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Pyrrolidinium Imides: Promising Ionic Liquids for Direct Capture of Elemental Mercury from Flue Gas  

Microsoft Academic Search

A new approach to vapor phase elemental mercury capture has been explored; this approach exploits an ionic liquid coating\\u000a layer to oxidize elemental mercury for subsequent immobilization by chelating ligands. The room temperature ionic liquid 1-butyl-1-methyl\\u000a pyrrolidinium bis(trifluoromethane sulfonyl)imide (P14) was selected for study based on its oxidation potential window, thermal stability, and low vapor pressure. Tests were also\\u000a completed

Lei Ji; Stephen W. Thiel; Neville G. Pinto



Synthesis and physicochemical characterization of pyrrolidinium based surfactants.  


Three new pyrrolidinium based surfactants were synthesized and characterized as pure aggregate components and in mixtures with 1,2-dimyristoyl-sn-glycero-3-phosphocholine to understand how the molecular structure of the cationic amphiphile and its mole percentage might affect the physicochemical properties of the resulting aggregates. The thermotropic behavior of the mixed liposomes was investigated by differential scanning calorimetry on multilamellar vesicles, whereas their size and surface potential were investigated on large unilamellar vesicles by dynamic laser light scattering and fluorescence experiments, respectively. The presence of either methoxy or hydroxy groups in the positions 3 and 4 of the pyrrolidinium ring as well as the presence of a second alkyl chain on pyrrolidinium nitrogen, controls the aggregates features. PMID:23141699

Bartoloni, Alessandra; Bombelli, Cecilia; Borocci, Stefano; Bonicelli, Maria Grazia; Galantini, Luciano; Giansanti, Luisa; Ierino, Marco; Mancini, Giovanna; Muschietti, Alessandra; Sperduto, Claudio



Physicochemical properties and toxicities of hydrophobicpiperidinium and pyrrolidinium ionic liquids  

SciTech Connect

Some properties are reported for hydrophobic ionic liquids (IL) containing 1-methyl-1-propyl pyrrolidinium [MPPyrro]{sup +}, 1-methyl-1-butyl pyrrolidinium [MBPyrro]{sup +}, 1-methyl-1-propyl piperidinium [MPPip]{sup +}, 1-methyl-1-butyl piperidinium [MBPip]{sup +}, 1-methyl-1-octylpyrrolidinium [MOPyrro]{sup +} and 1-methyl-1-octylpiperidinium [MOPip]{sup +} cations. These liquids provide new alternatives to pyridinium and imidazolium ILs. High thermal stability of an ionic liquid increases safety in applications like rechargeable lithium-ion batteries and other electrochemical devices. Thermal properties, ionic conductivities, viscosities, and mutual solubilities with water are reported. In addition, toxicities of selected ionic liquids have been measured using a human cancer cell-line. The ILs studied here are sparingly soluble in water but hygroscopic. We show some structure-property relationships that may help to design green solvents for specific applications. While ionic liquids are claimed to be environmentally-benign solvents, as yet few data have been published to support these claims.

Salminen, Justin; Papaiconomou, Nicolas; Kumar, R. Anand; Lee,Jong-Min; Kerr, John; Newman, John; Prausnitz, John M.



Pyrrolidinium-2-carboxyl-ate-4-nitro-phenol (1/2)  

PubMed Central

In the title compound, C5H9NO2·2C6H5NO3, the pyrrolidine ring of the pyrrolidinium-2-carboxyl­ate zwitterion adopts a twisted conformation on the –CH2—CH2– bond adjacent to the N atom. The mean plane of this pyrrolidine ring forms dihedral angles of 25.3?(3) and 32.1?(3)° with the two nitro­phenol rings. An intra­molecular N—H?O hydrogen bond occurs in the pyrrolidinium-2-carboxyl­ate mol­ecule. In the crystal, mol­ecules are linked via O—H?O and N—H?O hydrogen bonds, enclosing R 3 2(8) ring motifs, forming chains running parallel to the a axis. These chains are further cross-linked by O—H?O and C—H?O hydrogen bonds, forming undulating two-dimensional networks lying parallel to (001).

Sowmya, Narayanan Swarna; Vidyalakshmi, Yechuri; Sampathkrishnan, Sadasivam; Srinivasan, Thothadri; Velmurugan, Devadasan



Electrical conductivity and glass formation in nitrile-functionalized pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids: chain length and odd-even effects of the alkyl spacer between the pyrrolidinium ring and the nitrile group.  


The electrical conductivity of a series of pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids, functionalized with a nitrile (cyano) group at the end of an alkyl chain attached to the cation, was studied in the temperature range between 173 K and 393 K. The glass formation of the ionic liquids is influenced by the length of the alkyl spacer separating the nitrile function from the pyrrolidinium ring. The electrical conductivity and the viscosity do not show a monotonic dependence on the alkyl spacer length, but rather an odd-even effect. An explanation for this behavior is given, including the potential energy landscape picture for the glass transition. PMID:24740743

Leys, Jan; Tripathi, Chandra Shekhar Pati; Glorieux, Christ; Zahn, Stefan; Kirchner, Barbara; Longuemart, Stéphane; Lethesh, Kallidanthiyil Chellappan; Nockemann, Peter; Dehaen, Wim; Binnemans, Koen



New functionalized ionic liquids based on pyrrolidinium and piperidinium cations with two ether groups as electrolytes for lithium battery  

Microsoft Academic Search

Four new functionalized ILs based on piperidinium and pyrrolidinium cations with two ether groups and TFSI? anion are synthesized and characterized. Physical and electrochemical properties of these ILs, including melting point, thermal stability, viscosity, conductivity and electrochemical stability, are investigated. All the ILs are liquids at room temperature, and the viscosities of P(2o1)2-TFSI and P(2o1)(2o2)-TFSI are 55 and 53mPas at

Shaohua Fang; Zhengxi Zhang; Yide Jin; Li Yang; Shin-ichi Hirano; Kazuhiro Tachibana; Shingo Katayama



Effect of chemical modification on the ability of pyrrolidinium fullerene to induce apoptosis of cells transformed by JAK2 V617F mutant.  


JAK2 V617F mutant, a gene responsible for human myeloproliferative neoplasms (MPNs), causes not only cellular transformation but also resistance to various anti-cancer drugs. We previously reported that pyrrolidinium fullerene markedly induced the apoptosis of JAK2 V617F mutant-induced transformed cells through the reduction of apoptosis signal-regulating kinase 1 (ASK1), following inhibition of the c-Jun N-terminal kinase (JNK) pathway. In the current study, we found that the replacement of the 2-hydrogen atom (H) or N-methyl group (CH3) by the butyl group (C4C9) caused the more than 3-fold potent cytotoxic effects on cells transformed by the JAK2 V617F mutant. Strikingly, these chemical modification of pyrrolidinium fullerene resulted in more marked reduction of ASK1 protein and a more potent inhibitory effect on the JNK signaling cascade. On the other hand, when modified with a longer alkyl group, the derivatives lacked their cytotoxicity. These observations clearly indicate that the modification of pyrrolidinium fullerene with a suitable length of alkyl group such as butyl group enhances its apoptotic effect through inhibition of the ASK1-MKK4/7-JNK pathway. PMID:24631513

Funakoshi-Tago, Megumi; Tsukada, Masaki; Watanabe, Toshiro; Mameda, Yuka; Tago, Kenji; Ohe, Tomoyuki; Nakamura, Shigeo; Mashino, Tadahiko; Kasahara, Tadashi



Structure and phase transition in bis(pyrrolidinium) hexachlorometallates, (C 4H 8NH 2) 2MCl 6 (M=Sn, Te and Pt), studied by X-ray diffraction, 35Cl NQR and DSC  

NASA Astrophysics Data System (ADS)

Single crystal X-ray diffraction, 35Cl nuclear quadrupole resonance (NQR) and differential scanning calorimetry (DSC) measurements were taken for bis(pyrrolidinium) hexachlorometallates, (C 4H 8NH 2) 2MCl 6 (M=Sn, Te and Pt). A solid-solid phase transition was observed at 150(1), 159(1) and 134(1) K for stannate, tellurate and platinate, respectively. 35Cl NQR signals were observed in stannate and platinate, both of which showed a two-line spectrum in the high-temperature phase and a three-line spectrum in the low-temperature phase. The high-temperature phases of the three complexes were found to be isostructural with each other belonging to the space group C2/ m (#12). The C 4H 8NH 2+ and MCl 62- ions are connected by N-H⋯Cl hydrogen bonds forming parallel sheets in the crystals. Disorder of the cation ring appears in these high-temperature phases. Semi-empirical MO calculations were performed to estimate the stable structure of the pyrrolidinium ion.

Ishida, H.; Furukawa, Y.; Sato, S.; Kashino, S.



Selenium encapsulated into 3D interconnected hierarchical porous carbon aerogels for lithium-selenium batteries with high rate performance and cycling stability  

NASA Astrophysics Data System (ADS)

Selenium encapsulated into 3D interconnected hierarchical porous carbon aerogels (HPCA) as a carbon/selenium composite material is prepared for lithium-selenium batteries. Scanning electron microscope (SEM) and transmission electron microscope (TEM) observations show the hierarchical porous structures of the carbon aerogels and the homogeneous distribution of selenium in the composite. The performance of the HPCA/Se cathode is evaluated in lithium-selenium batteries using cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. It is found that the HPCA/Se cathode shows high rate performance, coulombic efficiency and cycling stability. The HPCA/Se cathode has a highest coulombic efficiency which is kept above 98% after 50th cycle in ionic liquid N-methyl-(n-butyl) pyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) modified electrolyte and retains 309 mAh g-1 after 100 discharge/charge cycles at a high rate of 0.5 C (337.5 mAh g-1) in LiNO3 modified electrolyte, respectively. Even at the current density of 5 C (3375 mAh g-1), it can still maintain at a reversible capacity of 301 mAh g-1. The excellent electrochemical properties benefit from the high electron conductivity and 3D interconnected hierarchical porous structures of the carbon aerogels, which contribute to disperse selenium and absorb polyselenides, and suppress the formation of residual Li2Se layer.

Jiang, Shaofeng; Zhang, Zhian; Lai, Yanqing; Qu, Yaohui; Wang, XiWen; Li, Jie



Limited thermal stability of imidazolium and pyrrolidinium ionic liquids  

SciTech Connect

Ionic liquids, with their vast applications, have been touted as being thermally stable to very high temperatures. However, decomposition not detected by standard TGA and NMR techniques are observed with spectroscopic techniques sensitive enough to see small amounts of impurities. Decomposition temperatures of common ionic liquids appear to occur at hundreds of degrees below those temperatures previously reported.

Del Sesto, Rico E [Los Alamos National Laboratory (LANL); Mccleskey, T [Los Alamos National Laboratory (LANL); Macomber, Clay [Los Alamos National Laboratory (LANL); Ott, Kevin [Los Alamos National Laboratory (LANL); Koppisch, Andrew [Los Alamos National Laboratory (LANL); Baker, Gary A [ORNL; Burrell, Anthony K [ORNL



Photodetachment and electron reactivity in 1-methyl-1-butyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide.  


