5 cellulases from Trichoderma viride, Thermogata maritima, and Pyrococcus horikoshii. Simulations of the three cellulases were conducted at a range of temperatures in various binary mixtures of the ionic liquid 1-ethyl-3-methyl-imidazolium acetate with water. Our analysis demonstrates that the effects of ionic liquids on the enzymes vary in each individual case from local structural disturbances to loss of much of one of the enzyme’s secondary structure. Enzymes with more negatively charged surfaces tend to resist destabilization by ionic liquids. Specific and unique structural changes in the enzymes are induced by the presence of ionic liquids. Disruption of the secondary structure, changes in dynamical motion, and local changes in the binding pocket are observed in less tolerant enzymes. Ionic-liquid-induced denaturation of one of the enzymes is indicated over the 500 ns timescale. In contrast, the most tolerant cellulase behaves similarly in water and in ionic-liquid-containing mixtures. Unlike the heuristic approaches that attempt to predict enzyme stability using macroscopic properties, molecular dynamics allows us to predict specific atomic-level structural and dynamical changes in an enzyme’s behavior induced by ionic liquids and other mixed solvents. Using these insights, we propose specific experimentally testable hypotheses regarding the origin of activity loss for each of the systems investigated in this study. PMID:25692593

Theoretical and experimental studies of water interaction in acetate based ionic liquids.

PubMed

Shi, Wei; Damodaran, Krishnan; Nulwala, Hunaid B; Luebke, David R

2012-12-05

Water interactions in 1-ethyl-3-methylimidazolium acetate ([emim][CH(3)COO]) were studied utilizing classical and ab initio simulation methods. The self-diffusivities for water and the ionic liquid (IL) were studied experimentally using pulse field gradient NMR spectroscopy and correlated with computational results. Water forms hydrogen bonding networks with the ionic liquid, and depending on the concentration of water, there are profound effects on the self-diffusivities of the various species. Both simulation and experiments show that the self-diffusivities for species in the water-[emim][CH(3)COO] system exhibit minima at 40-50 mol% water. Water interaction with the [CH(3)COO](-) anion predominates over the water-water and water-cation interactions at most water concentrations. Simulations further indicate that decreasing water-[CH(3)COO](-) interaction will increase the IL and water self-diffusivities. Self-diffusivities in the water-IL systems are dependent upon the cation in a complex way. Water interactions with [P(4444)][CH(3)COO] are reduced compared to [emim][CH(3)COO]. The [P(4444)](+) cation is bulkier than the [emim](+) cation and has a smaller self-diffusivity, but when water was introduced to [P(4444)] [CH(3)COO], the water-[CH(3)COO](-) hydrogen bonding network in the [P(4444)][CH(3)COO] was much smaller than the one observed in [emim][CH(3)COO].

Mass spectrometric studies of 1-ethyl-3-methylimidazolium and 1-propyl-2,3-dimethylimidazolium bis(trifluoromethyl)-sulfonylimides.

PubMed

Chilingarov, Norbert S; Medvedev, Artem A; Deyko, Grigoriy S; Kustov, Leonid M; Chernikova, Elena A; Glukhov, Lev M; Markov, Vitaliy Yu; Ioffe, Il'ya N; Senyavin, Vladimir M; Polyakova, Marina V; Sidorov, Lev N

2015-07-15

Ionic liquids ([Cat(+)][An(-)]) were believed to decompose before reaching vaporization temperatures, but recently some of them have been shown to vaporize congruently. Low-temperature vaporization of ionic substances is an intriguing phenomenon, so the vapor-phase composition and reactions of ionic liquids deserve more extensive study. Evaporation of two ionic liquids, [C2MIM(+)][Tf2 N(-)] and [C3MMIM(+)][Tf2N(-)], was studied by means of Knudsen effusion mass spectrometry. These liquids were also characterized using matrix-assisted laser desorption/ionization (MALDI) mass spectrometry, UV/Vis, IR, NMR spectroscopy, and elemental analysis. The vaporization enthalpies of (118 ± 3) and (124 ± 2) kJ·mol(-1) were determined for [C2MIM(+)][Tf2N(-)] and [C3MMIM(+)][Tf2N(-)], respectively. The corresponding equations for their saturated vapor pressures are: ln(p{[C2MIM(+)][Tf2N(-)]}/Pa) = -(14213 ± 325)/(T/K) + (26.57 ± 1.04), ln(p{[C2MMIM(+)][Tf2N(-)]}/Pa) = -(14868 ± 221)/(T/K) + (27.19 ± 0.60). The MALDI studies (positive and negative ion modes) enabled detection of monomeric [Cat(+)] and [An(-)] ions, the cluster ions {[Cat(+)]2 [An(-)]}(+) and {[Cat(+)][An(-)]2}(-), and some complex anions {2[An(-)] + Na(+)}(-), {2[An(-)] + K(+)}(-), {2[An(-)] + Cu(+)}(-) and {3[An(-)] + Ca(2+)}(-). Knudsen effusion mass spectrometry proved to be a valuable method to study the thermodynamics of ionic liquids. The saturated vapor pressure and vaporization enthalpy of [C3MMIM(+)][Tf2N(-)] were accurately determined for the first time. MALDI is also capable of providing indirect information on hydrogen bonding. Copyright © 2015 John Wiley & Sons, Ltd.

SOLVENT-FREE SONOCHEMICAL PREPARATION OF IONIC LIQUIDS

EPA Science Inventory

An ultrasound-assisted preparation of a series of ambient temperature ionic liquids, 1-alkyl-3-methylimidazolium (AMIM) halides, that proceeds via efficient reaction of 1-methyl imidazole with alkyl halides/terminal dihalides under solvent-free conditions, is described.

Supra-molecular inclusion complexation of ionic liquid 1-butyl-3-methylimidazolium octylsulphate with α- and β-cyclodextrins

NASA Astrophysics Data System (ADS)

Banjare, Manoj Kumar; Behera, Kamalakanta; Satnami, Manmohan L.; Pandey, Siddharth; Ghosh, Kallol K.

2017-12-01

Host-guest complexation between ionic liquid (IL) 1-butyl-3-methylimidazolium octylsulphate [Bmim][OS] and cyclodextrins (α- and β- CDs) have been studied. Surface tension, conductivity measurements revealed the formation of 1:1 (M) stoichiometry for inclusion complexes (ICs) and further confirmed by UV-Visible and FT-IR results. The nature of the complexes has been established using interfacial and thermodynamic parameters. The aggregation number, Stern-Volmer constants, association constants were obtained from fluorescence quenching and Benesi-Hildebrand methods. The critical micelle concentration (cmc) and association constants of [Bmim][OS] are higher for β-CD as compared to α-CD. FT-IR spectra indicated that CDs and [Bmim][OS] could from ICs with stoichiometry 1:1 (M).

Direct extraction of genomic DNA from maize with aqueous ionic liquid buffer systems for applications in genetically modified organisms analysis.

PubMed

Gonzalez García, Eric; Ressmann, Anna K; Gaertner, Peter; Zirbs, Ronald; Mach, Robert L; Krska, Rudolf; Bica, Katharina; Brunner, Kurt

2014-12-01

To date, the extraction of genomic DNA is considered a bottleneck in the process of genetically modified organisms (GMOs) detection. Conventional DNA isolation methods are associated with long extraction times and multiple pipetting and centrifugation steps, which makes the entire procedure not only tedious and complicated but also prone to sample cross-contamination. In recent times, ionic liquids have emerged as innovative solvents for biomass processing, due to their outstanding properties for dissolution of biomass and biopolymers. In this study, a novel, easily applicable, and time-efficient method for the direct extraction of genomic DNA from biomass based on aqueous-ionic liquid solutions was developed. The straightforward protocol relies on extraction of maize in a 10 % solution of ionic liquids in aqueous phosphate buffer for 5 min at room temperature, followed by a denaturation step at 95 °C for 10 min and a simple filtration to remove residual biopolymers. A set of 22 ionic liquids was tested in a buffer system and 1-ethyl-3-methylimidazolium dimethylphosphate, as well as the environmentally benign choline formate, were identified as ideal candidates. With this strategy, the quality of the genomic DNA extracted was significantly improved and the extraction protocol was notably simplified compared with a well-established method.

Ionic liquid-assisted sonochemical preparation of CeO 2 nanoparticles for CO oxidation

DOE PAGES

Alammar, Tarek; Noei, Heshmat; Wang, Yuemin; ...

2014-10-10

CeO 2 nanoparticles were synthesized via a one-step ultrasound synthesis in different kinds of ionic liquids based on bis(trifluoromethanesulfonylamide, [Tf 2N] –, in combination with various cations including 1-butyl-3-methylimidazolium ([C 4mim] +), 1-ethyl-2,3-dimethylimidazolium ([Edimim] +), butyl-pyridinium([Py 4] +), 1-butyl-1-methyl-pyrrolidinium ([Pyrr 14] +), and 2-hydroxyethyl-trimethylammonium ([N 1112OH] +). Depending on synthetic parameters, such as ionic liquid, Ce(IV) precursor, heating method, and precipitator, formed ceria exhibits different morphologies, varying from nanospheres, nanorods, nanoribbons, and nanoflowers. The morphology, crystallinity, and chemical composition of the obtained materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive X-raymore » spectroscopy (EDX), Raman spectroscopy, and N2 adsorption. The structural and electronic properties of the as-prepared CeO 2 samples were probed by CO adsorption using IR spectroscopy under ultrahigh vacuum conditions. The catalytic activities of CeO 2 nanoparticles were investigated in the oxidation of CO. CeO 2 nanospheres obtained sonochemically in [C 4mim][Tf 2N] exhibit the best performance for low-temperature CO oxidation. As a result, the superior catalytic performance of this material can be related to its mesoporous structure, small particle size, large surface area, and high number of surface oxygen vacancy sites.« less

Ab initio quantum chemical calculations of the interaction between radioactive elements and imidazolium based ionic liquids

NASA Astrophysics Data System (ADS)

Saravanan, A. V. Sai; Abishek, B.; Anantharaj, R.

2018-04-01

The fundamental natures of the molecular level interaction and charge transfer between specific radioactive elements and ionic liquids of 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide ([BMIM]+[NTf2]-), 1-Butyl-3-methylimidazolium ethylsulfate ([BMIM]+[ES]-) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]+[BF4]-) were investigated utilising HF theory and B3LYP hybrid DFT. The ambiguity in reaction mechanism of the interacting species dictates to employ Effective Core Potential (ECP) basis sets such as UGBS, SDD, and SDDAll to account for the relativistic effects of deep core electrons in the system involving potential, heavy and hazardous radioactive elements present in nuclear waste. The SCF energy convergence of each system validates the characterisation of the molecular orbitals as a linear combination of atomic orbitals utilising fixed MO coefficients and the optimized geometry of each system is visualised based on which Mulliken partial charge analysis is carried out to account for the polarising behaviour of the radioactive element and charge transfer between the IL phase by comparison with the bare IL species.

The influence of cations on lithium ion coordination and transport in ionic liquid electrolytes: a MD simulation study.

PubMed

Lesch, Volker; Li, Zhe; Bedrov, Dmitry; Borodin, Oleg; Heuer, Andreas

2016-01-07

The dynamical and structural properties in two ionic liquid electrolytes (ILEs) based on 1-ethyl-3-methylimidazolium bis-(trifluoromethanesulfonyl)-imide ([emim][TFSI]) and N-methyl-N-propylpyrrolidinium bis-(trifluoromethanesulfonyl)imide([pyr13][TFSI]) were compared as a function of lithium bis-(trifluoromethanesulfonyl)-imide (LiTFSI) salt concentrations using atomistic molecular dynamics (MD) simulations. The many-body polarizable APPLE&P force field has been utilized. The influence of anion polarization on the structure of the first coordination shell of Li(+) was examined. In particular, the reduction of the oxygen of the TFSI anion (OTFSI) polarizability from 1.36 Å(3) to 1.00 Å(3) resulted in an increased fraction of the TFSI anion bidentate coordination to the Li(+). While the overall dynamics in [pyr13][TFSI]-based ILEs was slower than in [emim][TFSI]-based ILEs, the exchange of TFSI anions in and out of the first coordination shell of Li(+) was found to be faster in pyr13-based systems. The Li(+) ion transference number is higher for these systems as well. These trends can be related to the difference in interaction of TFSI with the IL cation which is stronger for pyr13 than for emim.

Photo-Patterned Ion Gel Electrolyte-Gated Thin Film Transistors

NASA Astrophysics Data System (ADS)

Choi, Jae-Hong; Gu, Yuanyan; Hong, Kihyun; Frisbie, C. Daniel; Lodge, Timothy P.

2014-03-01

We have developed a novel fabrication route to pattern electrolyte thin films in electrolyte-gated transistors (EGTs) using a chemically crosslinkable ABA-triblock copolymer ion gel. In the self-assembly of poly[(styrene-r-vinylbenzylazide)-b-ethylene oxide-b-(styrene-r-vinylbenzylazide)] (SOS-N3) triblock copolymer and the ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]), the azide groups of poly(styrene-r-vinylbenzylazide) (PS-N3) end-blocks in the cores can be chemically cross-linked via UV irradiation (λ = 254 nm). Impedance spectroscopy and small-angle X-ray scattering confirmed that ion transport and microstructure of the ion gel are not affected by UV cross-linking. Using this chemical cross-linking strategy, we demonstrate a photo-patterning of ion gels through a patterned mask and the fabricated electrolyte-gated thin film transistors with photo-patterned ion gels as high-capacitance gate insulators exhibited high device performance (low operation voltages and high on/off current ratios).

High performance preconcentration of inorganic Se species by dispersive micro-solid phase extraction with a nanosilica-ionic liquid hybrid material

NASA Astrophysics Data System (ADS)

Llaver, Mauricio; Coronado, Eduardo A.; Wuilloud, Rodolfo G.

2017-12-01

A highly sensitive and efficient dispersive micro-solid phase extraction (D-μ-SPE) method was developed for inorganic Se speciation analysis. A novel ionic liquid (IL)-nanomaterial hybrid consisting of 1-dodecyl-3-methylimidazolium bromide-functionalized nanosilica was used for the efficient retention of Se(IV) complexed with ammonium pyrrolidine dithiocarbamate, followed by elution with an ethyl acetate/Triton X-114 mixture and determination by electrothermal atomic absorption spectroscopy. The Se(VI) species was selectively determined by difference between total inorganic Se and Se(IV) after pre-reduction. The IL-nanomaterial hybrid was characterized by Fourier transform infrared spectroscopy and transmission electronic microscopy. Likewise, Se(IV) sorption capacity of the retention material and maximum amount of IL loaded on its surface were determined. Several factors concerning the functionalization, extraction and elution steps were optimized, yielding a 100% extraction efficiency for Se(IV) under optimal conditions. A limit of detection of 1.1 ng L- 1, a relative standard deviation of 5.7% and a 110-fold enhancement factor were obtained. The D-μ-SPE method was successfully applied to several water samples from different origins and compositions, including rain, tap, underground, river and sea.

The acute toxic effects of 1-alkyl-3-methylimidazolium nitrate ionic liquids on Chlorella vulgaris and Daphnia magna.

PubMed

Zhang, Cheng; Zhang, Shuai; Zhu, Lusheng; Wang, Jinhua; Wang, Jun; Zhou, Tongtong

2017-10-01

Given their increasingly widespread application, the toxic effects of ionic liquids (ILs) have become the subject of significant attention in recent years. Therefore, the present study assessed the acute toxic effects of 1-alkyl-3-methylimidazolium nitrate ([C n mim]NO 3 (n = 2, 4, 6, 8, 10, 12)) on Chlorella vulgaris and Daphnia magna. The sensitivity of the tested organism Daphnia magna and the investigated IL concentrations in water using high-performance liquid chromatography (HPLC) were also evaluated to demonstrate the reliability of the present study. The results illustrated that Daphnia magna is indeed sensitive to the reference toxicant and the investigated ILs were stable in the aquatic environment. The 50% effect concentration (EC 50 ) was used to represent the acute toxic effects on Chlorella vulgaris and Daphnia magna. With the increasing alkyl-chain lengths, the toxicity of the investigated ILs increased in both the test organisms. Accordingly, the alkyl-chain lengths can cause significantly toxic effects on aquatic organisms, and Daphnia magna are much more sensitive than Chlorella vulgaris to the imidazolium-based ILs used in the present study. Furthermore, the present study provides more information on the acute toxic effects of 1-alkyl-3-methylimidazolium nitrate. Copyright © 2017 Elsevier Ltd. All rights reserved.

Monoenergetic source of kilodalton ions from Taylor cones of ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larriba, C.; Castro, S.; Fernandez de la Mora, J.

2007-04-15

The ionic liquid ion sources (ILISs) recently introduced by Lozano and Martinez Sanchez [J. Colloid Interface Sci. 282, 415 (2005)], based on electrochemically etched tungsten tips as emitters for Taylor cones of ionic liquids (ILs), have been tested with ionic liquids [A{sup +}B{sup -}] of increasing molecular weight and viscosity. These ILs have electrical conductivities well below 1 S/m and were previously thought to be unsuitable to operate in the purely ionic regime because their Taylor cones produce mostly charged drops from conventional capillary tube sources. Strikingly, all the ILs tried on ILIS form charged beams composed exclusively of smallmore » ions and cluster ions A{sup +}(AB){sub n} or B{sup -}(AB){sub n}, with abundances generally peaking at n=1. Particularly interesting are the positive and negative ion beams produced from the room temperature molten salts 1-methyl-3-pentylimidazolium tris(pentafluoroethyl) trifluorophosphate (C{sub 5}MI-(C{sub 2}F{sub 5}){sub 3}PF{sub 3}) and 1-ethyl-3-methylimidazolium bis(pentafluoroethyl) sulfonylimide (EMI-(C{sub 2}F{sub 5}SO{sub 3}){sub 2}N). We extend to these heavier species the previous conclusions from Lozano and Martinez Sanchez on the narrow energy distributions of the ion beams. In combination with suitable ILs, this source yields nanoamphere currents of positive and negative monoenergetic molecular ions with masses exceeding 2000 amu. Potential applications are in biological secondary ion mass spectrometry, chemically assisted high-resolution ion beam etching, and electrical propulsion. Advantages of the ILISs versus similar liquid metal ion sources include the possibility to form negative as well as positive ion beams and a much wider range of ion compositions and molecular masses.« less

Ordered mesoporous carbon modified carbon ionic liquid electrode for the electrochemical detection of double-stranded DNA.

PubMed

Zhu, Zhihong; Li, Xia; Zeng, Yan; Sun, Wei

2010-06-15

In this paper the direct electrochemistry of double-stranded DNA (dsDNA) was investigated on ordered mesoporous carbon (OMC) modified carbon ionic liquid electrode (CILE). CILE was prepared by mixing graphite powder with 1-ethyl-3-methylimidazolium ethylsulphate ([EMIM]EtOSO(3)) and liquid paraffin. A stable OMC film was formed on the surface of CILE with the help of Nafion to get a modified electrode denoted as Nafion-OMC/CILE. Due to the specific characteristics of OMC and IL present on the electrode surface, the fabricated electrode showed good electrochemical performances to different electroactive molecules. The electrochemical responses of dsDNA were carefully investigated on this electrode with two irreversible oxidation peak appeared at +1.250 V and +0.921 V (vs. SCE), which was corresponding to the oxidation of adenine and guanine residues in dsDNA structure. The electrochemical behaviors of dsDNA were carefully investigated on the Nafion-OMC/CILE. Experimental results indicated that the electron transfer rate was promoted with the increase of the oxidation peak current and the decrease of the oxidation peak potential, which was due to the electrocatalytic ability of OMC on the electrode surface. Under the optimal conditions the oxidation peak current increased with dsDNA concentration in the range of 10.0-600.0 microg mL(-1) by differential pulse voltammetry (DPV) with the detection limit of 1.2 microg mL(-1) (3sigma). Copyright 2010 Elsevier B.V. All rights reserved.

Generation of a platform strain for ionic liquid tolerance using adaptive laboratory evolution

DOE PAGES

Mohamed, Elsayed T.; Wang, Shizeng; Lennen, Rebecca M.; ...

2017-11-16

There is a need to replace petroleum-derived with sustainable feedstocks for chemical production. Certain biomass feedstocks can meet this need as abundant, diverse, and renewable resources. Specific ionic liquids (ILs) can play a role in this process as promising candidates for chemical pretreatment and deconstruction of plant-based biomass feedstocks as they efficiently release carbohydrates which can be fermented. However, the most efficient pretreatment ILs are highly toxic to biological systems, such as microbial fermentations, and hinder subsequent bioprocessing of fermentative sugars obtained from IL-treated biomass. To generate strains capable of tolerating residual ILs present in treated feedstocks, a tolerance adaptivemore » laboratory evolution (TALE) approach was developed and utilized to improve growth of two different Escherichia coli strains, DH1 and K-12 MG1655, in the presence of two different ionic liquids, 1-ethyl-3-methylimidazolium acetate ([C 2C 1Im][OAc] ) and 1-butyl-3-methylimidazolium chloride ([C 4C 1Im]Cl). For multiple parallel replicate populations of E. coli, cells were repeatedly passed to select for improved fitness over the course of approximately 40 days. Clonal isolates were screened and the best performing isolates were subjected to whole genome sequencing. The most prevalent mutations in tolerant clones occurred in transport processes related to the functions of mdtJI, a multidrug efflux pump, and yhdP, an uncharacterized transporter. Additional mutations were enriched in processes such as transcriptional regulation and nucleotide biosynthesis. Finally, the best-performing strains were compared to previously characterized tolerant strains and showed superior performance in tolerance of different IL and media combinations (i.e., cross tolerance) with robust growth at 8.5% (w/v) and detectable growth up to 11.9% (w/v) [C 2C 1Im][OAc]. The generated strains thus represent the best performing platform strains available for bioproduction utilizing IL-treated renewable substrates, and the TALE method was highly successful in overcoming the general issue of substrate toxicity and has great promise for use in tolerance engineering.« less

Generation of a platform strain for ionic liquid tolerance using adaptive laboratory evolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohamed, Elsayed T.; Wang, Shizeng; Lennen, Rebecca M.

There is a need to replace petroleum-derived with sustainable feedstocks for chemical production. Certain biomass feedstocks can meet this need as abundant, diverse, and renewable resources. Specific ionic liquids (ILs) can play a role in this process as promising candidates for chemical pretreatment and deconstruction of plant-based biomass feedstocks as they efficiently release carbohydrates which can be fermented. However, the most efficient pretreatment ILs are highly toxic to biological systems, such as microbial fermentations, and hinder subsequent bioprocessing of fermentative sugars obtained from IL-treated biomass. To generate strains capable of tolerating residual ILs present in treated feedstocks, a tolerance adaptivemore » laboratory evolution (TALE) approach was developed and utilized to improve growth of two different Escherichia coli strains, DH1 and K-12 MG1655, in the presence of two different ionic liquids, 1-ethyl-3-methylimidazolium acetate ([C 2C 1Im][OAc] ) and 1-butyl-3-methylimidazolium chloride ([C 4C 1Im]Cl). For multiple parallel replicate populations of E. coli, cells were repeatedly passed to select for improved fitness over the course of approximately 40 days. Clonal isolates were screened and the best performing isolates were subjected to whole genome sequencing. The most prevalent mutations in tolerant clones occurred in transport processes related to the functions of mdtJI, a multidrug efflux pump, and yhdP, an uncharacterized transporter. Additional mutations were enriched in processes such as transcriptional regulation and nucleotide biosynthesis. Finally, the best-performing strains were compared to previously characterized tolerant strains and showed superior performance in tolerance of different IL and media combinations (i.e., cross tolerance) with robust growth at 8.5% (w/v) and detectable growth up to 11.9% (w/v) [C 2C 1Im][OAc]. The generated strains thus represent the best performing platform strains available for bioproduction utilizing IL-treated renewable substrates, and the TALE method was highly successful in overcoming the general issue of substrate toxicity and has great promise for use in tolerance engineering.« less

A coarse-grained polarizable force field for the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

NASA Astrophysics Data System (ADS)

Zeman, Johannes; Uhlig, Frank; Smiatek, Jens; Holm, Christian

2017-12-01

We present a coarse-grained polarizable molecular dynamics force field for the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF6]). For the treatment of electronic polarizability, we employ the Drude model. Our results show that the new explicitly polarizable force field reproduces important static and dynamic properties such as mass density, enthalpy of vaporization, diffusion coefficients, or electrical conductivity in the relevant temperature range. In situations where an explicit treatment of electronic polarizability might be crucial, we expect the force field to be an improvement over non-polarizable models, while still profiting from the reduction of computational cost due to the coarse-grained representation.

Solid-state supercapacitors with ionic liquid based gel polymer electrolyte: Effect of lithium salt addition

NASA Astrophysics Data System (ADS)

Pandey, G. P.; Hashmi, S. A.

2013-12-01

Performance characteristics of the solid-state supercapacitors fabricated with ionic liquid (IL) incorporated gel polymer electrolyte and acid treated multiwalled carbon nanotube (MWCNT) electrodes have been studied. The effect of Li-salt (LiPF6) addition in the IL (1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate, EMImFAP) based gel electrolyte on the performance of supercapacitors has been specifically investigated. The LiPF6/IL/poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) gel electrolyte film possesses excellent electrochemical window of 4 V (from -2.0 to 2.0 V), high ionic conductivity ∼2.6 × 10-3 S cm-1 at 20 °C and high enough thermal stability. The comparative performance of supercapacitors employing electrolytes with and without lithium salt has been evaluated by impedance spectroscopy and cyclic voltammetric studies. The acid-treated MWCNT electrodes show specific capacitance of ∼127 F g-1 with IL/LiPF6 containing gel polymer electrolyte as compared to that with the gel polymer electrolyte without Li-salt, showing the value of ∼76 F g-1. The long cycling stability of the solid state supercapacitor based on the Li-salt containing gel polymer electrolyte confirms the electrochemical stability of the electrolyte.

Synthesis and Characterisation of ETS-10/Acetate-based Ionic Liquid/Chitosan Mixed Matrix Membranes for CO2/N2 Permeation

PubMed Central

Casado-Coterillo, Clara; López-Guerrero, María del Mar; Irabien, Ángel

2014-01-01

Mixed matrix membranes (MMMs) were prepared by incorporating organic surfactant-free hydrothermally synthesised ETS-10 and 1-ethyl-3-methylimidazolium acetate ionic liquid (IL) to chitosan (CS) polymer matrix. The membrane material characteristics and permselectivity performance of the two-component membranes were compared with the three-component membrane and the pure CS membrane. The addition of IL increased CO2 solubility of the polymer, and, thus, the CO2 affinity was maintained for the MMMs, which can be correlated with the crystallinity, measured by FT-IR, and void fraction calculations from differences between theoretical and experimental densities. The mechanical resistance was enhanced by the ETS-10 nanoparticles, and flexibility decreased in the two-component ETS-10/CS MMMs, but the flexibility imparted by the IL remained in three-component ETS-10/IL/CS MMMs. The results of this work provide insight into another way of facing the adhesion challenge in MMMs and obtain CO2 selective MMMs from renewable or green chemistry materials. PMID:24957178

Refolding of laccase in dilution additive mode with copper-based ionic liquid.

PubMed

Bae, Sang-Woo; Ahn, Kihun; Koo, Yoon-Mo; Ha, Sung Ho

2013-11-01

Ionic liquids (ILs) are molten salts which do not crystallize at room temperature. Tunable physicochemical properties of ILs including hydrophobicity and polarity facilitate their applications in many biological processes. In this study, a copper-based IL was employed in order to enhance the refolding efficiency of laccase from Trametes versicolor which requires copper as a cofactor. When 1-ethyl-3-methylimidazolium trichlorocuprate ([EMIM][CuCl₃]) was added to refolding buffer instead of urea, the laccase refolding yield was improved more than 2.7 times compared to the conventional refolding buffer which contains urea. When the refolding of laccase was carried out at different temperatures (4, 25, and 37 °C), the highest refolding yield was obtained at 25 °C. At low temperature, two conflicting effects, i.e., suppression of the aggregate formation and decrease of folding rate, influence the protein refolding. In contrast, a copper-based IL did not enhance the refolding of lysozyme, a non-copper-containing protein. From these results, we can conclude that this copper-based IL, [EMIM][CuCl₃], was exclusively effective on the refolding process of a copper-containing protein.

Ionic Liquid as a Solvent and Catalyst for Acylation of Maltodextrin

USDA-ARS?s Scientific Manuscript database

Catalyst-free esterification of maltodextrin was carried out in ionic liquid. Stearate esters of maltodextrin were obtained in various degree of substitution (DS) when vinyl stearate or stearic acid was heated with maltodextrin in ionic liquid, 1-butyl-3-methylimidazolium cyanamide (bmim[dca]). Re...

Effects of phosphonium-based ionic liquids on phospholipid membranes studied by small-angle X-ray scattering.

PubMed

Kontro, Inkeri; Svedström, Kirsi; Duša, Filip; Ahvenainen, Patrik; Ruokonen, Suvi-Katriina; Witos, Joanna; Wiedmer, Susanne K

2016-12-01

The effects of ionic liquids on model phospholipid membranes were studied by small-angle X-ray scattering, dynamic light scattering (DLS) and zeta potential measurements. Multilamellar 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine liposomes and large unilamellar vesicles composed of l-α-phosphatidylcholine (eggPC) and l-α-phosphatidylglycerol (eggPG) (80:20mol%) or eggPC, eggPG, and cholesterol (60:20:20mol%) were used as biomimicking membrane models. The effects of the phosphonium-based ionic liquids: tributylmethylphosphonium acetate, trioctylmethylphosphonium acetate, tributyl(tetradecyl)-phosphonium acetate, and tributyl(tetradecyl)-phosphonium chloride, were compared to those of 1-ethyl-3-methyl-imidazolium acetate. With multilamellar vesicles, the ionic liquids that did not disrupt liposomes decreased the lamellar spacing as a function of concentration. The magnitude of the effect depended on concentration for all studied ionic liquids. Using large unilamellar vesicles, first a slight decrease in the vesicle size, then aggregation of vesicles was observed by DLS for increasing ionic liquid concentrations. At concentrations just below those that caused aggregation of liposomes, large unilamellar vesicles were coated by ionic liquid cations, evidenced by a change in their zeta potential. The ability of phosphonium-based ionic liquids to affect liposomes is related to the length of the hydrocarbon chains in the cation. Generally, the ability of ionic liquids to disrupt liposomes goes hand in hand with inducing disorder in the phospholipid membrane. However, trioctylmethylphosphonium acetate selectively extracted and induced a well-ordered lamellar structure in phospholipids from disrupted cholesterol-containing large unilamellar vesicles. This kind of effect was not seen with any other combination of ionic liquids and liposomes. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

[Cu(I)(bpp)]BF4: the first extended coordination network prepared solvothermally in an ionic liquid solvent.

PubMed

Jin, Kun; Huang, Xiaoying; Pan, Long; Li, Jing; Appel, Aaron; Wherland, Scot; Pang, Long

2002-12-07

Use of an ionic liquid [bmim][BF4] (bmim = 1-butyl-3-methylimidazolium) as solvent has resulted in the first extended coordination structure, the two-dimensional network [Cu(bpp)]BF4 [bpp = 1,3-bis(4-pyridyl)propane], produced via a solvothermal route.

Liquid Salt as Green Solvent: A Novel Eco-Friendly Technique to Enhance Solubility and Stability of Poorly Soluble Drugs

NASA Astrophysics Data System (ADS)

Patel, Anant A.

As a result of tremendous efforts in past few decades, various techniques have been developed in order to resolve solubility issues associated with class II and IV drugs, However, majority of these techniques offer benefits associated with certain drawbacks; majorly including low drug loading, physical instability on storage and excessive use of environmentally challenging organic solvents. Hence, current effort was to develop an eco-friendly technique using liquid salt as green solvent, which can offer improvement in dissolution while maintaining long term stability. The liquid salt formulations (LSF) of poorly soluble model drugs ibuprofen, gemfibrozil and indomethacin were developed using 1-Ethyl-3-methylimidazolium ethyl sulfate (EMIM ES) as a non-toxic and environmentally friendly alternate to organic solvents. Liquid medications containing clear solutions of drug, EMIM ES and polysorbate 20, were adsorbed onto porous carrier Neusilin US2 to form free flowing powder. The LSF demonstrated greater rate and extent of dissolution compared to crystalline drugs. The dissolution data revealed that more than 80% drug release from LSF within 20 mins compared to less than 18% release from pure drugs. As high as 70% w/w liquid loading was achieved while maintaining good flowability and compressibility. In addition, the LSF samples exposed to high temperature and high humidity i.e. 40°C/80% RH for 8 weeks, demonstrated excellent physical stability without any signs of precipitation or crystallization. As most desirable form of administration is tablet, the developed liquid salt formulations were transformed into tablets using design of experiment approach by Design Expert Software. The tablet formulation composition and critical parameter were optimized using Box-Behnken Design. This innovative liquid salt formulation technique offered improvement in dissolution rate and extent as well as contributed to excellent physical stability on storage. Moreover, this formulation approach served as eco-friendly compelling alternate to conventional techniques involving organic solvents.

Electrochemical performance of microporous and mesoporous activated carbons in neat and diluted 1-ethyl-3-methylimidazolium tetrafluoroborate

NASA Astrophysics Data System (ADS)

Kumagai, Seiji; Hatomi, Masaki; Tashima, Daisuke

2017-03-01

1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIm·BF4), neat and diluted with propylene carbonate to 1 mol L-1, have been employed as electrolytes of electrical double-layer capacitors (EDLCs). The effects of microporosity and mesoporosity in activated carbon (AC) electrodes on the capacitive and resistive performances upon the use of neat and diluted EMIm·BF4 have been explored. In addition to cyclic voltammetry and galvanostatic charge-discharge tests, electrochemical impedance spectroscopy has been performed employing Kang's equivalent circuit model consisting of three resistances, three constant phase elements, and one bounded Warburg impedance. The overall impedance of the EDLC cell was separated into components of intrinsic resistance, bulk electrolyte, diffusion layer, and Helmholtz layer. The specific capacitance and the equivalent series resistance (ESR) of mesoporous AC were found to be highly dependent on the rate of ionic transfer. Lower cell voltage was identified as being responsible for lower specific capacitance and larger ESR of mesoporous AC, which was similarly seen in the neat and diluted EMIm·BF4, and could be alleviated by increasing the cell voltage. The inferior rate performance and the cell-voltage-dependent performance of mesoporous AC, which were more distinctly observed in the neat EMIm·BF4, could be attributed to the lower mobility of EMIm+ and BF4- in mesopores.

Microbundles of zinc oxide nanorods: Assembly in ionic liquid [EMIM]{sup +}[BF{sub 4}]{sup -}, photoluminescence and photocatalytic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang Li; Xu Shenzhi; Li Huijun

2011-03-15

A simple, efficient and low-temperature approach for the assembly of hierarchical Zinc oxide (ZnO) microstructures in ionic liquid [EMIM]{sup +}[BF{sub 4}]{sup -} is reported. The as-obtained ZnO superstructures are composed of microbundles of nanorods from the center points, with the diameter and length in the range of 100-150 nm and 2-4 {mu}m, which have been characterized by X-ray diffraction, scanning and transmission electron microscopy, and photoluminescence spectroscopy. The ZnO microstructures exhibit significant defect-related green-yellow emission and high photodegradation of dye Methyl Orange (5x10{sup -5} mol/L) under UV excitation within 80 min. -- Graphical abstract: Easy formation of microbundles of ZnOmore » nanorods were accomplished in low temperature with [EMIM]{sup +}[BF{sub 4}]{sup -} (1-ethyl-3-methylimidazolium tetrafluoroborate) ionic liquid, which exhibit significant green-yellow photoluminescence property and high photodegradation of Methyl Orange dye. Display Omitted Research highlights: {yields} Ionic liquid assisted solid-state route was introduced into synthesis of ZnO nanorods. {yields} The distinctive microbundles ZnO nanorod assembles was evidenced by SEM and TEM. {yields} ZnO nano-material exhibited high efficiency in photodegradation of Methyl Orange.« less

Salting-out homogenous extraction followed by ionic liquid/ionic liquid liquid-liquid micro-extraction for determination of sulfonamides in blood by high performance liquid chromatography.