The transient absorption spectrum in the range 500 nm-1000 nm was measured with ultrafast time resolution on a flowing neat, aliphatic, room-temperature ionic liquid following anion photodetachment. In this region the spectrum was shown to be a combination of absorption from the electron and the hole. Spectrally-resolved electron quenching determined a bimodal shape for the hole spectrum in agreement with recent computational predictions on a smaller aliphatic ionic liquid [Margulis et al., J. Am. Chem. Soc. 133, 20186 (2011)]. For time delays beyond 15 ps, spectral evolution qualitatively agrees with recent radiolysis experiments [Wishart et al., Faraday Discuss. 154, 353 (2012)]. However, the shape of the spectrum is different, reflecting the contrast in ionization energy between the two methods. Previously unobserved reactivity of the electron was found with a time constant of 300 fs. The results demonstrate solvent control of the rate coefficient for reaction between the electron and proton, with a rapid decline in the rate within the first picosecond. PMID:22830716

Molins i Domenech, Francesc; FitzPatrick, Benjamin; Healy, Andrew T; Blank, David A



Photodetachment and electron reactivity in 1-methyl-1-butyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide  

NASA Astrophysics Data System (ADS)

The transient absorption spectrum in the range 500 nm-1000 nm was measured with ultrafast time resolution on a flowing neat, aliphatic, room-temperature ionic liquid following anion photodetachment. In this region the spectrum was shown to be a combination of absorption from the electron and the hole. Spectrally-resolved electron quenching determined a bimodal shape for the hole spectrum in agreement with recent computational predictions on a smaller aliphatic ionic liquid [Margulis et al., J. Am. Chem. Soc. 133, 20186 (2011)]. For time delays beyond 15 ps, spectral evolution qualitatively agrees with recent radiolysis experiments [Wishart et al., Faraday Discuss. 154, 353 (2012)]. However, the shape of the spectrum is different, reflecting the contrast in ionization energy between the two methods. Previously unobserved reactivity of the electron was found with a time constant of 300 fs. The results demonstrate solvent control of the rate coefficient for reaction between the electron and proton, with a rapid decline in the rate within the first picosecond.

Molins i Domenech, Francesc; FitzPatrick, Benjamin; Healy, Andrew T.; Blank, David A.



Influence of Zn2+ and water on the transport properties of a pyrrolidinium dicyanamide ionic liquid.  


In order to expand our understanding of a potential zinc-based battery electrolyte, we have characterized the physical and transport properties of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium dicyanamide ([C4mpyr][dca]) containing various levels of both Zn(2+) and H2O. Detailed measurements of density, viscosity, conductivity, and individual anion and cation diffusion coefficients using pulsed-field-gradient (PFG) NMR combined with NMR chemical shifts and spin-lattice relaxation (T1) NMR experiments provide insights into the motion and chemical environment of all molecular species. We find that the various techniques for probing ion transport and dynamics form a coherent picture as a function of electrolyte composition. Zn(2+) addition causes a moderate reduction in the self-diffusion of the IL anion and cation, whereas the addition of H2O increases ion mobility by increasing the liquid's overall fluidity. Temperature-dependent (13)C T1 experiments of the dca carbon analyzed using Bloembergen-Purcell-Pound fits show monotonic slowing of anion dynamics with Zn(2+) addition, suggesting increased Zn(2+)/dca(-) association. T1 experiments show minimal change in the spin-lattice relaxation of cation or anion upon H2O addition, suggesting that H2O is playing no significant role in Zn(2+) speciation. Finally, we employ a novel electrophoretic NMR technique to directly determine the electrophoretic mobility of the C4mpyr cation, which we discuss in the context of impedance-based conductivity measurements. PMID:24712560

Simons, T J; Bayley, P M; Zhang, Z; Howlett, P C; MacFarlane, D R; Madsen, L A; Forsyth, M



Bulk and liquid-vapor interface of pyrrolidinium-based ionic liquids: a molecular simulation study.  


Using molecular dynamics simulations, we have studied the structure of three 1-butyl-1-methylpyrrolidinium ionic liquids whose anions are triflate, bis(trifluoromethanesulfonyl)imide, and tris(pentafluoroethyl)trifluorophosphate. The structure of the bulk phase of the three ionic liquids has been interpreted using radial and spatial distribution functions and structure factors that allows us to characterize the morphology of the polar and nonpolar domains present in this family of liquids. The size of the polar regions depends on the anion size, whereas the morphology of the nonpolar domains is anion-independent. Furthermore, the surface ordering properties of the ionic liquids and charge and density profiles were also studied using molecular simulations. The surface tension of the liquid-vapor interfaces of these ionic liquids was also predicted from our molecular simulations. In addition, microscopic structural analysis of orientational ordering at the interface and density profiles along the direction normal to the interface suggest that the alkyl chains of the cation tend to protrude toward the vacuum, and the presence of the interface leads to a strong organization of the liquid phase in the region close to the interface. In the interfacial area, the polar regions of the ionic liquids are more structured than those in the bulk phase, whereas the opposite behavior is observed for the nonpolar regions. PMID:24383956

Paredes, Xavier; Fernández, Josefa; Pádua, Agílio A H; Malfreyt, Patrice; Malberg, Friedrich; Kirchner, Barbara; Pensado, Alfonso S



Influence of Solute Charge and Pyrrolidinium Ionic Liquid Alkyl Chain Length on Probe Rotational Reorientation Dynamics  

SciTech Connect

In recent years, the effect of molecular charge on the rotational dynamics of probe solutes in room temperature ionic liquids (RTILs) has been a subject of growing interest. For the purpose of extending our understanding of charged solute behavior within RTILs, we have studied the rotational dynamics of three illustrative xanthene fluorescent probes within a series of N-alkylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Cnmpyr][Tf2N]) RTILs with different n-alkyl chain lengths (n = 3, 4, 6, 8, or 10) using time-resolved fluorescence anisotropy decay. The rotational dynamics of the neutral probe rhodamine B dye lies between the stick and slip boundary conditions due to the influence of specific hydrogen bonding interactions. The rotation of the negatively-charged sulforhodamine 640 is slower than that of its positively-charged counterpart rhodamine 6G. An analysis based upon Stokes-Einstein-Debye hydrodynamics indicates that SR640 adheres to stick boundary conditions due to specific interactions, whereas the faster rotation of R6G is attributed to weaker electrostatic interactions. No dependence of the rotational dynamics on the solvent alkyl chain length was observed for any of the three dyes, suggesting that the specific interactions between dyes and RTILs are independent of this solvent parameter.

Guo, Jianchang [ORNL] [ORNL; Mahurin, Shannon Mark [ORNL] [ORNL; Baker, Gary A [ORNL] [ORNL; Hillesheim, Patrick C [ORNL] [ORNL; Dai, Sheng [ORNL] [ORNL; Shaw, Robert W [ORNL] [ORNL



Effect of Titanium Substitution on the Compatiblity of Electrodeswith Pyrrolidinium-Based Ionic Liquid Electrolytes  

Microsoft Academic Search

The quest for the development of rechargeable lithium-metal batteries has attracted vigorous worldwide research efforts because this system offers the highest theoretical specific energy [1]. For this to be achieved, the repetitive deposition and stripping of lithium must be close to fully reversible. Thus, alternative electrolytes have been investigated, such as the room-temperature ionic liquid (RTILs). Lithium can be cycled

Juliette A. Saint; Joon-Ho Shin; Adam Best; Anthony Hollenkamp; John Kerr; Marca M. Doeff



‘Bucky gel’ of multiwalled carbon nanotubes as electrodes for high performance, flexible electric double layer capacitors  

NASA Astrophysics Data System (ADS)

We report the preparation of a gelled form of multiwalled carbon nanotubes (MWCNTs) with an ionic liquid 1-butyl-1-methyl pyrrolidinium bis(trifluoromethane sulfonyl)imide (BMPTFSI)), referred to as ‘bucky gel’, to be used as binderless electrodes in electrical double layer capacitors (EDLCs). The characteristics of gelled MWCNTs are compared with pristine MWCNTs using transmission electron microscopy, x-ray diffraction and Raman studies. A gel polymer electrolyte film consisting of a blend of poly(vinylidene fluoride-co-hexafluoropropylene) and BMPTFSI, exhibiting a room temperature ionic conductivity of 1.5 × 10-3 S cm-1, shows its suitability as an electrolyte/separator in flexible EDLCs. The performance of EDLCs, assembled with bucky gel electrodes, using impedance spectroscopy, cyclic voltammetry and charge-discharge analyses, are compared with those fabricated with pristine MWCNT-electrodes. An improvement in specific capacitance (from 19.6 to 51.3 F g-1) is noted when pristine MWCNTs are replaced by gelled MWCNT-binderless electrodes. Although the rate performance of the EDLCs with gelled MWCNT-electrodes is reduced, the pulse power of the device is sufficiently high (˜10.5 kW kg-1). The gelled electrodes offer improvements in energy and power densities from 2.8 to 8.0 Wh kg-1 and 2.0 to 4.7 kW kg-1, respectively. Studies indicate that the gel formation of MWCNTs with ionic liquid is an excellent route to obtain high-performance EDLCs.

Singh, Manoj K.; Kumar, Yogesh; Hashmi, S. A.



'Bucky gel' of multiwalled carbon nanotubes as electrodes for high performance, flexible electric double layer capacitors.  


We report the preparation of a gelled form of multiwalled carbon nanotubes (MWCNTs) with an ionic liquid 1-butyl-1-methyl pyrrolidinium bis(trifluoromethane sulfonyl)imide (BMPTFSI)), referred to as 'bucky gel', to be used as binderless electrodes in electrical double layer capacitors (EDLCs). The characteristics of gelled MWCNTs are compared with pristine MWCNTs using transmission electron microscopy, x-ray diffraction and Raman studies. A gel polymer electrolyte film consisting of a blend of poly(vinylidene fluoride-co-hexafluoropropylene) and BMPTFSI, exhibiting a room temperature ionic conductivity of 1.5 × 10(-3) S cm(-1), shows its suitability as an electrolyte/separator in flexible EDLCs. The performance of EDLCs, assembled with bucky gel electrodes, using impedance spectroscopy, cyclic voltammetry and charge-discharge analyses, are compared with those fabricated with pristine MWCNT-electrodes. An improvement in specific capacitance (from 19.6 to 51.3 F g(-1)) is noted when pristine MWCNTs are replaced by gelled MWCNT-binderless electrodes. Although the rate performance of the EDLCs with gelled MWCNT-electrodes is reduced, the pulse power of the device is sufficiently high (~10.5 kW kg(-1)). The gelled electrodes offer improvements in energy and power densities from 2.8 to 8.0 Wh kg(-1) and 2.0 to 4.7 kW kg(-1), respectively. Studies indicate that the gel formation of MWCNTs with ionic liquid is an excellent route to obtain high-performance EDLCs. PMID:24157648

Singh, Manoj K; Kumar, Yogesh; Hashmi, S A




SciTech Connect

Ionic liquids are often cited for their excellent thermal stability, a key property for their use as solvents and in the chemical processing of biofuels. However, there has been little supporting data on the long term aging effect of temperature on these materials. Imizadolium, quaternary ammonium, pyridinium, and pyrrolidnium-based ionic liquids with the bis(trifluoromethylsulfonyl)imide and bis(perfluoroethylsulfonyl)imide anions were aged for 2520 hours (15 weeks) at 200?C in air to determine the effects of an oxidizing environment on their chemical structure and thermal stability over time. It was found that the minor changes in the cation chemistry could greatly affect the properties of the ILs over time.

Fox, E.



Alkyl Chain Length and Temperature Effects on Structural Properties of Pyrrolidinium-Based Ionic Liquids: A Combined Atomistic Simulation and Small-Angle X-ray Scattering Study.  

SciTech Connect

Molecular dynamics (MD) simulations of 1-alkyl-1-methylpyrrolidinium 12 bis(trifluoromethanesulfonyl)imide ([CnMPy][Tf2N], n = 3, 4, 6, 8, 10) were conducted 13 using an all-atom model. Radial distribution functions (RDF) were computed and structure 14 functions were generated to compare with new X-ray scattering experimental results, 15 reported herein. The scattering peaks in the structure functions generally shift to lower Q 16 values with increased temperature for all the liquids in this series. However, the first sharp 17 diffraction peak (FSDP) in the longer alkyl chain liquids displays a marked shift to higher Q 18 values with increasing temperature. Alkyl chain-dependent ordering of the polar groups and 19 increased tail aggregation with increasing alkyl chain length were observed in the partial pair 20 correlation functions and the structure functions. The reasons for the observed alkyl chain- 21 dependent phenomena and temperature effects were explored.

Li, Song [ORNL] [ORNL; Banuelos, Jose Leo [ORNL] [ORNL; Guo, Jianchang [ORNL] [ORNL; Anovitz, Lawrence {Larry} M [ORNL; Rother, Gernot [ORNL] [ORNL; Shaw, Robert W [ORNL] [ORNL; Hillesheim, Patrick C [ORNL] [ORNL; Dai, Sheng [ORNL] [ORNL; Baker, Gary A [ORNL] [ORNL; Cummings, Peter T [ORNL] [ORNL



Hydrogen bonding Part 30. New IR spectra-structure correlations for tetraethylammonium, tetramethylammonium, and N, N-dimethyl-pyrrolidinium fluoride monohydrates, tetraethylammonium chloride monohydrate, and tetramethylammonium hydroxide dihydrate; evidence for a planar (H 2O·F -) 2 cluster  

NASA Astrophysics Data System (ADS)

Tetraethylammonium chloride is not dimorphous, as we had once suspected; material recrystallized from hot acetone is identical to that prepared by Loehlin and Kvick by a different route, and contains a planar (H 2O·Cl -) 2 cluster of C2h symmetry. Since the IR spectra of the water-fluoride cluster in tetraethylammonium and tetramethylammonium fluoride monohydrates are very similar to that of the water-chloride cluster in tetraethylammonium chloride monohydrate, we conclude that these hydrates contain a planar (H 2O·F -) 2 cluster, rather than the tetrahedral model previously proposed. IR spectra of N, N-dimethylpyrrolidinium fluoride monohydrate and monohydrate- d2, demonstrate that they contain similar clusters. The crystal structure of tetramethylammonium hydroxide dihydrate has recently been reported, which allows a final correlation of the IR spectrum and the structure of this hydrate.

Harmon, Kenneth M.; Gabriele, Julie M.; Harmon, Jennifer



Absorption ability and kinetics of a liquid electrolyte in PVDF–HFP copolymer containing or not SiO 2  

Microsoft Academic Search

Gel polymer electrolytes have been prepared from PVDF–HFP copolymer with various silica contents incorporating Gamma valerolactone (VL) or VL\\/EC (80\\/20 in mole) (EC: ethylene carbonate) solutions of lithium bis(trifluoromethane sulfone) imide (LiTFSI). The influence of temperature, salt content and silica addition on the kinetics of absorption and wettability of the copolymer has been investigated. An empirical model, taking into account

M Caillon-Caravanier; B Claude-Montigny; D Lemordant; G Bosser



Performance evaluation of PVdF gel polymer electrolytes  

Microsoft Academic Search

A series of gel polymer electrolytes containing PVdF as homo polymer, a mixture of 1:1 Ethylene Carbonate (EC) : Propylene\\u000a Carbonate (PC) as plasticizer and lithium-bistrifluoromethane sulphone imide [imide — LiN (CF3SO2)2] has been developed. Amounts of polymer (PVdF), plasticizer and the imide lithium salt have been varied as a function of\\u000a their weight ratio composition in this regard. Dimensionally

P. Periasamy; K. Tatsumi; N. Kalaiselvi; M. Shikano; T. Fiyieda; Y. Saito; T. Sakai; M. Mizukata; A. Kajinami; S. Deki



The preparation of quaternary ammonium-based ionic liquid containing a cyano group and its properties in a lithium battery electrolyte  

Microsoft Academic Search

A room temperature ionic liquid consisting of N,N,N,N-cyanomethyl trimethyl ammonium (CTMA) cation and bis(trifluoromethane sulfone)imide (TFSI) anion was newly synthesized, and its electrochemical properties were investigated. This ionic liquid has a melting point of 35°C and an order of conductivity of 10?4Scm?1. Lithium deposition\\/dissolution tests in 0.2moldm?3 LiTFSI\\/CTMATFSI electrolytes showed an improved cycle behavior compared with that of a Li

Minato Egashira; Shigeto Okada; Jun-ichi Yamaki; Diego Alejandro Dri; Francesco Bonadies; Bruno Scrosati



Cytotoxicity estimation of ionic liquids based on their effective structural features  

Microsoft Academic Search

Cytotoxicity of a diverse set of 227 ionic liquids (taken from UFT\\/Merck Ionic Liquids Biological Effects Database) containing 94 imidazolium, 53 pyridinium, 23 pyrrolidinium, 22 ammonium, 15 piperidinium, 10 morpholinium, 5 phosphanium, and 5 quinolinium cations in combination with 25 different types of anions to Leukemia Rat Cell Line (IPC-81) was estimated from their structural parameters using quantitative structure –

Mohammad H. Fatemi; Parisa Izadiyan



Estimation of toxicity of ionic liquids in Leukemia Rat Cell Line and Acetylcholinesterase enzyme by principal component analysis, neural networks and multiple lineal regressions  

Microsoft Academic Search

Multiple linear regression (MLR), radial basis network (RB), and multilayer perceptron (MLP) neural network (NN) models have been explored for the estimation of toxicity of ammonium, imidazolium, morpholinium, phosphonium, piperidinium, pyridinium, pyrrolidinium and quinolinium ionic liquid salts in the Leukemia Rat Cell Line (IPC-81) and Acetylcholinesterase (AChE) using only their empirical formulas (elemental composition) and molecular weights. The toxicity values

José S. Torrecilla; Julián García; Ester Rojo; Francisco Rodríguez



Tuning ionic liquids for hydrate inhibition.  


Pyrrolidinium cation-based ionic liquids were synthesized, and their inhibition effects on methane hydrate formation were investigated. It was found that the ionic liquids shifted the hydrate equilibrium line to a lower temperature at a specific pressure, while simultaneously delaying gas hydrate formation. PMID:21547283

Kim, Ki-Sub; Kang, Jeong Won; Kang, Seong-Pil



Bicyclic imidazolium ionic liquids as potential electrolytes for rechargeable lithium ion batteries  

SciTech Connect

A bicyclic imidazolium ionic liquids, 1-ethyl-2,3-trimethyleneimidazolium bis(tri fluoromethane sulfonyl)imide ([ETMIm][TFSI]), and reference imidazolium compounds, 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide ([EMIm][TFSI]) and 1, 2-dimethyl-3-butylimidazolium bis(trifluoromethane sulfonyl)imide ([DMBIm][TFSI]), were synthesized and investigated as solvents for lithium ion batteries. Although the alkylation at the C-2 position of the imidazolium ring does not affect the thermal stability of the ionic liquids, with or without the presence of 0.5 molar lithium bis(trifluoromethane sulfonyl)imide (LiTFSI), the stereochemical structure of the molecules has shown profound influences on the electrochemical properties of the corresponding ionic liquids. [ETMIm][TFSI] shows better reduction stability than do [EMIm][TFSI] and [DMBIm][TFSI], as confirmed by both linear sweep voltammery (LSV) and theoretical calculation. The Li||Li cell impedance of 0.5M LiTFSI/[ETMIm][TFSI] is stabilized, whereas that of 0.5M LiTFSI/[DMBIm][TFSI] is still fluctuating after 20 hours, indicating a relatively stable solid electrolyte interphase (SEI) is formed in the former. Furthermore, the Li||graphite half-cell based on 0.5M LiTFSI/[BTMIm][TFSI] exhibits reversible capacity of 250mAh g-1 and 70mAh g-1 at 25 C, which increases to 330 mAh g-1 and 250 mAh g-1 at 50 C, under the current rate of C/20 and C/10, respectively. For comparison, the Li||graphite half-cell based on 0.5M LiTFSI/[DMBIm][TFSI] exhibits poor capacity retention under the same current rate at both temperatures.

Liao, Chen [ORNL; Shao, Nan [ORNL; Bell, Jason R [ORNL; Guo, Bingkun [ORNL; Luo, Huimin [ORNL; Jiang, Deen [ORNL; Dai, Sheng [ORNL



Ionic liquids for rechargeable lithium batteries  

Microsoft Academic Search

We have investigated possible anticipated advantages of ionic-liquid electrolytes for use in lithium-ion batteries. Thermal stabilities and phase behavior were studied by thermal gravimetric analysis and differential scanning calorimetry. The ionic liquids studied include various imidazoliumTFSI systems, pyrrolidiniumTFSI, BMIMPF, BMIMBF, and BMIMTf. Thermal stabilities were measured for neat ionic liquids and for BMIMBF-LiBF, BMIMTf-LiTf, BMIMTFSI-LiTFSI mixtures. Conductivities have been measured

Justin Salminen; Nicolas Papaiconomou; John Kerr; John Prausnitz; John Newman



On the thermal behavior of model Li–Li x CoO 2 systems containing ionic liquids in standard electrolyte solutions  

Microsoft Academic Search

We report herein on the possibility of using ionic liquids (ILs) as additives to conventional electrolyte solutions, based on alkyl carbonates and LiPF6 for attenuating thermal reactions in Li battery systems. As a model, a Li–Li0.5CoO2 system was used. The ionic liquids chosen included cations based on derivatives of pyrrolidinium and imidazolium, and the anions bioxalato borate (C4O8B?, BOB), (CH3SO2)2N?

L. Larush; V. Borgel; E. Markevich; O. Haik; E. Zinigrad; D. Aurbach; G. Semrau; M. Schmidt



Carbon–ionic liquid double-layer capacitors  

Microsoft Academic Search

A series of electrochemical capacitors, based on activated carbon powders (ACP, specific surface area 870 and 2600 m2\\/g) and ionic liquids as electrolytes, were prepared and tested. The ionic liquids consisted of 1-ethyl-3-methyl imidazolium (EMIm+), 1-butyl-3-methyl imidazolium (BMIm+) and 1-methyl-1-propyl pyrrolidinium (BMPy+) cations, as well as of tetrafluoroborate, hexafluorophosphate and bis((trifluoromethyl)sulfonyl) imide anions. A typical capacitor consisted of two electrodes

A. Lewandowski; M. Galinski



Characteristics of ionic liquid-based electrolytes for chip type aluminum electrolytic capacitors  

Microsoft Academic Search

Since ionic liquids (ILs) possess several attractive properties, including chemical and thermal stability, nonflammability, high ionic conductivity, and negligible vapor pressure, a new electrolyte system based on ILs has been proposed for chip type aluminum electrolytic capacitors. Four ILs based on imidazolium\\/pyrrolidinium cations and maleate\\/phthalate anions have been synthesized and their thermal stabilities have been examined. The 25wt.% solutions of

Ye Song; Xufei Zhu; Xinlong Wang; Mingjie Wang



Ionic liquid-based electrolytes for capacitor applications  

Microsoft Academic Search

In this work we have synthesized several novel ionic liquids (ILs) based on imidazolium\\/pyrrolidinium cations and maleate\\/phthalate anions. The 1.5mol\\/L solutions of the ILs in gamma-butyrolactone (GBL) solvent were prepared as the electrolytes of electrochemical energy storage devices such as electrochemical capacitors and electrolytic capacitors. The conductivity, electrochemical stability, sparking voltage and thermal stability of these electrolytes have been investigated

Qing Zhu; Ye Song; Xufei Zhu; Xinlong Wang



Electrochemical stability of bis(trifluoromethanesulfonyl)imide-based ionic liquids at elevated temperature as a solvent for a titanium oxide bronze electrode  

Microsoft Academic Search

Four different electrolytes are prepared by dissolving a Li salt in three different room-temperature ionic liquids (RTILs) and also in a conventional organic solvent. The cathodic (electrochemical reduction) stability of these electrolytes is compared at both ambient and elevated temperature by potential cycling on a TiO2-B electrode. At room temperature, the stability of pyrrolidinium- and piperidinium-based RTILs is comparable with

Junyoung Mun; Yoon Seok Jung; Taeeun Yim; Hyun Yeong Lee; Hyo-Jin Kim; Young Gyu Kim; Seung M. Oh



Lithium-sulfur batteries based on nitrogen-doped carbon and an ionic-liquid electrolyte.  