PubMed

Liu, Zhongling; Yu, Wei; Zhang, Hanqi; Gu, Fanbin; Jin, Xiangqun

2016-12-01

Salting-out homogenous extraction followed by ionic liquid/ionic liquid dispersive liquid-liquid micro-extraction system was developed and applied to the extraction of sulfonamides in blood. High-performance liquid chromatography was applied to the determination of the analytes. The blood sample was centrifuged to obtain the serum. After the proteins in the serum were removed in the presence of acetonitrile, ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, dipotassium hydrogen phosphate, ionic liquid 1-Hexyl-3-methylimidazolium hexafluorophosphate were added into the resulting solution. After the resulting mixture was ultrasonically shaken and centrifuged, the precipitate was separated. The acetonitrile was added in the precipitate and the analytes were extracted into the acetonitrile phase. The parameters affecting the extraction efficiency, such as volume of ionic liquid, amount of dipotassium hydrogen phosphate, volume of dispersant, extraction time and temperature were investigated. The limits of detection of sulfamethizole (STZ), sulfachlorpyridazine (SCP), sulfamethoxazole (SMX) and Sulfisoxazole (SSZ) were 4.78, 3.99, 5.21 and 3.77μgL -1 , respectively. When the present method was applied to the analysis of real blood samples, the recoveries of analytes ranged from 90.0% to 113.0% and relative standard deviations were lower than 7.2%. Copyright © 2016 Elsevier B.V. All rights reserved.

Physical properties of ionic liquids consisting of the 1-butyl-3-methylimidazolium cation with various anions and the bis(trifluoromethylsulfonyl)imide anion with various cations.

PubMed

Jin, Hui; O'Hare, Bernie; Dong, Jing; Arzhantsev, Sergei; Baker, Gary A; Wishart, James F; Benesi, Alan J; Maroncelli, Mark

2008-01-10

Physical properties of 4 room-temperature ionic liquids consisting of the 1-butyl-3-methylimidazolium cation with various perfluorinated anions and the bis(trifluoromethylsulfonyl)imide (Tf2N-) anion with 12 pyrrolidinium-, ammonium-, and hydroxyl-containing cations are reported. Electronic structure methods are used to calculate properties related to the size, shape, and dipole moment of individual ions. Experimental measurements of phase-transition temperatures, densities, refractive indices, surface tensions, solvatochromic polarities based on absorption of Nile Red, 19F chemical shifts of the Tf2N- anion, temperature-dependent viscosities, conductivities, and cation diffusion coefficients are reported. Correlations among the measured quantities as well as the use of surface tension and molar volume for estimating Hildebrand solubility parameters of ionic liquids are also discussed.

ENZYMATIC POLYMERIZATION OF PHENOLS IN ROOM TEMPERATURE IONIC LIQUIDS

PubMed Central

Eker, Bilge; Zagorevski, Dmitri; Zhu, Guangyu; Linhardt, Robert J.; Dordick, Jonathan S.

2009-01-01

Soybean peroxidase (SBP) was used to catalyze the polymerization of phenols in room-temperature ionic liquids (RTILs). Phenolic polymers with number average molecular weights ranging from 1200 to 4100 D were obtained depending on the composition of the reaction medium and the nature of the phenol. Specifically, SBP was highly active in methylimidazolium-containing RTILs, including 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM(BF4)), and 1-butyl-3-methylpyridinium tetrafluoroborate (BMPy(BF4)) with the ionic liquid content as high as 90% (v/v); the balance being aqueous buffer. Gel permeation chromatography and MALDI-TOF analysis indicated that higher molecular weight polymers can be synthesized in the presence of higher RTIL concentrations, with selective control over polymer size achieved by varying the RTIL concentration. The resulting polyphenols exhibited high thermostability and possessed thermosetting properties. PMID:20161409

A "by-productless" cellulose foaming agent for use in imidazolium ionic liquids.

PubMed

Scott, Janet L; Unali, Gianfranco; Perosa, Alvise

2011-03-14

Cellulose foams, or sponges, are produced from solutions in ionic liquids by the aqueous acid mediated decomposition of 1-alkyl-3-methylimidazolium-2-carboxylates, where the alkyl group and acid may be selected such that the by-product is the ionic liquid solvent: a by-productless foaming.

Structural and conformational properties of 1-decyl-3-methylimidazolium tetrafluoroborate under high pressure

NASA Astrophysics Data System (ADS)

Chen, Liucheng; Li, Haining; Zhu, Xiang; Su, Lei; Yang, Kun; Yuan, Chaosheng; Yang, Guoqiang; Li, Xiaodong

2017-06-01

In situ crystalization of 1-decyl-3-methylimidazolium tetrafluoroborate ([C10MIM][BF4]) from melt has been investigated under high pressure up to 3.4 GPa at room temperature by using Raman spectroscopy and synchrotron X-ray diffraction measurement. Raman spectral analysis indicated that [C10MIM][BF4] experienced two successive phase transitions at about 0.3 GPa and 1.6 GPa. And the polymorphism was also discussed in view of the conformational isomerism of [C10MIM]+ cation between gauche and trans conformers. Notably, liquid-crystal and crystal-crystal phase transitions were further confirmed by synchrotron X-ray diffraction measurement. Moreover, it also indicated that high structural flexibility of the cations with long alkyl chain might have effect on the degree of disorder of pressure-induced crystallization for ionic liquids.

Biomass Pretreatment using Ionic Liquid and Glycerol Mixtures

NASA Astrophysics Data System (ADS)

Lynam, Joan Goerss

Lignocellulosic biomass is a renewable, sustainable resource that can replace or supplement fossil fuels use for liquid fuels and chemicals. However, its recalcitrant structure including interwoven cellulose, hemicelluloses, and lignin biomacromolecules is challenging to deconstruct. Pretreating biomass so that it can be converted to useful liquids dominates process economics. Many pretreatment methods exist, but most require hazardous chemicals or processing conditions. Many ionic liquids (ILs), salts molten below 100°C, can be used to deconstruct lignocellulosic biomass and are less hazardous than the volatile organic compounds typically used. While effective, relatively safe, and recyclable, ILs are expensive. To reduce costs, dilution with other safe compounds is desirable, if there is no impact on deconstruction efficiency. Glycerol, a food additive, is inexpensive and becoming even more so since it is a by-product of the burgeoning biodiesel industry. Use of glycerol as an additive or diluent for ILs is extensively evaluated in this work. Rice hulls are an abundant biomass, with over 100 million tons produced per year, but with little practical use. The IL 1-ethyl-3-methylimidazolium formate ([C2mim][O2CH] or EMIM Form) when mixed with an equal amount of glycerol has been shown to be effective in pretreating rice hulls. Ambient pressure, a pretreatment temperature of 110°C, and a reaction time of three hours produced rice hulls that could be enzymatically hydrolyzed to give reasonably good glucose and xylose yields considering the recalcitrance of this silica-armored biomass. The IL [C2mim][O2CH] was also effective when mixed with an equal amount of glycerol to pretreat loblolly pine, a fast-growing softwood. Loblolly pine was pretreated at 140°C for three hours to produce a solid rich in cellulose and hemicelluloses, while a lignin-rich product could be precipitated from the IL. Similar products were obtained from pretreatment with a mixture of 75% 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc] or EMIM Ac) and 25% glycerol. Enzymatic hydrolysis of the pretreated solids gave glucose, mannose, and xylose yields up to 18 times that of the raw pine. Viscosity measurements of pure glycerol, [C2mim][O2CH], [C2mim][OAc], and IL-glycerol mixtures were very different at ambient temperature, but were similar at typical biomass pretreatment temperatures. Biomass pretreated by mixtures with higher viscosity tended to give better carbohydrate yields after enzymatic hydrolysis. Higher excess molar volumes, Vm E, tended to align with better carbohydrate yields after enzymatic hydrolysis. This phenomenon may relate to more energy put into shearing flow of the IL-glycerol-biomass system resulting in biomass particle shearing or stretching that allowed better solvent access into the biomass.

Novel ascorbic acid based ionic liquids for the in situ synthesis of quasi-spherical and anisotropic gold nanostructures in aqueous medium.

PubMed

Dinda, Enakshi; Si, Satyabrata; Kotal, Atanu; Mandal, Tarun K

2008-01-01

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.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation.

PubMed

Chopade, Sujay A; Anderson, Evan L; Schmidt, Peter W; Lodge, Timothy P; Hillmyer, Marc A; Bühlmann, Philippe

2017-10-27

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.

Ionic-liquid-based ultrasound-assisted extraction of isoflavones from Belamcanda chinensis and subsequent screening and isolation of potential α-glucosidase inhibitors by ultrafiltration and semipreparative high-performance liquid chromatography.

PubMed

Li, Senlin; Li, Sainan; Huang, Yu; Liu, Chunming; Chen, Lina; Zhang, Yuchi

2017-06-01

The separation of a compound of interest from its structurally similar homologues to produce high-purity natural products is a challenging problem. This work proposes a novel method for the separation of iristectorigenin A from its structurally similar homologues by ionic-liquid-based ultrasound-assisted extraction and the subsequent screening and isolation of potential α-glucosidase inhibitors via ultrafiltration and semipreparative high-performance liquid chromatography. Ionic-liquid-based ultrasound-assisted extraction was successfully applied to the extraction of tectorigenin, iristectorigenin A, irigenin, and irisflorentin from Belamcanda chinensis. The optimum conditions for the efficient extraction of isoflavones were determined as 1.0 M 1-ethyl-3-methylimidazolium tetrafluoroborate with extraction time of 30 min and a solvent to solid ratio of 30 mL/g. Ultrafiltration with liquid chromatography and mass spectrometry was applied to screen and identify α-glucosidase inhibitors from B. chinensis, followed by the application of semipreparative high-performance liquid chromatography to separate and isolate the active constituents. Four major compounds including tectorigenin, iristectorigenin A, irigenin, and irisflorentin were screened and identified as α-glucosidase inhibitors, and then the four active compounds abovementioned were subsequently isolated by semipreparative high-performance liquid chromatography (99.89, 88.97, 99.79, and 99.97% purity, respectively). The results demonstrate that ionic liquid extraction can be successfully applied to the extraction of isoflavones from B. chinensis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The performance of fast-moving low-voltage electromechanical actuators based on single-walled carbon nanotubes and ionic liquids

NASA Astrophysics Data System (ADS)

Mukai, Ken; Asaka, Kinji; Hata, Kenji; Oike, Hideaki

2011-12-01

In this paper, we study the details of the mechanical and electrical properties of polymer-free single-walled carbon nanotube (SWNT) sheets containing different contents of ionic liquids (ILs). The polymer-free SWNT sheets were prepared by a previously reported finding that millimeter-long 'super-growth' carbon nanotubes (SG-SWNTs), produced by a water-assisted modified chemical vapor deposition (CVD) method, associate together tightly with ILs, affording a free-standing sheet with a superb conductivity. The Young's modulus, breaking strength and the electrical conductivity of the SG-SWNT sheet with 67 wt% 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMITFSI) showed large values, 0.63 GPa, 20 MPa, and 147 S cm-1, respectively, although it has large amounts of ILs. We also measure the frequency dependence of the displacement of the actuator composed of SG-SWNT sheets sandwiching an ionic-gel electrolyte layer (SG-SWNT actuator). At more than 50 wt% of EMITFSI content, the frequency response of the actuation of the SG-SWNT actuator is flat up to around 100 Hz. The results of the displacement measurements are discussed in relation to the mechanical and electrical properties of the SG-SWNT actuators.

Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room-Temperature Ionic Liquids. 1. Variation of Anionic Species.

PubMed

Sun, Liyuan; Morales-Collazo, Oscar; Xia, Han; Brennecke, Joan F

2015-12-03

A series of room temperature ionic liquids (RTILs) based on 1-ethyl-3-methylimidazolium ([emim](+)) with different aprotic heterocyclic anions (AHAs) were synthesized and characterized as potential electrolyte candidates for lithium ion batteries. The density and transport properties of these ILs were measured over the temperature range between 283.15 and 343.15 K at ambient pressure. The temperature dependence of the transport properties (viscosity, ionic conductivity, self-diffusion coefficient, and molar conductivity) is fit well by the Vogel-Fulcher-Tamman (VFT) equation. The best-fit VFT parameters, as well as linear fits to the density, are reported. The ionicity of these ILs was quantified by the ratio of the molar conductivity obtained from the ionic conductivity and molar concentration to that calculated from the self-diffusion coefficients using the Nernst-Einstein equation. The results of this study, which is based on ILs composed of both a planar cation and planar anions, show that many of the [emim][AHA] ILs exhibit very good conductivity for their viscosities and provide insight into the design of ILs with enhanced dynamics that may be suitable for electrolyte applications.

Electrospinning biopolymers from ionic liquids requires control of different solution properties than volatile organic solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zavgorodnya, Oleksandra; Shamshina, Julia L.; Bonner, Jonathan R.

Here, we report the correlation between key solution properties and spinability of chitin from the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C 2mim][OAc]), and the similarities and differences to electrospinning solutions of non-ionic polymers in volatile organic compounds (VOCs). We found that when electrospinning is conducted from ILs, conductivity and surface tension are not the key parameters regulating spinability, while solution viscosity and polymer concentration are. Contrarily, for electrospinning of polymers from VOCs, solution conductivity and viscosity have been reported to be among some of the most important factors controlling fiber formation. For chitin electrospun from [C 2mim][OAc], we found bothmore » a critical chitin concentration required for continuous fiber formation (> 0.20 wt%) and a required viscosity for the spinning solution (between ca. 450 – 1500 cP). The high viscosities of the biopolymer-IL solutions made it possible to electrospin solutions with low, less than 1 wt% of polymer concentration and produce thin fibers without the need to adjust the electrospinning parameters. These results suggest new prospects for the control of fiber architecture in non-woven mats, which is crucial for materials performance.« less

Electrospinning biopolymers from ionic liquids requires control of different solution properties than volatile organic solvents

DOE PAGES

Zavgorodnya, Oleksandra; Shamshina, Julia L.; Bonner, Jonathan R.; ...

2017-04-27

Here, we report the correlation between key solution properties and spinability of chitin from the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C 2mim][OAc]), and the similarities and differences to electrospinning solutions of non-ionic polymers in volatile organic compounds (VOCs). We found that when electrospinning is conducted from ILs, conductivity and surface tension are not the key parameters regulating spinability, while solution viscosity and polymer concentration are. Contrarily, for electrospinning of polymers from VOCs, solution conductivity and viscosity have been reported to be among some of the most important factors controlling fiber formation. For chitin electrospun from [C 2mim][OAc], we found bothmore » a critical chitin concentration required for continuous fiber formation (> 0.20 wt%) and a required viscosity for the spinning solution (between ca. 450 – 1500 cP). The high viscosities of the biopolymer-IL solutions made it possible to electrospin solutions with low, less than 1 wt% of polymer concentration and produce thin fibers without the need to adjust the electrospinning parameters. These results suggest new prospects for the control of fiber architecture in non-woven mats, which is crucial for materials performance.« less

Ionic Liquid Confined in Mesoporous Polymer Membrane with Improved Stability for CO2/N2 Separation

PubMed Central

Tan, Ming; Lu, Jingting; Zhang, Yang; Jiang, Heqing

2017-01-01

Supported ionic liquid membranes (SILMs) have a promising prospect of application in flue gas separation, owing to its high permeability and selectivity of CO2. However, existing SILMs have the disadvantage of poor stability due to the loss of ionic liquid from the large pores of the macroporous support. In this study, a novel SILM with high stability was developed by confining ionic liquid in a mesoporous polymer membrane. First, a mesoporous polymer membrane derived from a soluble, low-molecular-weight phenolic resin precursor was deposited on a porous Al2O3 support, and then 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF4]) was immobilized inside mesopores of phenolic resin, forming the SILM under vacuum. Effects of trans-membrane pressure difference on the SILM separation performance were investigated by measuring the permeances of CO2 and N2. The SILM exhibits a high ideal CO2/N2 selectivity of 40, and an actual selectivity of approximately 25 in a mixed gas (50% CO2 and 50% N2) at a trans-membrane pressure difference of 2.5 bar. Compared to [emim][BF4] supported by polyethersulfone membrane with a pore size of around 0.45 μm, the [emim][BF4] confined in a mesoporous polymer membrane exhibits an improved stability, and its separation performance remained stable for 40 h under a trans-membrane pressure difference of 1.5 bar in a mixed gas before the measurement was intentionally stopped. PMID:28961187

Polymer electrolyte based on crosslinked poly(glycidyl methacrylate) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fei, Beatrice Wong Chui; Hanifah, Sharina Abu; Ahmad, Azizan

2015-09-25

Polymer electrolytes based on crosslinked poly(glycidyl methacrylate) as polymer host and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimTFSI) as incorporated salt were prepared by in-situ photopolymerization technique. The complexes with different mass ratio of glycidyl methacrylate (GMA) monomer to BmimTFSI were investigated. The ionic conductivity of the polymer electrolyte was increased and reach the highest value of 7.50 × 10{sup −4} S cm{sup −1} at the ratio of 3:7 (GMA: BmimTFSI). The interaction between the polymer host and ionic liquid was proved by Attenuated Total Reflectance-Fourier Transformation Infra-Red Spectroscopy (ATR-FTIR). Meanwhile, the X-ray diffraction analysis shows the amorphousity of the polymer electrolyte film increasemore » with the ionic liquid ratio.« less

The influence of water on the physicochemical characteristics of 1-butyl-3-methylimidazolium bromide ionic liquid

NASA Astrophysics Data System (ADS)

Ramenskaya, L. M.; Grishina, E. P.; Pimenova, A. M.; Gruzdev, M. S.

2008-07-01

A modified synthesis of 1-butyl-3-methylimidazolium bromide (BMImBr) was suggested and performed, and some physicochemical properties of the product containing 0.64 13.6 wt % water were determined. Water increased the electrical conductivity and decreased the viscosity and melting point of the substance but weakly influenced its density. Water in amounts of 5 8 wt % (45 50 mol %) caused structural changes. The BMImBr · 0.5H2O crystal hydrate was found to be stable thermodynamically.

Green synthesis of a typical chiral stationary phase of cellulose-tris(3, 5-dimethylphenylcarbamate)

PubMed Central

2013-01-01

Background At present, the study on the homogeneous-phase derivatization of cellulose in ionic liquid is mainly focused on its acetylation. To the best of our knowledge, there has been no such report on the preparation of cellulose-tris(3,5-dimethylphenylcarbamate) (CDMPC) with ionic liquid 1-allyl-3-methyl-imidazolium chloride (AmimCl) so far. Results With ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as a reaction solvent, cellulose-tris(3,5-dimethylphenylcarbamate) (CDMPC) was synthesized by the reaction of 3,5-dimethylphenyl isocyanate and soluble microcrystalline cellulose in a homogeneous phase. The synthesized CDMPC was then coated onto the surfaces of aminopropyl silica gel to prepare a chiral stationary phase (CSP). The prepared CSP was successfully used in chiral separation of seven racemic pesticides by high performance liquid chromatography (HPLC). Good chiral separation was obtained using n-hexane and different modifiers as the mobile phases under the optimal percentage and column temperature, with the resolution of metalaxyl, diniconazole, flutriafol, paclobutrazol, hexaconazole, myclobutanil and hexythiazox of 1.73, 1.56, 1.26, 1.00, 1.18, 1.14 and 1.51, respectively. The experimental results suggested it was a good choice using a green solvent of AmimCl for cellulose functionalization. Conclusion CDMPC was successfully synthesized as the chiral selector by reacting 3, 5-dimethylphenyl isocyanate with dissolved microcrystalline cellulose in a green ionic liquid of AmimCl. PMID:23890199

Advances in the electrodeposition of aluminum from ionic liquid based electrolytes

NASA Astrophysics Data System (ADS)

Leadbetter, Kirt C.

Aluminum plating is of considerable technical and economic interest because it provides an eco-friendly substitute for cadmium coatings used on many military systems. However, cadmium has been determined to be a significant environmental safety and occupational health (ESOH) hazard because of its toxicity and carcinogenic nature. Furthermore, the cost of treating and disposing of generated wastes, which often contain cyanide, is costly and is becoming prohibitive in the face of increasingly stringent regulatory standards. The non-toxic alternative aluminum is equivalent or superior in performance to cadmium. In addition, it could serve to provide an alternative to hexavalent chromium coatings used on military systems for similar reasons to that of cadmium. Aluminum is a beneficial alternative in that it demonstrates self-healing corrosion resistance in the form of a tightly-bound, impervious oxide layer. A successfully plated layer would be serviceable over a wider temperature range, 925 °F for aluminum compared to 450 oF for cadmium. In addition, an aluminum layer can be anodized to make it non-conducting and colorable. In consideration of the plating process, aluminum cannot be deposited from aqueous solutions because of its reduction potential. Therefore, nonaqueous electrolytes are required for deposition. Currently, aluminum can be electrodeposited in nonaqueous processes that use hazardous chemicals such as toluene and pyrophoric aluminum alkyls. Electrodeposition from ionic liquids provides the potential for a safer method that could be easily scaled up for industrial application. The plating process could be performed at a lower temperature and higher current density than other commercially available aluminum electrodeposition processes; thus a reduced process cost could be possible. The current ionic liquid based electrolytes are more expensive; however production on a larger scale and a long electrolyte lifetime are associated with a reduction in price. Advancements of this nonaqueous aluminum plating process have the potential to lead to a novel and competitive commercial aluminum deposition process. In this investigation aluminum electrodeposition from ionic liquid based electrolytes onto steel, copper and magnesium substrates without conversion coatings or strike layers was evaluated in six different ionic liquid based electrolytes in two technical setups. Three of which are commercially available aluminum plating electrolytes, three of which, discussed in literature were created on site by research personnel in the laboratory. The three commercially available electrolytes were: 1-Butyl-3-methylimidazolium chloride ([BMIm]Cl) * 1.5 AlCl3 with proprietary additives from IoLiTec, 1-Ethyl-3-methylimidazolium chloride ([EMIm]Cl) * 1.5 AlCl3 with proprietary additives from IoLiTec, and BasionicsTM AL-02, an aluminum plating electrolyte containing [EMIm]Cl * 1.5 AlCl3 with additives from BASF. The three electrolytes created on site were based on the 1-ethyl-3-methylimidazolium chloride ionic liquid with added 1.5 AlCl3 and one with added sodium dodecyl sulfate. Small scale plating tests in a 25-mL plating cell were conducted to provide a comparative analysis of the six different electrolytes considered. From these investigations, two were chosen to be evaluated in a larger 1-liter plating cell; designed and constructed to provide a more realistic evaluation of plating parameters with selected electrolytes to better portray industrial electroplating conditions. The effect of current density (10-40 mA/cm 2), temperature (30-90° Celsius) and plating bath agitation on current efficiency, corrosion resistance by the ASTM B117 method, adhesion, microstructure, and chemical composition (evaluated with energy-dispersive x-ray spectroscopy) of the plated Al-layer was explored in both the 25-mL and 1-L plating cell investigations. In addition development of pre- and post-treatment processes for the metal substrates was attempted. While previous investigations focused on one or two of these topics, this research seeks to investigate all discussed phenomena and characteristics. Additionally, there is little research that reports on the adhesion performance of aluminum coatings from ionic liquids. Also, corrosion investigations are limited to all but a few publications. So too, the deposition of aluminum in a larger, more realistic plating cell has never been thoroughly investigated. This is key if a practical application of the technology is ever to be realized. In sum, correlations were drawn between electrolyte, current density, temperature and bath agitation with quality and characteristic of electrodeposited aluminum layers. The overriding goal to create an acceptably competitive aluminum coating process to replace cadmium and compete with other commercial aluminum deposition processes was not successful. Competitiveness was evaluated as per the discussed characteristics and so also, by a comparison to physical samples created in a more realistic plating cell to AlumiPlate aluminum coatings.

Stability of nicotinate and dodecyl sulfate in a Lewis acidic ionic liquid for aluminum electroplating and characterization of their degradation products.

PubMed

Kosmus, Patrick; Steiner, Oliver; Goessler, Walter; Gollas, Bernhard; Fauler, Gisela

2016-04-01

Plating bath additives are essential for optimization of the morphology of electroplated layers. The ionic liquid 1-ethyl-3-methylimidazolium (EMIM) chloride plus 1.5 mol equivalents of AlCl3 has great potential for electroplating of aluminum. In this study, the chemical and electrochemical stability of the additives EMIM-nicotinate and sodium dodecyl sulfate and their effect on the stability of EMIM was investigated and analyzed. Nicotinate and its electrochemical decomposition product β-picoline could be detected and we show with a single HPLC-UV-MS method that EMIM is not affected by the decomposition of this additive. An adapted standard HPLC-UV-MS method together with GC-MS and ion chromatography was used to analyze the decomposition products of SDS and possible realkylation products of EMIM. Several volatile medium and short chain-length alkanes as well as sulfate ions have been found as decomposition products of SDS. Alkenium ions formed as intermediates during the decomposition of SDS realkylate EMIM to produce mono- up to pentasubstituted alkyl-imidazoles. A reaction pathway involving Wagner-Meerwein rearrangements and Friedel-Crafts alkylations has been suggested to account for the formation of the detected products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Effect of Ionic Liquid Pretreatment on the Bioconversion of Tomato Processing Waste to Fermentable Sugars and Biogas.

PubMed

Allison, Brittany J; Cádiz, Juan Canales; Karuna, Nardrapee; Jeoh, Tina; Simmons, Christopher W

2016-08-01

Tomato pomace is an abundant lignocellulosic waste stream from industrial tomato processing and therefore a potential feedstock for production of renewable biofuels. However, little research has been conducted to determine if pretreatment can enhance release of fermentable sugars from tomato pomace. Ionic liquids (ILs) are an emerging pretreatment technology for lignocellulosic biomass to increase enzymatic digestibility and biofuel yield while utilizing recyclable chemicals with low toxicity. In this study, pretreatment of tomato pomace with the ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) was investigated. Changes in pomace enzymatic digestibility were affected by pretreatment time and temperature. Certain pretreatment conditions significantly improved reducing sugar yield and hydrolysis time compared to untreated pomace. Compositional analyses suggested that pretreatment primarily removed water-soluble compounds and enriched for lignocellulose in pomace, with only subtle changes to the composition of the lignocellulose. While tomato pomace was effectively pretreated with [C2mim][OAc] to improve enzymatic digestibility, as of yet, unknown factors in the pomace caused ionic liquid pretreatment to negatively affect anaerobic digestion of pretreated material. This result, which is unique compared to similar studies on IL pretreatment of grasses and woody biomass, highlights the need for additional research to determine how the unique chemical composition of tomato pomace and other lignocellulosic fruit residues may interact with ionic liquids to generate inhibitors for downstream fermentation to biofuels.

Interaction between amphiphilic ionic liquid 1-butyl-3-methylimidazolium octyl sulfate and anionic polymer of sodium polystyrene sulfonate in aqueous medium

NASA Astrophysics Data System (ADS)

Barhoumi, Z.; Saini, M.; Amdouni, N.; Pal, A.

2016-09-01

The micellization of an aqueous solution of the surface active ionic liquid (SAIL), 1-butyl-3-methylimidazolium octylsufate (C4mim)(C8OSO3) and its interaction with an anionic polymer sodium polystyrene sulfonate, (NaPSS) were studied using conductimetry, tensiometry and fluorimetry. Surface tension profile shows a more dramatic increase in the value of surface tension of aqueous (C4mim)(C8OSO3) before the critical micelle concentration (cmc) of IL. The critical micelle concentration (cmc) value of this surfactant was found out from conductance measurements. The thermodynamic parameters, i.e., Gibb's free energy, enthalpy, and entropy of micellization of the IL in aqueous solution have been calculated. Behavior of fluorescence probe confirms the binding interactions between SAIL and the polyelectrolyte.

Long Periodic Structure of a Room-Temperature Ionic Liquid by High-Pressure Small-Angle X-Ray Scattering and Wide-Angle X-Ray Scattering: 1-Decyl-3-Methylimidazolium Chloride.

PubMed

Abe, Hiroshi; Hamaya, Nozomu; Koyama, Yoshihiro; Kishimura, Hiroaki; Takekiyo, Takahiro; Yoshimura, Yukihiro; Wakabayashi, Daisuke; Funamori, Nobumasa; Matsuishi, Kiyoto

2018-04-23

The Bragg reflections of 1-decyl-3-methylimidazolium chloride ([C 10 mim][Cl]), a room-temperature ionic liquid, are observed in a lowly scattered wavevector (q) region using high-pressure (HP) small-angle X-ray scattering methods. The HP crystal of [C 10 mim][Cl] was characterized by an extremely long periodic structure. The peak position at the lowest q (1.4 nm -1 ) was different from that of the prepeak observed in the liquid state (2.3 nm -1 ). Simultaneously, Bragg reflections at high-q were detected using HP wide-angle X-ray scattering. The longest lattice constant was estimated to be 4.3 nm using structural analysis. The crystal structure of HP differed from that of the low-temperature (LT) crystal and the LT liquid crystal. With increasing pressure, Bragg reflections in the high-q component became much broader, and were accompanied by phase transition, although those in the low-q component were observed to be relatively sharp. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Esterification of Starch in Ionic Liquids

USDA-ARS?s Scientific Manuscript database

We shall discuss the use of various ionic liquids in the preparation of starch esters. Starch was reacted with vinyl acetate in different 1-butyl-3-methylimidazolium (bmim) salts as solvents in an effort to produce starches with different acetylation patterns. Overall degree of substitution (DS) w...

Application of Ionic Liquids in the Microwave-Assisted Extraction of Proanthocyanidins from Larix gmelini Bark

PubMed Central

Yang, Lei; Sun, Xiaowei; Yang, Fengjian; Zhao, Chunjian; Zhang, Lin; Zu, Yuangang

2012-01-01

Ionic liquid based, microwave-assisted extraction (ILMAE) was successfully applied to the extraction of proanthocyanidins from Larix gmelini bark. In this work, in order to evaluate the performance of ionic liquids in the microwave-assisted extraction process, a series of 1-alkyl-3-methylimidazolium ionic liquids with different cations and anions were evaluated for extraction yield, and 1-butyl-3-methylimidazolium bromide was selected as the optimal solvent. In addition, the ILMAE procedure for the proanthocyanidins was optimized and compared with other conventional extraction techniques. Under the optimized conditions, satisfactory extraction yield of the proanthocyanidins was obtained. Relative to other methods, the proposed approach provided higher extraction yield and lower energy consumption. The Larix gmelini bark samples before and after extraction were analyzed by Thermal gravimetric analysis, Fourier-transform infrared spectroscopy and characterized by scanning electron microscopy. The results showed that the ILMAE method is a simple and efficient technique for sample preparation. PMID:22606036

Isothermogravimetric determination of the enthalpies of vaporization of 1-alkyl-3-methylimidazolium ionic liquids.

PubMed

Luo, Huimin; Baker, Gary A; Dai, Sheng

2008-08-21

Vaporization enthalpies for two series of ionic liquids (ILs) composed of 1- n-alkyl-3-methylimidazolium cations, [Imm1+] (m=2, 3, 4, 6, 8, or 10), paired with either the bis(trifluoromethanesulfonyl)amide, [Tf2N-], or the bis(perfluoroethylsulfonyl)amide anion, [beti-], were determined using a simple, convenient, and highly reproducible thermogravimetric approach, and from these values, Hildebrand solubility parameters were estimated. Our results reveal two interesting and unanticipated outcomes: (i) methylation at the C2 position of [Imm1+] affords a significantly higher vaporization enthalpy; (ii) in all cases, the [beti-] anion served to lower the enthalpy of vaporization relative to [Tf2N-]. The widespread availability of the apparatus required for these measurements coupled with the ease of automation suggests the broad potential of this methodology for determining this critical parameter in a multitude of ILs.

Solvent-Free Mechanochemical Synthesis of Nitrogen-Doped Nanoporous Carbon for Electrochemical Energy Storage.

PubMed

Schneidermann, Christina; Jäckel, Nicolas; Oswald, Steffen; Giebeler, Lars; Presser, Volker; Borchardt, Lars

2017-06-09

Nitrogen-doped nanoporous carbons were synthesized by a solvent-free mechanochemically induced one-pot synthesis. This facile approach involves the mechanochemical treatment and carbonization of three solid materials: potassium carbonate, urea, and lignin, which is a waste product from pulp industry. The resulting nitrogen-doped porous carbons offer a very high specific surface area up to 3000 m 2  g -1 and large pore volume up to 2 cm 3  g -1 . The mechanochemical reaction and the impact of activation and functionalization are investigated by nitrogen and water physisorption and high-resolution X-ray photoelectron spectroscopy (XPS). Our N-doped carbons are highly suitable for electrochemical energy storage as supercapacitor electrodes, showing high specific capacitances in aqueous 1 m Li 2 SO 4 electrolyte (177 F g -1 ), organic 1 m tetraethylammonium tetrafluoroborate in acetonitrile (147 F g -1 ), and an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate; 192 F g -1 ). This new mechanochemical pathway synergistically combines attractive energy-storage ratings with a scalable, time-efficient, cost-effective, and environmentally favorable synthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular dynamics study of congruent melting of the equimolar ionic liquid-benzene inclusion crystal [emim][NTf2]•C6H6

NASA Astrophysics Data System (ADS)

Kowsari, M. H.; Alavi, Saman; Ashrafizaadeh, Mahmud; Najafi, Bijan

2010-01-01

We use molecular dynamics simulations to study the structure, dynamics, and details of the mechanism of congruent melting of the equimolar mixture of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide with benzene, [emim][NTf2]•C6H6. Changes in the molecular arrangement, radial distribution functions, and the dynamic behavior of species are used to detect the solid to liquid transition, show an indication of the formation of polar islands by aggregating of the ions in the liquid phase, and characterize the melting process. The predicted enthalpy of melting ΔHm=38±2 kJ mol-1 for the equimolar inclusion mixture at 290 K is in good agreement with the differential scanning calorimetry experimental results of 42±2 kJ mol-1. The dynamics of the ions and benzene molecules were studied in the solid and liquid states by calculating the mean-square displacement (MSD) and the orientational autocorrelation function. The MSD plots show strong association between ion pairs of the ionic liquid in the inclusion mixture. Indeed, the presence of a stoichiometric number of benzene molecules does not affect the nearest neighbor ionic association between [emim]+ and [NTf2]-, but increases the MSDs of both cations and anions compared to pure liquid [emim][NTf2], showing that second shell ionic associations are weakened. We monitored the rotational motion of the alkyl chain sides of imidazolium cations and also calculated the activation energy for rotation of benzene molecules about their C6 symmetry axes in their lattice sites prior to melting.

Phase Transitions of Triflate-Based Ionic Liquids under High Pressure.

PubMed

Faria, Luiz F O; Ribeiro, Mauro C C

2015-11-05

Raman spectroscopy has been used to study phase transitions of ionic liquids based on the triflate anion, [TfO](-), as a function of pressure or temperature. Raman spectra of ionic liquids containing the cations 1-butyl-3-methylimidazolium, [C4C1Im](+), 1-octyl-3-methylimidazolium, [C8C1Im](+), 1-butyl-2,3-dimethylimidazolium, [C4C1C1Im](+), and 1-butyl-1-methylpyrrolidinium, [C4C1Pyr](+), were compared. Vibrational frequencies and binding energy of ionic pairs were calculated by quantum chemistry methods. The ionic liquids [C4C1Im][TfO] and [C4C1Pyr][TfO] crystallize at 1.0 GPa when the pressure is increased in steps of ∼ 0.2 GPa from the atmospheric pressure, whereas [C8C1Im][TfO] and [C4C1C1Im][TfO] do not crystallize up to 2.3 GPa of applied pressure. The low-frequency range of the Raman spectrum of [C4C1Im][TfO] indicates that the system undergoes glass transition, rather than crystallization, when the pressure applied on the liquid has been increased above 2.0 GPa in a single step. Strong hysteresis of spectral features (frequency shift and bandwidth) of the high-pressure crystalline phase when the pressure was released stepwise back to the atmospheric pressure has been found .

The evaporation study of silicon-containing ionic liquid

NASA Astrophysics Data System (ADS)

Chilingarov, Norbert S.; Medvedev, Artem A.; Deyko, Grigoriy S.; Kustov, Leonid M.; Chernikova, Elena A.; Glukhov, Lev M.; Polyakova, Marina V.; Ioutsi, Vitaliy A.; Markov, Vitaliy Yu.; Sidorov, Lev N.

2016-07-01

1,2-Dimethyl-3-(1‧,1‧,3‧,3‧-tetramethyl-3‧-phenyldisiloxanyl)methylimidazolium bis(trifluoromethanesulfonyl)amide ([PhC5OSi2MMIm+][Tf2N-]) is the first silicon-containing ionic liquid which was characterized with the vaporization enthalpy, (138.5 ± 1.8) kJ mol-1, and saturated vapor pressure, ln(p/Pa) = -(16656 ± 219)/(T/K) + (30.69 ± 0.92). This compound is a unique ionic liquid giving ions, retaining both cationic and anionic portions, in the electron impact ionization (EI) mass spectrum.

High Packing Density Unidirectional Arrays of Vertically Aligned Graphene with Enhanced Areal Capacitance for High-Power Micro-Supercapacitors.

PubMed

Zheng, Shuanghao; Li, Zhilin; Wu, Zhong-Shuai; Dong, Yanfeng; Zhou, Feng; Wang, Sen; Fu, Qiang; Sun, Chenglin; Guo, Liwei; Bao, Xinhe

2017-04-25

Interfacial integration of a shape-engineered electrode with a strongly bonded current collector is the key for minimizing both ionic and electronic resistance and then developing high-power supercapacitors. Herein, we demonstrated the construction of high-power micro-supercapacitors (VG-MSCs) based on high-density unidirectional arrays of vertically aligned graphene (VG) nanosheets, derived from a thermally decomposed SiC substrate. The as-grown VG arrays showed a standing basal plane orientation grown on a (0001̅) SiC substrate, tailored thickness (3.5-28 μm), high-density structurally ordering alignment of graphene consisting of 1-5 layers, vertically oriented edges, open intersheet channels, high electrical conductivity (192 S cm -1 ), and strong bonding of the VG edges to the SiC substrate. As a result, the demonstrated VG-MSCs displayed a high areal capacitance of ∼7.3 mF cm -2 and a fast frequency response with a short time constant of 9 ms. Furthermore, VG-MSCs in both an aqueous polymer gel electrolyte and nonaqueous ionic liquid of 1-ethyl-3-methylimidazolium tetrafluoroborate operated well at high scan rates of up to 200 V s -1 . More importantly, VG-MSCs offered a high power density of ∼15 W cm -3 in gel electrolyte and ∼61 W cm -3 in ionic liquid. Therefore, this strategy of producing high-density unidirectional VG nanosheets directly bonded on a SiC current collector demonstrated the feasibility of manufacturing high-power compact supercapacitors.

Extraction of ranitidine and nizatidine with using imidazolium ionic liquids prior spectrophotometric and chromatographic detection.

PubMed

Kiszkiel, Ilona; Starczewska, Barbara; Leśniewska, Barbara; Późniak, Patrycja

2015-03-15

A new extraction medium was proposed for liquid-liquid extraction of the histamine H2 receptor antagonists ranitidine (RNT) and nizatidine (NZT). The ionic liquids with low vapor pressure and favorable solvating properties for a range of compounds such as 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6] and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C4mim][Tf2N] were tested for isolation of analytes. The extraction parameters of RNT and NZT, namely, amount of ionic liquid, pH of sample solution, shaking and centrifugation time were optimized. The isolation processes were performed with 1 mL of the ionic liquids. The extracted samples (pH values near 4) were shaken at 1750 rpm. The influence of interfering substances on the efficiency of extraction process was also studied. Methods for the histamine H2 receptor antagonists (ranitidine and nizatidine) determination after their separation using imidazolium ionic liquids by high performance liquid chromatography (HPLC) combined with UV spectrophotometry were developed. The application of ionic liquids in extraction step allows for selective isolation of analytes from aqueous matrices and their preconcentration. The above methods were applied to the determination of RNT and NZT in environmental samples (river water and wastewater after treatment). Copyright © 2014 Elsevier B.V. All rights reserved.

IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

EPA Science Inventory

A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

Glucose recovery from aqueous solutions by adsorption in metal–organic framework MIL-101: a molecular simulation study

PubMed Central

Gupta, Krishna M.; Zhang, Kang; Jiang, Jianwen

2015-01-01

A molecular simulation study is reported on glucose recovery from aqueous solutions by adsorption in metal-organic framework MIL-101. The F atom of MIL-101 is identified to be the most favorable adsorption site. Among three MIL-101-X (X = H, NH2 or CH3), the parent MIL-101 exhibits the highest adsorption capacity and recovery efficacy. Upon functionalization by -NH2 or -CH3 group, the steric hindrance in MIL-101 increases; consequently, the interactions between glucose and framework become less attractive, thus reducing the capacity and mobility of glucose. The presence of ionic liquid, 1-ethyl-3-methyl-imidazolium acetate, as an impurity reduces the strength of hydrogen-bonding between glucose and MIL-101, and leads to lower capacity and mobility. Upon adding anti-solvent (ethanol or acetone), a similar adverse effect is observed. The simulation study provides useful structural and dynamic properties of glucose in MIL-101, and it suggests that MIL-101 might be a potential candidate for glucose recovery. PMID:26242874

Glucose recovery from aqueous solutions by adsorption in metal-organic framework MIL-101: a molecular simulation study

NASA Astrophysics Data System (ADS)

Gupta, Krishna M.; Zhang, Kang; Jiang, Jianwen

2015-08-01

A molecular simulation study is reported on glucose recovery from aqueous solutions by adsorption in metal-organic framework MIL-101. The F atom of MIL-101 is identified to be the most favorable adsorption site. Among three MIL-101-X (X = H, NH2 or CH3), the parent MIL-101 exhibits the highest adsorption capacity and recovery efficacy. Upon functionalization by -NH2 or -CH3 group, the steric hindrance in MIL-101 increases; consequently, the interactions between glucose and framework become less attractive, thus reducing the capacity and mobility of glucose. The presence of ionic liquid, 1-ethyl-3-methyl-imidazolium acetate, as an impurity reduces the strength of hydrogen-bonding between glucose and MIL-101, and leads to lower capacity and mobility. Upon adding anti-solvent (ethanol or acetone), a similar adverse effect is observed. The simulation study provides useful structural and dynamic properties of glucose in MIL-101, and it suggests that MIL-101 might be a potential candidate for glucose recovery.

Screening out the non-Arrhenius behaviour of nematic-isotropic transition by room temperature ionic liquid.

PubMed

Dan, K; Datta, A; Yoshida, Y; Saito, G; Yoshikawa, K; Roy, M

2016-02-28

Differential Scanning Calorimetry (DSC) and optical polarization microscopy of a mixture of the liquid crystalline material (N-(4-methoxybenzylidene)-4-butylaniline, MBBA) and a Fe-based room temperature ionic liquid 1-ethyl-3-methylimidazolium tetrachloroferrate ([Emim](+) [FeCl4](-), EMIF) indicate a decrease in the nematic-isotropic (N-I) phase transition temperature (T(NI)) with an increase in EMIF concentration, explained by a proposed model of Coulomb "screening" of MBBA quadrupoles by the EMIF ions along with ionic "self screening." DSC studies of EMIF-MBBA and pure EMIF and comparison with pure MBBA results show that the major transitions in pure EMIF have Arrhenius behaviour, but more importantly the previously found convex Arrhenius behaviour of the pristine MBBA [K. Dan et al., Europhys. Lett. 108, 36007 (2014)] becomes Arrhenius in the mixture, indicating a conversion of the entropic N-I activation barrier to an enthalpic one. In presence of EMIF, a drastic decrease in the intensity of out-of-plane distortions of benzene rings in MBBA is found from Fourier transform infrared spectroscopy, consistent with significant reduction in the conformational states of MBBA. This suppression of large amplitude motion is again consistent with a Coulomb screening and gives a molecular basis for the entropic-to-enthalpic conversion of the N-I activation barrier.

A monolithic functional film of nanotubes/cellulose/ionic liquid for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Basiricò, Lucia; Lanzara, Giulia

2014-12-01

A novel monolithic, pre-fabricated, fully functional film made of a nanostructured free-standing layer is presented for a new and competitive class of easy-to-assemble flexible supercapacitors whose design is in-between the all solid state and the traditional liquid electrolyte. The film is made of two vertically aligned multi-walled carbon nanotube (VANT) electrodes that store ions, embedded-in, and monolithically interspaced by a solution of microcrystalline cellulose in a room temperature ionic liquid (RTIL) electrolyte (1-ethyl-3-methylimidazolium acetate-EMIM Ac). The fine tuning of VANTs length and electrolyte/cellulose amount leads, in a sole and continuous block, to ions storage and physical separation between the electrodes without the need of the additional separator layer that is typically used in supercapacitors. Thus, physical discontinuities that can induce disturbances to ions mobility, are fully eliminated significantly reducing the equivalent series resistance and increasing the knee frequency, hence outclassing the best supercapacitors based on VANTs and non-aqueous electrolytes. The excellent electrochemical response can also be addressed to the chosen electrolyte that, not only has the advantage of leading to a significantly simpler and more affordable fabrication procedure, but has higher ionic conductivity, lower viscosity and higher ions mobility than other electrolytes capable of dissolving cellulose.

Direct electrochemistry and electrocatalysis of hemoglobin in graphene oxide and ionic liquid composite film.

PubMed

Sun, Wei; Gong, Shixing; Shi, Fan; Cao, Lili; Ling, Luyang; Zheng, Weizhe; Wang, Wencheng

2014-07-01

In this paper a novel sensing platform based on graphene oxide (GO), ionic liquid (IL) 1-ethyl-3-methylimidazolium tetrafluoroborate and Nafion for the immobilization of hemoglobin (Hb) was adopted with a carbon ionic liquid electrode (CILE) as the substrate electrode, which was denoted as Nafion/Hb-GO-IL/CILE. Spectroscopic results suggested that Hb molecules were not denatured in the composite. A pair of well-defined redox peaks appeared on the cyclic voltammogram, which was attributed to the realization of direct electron transfer of Hb on the electrode. Electrochemical behaviors of Hb entrapped in the film were carefully investigated by cyclic voltammetry with the electrochemical parameters calculated. Based on the catalytic ability of the immobilized Hb, Nafion/Hb-GO-IL/CILE exhibited excellent electrocatalytic behavior towards the reduction of different substrates such as trichloroacetic acid in the concentration range from 0.01 to 40.0mM with the detection limit as 3.12 μM (3σ), H2O2 in the concentration range from 0.08 to 635.0 μM with the detection limit as 0.0137 μM (3σ) and NaNO2 in the concentration range from 0.5 to 800.0 μM with the detection limit as 0.0104 μM (3σ). So the proposed bioelectrode could be served as a new third-generation electrochemical sensor without mediator. Copyright © 2014 Elsevier B.V. All rights reserved.

The influence of mesoscopic confinement on the dynamics of imidazolium-based room temperature ionic liquids in polyether sulfone membranes.

PubMed

Thomaz, Joseph E; Bailey, Heather E; Fayer, Michael D

2017-11-21

The structural dynamics of a series of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C n mimNTf 2 , n = 2, 4, 6, 10: ethyl-Emim; butyl-Bmim; hexyl-Hmim; decyl-Dmim) room temperature ionic liquids confined in the pores of polyether sulfone (PES 200) membranes with an average pore size of ∼350 nm and in the bulk liquids were studied. Time correlated single photon counting measurements of the fluorescence of the fluorophore coumarin 153 (C153) were used to observe the time-dependent Stokes shift (solvation dynamics). The solvation dynamics of C153 in the ionic liquids are multiexponential decays. The multiexponential functional form of the decays was confirmed as the slowest decay component of each bulk liquid matches the slowest component of the liquid dynamics measured by optical heterodyne-detected optical Kerr effect (OHD-OKE) experiments, which is single exponential. The fact that the slowest component of the Stokes shift matches the OHD-OKE data in all four liquids identifies this component of the solvation dynamics as arising from the complete structural randomization of the liquids. Although the pores in the PES membranes are large, confinement on the mesoscopic length scale results in substantial slowing of the dynamics, a factor of ∼4, for EmimNTf 2 , with the effect decreasing as the chain length increases. By DmimNTf 2 , the dynamics are virtually indistinguishable from those in the bulk liquid. The rotation relaxation of C153 in the four bulk liquids was also measured and showed strong coupling between the C153 probe and its environment.

Ionic liquids as novel solvents for biosynthesis of octenyl succinic anhydride-modified waxy maize starch.

PubMed

Li, Dandan; Zhang, Xiwen; Tian, Yaoqi

2016-05-01

Biosynthesis of octenyl succinic anhydride (OSA) starch was investigated using ionic liquids (ILs) as reaction media. Waxy maize starch was pretreated in 1-butyl-3-methylimidazolium chlorine and then esterified with OSA in 1-octyl-3-methylimidazolium nitrate by using Novozyme 435 as catalyst. The degree of substitution of OSA starch reached 0.0130 with 5 wt% starch concentration and 1 wt% lipase dosage based on ILs weight at 50 °C for 3h. The formation of OSA starch was confirmed by fourier transform infrared spectroscopy. Scanning electron microscopy and X-ray diffraction revealed that the morphology and crystal structure of starch were significantly destroyed. Thermogravimetric analysis showed that esterification decreased the thermal stability of starch. The successful lipase-catalyzed synthesis of OSA starch in ILs suggests that ILs are potential replacement of traditional organic solvents for starch ester biosynthesis. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of the solubility parameter of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate by inverse gas chromatography.

PubMed

Ma, Xiaohong; Wang, Qiang; Li, Xiaoping; Tang, Jun; Zhang, Zhengfang

2015-11-01

Thermodynamic properties of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM] BF4) were determined via inverse gas chromatography (IGC). Two groups of solvents with different chemical natures and polarities were used to obtain information about [BMIM] BF4-solvent interactions. The specific retention volume, molar heat of sorption, weight fraction activity coefficient, Flory-Huggins interaction parameter as well as solubility parameter were also determined in a temperature range of 333 - 373 K. The results showed that the selected solvents n-C10 to n-C12, carbon tetrachloride, cyclohexane and toluene were poor solvents for [BMIM] BF4, while dichloromethane, acetone, chloroform, methyl acetate, ethanol and methanol were favorite solvents for [BMIM] BF4. In addition, the solubility parameter of [ BMIM] BF4 was determined as 23.39 (J/cm3)0.5 by the extrapolation at 298 K. The experiment proved that IGC was a simple and accurate method to obtain the thermodynamic properties of ionic liquids. This study could be used as a reference to the application and research of the ionic liquids.

Influence of the ionic liquid 1-butyl-3-methylimidazolium bromide on amyloid fibrillogenesis in lysozyme: Evidence from photophysical and imaging studies.

PubMed

Basu, Anirban; Bhattacharya, Subhash Chandra; Kumar, Gopinatha Suresh

2018-02-01

Many proteins can abnormally fold to form pathological amyloid deposits/aggregates that are responsible for various degenerative disorders called amyloidosis. Here we have examined the anti-amyloidogenic potency of an ionic liquid, 1-butyl-3-methylimidazolium bromide, using lysozyme as a model system. Thioflavin T fluorescence assay demonstrated that the ionic liquid suppressed the formation of lysozyme fibrils significantly. This observation was further confirmed by the Congo red assay. Fluorescence microscopy, intrinsic fluorescence studies, nile red fluorescence assay, ANS binding assay and circular dichroism studies also testified diminishing of the fibrillogenesis in the presence of ionic liquid. Formation of amyloid fibrils was also characterized by α to β conformational transition. From far-UV circular dichroism studies it was observed that the β-sheet content of the lysozyme samples decreased in the presence of the ionic liquid which in turn implied that fibrillogenesis was supressed by the ionic liquid. Atomic force microscopy imaging unequivocally established that the ionic liquid attenuated fibrillogenesis in lysozyme. These results may be useful for the development of more effective therapeutics for amyloidosis. Copyright © 2017 Elsevier B.V. All rights reserved.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chopade, Sujay A.; Anderson, Evan L.; Schmidt, Peter W.

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethylmore » sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.« less

Physiological and biochemical responses of wheat (Triticum aestivum L.) seedlings to three imidazolium-based ionic liquids in soil.

PubMed

Xu, Yaqi; Wang, Jun; Zhu, Lusheng; Du, Zhongkun; Wang, Jinhua; Wei, Kai

2018-01-01

Ionic liquids (ILs) are considered environmentally friendly solvents and are widely applied in various fields; however, some researchers have noted the toxicity of ILs to plants cultivated in nutrient solution. To evaluate the toxicities of ILs to wheat seedlings in soil, the natural growth environment of plants, a study was performed using three imidazolium-based ionic liquids with different anions: 1-octyl-3-methylimidazolium chloride ([C 8 mim]Cl), 1-octyl-3-methylimidazolium bromide ([C 8 mim]Br) and 1-octyl-3-methylimidazolium tetrafluoroborate ([C 8 mim]BF 4 ). After 13 d of exposure to these three ILs at 0, 100, 200, 400, 600 and 800 mg kg -1 in brown soil, wheat seedlings were randomly sampled to evaluate growth (shoot length, root length, pigment content and proline content), lipid peroxidation, oxygen species (H 2 O 2 and O 2 - ) and activities of the detoxification enzyme glutathione-s-transferase and other antioxidant enzymes, including superoxide dismutase, catalase and peroxidase. The experimental results showed that all three ILs had inhibitory effects on the growth of wheat seedlings and induced the generation of reactive oxygen species, which indicated that the wheat seedlings suffered oxidative stress. Moreover, antioxidant enzyme activity was enhanced after exposure to [C 8 mim]Cl, [C 8 mim]Br and [C 8 mim]BF 4 , demonstrating that oxidative damage may be the primary underlying mechanism of IL toxicity in wheat. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sensitivity of electrospray molecular dynamics simulations to long-range Coulomb interaction models

NASA Astrophysics Data System (ADS)

Mehta, Neil A.; Levin, Deborah A.

2018-03-01

Molecular dynamics (MD) electrospray simulations of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) ion liquid were performed with the goal of evaluating the influence of long-range Coulomb models on ion emission characteristics. The direct Coulomb (DC), shifted force Coulomb sum (SFCS), and particle-particle particle-mesh (PPPM) long-range Coulomb models were considered in this work. The DC method with a sufficiently large cutoff radius was found to be the most accurate approach for modeling electrosprays, but, it is computationally expensive. The Coulomb potential energy modeled by the DC method in combination with the radial electric fields were found to be necessary to generate the Taylor cone. The differences observed between the SFCS and the DC in terms of predicting the total ion emission suggest that the former should not be used in MD electrospray simulations. Furthermore, the common assumption of domain periodicity was observed to be detrimental to the accuracy of the capillary-based electrospray simulations.

Sensitivity of electrospray molecular dynamics simulations to long-range Coulomb interaction models.

PubMed

Mehta, Neil A; Levin, Deborah A

2018-03-01

Molecular dynamics (MD) electrospray simulations of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF_{4}) ion liquid were performed with the goal of evaluating the influence of long-range Coulomb models on ion emission characteristics. The direct Coulomb (DC), shifted force Coulomb sum (SFCS), and particle-particle particle-mesh (PPPM) long-range Coulomb models were considered in this work. The DC method with a sufficiently large cutoff radius was found to be the most accurate approach for modeling electrosprays, but, it is computationally expensive. The Coulomb potential energy modeled by the DC method in combination with the radial electric fields were found to be necessary to generate the Taylor cone. The differences observed between the SFCS and the DC in terms of predicting the total ion emission suggest that the former should not be used in MD electrospray simulations. Furthermore, the common assumption of domain periodicity was observed to be detrimental to the accuracy of the capillary-based electrospray simulations.

Predicting the partitioning of biological compounds between room-temperature ionic liquids and water by means of the solvation-parameter model.

PubMed

Padró, Juan M; Ponzinibbio, Agustín; Mesa, Leidy B Agudelo; Reta, Mario

2011-03-01

The partition coefficients, P(IL/w), for different probe molecules as well as for compounds of biological interest between the room-temperature ionic liquids (RTILs) 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF(6)], 1-hexyl-3-methylimidazolium hexafluorophosphate, [HMIM][PF(6)], 1-octyl-3-methylimidazolium tetrafluoroborate, [OMIM][BF(4)] and water were accurately measured. [BMIM][PF(6)] and [OMIM][BF(4)] were synthesized by adapting a procedure from the literature to a simpler, single-vessel and faster methodology, with a much lesser consumption of organic solvent. We employed the solvation-parameter model to elucidate the general chemical interactions involved in RTIL/water partitioning. With this purpose, we have selected different solute descriptor parameters that measure polarity, polarizability, hydrogen-bond-donor and hydrogen-bond-acceptor interactions, and cavity formation for a set of specifically selected probe molecules (the training set). The obtained multiparametric equations were used to predict the partition coefficients for compounds not present in the training set (the test set), most being of biological interest. Partial solubility of the ionic liquid in water (and water into the ionic liquid) was taken into account to explain the obtained results. This fact has not been deeply considered up to date. Solute descriptors were obtained from the literature, when available, or else calculated through commercial software. An excellent agreement between calculated and experimental log P(IL/w) values was obtained, which demonstrated that the resulting multiparametric equations are robust and allow predicting partitioning for any organic molecule in the biphasic systems studied.

High-performance dye-sensitized solar cells based on solvent-free electrolytes produced from eutectic melts.

PubMed

Bai, Yu; Cao, Yiming; Zhang, Jing; Wang, Mingkui; Li, Renzhi; Wang, Peng; Zakeeruddin, Shaik M; Grätzel, Michael

2008-08-01

Low-cost excitonic solar cells based on organic optoelectronic materials are receiving an ever-increasing amount of attention as potential alternatives to traditional inorganic photovoltaic devices. In this rapidly developing field, the dye-sensitized solar cell (DSC) has achieved so far the highest validated efficiency of 11.1% (ref. 2) and remarkable stability. However, the cells with the best performance use volatile solvents in their electrolytes, which may be prohibitive for outdoor solar panels in view of the need for robust encapsulation. Solvent-free room-temperature ionic liquids have been pursued as an attractive solution to this dilemma, and device efficiencies of over 7% were achieved by using some low-viscosity formulations containing 1-ethyl-3-methylimidazolium thiocyanate, selenocyanate, tricyanomethide or tetracyanoborate. Unfortunately, apart from tetracyanoborate, all of these low-viscosity melts proved to be unstable under prolonged thermal stress and light soaking. Here, we introduce the concept of using eutectic melts to produce solvent-free liquid redox electrolytes. Using a ternary melt in conjunction with a nanocrystalline titania film and the amphiphilic heteroleptic ruthenium complex Z907Na (ref. 10) as a sensitizer, we reach excellent stability and an unprecedented efficiency of 8.2% under air-mass 1.5 global illumination. Our results are of importance to realize large-scale outdoor applications of mesoscopic DSCs.

Pressure-induced phase transition of 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6

NASA Astrophysics Data System (ADS)

Takekiyo, Takahiro; Hatano, Naohiro; Imai, Yusuke; Abe, Hiroshi; Yoshimura, Yukihiro

2011-03-01

We have investigated the pressure-induced Raman spectral change of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) using Raman spectroscopy. The relative Raman intensity at 590 cm-1 of the CH2 rocking band assigned to the gauche conformer of the NCCC dihedral angle of the butyl group in the [bmim]+ cation increases when the pressure-induced liquid-crystalline phase transition occurs, while that at 610 cm-1 assigned to the trans conformer decreases. Our results show that the high-pressure phase transition of [bmim][PF6] causes the increase of the gauche conformer of the [bmim]+ cation.

Oxidative desulfurization of dibenzothiophene from model oil using ionic liquids as extracting agent

NASA Astrophysics Data System (ADS)

Taha, Mohd F.; Atikah, N.; Chong, F. K.; Shaharun, Maizatul S.

2012-09-01

The oxidative desulfurization of dibenzothiophene (DBT) from model oil (in n-dodecane) was carried out using ionic liquid as the extractant and catalyst, and hydrogen peroxide (H2O2) in combination with acetic acid (CH3COOH) and sulphuric acid (H2SO4) as the oxidant. The ionic liquids used were 1-butyl-3-methylimidazolium octyl sulphate ([Bmim][OcSO4]) and 1-butyl-3-methylimidazolium acetate ([Bmim][Ac]). The effect of the amounts of H2O2 on oxidative desulphurization of model oil was first investigated without the usage of ionic liquids at room temperature. The results indicate that greater amount of H2O2 give higher desulfurization and the maximum desulfurization in this study, i.e. 34 %, was occurred when the molar ratio of H2O2 to sulfur was 5:1. With the usage of ionic liquid and the molar ratio of 5:1 (H2O2:sulfur), the efficiency of DBT removal from model oil was increased significantly in terms of percent removal and removal time. Ionic liquid of [Bmim][OcSO4] performed better than [Bmim][Ac] with 72 % DBT removal. When molar ratio of H2O2 to sulphur was 5:1, volume ratio of ionic liquid to model oil was 1:1 and mixing time was 60 min at room temperature. The results indicate the potential of ionic liquids as the extractant and catalyst for oxidative desulfurization of hydrocarbon fuels.

Environmental Screening of Electrode Materials for a Rechargeable Aluminum Battery with an AlCl₃/EMIMCl Electrolyte.

PubMed

Ellingsen, Linda Ager-Wick; Holland, Alex; Drillet, Jean-Francois; Peters, Willi; Eckert, Martin; Concepcion, Carlos; Ruiz, Oscar; Colin, Jean-François; Knipping, Etienne; Pan, Qiaoyan; Wills, Richard G A; Majeau-Bettez, Guillaume

2018-06-01

Recently, rechargeable aluminum batteries have received much attention due to their low cost, easy operation, and high safety. As the research into rechargeable aluminum batteries with a room-temperature ionic liquid electrolyte is relatively new, research efforts have focused on finding suitable electrode materials. An understanding of the environmental aspects of electrode materials is essential to make informed and conscious decisions in aluminum battery development. The purpose of this study was to evaluate and compare the relative environmental performance of electrode material candidates for rechargeable aluminum batteries with an AlCl₃/EMIMCl (1-ethyl-3-methylimidazolium chloride) room-temperature ionic liquid electrolyte. To this end, we used a lifecycle environmental screening framework to evaluate 12 candidate electrode materials. We found that all of the studied materials are associated with one or more drawbacks and therefore do not represent a "silver bullet" for the aluminum battery. Even so, some materials appeared more promising than others did. We also found that aluminum battery technology is likely to face some of the same environmental challenges as Li-ion technology but also offers an opportunity to avoid others. The insights provided here can aid aluminum battery development in an environmentally sustainable direction.

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. I. Structural properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2006-05-14

Molecular dynamics (MD) simulations have been performed for prototype models of polymer electrolytes in which the salt is an ionic liquid based on 1-alkyl-3-methylimidazolium cations and the polymer is poly(ethylene oxide), PEO. The MD simulations were performed by combining the previously proposed models for pure ionic liquids and polymer electrolytes containing simple inorganic ions. A systematic investigation of ionic liquid concentration, temperature, and the 1-alkyl- chain length, [1,3-dimethylimidazolium]PF6, and [1-butyl-3-methylimidazolium]PF6, effects on resulting equilibrium structure is provided. It is shown that the ionic liquid is dispersed in the polymeric matrix, but ionic pairs remain in the polymer electrolyte. Imidazolium cations are coordinated by both the anions and the oxygen atoms of PEO chains. Probability density maps of occurrences of nearest neighbors around imidazolium cations give a detailed physical picture of the environment experienced by cations. Conformational changes on PEO chains upon addition of the ionic liquid are identified. The equilibrium structure of simulated systems is also analyzed in reciprocal space by using the static structure factor, S(k). Calculated S(k) display a low wave-vector peak, indicating that spatial correlation in an extended-range order prevail in the ionic liquid polymer electrolytes. Long-range correlations are assigned to nonuniform distribution of ionic species within the simulation box.

Determination of atenolol in human plasma using ionic-liquid-based ultrasound-assisted in situ solvent formation microextraction followed by high-performance liquid chromatography.

PubMed

Zeeb, Mohsen; Farahani, Hadi; Papan, Mohammad Kazem

2016-06-01

An efficient analytical method called ionic-liquid-based ultrasound-assisted in situ solvent formation microextraction followed by high-performance liquid chromatography was developed for the determination of atenolol in human plasma. A hydrophobic ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) was formed by the addition of a hydrophilic ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) to a sample solution containing an ion-pairing agent during microextraction. The analyte was extracted into the ionic liquid phase while the microextraction solvent was dispersed throughout the sample by utilizing ultrasound. The sample was then centrifuged, and the extracting phase retracted into the microsyringe and injected to liquid chromatography. After optimization, the calibration curve showed linearity in the range of 2-750 ng/mL with the regression coefficient corresponding to 0.998. The limits of detection (S/N = 3) and quantification (S/N = 10) were 0.5 and 2 ng/mL, respectively. A reasonable relative recovery range of 90-96.7% and satisfactory intra-assay (4.8-5.1%, n = 6) and interassay (5.0-5.6%, n = 9) precision along with a substantial sample clean-up demonstrated good performance of the procedure. It was applied for the determination of atenolol in human plasma after oral administration and some pharmacokinetic data were obtained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction for the separation and determination of estrogens in water samples by high-performance liquid chromatography with fluorescence detection.

PubMed

Zhang, Rui; Wang, Chuanliu; Yue, Qiaohong; Zhou, Tiecheng; Li, Na; Zhang, Hanqi; Hao, Xiaoke

2014-11-01

An ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction method was proposed for the extraction and concentration of 17-α-estradiol, 17-β-estradiol-benzoate, and quinestrol in environmental water samples by high-performance liquid chromatography with fluorescence detection. 1-Hexyl-3-methylimidazolium tetrafluoroborate was applied as foaming agent in the foam flotation process and dispersive solvent in microextraction. The introduction of the ion-pairing and salting-out agent NH4 PF6 was beneficial to the improvement of recoveries for the hydrophobic ionic liquid phase and analytes. Parameters of the proposed method including concentration of 1-hexyl-3-methylimidazolium tetrafluoroborate, flow rate of carrier gas, floatation time, types and concentration of ionic liquids, salt concentration in samples, extraction time, and centrifugation time were evaluated. The recoveries were between 98 and 105% with relative standard deviations lower than 7% for lake water and well water samples. The isolation of the target compounds from the water was found to be efficient, and the enrichment factors ranged from 4445 to 4632. This developing method is free of volatile organic solvents compared with regular extraction. Based on the unique properties of ionic liquids, the application of foam floatation, and dispersive liquid-liquid microextraction was widened. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Developing energy efficient lignin biomass processing - towards understanding mediator behaviour in ionic liquids.

PubMed

Eshtaya, Majd; Ejigu, Andinet; Stephens, Gill; Walsh, Darren A; Chen, George Z; Croft, Anna K

2016-08-15

Environmental concerns have brought attention to the requirement for more efficient and renewable processes for chemicals production. Lignin is the second most abundant natural polymer, and might serve as a sustainable resource for manufacturing fuels and aromatic derivatives for the chemicals industry after being depolymerised. In this work, the mediator 2,2'-azino-bis(3-ethylbenthiazoline-6-sulfonic acid) diammonium salt (ABTS), commonly used with enzyme degradation systems, has been evaluated by means of cyclic voltammetry (CV) for enhancing the oxidation of the non-phenolic lignin model compound veratryl alcohol and three types of lignin (organosolv, Kraft and lignosulfonate) in the ionic liquid 1-ethyl-3-methylimidazolium ethyl sulfate, ([C2mim][C2SO4]). The presence of either veratryl alcohol or organosolv lignin increased the second oxidation peak of ABTS under select conditions, indicating the ABTS-mediated oxidation of these molecules at high potentials in [C2mim][C2SO4]. Furthermore, CV was applied as a quick and efficient way to explore the impact of water in the ABTS-mediated oxidation of both organosolv and lignosulfonate lignin. Higher catalytic efficiencies of ABTS were observed for lignosulfonate solutions either in sodium acetate buffer or when [C2mim][C2SO4] (15 v/v%) was present in the buffer solution, whilst there was no change found in the catalytic efficiency of ABTS in [C2mim][C2SO4]-lignosulfonate mixtures relative to ABTS alone. In contrast, organosolv showed an initial increase in oxidation, followed by a significant decrease on increasing the water content of a [C2mim][C2SO4] solution.

Communication: Potentials of mean force study of ionic liquid ion pair aggregation in polar covalent molecule solvents

NASA Astrophysics Data System (ADS)

Bandlamudi, Santosh Rathan Paul; Benjamin, Kenneth M.

2018-05-01

Molecular dynamics (MD) simulations were conducted for 1-ethyl-3-methylimidazolium methylsulfate [EMIM][MeSO4] dissolved in six polar covalent molecules [acetic acid, acetone, chloroform, dimethyl sulfoxide (DMSO), isopropyl alcohol, and methanol] to understand the free energies of ionic liquid (IL) ion pairing/aggregation in the limit of infinite dilution. Free energy landscapes or potentials of mean force (PMF) were computed using umbrella sampling and the weighted histogram analysis method. The PMF studies showed the strongest IL ion pairing in chloroform, and the strength of IL ion pairing decreases in the order of chloroform, acetone, propanol, acetic acid, DMSO, and methanol. In the limit of infinite dilution, the free energy curves for IL ion aggregation in co-solvents were characterized by two distinct minima [global (˜3.6 Å) and local (˜5.7 Å)], while free energy values at these minima differed significantly for IL in each co-solvent. The PMF studies were extended for determining the free energy of IL ion aggregation as a function of concentration of methanol. Studies showed that as the concentration of methanol increased, the free energy of ion aggregation decreased, suggesting greater ion pair stability, in agreement with previously reported MD clustering and radial distribution function data.

Spectroscopic properties and amplified spontaneous emission of fluorescein laser dye in ionic liquids as green media

NASA Astrophysics Data System (ADS)

AL-Aqmar, Dalal M.; Abdelkader, H. I.; Abou Kana, Maram T. H.

2015-09-01

The use of ionic liquids (ILs) as milieu materials for laser dyes is a promising field and quite competitive with volatile organic solvents and solid state-dye laser systems. This paper investigates some photo-physical parameters of fluorescein dye incorporated into ionic liquids; 1-Butyl-3-methylimidazolium chloride (BMIM Cl), 1-Butyl-3-methylimidazolium tetrachloroaluminate (BMIM AlCl4) and 1-Butyl-3-methylimidazolium tetrafluoroborate (BMIM BF4) as promising host matrix in addition to ethanol as reference. These parameters are: absorption and emission cross-sections, fluorescence lifetime and quantum yield, in addition to the transition dipole moment, the attenuation length and oscillator strength were also investigated. Lasing characteristics such as amplified spontaneous emission (ASE), the gain, and the photostability of fluorescein laser dye dissolved in different host materials were assessed. The composition and properties of the matrix of ILs were found that it has great interest in optimizing the laser performance and photostability of the investigated laser dye. Under transverse pumping of fluorescein dye by blue laser diode (450 nm) of (400 mW), the initial ASE for dye dissolved in BMIM AlCl4 and ethanol were decreased to 39% and 36% respectively as time progressed 132 min. Relatively high efficiency and high fluorescence quantum yield (11.8% and 0.82% respectively) were obtained with good photostability in case of fluorescein in BMIM BF4 that was decreased to ∼56% of the initial ASE after continuously pumping with 400 mW for 132 min.