Nitrogen-doped mesoporous carbon (NC) and sulfur were used to prepare an NC/S composite cathode, which was evaluated in an ionic-liquid electrolyte of 0.5 M lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) in methylpropylpyrrolidinium bis(trifluoromethane sulfonyl)imide ([MPPY][TFSI]) by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and cycle testing. To facilitate the comparison, a C/S composite based on activated carbon (AC) without nitrogen doping was also fabricated under the same conditions. Compared with the AC/S composite, the NC/S composite showed enhanced activity toward sulfur reduction, as evidenced by the lower onset sulfur reduction potential, higher redox current density in the CV test, and faster charge-transfer kinetics, as indicated by EIS measurements. At room temperature under a current density of 84 mA g(-1) (C/20), the battery based on the NC/S composite exhibited a higher discharge potential and an initial capacity of 1420 mAh g(-1), whereas the battery based on the AC/S composite showed a lower discharge potential and an initial capacity of 1120 mAh g(-1). Both batteries showed similar capacity fading with cycling due to the intrinsic polysulfide solubility and the polysulfide shuttle mechanism; capacity fading can be improved by further cathode modification. PMID:22847977

Sun, Xiao-Guang; Wang, Xiqing; Mayes, Richard T; Dai, Sheng



Sol–gel synthesis of vanadium pentoxide nanoparticles in air- and water-stable ionic liquids  

Microsoft Academic Search

Vanadium pentoxide (V2O5) nanoparticles were synthesized at moderate reaction temperatures by hydrolysis of VO[OCH(CH3)2]3 in two different air- and water-stable ionic liquids with the same anion: 1-butyl-1-methyl pyrrolidinium bis(trifluoromethylsulfonyl)amide\\u000a ([Py1,4]Tf2N) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMIM]Tf2N) via the sol–gel method using acetone and isopropanol either as refluxing solvents or as co-solvents. The cation type of\\u000a the ionic liquid affects the crystallinity, morphology,

Mohammad Al Zoubi; Hala K. Farag; Frank Endres



Method for measuring surface temperature  

SciTech Connect

The present invention relates to a method for measuring a surface temperature using is a fluorescent temperature sensor or optical thermometer. The sensor includes a solution of 1,3-bis(1-pyrenyl)propane within a 1-butyl-1-1-methyl pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid solvent. The 1,3-bis(1-pyrenyl)propane remains unassociated when in the ground state while in solution. When subjected to UV light, an excited state is produced that exists in equilibrium with an excimer. The position of the equilibrium between the two excited states is temperature dependent.

Baker, Gary A. (Los Alamos, NM); Baker, Sheila N. (Los Alamos, NM); McCleskey, T. Mark (Los Alamos, NM)



Carboxyl-functionalized task-specific ionic liquids for solubilizing metal oxides.  


Imidazolium, pyridinium, pyrrolidinium, piperidinium, morpholinium, and quaternary ammonium bis(trifluoromethylsulfonyl)imide salts were functionalized with a carboxyl group. These ionic liquids are useful for the selective dissolution of metal oxides and hydroxides. Although these hydrophobic ionic liquids are immiscible with water at room temperature, several of them form a single phase with water at elevated temperatures. Phase separation occurs upon cooling. This thermomorphic behavior has been investigated by (1)H NMR, and it was found that it can be attributed to the temperature-dependent hydration and hydrogen-bond formation of the ionic liquid components. The crystal structures of four ionic liquids and five metal complexes have been determined. PMID:18841931

Nockemann, Peter; Thijs, Ben; Parac-Vogt, Tatjana N; Van Hecke, Kristof; Van Meervelt, Luc; Tinant, Bernard; Hartenbach, Ingo; Schleid, Thomas; Ngan, Vu Thi; Nguyen, Minh Tho; Binnemans, Koen



Systems with ionic liquids: Measurement of VLE and ? ? data and prediction of their thermodynamic behavior using original UNIFAC, mod. UNIFAC(Do) and COSMO-RS(Ol)  

Microsoft Academic Search

Vapor–liquid equilibria (VLE) for six systems at 353K and activity coefficients at infinite dilution (??) for various solutes (alkanes, alkenes, cycloalkanes, cycloalkenes, aromatics, alcohols, ketones, esters, ethers, and water) in the ionic liquids; 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [EMIM][BTI], 1-hexyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [HMIM][BTI], 1-octyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [OMIM][BTI], and 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [BMPYR][BTI] have been determined in the temperature range from (303 to 333)K. Additionally, ?i? were

Ryo Kato; Jürgen Gmehling



Cycling and rate performance of Li–LiFePO 4 cells in mixed FSI–TFSI room temperature ionic liquids  

Microsoft Academic Search

A study is conducted of the performance of lithium iron(II) phosphate, LiFePO4, as a cathode material in a lithium secondary battery that features an ionic liquid electrolyte solution and a metallic lithium anode. The electrolyte solution comprises an ionic liquid of a N-methyl-N-alkyl-pyrrolidinium (alkyl=n-propyl or n-butyl) cation and either the bis(fluorosulfonyl)imide [(FSO2)2N?] or bis(trifluoromethanesulfonyl)imide [(F3CSO2)2N?] anion, together with 0.5molkg?1 of

A. P. Lewandowski; A. F. Hollenkamp; S. W. Donne; A. S. Best



Effect of lithium ions on oxygen reduction in ionic liquid-based electrolytes  

Microsoft Academic Search

The effect of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) on the oxygen redox reaction (ORR) in several pyrrolidinium-based ionic liquids (ILs) is investigated by cyclic voltammetry. The results are compared to those found with LiTFSI-tetraglyme and LiTFSI-1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidone solutions. The effect of the addition of tris(pentafluorophenyl) borane (TPFPB) to IL-LiTFSI solutions is also investigated. The results demonstrate that the presence of 0.1M Li+ renders

Francesca De Giorgio; Francesca Soavi; Marina Mastragostino



B2O3-added lithium aluminium germanium phosphate solid electrolyte for Li-O2 rechargeable batteries.  


B2O3-added Li1.5Al0.5Ge1.5(PO4)3 (LAGP) glass ceramics showing a room temperature ionic conductivity of 0.67 mS cm(-1) have been synthesized by using a melt-quenching method. The prepared glass ceramics are observed to be stable in tetraethylene glycol dimethyl ether containing lithium bis(trifluoromethane) sulfonamide. The augmented conductivity of the B2O3-added LAGP glass ceramic has improved the plateau potential during discharge. Furthermore, the B2O3-added LAGP glass ceramics are successfully employed as a solid electrolyte in a Li-O2 battery to obtain a stable cycling lifetime of up to 15 cycles with the limited capacity protocol. PMID:24953185

Jadhav, Harsharaj S; Kalubarme, Ramchandra S; Jang, Seong-Yong; Jung, Kyu-Nam; Shin, Kyoung-Hee; Park, Chan-Jin



Studies on thermal properties of selected aprotic and protic ionic liquids  

SciTech Connect

We describe herein the thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) investigations of the thermal properties of selected room-temperature ionic liquids (RTILs). The dependence of the thermal properties on both cation and anion structures of RTILs was systematically studied. The ionic liquids (ILs) investigated here include 28 different imidazolium-based ILs, 22 ammonium-based ILs, and 16 amide-based ILs. In general, these three cation classes exhibit different thermal behaviors but follow a quite systematic trend as expected from the corresponding structural variation. The ILs with bromide as the conjugate anion have lower thermal stabilities than those with bis(trifluoromethane sulfonyl) imide or bis(perfluoroethyl sulfonyl) imide as the conjugate anion. The mass of TGA samples and scan rate were found to have a systematic effect on the decomposition temperature of ILs, highlighting the caution needed in reporting TGA results.

Luo, Huimin [ORNL; Dai, Sheng [ORNL; Huang, Jing-Fang [ORNL



Studies on the effect of dispersoid(ZrO2) in PVdF-co-HFP based gel polymer electrolytes  

NASA Astrophysics Data System (ADS)

Gel polymer electrolytes containing poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) / Lithium bis(trifluoromethane sulfon)imide (LiTFSI) / mixture of ethylene carbonate and propylene carbonate (EC+PC) with different concendration of ZrO2 has been prepared using the solution casting technique. The conductivity of the prepared electrolyte sample has been determined by AC impedance technique in the range 303-353K. The temperature dependent ionic conductivity plot seems to obey VTF relation. The maximum ionic conductivity value of 4.46 × 10-3S/cm has been obtained for PVdF-co-HFP(32%) - LiTFSI(8%) - EC+PC (60%) + ZrO2(6wt%) based polymer electrolyte. The surface morphology of the prepared electrolyte sample has been studied using SEM.

Sivakumar, M.; Subadevi, R.; Muthupradeepa, R.



A joint theoretical/experimental study of the structure, dynamics, and Li+ transport in bis([tri]fluoro[methane]sulfonyl)imide [T]FSI-based ionic liquids  

NASA Astrophysics Data System (ADS)

The structure and dynamics of N-butyl-N-methyl pyrrolidinium+ bis([tri]fluoro[methane]sulfonyl)imide- (PYR14+-[T]FSI-) ionic liquids doped with Li(T)FSI are investigated by combining experimental measurements to molecular dynamics simulations. The polarizable force field calculations indicate that the lithium cations are coordinated by (T)FSI anion oxygens forming lithium adducts stabilized over a large temperature range by strong Li-O bonds. Lithium aggregation is found to be negligible at the doping level considered here (10% mole fraction), and Li+ diffusion occurs primarily by exchanging the (T)FSI anions in their first coordination shell. The resulting calculated transport properties are in good agreement with the corresponding nuclear magnetic resonance data.

Solano, C. J. F.; Jeremias, S.; Paillard, E.; Beljonne, D.; Lazzaroni, R.



A comparison of phosphorus and fluorine containing IL lubricants for steel on aluminium.  


Ionic liquids have been shown to be highly effective lubricants for a steel on aluminium system. This work shows that the chemistry of the anion and cation are critical in achieving maximum wear protection. The performance of the ILs containing a diphenylphosphate (DPP) anion all showed low wear, as did some of the tris(pentafluoroethyl)trifluorophosphate (FAP) and bis(trifluoromethanesulfonyl)amide (NTf(2)) anion containing ILs. However, in the case of the FAP and NTf(2) based systems, a cation dependence was observed, with relatively poor wear resistance obtained in the case of an imidazolium FAP and two pyrrolidinium NTf(2) salts, probably due to tribocorrosion caused by the fluorine reaction with the aluminium substrate. The systems exhibiting poor performance generally had a lower viscosity, which also impacts on their tribological properties. Those ILs that exhibited low wear were shown to have formed protective tribofilms on the aluminium alloy surface. PMID:22555280

Somers, Anthony E; Biddulph, Shannon M; Howlett, Patrick C; Sun, Jiazeng; MacFarlane, Douglas R; Forsyth, Maria



Supported phospholipid bilayer interaction with components found in typical room-temperature ionic liquids - a QCM-D and AFM Study.  


Quartz crystal microbalance with dissipation (QCM-D) monitoring and atomic force microscopy (AFM) were combined to evaluate the defects created by an ionic liquid anion and a cation in a supported phospholipid bilayer composed of zwitterionic lipids on a silica surface. The cation 1-octyl-3-methyl imidazolium (OMIM(+)) was shown to remove lipids from the bilayer, increase the roughness to approximately 2.8 nm (~0.2 for stable supported bilayer) and possibly redeposit lipids with entrapped water. The anion bis(trifluoromethylsulfonyl)imide (Tf(2)N(-)) was found to leave distinct defects within the bilayer that had large pore-like interiors which left the surrounding bilayer intact. However, the ionic liquid 1-butyl-1-methyl pyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-Tf(2)N) formed a film over the supported bilayer. This work demonstrates, for the first time, the direct effects common components of ionic liquids have on a supported phospholipids bilayer. PMID:19325765

Evans, Kervin O



A joint theoretical/experimental study of the structure, dynamics, and Li+ transport in bis([tri]fluoro[methane]sulfonyl)imide [T]FSI-based ionic liquids.  


The structure and dynamics of N-butyl-N-methyl pyrrolidinium(+) bis([tri]fluoro[methane]sulfonyl)imide(-) (PYR14(+)-[T]FSI(-)) ionic liquids doped with Li(T)FSI are investigated by combining experimental measurements to molecular dynamics simulations. The polarizable force field calculations indicate that the lithium cations are coordinated by (T)FSI anion oxygens forming lithium adducts stabilized over a large temperature range by strong Li-O bonds. Lithium aggregation is found to be negligible at the doping level considered here (10% mole fraction), and Li(+) diffusion occurs primarily by exchanging the (T)FSI anions in their first coordination shell. The resulting calculated transport properties are in good agreement with the corresponding nuclear magnetic resonance data. PMID:23883042

Solano, C J F; Jeremias, S; Paillard, E; Beljonne, D; Lazzaroni, R



Cytotoxicity estimation of ionic liquids based on their effective structural features.  