Acoustic cavitation in 1-butyl-3-methylimidazolium bis(triflluoromethyl-sulfonyl)imide based ionic liquid.

PubMed

Merouani, Slimane; Hamdaoui, Oualid; Haddad, Boumediene

2018-03-01

In this work, a comparison between the temperatures/pressures within acoustic cavitation bubble in an imidazolium-based room-temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium bis(triflluoromethyl-sulfonyl)imide ([BMIM][NTf 2 ]), and in water has been made for a wide range of cavitation parameters including frequency (140-1000kHz), acoustic intensity (0.5-1Wcm -2 ), liquid temperature (20-50°C) and external static pressure (0.7-1.5atm). The used cavitation model takes into account the liquid compressibility as well as the surface tension and the viscosity of the medium. It was found that the bubble temperatures and pressures were always much higher in the ionic liquid compared to those predicted in water. The valuable effect of [BMIM][NTf 2 ] on the bubble temperature was more pronounced at higher acoustic intensity and liquid temperature and lower frequency and external static pressure. However, confrontation between the predicted and the experimental estimated temperatures in ionic liquids showed an opposite trend as the temperatures measured in some pure ionic liquids are of the same order as those observed in water. The injection of liquid droplets into cavitation bubbles, the pyrolysis of ionic liquids at the bubble-solution interface as well as the lower number of collapsing bubbles in the ionic liquid may be the responsible for the lower measured bubble temperatures in ionic liquids, as compared with water. Copyright © 2017 Elsevier B.V. All rights reserved.

Liquid-liquid extraction of neodymium(III) by dialkylphosphate ionic liquids from acidic medium: the importance of the ionic liquid cation.

PubMed

Rout, Alok; Kotlarska, Justyna; Dehaen, Wim; Binnemans, Koen

2013-10-21

The ionic liquids 1-hexyl-3-methylimidazolium bis(2-ethylhexyl)phosphate, [C6mim][DEHP], 1-hexyl-1-methylpyrrolidinium bis(2-ethylhexyl)phosphate, [C6mpyr][DEHP], and tetrabutylammonium bis(2-ethylhexyl)phosphate, [N4444][DEHP], were prepared and characterized using (1)H and (13)C NMR spectroscopy. The extraction behavior of neodymium(iii) from nitrate medium by these ionic liquids, diluted with the room temperature ionic liquids 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C6mim][NTf2], 1-hexyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C6mpyr][NTf2], and tributylmethylammonium bis(trifluoromethylsulfonyl)imide, [N1444][NTf2], was studied. The distribution ratio of neodymium(iii) was measured as a function of various parameters, such as pH, concentration of the ionic liquid extractant, nature of diluents, concentration of ionic liquid cations and nitrate anions in the aqueous phase. The extraction behavior was compared with that obtained for a solution of the molecular extractant bis(2-ethylhexyl)phosphoric acid (DEHPA) in an ionic liquid diluent. The extraction of neodymium(iii) in the ionic liquids [C6mim][DEHP] and [C6mpyr][DEHP] showed markedly different extraction properties in comparison with that of the quaternary ammonium analogue [N4444][DEHP], especially concerning the pH dependence of the extraction process. These results show that the extraction process can be tuned by the selection of the ionic liquid cation. The extraction experiments also included the trivalent rare-earth ions lanthanum(iii), cerium(iii), praseodymium(iii), ytterbium(iii) and yttrium(iii). Studies of the stripping behavior and the reusability of the ionic liquids were carried out, which indicate that the ionic liquids can be reused with no loss in activity.

Study and development of non-aqueous silicon-air battery

NASA Astrophysics Data System (ADS)

Cohn, Gil; Ein-Eli, Yair

Silicon-air battery utilizing a single-crystal heavily doped n-type silicon wafer anode and an air cathode is reported in this paper. The battery employs hydrophilic 1-ethyl-3-methylimidazolium oligofluorohydrogenate [EMI·(HF) 2.3F] room temperature ionic liquid electrolyte. Electrochemical studies, including polarization and galvanostatic experiments, performed on various silicon types reveal the predominance performance of heavily doped n-type. Cell discharging at constant current densities of 10, 50, 100 and 300 μA cm -2 in ambient atmosphere, shows working voltages of 1.1-0.8 V. The study shows that as discharge advances, the moist interface of the air electrode is covered by discharge products, which prevent a continuous diffusion of oxygen to the electrode-electrolyte interface. The oxygen suffocation, governed by the settlement of the cell reaction products, is the main factor for an early failure of the cells. Based on the results obtained from scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy studies, we propose a series of reactions governing the discharge process in silicon-air batteries, as well as a detailed mechanism for silicon oxide deposition on the air electrode porous carbon.

Electrolyte-gated transistors based on phenyl-C61-butyric acid methyl ester (PCBM) films: bridging redox properties, charge carrier transport and device performance.

PubMed

Lan, Tian; Soavi, Francesca; Marcaccio, Massimo; Brunner, Pierre-Louis; Sayago, Jonathan; Santato, Clara

2018-05-24

The n-type organic semiconductor phenyl-C61-butyric acid methyl ester (PCBM), a soluble fullerene derivative well investigated for organic solar cells and transistors, can undergo several successive reversible, diffusion-controlled, one-electron reduction processes. We exploited such processes to shed light on the correlation between electron transfer properties, ionic and electronic transport as well as device performance in ionic liquid (IL)-gated transistors. Two ILs were considered, based on bis(trifluoromethylsulfonyl)imide [TFSI] as the anion and 1-ethyl-3-methylimidazolium [EMIM] or 1-butyl-1-methylpyrrolidinium [PYR14] as the cation. The aromatic structure of [EMIM] and its lower steric hindrance with respect to [PYR14] favor a 3D (bulk) electrochemical doping. As opposed to this, for [PYR14] the doping seems to be 2D (surface-confined). If the n-doping of the PCBM is pursued beyond the first electrochemical process, the transistor current vs. gate-source voltage plots in [PYR14][TFSI] feature a maximum that points to the presence of finite windows of high conductivity in IL-gated PCBM transistors.

3 V omni-directionally stretchable one-body supercapacitors based on a single ion-gel matrix and carbon nanotubes.

PubMed

Kim, Wonbin; Kim, Woong

2016-06-03

Stretchable supercapacitors often have laminated structures consisting of electrode, electrolyte, and supporting layers. Since the layers are likely to be composed of different materials, delamination is a major cause of failure upon stretching. In this study, we demonstrate delamination-free stretchable supercapacitors where all the component layers are prepared with a single matrix, which is composed of a polymer, poly(vinylidene fluoride-hexafluoropropylene) and an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Since the ionic liquid in the composite plays a role as both an electrolyte and a plasticizer, this composite can be used as an electrolyte and a supporting layer in the stretchable supercapacitor. The electrode layer can be fabricated by incorporating carbon nanotubes in the common matrix. Then, all the layers can be seamlessly fused into one body by dissolving the surface of the composite with acetone, which evaporates after the integration, leaving no borders between the layers. This one-body stretchable supercapacitor not only has high durability against repetitive stretches but also is stretchable in all directions. This feature clearly distinguishes them from conventional stretchable supercapacitors fabricated using buckled structures, which are stretchable only in one or two directions. Moreover, this supercapacitor has high cell voltage (∼3 V) owing to the ionic liquid-based gel electrolytes. Our demonstration of isotropically stretchable high-durability supercapacitors may have a great implication in the development of stretchable energy storage devices for real applications.

Biochemical toxicity and DNA damage of imidazolium-based ionic liquid with different anions in soil on Vicia faba seedlings.

PubMed

Liu, Tong; Zhu, Lusheng; Wang, Jinhua; Wang, Jun; Zhang, Jun; Sun, Xi; Zhang, Cheng

2015-12-17

In the present study, the toxic effects of 1-octyl-3-methylimidazolium chloride ([Omim]Cl), 1-octyl-3-methylimidazolium bromide ([Omim]Br) and 1-octyl-3-methylimidazolium tetrafluoroborate ([Omim]BF4) in soil on Vicia faba (V. faba) seedlings at 0, 100, 200, 400, 600 and 800 mg kg(-1) were assessed for the first time at the cellular and molecular level. Moreover, the toxicity of these three ionic liquids (ILs) was evaluated, and the influence of anions on the toxicity of the ILs was assessed. The results showed that even at 100 mg kg(-1), the growth of V. faba seedlings was inhibited after exposure to the three ILs, and the inhibitory effect was enhanced with increasing concentrations of the three ILs. The level of reactive oxygen species (ROS) was increased after exposure to the three ILs, which resulted in lipid peroxidation, DNA damage and oxidative damage in the cells of the V. faba seedlings. In addition, the anion structure could influence the toxicity of ILs, and toxicity of the three tested ILs decreased in the following order: [Omim]BF4 > [Omim]Br > [Omim]Cl. Moreover, oxidative damage is the primary mechanism by which ILs exert toxic effects on crops, and ILs could reduce the agricultural productivity.

Perfluoroalkyltricyanoborate and Perfluoroalkylcyanofluoroborate Anions: Building Blocks for Low-Viscosity Ionic Liquids.

PubMed

Landmann, Johannes; Sprenger, Jan A P; Hennig, Philipp T; Bertermann, Rüdiger; Grüne, Matthias; Würthner, Frank; Ignat'ev, Nikolai V; Finze, Maik

2018-01-12

The potassium perfluoroalkyltricyanoborates K[C n F 2 n+1 B(CN) 3 ] [n=1 (1 d), 2 (2 d)] and the potassium mono(perfluoroalkyl)cyanofluoroborates K[C n F 2 n+1 BF(CN) 2 ] [n=1 (1 c), 2 (2 c)] and [C n F 2 n+1 BF 2 (CN)] - [n=1 (1 b), 2 (2 b), 3 (3 b), 4 (4 b)] are accessible with perfect selectivities on multi-gram scales starting from K[C n F 2 n+1 BF 3 ] and Me 3 SiCN. The K + salts are starting materials for the preparation of salts with organic cations, for example, [EMIm] + (EMIm=1-ethyl-3-methylimidazolium). These [EMIm] + salts are hydrophobic room-temperature ionic liquids (RTILs) that are thermally, chemically and electrochemically very robust, offering electrochemical windows up to 5.8 V. The RTILs described herein, exhibit very low viscosities with a minimum of 14.0 mPa s at 20 °C for [EMIm]1 c, low melting points down to -57 °C for [EMIm]2 b and extraordinary high conductivities up to 17.6 mS cm -1 at 20 °C for [EMIm]1 c. The combination of these properties makes these ILs promising materials for electrochemical devices as exemplified by the application of selected RTILs as component of electrolytes in dye-sensitised solar cells (DSSCs, Grätzel cells). The efficiency of the DSSCs was found to increase with a decreasing viscosity of the neat ionic liquid. In addition to the spectroscopic characterisation, single crystals of the potassium salts of the anions 1 b-d, 2 d, 3 b and 4 c as well as of [nBu 4 N]2 c have been studied by X-ray diffraction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using ethane and butane as probes to the molecular structure of 1-alkyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] imide ionic liquids.

PubMed

Costa Gomes, Margarida F; Pison, Laure; Pensado, Alfonso S; Pádua, Agilio A H

2012-01-01

In this work, we have studied the solubility and the thermodynamic properties of solvation, between 298 and 343 K and at pressures close to atmospheric, of ethane and n-butane in several ionic liquids based on the bis[(trifluoromethyl) sulfonyl]imide anion and on 1-alkyl-3-methylimidazolium cations, [CnC1Im] [NTf2], with alkyl side-chains varying from two to ten carbon atoms. The solubility of butane is circa one order of magnitude larger than that of ethane with mole fractions as high as 0.15 in [C10C1Im][NTf2] at 300 K. The solubilities of both n-butane and ethane gases are higher for ionic liquids with longer alkyl chains. The behaviour encountered is explained by the preferential solvation of the gases in the non-polar domains of the solvents, the larger solubility of n-butane being attributed to the dispersive contributions to the interaction energy. The rise in solubility with increasing size of the alkyl-side chain is explained by a more favourable entropy of solvation in the ionic liquids with larger cations. These conclusions are corroborated by molecular dynamics simulation studies.

Direct current dielectrophoretic manipulation of the ionic liquid droplets in water.

PubMed

Zhao, Kai; Li, Dongqing

2018-07-13

The ionic liquids (ILs) as the environmentally benign solvents show great potentials in microemulsion carrier systems and have been widely used in the biochemical and pharmaceutical fields. In the work, the ionic liquid-in-water microemulsions were fabricated by using two kinds of hydrophobic ionic liquid, 1-Butyl-3-methylimidazolium hexafluorophosphate [Bmim][PF 6 ] and 1-Hexyl-3-methylimidazolium hexafluorophosphate [Hmim][PF 6 ] with Tween 20. The ionic liquid droplets in water experience the dielectrophoretic (DEP) forces induced by applying electrical field via a nano-orifice and a micron orifice on the opposite channel walls of a microchannel. The dielectrophoretic behaviors of the ionic liquid-in-water emulsion droplets were investigated under direct current (DC) electric field. The positive and negative DEP behaviors of the ionic liquid-in-water droplets varying with the electrical conductivity of the suspending medium were investigated and two kinds of the ionic liquid droplets of similar sizes were separated by their different DEP behaviors. In addition, the separation of the ionic liquid-in-water droplets by size was conducted. This paper, for the first time to our knowledge, presents the DC-DEP manipulation of the ionic liquid-in-water emulsion droplets by size and by type. This method provides a platform to manipulate the ionic liquid droplets individually. Copyright © 2018 Elsevier B.V. All rights reserved.

Calorimetric determination of the enthalpy of 1-butyl-3-methylimidazolium bromide synthesis: a key quantity in thermodynamics of ionic liquids.

PubMed

Paulechka, Yauheni U; Kabo, Andrey G; Blokhin, Andrey V

2009-11-05

The enthalpy of the 1-butyl-3-methylimidazolium bromide [C(4)mim]Br ionic liquid synthesis reaction 1-methylimidazole (liq) + 1-bromobutane (liq) --> [C(4)mim]Br (liq) was determined in a homemade small-volume isoperibol calorimeter to be Delta(r)H degrees (298) = -87.7 +/- 1.6 kJ x mol(-1). The activation energy for this reaction in a homogeneous system E(A) = 73 +/- 4 kJ x mol(-1) was found from the results of calorimetric measurements. The formation enthalpies for the crystalline and liquid [C(4)mim]Br were determined from the calorimetric data: Delta(f)H degrees (298)(cr) = -178 +/- 5 kJ x mol(-1) and Delta(f)H degrees (298)(liq) = -158 +/- 5 kJ x mol(-1). The ideal-gas formation enthalpy of this compound Delta(f)H degrees (298)(g) = 16 +/- 7 kJ x mol(-1) was calculated using the methods of quantum chemistry and statistical thermodynamics. The vaporization enthalpy of [C(4)mim]Br, Delta(vap)H degrees (298) = 174 +/- 9 kJ x mol(-1), was estimated from the experimental and calculated formation enthalpies. It was demonstrated that vapor pressure of this ionic liquid cannot be experimentally determined.

Soft and flexible PEDOT/PSS films for applications to soft actuators

NASA Astrophysics Data System (ADS)

Li, Yuechen; Tanigawa, Ryo; Okuzaki, Hidenori

2014-07-01

Stretchable and highly conductive PEDOT/PSS/Xyl films were prepared by casting an aqueous dispersion of poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate) (PEDOT/PSS) as colloidal gel particles containing xylitol (Xyl) and subsequent heating. The electrical conductivity of the PEDOT/PSS/Xyl film containing 50 wt% of xylitol significantly increased from 115 S cm-1 to 407 S cm-1 by heating at 140 °C in air for 1 h. It was found that the xylitol had two functions as (i) a plasticizer to weaken hydrogen bonds between PSS of colloidal particles by replacing with that between xylitol and PSS and (ii) the additional capability of increasing the mobility of charge carriers between the colloidal particles. The transparent ionic liquid/polyurethane (IL/PU) gels were fabricated by dissolving thermoplastic polyurethane and ionic liquid of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. By increasing the IL content from 0 wt% to 70 wt%, both ionic conductivity and electric-double-layer capacitance under an electric field increased, while Young’s modulus, strength and elongation at break decreased. The IL/PU/PEDOT/PSS/Xyl composites were fabricated by sandwiching the IL/PU gel between two soft and flexible PEDOT/PSS/Xyl films. Upon application of 2 V, the IL/PU/PEDOT/PSS/Xyl composite (IL = 70%) showed quick and intensive bending toward anode, where the bending displacement at 0.1 Hz attained 2.9 mm, corresponding to the strain of 0.15%, and still worked at frequencies higher than 50 Hz.

Properties of fluorosulfate-based ionic liquids and geometries of (FO2SOH)OSO2F- and (FO2SOH)2O2SOF-.

PubMed

Enomoto, Takeshi; Matsumoto, Kazuhiko; Hagiwara, Rika

2011-12-14

A room temperature ionic liquid (IL) based on the fluorosulfate anion (SO(3)F(-)) has been synthesized by the reaction of 1-ethyl-3-methylimidazolium (EMIm(+)) chloride and fluorosulfuric acid (HOSO(2)F). The viscosity, ionic conductivity, and electrochemical window of EMImSO(3)F at 25 °C are 46.6 mPa s, 10.8 mS cm(-1), and 4.3 V, respectively. According to a solvatochromic measurement using ILs, there is a trend in the donor ability of fluoro- and oxofluoroanions, PF(6)(-) < BF(4)(-) < N(SO(2)CF(3))(2)(-) < SO(3)CF(3)(-) < SO(3)F(-) < PO(2)F(2)(-), which is explained by the atomic charges obtained from quantum mechanical calculations. The 1 : 2 and 1 : 3 stoichiometric reactions of EMImCl and HOSO(2)F give EMIm(FO(2)SOH)OSO(2)F and EMIm(FO(2)SOH)(2)O(2)SOF, respectively. Both the salts are liquid at room temperature without a HOSO(2)F dissociation pressure (< 1 Pa) and have low viscosity and high ionic conductivity (9.2 mPa s and 30.8 mS cm(-1) for EMIm(FO(2)SOH)OSO(2)F and 5.1 mPa s and 43.2 mS cm(-1) for EMIm(FO(2)SOH)(2)O(2)SOF). The vibrational modes and bonding properties of these anionic species are discussed with the aid of quantum mechanical calculations. The (FO(2)SOH)OSO(2)F(-) anion in EMIm(FO(2)SOH)OSO(2)F does not have an inversion centre, which stands in contrast to the one with an inversion centre (e.g. observed in solid Cs(FO(2)SOH)OSO(2)F). The (FO(2)SOH)(2)O(2)SOF(-) anion in EMIm(FO(2)SOH)(2)O(2)SOF is characterized by vibrational spectroscopy under C(s) symmetry.

Deuterium and oxygen-18 isotope effects on nucleophilic displacement by water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, J.

1981-01-01

Kinetic deuterium isotope effects (k/sub H/sub 2/O//k/sub D/sub 2/O/) have been measured for nucleophilic attack by water at primary alkyl carbon (S-methylthiophenium ion (MeTh+), methyl trifluoromethane-sulfonate (MeOTf), methyl and ethyl perchlorate (MeOClO/sub 3/, EtOClO/sub 3/)) in aprotic solvents (acetonitrile (MeCN) and tetrahydrothiophene-1, 1-dioxide (TMSO/sub 2/; solfolane)) and L/sub 2/O. In L/sub 2/O solvent k/sub H/sub 2/O//k/sub D/sub 2/O/ is significantly greater than unity while it is reduced to near unity in aprotic solvents. The oxygen-18 isotope effect has also been observed to be 1.002 +- 0.004 for the reaction of MeTh/sup +/ with dilute H/sub 2/O in TMSO/sub 2/ atmore » 35/sup 0/C. For the reaction of MeTh/sup +/ and MeOClO/sub 3/ in aprotic solvents the chemical reaction kinetics are discussed.« less

Rapid determination of alkaloids in Macleaya cordata using ionic liquid extraction followed by multiple reaction monitoring UPLC-MS/MS analysis.

PubMed

Li, Linqiu; Huang, Mingyuan; Shao, Junli; Lin, Bokun; Shen, Qing

2017-02-20

The ultrasonic-assisted extraction (UAE) and ionic liquid based dispersive liquid-liquid microextraction (IL-DLLME) have been successfully applied in extracting of six alkaloids from M. cordata. 1-hexyl-3-methylimidazolium tetrafluoroborate ([C 6 MIM][BF 4 ]) aqueous solution was used as extraction solvent. The target analytes in raw material were deposited into a single drop of 1-hexyl-3-methylimidazolium hexafluorophosphate ([C 6 MIM][PF 6 ]), which was in situ formed by mixing [C 6 MIM][BF 4 ] and potassium hexafluorophosphate ([K][PF 6 ]. Afterwards, the extract was analyzed by ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) in multiple-reaction monitoring (MRM) mode. The proposed method was fully validated in terms of linearity (0.9983-0.9992), LOD (0.080ngmL -1 ), LOQ (0.25ngmL -1 ), intra-day precision (<5.46%), inter-day precision (<6.36%), and recovery (86.42-112.48%). The results indicate that the approach of combining IL-DLLME with UPLC-MS/MS is powerful and practical for analyzing alkaloids in M. cordata., and it also has great potential for comprehensive quality control of other herbal medicines. Copyright © 2016 Elsevier B.V. All rights reserved.

Volumetric Properties of the Ionic Liquid, 1-Butyl-3-methylimidazolium Tetrafluoroborate, in Organic Solvents at T = 298.15K

NASA Astrophysics Data System (ADS)

Shekaari, Hemayat; Zafarani-Moattar, Mohammed Taghi

2008-04-01

Apparent molar volumes, V_φ , and compressibilities, kappa _φ , of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) have been determined from precise density and speed-of-sound measurements in organic solvents, methanol (MeOH), acetonitrile (MeCN), tetrahydrofuran (THF), N, N-dimethylacetamide (DMA), and dimethylsulfoxide (DMSO) in the dilute region of the ionic liquid. Corresponding values at infinite dilution are estimated by the Redlich-Mayer and Pitzer equations. The results have been interpreted by the interaction of the [BMIm][BF4] in the organic solvents. Results show that the structure and dielectric constant of the organic solvents play an important role for the ion-solvent interactions in these mixtures. It was found that the strength of interaction between [BMIm][BF4] with the studied organic solvents has the order DMSO > DMA > MeOH > MeCN > THF.

Synergistic tungsten oxide/organic framework hybrid nanofibers for electrochromic device application

NASA Astrophysics Data System (ADS)

Dulgerbaki, Cigdem; Komur, Ali Ihsan; Nohut Maslakci, Neslihan; Kuralay, Filiz; Uygun Oksuz, Aysegul

2017-08-01

We report the first successful applications of tungsten oxide/conducting polymer hybrid nanofiber assemblies in electrochromic devices. Poly(3,4-ethylenedioxythiophene)/tungsten oxide (PEDOT/WO3) and polypyrrole/tungsten oxide (PPy/WO3) composites were prepared by an in situ chemical oxidative polymerization of monomers in different ionic liquids; 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide (BMIMTFSI) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide (BMPTFSI). Electrospinning process was used to form hybrid nanofibers from chemically synthesized nanostructures. The electrospun hybrid samples were compared from both morphological and electrochemical perspectives. Importantly, deposition of nanofibers from chemically synthesized hybrids can be achieved homogenously, on nanoscale dimensions. The morphologies of these assemblies were evaluated by SEM, whereas their electroactivity was characterized by cyclic voltammetry. Electrochromic devices made from hybrid nanofiber electrodes exhibited highest chromatic contrast of 37.66% for PEDOT/WO3/BMIMPF6, 40.42% for PPy/WO3/BMIMBF4 and show a strong electrochromic color change from transparent to light brown. Furthermore, the nanofiber devices exhibit outstanding stability when color switching proceeds, which may ensure a versatile platform for color displays, rear-view mirrors and smart windows.

Transfer printing of thermoreversible ion gels for flexible electronics.

PubMed

Lee, Keun Hyung; Zhang, Sipei; Gu, Yuanyan; Lodge, Timothy P; Frisbie, C Daniel

2013-10-09

Thermally assisted transfer printing was employed to pattern thin films of high capacitance ion gels on polyimide, poly(ethylene terephthalate), and SiO2 substrates. The ion gels consisted of 20 wt % block copolymer poly(styrene-b-ethylene oxide-b-styrene and 80 wt % ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)amide. Patterning resolution was on the order of 10 μm. Importantly, ion gels containing the block polymer with short PS end blocks (3.4 kg/mol) could be transfer-printed because of thermoreversible gelation that enabled intimate gel-substrate contact at 100 °C, while gels with long PS blocks (11 kg/mol) were not printable at the same temperature due to poor wetting contact between the gel and substrates. By using printed ion gels as high-capacitance gate insulators, electrolyte-gated thin-film transistors were fabricated that operated at low voltages (<1 V) with high on/off current ratios (∼10(5)). Statistical analysis of carrier mobility, turn-on voltage, and on/off ratio for an array of printed transistors demonstrated the excellent reproducibility of the printing technique. The results show that transfer printing is an attractive route to pattern high-capacitance ion gels for flexible thin-film devices.

Printable polymer actuators from ionic liquid, soluble polyimide, and ubiquitous carbon materials.

PubMed

Imaizumi, Satoru; Ohtsuki, Yuto; Yasuda, Tomohiro; Kokubo, Hisashi; Watanabe, Masayoshi

2013-07-10

We present here printable high-performance polymer actuators comprising ionic liquid (IL), soluble polyimide, and ubiquitous carbon materials. Polymer electrolytes with high ionic conductivity and reliable mechanical strength are required for high-performance polymer actuators. The developed polymer electrolytes comprised a soluble sulfonated polyimide (SPI) and IL, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C2mim][NTf2]), and they exhibited acceptable ionic conductivity up to 1 × 10(-3) S cm(-1) and favorable mechanical properties (elastic modulus >1 × 10(7) Pa). Polymer actuators based on SPI/[C2mim][NTf2] electrolytes were prepared using inexpensive activated carbon (AC) together with highly electron-conducting carbon such as acetylene black (AB), vapor grown carbon fiber (VGCF), and Ketjen black (KB). The resulting polymer actuators have a trilaminar electric double-layer capacitor structure, consisting of a polymer electrolyte layer sandwiched between carbon electrode layers. Displacement, response speed, and durability of the actuators depended on the combination of carbons. Especially the actuators with mixed AC/KB carbon electrodes exhibited relatively large displacement and high-speed response, and they kept 80% of the initial displacement even after more than 5000 cycles. The generated force of the actuators correlated with the elastic modulus of SPI/[C2mim][NTf2] electrolytes. The displacement of the actuators was proportional to the accumulated electric charge in the electrodes, regardless of carbon materials, and agreed well with the previously proposed displacement model.

New insight into the environmental impact of two imidazolium ionic liquids. Effects on seed germination and soil microbial activity.

PubMed

Salgado, J; Parajó, J J; Teijeira, T; Cruz, O; Proupín, J; Villanueva, M; Rodríguez-Añón, J A; Verdes, P V; Reyes, O

2017-10-01

The next generation of ionic liquids must be synthetized taking into account structures that guarantee the suitable properties for a defined application as well as ecological data. Thus, searching of the right methodologies to know, quickly and efficiently, the ecological effects of these compounds is a preliminary task. The effects of two imidazolium based ionic liquids with different anions, 1-butyl-3-methylimidazolium tetrafluoroborate, [C 4 C 1 Im][BF 4 ], and 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C 3 C 1 Im][NTf 2 ], on seedling emergence of six tree species and on the microbial behaviour of two soils were determined in this work. Results showed that the highest doses of both ionic liquids caused the total inhibition of germination for almost all the species studied and that the seeds are more sensitive to the presence of these compounds than soil microbial activity. Nevertheless, signals of stress and death are observed from the results of heat released by microorganisms after the addition of the highest doses of both ionic liquids. The novelty of this work resides in the enlargement of knowledge of toxicity of ILs on complex organisms such as arboreal species and microbial activity of soils studied for the first time through a microcalorimetric technique. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparison of three different dispersive liquid-liquid microextraction modes performed on their most usual configurations for the extraction of phenolic, neutral aromatic, and amino compounds from waters.

PubMed

Saraji, Mohammad; Ghambari, Hoda

2018-06-21

In this work we seek clues to select the appropriate dispersive liquid-liquid microextraction mode for extracting three categories of compounds. For this purpose, three common dispersive liquid-liquid microextraction modes were compared under optimized conditions. Traditional dispersive liquid-liquid microextraction, in situ ionic liquid dispersive liquid-liquid microextraction and conventional ionic liquid dispersive liquid-liquid microextraction using chloroform, 1-butyl-3-methylimidazolium tetrafluoroborate, and 1-hexyl-3-methylimidazolium hexafluorophosphate as the extraction solvent, respectively, were considered in this work. Phenolic, neutral aromatic and amino compounds (each category included six members) were studied as analytes. The analytes in the extracts were determined by high-performance liquid chromatography with UV detection. For the analytes with polar functionalities, the in situ ionic liquid dispersive liquid-liquid microextraction mode mostly led to better results. In contrast, for neutral hydrocarbons without polar functionalities, traditional dispersive liquid-liquid microextraction using chloroform produced better results. In this case, where dispersion forces were the dominant interactions in the extraction, the refractive index of solvent and analyte predicted the extraction performance better than the octanol-water partition coefficient. It was also revealed that none of the methods were successful in extracting very hydrophilic analytes (compounds with the log octanol-water partition coefficient < 2). The results of this study could be helpful in selecting a dispersive liquid-liquid microextraction mode for the extraction of various groups of compounds. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Charge Transport and Phase Behavior of Imidazolium-Based Ionic Liquid Crystals from Fully Atomistic Simulations.

PubMed

Quevillon, Michael J; Whitmer, Jonathan K

2018-01-02

Ionic liquid crystals occupy an intriguing middle ground between room-temperature ionic liquids and mesostructured liquid crystals. Here, we examine a non-polarizable, fully atomistic model of the 1-alkyl-3-methylimidazolium nitrate family using molecular dynamics in the constant pressure-constant temperature ensemble. These materials exhibit a distinct "smectic" liquid phase, characterized by layers formed by the molecules, which separate the ionic and aliphatic moieties. In particular, we discuss the implications this layering may have for electrolyte applications.

Study of Crystallinity Index (CrI) of Oil Palm Frond Pretreatment using Aqueous [EMIM][OAc] in a Closed System

NASA Astrophysics Data System (ADS)

Abu Darim, R.; Azizan, A.; Salihon, J.

2018-05-01

The objective of this preliminary study is to identify the Crystalinity Index (CrI) of Oil Palm Frond (OPF) pretreated with 40% concentration of 1-ethyl-3-methylimidazolium acetate ionic liquid ([EMIM][OAc]) in a closed system. The morphology and structural changes of the pretreated OPF were examined by using Fourier Transform Infrared Spectrometer (FTIR) and X-Ray Diffraction (XRD). The pretreatment process was carried out in triplicates by loading 40% of [EMIM][OAc] concentration with 10 wt% of OPF loading in the Bio-ionic liquid-reactor. The pretreatment process was conducted for 3 hours with working volume of 70 mL and temperature of 110°C. A Bio-ionic liquid reactor was purposely designed for the lignocellulosic pretreatment by using aqueous ionic liquid at high temperature (higher than boiling point of water). The CrI of OPF pretreated with 40% concentration of [EMM][OAc] in a closed system observed was 9% lower from the untreated OPF and the result showed significant difference with 95% confidence level. Further examination of the untreated and pretreated OPF by using XRD showed that the diffraction pattern of the pretreated OPF samples was decreasing compared to the untreated OPF. The characteristic of the FTIR spectra of the pretreated OPF showed the presence of the cellulose I and occurrence of amorphous cellulosic in the samples. The findings from this study are expected to improve knowledge on pretreatment of OPF by using aqueous [EMIM][OAc] as a green economically viable process for future renewable energy.

Comparison of the effect of ionic liquids containing hexafluorophosphate and trifluoroacetate anions on the inhibition of growth and oxidative stress in spring barley and common radish.

PubMed

Biczak, Robert; Pawłowska, Barbara; Feder-Kubis, Joanna; Telesiński, Arkadiusz

2017-08-01

Ionic liquids are a group of chemical compounds with chemical properties that are of great interest to various fields of science and industry. However, commercial use of these substances raises concern because they may threaten the natural ecosystems. The present study used 2 types of (-)-menthol-containing imidazolium chiral ionic liquids: 1-[(1R,2S,5R)-(-)-menthoxymethyl]-3-methylimidazolium hexafluorophosphate [Im-Men][PF 6 ] and 1-[(1R,2S,5R)-(-)-menthoxymethyl]-3-methylimidazolium trifluoroacetate [Im-Men][CF 3 CO 2 ]. The effects of these compounds on growth and development of spring barley (Hordeum vulgare) and common radish (Raphanus sativus L. subvar. radicula Pers.) were investigated. The present study demonstrated that chiral ionic liquids produced a relatively high phytotoxicity, by shortening the plants' lengths and roots, thus causing a decline in the experimental plants' fresh weights. The investigated ionic liquids also led to a reduction in photosynthetic pigment levels, changes in hydrogen peroxide and malondialdehyde content, and changes in the activities of superoxide dismutase, catalase, and peroxidase in both plants. Changes in these enzymes were used to indicate oxidative stress levels in spring barley and common radish. It was demonstrated that imidazolium ionic liquid-induced phytotoxicity depended largely on the type of anion. The liquid [Im-Men][PF 6 ] exhibited higher toxicity toward spring barley and common radish seedlings. Common radish was more resistant to chiral ionic liquids. Environ Toxicol Chem 2017;36:2167-2177. © 2017 SETAC. © 2017 SETAC.

Unraveling the effects of amino acid substitutions enhancing lipase resistance to an ionic liquid: a molecular dynamics study.

PubMed

Zhao, Jing; Frauenkron-Machedjou, Victorine Josiane; Fulton, Alexander; Zhu, Leilei; Davari, Mehdi D; Jaeger, Karl-Erich; Schwaneberg, Ulrich; Bocola, Marco

2018-04-04

Understanding of the structural and dynamic properties of enzymes in non-aqueous media (e.g., ionic liquids, ILs) is highly attractive for protein engineers and synthetic biochemists. Despite a growing number of molecular dynamics (MD) simulation studies on the influence of different ILs on wild-type enzymes, the effects of various amino acid substitutions on the stability and activity of enzymes in ILs remain to be unraveled at the molecular level. Herein, we selected fifty previously reported Bacillus subtilis lipase A (BSLA) variants with increased resistance towards an IL (15 vol% 1-butyl-3-methylimidazolium trifluoromethanesulfonate; [Bmim][TfO]), and also ten non-resistant BSLA variants for a MD simulation study to identify the underlying molecular principles. Some important properties differentiating resistant and non-resistant BSLA variants from wild-type were elucidated. Results show that, in 15 vol% [Bmim][TfO] aqueous solution, 40% and 60% of non-resistant variants have lower and equal probabilities to form a catalytically important hydrogen bond between S77 and H156 compared to wild-type, whereas 36% and 56% of resistant variants show increased and equal probabilities, respectively. Introducing positively charged amino acids close to the substrate-binding cleft for instance I12R is beneficial for the BSLA resistance towards 15 vol% [Bmim][TfO], likely due to the reduced probability of [Bmim]+ cations clustering near the cleft. In contrast, substitution with a large hydrophobic residue like I12F can block the cleft through hydrophobic interaction with a neighboring nonpolar loop 134-137 or/and an attractive π-π interaction with [Bmim]+ cations. In addition, the resistant variants having polar substitutions on the surface show higher ability to stabilize the surface water molecule network in comparison to non-resistant variants. This study can guide experimentalists to rationally design promising IL-resistant enzymes, and contribute to a deeper understanding of protein-IL interactions at the molecular level.