Cytotoxicity of a diverse set of 227 ionic liquids (taken from UFT/Merck Ionic Liquids Biological Effects Database) containing 94 imidazolium, 53 pyridinium, 23 pyrrolidinium, 22 ammonium, 15 piperidinium, 10 morpholinium, 5 phosphanium, and 5 quinolinium cations in combination with 25 different types of anions to Leukemia Rat Cell Line (IPC-81) was estimated from their structural parameters using quantitative structure - toxicity relationship "QSTR" methodology. Linear and nonlinear models were developed using genetic algorithm (GA), multiple linear regressions (MLR) and multilayer perceptron neural network (MLP NN) approaches. Robustness and reliability of the constructed models were evaluated through internal and external validation methods. Furthermore, chemical applicability domain was determined via leverage approach. In this work, it was revealed that the cationic moieties make the major contribution to cytotoxicity and the anionic parts play a secondary role in cytotoxicity of the ionic liquids studied here. Structural information represented in this work, can be used for a rational design of safer ILs. PMID:21549407

Fatemi, Mohammad H; Izadiyan, Parisa



Estimation of toxicity of ionic liquids in Leukemia Rat Cell Line and Acetylcholinesterase enzyme by principal component analysis, neural networks and multiple lineal regressions.  


Multiple linear regression (MLR), radial basis network (RB), and multilayer perceptron (MLP) neural network (NN) models have been explored for the estimation of toxicity of ammonium, imidazolium, morpholinium, phosphonium, piperidinium, pyridinium, pyrrolidinium and quinolinium ionic liquid salts in the Leukemia Rat Cell Line (IPC-81) and Acetylcholinesterase (AChE) using only their empirical formulas (elemental composition) and molecular weights. The toxicity values were estimated by means of decadic logarithms of the half maximal effective concentration (EC(50)) in microM (log(10)EC(50)). The model's performances were analyzed by statistical parameters, analysis of residuals and central tendency and statistical dispersion tests. The MLP model estimates the log(10)EC(50) in IPC-81 and AchE with a mean prediction error less than 2.2 and 3.8%, respectively. PMID:18805639

Torrecilla, José S; García, Julián; Rojo, Ester; Rodríguez, Francisco



Spectroscopic and computational analysis of the molecular interactions in the ionic liquid ion pair [BMP]{sup +}[TFSI]{sup -}  

SciTech Connect

1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP]{sup +}[TFSI]{sup ?}) ion pairs were studied using DFT at the B3LYP/6-31 + G(d) level. Nine locally stable conformations of the ion pair were located. In the most stable conformation, [TFSI]{sup ?} takes a cis conformation and lies below the pyrrolidinium ring. Atoms-in-molecules (AIM) and electron density analysis indicated the existence of nine hydrogen bonds. Interaction energies were recalculated at the Second-order Møller–Plesset (MP2) level to show the importance of dispersion interaction. Further investigation through natural bond orbital (NBO) analysis provided insight into the importance of charge transfer interactions in the ion pair. Harmonic vibrations of the ion pair were calculated and compared with vibrations of the free ions as well as the experimental infrared spectrum. Assignments and frequency shifts are discussed in light of the inter-ionic interactions.

Mao, James X.; Nulwala, Hunaid B.; Luebke, David R.; Damodaran, Krishnan



A simultaneous voltammetric temperature and humidity sensor.  


We report the simultaneous measurement of temperature and humidity by analysing square wave voltammetric responses of two ferrocene derivatives, decamethylferrocene (DmFc) and 1,2-diferrocenylethylene (bisferrocene, BisFc) in 1-(2-methoxyethyl)-1-methyl-pyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Moepyrr][FAP]). These two molecules produce three peaks in square wave voltammetry. Through study of the peak potentials of BisFc/BisFc(+) (vs. DmFc/DmFc(+)) and BisFc(+)/BisFc(2+) (vs. DmFc/DmFc(+)) over a temperature range of 298 K to 318 K and humidity range of 1% to 50% using square wave voltammetry, the temperature and humidity dependences of the relative peak potentials were investigated. A reliable method to calculate the humidity and temperature based on the voltammetric experiment is characterised and demonstrated. PMID:23001184

Xiong, Linhongjia; Fletcher, Ai M; Davies, Stephen G; Norman, Sarah E; Hardacre, Christopher; Compton, Richard G



Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers  

NASA Technical Reports Server (NTRS)

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

Tigelaar, Dean M.; Meador, Mary Ann B.; Bennett, William R.



Temperature effects on the electrochemical behavior of spinel LiMn(2)O(4) in quaternary ammonium-based ionic liquid electrolyte.  


Temperature dependence of the physiochemical characteristics of a room-temperature ionic liquid consisting of trimethylhexylammonium (TMHA) cation and bis(trifluoromethane) sulfonylimide (TFSI) anion containing different concentrations of LiTFSI salt was examined. Electrochemical properties of a spinel LiMn(2)O(4) electrode in 1 M LiTFSI/TMHA-TFSI ionic electrolyte were investigated at different temperatures by using cyclic voltammetry, galvanostatic measurements, and electrochemical impedance spectroscopy. The Li/ionic electrolyte/LiMn(2)O(4) cell exhibited satisfactory electrochemical properties with a discharge capacity of 108.2 mA h/g and 91.4% coulombic efficiency in the first cycle under room temperature. At decreased temperature, reversible capacity of the cell could not attain a satisfactory value due to the high internal resistance of the cell and the large activation energy for lithium ion transfer through the electrode/electrolyte interface. Anodic electrolyte oxidation results in the decrease of coulombic efficiency with increasing temperature. Irreversible structural conversion of the spinel LiMn(2)O(4) in the ionic electrolyte, possibly associated with the formation of TMHA intercalated compounds and/or Jahn-Teller distortion, was considered to be responsible for the electrochemical decay with increasing cycles. PMID:16852714

Zheng, Honghe; Zhang, Hucheng; Fu, Yanbao; Abe, Takeshi; Ogumi, Zempachi



Absorption ability and kinetics of a liquid electrolyte in PVDF-HFP copolymer containing or not SiO 2  

NASA Astrophysics Data System (ADS)

Gel polymer electrolytes have been prepared from PVDF-HFP copolymer with various silica contents incorporating Gamma valerolactone (VL) or VL/EC (80/20 in mole) (EC: ethylene carbonate) solutions of lithium bis(trifluoromethane sulfone) imide (LiTFSI). The influence of temperature, salt content and silica addition on the kinetics of absorption and wettability of the copolymer has been investigated. An empirical model, taking into account gel swelling during the absorption allows us to relate, at constant temperature, the wetting time and the volumetric fraction of trapped electrolyte, which is a critical factor for ionic conductivity of the gel. Increasing the silica content in the dry copolymer increases the porosity and consequently the rate of absorption and thus the amount of incorporated liquid phase at saturation. To a lower extent, an increase in the temperature of absorption has the same effects. The prepared gels have good mechanicals properties and conductivities. As an example, a gel of composition: PVDF- HFP/ SiO2/ VL/ EC/ LiTFSI of molar percentages 36/6.7/42/10.5/4.8 exhibits a conductivity of 2.9 mS cm - 1 at 293 K.

Caillon-Caravanier, M.; Claude-Montigny, B.; Lemordant, D.; Bosser, G.


Gas Permeation through Polystyrene-Poly(ethylene oxide) Block Copolymers  

NASA Astrophysics Data System (ADS)

Lithium air batteries are a potential technology for affordable energy storage. They consist of a lithium metal anode and a porous air cathode separated by a solid polymer electrolyte membrane, such as PEO/LiTFSI (PEO = poly(ethylene oxide), LiTFSI = lithium bis-trifluoromethane sulfonimide). For extended operation of such a battery, the polymer electrolyte must conduct lithium ions while blocking electrons and gases present in air. In order to maintain a pressure difference the membrane must be mechanically robust, which can be achieved by incorporating the PEO into a block copolymer with a glassy block such as PS (PS = polystyrene). To protect the lithium electrode, the membrane must have low permeability to gases in air such as CO2, N2, and O2. We have therefore studied the permeation of pure gases through a PS-PEO block copolymer. A high molecular weight, symmetric block copolymer with a lamellar morphology was used to cast free-standing membranes. Gas permeability was measured through these membranes with a standard, pressure-based technique. A model was developed to account for transport through the polymer membrane consisting of semi-crystalline PEO lamellae and amorphous PS lamellae. PEO crystallinity was extracted from the permeation model and compares well with values from differential scanning calorimetry measurements.

Hallinan, Daniel, Jr.; Minelli, Matteo; Giacinti-Baschetti, Marco; Balsara, Nitash



Darifenacin hydro-bromide.  


In the title compound {systematic name: (S)-3-[(aminocar-bonyl)diphenylmethyl]-1-[2-(2,3-di-hy-dro-benzofuran-5-yl)ethyl]pyrrolidinium bromide}, C(28)H(31)N(2)O(2) (+)·Br(-), the pyrrolidine rings adopts an envelope conformation. The two phenyl rings make a dihedral angle of 72.5?(1)°. The four coplanar atoms of the pyrrolidine ring makes dihedral angles of 33.1?(2) and 82.8?(2)° with the two phenyl rings. The mol-ecular conformation is influenced by a C-H?O inter-action. In the crystal packing, there are two N-H?Br hydrogen bonds running in opposite directions. They appear to form C(10) and C(9) chain motifs in the unit cell. In addition, the mol-ecular packing is further stabilized by C-H?Br and C-H?O hydrogen bonds. The C atom bonded to the benzofuran ring system is disordered in a 0.66:0.34 ratio. PMID:21583148

Selvanayagam, S; Sridhar, B; Ravikumar, K



Single kaolinite nanometer layers prepared by an in situ polymerization-exfoliation process in the presence of ionic liquids.  


A simple chemical route for the exfoliation of kaolinite in the presence of polymerizable ionic liquids and the resulting obtainment of exfoliated nanocomposites is reported. The exfoliation was achieved using three different ionic liquids structurally bearing a vinyl group: 1-methyl-3-(4-vinylbenzyl)imidazolium chloride salt (IL_1), 1-methyl-1-(4-vinylbenzyl)pyrrolidinium chloride (IL_2), and 1-methyl-3-vinyl imidazolium iodide (IL_3) and a urea-kaolinite intercalate as precursor. The reaction was done in one step by an in situ polymerization-exfoliation process. (13)C CP/MAS NMR spectra confirmed the spontaneous polymerization of the ionic liquid during the exfoliation process to afford atactic polystyrene derivatives in the case of IL_1 and IL_2. The amount of organic material in the exfoliated nanocomposite was close to 30% as shown by thermal gravimetric analysis. This amount is small in comparison to the amount obtained when the exfoliation was done using sodium polyacrylate (Letaief and Detellier, Langmuir2009, 25, 10975). XRD as well as SEM analysis confirmed a total exfoliation of the kaolinite when the reaction was done using urea kaolinite, whereas a microcomposite, made predominantly of kaolinite platelet aggregates dispersed in the polymeric matrix, was formed when dimethylsulfoxide kaolinite was used as the precursor. PMID:22073925

Letaief, Sadok; Leclercq, Jérôme; Liu, Yun; Detellier, Christian



Nonaborane and decaborane cluster anions can enhance the ignition delay in hypergolic ionic liquids and induce hypergolicity in molecular solvents.  


The dissolution of nido-decaborane, B10H14, in ionic liquids that are hypergolic (fuels that spontaneously ignite upon contact with an appropriate oxidizer), 1-butyl-3-methylimidazolium dicyanamide, 1-methyl-4-amino-1,2,4-triazolium dicyanamide, and 1-allyl-3-methylimidazolium dicyanamide, led to the in situ generation of a nonaborane cluster anion, [B9H14](-), and reductions in ignition delays for the ionic liquids suggesting salts of borane anions could enhance hypergolic properties of ionic liquids. To explore these results, four salts based on [B10H13](-) and [B9H14](-), triethylammonium nido-decaborane, tetraethylammonium nido-decaborane, 1-ethyl-3-methylimidazolium arachno-nonaborane, and N-butyl-N-methyl-pyrrolidinium arachano-nonaborane were synthesized from nido-decaborane by reaction of triethylamine or tetraethylammonium hydroxide with nido-decaborane in the case of salts containing the decaborane anion or via metathesis reactions between sodium nonaborane (Na[B9H14]) and the corresponding organic chloride in the case of the salts containing the nonaborane anion. These borane cluster anion salts form stable solutions in some combustible polar aprotic solvents such as tetrahydrofuran and ethyl acetate and trigger hypergolic reactivity of these solutions. Solutions of these salts in polar protic solvents are not hypergolic. PMID:24716643

McCrary, Parker D; Barber, Patrick S; Kelley, Steven P; Rogers, Robin D



Effect of cation type, alkyl chain length, adsorbate size on adsorption kinetics and isotherms of bromide ionic liquids from aqueous solutions onto microporous fabric and granulated activated carbons.  


The adsorption from aqueous solution of imidazolium, pyrrolidinium and pyridinium based bromide ionic liquids (ILs) having different alkyl chain lengths was investigated on two types of microporous activated carbons: a fabric and a granulated one, well characterized in terms of surface chemistry by "Boehm" titrations and pH of point of zero charge measurements and of porosity by N2 adsorption at 77 K and CO2 adsorption at 273 K. The influence of cation type, alkyl chain length and adsorbate size on the adsorption properties was analyzed by studying kinetics and isotherms of eight different ILs using conductivity measurements. Equilibrium studies were carried out at different temperatures in the range [25-55 °C]. The incorporation of ILs on the AC porosity was studied by N2 adsorption-desorption measurements at 77 K. The experimental adsorption isotherms data showed a good correlation with the Langmuir model. Thermodynamic studies indicated that the adsorption of ILs onto activated carbons was an exothermic process, and that the removal efficiency increased with increase in alkyl chain length, due to the increase in hydrophobicity of long chain ILs cations determined with the evolution of the calculated octanol-water constant (Kow). The negative values of free energies indicated that adsorption of ILs with long chain lengths having hydrophobic cations was more spontaneous at the investigated temperatures. PMID:24929502

Hassan, Safia; Duclaux, Laurent; Lévêque, Jean-Marc; Reinert, Laurence; Farooq, Amjad; Yasin, Tariq



Inhibition of ( sup 3 H)dopamine uptake into rat striatal slices by quaternary N-methylated nicotine metabolites  

SciTech Connect

The effects of quaternary N-methylated nicotine derivatives were examined on in vitro uptake of ({sup 3}H)dopamine (({sup 3}H)DA) in rat striatal slices. Striatal slices were incubated with a 10 {mu}M concentration of the following compounds: N-methylnicotinium, N-methylnornicotinium, N-methylcotininium, N,N{prime}-dimethylnicotinium and N{prime}-methylnicotinium salts. The results clearly indicated that significant inhibition of ({sup 3}H)DA uptake occurred with those compounds possessing a N-methylpyridinium group; whereas, compounds that were methylated at the N{prime}-pyrrolidinium position were less effective or exhibited no inhibition of ({sup 3}H)DA uptake. The results suggest that high concentrations of quaternary N-methylated nicotine metabolites which are structurally related to the neurotoxin MPP{sup +}, and which may be formed in the CNS, may protect against Parkinson's Disease and explain the inverse relationship between smoking and Parkinsonism reported in epidemiologic studies.

Dwoskin, L.P.; Leibee, L.L.; Jewell, A.L.; Fang, Zhaoxia; Crooks, P.A. (Univ. of Kentucky, Lexington (United States))



Factors stabilizing the gas-phase ionic species of crystals of organic salts - Experimental and theoretical study  

NASA Astrophysics Data System (ADS)

The paper studied factors of the gas phase (GP) ionic stabilization of molecular organic crystals of salts. The single crystal X-ray diffraction, electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) mass spectrometric (MS) methods are employed. The GP phenomena are explained by the comprehensive quantum-chemical theoretical models, providing significant information for the electronic structures and thermodynamics of the observed MS species. The n-chloro-alkyl aliphatic heterocyclic 5-sulfosalicylates i.e. 1-(2-chloroethyl) pyrrolidinium 5-sulfosalicylicilate (1), 1-(2-chloroethyl)-piperidinium 5-sulfosalicylicilate (2), and 1-(3-chloropropyl) piperidinium 5-sulfosalicylicilate (3) are examined. The ionic systems that contain N+H-heterocyclic fragments, a complex MS image variety of monocations, quaternary ammonium dications and hydrogen bonded molecular complexes revealed. Their stabilization is explained by proton transfer (PT), charge-transfer (CT) and Jahn-Teller (JT) effects. The 4-(2-chloroethyl) morpholinium hydrochloride crystals (4) yielded quaternary ammonium adduct which structure is crystallographically determined. In parallel the GP stabilized ions of 4 are analyzed. The complementary application of the single-crystal X-ray diffraction and MS methods provided unique structural evidences in condenses and in the GP able to understand the competitive intramolecular and environmental factors contributing to the thermodynamics stability of the ionic species. Therefore, the data reported are helped for more comprehensive knowledge of the basic mass spectrometric GP and phase transition phenomena with both its methodological development and used robust analytical technique application.

Ivanova, Bojidarka B.; Spiteller, Michael



Correlating the structure and composition of ionic liquids with their toxicity on Vibrio fischeri: A systematic study.  


A systematic screening of the toxicity of ionic liquids (IL) towards Vibrio fischeri, a bioluminescent marine bacteria generally used in ecotoxicological bioassays, was carried out. The objectives of this work were to find hydrophilic or hydrophobic low toxicity IL and to investigate structure-toxicity relationship of IL. Toxicity of 54 IL to V. fischeri have been measured, some referring to new IL based on quinuclidinol or tropinol and some to generic IL (i.e., imidazolium, pyridinium, pyrrolidinium or piperidinium). For 47 of them, toxicity values have not been reported elsewhere. Water-soluble IL containing hydrophilic anions halide, thiocyanate, dicyanamide, trifluoromethansulfonate were studied. Some IL were found to exhibit very low toxicity towards V. fisheri. Hydrophobic IL based on bis(trifluoromethanesulfonyl)imide, tetrafluoroborate tetraphenylborate and tetracyanoborate were also studied. Toxicity was measured in a consistent way starting from aqueous solutions saturated with IL. The least toxic hydrophobic IL found in this study was [EMIM][B(CN)(4)]. A multifactorial analysis was found to be convenient for finding relevant structure parameters influencing the toxicity of IL. From this analysis, the planarity of the cation ring appeared to be a relevant parameter. Finally, good linear correlations were found when toxicity of IL was plotted either against the number of aliphatic carbons surrounding a pyridinium cation or the total number of carbons of a cation. PMID:22417395

Viboud, Sylvie; Papaiconomou, Nicolas; Cortesi, Aurélien; Chatel, Grégory; Draye, Micheline; Fontvieille, Dominique



Extraction Separation of Rare-Earth Ions via Competitive Ligand Complexations between Aqueous and Ionic-Liquid Phases  

SciTech Connect

The extraction separation of rare earth elements is the most challenging separation processes in hydrometallurgy and advanced nuclear fuel cycles. The TALSPEAK process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Komplexes) is a prime example of these separation processes. The objective of this paper is to explore the use of ionic liquids (ILs) for the TALSPEAK-like process, to further enhance its extraction efficiencies for lanthanides, and to investigate the potential of using this modified TALSPEAK process for separation of lanthanides among themselves. Eight imidazolium ILs ([Cnmim][NTf2] and [Cnmim][BETI], n=4,6,8,10) and one pyrrolidinium IL ([C4mPy][NTf2]) were investigated as diluents using di(2-ethylhexyl)phosphoric acid (HDEHP) as an extractant for separation of lanthanide ions from aqueous solutions of 50 mM glycolic acid or citric acid and 5 mM diethylenetriamine pentaacetic acid (DTPA). The extraction efficiencies were studied in comparison with diisopropylbenzene (DIPB), an organic solvent used as diluent for the conventional TALSPEAK extraction system. Excellent extraction efficiencies and selectivities were found for a number of lanthanide ions using HDEHP as an extractant in these ILs. The effects of different alkyl chain lengths in the cations of ILs and anions on extraction efficiencies and selectivities of lanthanide ions are also presented in this paper.

Luo, Huimin [ORNL; Sun, Xiaoqi [ORNL; Bell, Jason R [ORNL; Dai, Sheng [ORNL



Separation of carbon dioxide from nitrogen or methane by supported ionic liquid membranes (SILMs): influence of the cation charge of the ionic liquid.  


Supported ionic liquid membranes (SILMs) are promising tools for the separation of carbon dioxide from other gases. In this paper, new imidazolium, pyrrolidinium, piperidinium, and morpholinium ionic liquids with a triethylene glycol side chain and tosylate anions, as well as their symmetrical dicationic analogues, have been synthesized and incorporated into SILMs. The selectivities for CO2/N2 and CO2/CH4 separations have been measured. The selectivities exhibited by the dicationic ionic liquids are up to two times higher than the values of the corresponding monocationic ionic liquids. Quantum chemical calculations have been used to investigate the difference in the interaction of carbon dioxide with monocationic and dicationic ionic liquids. The reason for the increased gas separation selectivity of the dicationic ionic liquids is two-fold: (1) a decrease in permeance of nitrogen and methane through the ionic liquid layer, presumably due to their less favorable interactions with the gases, while the permeance of carbon dioxide is reduced much less; (2) an increase in the number of interaction sites for the interactions with the quadrupolar carbon dioxide molecules in the dicationic ionic liquids, compared to the monocationic analogues. PMID:24199938

Hojniak, Sandra D; Khan, Asim Laeeq; Hollóczki, Oldamur; Kirchner, Barbara; Vankelecom, Ivo F J; Dehaen, Wim; Binnemans, Koen



Structural and electrochemical properties of succinonitrile-based gel polymer electrolytes: role of ionic liquid addition.  


Experimental studies on the novel compositions of gel polymer electrolytes, comprised of plastic crystal succinonitrile (SN) dispersed with pyrrolidinium and imidazolium-based ionic liquids (ILs) entrapped in a host polymer poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP), are reported. The gel electrolytes are in the form of free-standing films with excellent mechanical, thermal, and electrochemical stability. The introduction of even a small content (~1 wt %) of ionic liquid (1-butyl-1-methylpyrrolidinium bis(trifluoromethyl-sulfonyl)imide (BMPTFSI) or 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMITf) in the PVdF-HFP/SN system (1:4 w/w) enhances the electrical conductivity by 4 orders of magnitude, that is, from ~10(-7) to ~10(-3) S cm(-1) at room temperature. The structural changes due to the entrapment of SN or SN/ILs mixtures and ion-SN-polymer interactions are examined by Fourier transform infrared (FTIR)/Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and differential scanning calorimmetry (DSC). Various physicochemical properties and fast ion conduction in the gel polymer membranes show their promising characteristics as electrolytes in different ionic devices including supercapacitors. PMID:23758408

Suleman, Mohd; Kumar, Yogesh; Hashmi, S A



Nonhumidified intermediate temperature fuel cells using protic ionic liquids.  