Efficient dehydration and recovery of ionic liquid after lignocellulosic processing using pervaporation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Jian; Shi, Jian; Murthy Konda, N. V. S. N.

Background Biomass pretreatment using certain ionic liquids (ILs) is very efficient, generally producing a substrate that is amenable to saccharification with fermentable sugar yields approaching theoretical limits. Although promising, several challenges must be addressed before an IL pretreatment technology can become commercially viable. One of the most significant challenges is the affordable and scalable recovery and recycle of the IL itself. Pervaporation (PV) is a highly selective and scalable membrane separation process for quantitatively recovering volatile solutes or solvents directly from non-volatile solvents that could prove more versatile for IL dehydration. Results We evaluated a commercially available PV system formore » IL dehydration and recycling as part of an integrated IL pretreatment process using 1-ethyl-3-methylimidazolium acetate ([C 2 C 1 Im][OAc] ) that has been proven to be very effective as a biomass pretreatment solvent. Separation factors as high as 1500 were observed. We demonstrate that > 99.9 wt% [C 2 C 1 Im][OAc] can be recovered from aqueous solution (≤20 wt% IL) and recycled five times. A preliminary technoeconomic analysis validated the promising role of PV in improving overall biorefinery process economics, especially in the case where other IL recovery technologies might lead to significant losses. Conclusions These findings establish the foundation for further development of PV as an effective method of recovering and recycling ILs using a commercially viable process technology.« less

Efficient dehydration and recovery of ionic liquid after lignocellulosic processing using pervaporation

DOE PAGES

Sun, Jian; Shi, Jian; Murthy Konda, N. V. S. N.; ...

2017-06-15

Background Biomass pretreatment using certain ionic liquids (ILs) is very efficient, generally producing a substrate that is amenable to saccharification with fermentable sugar yields approaching theoretical limits. Although promising, several challenges must be addressed before an IL pretreatment technology can become commercially viable. One of the most significant challenges is the affordable and scalable recovery and recycle of the IL itself. Pervaporation (PV) is a highly selective and scalable membrane separation process for quantitatively recovering volatile solutes or solvents directly from non-volatile solvents that could prove more versatile for IL dehydration. Results We evaluated a commercially available PV system formore » IL dehydration and recycling as part of an integrated IL pretreatment process using 1-ethyl-3-methylimidazolium acetate ([C 2 C 1 Im][OAc] ) that has been proven to be very effective as a biomass pretreatment solvent. Separation factors as high as 1500 were observed. We demonstrate that > 99.9 wt% [C 2 C 1 Im][OAc] can be recovered from aqueous solution (≤20 wt% IL) and recycled five times. A preliminary technoeconomic analysis validated the promising role of PV in improving overall biorefinery process economics, especially in the case where other IL recovery technologies might lead to significant losses. Conclusions These findings establish the foundation for further development of PV as an effective method of recovering and recycling ILs using a commercially viable process technology.« less

Capacitively Coupled Plasma Discharge of Ionic Liquid Solutions to Synthesize Carbon Dots as Fluorescent Sensors.

PubMed

Ke, Ching-Bin; Lu, Te-Ling; Chen, Jian-Lian

2018-05-26

Oxygen and nitrogen capacitively coupled plasma (CCP) was used to irradiate mixtures of aliphatic acids in high boiling point solvents to synthesize fluorescent carbon dots (C-dots). With a high fluorescence intensity, the C-dots obtained from the O₂/CCP radiation of a 1-ethyl-3-methylimidazolium dicyanamide ionic liquid solution of citric acid were characterized with an average diameter of 8.6 nm (σ = 1.1 nm), nitrogen and oxygen bonding functionalities, excitation-independent emissions, and upconversion fluorescence. Through dialysis of the CCP-treated C-dots, two emissive surface states corresponding to their respective functionalities and emissions were identified. The fluorescence spectrum of the CCP-treated C-dots was different from that of the microwave irradiation and possessed higher intensity than that of hydrothermal pyrolysis. By evaluation of the fluorescence quenching effect on flavonoids and metal ions, the CCP-treated C-dots showed a high selectivity for quercetin and sensitivity to Hg 2+ . Based on the Perrin model, a calibration curve ( R ² = 0.9992) was established for quercetin ranging from 2.4 μM to 119 μM with an LOD (limit of detection) = 0.5 μM. The quercetin in the ethanol extract of the sun-dried peel of Citrus reticulata cv. Chachiensis was determined by a standard addition method to be 4.20 ± 0.15 mg/g with a matrix effect of 8.16%.

Enhanced Mixed Feedstock Processing Using Ionic Liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simmons, Blake A

2016-10-22

Biomass pretreatment using certain ionic liquids (ILs) is very efficient, generally producing a substrate that is amenable to saccharification with fermentable sugar yields approaching theoretical limits. Although promising, several challenges must be addressed before IL pretreatment technology becomes commercially viable. Once of the most significant challenges is the affordable and scalable recovery and recycle or the IL itself. Pervaporation is a highly selective and scalable membrane separation process for quantitatively recovering volatile solutes or solvents directly from non-volatile solvents that could prove more versatile for IL dehydration than traditional solvent extraction processes, as well as efficient and energetically more advantageousmore » than standard evaporative techniques. In this study we evaluated a commercially available pervaporation system for IL dehydration and recycling as part of an integrated IL pretreatment process using 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) that has been proven to be very effective as a biomass pretreatment solvent. We demonstrate that >99.9 wt% [C2C1Im][OAc] can be recovered from aqueous solution and recycled at least five times. A preliminary techno-economic analysis validated the promising role of pervaporation in improving overall biorefinery process economics, especially in the case where other IL recovery technologies might lead to significant losses. These findings establish the foundation for further development of pervaporation as an effective method of recovering and recycling ILs using a commercially viable process technology.« less

Application of modified stir bar with nickel:zinc sulphide nanoparticles loaded on activated carbon as a sorbent for preconcentration of losartan and valsartan and their determination by high performance liquid chromatography.

PubMed

Pebdani, Arezou Amiri; Dadfarnia, Shayesteh; Shabani, Ali Mohammad Haji; Khodadoust, Saeid; Haghgoo, Soheila

2016-03-11

In this study, the stir bar was coated for the first time with the ​nicel:zins sulphide nanoparticles (Ni:ZnS NPs) loaded on activated carbon (AC) (Ni:ZnS-AC) as well as 1-ethyl-3-methylimidazolium hexafluorophosphate ionic liquid (IL) using sol gel technique and was used for stir bar sorptive extraction (SBSE) of losartan (LOS) and valsartan (VAL) as the model compounds. The extracted analytes were then quantified by high performance liquid chromatography (HPLC) equipped with an ultra violet detector. The best extraction performance for LOS and VAL was obtained through the optimization of the parameters affecting SBSE including pH of sample solution, ionic strength, extraction time, volume of desorption solvent, desorption time, and stirring speed. The fractional factorial design (FFD) was used to find the most important parameters, which were then optimized by the central composite design (CCD) and the desirability function (DF). Under the optimal experimental conditions, wide linear ranges of 0.4-50μgL(-1) and 0.5-50μgL(-1) and good RSDs (at level of 5μgL(-1) and n=6) of 4.4 and 4.9% were obtained for LOS and VAL, respectively. With the enrichment factors (EFs) of 188.6 and 184.8-fold, the limits of detection (LODs, S/N=3) of the developed method were found to be 0.12 and 0.15μgL(-1) for LOS and VAL, respectively. The developed method was successfully applied to the determination of LOS and VAL in urine and plasma matrices. Copyright © 2016 Elsevier B.V. All rights reserved.

Solubility of CO2 and N2O in an Imidazolium-Based Lipidic Ionic Liquid.

PubMed

Langham, Jacob V; O'Brien, Richard A; Davis, James H; West, Kevin N

2016-10-13

Imidazolium-based ionic liquids have been extensively studied for their ability to dissolve a wide variety of gases and for their potential to be used as separation agents in industrial processes. For many short chain 1-alkyl-3-methylimidazolium bistriflimde salts, CO 2 and N 2 O solublities are very similar. In this work, the solubility of CO 2 and N 2 O has been measured in the lipidic ionic liquid 1-methyl-3-(Z-octadec-9-enyl)imidazolium bistriflimide ([oleyl-mim][NTf 2 ]) at 298 K, 310 and 323 K up to ∼2 MPa. N 2 O was found to have higher solubility than CO 2 under the same conditions, similar to the behavior observed when olive oil, a natural lipid, was the liquid solvent. However, the solubility of each gas on a mole fraction basis is lower in the ionic liquid than in olive oil. Comparison of the gas solubilities on a mass fraction basis demonstrates that CO 2 solubility is nearly identical in both liquids; N 2 O solubility is higher than CO 2 for both liquids, but more so in the olive oil. The difference is attributed to the high mass fraction of the olive oil that is lipid-like in character. The differential solubility of N 2 O/CO 2 in this ionic liquid, in contrast to that of shorter chain 1-alkyl-3-methylimidazolium bistriflimide salts, gives physical insight into the solvent properties of this class of ionic liquids and provides further support for their lipid-like character.

Dynamics of a Room Temperature Ionic Liquid in Supported Ionic Liquid Membranes vs the Bulk Liquid: 2D IR and Polarized IR Pump-Probe Experiments.

PubMed

Shin, Jae Yoon; Yamada, Steven A; Fayer, Michael D

2017-01-11

Supported ionic liquid membranes (SILMs) are membranes that have ionic liquids impregnated in their pores. SILMs have been proposed for advanced carbon capture materials. Two-dimensional infrared (2D IR) and polarization selective IR pump-probe (PSPP) techniques were used to investigate the dynamics of reorientation and spectral diffusion of the linear triatomic anion, SeCN - , in poly(ether sulfone) (PES) membranes and room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf 2 ). The dynamics in the bulk EmimNTf 2 were compared to its dynamics in the SILM samples. Two PES membranes, PES200 and PES30, have pores with average sizes, ∼300 nm and ∼100 nm, respectively. Despite the relatively large pore sizes, the measurements reveal that the reorientation of SeCN - and the RTIL structural fluctuations are substantially slower in the SILMs than in the bulk liquid. The complete orientational randomization, slows from 136 ps in the bulk to 513 ps in the PES30. 2D IR measurements yield three time scales for structural spectral diffusion (SSD), that is, the time evolution of the liquid structure. The slowest decay constant increases from 140 ps in the bulk to 504 ps in the PES200 and increases further to 1660 ps in the PES30. The results suggest that changes at the interface propagate out and influence the RTIL structural dynamics even more than a hundred nanometers from the polymer surface. The differences between the IL dynamics in the bulk and in the membranes suggest that studies of bulk RTIL properties may be poor guides to their use in SILMs in carbon capture applications.

Proteomic alterations induced by ionic liquids in Aspergillus nidulans and Neurospora crassa.

PubMed

Martins, Isabel; Hartmann, Diego O; Alves, Paula C; Planchon, Sébastien; Renaut, Jenny; Leitão, M Cristina; Rebelo, Luís P N; Silva Pereira, Cristina

2013-12-06

This study constitutes the first attempt to understand at the proteomic level the fungal response to ionic liquid stress. Ascomycota are able to grow in media supplemented with high concentrations of an ionic liquid, which, in turn, lead to major alterations in the fungal metabolic footprint. Herein, we analysed the differential accumulation of mycelial proteins in Aspergillus nidulans and Neurospora crassa after their exposure to two of the most commonly used ionic liquids: 1-ethyl-3-methylimidazolium chloride or cholinium chloride. Data obtained showed that numerous stress-responsive proteins (e.g. anti-ROS defence proteins) as well as several critical biological processes and/or pathways were affected by either ionic liquid. Amongst other changes, these compounds altered developmental programmes in both fungi (e.g. promoting the development of Hülle cells or conidiation) and led to accumulation of osmolytes, some of which may play an important role in multiple stress responses. In particular, in N. crassa, both ionic liquids increased the levels of proteins which are likely involved in the biosynthesis of unusual metabolites. These data potentially open new perspectives on ionic liquid research, furthering their conscious design and their use to trigger production of targeted metabolites. The present study emphasises the importance of understanding ionic liquid's stress responses, crucial to further their safe large-scale usage. Knowledge of the alterations prompted at a cellular and biochemical level gives also fresh perspectives on how to employ these "novel" compounds to manipulate proteins or pathways of biotechnological value. The results presented here provide meaningful insights into the understanding of fungi stress and adaptation responses to anthropogenic chemicals used in industry. © 2013.

Understanding the high solubility of CO2 in an ionic liquid with the tetracyanoborate anion.

PubMed

Babarao, Ravichandar; Dai, Sheng; Jiang, De-en

2011-08-18

The ionic liquid 1-ethyl-3-methylimidazolium tetracyanoborate, [emim][B(CN)(4)], shows greater CO(2) solubility than several popular ionic liquids (ILs) of different anions including [emim]bis(trifluoromethylsulfonyl)imide [emim][Tf(2)N]. Herein, both classical molecular dynamics simulation and quantum mechanical calculations were used to understand the high solubility of CO(2) in the [emim][B(CN)(4)] IL. We found that the solubility is dictated by the cation-anion interaction, while the CO(2)-anion interaction plays a secondary role. The atom-atom radial distribution functions (RDFs) between cation and anion show weaker interaction in [emim][B(CN)(4)] than in [emim][Tf(2)N]. A good correlation is observed between gas-phase cation-anion interaction energy with CO(2) solubility at 1 bar and 298 K, suggesting that weaker cation-anion interaction leads to higher CO(2) solubility. MD simulation of CO(2) in the ILs showed that CO(2) is closer to the anion than to the cation and that it interacts more strongly with [B(CN)(4)] than with [Tf(2)N]. Moreover, a higher volume expansion is observed in [emim][B(CN)(4)] than in [emim][Tf(2)N] at different mole fractions of CO(2). These results indicate that [B(CN)(4)] as a small and highly symmetric anion is unique in giving a high CO(2) solubility by interacting weakly with the cation and thus allowing easy creation of cavity for close contact with CO(2).

Synthesis of β-Nicotinamide Riboside Using an Efficient Two-Step Methodology.

PubMed

Zhang, Ning; Sauve, Anthony A

2017-12-24

A two-step chemical method for the synthesis of β-nicotinamide riboside (NR) is described. NR has achieved wide use as an NAD + precursor (vitamin B3) and can significantly increase central metabolite NAD + concentrations in mammalian cells. β-NR can be prepared with an efficient two-step procedure. The synthesis is initiated via coupling of commercially available 1,2,3,5-tetra-O-acetyl-β-D-ribofuranose with ethyl nicotinate in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf). 1 H NMR showed that the product was formed with complete stereoselectivity to produce only the β-isomer in high yield (>90% versus starting sugar). The clean stereochemical result suggests that the coupling proceeds via a cationic cis-1,2-acyloxonium-sugar intermediate, which controls addition by nucleophiles to generate predominantly β-stereochemistry. The subsequent deprotection of esters in methanolic ammonia generates the desired product in 85% overall yield versus sugar. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

Ultrasonic Relaxation Study of 1-Alkyl-3-methylimidazolium-Based Room-Temperature Ionic Liquids: Probing the Role of Alkyl Chain Length in the Cation.

PubMed

Zorębski, Michał; Zorębski, Edward; Dzida, Marzena; Skowronek, Justyna; Jężak, Sylwia; Goodrich, Peter; Jacquemin, Johan

2016-04-14

Ultrasound absorption spectra of four 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides were determined as a function of the alkyl chain length on the cation from 1-propyl to 1-hexyl from 293.15 to 323.15 K at ambient pressure. Herein, the ultrasound absorption measurements were carried out using a standard pulse technique within a frequency range from 10 to 300 MHz. Additionally, the speed of sound, density, and viscosity have been measured. The presence of strong dissipative processes during the ultrasound wave propagation was found experimentally, i.e., relaxation processes in the megahertz range were observed for all compounds over the whole temperature range. The relaxation spectra (both relaxation amplitude and relaxation frequency) were shown to be dependent on the alkyl side chain length of the 1-alkyl-3-methylimidazolium ring. In most cases, a single-Debye model described the absorption spectra very well. However, a comparison of the determined spectra with the spectra of a few other imidazolium-based ionic liquids reported in the literature (in part recalculated in this work) shows that the complexity of the spectra increases rapidly with the elongation of the alkyl chain length on the cation. This complexity indicates that both the volume viscosity and the shear viscosity are involved in relaxation processes even in relatively low frequency ranges. As a consequence, the sound velocity dispersion is present at relatively low megahertz frequencies.

Engineering the electrochemical capacitive properties of graphene sheets in ionic-liquid electrolytes by correct selection of anions.

PubMed

Shi, Minjie; Kou, Shengzhong; Yan, Xingbin

2014-11-01

Graphene sheet (GS)-ionic liquid (IL) supercapacitors are receiving intense interest because their specific energy density far exceeds that of GS-aqueous electrolytes supercapacitors. The electrochemical properties of ILs mainly depend on their diverse ions, especially anions. Therefore, identifying suitable IL electrolytes for GSs is currently one of the most important tasks. The electrochemical behavior of GSs in a series of ILs composed of 1-ethyl-3-methylimidazolium cation (EMIM(+)) with different anions is systematically studied. Combined with the formula derivation and building models, it is shown that the viscosity, ion size, and molecular weight of ILs affect the electrical conductivity of ILs, and thus, determine the electrochemical performances of GSs. Because the EMIM-dicyanamide IL has the lowest viscosity, ion size, and molecular weight, GSs in it exhibit the highest specific capacitance, smallest resistance, and best rate capability. In addition, because the tetrafluoroborate anion (BF4(-)) has the best electrochemical stability, the GS-[EMIM][BF4] supercapacitor has the widest potential window, and thus, displays the largest energy density. These results may provide valuable information for selecting appropriate ILs and designing high-performance GS-IL supercapacitors to meet different needs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoporous carbon supercapacitors in an ionic liquid: a computer simulation study.

PubMed

Shim, Youngseon; Kim, Hyung J

2010-04-27

Supercapacitors composed of carbon nanotube (CNT) micropores in the room-temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI+BF4(-)) are studied via molecular dynamics (MD)computer simulations. It is found that the distribution of RTIL ions inside the micropore varies significantly with the pore size. Internal solvation of small (6,6) and (7,7) CNTs with an electrified interior wall is effected almost exclusively via counterions. Surprisingly, these counterions, even though they all have the same charge, lead to a charge density characterized by multiple layers with alternating signs. This intriguing feature is attributed to the extended nature of RTIL ion charge distributions, which result in charge separation through preferential orientation inside the electrified nanotubes. In the case of larger (10,10) and (15,15) CNTs, counterions and coions develop multilayer solvation structures. The specific capacitance normalized to the pore surface area is found to increase as the CNT diameter decreases from (15,15) to (7,7). As the pore size further reduces from (6,6) to(5,5), however, the specific capacitance diminishes rapidly. These findings are in excellent agreement with recent experiments with carbon-based materials. A theoretical model based on multiple charge layers is proposed to understand both the MD and experimental results.

Carbon Dioxide Absorption by the Imidazolium-Amino Acid Ionic Liquids, Kinetics, and Mechanism Approach.

PubMed

Rezaeian, Mojtaba; Izadyar, Mohammad; Nakhaei Pour, Ali

2018-06-25

The kinetics and mechanism of CO 2 absorption by ionic liquids (ILs) were studied, theoretically. The studied ILs are composed of 1-ethyl-3-methylimidazolium [Emim] + as the cation with a general formula of the [Emim][X] (X = Gly - , Ala - , Lys - , Arg - ). To investigate the alkyl chain length and the number of the amine group effects on the CO 2 absorption, different amino acid anions were chosen. On the basis of the enthalpy changes during CO 2 capture, a chemisorption nature is confirmed. An increase in the number of amine (-NH 2 ) groups in the ILs structures, facilitates the CO 2 absorption. According to kinetic results, the rate of CO 2 absorption by [Emim][Gly] is higher than that of [Emim][Ala]. This can be interpreted by a higher steric hindrance in [Emim][Ala] due to an additional methyl group in the amino acid chain. Donor-acceptor interactions and C-N bond formation were investigated by natural bond orbital analysis. Moreover, topological studies show a covalent nature for the C-N bond critical point that showing CO 2 capture is a chemisorption process. Finally, on the basis of kinetic energy results, donor-acceptor interaction and topological analysis, [Emim][Arg] is proposed as the best candidate for CO 2 absorption from the kinetic and thermodynamic viewpoints.

Enhanced Photocatalytic Reduction of CO2 to CO through TiO2 Passivation of InP in Ionic Liquids.

PubMed

Zeng, Guangtong; Qiu, Jing; Hou, Bingya; Shi, Haotian; Lin, Yongjing; Hettick, Mark; Javey, Ali; Cronin, Stephen B

2015-09-21

A robust and reliable method for improving the photocatalytic performance of InP, which is one of the best known materials for solar photoconversion (i.e., solar cells). In this article, we report substantial improvements (up to 18×) in the photocatalytic yields for CO2 reduction to CO through the surface passivation of InP with TiO2 deposited by atomic layer deposition (ALD). Here, the main mechanisms of enhancement are the introduction of catalytically active sites and the formation of a pn-junction. Photoelectrochemical reactions were carried out in a nonaqueous solution consisting of ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM]BF4), dissolved in acetonitrile, which enables CO2 reduction with a Faradaic efficiency of 99% at an underpotential of +0.78 V. While the photocatalytic yield increases with the addition of the TiO2 layer, a corresponding drop in the photoluminescence intensity indicates the presence of catalytically active sites, which cause an increase in the electron-hole pair recombination rate. NMR spectra show that the [EMIM](+) ions in solution form an intermediate complex with CO2(-), thus lowering the energy barrier of this reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of autohydrolysis and ionic liquid 1-butyl-3-methylimidazolium acetate pretreatment to enhance enzymatic hydrolysis of sugarcane bagasse

DOE PAGES

Hashim, Muzna; Univ. of Tennessee, Knoxville, TN; Sun, Qining; ...

2016-11-02

The aim of this work was to evaluate the efficiency of an ionic liquid (IL) 1-butyl-3-methylimidazolium acetate ([C4mim][OAc]) pretreatment (110 C for 30 min) in comparison to high severity autohydrolysis pretreatment in terms of delignification, cellulose crystallinity and enzymatic digestibility. The increase in severity of autohydrolysis pretreatment had positive effect on glucan digestibility, but was limited by the crystallinity of cellulose. [C4mim][OAc] pretreated sugarcane bagasse exhibited a substantial decrease in lignin content, reduced cellulose crystallinity, and enhanced glucan and xylan digestibility. Glucan and xylan digestibility was determined as 97.4% and 98.6% from [C4mim][OAc] pretreated bagasse, and 62.1% and 57.5% frommore » the bagasse autohydrolyzed at 205 C for 6 min, respectively. The results indicated the improved digestibility and hydrolysis rates after [C4mim][OAc] pretreatment when compared against a comparable autohydrolyzed biomass.« less

Synthesis of an Ionic Liquid and Its Application as Template for the Preparation of Mesoporous Material MCM-41: A Comprehensive Experiment for Undergraduate Students

ERIC Educational Resources Information Center

Hu, Jun; Yin, Jinxiang; Lin, Tianshu; Li, Guangtao

2012-01-01

A new solvent-free microwave experiment to synthesize the ionic liquid 1-hexadecyl-3-methylimidazolium bromide (HDMIm-Br) in high yield is presented. The structure is confirmed by IR and [superscript 1]H NMR spectra. HDMIm-Br is then used to prepare an organic-inorganic mesoporous material MCM-41. The microscopic arrangements of mesoporous…

Infrared spectroscopic studies of the conformation in ethyl alpha-haloacetates in the vapor, liquid and solid phases.

PubMed

Jassem, Naserallah A; El-Bermani, Muhsin F

2010-07-01

Infrared spectra of ethyl alpha-fluoroacetate, ethyl alpha-chloroacetate, ethyl alpha-bromoacetate and ethyl alpha-iodoacetate have been measured in the solid, liquid and vapor phases in the region 4000-200 cm(-1). Vibrational frequency assignment of the observed bands to the appropriate modes of vibration was made. Calculations at DFT B3LYP/6-311+G** level, Job: conformer distribution, using Spartan program '08, release 132 was made to determine which conformers exist in which molecule. The results indicated that the first compound exists as an equilibrium mixture of cis and trans conformers and the other three compounds exist as equilibrium mixtures of cis and gauche conformers. Enthalpy differences between the conformers have been determined experimentally for each compound and for every phase. The values indicated that the trans of the first compound is more stable in the vapor phase, while the cis is the more stable in both the liquid and solid phases. In the other three compounds the gauche is more stable in the vapor and liquid phases, while the cis conformer is the more stable in the solid phase for each of the second and third compound, except for ethyl alpha-iodoacetate, the gauche conformer is the more stable over the three phases. Molar energy of activation Ea and the pseudo-thermodynamic parameters of activation DeltaH(double dagger), DeltaS(double dagger) and DeltaG(double dagger) were determined in the solid phase by applying Arrhenius equation; using bands arising from single conformers. The respective E(a) values of these compounds are 5.1+/-0.4, 6.7+/-0.1, 7.5+/-1.3 and 12.0+/-0.6 kJ mol(-1). Potential energy surface calculations were made at two levels; for ethyl alpha-fluoroacetate and ethyl alpha-chloroacetate; the calculations were established at DFT B3LYP/6-311+G** level and for ethyl alpha-bromoacetate and ethyl alpha-iodoacetate at DFT B3LYP/6-311G* level. The results showed no potential energy minimum exists for the gauche conformer in ethyl alpha-fluoroacetate. Copyright 2010 Elsevier B.V. All rights reserved.

One-pot integrated biofuel production using low-cost biocompatible protic ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Jian; Konda, N. V. S. N. Murthy; Parthasarathi, Ramakrishnan

The transformation of biomass into liquid fuels is of great importance. Previous work has demonstrated the capability of specific ionic liquids (ILs), such as 1-ethyl-3-methylimidazolium acetate ([C(2)C(1)Im][OAc]) and cholinium lysinate ([Ch][Lys]), to be effective biomass pretreatment solvents. Using these ILs for an integrated biomass-to-biofuel configuration is still challenging due to a significant water-wash related to the high toxicity of [C(2)C(1)Im][OAc] and pH adjustment prior to saccharification for the highly basic [Ch][Lys]. In this work, we demonstrate, for the first time, that a one-pot integrated biofuel production is enabled by a low cost (similar to$1 per kg) and biocompatible protic ILmore » (PIL), ethanolamine acetate, without pH adjustments, water-wash and solid-liquid separations. After pretreatment, the whole slurry is directly used for simultaneous saccharification and fermentation (SSF) with commercial enzyme cocktails and wild type yeast strains, generating 70% of the theoretical ethanol yield (based on switchgrass). The structure-performance relationships of PILs in terms of lignin removal, net basicity, and pH value are systematically studied. A technoeconomic analysis (TEA) revealed that an integrated biorefinery concept based on this PIL process could potentially reduce the minimum ethanol selling price by more than 40% compared to scenarios that require pH adjustment prior to SSF. Improvement of the economic performance will be made by reducing the dilution and enzyme loading during SSF as identified by TEA. This study demonstrates the impact of a biocompatible IL in terms of process optimization and conversion efficiency, and opens up avenues for realizing an IL based efficiently integrated biomass conversion technology.« less

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend

NASA Astrophysics Data System (ADS)

Costa, Luciano T.; Sun, Bing; Jeschull, Fabian; Brandell, Daniel

2015-07-01

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li+ coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSIṡ1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend.

PubMed

Costa, Luciano T; Sun, Bing; Jeschull, Fabian; Brandell, Daniel

2015-07-14

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li(+) coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend

DOE Office of Scientific and Technical Information (OSTI.GOV)

Costa, Luciano T., E-mail: ltcosta@id.uff.br; Sun, Bing; Jeschull, Fabian

2015-07-14

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li{sup +} coordination and transportation were studied in the ternary electrolyte system, i.e., PEO{sub 16}LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generatedmore » significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.« less

Amino acid ionic liquids.

PubMed

Ohno, Hiroyuki; Fukumoto, Kenta

2007-11-01

The preparation of ionic liquids derived from amino acids, and their properties, are outlined. Since amino acids have both a carboxylic acid residue and an amino group in a single molecule, they can be used as either anions or cations. These groups are also useful in their ability to introduce functional group(s). Twenty different natural amino acids were used as anions, to couple with the 1-ethyl-3-methylimidazolium cation. The salts obtained were all liquid at room temperature. The properties of the resulting ionic liquids (AAILs) depend on the side groups of the amino acids involved. These AAILs, composed of an amino acid with some functional groups such as a hydrogen bonding group, a charged group, or an aromatic ring, had an increased glass transition (or melting) temperature and/or higher viscosity as a result of additional interactions among the ions. Viscosity is reduced and the decomposition temperature of imidazolium-type salts is improved by using the tetrabutylphosphonium cation. The chirality of AAILs was maintained even upon heating to 150 degrees C after acetylation of the free amino group. The amino group was also modified to introduce a strong acid group so as to form hydrophobic and chiral ionic liquids. Unique phase behavior of the resulting hydrophobic ionic liquids and water mixture is found; the mixture is clearly phase separated at room temperature, but the solubility of water in this IL increases upon cooling, to give a homogeneous solution. This phase change is reversible, and separation occurs again by raising the temperature a few degrees. It is extraordinary for an IL/water mixture to display such behavior with a lower critical solution temperature. Some likely applications are proposed for these amino acid derived ionic liquids.

Improved Activity of a Thermophilic Cellulase, Cel5A, from Thermotoga maritima on Ionic Liquid Pretreated Switchgrass

PubMed Central

Chen, Zhiwei; Pereira, Jose H.; Liu, Hanbin; Tran, Huu M.; Hsu, Nathan S. Y.; Dibble, Dean; Singh, Seema; Adams, Paul D.; Sapra, Rajat; Hadi, Masood Z.; Simmons, Blake A.; Sale, Kenneth L.

2013-01-01

Ionic liquid pretreatment of biomass has been shown to greatly reduce the recalcitrance of lignocellulosic biomass, resulting in improved sugar yields after enzymatic saccharification. However, even under these improved saccharification conditions the cost of enzymes still represents a significant proportion of the total cost of producing sugars and ultimately fuels from lignocellulosic biomass. Much of the high cost of enzymes is due to the low catalytic efficiency and stability of lignocellulolytic enzymes, especially cellulases, under conditions that include high temperatures and the presence of residual pretreatment chemicals, such as acids, organic solvents, bases, or ionic liquids. Improving the efficiency of the saccharification process on ionic liquid pretreated biomass will facilitate reduced enzyme loading and cost. Thermophilic cellulases have been shown to be stable and active in ionic liquids but their activity is typically at lower levels. Cel5A_Tma, a thermophilic endoglucanase from Thermotoga maritima, is highly active on cellulosic substrates and is stable in ionic liquid environments. Here, our motivation was to engineer mutants of Cel5A_Tma with higher activity on 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) pretreated biomass. We developed a robotic platform to screen a random mutagenesis library of Cel5A_Tma. Twelve mutants with 25–42% improvement in specific activity on carboxymethyl cellulose and up to 30% improvement on ionic-liquid pretreated switchgrass were successfully isolated and characterized from a library of twenty thousand variants. Interestingly, most of the mutations in the improved variants are located distally to the active site on the protein surface and are not directly involved with substrate binding. PMID:24244549

Improved activity of a thermophilic cellulase, Cel5A, from Thermotoga maritima on ionic liquid pretreated switchgrass.

PubMed

Chen, Zhiwei; Pereira, Jose H; Liu, Hanbin; Tran, Huu M; Hsu, Nathan S Y; Dibble, Dean; Singh, Seema; Adams, Paul D; Sapra, Rajat; Hadi, Masood Z; Simmons, Blake A; Sale, Kenneth L

2013-01-01

Ionic liquid pretreatment of biomass has been shown to greatly reduce the recalcitrance of lignocellulosic biomass, resulting in improved sugar yields after enzymatic saccharification. However, even under these improved saccharification conditions the cost of enzymes still represents a significant proportion of the total cost of producing sugars and ultimately fuels from lignocellulosic biomass. Much of the high cost of enzymes is due to the low catalytic efficiency and stability of lignocellulolytic enzymes, especially cellulases, under conditions that include high temperatures and the presence of residual pretreatment chemicals, such as acids, organic solvents, bases, or ionic liquids. Improving the efficiency of the saccharification process on ionic liquid pretreated biomass will facilitate reduced enzyme loading and cost. Thermophilic cellulases have been shown to be stable and active in ionic liquids but their activity is typically at lower levels. Cel5A_Tma, a thermophilic endoglucanase from Thermotoga maritima, is highly active on cellulosic substrates and is stable in ionic liquid environments. Here, our motivation was to engineer mutants of Cel5A_Tma with higher activity on 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) pretreated biomass. We developed a robotic platform to screen a random mutagenesis library of Cel5A_Tma. Twelve mutants with 25-42% improvement in specific activity on carboxymethyl cellulose and up to 30% improvement on ionic-liquid pretreated switchgrass were successfully isolated and characterized from a library of twenty thousand variants. Interestingly, most of the mutations in the improved variants are located distally to the active site on the protein surface and are not directly involved with substrate binding.

An Expedient Regio- and Diastereoselective Synthesis of Hybrid Frameworks with Embedded Spiro[9,10]dihydroanthracene [9,3']-pyrrolidine and Spiro[oxindole-3,2'-pyrrolidine] Motifs via an Ionic Liquid-Mediated Multicomponent Reaction.

PubMed

Arumugam, Natarajan; Almansour, Abdulrahman I; Kumar, Raju Suresh; Menéndez, J Carlos; Sultan, Mujeeb A; Karama, Usama; Ghabbour, Hazem A; Fun, Hoong-Kun

2015-09-03

A series of hitherto unreported anthracene-embedded dispirooxindoles has been synthesized via a one-pot three-component 1,3-dipolar cycloaddition reaction of an azomethine ylide, generated in situ from the reaction of isatin and sarcosine to 10-benzylideneanthracen-9(10H)-one as a dipolarophile in 1-butyl-3-methylimidazolium bromide([bmim]Br), an ionic liquid. This reaction proceeded regio- and diastereoselectively, in good to excellent yields.

Recalcitrance Assessment of the Agro-industrial Residues from Five Agave Species: Ionic Liquid Pretreatment, Saccharification and Structural Characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mittal, Ashutosh; Sykes, Robert W; Perez-Pimienta, Jose A.