In this paper, the characterization of a protic ionic liquid, diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]), as a proton conductor for a fuel cell and the fabrication of a membrane-type fuel cell system using [dema][TfO] under nonhumidified conditions at intermediate temperatures are described in detail. In terms of physicochemical and electrochemical properties, [dema][TfO] exhibits high activity for fuel cell electrode reactions (i.e., the hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR)) at a Pt electrode, and the open circuit voltage (OCV) of a liquid fuel cell is 1.03 V at 150 degrees C, as has reported in ref 27. However, diethylmethylammonium bis(trifluoromethane sulfonyl)amide ([dema][NTf(2)]) has relatively low HOR and ORR activity, and thus, the OCV is ca. 0.7 V, although [dema][NTf(2)] and [dema][TfO] have an identical cation ([dema]) and similar thermal and bulk-transport properties. Proton conduction occurs mainly via the vehicle mechanism in [dema][TfO] and the proton transference number (t(+)) is 0.5-0.6. This relatively low t(+) appears to be more disadvantageous for a proton conductor than for other electrolytes such as hydrated sulfonated polymer electrolyte membranes (t(+) = 1.0). However, fast proton-exchange reactions occur between ammonium cations and amines in a model compound. This indicates that the proton-exchange mechanism contributes to the fuel cell system under operation, where deprotonated amines are continuously generated by the cathodic reaction, and that polarization of the cell is avoided. Six-membered sulfonated polyimides in the diethylmethylammonium form exhibit excellent compatibility with [dema][TfO]. The composite membranes can be obtained up to a [dema][TfO] content of 80 wt % and exhibit good thermal stability, high ionic conductivity, and mechanical strength and gas permeation comparable to those of hydrated Nafion. H(2)/O(2) fuel cells prepared using the composite membranes can successfully operate at temperatures from 30 to 140 degrees C under nonhumidified conditions, and a current density of 250 mA cm(-2) is achieved at 120 degrees C. The protic ionic liquid and its composite membrane are a possible candidate for an electrolyte of a H(2)/O(2) fuel cell that operates under nonhumidified conditions. PMID:20578771

Lee, Seung-Yul; Ogawa, Atsushi; Kanno, Michihiro; Nakamoto, Hirofumi; Yasuda, Tomohiro; Watanabe, Masayoshi



Raman spectroscopic study, DFT calculations and MD simulations on the conformational isomerism of N-alkyl-N-methylpyrrolidinium bis-(trifluoromethanesulfonyl) amide ionic liquids.  


The conformational behaviors of N-alkyl-N-methylpyrrolidinium bis-(trifluoromethanesulfonyl) amide ionic liquids (alkyl; propyl and butyl, [P(1n)][TFSA]; n = 3 and 4) were studied by Raman spectroscopy in the frequency range of 200-1700 cm(-1) at different temperatures. Observed Raman spectra in the frequency range 870-960 cm(-1) for [P(13)][TFSA] and at 860-950 cm(-1) for [P(14)][TFSA] depend on the temperature, indicating that pseudo rotational isomerization of the pyrrolidinium ring exists in the ionic liquids. DFT calculations revealed that the pseudo rotational potential energy surfaces for P(13)(+) and P(14)(+) ions were similar to each other, i.e., the e6 isomer is the global minimum, whereas the three other isomers e1, e4, and e5 are ca. 3 kJ mol(-1) higher in energy. Optimized geometries with no imaginary frequency were successfully obtained for the e6, e1, and e4 isomers. For both cations, the theoretical Raman spectra of the e6 isomers reproduce well the observed data. To explain their observed Raman spectra in a reasonable way, it is necessary to consider one or more species as predicted by DFT calculations, i.e., the e4 isomer of P(13)(+) rather than the e1, or the e1 isomer of P(14)(+) rather than the e4. In addition, the torsion energy potentials of the alkyl chains of the cations were scanned by DFT calculations. It turns out that the alkyl chains of the cations prefer all trans conformations. It should be emphasized that the alkyl chains of the pyrrolidinium cations show remarkably different conformational behaviors comparing with those of the imidazolium. The isomerization enthalpies Delta(iso)H degrees from the e6 to the e4 isomer of P(13)(+) and to e1 of P(14)(+) were reasonably estimated from the temperature dependence of Raman spectra based on our proposed assignments to be 2.9 kJ mol(-1) for P(13)(+) and 4.2 kJ mol(-1) for P(14)(+), respectively. Thus evaluated experimental Delta(iso)H degrees values, which may contain some uncertainties, are in agreement with those predicted by DFT calculations and MD simulations suggesting that pseudo rotational isomerization equilibria are established in the examined N-alkyl-N-methylpyrrolidinium ionic liquids. The conformational behavior of TFSA(-) was also investigated. The Delta(iso)H degrees from the trans (trifluoromethyl groups on opposite sides of the S-N-S plane) to the cis isomer were evaluated to be 4.2 kJ mol(-1) for [P(13)][TFSA] and 3.5 kJ mol(-1) for [P(14)][TFSA], respectively, which are similar to that for the 1-ethyl-3methylimidazolium ionic liquid. PMID:19281201

Umebayashi, Yasuhiro; Mitsugi, Takushi; Fujii, Kenta; Seki, Shiro; Chiba, Kazumi; Yamamoto, Hideo; Canongia Lopes, José N; Pádua, Agílio A H; Takeuchi, Munetaka; Kanzaki, Ryo; Ishiguro, Shin-ichi



Functionalized fullerenes mediate photodynamic killing of cancer cells: Type I versus Type II photochemical mechanism  

PubMed Central

Photodynamic therapy (PDT) employs the combination of non-toxic photosensitizers (PS) and harmless visible light to generate reactive oxygen species (ROS) and kill cells. Most clinically studied PS are based on the tetrapyrrole structure of porphyrins, chlorins and related molecules, but new non-tetrapyrrole PS are being sought. Fullerenes are soccer-ball shaped molecules composed of sixty or seventy carbon atoms and have attracted interest in connection with the search for biomedical applications of nanotechnology. Fullerenes are biologically inert unless derivatized with functional groups, whereupon they become soluble and can act as PS. We have compared the photodynamic activity of six functionalized fullerenes with 1, 2, or 3 hydrophilic or 1, 2, or 3 cationic groups. The octanol-water partition coefficients were determined and the relative contributions of Type I photochemistry (photogeneration of superoxide in the presence of NADH) and Type II photochemistry (photogeneration of singlet oxygen) were studied by measurement of oxygen consumption, 1270-nm luminescence and EPR spin-trapping of the superoxide product. We studied three mouse cancer cell lines: (J774, LLC and CT26) incubated for 24 h with fullerenes and illuminated with white light. The order of effectiveness as PS was inversely proportional to the degree of substitution of the fullerene nucleus for both the neutral and cationic series. The mono-pyrrolidinium fullerene was the most active PS against all cell lines and induced apoptosis 4–6 hours after illumination. It produced diffuse intracellular fluorescence when dichlorodihydrofluorescein was added as an ROS probe suggesting a Type I mechanism for phototoxicity. We conclude that certain functionalized fullerenes have potential as novel PDT agents and phototoxicity may be mediated both by superoxide and by singlet oxygen.

Mroz, Pawel; Pawlak, Anna; Satti, Minahil; Lee, Haeryeon; Wharton, Tim; Gali, Hariprasad; Sarna, Tadeusz; Hamblin, Michael R.



CNT loading into cationic cholesterol suspensions show improved DNA binding and serum stability and ability to internalize into cancer cells  

NASA Astrophysics Data System (ADS)

Methods which disperse single-walled carbon nanotubes (SWNTs) in water as ‘debundled’, while maintaining their unique physical properties are highly useful. We present here a family of cationic cholesterol compounds (Chol+) {Cholest-5en-3?-oxyethyl pyridinium bromide (Chol-PB+), Cholest-5en-3?-oxyethyl N-methyl pyrrolidinium bromide (Chol-MPB+), Cholest-5en-3?-oxyethyl N-methyl morpholinium bromide (Chol-MMB+) and Cholest-5en-3?-oxyethyl diazabicyclo octanium bromide (Chol-DOB+)}. Each of these could be easily dispersed in water. The resulting cationic cholesterol (Chol+) suspensions solubilized single-walled carbon nanotubes (SWCNTs) by the non-specific physical adsorption of Chol+ to form stable, transparent, dark aqueous suspensions at room temperature. Electron microscopy reveals the existence of highly segregated CNTs in these samples. Zeta potential measurements showed an increase in potential of cationic cholesterol aggregates on addition of CNTs. The CNT-Chol+ suspensions were capable of forming stable complexes with genes (DNA) efficiently. The release of double-helical DNA from such CNT-Chol+ complexes could be induced upon the addition of anionic micellar solution of SDS. Furthermore, the CNT-based DNA complexes containing cationic cholesterol aggregates showed higher stability in fetal bovine serum media at physiological conditions. Confocal studies confirm that CNT-Chol+ formulations adhere to HeLa cell surfaces and get internalized more efficiently than the cationic cholesterol suspensions alone (devoid of any CNTs). These cationic cholesterol-CNT suspensions therefore appear to be a promising system for further use in biological applications.

Chhikara, Bhupender S.; Misra, Santosh K.; Bhattacharya, Santanu



Muscarinic subtype affinity and functional activity profile of 1-methyl-2-(2-methyl-1,3-dioxolan-4-yl)pyrrolidine and 1-methyl-2-(2-methyl-1,3-oxathiolan-5-yl)pyrrolidine derivatives.  


Starting from two previously studied muscarinic full agonists, characterized by a 1,3-dioxolane ((+)-1) and a 1,3-oxathiolane ((+)-2) cycle, two new series of muscarinic ligands were designed, obtained by the steric complication of the parent compounds produced by freezing the aminoalkyl chain into a pyrrolidine ring. Both tertiary amines and the corresponding iodomethyl derivatives were synthesised and studied, and several compounds of the series which behaved as muscarinic agonists have been selected, on the basis of preliminary binding experiments on rat cortex homogenates, for the present work. Results are presented obtained from testing the affinity of the selected compounds against cloned human muscarinic receptors expressed in CHO cells, in order to evaluate subtype selectivity. Their functional activity on classical models of M1-M4 receptors, in guinea pig and rabbit tissues is also reported. With respect to parent compounds, the new molecules present some selectivity toward hm2 receptors; fair M2 selectivity is also evident in functional studies, where these compounds behave as partial agonists. Among the other compounds of the series (2S, 4'R, 2'S)-1,1-dimethyl-2-(2-methyl-1,3-dioxolan-4-yl)pyrrolidinium iodide (-)-3 and (2R, 5'S, 2'S)-1-methyl-2-(2-methyl-1,3-oxathiolan-5-yl)pyrrolidine (+)-5 present a promising pharmacological profile. Compound (-)-3 shows modest hm2 selectivity in binding experiments but a clearcut M2 selectivity in functional tests, where it behaves as a weak antagonist on M1 and M4 subtypes, as a weak full agonist on the M3 subtype and as a potent partial agonist on M2 subtype. Tertiary amine (+)-5 presents a quite similar profile but appears more interesting since, lacking a permanent charge on the nitrogen atom, it may represent an interesting tool to study CNS muscarinic receptors. Our results confirm that sterical complication of parent compounds (+)-1 and (+)-2 produces more selective muscarinic agonists. PMID:15896343

Dei, Silvia; Angeli, Piero; Bellucci, Cristina; Buccioni, Michela; Gualtieri, Fulvio; Marucci, Gabriella; Manetti, Dina; Matucci, Rosanna; Romanelli, Maria Novella; Scapecchi, Serena; Teodori, Elisabetta



Effects of some isomers and analogues of nicotine on junctional transmission  

PubMed Central

A number of isomers and homologues of nicotine, (2-, 3- and 4-pyridylmethyl)- and [2-(2-, 3- and 4-pyridyl)ethyl]- dialkylamines and trialkylammonium salts, have been prepared. They have been tested for their ability to act like acetylcholine in causing contracture of the chick biventer-cervicis and, some of them, for their ability to stimulate the superior cervical ganglion of the cat, causing contracture of the nictitating membrane. All the compounds have been tested for their ability to block transmission on the superior cervical ganglion of the cat and on the rat diaphragm preparation, and most of them for ability to inhibit the enzymatic hydrolysis of acetylcholine, using an acetone-powder of dog caudate nucleus as a source of acetylcholinesterase. The dissociation constants of the compounds have been measured by electrometric titration. The dissociation constants were used to compute the amount of monovalent ion present in the conditions of the biological tests, and the activities of the compounds have, accordingly, been compared on an ionic, as well as on a molecular, basis. The two sets of figures do not differ greatly. Trimethyl[2-(3-pyridyl)ethyl]ammonium (23) was the most potent compound on the chick and cat preparations. On an ionic basis (that is, compared with the monovalent nicotinium ion) this was 2.6 times as active as nicotine on the chick biventer and 11 times as active on the cat superior cervical ganglion. On the rat diaphragm it was 7.1 times as active as nicotine and less active than 1-methyl-1-(3-pyridylmethyl)-pyrrolidinium (26) (9.5 times the nicotinium ion) and trimethyl(4-pyridylmethyl)-ammonium (21) (11 times). The relationships between structure and dissociation constant, anticholinesterase activity, and activity in the pharmacological tests have been discussed.