Agave has recently shown its potential as a bioenergy feedstock with promising features such as higher biomass productivity than leading bioenergy feedstock while at the same time being drought-resistant with low water requirements and high sugar to ethanol conversion using ionic liquid (IL) pretreatment. IL pretreatment was studied to develop the first direct side-by-side comparative recalcitrance assessment of the agro-industrial residues from five Agave species [Agave americana (AME), A. angustifolia (ANG), A. fourcroydes (FOU), A. salmiana (SAL), and A. tequilana (TEQ)] using compositional analysis, X-ray diffraction, and the lignin syringyl/guaiacyl subunit ratio (S/G) by pyrolysis molecular beam mass spectrometry (PyMBMS).more » Prominent calcium oxalate peaks were found only in unpretreated AME, SAL, and TEQ. The S/G ratios of all five unpretreated Agave species were between 1.27 and 1.57 while the IL-pretreated samples were from 1.39 to 1.72. The highest overall sugar production was obtained with IL-pretreated FOU with 492 mg glucose/g biomass and 157 mg xylose/g biomass at 120 degrees C and 3 h using 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]). An estimated theoretical ethanol yield from the studied agro-industrial residues from the five Agave species was in the range of 1060 to 5800 L ethanol/ha/year. These comparison results demonstrate the potential of the Agave spp. as a suitable biofuel feedstock which can be employed within a biorefinery scheme.« less

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. II. Dynamical properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2007-10-28

Dynamical properties of polymer electrolytes based on poly(ethylene oxide) (PEO) and ionic liquids of 1-alkyl-3-methylimidazolium cations were calculated by molecular dynamics simulations with previously proposed models [L. T. Costa and M. C. Ribeiro, J. Chem. Phys. 124, 184902 (2006)]. The effect of changing the ionic liquid concentration, temperature, and the 1-alkyl-chain lengths, [1,3-dimethylimidazolium]PF(6) and [1-butyl-3-methylimidazolium]PF(6) ([dmim]PF(6) and [bmim]PF(6)), was investigated. Cation diffusion coefficient is higher than those of anion and oxygen atoms of PEO chains. Ionic mobility in PEO[bmim]PF(6) is higher than in PEO[dmim]PF(6), so that the ionic conductivity kappa of the former is approximately ten times larger than the latter. The ratio between kappa and its estimate from the Nernst-Einstein equation kappa/kappa(NE), which is inversely proportional to the strength of ion pairs, is higher in ionic liquid polymer electrolytes than in polymer electrolytes based on inorganic salts with Li(+) cations. Calculated time correlation functions corroborate previous evidence from the analysis of equilibrium structure that the ion pairs in ionic liquid polymer electrolytes are relatively weak. Structural relaxation at distinct spatial scales is revealed by the calculation of the intermediate scattering function at different wavevectors. These data are reproduced with stretched exponential functions, so that temperature and wavevector dependences of best fit parameters can be compared with corresponding results for polymer electrolytes containing simpler ions.

Replica-exchange molecular dynamics simulations of cellulose solvated in water and in the ionic liquid 1-butyl-3-methylimidazolium chloride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mostofian, Barmak; Cheng, Xiaolin; Smith, Jeremy C.

2014-09-02

Ionic liquids have become a popular solvent for cellulose pretreatment in biorefineries due to their efficiency in dissolution and their reusability. Understanding the interactions between cations, anions, and cellulose is key to the development of better solvents and the improvement of pretreatment conditions. While previous studies described the interactions between ionic liquids and cellulose fibers, shedding light on the initial stages of the cellulose dissolution process, we study the end state of that process by exploring the structure and dynamics of a single cellulose decamer solvated in 1-butyl-3-methyl-imidazolium chloride (BmimCl) and in water using replica-exchange molecular dynamics. In both solvents,more » global structural features of the cellulose chain are similar. However, analyses of local structural properties show that cellulose explores greater conformational variability in the ionic liquid than in water. For instance, in BmimCl the cellulose intramolecular hydrogen bond O3H'••• O5 is disrupted more often resulting in greater flexibility of the solute. Our results indicate that the cellulose chain is more dynamic in BmimCl than in water, which may play a role in the favorable dissolution of cellulose in the ionic liquid. Here, the calculation of the configurational entropy of the cellulose decamer confirms its higher conformational flexibility in BmimCl than in water at elevated temperatures.« less

Effect of cation-anion interactions on the structural and vibrational properties of 1-buthyl-3-methyl imidazolium nitrate ionic liquid

NASA Astrophysics Data System (ADS)

Kausteklis, Jonas; Aleksa, Valdemaras; Iramain, Maximiliano A.; Brandán, Silvia Antonia

2018-07-01

The cation-anion interactions present in the 1-butyl-3-methylimidazolium nitrate ionic liquid [BMIm][NO3] were studied by using density functional theory (DFT) calculations and the experimental FT-Raman spectrum in liquid phase and its available FT-IR spectrum. For the three most stable conformers found in the potential energy surface and their 1-butyl-3-methylimidazolium [BMIm] cation, the atomic charges, molecular electrostatic potentials, stabilization energies, bond orders and topological properties were computed by using NBO and AIM calculations and the hybrid B3LYP level of theory with the 6-31G* and 6-311++G** basis sets. The force fields, force constants and complete vibrational assignments were also reported for those species by using their internal coordinates and the scaled quantum mechanical force field (SQMFF) approach. The dimeric species of [BMIm][NO3] were also considered because their presence could probably explain the most intense bands observed at 1344 and 1042 cm-1 in both experimental FT-IR and FT-Raman spectra, respectively. The geometrical parameters suggest monodentate cation-anion coordination while the studies by charges, NBO and AIM calculations support bidentate coordinations between those two species. Additionally several quantum chemical descriptors were also calculated in order to interpret various molecular properties such as electronic structure, reactivity of those species and predict their gas phase behaviours.

Charge Transport and Phase Behavior of Imidazolium-Based Ionic Liquid Crystals from Fully Atomistic Simulations

PubMed Central

2018-01-01

Ionic liquid crystals occupy an intriguing middle ground between room-temperature ionic liquids and mesostructured liquid crystals. Here, we examine a non-polarizable, fully atomistic model of the 1-alkyl-3-methylimidazolium nitrate family using molecular dynamics in the constant pressure–constant temperature ensemble. These materials exhibit a distinct “smectic” liquid phase, characterized by layers formed by the molecules, which separate the ionic and aliphatic moieties. In particular, we discuss the implications this layering may have for electrolyte applications. PMID:29301305

Environmentally friendly ionic liquid-in-water microemulsions for extraction of hydrophilic and lipophilic components from Flos Chrysanthemi.

PubMed

Chen, Jue; Cao, Jun; Gao, Wen; Qi, Lian-Wen; Li, Ping

2013-10-21

Ionic liquids (ILs) have numerous chemical applications as environmentally green solvents that are extending into microemulsion applications. In this work, a novel benign IL-in-water microemulsion system modified by an IL surfactant has been proposed for simultaneous extraction of hydrophilic and lipophilic constituents from Flos Chrysanthemi (Chrysanthemum morifolium). Constituents were analyzed by rapid-resolution liquid chromatography coupled with quadrupole time-of-flight mass spectrometry. A mixture-design approach was used to optimize the IL surfactant and the IL oil phase in the microemulsion system. Microemulsions consisting of 6.0% 1-dodecyl-3-methylimidazolium hydrogen sulfate, 0.1% 1-vinyl-3-methylimidazolium hexafluorophosphate and 93.9% water offered the acceptable extract efficiency that are comparable to or even better than conventional volatile organic solvents. This assay was fully validated with respect to the linearity of response (r(2) > 0.999 over two orders of magnitude), precision (intra-RSD < 0.49 and inter-day RSD < 2.21), and accuracy (recoveries ranging from 93.73% to 101.84%). The proposed IL-in-water microemulsion method provided an environmentally friendly alternative for efficient extraction of compounds from Flos Chrysanthemi and could be extended to complex environmental and pharmaceutical samples.

Ionic Liquids as a Medium for Ionic Chain Polymerizations: An Environmentally Responsible Approach to Macromolecular Synthesis with Controlled Architecture

DTIC Science & Technology

2004-09-16

published in non peer-reviewed journals: 1. Gross, SM, Hamilton JL. "Polymer Gels for Use in Lithium Polymer Batteries", Nebraska Academy of Science...a process for the anionic polymerization of styrene and methyl methacrylate in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ...Current polymer electrolyte composites used for these applications typically comprise polyethers with ethylene carbonate solvents containing lithium

Effect of Ion Rigidity on Physical Properties of Ionic Liquids Studied by Molecular Dynamics Simulation.

PubMed

Ramírez-González, Pedro E; Ren, Gan; Saielli, Giacomo; Wang, Yanting

2016-06-30

In this work, we have performed molecular dynamics (MD) simulations to compare the structural and dynamical properties of three ionic liquids (ILs), 1-ethyl-3-methyl-imidazolium tetrafluorborate ([EMI(+)][BF4(-)]), 1,1'-dimethyl-4,4'-bipyridinium bis(tetrafluorborate) ([VIO(2+)][BF4(-)]2), and 1,1'-dimethyl-4,4'-bipyridinium bis(trifluoromethylsulfonyl)imide (bistriflimide in short) ([VIO(2+)][Tf2N(-)]2), aiming to discover the influence of ion rigidity on the physical properties of ILs. [VIO(2+)] is more rigid than [EMI(+)], and [BF4(-)] is more rigid than [Tf2N(-)]. [VIO(2+)][BF4(-)]2 has an anion distribution different from the other two by the higher and sharper peaks in the cation-anion radial distribution functions, reflecting a close-packed local structure of anions around cations. [VIO(2+)][BF4(-)]2 and [VIO(2+)][Tf2N(-)]2 have similar dynamics much slower than [EMI(+)][BF4(-)], and [VIO(2+)][Tf2N(-)]2 shows a more isotropic molecular distribution than [VIO(2+)][BF4(-)]2 and [EMI(+)][BF4(-)]. Additionally, we have simulated two modified viologen-based ILs to reinforce our interpretations. We conclude from the above simulation results that the rigidity of anions influences the alignment of cations and that the rigidity of cations shows a large obstacle to their rotational capacity. Moreover, we have observed a slower diffusion of [VIO(2+)][BF4(-)]2 due to the electrostatic correlations, which stabilizes the ion-cage effect.

Regenerated cellulose fiber and film immobilized with lysozyme

USDA-ARS?s Scientific Manuscript database

The present work reports an initial engineering approach for fabricating lysozyme-bound regenerated cellulose fiber and film. Glycine-esterified cotton was dissolved in an ionic liquid solvent 1–Butyl–3–methylimidazolium Chloride (BMIMCl) in which lysozyme was activated and covalently attached to c...

Structure, conformations, vibrations, and ideal-gas properties of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic pairs and constituent ions.

PubMed

Paulechka, Yauheni U; Kabo, Gennady J; Emel'yanenko, Vladimir N

2008-12-11

Energies, geometries, and frequencies of normal vibrations have been calculated by quantum-chemical methods for different conformers of a bis(trifluoromethylsulfonyl)imide anion (NTf2-), 1-alkyl-3-methylimidazolium cations ([C(n)mim]+, n = 2, 4, 6, 8), and [C(n)mim]NTf2 ionic pairs. The assignment of frequencies for NTf2-, [C2mim]+, and [C4mim]+ in the vibrational spectra of ionic liquids have been performed. Thermodynamic properties of [C(n)mim]NTf2, [C(n)mim]+, and NTf2- in the gas state have been calculated by the statistical thermodynamic methods. The resulting entropies are in satisfactory agreement with the values obtained from the experimental data previously reported in literature.

Hydrophilic magnetic ionic liquid for magnetic headspace single-drop microextraction of chlorobenzenes prior to thermal desorption-gas chromatography-mass spectrometry.

PubMed

Fernández, Elena; Vidal, Lorena; Canals, Antonio

2017-11-23

A new, fast, easy to handle, and environmentally friendly magnetic headspace single-drop microextraction (Mag-HS-SDME) based on a magnetic ionic liquid (MIL) as an extractant solvent is presented. A small drop of the MIL 1-ethyl-3-methylimidazolium tetraisothiocyanatocobaltate(II) ([Emim] 2 [Co(NCS) 4 ]) is located on one end of a small neodymium magnet to extract nine chlorobenzenes (1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,2,3,4-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, and pentachlorobenzene) as model analytes from water samples prior to thermal desorption-gas chromatography-mass spectrometry determination. A multivariate optimization strategy was employed to optimize experimental parameters affecting Mag-HS-SDME. The method was evaluated under optimized extraction conditions (i.e., sample volume, 20 mL; MIL volume, 1 μL; extraction time, 10 min; stirring speed, 1500 rpm; and ionic strength, 15% NaCl (w/v)), obtaining a linear response from 0.05 to 5 μg L -1 for all analytes. The repeatability of the proposed method was evaluated at 0.7 and 3 μg L -1 spiking levels and coefficients of variation ranged between 3 and 18% (n = 3). Limits of detection were in the order of nanograms per liter ranging from 4 ng L -1 for 1,4-dichlorobenzene and 1,2,3,4-tetrachlorobenzene to 8 ng L -1 for 1,2,4,5-tetrachlorobenzene. Finally, tap water, pond water, and wastewater were selected as real water samples to assess the applicability of the method. Relative recoveries varied between 82 and 114% showing negligible matrix effects. Graphical abstract Magnetic headspace single-drop microextraction followed by thermal desorption-gas chromatography-mass spectrometry.

Vibrational sum-frequency generation spectroscopy of ionic liquid 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate at the air-water interface

NASA Astrophysics Data System (ADS)

Saha, Ankur; SenGupta, Sumana; Kumar, Awadhesh; Choudhury, Sipra; Naik, Prakash D.

2016-08-01

The structure and orientation of room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate [PF3(C2F5)3], commonly known as [bmim][fap], have been investigated at the air-[bmim][fap] and air-water interfaces, employing vibrational sum-frequency generation (VSFG) spectroscopy. The VSFG spectra in the CH stretch region suggest presence of the [bmim] cation at the interfaces. Studies reveal that the butyl chain protrudes out into air, and the imidazolium ring lies almost planar to the interface. The CH stretch intensities get enhanced at the air-water interface, mainly because of polar orientation of imidazolium cation induced by interfacial water molecules. The OH stretch intensities are also enhanced at the air-water interface due to polar orientation of interfacial water molecules induced by [bmim][fap]. The Brewster angle microscopy suggests self aggregation of [bmim][fap] in the presence of water, and the aggregation becomes extensive showing dense surface domains with time. However, the surface pressure is almost unaffected due to aggregation.

Multi-scale modelling of supercapacitors: From molecular simulations to a transmission line model

NASA Astrophysics Data System (ADS)

Pean, C.; Rotenberg, B.; Simon, P.; Salanne, M.

2016-09-01

We perform molecular dynamics simulations of a typical nanoporous-carbon based supercapacitor. The organic electrolyte consists in 1-ethyl-3-methylimidazolium and hexafluorophosphate ions dissolved in acetonitrile. We simulate systems at equilibrium, for various applied voltages. This allows us to determine the relevant thermodynamic (capacitance) and transport (in-pore resistivities) properties. These quantities are then injected in a transmission line model for testing its ability to predict the charging properties of the device. The results from this macroscopic model are in good agreement with non-equilibrium molecular dynamics simulations, which validates its use for interpreting electrochemical impedance experiments.

Toward the Elucidation of the Competing Role of Evaporation and Thermal Decomposition in Ionic Liquids: A Multitechnique Study of the Vaporization Behavior of 1-Butyl-3-methylimidazolium Hexafluorophosphate under Effusion Conditions.

PubMed

Volpe, V; Brunetti, B; Gigli, G; Lapi, A; Vecchio Ciprioti, S; Ciccioli, A

2017-11-16

The evaporation/decomposition behavior of the imidazolium ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMImPF 6 ) was investigated in the overall temperature range 425-551 K by means of the molecular-effusion-based techniques Knudsen effusion mass loss (KEML) and Knudsen effusion mass spectrometry (KEMS), using effusion orifices of different size (from 0.2 to 3 mm in diameter). Specific effusion fluxes measured by KEML were found to depend markedly on the orifice size, suggesting the occurrence of a kinetically delayed evaporation/decomposition process. KEMS experiments revealed that other species are present in the vapor phase besides the intact ion pair BMImPF 6 (g) produced by the simple evaporation BMImPF 6 (l) = BMImPF 6 (g), with relative abundances depending on the orifice size-the larger the orifice, the larger the contribution of the BMImPF 6 (g) species. By combining KEML and KEMS results, the conclusion is drawn that in the investigated temperature range, when small effusion orifices are used, a significant part of the mass loss/volatility of BMImPF 6 is due to molecular products formed by decomposition/dissociation processes rather than to evaporated intact ion pairs. Additional experiments performed by nonisothermal thermogravimetry-differential thermal analysis (TG-DTA) further support the evidence of simultaneous evaporation/decomposition, although the conventional decomposition temperature derived from TG curves is much higher than the temperatures covered in effusion experiments. Partial pressures of the BMImPF 6 (g) species were derived from KEMS spectra and analyzed by second- and third-law methods giving a value of Δ evap H 298K ° = 145.3 ± 2.9 kJ·mol -1 for the standard evaporation enthalpy of BMImPF 6 . A comparison is done with the behavior of the 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide (BMImNTf 2 ) ionic liquid.

Interaction of copper with dinitrogen tetroxide in 1-butyl-3-methylimidazolium-based ionic liquids.

PubMed

Morozov, I V; Deeva, E B; Glazunova, T Yu; Troyanov, S I; Guseinov, F I; Kustov, L M

2017-03-27

Ionic liquids that are stable toward oxidation and nitration and are based on the 1-n-butyl-3-methylimidazolium cation (BMIm + ) can be used as solvents and reaction media for copper dissolution in liquid dinitrogen tetraoxide N 2 O 4 . The ionic liquid not only favors the dissociation of N 2 O 4 into NO + and NO 3 - , but also takes part in the formation of different crystalline products. Thus, NO[BF 4 ], NO[Cu(NO 3 ) 3 ] and (BMIm) 2 [Cu 2 (CF 3 COO) 6 ] were prepared using (BMIm)A, A - = [BF 4 ] - , (CF 3 SO 2 ) 2 N - , CF 3 COO - , respectively. The formation of a certain product is determined by the nature of the anion A - and the relative solubility of the reaction products in the ionic liquid. Crystals of NO[BF 4 ] were also prepared directly from a mixture of N 2 O 4 and BMImBF 4 . According to XRD single-crystal structure analysis, the structure of NO[BF 4 ] consists of tetrahedral [BF 4 ] - anions and nitrosonium NO + cations; the formation of these ions prove the heterolytic dissociation of N 2 O 4 dissolved in the ionic liquid. The crystal structure of the earlier unknown binuclear copper trifluoroacetate (BMIm) 2 [Cu 2 (CF 3 COO) 6 ] were determined by X-ray diffraction. The peculiarity of this dimer compared to the majority of known dimeric copper(ii) carboxylates is the unusually long CuCu distance (3.15 Å), with Cu(ii) ions demonstrating an atypical coordination of a distorted trigonal bipyramid formed by five O atoms of five trifluoroacetate groups.

The electronegativity equalization method fused with molecular mechanics: a fluctuating charge and flexible body potential function for [Emim][Gly] ionic liquids.

PubMed

Wu, Yang; Li, Yao; Hu, Na; Hong, Mei

2014-02-14

Recently, experimental and theoretical studies on amino acid ionic liquid (AAIL) systems have attracted much attention. A transferable intermolecular potential approach that includes fluctuating charges and a flexible body based on a combination of the electronegativity equalization method and molecular mechanics (EEM/MM), and its application to an AAIL system containing 1-ethyl-3-methylimidazolium ([Emim](+)) and glycine ([Gly](-)) are explored and tested in this study. A consistent integration of EEM with MM requires the input of the EEM charges of all atoms into the MM intermolecular electrostatic interaction term. Compared with ionic liquid (IL) force fields, the EEM/MM model has an outstanding feature: the EEM/MM model not only presents the electrostatic interaction of atoms and their changes in response to different ambient environments but also introduces "the H-bond interaction region" in which a new parameter kHB(RHB) is used to describe the electrostatic interaction of hydrogen atoms in [Emim](+) and oxygen atoms in [Gly](-), which can form hydrogen bonds. The EEM/MM model gives quite accurate predictions for gas-phase state properties of [Emim](+), [Gly](-), and ion pairs, such as optimized geometries, dipole moments, vibrational frequencies, and cluster interaction energies. Due to its explicit description of charges and hydrogen bonds, the EEM/MM model also performs well for the liquid-phase properties of [Emim][Gly] under ambient conditions. The calculated properties, such as density, heat of vaporization, the self-diffusion coefficient, and ionic conductivity, are fairly consistent with available experimental results.

Additive-containing ionic liquid electrolytes for secondary lithium battery

NASA Astrophysics Data System (ADS)

Xu, Jinqiang; Yang, Jun; NuLi, Yanna; Wang, Jiulin; Zhang, Zongshuang

Room temperature ionic liquid (RTIL) consisting of N-methyl- N-propylpiperidinium (PP13) cation and bis(trifluoromethanesulfonyl)imide (TFSI) anion was synthesized and its electrochemical stability was investigated in comparison with 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF 4) and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF 6). The electrochemical window of PP13-TFSI (5.8 V versus Li/Li +) is wider than that of BMIBF 4 (4.7 V) and BMIPF 6 (4.5 V). The cathodic limit of the PP13-TFSI is about -0.3 V versus Li/Li +, against 0.7 V for BMIPF 6 and BMIBF 4, so it may be used as the electrolyte for second lithium batteries based on lithium anode. In this work, charge efficiency of lithium plating/striping on nickel substrate and the cycle life have been measured using 0.4 M LiTFSI/PP13-TFSI electrolyte both without and with additives such as vinyl acetate (VA), ethylene sulfite (ES), and ethylene carbonate (EC). Remarkable improvement in cycling efficiency and cycle life was found for EC as additive.

Pretreatment of eucalyptus with recycled ionic liquids for low-cost biorefinery.

PubMed

Xu, Jikun; Liu, Bingchuan; Hou, Huijie; Hu, Jingping

2017-06-01

It is urgent to develop recycled ionic liquids (ILs) as green solvents for sustainable biomass pretreatment. The goal of this study is to explore the availability and performance of reusing 1-allyl-3-methylimidazolium chloride ([amim]Cl) and 1-butyl-3-methylimidazolium acetate ([bmim]OAc) for pretreatment, structural evolution, and enzymatic hydrolysis of eucalyptus. Cellulose enzymatic digestibility slightly decreased with the increased number of pretreatment recycles. The hydrolysis efficiencies of eucalyptus pretreated via 4th recycled ILs were 54.3% for [amim]Cl and 72.8% for [bmim]OAc, which were 5.0 and 6.7-folds higher than that of untreated eucalyptus. Deteriorations of ILs were observed by the relatively lower sugar conversion and lignin removal from eucalyptus after 4th reuse. No appreciable changes in fundamental framework and thermal stability of [amim]Cl were observed even after successive pretreatments, whereas the anionic structure of [bmim]OAc was destroyed or replaced. This study suggested that the biomass pretreatment with recycled ILs was a potential alternative for low-cost biorefinery. Copyright © 2017 Elsevier Ltd. All rights reserved.

Advanced intermediate temperature sodium copper chloride battery

NASA Astrophysics Data System (ADS)

Yang, Li-Ping; Liu, Xiao-Min; Zhang, Yi-Wei; Yang, Hui; Shen, Xiao-Dong

2014-12-01

Sodium metal chloride batteries, also called as ZEBRA batteries, possess many merits such as low cost, high energy density and high safety, but their high operation temperature (270-350 °C) may cause several issues and limit their applications. Therefore, decreasing the operation temperature is of great importance in order to broaden their usage. Using a room temperature ionic liquid (RTIL) catholyte composed of sodium chloride buffered 1-ethyl-3-methylimidazolium chloride-aluminum chloride and a dense β″-aluminates solid electrolyte film with 500 micron thickness, we report an intermediate temperature sodium copper chloride battery which can be operated at only 150 °C, therefore alleviating the corrosion issues, improving the material compatibilities and reducing the operating complexities associated with the conventional ZEBRA batteries. The RTIL presents a high ionic conductivity (0.247 S cm-1) at 150 °C and a wide electrochemical window (-2.6 to 2.18 vs. Al3+/Al). With the discharge plateau at 2.64 V toward sodium and the specific capacity of 285 mAh g-1, this intermediate temperature battery exhibits an energy density (750 mWh g-1) comparable to the conventional ZEBRA batteries (728-785 mWh g-1) and superior to commercialized Li-ion batteries (550-680 mWh g-1), making it very attractive for renewable energy integration and other grid related applications.

Hierarchical micro- and mesoporous carbide-derived carbon as a high-performance electrode material in supercapacitors.

PubMed

Rose, Marcus; Korenblit, Yair; Kockrick, Emanuel; Borchardt, Lars; Oschatz, Martin; Kaskel, Stefan; Yushin, Gleb

2011-04-18

Ordered mesoporous carbide-derived carbon (OM-CDC) materials produced by nanocasting of ordered mesoporous silica templates are characterized by a bimodal pore size distribution with a high ratio of micropores. The micropores result in outstanding adsorption capacities and the well-defined mesopores facilitate enhanced kinetics in adsorption processes. Here, for the first time, a systematic study is presented, in which the effects of synthesis temperature on the electrochemical performance of these materials in supercapacitors based on a 1 M aqueous solution of sulfuric acid and 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid are reported. Cyclic voltammetry shows the specific capacitance of the OM-CDC materials exceeds 200 F g(-1) in the aqueous electrolyte and 185 F g(-1) in the ionic liquid, when measured in a symmetric configuration in voltage ranges of up to 0.6 and 2 V, respectively. The ordered mesoporous channels in the produced OM-CDC materials serve as ion-highways and allow for very fast ionic transport into the bulk of the OM-CDC particles. At room temperature the enhanced ion transport leads to 75% and 90% of the capacitance retention at current densities in excess of ∼10 A g(-1) in ionic liquid and aqueous electrolytes, respectively. The supercapacitors based on 250-300 μm OM-CDC electrodes demonstrate an operating frequency of up to 7 Hz in aqueous electrolyte. The combination of high specific capacitance and outstanding rate capabilities of the OM-CDC materials is unmatched by state-of-the art activated carbons and strictly microporous CDC materials. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CRYSTAL POLYMORPHISM IN 1-BUTYL-3-METHYLIMIDAZOLIUM HALIDES: SUPPORTING IONIC LIQUID FORMATION THROUGH INHIBITION OF CRYSTALLIZATION. (R828257)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Molecular dynamics simulation of amino acid ionic liquids near a graphene electrode: effects of alkyl side-chain length.

PubMed

Sadeghi Moghadam, Behnoosh; Razmkhah, Mohammad; Hamed Mosavian, Mohammad Taghi; Moosavi, Fatemeh

2016-12-07

Electric double layer (EDL) supercapacitors, using ionic liquid electrolytes, have been receiving a great deal of attention in response to the growing demand for energy storage systems. In the present study, the nanoscopic structure of amino acid ionic liquids (AAILs) as biodegradable electrolytes near a neutral graphene surface was studied by molecular dynamics (MD) simulation. In order to explore the influence of the anion type and structure, the effect of the alkyl side-chain length of amino acids on the EDL was investigated. The results for the AAILs, composed of 1-ethyl-3-methylimidazolium ([EMIM]) cations near alanine ([ALA]) and isoleucine ([ILE]) anions, were compared to a conventional electrolyte, [EMIM][PF 6 ]. A lower mobility of AAIL compared to [EMIM][PF 6 ], with diffusions as low as 10 -11 m 2 s -1 , was observed. The structural results demonstrated a layered structure near the surface and most of the adsorbed imidazolium cation rings lay flat on the graphene surface. Both MD and quantum computations were performed to shed light on the charge behavior of AAIL electrolytes. As the current results demonstrate, an increase in the anion side-chain length leads to a decrease in both the number of adsorbed ions on the surface and the thickness of the first adsorbed layer. More impressively, it was observed that a low charge concentration in the EDL of AAILs is due to more side-side interactions. This remarkable feature could introduce AAILs as more efficient electrolyte materials than conventional [EMIM][PF 6 ].

Ionic Liquids Can Selectively Change the Conformational Free-Energy Landscape of Sugar Rings.

PubMed

Jarin, Zack; Pfaendtner, Jim

2014-02-11

We investigated the conformational free energy landscape of glucose solvated in water and in the ionic liquids (ILs) 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) and 1-butyl-3-methylimidazoulim boron tetrafluoride ([Bmim][BF4]). To quantify equilibrium thermodynamic solvent effects, molecular dynamics simulations in conjunction with enhanced sampling based on the metadynamics framework were used. The results show that the solvent choice induces significant differences in the equilibrium ring structures, which may help further resolve the molecular mechanism governing IL-mediated cellulose dissolution.

Hydrogels dispersed by doped rare earth fluoride nanocrystals: ionic liquid dispersion and down/up-conversion luminescence.

PubMed

Yan, Zhi-Yuan; Jia, Li-Ping; Yan, Bing

2014-01-01

Two typical kinds of rare earth fluoride nanocrystals codoped with rare earth ions (Eu(3+) and Tm(3+)/Er(3+),Yb(3+)) are synthesized and dispersed in ionic liquid compound (1-chlorohexane-3-methylimidazolium chloride, abbreviated as [C6mim][Cl]). Assisted by agarose, the luminescent hydrogels are prepared homogeneously. The down/up-conversion luminescence of these hydrogels can be realized for the dispersed rare earth fluoride nanocrystals. The results provide a strategy to prepare luminescent (especially up-conversion luminescent) hydrogels with ionic liquid to disperse rare earth fluoride nanocrystals. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrochemical preparation of nanostructured lanthanum using lanthanum chloride as a precursor in 1-butyl-3-methylimidazolium dicyanamide ionic liquid.

PubMed

Zhang, Q B; Yang, C; Hua, Y X; Li, Y; Dong, P

2015-02-14

Nanostructured lanthanum was electrochemically prepared on a platinum (Pt) substrate in the room temperature ionic liquid 1-butyl-3-methylimidazolium dicyanamide (BMI-DCA) containing anhydrous LaCl3 at 333 K. The electrochemical reduction behavior of La(iii) was investigated using cyclic voltammetry and chronoamperometry techniques. Cyclic voltammogram revealed that the reduction of La(iii) in BMI-DCA involved an irreversible process controlled by diffusion. Chronoamperometric transient analysis confirmed the diffusion controlled electrodeposition process with the diffusion coefficient of La(iii) species in the range of 10(-10) cm(2) s(-1). The strong complexing capability of DCA(-) anions facilitated the displacement of chloride ligands and induced the solubility of LaCl3. The subsequent coordination of La(iii) and DCA(-) anions forming [La(DCA)4](-) complex anions was monitored by designing amperometric titration experiments. Potentiostatically deposited La-deposits with different nanostructures were characterized by SEM, XRD and XPS analyses. The electrodeposition potential was found to play an important role in controlling the nucleation and growth kinetics of the nanocrystal during the electrodeposition process. Depending on the deposition potential, metallic lanthanum with either nanoparticles or nanoporous structures was obtained.

Rapid method for the determination of coumarin, vanillin, and ethyl vanillin in vanilla extract by reversed-phase liquid chromatography with ultraviolet detection.

PubMed

Ali, Laila; Perfetti, Gracia; Diachenko, Gregory

2008-01-01

A method is described for determining coumarin, vanillin, and ethyl vanillin in vanilla extract products. A product is diluted one-thousand-fold and then analyzed by reversed-phase liquid chromatography using a C18 column and a mobile phase consisting of 55% acetonitrile-45% aqueous acetic acid (1%) solution at a flow rate of 1.0 mL/min. Peaks are detected with a UV detector set at 275 nm. Vanilla extracts were spiked with 250, 500, and 1000 microg/g each of coumarin, vanillin, and ethyl vanillin. Recoveries averaged 97.4, 97.8, and 99.8% for coumarin, vanillin, and ethyl vanillin, respectively, with coefficient of variation values of 1.8, 1.3, and 1.3%, respectively. No significant difference was observed among the 3 spiking levels. A survey of 23 domestic and imported vanilla extract products was conducted using the method. None of the samples contained coumarin. The surveyed samples contained between 0.4 to 13.1 and 0.4 to 2.2 mg/g vanillin and ethyl vanillin, respectively.

Environmental Impact of Ionic Liquids: Automated Evaluation of the Chemical Oxygen Demand of Photochemically Degraded Compounds.

PubMed

Costa, Susana P F; Pereira, Sarah A P; Pinto, Paula C A G; Araujo, André R T S; Passos, Marieta L C; Saraiva, M Lúcia M F S

2017-05-19

A novel automated fluorimetric technique was developed for the assessment of the chemical oxygen demand (COD) of ionic liquids (ILs) and combined with a photodegradation step to promote IL degradation. The method was implemented on a sequential injection analysis (SIA) system and is based on the reduction of cerium(IV) in the presence of irradiated ILs. Compounds incorporating the chloride anion were found to exhibit higher COD values and 1-butyl-3-methylimidazolium chloride ([bmim] + [Cl] - ), 1-butyl-1-methylpyrrolidinium chloride ([bmpyr] + [Cl] - ), and1-hexyl-3-methylimidazolium chloride ([hmim] + [Cl] - ) also exhibited considerable photodegradability, whereas the cholinium cation and methanesulfonate and tetrafluoroborate anions showed resistance to photolysis. The developed methodology proved to be a simple, affordable, and robust method, showing good repeatability under the tested conditions (rsd <3.5 %, n=10). Therefore, it is expected that the developed approach can be used as a screening method for the preliminary evaluation of compounds' potential impact in the aquatic field. Additionally, the photolysis step presents an attractive option to promote degradation of ILs prior to their release into wastewater. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of the conditions of anodizing on the morphology of nanotitania

NASA Astrophysics Data System (ADS)

Root, N. V.; Kultin, D. Yu.; Kustov, L. M.; Kudryavtsev, I. K.; Lebedeva, O. K.

2017-02-01

The effect the current density, treatment time, surface pretreatment, and electrolyte composition have on the morphology of titania obtained via electrochemical treatment in such ionic liquids (ILs) as 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM][NTf2] and 1-butyl-3-methylimidazolium chloride [BMIM]Cl is studied. The anodic formation of titania nanostructures in the form of nanotubes or nanorods is found to occur in times of up to 100 s. The role of water in the formation of these titania nanostructures is shown. Pretreatment has no effect on the morphology of the formed oxide. The formation of products that are poorly soluble in ILs (e.g., hydrated oxides) results in the emergence of a layer partially covering the open parts of nanotubes, preventing their further growth.

Atomistic Simulation and Electronic Structure of Lithium Doped Ionic Liquids: Structure, Transport, and Electrochemical Stability

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Bauschlicher, Charles W.; Lawson, John W.

2015-01-01

Zero-temperature density functional theory (DFT), density functional theory molecular dynamics (DFT-MD), and classical molecular dynamics using polarizable force fields (PFF-MD) are employed to evaluate the influence of Lithium ion on the structure, transport, and electrochemical stability of three potential ionic liquid electrolytes: N--methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([pyr14][TFSI]), N--methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide ([pyr13][FSI]), and 1-ethyl-3--methylimidazolium boron tetrafluoride ([EMIM][BF4]). We characterize the Lithium ion solvation shell through zero-temperature DFT simulations of [Li(Anion)sub n](exp n-1) -clusters, DFT-MD simulations of isolated lithium ions in small ionic liquid systems, and PFF-MD simulations with high Li-doping levels in large ionic liquid systems. At low levels of Li-salt doping, highly stable solvation shells having 2-3 anions are seen in both [pyr14][TFSI] and [pyr13][FSI], while solvation shells with 4 anions dominate in [EMIM][BF sub 4]. At higher levels of doping, we find the formation of complex Li-network structures that increase the frequency of 4 anion-coordinated solvation shells. A comparison of computational and experimental Raman spectra for a wide range of [Li(Anion) sub n](exp n -1) - clusters shows that our proposed structures are consistent with experiment. We estimate the ion diffusion coefficients and quantify both size and simulation time effects. We find estimates of lithium ion diffusion are a reasonable order of magnitude and can be corrected for simulation time effects. Simulation size, on the other hand, is also important, with diffusion coefficients from long PFF-MD simulations of small cells having 20-40% error compared to large-cell values. Finally, we compute the electrochemical window using differences in electronic energy levels of both isolated cation/anion pairs and small ionic liquid systems with Li-salt doping. The single pair and liquid-phase systems provide similar estimates of electrochemical window, while Li-doping in the liquid-phase systems results in electrochemical windows little changed from the neat systems. Pure and hybrid functionals systematically provide an upper and lower bound, respectively, to the experimental electrochemical window for the systems studied here.

Molecular dynamics study of polysaccharides in binary solvent mixtures of an ionic liquid and water.

PubMed

Liu, Hanbin; Sale, Kenneth L; Simmons, Blake A; Singh, Seema

2011-09-01

Some ionic liquids (ILs) have great promise as effective solvents for biomass pretreatment, and there are several that have been reported that can dissolve large amounts of cellulose. The solubilized cellulose can then be recovered by addition of antisolvents, such as water or ethanol, and this regeneration process plays an important role in the subsequent enzymatic saccharification reactions and in the recovery of the ionic liquid. To date, little is known about the fundamental intermolecular interactions that drive the dissolution and subsequent regeneration of cellulose in complex mixtures of ionic liquids, water, and cellulose. To investigate these interactions, in this work, molecular dynamics (MD) simulations were carried out to study binary and ternary mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) with water and a cellulose oligomer. Simulations of a cellulose oligomer dissolved in three concentrations of binary mixtures of [C2mim][OAc] and water were used to represent the ternary system in the dissolution phase (high [C2mim][OAc] concentration) and present during the initial phase of the regeneration step (intermediate and low [C2mim][OAc] concentrations). The MD analysis of the structure and dynamics that exist in these binary and ternary mixtures provides information on the key intermolecular interactions between cellulose and [C2mim][OAc] that lead to dissolution of cellulose and the key intermolecular interactions in the intermediate states of cellulose precipitation as a function of water content in the cellulose/IL/water system. The analysis of this intermediate state provides new insight into the molecular driving forces present in this ternary system. © 2011 American Chemical Society

Antisolvent crystallization of a cardiotonic drug in ionic liquids: Effect of mixing on the crystal properties

NASA Astrophysics Data System (ADS)

de Azevedo Jacqueline, Resende; Fabienne, Espitalier; Jean-Jacques, Letourneau; Inês, Ré Maria

2017-08-01

LASSBio-294 (3,4-methylenedioxybenzoyl-2-thienylhydrazon) is a poorly soluble drug which has been proposed to have major advantages over other cardiotonic drugs. Poorly water soluble drugs present limited bioavailability due to their low solubility and dissolution rate. An antisolvent crystallization processing can improve the dissolution rate by decreasing the crystals particle size. However, LASSBio-294 is also poorly soluble in organic solvents and this operation is limited. In order to open new perspectives to improve dissolution rate, this work has investigated LASSBio-294 in terms of its antisolvent crystallization in 1-ethyl-3-methylimidazolium methyl phosphonate [emim][CH3O(H)PO2] as solvent and water as antisolvent. Two modes of mixing are tested in stirred vessel with different pre-mixers (Roughton or T-mixers) in order to investigate the mixing effect on the crystal properties (crystalline structure, particle size distribution, residual solvent and in vitro dissolution rate). Smaller drug particles with unchanged crystalline structure were obtained. Despite the decrease of the elementary particles size, the recrystallized particles did not achieve a better dissolution profile. However, this study was able to highlight a certain number of findings such as the impact of the hydrodynamic conditions on the crystals formation and the presence of a gel phase limiting the dissolution rate.

A general strategy for the experimental study of the thermochemistry of protic ionic liquids: enthalpy of formation and vaporisation of 1-methylimidazolium ethanoate.

PubMed

Vitorino, Joana; Bernardes, Carlos E S; Minas da Piedade, Manuel E

2012-04-07

A general strategy to determine enthalpies of formation of protic ionic liquids, based solely on enthalpy of solution measurements, was conceived and tested for 1-methylimidazolium ethanoate, leading to Δ(f)H°(m){[Hmim][O(2)CCH(3)], 1} = -(425.7 ± 1.2) kJ mol(-1). This result in conjunction with the enthalpy of formation of gaseous 1-methylimidazole (mim) proposed in this work, Δ(f)H°(m)(mim, g) = 126.5 ± 1.1 kJ mol(-1), and Δ(f)H°(m)(CH(3)COOH, g) taken from the literature, allowed the calculation of the enthalpy of the vaporisation process [Hmim][O(2)CCH(3)](l) → mim(g) + CH(3)COOH(g) as Δ(vap)H°(m){[Hmim][O(2)CCH(3)]} = 119.4 ± 3.0 kJ mol(-1). The agreement between this value and Δ(vap)H°(m){[Hmim][O(2)CCH(3)]} = 117.3 ± 0.5 kJ mol(-1), obtained for the direct vaporisation of [Hmim][O(2)CCH(3)], by Calvet-drop microcalorimetry, gives a good indication that, as previously suggested by Fourier transform ion cyclotron resonance mass spectrometry, Raman spectroscopy, and GC-MS experiments, the vaporisation of [Hmim][O(2)CCH(3)] essentially involves a proton transfer mechanism with formation of the two volatile neutral precursor molecules (mim and CH(3)COOH). Although being a low ionicity protic ionic liquid, [Hmim][O(2)CCH(3)] was chosen to validate the methodology proposed here, since its vaporisation mechanism has been unequivocally demonstrated by different methods and for different pressure ranges.

Small angle neutron scattering from 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids ([Cnmim][PF6], n=4, 6, and 8)

NASA Astrophysics Data System (ADS)

Hardacre, Christopher; Holbrey, John D.; Mullan, Claire L.; Youngs, Tristan G. A.; Bowron, Daniel T.

2010-08-01

The presence of local anisotropy in the bulk, isotropic, and ionic liquid phases—leading to local mesoscopic inhomogeneity—with nanoscale segregation and expanding nonpolar domains on increasing the length of the cation alkyl-substituents has been proposed on the basis of molecular dynamics (MD) simulations. However, there has been little conclusive experimental evidence for the existence of intermediate mesoscopic structure between the first/second shell correlations shown by neutron scattering on short chain length based materials and the mesophase structure of the long chain length ionic liquid crystals. Herein, small angle neutron scattering measurements have been performed on selectively H/D-isotopically substituted 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids with butyl, hexyl, and octyl substituents. The data show the unambiguous existence of a diffraction peak in the low-Q region for all three liquids which moves to longer distances (lower Q), sharpens, and increases in intensity with increasing length of the alkyl substituent. It is notable, however, that this peak occurs at lower values of Q (longer length scale) than predicted in any of the previously published MD simulations of ionic liquids, and that the magnitude of the scattering from this peak is comparable with that from the remainder of the amorphous ionic liquid. This strongly suggests that the peak arises from the second coordination shells of the ions along the vector of alkyl-chain substituents as a consequence of increasing the anisotropy of the cation, and that there is little or no long-range correlated nanostructure in these ionic liquids.

Computational and Experimental Investigation of Li-doped Ionic Liquid Electrolytes: [pyr14][tfsi], [pyr13][fsi], and [EMIM][BF4

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Bennett, William R.; Wu, James J.; Hernandez, Dionne M.; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W.; Lawson, John W.

2014-01-01

We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N -methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 xLi+ 0.33) and temperature (298 K T 393 K). Structurally, Li+ is shown to be solvated by three anion neigh- bors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi+ we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi+, the contribution of Li+ to ionic conductivity increases until reach- ing a saturation doping level of xLi+ 0.10. Comparatively, the Li+ conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. Our transport results also demonstrate the necessity of long MD simulation runs ( 200 ns) required to converge transport properties at room T. The differences in Li+ transport are reflected in the residence times of Li+ with the anions (Li), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li+ transport in each liquid, we find that while the net motion of Li+ with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange (hopping) increases at high xLi+ and in liquids with large anions.

Modeling solubility of CO2/hydrocarbon gas in ionic liquid ([emim][FAP]) using Aspen Plus simulations.

PubMed

Bagchi, Bishwadeep; Sati, Sushmita; Shilapuram, Vidyasagar

2017-08-01

The Peng-Robinson equation of state with quadratic van der Waals (vdW) mixing rule model was chosen to perform the thermodynamic calculations in Flash3 column of Aspen Plus to predict the solubility of CO 2 or any one of the hydrocarbons (HCs) among methane, ethane, propane, and butane in an ionic liquid 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([emim][FAP]). Bubble point pressure, solubility, bubble point temperature, fugacity, and partial molar volume at infinite dilution were obtained from the simulations, and enthalpy of absorption, Gibbs free energy of solvation, and entropy change of absorption were estimated by thermodynamic relations. Results show that carbon chain length has a significant effect on the bubble point pressure. Methane has the highest bubble point pressure among all the considered HCs and CO 2 . The bubble point pressure and fugacity variation with temperature is different for CO 2 as compared to HCs for mole fractions above 0.2. Two different profiles are noticed for enthalpy of absorption when plotted as a function of mole fraction of gas soluble in IL. Partial molar volume of CO 2 decreases with increase in temperature in [emim][FAP], while it is increased for HCs. Bubble point temperature decreases with increase in the mole fraction of the solute. Entropy of solvation increases with temperature till a particular value followed by a decrease with further increase in temperature. Gibbs free energy change of solvation showed that the process of solubility was spontaneous.

Molecular dynamics study of thermodynamic scaling of the glass-transition dynamics in ionic liquids over wide temperature and pressure ranges.

PubMed

Habasaki, J; Casalini, R; Ngai, K L

2010-03-25

Experimentally, superpositioning of dynamic properties such as viscosity, relaxation times, or diffusion coefficients under different conditions of temperature T, pressure P, and volume V by the scaling variable TV(gamma) (where gamma is a material constant) has been reported as a general feature of many kinds of glass-forming materials. In the present work, molecular dynamics (MD) simulations have been performed to study the scaling of dynamics near the glass-transition regime of ionic liquids. Scaling in the simulated 1-ethyl-3-methylimidazolium nitrate (EMIM-NO(3)) system has been tested over wide ranges of temperatures and pressures. TV(gamma) scaling of the dynamics is well described by master curves with gamma = 4.0 +/- 0.2 and 3.8 +/- 0.2 for cation and anion, respectively. Structures and Coulombic terms of the corresponding states are found to be quite similar. The temperature and pressure dependence of the pair correlation function show similar trends and therefore can be superpositioned onto the master curve. Although the behaviors with gamma = 4 might be expected from the relation, gamma = n/3, for the dynamics with the soft-core-type potential U = epsilon(sigma/r)(n), with n = 12, pair potentials used in the MD simulation have a more complex form, and not all the repulsive terms can play their roles in the heterogeneous structures determined by ion-ion interactions. Scaling is related to the common part of effective potentials related to the pair correlation functions, including the many-body effect in real space.

Porous carbon nanotube/graphene composites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Li, Jing; Tang, Jie; Yuan, Jinshi; Zhang, Kun; Yu, Xiaoliang; Sun, Yige; Zhang, Han; Qin, Lu-Chang

2018-02-01

Carbon nanotubes (CNTs) are an effective spacer to prevent the re-stacking of graphene layers. However, the aggregation of CNTs always reduces the specific surface area of resulting CNT/graphene composites. Meanwhile, different pores always have different contributions to the specific capacitance. In this study, CNT/graphene composites with different porous structures are synthesized by co-reduction of oxidized CNTs and graphene oxide with different mixing ratios. With an optimized CNT content of 20%, the CNT/graphene composite shows 206 F g-1 in 1-ethyl-3-methylimidazolium tetrafluoroborate electrolyte. It is found that pores larger than twice the size of electrolyte ions can make greater contributions to the specific capacitance.

Effects of the ionic liquid 1-hexyl-3-methylimidazolium bromide on root gravitropism in Arabidopsis seedlings.

PubMed

Zhang, Liang; Wang, Tianqi; Zheng, Fengxia; Ma, Lingyu; Li, Jingyuan

2016-03-01

The toxic effects of ionic liquids (ILs) have attracted increasing attention in recent years. However, the knowledge about the toxic effects of ILs on tropism in organisms remains quite limited. In this study, the effects of 1-hexyl-3-methylimidazolium bromide [C6mim]Br on root gravitropism were evaluated using Arabidopsis seedlings. Our results showed that the root growth and gravity response were significantly inhibited with increasing IL concentration. [C6mim]Br treatment affected the amount and distribution pattern of amyloplasts in root cap compared with controls. The auxin distribution marked with DR5rev::VENUS was altered in IL-treated seedlings. The signal intensity and gene expression of auxin efflux carriers PIN2 and PIN3 were obviously decreased by IL stress. Moreover, as consequences in response to gravity stimulus, the asymmetric DR5 signals in control root apex were impaired by IL treatment. The predominant PIN2 signals along the lower flank of root and PIN3 polarization in columella cells were also significantly reduced in seedlings exposed to IL. Our results suggest that the ionic liquid [C6mim]Br affects the amount and distribution of amyloplasts and disturbs the deployment of PIN2 and PIN3, thus impairing auxin flows in response to gravity stimulus and causing deficient root gravitropism in Arabidopsis seedlings. Copyright © 2015 Elsevier Inc. All rights reserved.

Acetylation of Starch with Vinyl Acetate in Imidazolium Ionic Liquids and Characterization of Acetate Distribution

USDA-ARS?s Scientific Manuscript database

Starch was acetylated with vinyl acetate in different 1-butyl-3-methylimidazolium (BMIM) salts as solvent in effort to produce starches with different acetylation patterns. Overall degree of substitution was much higher for basic anions such as acetate and dicyanimide (dca) than for neutral anions ...

Electrodeposition of Nanocrystalline Ni–Fe Alloy Coatings Based on 1-Butyl-3-Methylimidazolium-Hydrogen Sulfate Ionic Liquid.

PubMed

He, Xinkuai; Zhang, Chuang; Zhu, Qingyun; Lu, Haozi; Cai, Youxing; Wu, Luye

2017-02-01

The electrodeposition of nanocrystalline Ni–Fe alloy coatings and associated nucleation/growth processes are investigated on the glassy carbon (GC) electrode in 1-butyl-3-methylimidazolium-hydrogen sulfate ([BMIM]HSO4) ionic liquid (IL). Cyclic voltammetric data suggest that the co-electrodeposition of Ni–Fe alloys is quasi-reversible. Moreover, chronoamperometry results indicate that the electrodeposition proceeds via a simultaneous nucleation and three-dimensional growth mechanism. In addition, the effects of electrodeposition potential and electrolyte temperature on the coating thickness and Fe content are also studied. The microstructure and composition of the Ni–Fe alloy coatings on Cu substrate are investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive spectroscopy (EDS). SEM observations show that these electrodeposits present a dense and compact structure, EDS analysis indicates that the coatings are composed of Ni and Fe, XRD pattern shows the coatings are crystalline with a face-centred cubic (fcc) structure. Tafel plots reveal that the Ni–Fe alloy prepared from [BMIM]HSO4 IL presents better corrosion resistance than that of pure Ni.

Thermophysical Properties of Ionic Liquid, 1-Pentyl-3-methylimidazolium Chloride in Water at Different Temperatures

NASA Astrophysics Data System (ADS)

Shekaari, Hemayat; Mousavi, Sedighehnaz S.; Mansoori, Yagoub

2009-04-01

Osmotic coefficients, {φ}, electrical conductance data, Λ, and refractive indices, n D, of aqueous solutions of the ionic liquid, 1-pentyl-3-methylimidazolium chloride [PnMIm]Cl have been measured at T = (298.15, 308.15, 318.15, and 328.15) K. Measurements of osmotic coefficients were carried out by the vapor-pressure osmometry method (VPO). Osmotic coefficient values show that ion-solvent interactions are stronger at lower temperature. The osmotic coefficients were correlated to the Pitzer-ion interaction and modified NRTL (MNRTL) models. From these data, mean molal activity coefficients, γ±, and excess Gibbs free energies, G E, have been calculated. Electrical conductance data have been applied for determination of association constants, K a, and limiting molar conductances, Λ 0, using the low concentration chemical model (lcCM). Calculated ion-association constant, K a, values show that ion-association effects increase at high temperatures which is in agreement with osmotic coefficient results. Experimental results of refractive indices for the binary system are reported, and have been fitted by a polynomial expansion.

Photoinduced electron transfer in a room temperature ionic liquid 1-butyl-3-methylimidazolium octyl sulfate micelle: a temperature dependent study.

PubMed

Sarkar, Souravi; Mandal, Sarthak; Pramanik, Rajib; Ghatak, Chiranjib; Rao, Vishal Govind; Sarkar, Nilmoni

2011-05-19

The effect of temperature on the dynamics of photoinduced electron transfer (PET) between different coumarin dyes and N,N-dimethyl aniline in a room temperature ionic liquid 1-butyl-3-methylimidazolium octyl sulfate ([C(4)mim][C(8)SO(4)]) micelle have been investigated using steady-state and time-resolved fluorescence quenching measurements at four different temperatures: 208, 298, 308, and 318 K. The quenching rates (k(q)(TR)) of the PET process in this micellar system are found to be lower than the PET rate in sodium dodecyl sulfate and Triton-X 100 micelle and almost comparable to the dodecyl trimethyl ammonium bromide and cetyl trimethyl ammonium bromide micelle due to larger donor–acceptor separation in the micellar phase. The temperature dependent PET rates are well correlated with the Arrhenius type of correlation for all the coumarin dyes. Marcus type of inversion in PET rates has been observed at relatively lower exergonicity, and the correlation plots gradually move upward with the increase of temperature. © 2011 American Chemical Society

Electrochemical characterisations and ageing of ionic liquid/γ-butyrolactone mixtures as electrolytes for supercapacitor applications over a wide temperature range

NASA Astrophysics Data System (ADS)

Dagousset, Laure; Pognon, Grégory; Nguyen, Giao T. M.; Vidal, Frédéric; Jus, Sébastien; Aubert, Pierre-Henri

2017-08-01

Electrochemical properties in mesoporous media of three different ionic liquids (1-propyl-1-methylpyrrolidinium-bis(fluorosulfonyl)imide - Pyr13FSI, 1-butyl-1-methylpyrrolidinium-bis(trifluoromethanesulfonyl)imide - Pyr14TFSI and 1-ethyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)imide - EMITFSI) are investigated from -50 °C to 100 °C and compared with binary mixtures with γ-butyrolactone (GBL). Buckypaper composed of Single-Wall Carbon Nanotubes (SWCNTs) are used to prepare and study coin-cell supercapacitors. Supercapacitor using Pyr13FSI/GBL present a rapid loss of capacitance after only a thousand cycles at 100 °C. On the contrary, EMITFSI/GBL and Pyr14TFSI/GBL prove to be very promising at high temperature (the capacitance loss after 10,000 cycles is 9% and 10%). More drastic ageing tests such as floating are also carried out for these two mixtures at 100 °C and -50 °C. 23% and 15% capacitance losses have been recorded after 500 h of floating at 100 °C for EMITFSI/GBL and Pyr14TFSI/GBL. The capacitance of supercapacitors based on Pyr14TFSI/GBL dropped by 20% after 200 h of floating at -50 °C rather than EMITFSI/GBL show a remarkable stability during floating at -50 °C, with 6.6% capacitance loss after 500 h (3 V at -50 °C). These results show that the mixture EMITFSI/GBL works properly all along the broad range of temperature [-50 °C to +100 °C] and thus proved that our approach is very promising for the development of high performances supercapacitors specifically adapted for extreme environment.

Novel Guanidinium-Based Ionic Liquids for Highly Efficient SO2 Capture.

PubMed

Lu, Xiaoxing; Yu, Jing; Wu, Jianzhou; Guo, Yongsheng; Xie, Hujun; Fang, Wenjun

2015-06-25

The application of ionic liquids (ILs) for acidic gas absorption has long been an interesting and challenging issue. In this work, the ethyl sulfate ([C2OSO3](-)) anion has been introduced into the structure of guanidinium-based ILs to form two novel low-cost ethyl sulfate ILs, namely 2-ethyl-1,1,3,3-tetramethylguanidinium ethyl sulfate ([C2(2)(C1)2(C1)2(3)gu][C2OSO3]) and 2,2-diethyl-1,1,3,3-tetramethylguanidinium ethyl sulfate ([(C2)2(2)(C1)2(C1)2(3)gu][C2OSO3]). The ethyl sulfate ILs, together with 2-ethyl-1,1,3,3-tetramethylguanidinium bis(trifluoromethylsulfonyl)imide ([C2(2)(C1)2(C1)2(3)gu][NTf2]) and 2,2-diethyl-1,1,3,3-tetramethylguanidinium bis(trifluoromethylsulfonyl)imide ([(C2)2(2)(C1)2(C1)2(3)gu][NTf2]), are employed to evaluate the SO2 absorption and desorption performance. The recyclable ethyl sulfate ILs demonstrate high absorption capacities of SO2. At a low pressure of 0.1 bar and at 20 °C, 0.71 and 1.08 mol SO2 per mole of IL can be captured by [C2(2)(C1)2(C1)2(3)gu][C2OSO3] and [(C2)2(2)(C1)2(C1)2(3)gu][C2OSO3], respectively. The absorption enthalpy for SO2 absorption with [C2(2)(C1)2(C1)2(3)gu][C2OSO3] and [(C2)2(2)(C1)2(C1)2(3)gu][C2OSO3] are -3.98 and -3.43 kcal mol(-1), respectively. While those by [C2(2)(C1)2(C1)2(3)gu][NTf2] and [(C2)2(2)(C1)2(C1)2(3)gu][NTf2] turn out to be only 0.17 and 0.24 mol SO2 per mole of IL under the same conditions. It can be concluded that the guanidinium ethyl sulfate ILs show good performance for SO2 capture. Quantum chemistry calculations reveal nonbonded weak interactions between the ILs and SO2. The anionic moieties of the ILs play an important role in SO2 capture on the basis of the consistently experimental and computational results.

Glycoside hydrolase activities of thermophilic bacterial consortia adapted to switchgrass.

PubMed

Gladden, John M; Allgaier, Martin; Miller, Christopher S; Hazen, Terry C; VanderGheynst, Jean S; Hugenholtz, Philip; Simmons, Blake A; Singer, Steven W

2011-08-15

Industrial-scale biofuel production requires robust enzymatic cocktails to produce fermentable sugars from lignocellulosic biomass. Thermophilic bacterial consortia are a potential source of cellulases and hemicellulases adapted to harsher reaction conditions than commercial fungal enzymes. Compost-derived microbial consortia were adapted to switchgrass at 60°C to develop thermophilic biomass-degrading consortia for detailed studies. Microbial community analysis using small-subunit rRNA gene amplicon pyrosequencing and short-read metagenomic sequencing demonstrated that thermophilic adaptation to switchgrass resulted in low-diversity bacterial consortia with a high abundance of bacteria related to thermophilic paenibacilli, Rhodothermus marinus, and Thermus thermophilus. At lower abundance, thermophilic Chloroflexi and an uncultivated lineage of the Gemmatimonadetes phylum were observed. Supernatants isolated from these consortia had high levels of xylanase and endoglucanase activities. Compared to commercial enzyme preparations, the endoglucanase enzymes had a higher thermotolerance and were more stable in the presence of 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]), an ionic liquid used for biomass pretreatment. The supernatants were used to saccharify [C2mim][OAc]-pretreated switchgrass at elevated temperatures (up to 80°C), demonstrating that these consortia are an excellent source of enzymes for the development of enzymatic cocktails tailored to more extreme reaction conditions.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid-liquid microextraction for determination of 2,4,6-trinitrotoluene.

PubMed

Fernández, Elena; Vidal, Lorena; Iniesta, Jesús; Metters, Jonathan P; Banks, Craig E; Canals, Antonio

2014-03-01

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid-liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett-Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L(-1) and 9 μg L(-1), respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L(-1)), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

Electrochemical behavior of high performance on-chip porous carbon films for micro-supercapacitors applications in organic electrolytes

NASA Astrophysics Data System (ADS)

Brousse, K.; Huang, P.; Pinaud, S.; Respaud, M.; Daffos, B.; Chaudret, B.; Lethien, C.; Taberna, P. L.; Simon, P.

2016-10-01

Carbide derived carbons (CDCs) are promising materials for preparing integrated micro-supercapacitors, as on-chip CDC films are prepared via a process fully compatible with current silicon-based device technology. These films show good adherence on the substrate and high capacitance thanks to their unique nanoporous structure which can be fine-tuned by adjusting the synthesis parameters during chlorination of the metallic carbide precursor. The carbon porosity is mostly related to the synthesis temperature whereas the thickness of the films depends on the chlorination duration. Increasing the pore size allows the adsorption of large solvated ions from organic electrolytes and leads to higher energy densities. Here, we investigated the electrochemical behavior and performance of on-chip TiC-CDC in ionic liquid solvent mixtures of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) diluted in either acetonitrile or propylene carbonate via cyclic voltammetry and electrochemical impedance spectroscopy. Thin CDC films exhibited typical capacitive signature and achieved 169 F cm-3 in both electrolytes; 65% of the capacitance was still delivered at 1 V s-1. While increasing the thickness of the films, EMI+ transport limitation was observed in more viscous PC-based electrolyte. Nevertheless, the energy density reached 90 μW h cm-2 in 2M EMIBF4/ACN, confirming the interest of these CDC films for micro-supercapacitors applications.

Investigation of the gas-phase structure and rotational barrier of trimethylsilyl trifluoromethanesulfonate and comparison with covalent sulfonates

NASA Astrophysics Data System (ADS)

Defonsi Lestard, María E.; Tuttolomondo, María E.; Varetti, Eduardo L.; Wann, Derek A.; Robertson, Heather E.; Rankin, David W. H.; Altabef, Aida Ben

2010-12-01

The molecular structure of trimethylsilyl trifluoromethanesulfonate, CF 3SO 2OSi(CH 3) 3, has been determined in the gas phase from electron-diffraction data supplemented by ab initio (MP2) and DFT calculations using 6-31G(d), 6-311++G(d,p) and 6-311G++(3df,3pd) basis sets. Both experimental and theoretical data indicate that only one gauche conformer is possible by rotating about the O-S bond. The anomeric effect is a fundamental stereoelectronic interaction and presents a profound influence on the electronic geometry. We have investigated the origin of the anomeric effect by means of NBO and AIM analysis. A natural bond orbital analysis showed that the lpπ[O bonded to Si)] → σ *[C-S] hyperconjugative interaction favors the gauche conformation. In addition, comparison of the structural and stereoelectronic properties of the title molecule with those of silyl trifluoromethanesulfonate and methyl trifluoromethanesulfonate has been carried out.

Synthesis of the zeolitic imidazolate framework ZIF-4 from the ionic liquid 1-butyl-3-methylimidazolium imidazolate

NASA Astrophysics Data System (ADS)

Hovestadt, Maximilian; Schwegler, Johannes; Schulz, Peter S.; Hartmann, Martin

2018-05-01

A new synthesis route for the zeolitic imidazolate framework ZIF-4 using imidazolium imidazolate is reported. Additionally, the ionic liquid-derived material is compared to conventional ZIF-4 with respect to the powder X-ray diffraction pattern pattern, nitrogen uptake, particle size, and separation potential for olefin/paraffin gas mixtures. Higher synthesis yields were obtained, and the different particle size affected the performance in the separation of ethane and ethylene.

Synthesis and application of imidazolium-based ionic liquids as extraction solvent for pretreatment of triazole fungicides in water samples.

PubMed

Yang, Jiale; Fan, Chen; Kong, Dandan; Tang, Gang; Zhang, Wenbing; Dong, Hongqiang; Liang, You; Wang, Deng; Cao, Yongsong

2018-02-01

Five novel ionic liquids (ILs), 1,3-dibutylimidazolium bromide [BBMIm][Br], 1-pentyl-3-butylimidazolium bromide [BPMIm][Br], 1-hexyl-3-butylimidazolium bromide [BHMIm][Br], 1,1'-(butane-1,4-diyl)bis(3-butylimidazolium) bromide [C 4 (BMIm) 2 ][Br 2 ], and 1,1'-(butane-1,4-diyl)bis(3-methylimidazolium) bromide [C 4 (MIm) 2 ][Br 2 ], were prepared and used in situ to react with bis(trifluoromethane)sulfonamide lithium salt to extract the myclobutanil, tebuconazole, cyproconazole, and prothioconazole from water samples. The results showed that mono-cationic ILs had much better recovery than dicationic ILs, and mono-imidazolium IL bearing butyl groups at N-1 and N-3 sites had the best recovery. When the length of the alkyl substituent group was more than four carbons at N-3 site, the recovery decreased with increase of alkyl chain length of 1-butylimidazolium IL. The extraction efficiency order of triazoles from high to low was [BBMIm][Br], [BPMIm][Br], [BHMIm][Br], [BMIm][Br] (1-butyl-3-methylimidazolium bromide), [C 4 (BMIm) 2 ]Br 2 , [C 4 (MIm) 2 ]Br 2 . An in situ ionic liquid dispersive liquid-liquid microextraction combined with ultrasmall superparamagnetic Fe 3 O 4 was established as a pretreatment method for enrichment of triazole fungicides in water samples by using the synthetic [BBMIm][Br] as the cationic IL and used to detect analytes followed by high-performance liquid chromatography. Under the optimized conditions, the proposed method showed a good linearity within a range of 5-250 μg L -1 , with the determination coefficient (r 2 ) varying from 0.998 to 0.999. High mean enrichment factors were achieved ranging from 187 to 323, and the recoveries of the target analytes from real water samples at spiking levels of 10.0, 20.0, and 50.0 μg L -1 were between 70.1% and 115.0%. The limits of detection for the analytes were 0.74-1.44 μg L -1 , and the intra-day relative standard deviations varied from 5.23% to 8.65%. The proposed method can be further applied to analyze and monitor pesticides in other related samples. Graphical Abstract The scheme of the in-situ DLLME method for the determination of triazoles using the imidazolium-based ionic liquids.

Prominent roles of impurities in ionic liquid for catalytic conversion of carbohydrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Haibo; Brown, Heather M.; Holladay, Johnathan E.

2012-02-07

In the last two decades, ionic liquids have emerged as new and versatile solvents, and many of them are also catalysts for a broad range of catalytic reactions. Certain ionic liquids have been found to possess the unique capability of dissolving cellulosic biomass. The potential of such ionic liquids as solvent to enable catalytic conversion of cellulosic polymers was first explored and demonstrated by Zhao et al. This field of research has since experienced a rapid growth. Most ionic liquids have negligible vapor pressure and excellent thermal stability over a wide temperature range. For example, ionic liquids composed of 1-ethyl-3-methylimidazoliummore » (EMIM+) cation and Cl- anion was reported to be stable up to 285 C, while salts of the same cation with other anions such as BF4- and PF6- are thermally stable above 380 C under inert atmosphere. It is well known that presence of impurities in ionic liquids typically causes changes in physical properties, e.g. decreasing in melting point and viscosity. Addition of Lewis acidic metal chlorides, e.g. AlCl3 to 1-alkyl-3-methylimidazolium chloride, [AMIM]Cl, is an exothermic reaction and considerably reduces the melting point by forming [AMIM]AlCl4 or [AMIM]Al2Cl7 that are also ionic liquids but have much lower melting point than the parent [AMIM]Cl. While most early research on catalysis of ionic liquids involving metallohalide anions were typically conducted from stoichiometric ratio of such anions to organic cations, e.g. [AMIM]+, the use of pure ionic liquids only as a solvent to carry out catalysis by a catalytic amount of a metal halide as catalyst truly displayed the solvent property of such ionic liquids.4 In such reaction systems, catalytic amounts of metal halides were used to catalyze the conversion of glucose and cellulose.4,11,12 The metal chloride catalyst concentration was in the order of 10-3 M. The presence of another metal chloride in the ionic liquids, even in the order of 10-5 M concentration was found to bring a dramatic synergistic effect. Therefore, the catalytic performance of the metal halide catalyst for the conversion of carbohydrates in the ionic liquid systems is highly sensitive to the presence of impurities. This work presents findings on the role of impurities that were present in some commercially available ionic liquids used for the conversion of the cellulose.« less

NMR relaxometric probing of ionic liquid dynamics and diffusion under mesoscopic confinement within bacterial cellulose ionogels

NASA Astrophysics Data System (ADS)

Smith, Chip J.; Gehrke, Sascha; Hollóczki, Oldamur; Wagle, Durgesh V.; Heitz, Mark P.; Baker, Gary A.

2018-05-01

Bacterial cellulose ionogels (BCIGs) represent a new class of material comprising a significant content of entrapped ionic liquid (IL) within a porous network formed from crystalline cellulose microfibrils. BCIGs suggest unique opportunities in separations, optically active materials, solid electrolytes, and drug delivery due to the fact that they can contain as much as 99% of an IL phase by weight, coupled with an inherent flexibility, high optical transparency, and the ability to control ionogel cross-sectional shape and size. To allow for the tailoring of BCIGs for a multitude of applications, it is necessary to better understand the underlying principles of the mesoscopic confinement within these ionogels. Toward this, we present a study of the structural, relaxation, and diffusional properties of the ILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([bmpy][Tf2N]), using 1H and 19F NMR T1 relaxation times, rotational correlation times, and diffusion ordered spectroscopy (DOSY) diffusion coefficients, accompanied by molecular dynamics (MD) simulations. We observed that the cation methyl groups in both ILs were primary points of interaction with the cellulose chains and, while the pore size in cellulose is rather large, [emim]+ diffusion was slowed by ˜2-fold, whereas [Tf2N]- diffusion was unencumbered by incorporation in the ionogel. While MD simulations of [bmpy][Tf2N] confinement at the interface showed a diffusion coefficient decrease roughly 3-fold compared to the bulk liquid, DOSY measurements did not reveal any significant changes in diffusion. This suggests that the [bmpy][Tf2N] alkyl chains dominate diffusion through formation of apolar domains. This is in contrast to [emim][Tf2N] where delocalized charge appears to preclude apolar domain formation, allowing interfacial effects to be manifested at a longer range in [emim][Tf2N].

Lipid extraction from microalgae using a single ionic liquid

DOEpatents

Salvo, Roberto Di; Reich, Alton; Dykes, Jr., H. Waite H.; Teixeira, Rodrigo

2013-05-28

A one-step process for the lysis of microalgae cell walls and separation of the cellular lipids for use in biofuel production by utilizing a hydrophilic ionic liquid, 1-butyl-3-methylimidazolium. The hydrophilic ionic liquid both lyses the microalgae cell walls and forms two immiscible layers, one of which consists of the lipid contents of the lysed cells. After mixture of the hydrophilic ionic liquid with a suspension of microalgae cells, gravity causes a hydrophobic lipid phase to move to a top phase where it is removed from the mixture and purified. The hydrophilic ionic liquid is recycled to lyse new microalgae suspensions.

Ionic liquids as advantageous solvents for headspace gas chromatography of compounds with low vapor pressure.

PubMed

Andre, M; Loidl, J; Laus, G; Schottenberger, H; Bentivoglio, G; Wurst, K; Ongania, K-H

2005-01-15

The potential of ionic liquids as solvents for headspace gas chromatography was investigated. Three compounds with boiling points above 200 degrees C were selected to demonstrate the feasibility of the concept described. 2-Ethylhexanoic acid, formamide, and tri-n-butylamine as examples of acidic, neutral, and basic analytes were dissolved in acidic 1-n-butyl-3-methylimidazolium hydrogen sulfate (1), neutral 1-n-butyl-2,3-dimethylimidazolium dicyanamide (2), and 2 containing 1,8-diazabicyclo[5.4.0]undec-7-ene to adjust basic conditions. All analytes could be determined with limits of detection and limits of quantification in the low-ppm concentration range.

Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI], [EMIM][BF4

NASA Technical Reports Server (NTRS)

Haskins, Justin Bradley; Bennett, William Raymond; Wu, James J.; Hernandez, Dionne M.; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W., Jr.; Watson, John W.

2014-01-01

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li (-) salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing xLi, the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI] and [EMIM][BF4

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Bennett, William R.; Hernandez-Lugo, Dione M.; Wu, James; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W.; Lawson, John W.

2014-01-01

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-Nbutylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-Npropylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of x(sub Li) we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing x(sub Li), the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of x(sub Li) is approximately 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1 - 0.3 mS/cm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

Sono- and photoelectrocatalytic processes for the removal of ionic liquids based on the 1-butyl-3-methylimidazolium cation.

PubMed

Mena, Ismael F; Cotillas, Salvador; Díaz, Elena; Sáez, Cristina; Mohedano, Ángel F; Rodrigo, Manuel A

2017-12-06

In this work, sono- and photoelectrolysis of synthetic wastewaters polluted with the ionic liquids 1-Butyl-3-methylimidazolium acetate (BmimAc) and chloride (BmimCl) were investigated with diamond anodes. The results were compared to those attained by enhancing bare electrolysis with irradiation by UV light or with the application of high-frequency ultrasound (US). Despite its complex heterocyclic structure, the Bmim + cation was successfully depleted with the three technologies that were tested and was mainly transformed into four different organic intermediates, an inorganic nitrogen species and carbon dioxide. Regardless of the technology that was evaluated, removal of the heterocyclic ring is much less efficient (and much slower) than oxidation of the counter ion. In turn, the counter ion influences the rate of removal of the ionic liquid cation. Thus, the electrolysis and photoelectrolysis of BmimAc are much less efficient than sonoelectrolysis, but their differences become much less important in the case of BmimCl. In this later case, the most efficient technology is photoelectrolysis. This result is directly related to the generation of free radicals in the solution by irradiation of the electrochemical system with UV light, which contributes significantly to the removal of Bmim + . Copyright © 2017 Elsevier B.V. All rights reserved.

Enzymatic catalysis of formation of Z-aspartame in ionic liquid - An alternative to enzymatic catalysis in organic solvents.

PubMed

Erbeldinger, M; Mesiano, A J; Russell, A J

2000-01-01

We present the first report of enzymatic catalysis in an ionic liquid. The virtually nonexistent vapor pressure makes ionic liquids an exciting new alternative for enzyme-catalyzed syntheses in environmentally friendly environments. Z-aspartame was synthesized in a thermolysin-catalyzed reaction of carbobenzoxy-L-aspartate and L-phenylalanine methyl ester hydrochloride in 1-butyl-3-methylimidazolium hexafluorophosphate (BP6). Ionic liquids such as BP6 are thermally stable and have a remarkable range of temperatures over which they remain liquid (300 degrees C). With an initial rate of 1.2 +/- 0.1 nmol min(-)(1) mg(-)(1), we observed a competitive rate in comparison to that of enzymatic synthesis in organic solvent. Additionally, the enzyme exhibits outstanding stability, which would normally require immobilization.

Compatible ionic liquid-cellulases system for hydrolysis of lignocellulosic biomass.

PubMed

Wang, Ying; Radosevich, Mark; Hayes, Douglas; Labbé, Nicole

2011-05-01

Ionic liquids (ILs) have been increasingly recognized as novel solvents for dissolution and pretreatment of cellulose. However, cellulases are inactivated in the presence of ILs, even when present at low concentrations. To more fully exploit the benefits of ILs it is critical to develop a compatible IL-cellulases system in which the IL is able to effectively solubilize and activate the lignocellulosic biomass, and the cellulases possess high stability and activity. In this study, we investigated the stability and activity of a commercially available cellulases mixture in the presence of different concentrations of 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]). A mixture of cellulases and β-glucosidase (Celluclast1.5L, from Trichoderma reesei, and Novozyme188, from Aspergillus niger, respectively) retained 77% and 65% of its original activity after being pre-incubated in 15% and 20% (w/v) IL solutions, respectively, at 50°C for 3 h. The cellulases mixture also retained high activity in 15% [Emim][OAc] to hydrolyze Avicel, a model substrate for cellulose analysis, with conversion efficiency of approximately 91%. Notably, the presence of different amounts of yellow poplar lignin did not interfere significantly with the enzymatic hydrolysis of Avicel. Using this IL-cellulase system (15% [Emim][OAc]), the saccharification of yellow poplar biomass was also significantly improved (33%) compared to the untreated control (3%) during the first hour of enzymatic hydrolysis. Together, these findings provide compelling evidence that [Emim][OAc] was compatible with the cellulase mixture, and this compatible IL-cellulases system is promising for efficient activation and hydrolysis of native biomass to produce biofuels and co-products from the individual biomass components. Copyright © 2010 Wiley Periodicals, Inc.

Application of ionic liquids based microwave-assisted simultaneous extraction of carnosic acid, rosmarinic acid and essential oil from Rosmarinus officinalis.

PubMed

Liu, Tingting; Sui, Xiaoyu; Zhang, Rongrui; Yang, Lei; Zu, Yuangang; Zhang, Lin; Zhang, Ying; Zhang, Zhonghua

2011-11-25

An ionic liquid based microwave-assisted simultaneous extraction and distillation (ILMSED) method has been developed for the effective extraction of carnosic acid (CA), rosmarinic acid (RA) and essential oil (EO) from Rosmarinus officinalis. A series of 1-alkyl-3-methylimidazolium ionic liquids differing in composition of anion and cation were evaluated for extraction yield in this work. The results obtained indicated that the anions and cations of ionic liquids had influences on the extraction of CA and RA, 1.0M 1-octyl-3-methylimidazolium bromide ([C8mim]Br) solution was selected as solvent. In addition, the ILMSED procedures for the three target ingredients were optimized and compared with other conventional extraction techniques. ILMSED gave the best result due to the highest extraction yield within the shortest extraction time for CA and RA. The novel process developed offered advantages in term of yield and selectivity of EO and shorter isolation time (20 min in comparison of 4h of hydrodistillation), and provides a more valuable EO (with high amount of oxygenated compounds). The microstructures and chemical structures of rosemary samples before and after extraction were also investigated. Moreover, the proposed method was validated by the stability, repeatability and recovery experiments. The results indicated that the developed ILMSED method provided a good alternative for the both extraction of non-volatile compounds (CA and RA) and EO from rosemary as well as other herbs. Copyright © 2011 Elsevier B.V. All rights reserved.

Reversible capture of SO2 through functionalized ionic liquids.

PubMed

Yang, Dezhong; Hou, Minqiang; Ning, Hui; Ma, Jun; Kang, Xinchen; Zhang, Jianling; Han, Buxing

2013-07-01

Emission of SO2 in flue gas from the combustion of fossil fuels leads to severe environmental problems. Exploration of green and efficient methods to capture SO2 is an interesting topic, especially at lower SO2 partial pressures. In this work, ionic liquids (ILs) 1-(2-diethylaminoethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Et2 NEMim][Tf2 N]) and 1-(2-diethylaminoethyl)-3-methylimidazolium tetrazolate ([Et2 NEMim][Tetz]) were synthesized. The performances of the two ILs to capture SO2 were studied under different conditions. It was demonstrated that the ILs were very efficient for SO2 absorption. The [Et2 NEMim][Tetz] IL designed in this work could absorb 0.47 g(SO2)g(IL)(-1) at 0.0101 MPa SO2 partial pressure, which is the highest capacity reported to date under the same conditions. The main reason for the large capacity was that both the cation and the anion could capture SO2 chemically. In addition, the IL could easily be regenerated, and the very high absorption capacity and rapid absorption/desorption rates were not changed over five repeated cycles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of two imidazolium derivatives of ionic liquids on the structure and activity of adenosine deaminase.

PubMed

Ajloo, Davood; Sangian, Masoomeh; Ghadamgahi, Maryam; Evini, Mina; Saboury, Ali Akbar

2013-04-01

The effect of two ionic liquids, 1-allyl 3-methyl-imidazolium (IL1) and 1-octhyl 3-methyl-imidozolium chlorides (IL2), on the structure and activity of adenosine deaminase (ADA) were described by UV-vis and fluorescence spectrophotometry in phosphate buffer and results were compared with docking and molecular dynamics (MD) simulation studies. All results showed that inhibition of activity and reduction of enzyme tertiary structure are more for octhyl than allyl derivative due to the more hydrophobic property of it. Finally structure parameters obtained from MD simulation showed that ionic liquid reduces intermolecular hydrogen bond and unfold enzyme structure. Calculation results are in good agreement with spectrophotometric studies. Copyright © 2013 Elsevier B.V. All rights reserved.

Thermophysical properties of tri-n-butylphosphate-ionic liquid mixture

NASA Astrophysics Data System (ADS)

Rout, Alok; Mishra, Satyabrata; Venkatesan, K. A.; Antony, M. P.; Pandey, N. K.

2018-04-01

Thermophysical properties such as viscosity, density, energy of activation and coefficient of thermal expansion were measured for the solvent phase composed of tri-n-butylphosphate (TBP), 1-butyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide ([C4mim][NTf2]) and 1.1 M TBP/[C4mim][NTf2]. The results were compared with that of nitric acid equilibrated [C4mim][NTf2] and 1.1M TBP/[C4mim][NTf2]. Thermal stability of the ionic liquid phase was assessed by using differential scanning calorimetric (DSC) technique. Other important physical properties such as refractive index and surface tension of the ionic liquid phase composition were evaluated before and after acid saturation.

Determination of the enthalpy of vaporization and prediction of surface tension for ionic liquid 1-alkyl-3-methylimidazolium propionate [C(n)mim][Pro](n = 4, 5, 6).

PubMed

Tong, Jing; Yang, Hong-Xu; Liu, Ru-Jing; Li, Chi; Xia, Li-Xin; Yang, Jia-Zhen

2014-11-13

With the use of isothermogravimetrical analysis, the enthalpies of vaporization, Δ(g)lH(o)m(T(av)), at the average temperature, T(av) = 445.65 K, for the ionic liquids (ILs) 1-alkyl-3-methylimidazolium propionate [C(n)mim][Pro](n = 4, 5, 6) were determined. Using Verevkin's method, the difference of heat capacities between the vapor phase and the liquid phase, Δ(g)lC(p)(o)m, for [C(n)mim][Pro](n = 2, 3, 4, 5, 6), were calculated based on the statistical thermodynamics. Therefore, with the use of Δ(g)lC(p)(o)m, the values of Δ(g)lH(o)m(T(av)) were transformed into Δ(g)lH(o)m(298), 126.8, 130.3, and 136.5 for [C(n)mim][Pro](n = 4, 5, 6), respectively. In terms of the new scale of polarity for ILs, the order of the polarity of [C(n)mim][Pro](n = 2, 3, 4, 5, 6) was predicted, that is, the polarity decreases with increasing methylene. A new model of the relationship between the surface tension and the enthalpy of vaporization for aprotic ILs was put forward and used to predict the surface tension for [C(n)mim][Pro](n = 2, 3, 4, 5, 6) and others. The predicted surface tension for the ILs is in good agreement with the experimental one.

Effective charges of ionic liquid determined self-consistently through combination of molecular dynamics simulation and density-functional theory.

PubMed

Ishizuka, Ryosuke; Matubayasi, Nobuyuki

2017-11-15

A self-consistent scheme combining the molecular dynamics (MD) simulation and density functional theory (DFT) was recently proposed to incorporate the effects of the charge transfer and polarization of ions into non-poralizable force fields of ionic liquids for improved description of energetics and dynamics. The purpose of the present work is to analyze the detailed setups of the MD/DFT scheme by focusing on how the basis set, exchange-correlation (XC) functional, charge-fitting method or force field for the intramolecular and Lennard-Jones interactions affects the MD/DFT results of 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl) imide ( [C1mim][NTf2]) and 1-ethyl-3-methylimidazolium glycinate ( [C2mim][Gly]). It was found that the double-zeta valence polarized or larger size of basis set is required for the convergence of the effective charge of the ion. The choice of the XC functional was further not influential as far as the generalized gradient approximation is used. The charge-fitting method and force field govern the accuracy of the MD/DFT scheme, on the other hand. We examined the charge-fitting methods of Blöchl, the iterative Hirshfeld (Hirshfeld-I), and REPEAT in combination with Lopes et al.'s force field and general AMBER force field. There is no single combination of charge fitting and force field that provides good agreements with the experiments, while the MD/DFT scheme reduces the effective charges of the ions and leads to better description of energetics and dynamics compared to the original force field with unit charges. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

An Approach to Solid-State Electrical Double Layer Capacitors Fabricated with Graphene Oxide-Doped, Ionic Liquid-Based Solid Copolymer Electrolytes

PubMed Central

Fattah, N. F. A.; Ng, H. M.; Mahipal, Y. K.; Numan, Arshid; Ramesh, S.; Ramesh, K.

2016-01-01

Solid polymer electrolyte (SPE) composed of semi-crystalline poly (vinylidene fluoride-hexafluoropropylene) [P(VdF-HFP)] copolymer, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulphonyl) imide [EMI-BTI] and graphene oxide (GO) was prepared and its performance evaluated. The effects of GO nano-filler were investigated in terms of enhancement in ionic conductivity along with the electrochemical properties of its electrical double layer capacitors (EDLC). The GO-doped SPE shows improvement in ionic conductivity compared to the P(VdF-HFP)-[EMI-BTI] SPE system due to the existence of the abundant oxygen-containing functional group in GO that assists in the improvement of the ion mobility in the polymer matrix. The complexation of the materials in the SPE is confirmed in X-ray diffraction (XRD) and thermogravimetric analysis (TGA) studies. The electrochemical performance of EDLC fabricated with GO-doped SPE is examined using cyclic voltammetry and charge–discharge techniques. The maximum specific capacitance obtained is 29.6 F∙g−1, which is observed at a scan rate of 3 mV/s in 6 wt % GO-doped, SPE-based EDLC. It also has excellent cyclic retention as it is able keep the performance of the EDLC at 94% even after 3000 cycles. These results suggest GO doped SPE plays a significant role in energy storage application. PMID:28773573

An Approach to Solid-State Electrical Double Layer Capacitors Fabricated with Graphene Oxide-Doped, Ionic Liquid-Based Solid Copolymer Electrolytes.

PubMed

Fattah, N F A; Ng, H M; Mahipal, Y K; Numan, Arshid; Ramesh, S; Ramesh, K

2016-06-06

Solid polymer electrolyte (SPE) composed of semi-crystalline poly (vinylidene fluoride-hexafluoropropylene) [P(VdF-HFP)] copolymer, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulphonyl) imide [EMI-BTI] and graphene oxide (GO) was prepared and its performance evaluated. The effects of GO nano-filler were investigated in terms of enhancement in ionic conductivity along with the electrochemical properties of its electrical double layer capacitors (EDLC). The GO-doped SPE shows improvement in ionic conductivity compared to the P(VdF-HFP)-[EMI-BTI] SPE system due to the existence of the abundant oxygen-containing functional group in GO that assists in the improvement of the ion mobility in the polymer matrix. The complexation of the materials in the SPE is confirmed in X-ray diffraction (XRD) and thermogravimetric analysis (TGA) studies. The electrochemical performance of EDLC fabricated with GO-doped SPE is examined using cyclic voltammetry and charge-discharge techniques. The maximum specific capacitance obtained is 29.6 F∙g -1 , which is observed at a scan rate of 3 mV/s in 6 wt % GO-doped, SPE-based EDLC. It also has excellent cyclic retention as it is able keep the performance of the EDLC at 94% even after 3000 cycles. These results suggest GO doped SPE plays a significant role in energy storage application.

Regioselctive Thiocyanation of Aromatic and Heteroaromatic Compounds Using a Novel Bronsted Acidic Ionic Liquid.

PubMed

Rezayati, Sobhan; Sheikholeslami-Farahani, Fatemeh; Hossaini, Zinatossadat; Hajinasiri, Rahimeh; Abad, Saeid Afshari Sharif

2016-01-01

A convenient procedure for the preparation of 1-(1-Propylsulfonic)-3- methylimidazolium thiocyanate as a novel Brønsted acidic ionic liquid thiocyanation agent and highly efficient heterogeneous catalytic is described. This catalyst is used in regioselective thiocyanation of indoles, anilines, pyrroles and their derivatives (aromatic and heteroaromatic organic compounds) in the presence of H2O2 as a mild and oxidant in EtOH:H2O (1:1 v/v). These reactions are performed under mild and simple conditions and give regioselective products in high yields and short reaction time.

Electrochemical determination of hydroquinone using hydrophobic ionic liquid-type carbon paste electrodes

PubMed Central

2010-01-01

Three types of carbon paste electrodes (CPEs) with different liquid binders were fabricated, and their electrochemical behavior was characterized via a potassium hexacyanoferrate(II) probe. 1-Octyl-3-methylimidazolium hexafluorophosphate ionic liquid (IL) as a hydrophobic conductive pasting binder showed better electrochemical performance compared with the commonly employed binder. The IL-contained CPEs demonstrated excellent electroactivity for oxidation of hydroquinone. A diffusion control mechanism was confirmed and the diffusion coefficient (D) of 5.05 × 10-4 cm2 s-1 was obtained. The hydrophobic IL-CPE is promising for the determination of hydroquinone in terms of high sensitivity, easy operation, and good durability. PMID:20977733

Can the tricyanomethanide anion improve CO2 absorption by acetate-based ionic liquids?

PubMed

Lepre, L F; Szala-Bilnik, J; Pison, L; Traïkia, M; Pádua, A A H; Ando, R A; Costa Gomes, M F

2017-05-17

Carbon dioxide absorption by mixtures of two ionic liquids with a common cation-1-butyl-3-methylimidazolium acetate, [C 4 C 1 Im][OAc], and 1-butyl-3-methylimidazolium tricyanomethanide, [C 4 C 1 Im][C(CN) 3 ]-was determined experimentally at pressures below atmospheric pressure as a function of temperature between 303 K and 343 K, and at 303 K as a function of pressure up to 10 bar. It is observed that the absorption of carbon dioxide decreases with increasing tricyanomethanide anion concentration and with increasing temperature, showing a maximum of 0.4 mole fraction of carbon dioxide in pure [C 4 C 1 Im][OAc] at 303 K. At this temperature, the CO 2 absorption in the mixtures [C 4 C 1 Im][OAc] (1-x) [C(CN) 3 ] x is approximately the mole-fraction average of that in the pure ionic liquids. By applying an appropriate thermodynamic treatment, after identification of the species in solution, it was possible to calculate both the equilibrium constant, K eq , and Henry's law constant, K H , in the different mixtures studied thus obtaining an insight into the relative contribution of chemical and physical absorption of the gas. It is shown that chemical sorption proceeds through a 1 : 2 stoichiometry between CO 2 and acetate-based ionic liquid. The presence of the C(CN) 3 - anion does not significantly affect the chemical reaction of the gas with the solvent (K eq = 75 ± 2 at 303 K) but leads to lower Henry's law constants (from K H = 77.8 ± 0.6 bar to K H = 49.5 ± 0.5 bar at 303 K), thus pointing towards larger physical absorption of the gas. The tricyanomethanide anion considerably improves the mass transfer by increasing the fluidity of the absorbent as proven by the larger diffusivities of all the ions when the concentration of the C(CN) 3 - anion increases in the mixtures.

Swelling and hydrolysis kinetics of Kraft pulp fibers in aqueous 1-butyl-3-methylimidazolium hydrogen sulfate solutions.

PubMed

Mao, Jia; Abushammala, Hatem; Pereira, Laura Barcellos; Laborie, Marie-Pierre

2016-11-20

1Butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO4) is efficient at extracting cellulose nanocrystals from pulp fibers. To shed some light on the respective contributions of swelling and hydrolysis of pulp fibers by [Bmim]HSO4, the physical, structural and morphological characteristics of hardwood Kraft pulp fibers were monitored under various conditions of temperature, water content and time. Swelling was largely compounded by hydrolysis at the highest temperatures (120°C) as evidenced by mass loss and reduced degree of polymerization (DPn) at this temperature. At 120°C only, water content appeared to play a significant role on the extent of hydrolysis. At this temperature, a heterogeneous kinetic model involving weak links and amorphous regions best described the experimental data. Hydrolysis rates were maximum at 25% water content in the aqueous ionic liquid. Copyright © 2016 Elsevier Ltd. All rights reserved.

Comparison and Characterisation of Regenerated Chitosan from 1-Butyl-3-methylimidazolium Chloride and Chitosan from Crab Shells

PubMed Central

Arnold, Lyndon

2015-01-01

Chitosan is a biopolymer derived from chitin which is naturally occurring in the exoskeleton of crustaceans. This paper reports dissolution and regeneration of chitosan by directly dissolving in an ionic liquid solvent, 1-butyl-3-methylimidazolium chloride (BMIMCl). This will provide an ideal platform to solubilise these kinds of polymers to achieve the dissolution. The current study dissolved chitosan from crab shell utilising BMIMCl as a solvent and characterised the resultant regenerated polymer. The regenerated chitosan showed increased hydrogen bonding when characterised by Fourier transform infrared (FTIR) spectral analysis. In addition, the study also compared the characteristics of regenerated and generic chitosan. The regenerated chitosan was also evaluated for antimicrobial properties and showed to possess antibacterial features similar to the commercial grade. This method can be utilised in future for blending of polymers with chitosan in a dissolved phase. PMID:26090452

Heterogeneous dynamics of ionic liquids: A four-point time correlation function approach

NASA Astrophysics Data System (ADS)

Liu, Jiannan; Willcox, Jon A. L.; Kim, Hyung J.

2018-05-01

Many ionic liquids show behavior similar to that of glassy systems, e.g., large and long-lasted deviations from Gaussian dynamics and clustering of "mobile" and "immobile" groups of ions. Herein a time-dependent four-point density correlation function—typically used to characterize glassy systems—is implemented for the ionic liquids, choline acetate, and 1-butyl-3-methylimidazolium acetate. Dynamic correlation beyond the first ionic solvation shell on the time scale of nanoseconds is found in the ionic liquids, revealing the cooperative nature of ion motions. The traditional solvent, acetonitrile, on the other hand, shows a much shorter length-scale that decays after a few picoseconds.

1-Butyl-3-Methylimidazolium Tetrafluoroborate Film as a Highly Selective Sensing Material for Non-Invasive Detection of Acetone Using a Quartz Crystal Microbalance.

PubMed

Tao, Wenyan; Lin, Peng; Liu, Sili; Xie, Qingji; Ke, Shanming; Zeng, Xierong

2017-01-20

Breath acetone serves as a biomarker for diabetes. This article reports 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), a type of room temperature ionic liquid (RTIL), as a selective sensing material for acetone. The RTIL sensing layer was coated on a quartz crystal microbalance (QCM) for detection. The sensing mechanism is based on a decrease in viscosity and density of the [bmim][BF₄] film due to the solubilization of acetone leading to a positive frequency shift in the QCM. Acetone was detected with a linear range from 7.05 to 750 ppmv. Sensitivity and limit of detection were found to be 3.49 Hz/ppmv and 5.0 ppmv, respectively. The [bmim][BF₄]-modified QCM sensor demonstrated anti-interference ability to commonly found volatile organic compounds in breath, e.g., isoprene, 1,2-pentadiene, d -limonene, and dl -limonene. This technology is useful for applications in non-invasive early diabetic diagnosis.

1-Butyl-3-Methylimidazolium Tetrafluoroborate Film as a Highly Selective Sensing Material for Non-Invasive Detection of Acetone Using a Quartz Crystal Microbalance

PubMed Central

Tao, Wenyan; Lin, Peng; Liu, Sili; Xie, Qingji; Ke, Shanming; Zeng, Xierong

2017-01-01

Breath acetone serves as a biomarker for diabetes. This article reports 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), a type of room temperature ionic liquid (RTIL), as a selective sensing material for acetone. The RTIL sensing layer was coated on a quartz crystal microbalance (QCM) for detection. The sensing mechanism is based on a decrease in viscosity and density of the [bmim][BF4] film due to the solubilization of acetone leading to a positive frequency shift in the QCM. Acetone was detected with a linear range from 7.05 to 750 ppmv. Sensitivity and limit of detection were found to be 3.49 Hz/ppmv and 5.0 ppmv, respectively. The [bmim][BF4]-modified QCM sensor demonstrated anti-interference ability to commonly found volatile organic compounds in breath, e.g., isoprene, 1,2-pentadiene, d-limonene, and dl-limonene. This technology is useful for applications in non-invasive early diabetic diagnosis. PMID:28117697

Robust solid polymer electrolyte for conducting IPN actuators

NASA Astrophysics Data System (ADS)

Festin, Nicolas; Maziz, Ali; Plesse, Cédric; Teyssié, Dominique; Chevrot, Claude; Vidal, Frédéric

2013-10-01

Interpenetrating polymer networks (IPNs) based on nitrile butadiene rubber (NBR) as first component and poly(ethylene oxide) (PEO) as second component were synthesized and used as a solid polymer electrolyte film in the design of a mechanically robust conducting IPN actuator. IPN mechanical properties and morphologies were mainly investigated by dynamic mechanical analysis and transmission electron microscopy. For 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide (EMITFSI) swollen IPNs, conductivity values are close to 1 × 10-3 S cm-1 at 25 ° C. Conducting IPN actuators have been synthesized by chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) within the PEO/NBR IPN. A pseudo-trilayer configuration has been obtained with PEO/NBR IPN sandwiched between two interpenetrated PEDOT electrodes. The robust conducting IPN actuators showed a free strain of 2.4% and a blocking force of 30 mN for a low applied potential of ±2 V.

Synthesis of cellulose-2,3-bis(3,5-dimethylphenylcarbamate) in an ionic liquid and its chiral separation efficiency as stationary phase.

PubMed

Liu, Runqiang; Zhang, Yijun; Bai, Lianyang; Huang, Mingxian; Chen, Jun; Zhang, Yuping

2014-04-11

A chiral selector of cellulose-2,3-bis(3,5-dimethylphenylcarbamate) (CBDMPC) was synthesized by reacting 3,5-dimethylphenyl isocyanate with microcrystalline cellulose dissolved in an ionic liquid of 1-allyl-3-methyl-imidazolium chloride (AMIMCl). The obtained chiral selector was effectively characterized by infrared spectroscopy, elemental analysis and 1H NMR. The selector was reacted with 3-aminopropylsilanized silica gel and the CBDMPC bonded chiral stationary phase (CSP) was obtained. Chromatographic evaluation of the prepared CSPs was conducted by high performance liquid chromatographic (HPLC) and baseline separation of three typical fungicides including hexaconazole, metalaxyl and myclobutanil was achieved using n-hexane/isopropanol as the mobile phase with a flow rate 1.0 mL/min. Experimental results also showed that AMIMCl could be recycled easily and reused in the preparation of CSPs as an effective reaction media.

Synthesis of Cellulose-2,3-bis(3,5-dimethylphenylcarbamate) in an Ionic Liquid and Its Chiral Separation Efficiency as Stationary Phase

PubMed Central

Liu, Runqiang; Zhang, Yijun; Bai, Lianyang; Huang, Mingxian; Chen, Jun; Zhang, Yuping

2014-01-01

A chiral selector of cellulose-2,3-bis(3,5-dimethylphenylcarbamate) (CBDMPC) was synthesized by reacting 3,5-dimethylphenyl isocyanate with microcrystalline cellulose dissolved in an ionic liquid of 1-allyl-3-methyl-imidazolium chloride (AMIMCl). The obtained chiral selector was effectively characterized by infrared spectroscopy, elemental analysis and 1H NMR. The selector was reacted with 3-aminopropylsilanized silica gel and the CBDMPC bonded chiral stationary phase (CSP) was obtained. Chromatographic evaluation of the prepared CSPs was conducted by high performance liquid chromatographic (HPLC) and baseline separation of three typical fungicides including hexaconazole, metalaxyl and myclobutanil was achieved using n-hexane/isopropanol as the mobile phase with a flow rate 1.0 mL/min. Experimental results also showed that AMIMCl could be recycled easily and reused in the preparation of CSPs as an effective reaction media. PMID:24733066

(1)H NMR-based DS determination of barley starch sulfates prepared in 1-allyl-3-methylimidazolium chloride.

PubMed

Kärkkäinen, Johanna; Wik, Tiia-Riikka; Niemelä, Matti; Lappalainen, Katja; Joensuu, Päivi; Lajunen, Marja

2016-01-20

The use of natural resources in a development of products and materials is currently increasing. Starch is one of the investigated resources due to its bioavailability, biodegradability, safety and affordability. In this study, native barley starch was sulfated using a SO3-pyridine complex. The reaction was carried out for the first time using 1-allyl-3-methylimidazolium chloride ionic liquid, an excellent solvent for the starch modification. Reaction conditions (temperature, time and amount of the reagent) were studied using an experimental design. Starch sulfates with the degree of substitution (DS) 1.37 were obtained when the reaction was carried out at 40 °C for 75 min with 4:1 molar ratio of SO3-pyridine complex:anhydroglucose unit. The determination of DS was based on (1)H NMR instead of elemental analysis, which showed overestimated DS values in this study. Starch sulfates were analyzed with FTIR and HPLC, which showed that products contained small and large sulfated molecules. Copyright © 2015 Elsevier Ltd. All rights reserved.

Tube Radial Distribution Flow Separation in a Microchannel Using an Ionic Liquid Aqueous Two-Phase System Based on Phase Separation Multi-Phase Flow.

PubMed

Nagatani, Kosuke; Shihata, Yoshinori; Matsushita, Takahiro; Tsukagoshi, Kazuhiko

2016-01-01

Ionic liquid aqueous two-phase systems were delivered into a capillary tube to achieve tube radial distribution flow (TRDF) or annular flow in a microspace. The phase diagram, viscosity of the phases, and TRDF image of the 1-butyl-3-methylimidazolium chloride and NaOH system were examined. The TRDF was formed with inner ionic liquid-rich and outer ionic liquid-poor phases in the capillary tube. The phase configuration was explained using the viscous dissipation principle. We also examined the distribution of rhodamine B in a three-branched microchannel on a microchip with ionic liquid aqueous two-phase systems for the first time.

SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hirosawa, Kazu; Fujii, Kenta; Ueki, Takeshi

Here, we utilized small-angle neutron scattering (SANS) to quantitatively characterize the LCST-type phase behavior of the poly(benzyl methacrylate) (PBnMA) derivative poly(2-phenylethyl methacrylate) (PPhEtMA) in the deuterated ionic liquid (IL) d 8-1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (d 8-[C 2mIm +][TFSA -]). The SANS curves showed a discontinuous change from those characteristics of dispersed polymer chains to those of large aggregates of PPhEtMA chains suspended in the IL solution, indicating that phase separation occurs discontinuously at T c. We also evaluated the enthalpic and entropic contributions to the effective interaction parameter χ eff of PPhEtMA in [C 2mIm +][TFSA -] and compared them with thosemore » of PBnMA. The absolute value of the enthalpic contribution observed for PPhEtMA was smaller than that for PBnMA. This difference in the enthalpic term can be attributed to the unfavorable interaction between the IL and the alkyl group in the side chain of PPhEtMA. In addition, the temperature dependence of χ eff was smaller than the previously reported value for a thermo-responsive polymer in an aqueous system. Finally, it was found out that the strong dependence of T c on the chemical structure in IL systems originated from the relatively smaller temperature dependence of χ eff.« less

SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid

DOE PAGES

Hirosawa, Kazu; Fujii, Kenta; Ueki, Takeshi; ...

2016-06-17

Here, we utilized small-angle neutron scattering (SANS) to quantitatively characterize the LCST-type phase behavior of the poly(benzyl methacrylate) (PBnMA) derivative poly(2-phenylethyl methacrylate) (PPhEtMA) in the deuterated ionic liquid (IL) d 8-1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (d 8-[C 2mIm +][TFSA -]). The SANS curves showed a discontinuous change from those characteristics of dispersed polymer chains to those of large aggregates of PPhEtMA chains suspended in the IL solution, indicating that phase separation occurs discontinuously at T c. We also evaluated the enthalpic and entropic contributions to the effective interaction parameter χ eff of PPhEtMA in [C 2mIm +][TFSA -] and compared them with thosemore » of PBnMA. The absolute value of the enthalpic contribution observed for PPhEtMA was smaller than that for PBnMA. This difference in the enthalpic term can be attributed to the unfavorable interaction between the IL and the alkyl group in the side chain of PPhEtMA. In addition, the temperature dependence of χ eff was smaller than the previously reported value for a thermo-responsive polymer in an aqueous system. Finally, it was found out that the strong dependence of T c on the chemical structure in IL systems originated from the relatively smaller temperature dependence of χ eff.« less

Aqueous ionic liquids and their influence on peptide conformations: denaturation and dehydration mechanisms.

PubMed

Diddens, Diddo; Lesch, Volker; Heuer, Andreas; Smiatek, Jens

2017-08-09

Low concentrated aqueous ionic liquids (ILs) and their influence on protein structures have attracted a lot of interest over the last few years. This can be mostly attributed to the fact that aqueous ILs, depending on the ion species involved, can be used as protein protectants or protein denaturants. Atomistic molecular dynamics (MD) simulations are performed in order to study the influence of different aprotic ILs on the properties of a short hairpin peptide. Our results reveal distinct binding and denaturation effects for 1-ethyl-3-methylimidazolium (EMIM) in combination with different anions, namely, chloride (CL), tetrafluoroborate (BF4) and acetate (ACE). The simulation outcomes demonstrate that the studied ILs with larger anions reveal a more pronounced accumulation behavior of the individual ion species around the peptide, which is accomplished by a stronger dehydration effect. We can relate these findings to the implications of the Kirkwood-Buff theory, which provides a thermodynamic explanation for the denaturation strength in terms of the IL accumulation behavior. The results for the spatial distribution functions, the binding energies and the local/bulk partition coefficients are in good agreement with metadynamics simulations in order to determine the energetically most stable peptide conformations. The free energy landscapes indicate a decrease of the denaturation strength in the order EMIM/ACE, EMIM/BF4 and EMIM/CL, which coincides with a decreasing size of the anion species. An analysis of the potential binding energies reveals that this effect is mainly of enthalpic nature.

Influence of the current density on the electrochemical treatment of concentrated 1-butyl-3-methylimidazolium chloride solutions on diamond electrodes.

PubMed

Marcionilio, Suzana M L de Oliveira; Alves, Gisele M; E Silva, Rachel B Góes; Marques, Pablo J Lima; Maia, Poliana D; Neto, Brenno A D; Linares, José J

2016-10-01

This paper focuses on the influence of the current density treatment of a concentrated 1-butyl-3-methylimidazolium chloride (BMImCl) solution on an electrochemical reactor with a boron-doped diamond (BDD) anode. The decrease in the total organic carbon (TOC) and the BMImCl concentration demonstrate the capability of BDD in oxidizing ionic liquids (ILs) and further mineralizing (to CO2 and NO3 (-)) more rapidly at higher current densities in spite of the reduced current efficiency of the process. Moreover, the presence of Cl(-) led to the formation of oxychlorinated anions (mostly ClO3 (-) and ClO4 (-)) and, in combination with the ammonia generated in the cathode from the nitrate reduction, chloramines, more intensely at higher current density. Finally, the analysis of the intermediates formed revealed no apparent influence of the current density on the BMImCl degradation mechanism. The current density presents therefore a complex influence on the IL treatment process that is discussed throughout this paper.

Synthesis and characterization of ionic liquid immobilized on magnetic nanoparticles: A recyclable heterogeneous organocatalyst for the acetylation of alcohols

NASA Astrophysics Data System (ADS)

Ghorbani-Choghamarani, Arash; Norouzi, Masoomeh

2016-03-01

Herein, we describe a simple and efficient procedure for the preparation of 3-((3-(trisilyloxy)propyl)propionamide)-1-methylimidazolium chloride ionic liquid supported on magnetic nanoparticle (TPPA-IL-Fe3O4). The structure of this magnetic ionic liquid is fully characterized by FT-IR, TGA, XRD, VSM, SEM, EDX and DLS techniques. TPPA-IL-Fe3O4 is employed as a catalyst for the acetylation of alcohols with acetic anhydride under mild and heterogeneous conditions at room temperature with good to excellent yields. The magnetic catalyst could be readily separate from the reaction media by simple magnetic decantation, and reused several times without significant loss of its catalytic activity.