Barlow, R. B.; Hamilton, J. T.



Identification of degradation products of ionic liquids in an ultrasound assisted zero-valent iron activated carbon micro-electrolysis system and their degradation mechanism.  


Ionic liquids (ILs) have potential applications in many areas of chemical industry because of their unique properties. However, it has been shown that the ILs commonly used to date are toxic and not biodegradable in nature, thus development of efficient chemical methods for the degradation of ILs is imperative. In this work, degradation of imidazolium, piperidinium, pyrrolidinium and morpholinium based ILs in an ultrasound and zero-valent iron activated carbon (ZVI/AC) micro-electrolysis system was investigated, and some intermediates generated during the degradation were identified. It was found that more than 90% of 1-alkyl-3-methylimidazolium bromide ([Cnmim]Br, n = 2, 4, 6, 8, 10) could be degraded within 110 min, and three intermediates 1-alkyl-3-methyl-2,4,5-trioxoimidazolidine, 1-alkyl-3-methylurea and N-alkylformamide were detected. On the other hand, 1-butyl-1-methylpiperidinium bromide ([C4mpip]Br), 1-butyl-1-methylpyrrolidinium bromide ([C4mpyr]Br) and N-butyl-N-methylmorpholinium bromide ([C4mmor]Br) were also effectively degraded through the sequential oxidization into hydroxyl, carbonyl and carboxyl groups in different positions of the butyl side chain, and then the N-butyl side chain was broken to form the final products of N-methylpiperidinium, N-methylpyrrolidinium and N-methylmorpholinium, respectively. Based on these intermediate products, degradation pathways of these ILs were suggested. These findings may provide fundamental information on the assessment of the factors related to the environmental fate and environmental behavior of these commonly used ILs. PMID:23623468

Zhou, Haimei; Lv, Ping; Shen, Yuanyuan; Wang, Jianji; Fan, Jing



The Influence of receptor kinetics on the onset and duration of action and the therapeutic index of NVA237 and tiotropium.  


Studies under nonphysiological conditions suggest that long receptor residency time is responsible for the 24-h duration of action of the long-acting muscarinic antagonist (LAMA) tiotropium. Our aim was to determine how clinically relevant dissociation rates under more physiological conditions influence the differences in onset of action between tiotropium and 3-[(cyclopentylhydroxyphenylacetyl oxy]-1,1-dimethyl-pyrrolidinium bromide (NVA237), a once-daily dry-powder formulation of the LAMA glycopyrronium bromide in development for chronic obstructive pulmonary disease. In addition, we have investigated kinetic selectivity at each of the muscarinic receptor subtypes to determine whether the improved cardiovascular therapeutic index obtained with NVA237 in animal models is attributable to differences in kinetic rate constants. The binding of radioligand [3H]N-methyl-scopolamine was measured in the presence/absence of several concentrations of unlabeled competitors, and data were analyzed using a competition kinetic model to provide on/off rates for the competitor. We found shorter dissociation half-lives for NVA237 and tiotropium under physiological (11.4 and 46.2 min, respectively) versus nonphysiological conditions (173 and 462 min, respectively). NVA237 had a more rapid onset of action (3-4.8 times) versus tiotropium, determined in an vitro calcium and rat tracheal strip assay. Simulations suggested that the more rapid onset of NVA237 action could be explained by differences in kinetic parameters. NVA237 had greater equilibrium binding and kinetic selectivity for muscarinic type 3 (M3) versus muscarinic type 2 (M2) receptors, with a faster off rate from M2 versus M3 receptors than tiotropium, potentially affording it a more favorable therapeutic index. This study suggests that the 24-h duration of action of NVA237 and tiotropium is not solely the result of their slow dissociation from the M3 receptor and highlights the importance of conducting in vitro experiments in conditions reflecting those in vivo. PMID:22854200

Sykes, David A; Dowling, Mark R; Leighton-Davies, Juliet; Kent, Toby C; Fawcett, Lindsay; Renard, Emilie; Trifilieff, Alexandre; Charlton, Steven J



Probing Local Environments in Ionic Liquids  

NASA Astrophysics Data System (ADS)

The polarity and solvation properties were investigated for four ionic liquids with non-aromatic cation. The four ionic liquids studied were: N-methyl-N-butylpyrrolidinium bis(trifluoromethylsulfonyl)-imide (Pyrr14+/NTf2-), N-methyl-N-ethoxyethylpyrrolidinium bis(trifluoromethylsulfonyl)-imide (Pyrr1(202)+/NTf2-), N-methyl-tri-N-butylammonium bis(trifluoromethylsulfonyl) -imide (N1444+/NTf2-) and N-hexyl-tri-N-butylammonium bis(trifluoromethylsulfonyl) -imide (N6444+/NTf2-). The ammonium based ILs exhibit slightly higher polarity than pyrrolidinium based ILs. The solvation dynamics of the fluorescence probe molecule Coumarin 153 exhibits multi-exponential character in all four ILs. The observed solvation dynamics occur on timescales orders of magnitude longer than for most organic solvents. The reorientational dynamics investigated by method of time-resolved fluorescence anisotropy decay is faster than predicted by hydrodynamic theory. The ionic liquid/water interaction were characterized for hydrophobic and water- miscible ionic liquids. The two ionic liquids studied were: 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (Pyrr14+ /NTf 2-) and 1-butyl-1-methylpyrrolidinium Trifloromethylsulfonate (Pyrr14+/OTf-). The concentration dependence of water proton chemical shift deltaH2O reveals different water-anion interaction in these two ILs. The diffusion properties were investigated in the system IL/water by pulse gradient DOSY experiments. The diffusional behavior of cations and anions is very similar whereas water exhibits anomalously high diffusion rate. The diffusional properties of water are different in two ILs. The ratio D H2O / Dcation is higher for more hydrophobic Pyrr14 + /NTf2- that confirms weaker water-anion interaction in this liquid.

Fadeeva, Tatiana A.


Symposium Report. Battery materials : amorphous carbons and polymer electrolytes.  

SciTech Connect

The motivation for research in battery materials lies in the expanding consumer demand for compact, high-energy density power sources for portable electronic devices, and environmental issues such as global warming and air pollution that have provided the impetus for mass transportation by electric vehicles. The Battery Materials Symposium, chaired by Jacqueline Johnson (ANL), focused on three topics: the structure and electrochemical properties of new and existing electrolytes, devices for fabricating and investigating thin films, and large-scale computer simulations. The symposium opened with a presentation by the author on a recently invented device for in situ investigations of batteries using nuclear magnetic resonance. Joop Schoonman (Delft University) described several methods for preparing and analyzing thin films made of solid electrolytes. These methods included chemical vapor deposition, electrostatic spray deposition and the Solufill process. Aiichiro Nakano discussed large-scale (10 million to 2 billion atoms) computer simulations of polymer and ceramic systems. An overview was given of a DOE Cooperative Research 2000 program, in the initial stages, that was set up to pursue these atomistic simulations. Doug MacFarlane (Monash University) described conductive plastic crystals based on pyrrolidinium imides. Joseph Pluth (U of Chicago) presented his recent crystallographic studies of Pb compounds found in the ubiquitous lead-acid battery. He showed the structures of tribasic lead sulfate and tetrabasic lead sulfate. Austen Angell (Arizona State Univ.) discussed the general problem of electrolyte polarization in Li-ion battery systems with cation transference numbers less than unity. Steven Greenbaum (Hunter College) provided an introduction of NMR interactions that are useful for investigations of lithium-ion battery materials. Analysis by NMR is nuclear specific, probes local environments and dynamics, and is non-destructive. He discussed {sup 7}Li NMR results of a solid electrolyte system composed of LiI dissolved in PEO. Work on oriented polymer electrolyte samples is ongoing. Yuri Andreev (U. of St. Andrews) gave a historical overview of a number of crystal structures of polymer electrolytes solved using XRD in the group of Peter Bruce. The last speaker of the symposium was Peter Papanek (U. of Pennsylvania). He spoke about various disordered carbon materials used as anodes in Li-ion batteries. He also described his inelastic neutron scattering studies of carbon materials derived from pyrolyzed epoxy novolak resins. His data supports the graphene sheet model and is also consistent with calculations of interior and edge carbon atoms in pyrene that chemically reacted with lithium.

Gerald, R. E., II; Chemical Engineering



Kinetics and Thermodynamics of H(-)/H•/H(+) Transfer from a Rhodium(III) Hydride.  


The thermodynamics and kinetics of all three cleavage modes for Rh-H, the transfer of H(-), H(+), or H•, have been studied for the Rh(III) hydride complex Cp*Rh(2-(2-pyridyl)phenyl)H (1a). The thermodynamic hydricity, ?G°H(-), for 1a has been measured (49.5(1) kcal/mol) by heterolytic cleavage of H2 with Et3N in CH3CN. The transfer of H(-) from 1a to 1-(1-phenylethylidene)pyrrolidinium is remarkably fast (kH(-) = 3.5(1) × 10(5) M(-1) s(-1)), making 1a a very efficient catalyst for the ionic hydrogenation of iminium cations. The pKa of 1a in CH3CN has been measured as 30.3(2) with (tert-butylimino)tris(pyrrolidino)phosphorane (12), and the rate constant for H(+) transfer from 1a to 12 has been estimated (kH(+) = 5(1) × 10(-4) M(-1) s(-1)) from the half-life of the equilibration. Thus, 1a is a poor H(+) donor both thermodynamically and kinetically. However, 1a transfers H• to TEMPO smoothly, forming a stable Rh(II) radical Cp*Rh(2-(2-pyridyl)phenyl)• (14a) that can activate H2 at room temperature and 1 atm. The metalloradical 14a has a g value of 2.0704 and undergoes reversible one-electron reduction at -1.85 V vs Fc(+)/Fc in benzonitrile, implying a bond-dissociation enthalpy for the Rh-H bond of 1a of 58.2(3) kcal/mol-among the weakest Rh(III)-H bonds reported. The transfer of H• from 1a to Ar3C• (Ar = p-(t)BuC6H4) is fast, with kH• = 1.17(3) × 10(3) M(-1) s(-1). Thus, 1a is a good H(-) and H• donor but a poor H(+) donor, a combination that reflects the high energy of the Rh(I) anion [Cp*Rh(2-(2-pyridyl)phenyl)](-). PMID:24666137

Hu, Yue; Norton, Jack R



Designed Chemical Intervention with Thiols for Prophylactic Contraception  

PubMed Central

Unlike somatic cells, sperm have several-fold more available-thiols that are susceptible to redox-active agents. The present study explains the mechanism behind the instant sperm-immobilizing and trichomonacidal activities of pyrrolidinium pyrrolidine-1-carbodithioate (PPC), a novel thiol agent rationally created for prophylactic contraception by minor chemical modifications of some known thiol drugs. PPC, and its three derivatives (with potential active-site blocked by alkylation), were synthesized and evaluated against live human sperm and metronidazole-susceptible and resistant Trichomonas vaginalis, in vitro. Sperm hexokinase activity was evaluated by coupled enzyme assay. PPC irreversibly immobilized 100% human sperm in ?30 seconds and totally eliminated Trichomonas vaginalis more efficiently than nonoxynol-9 and metronidazole. It significantly inhibited (P<0.001) thiol-sensitive sperm hexokinase. However, the molecule completely lost all its biological activities once its thiol group was blocked by alkylation. PPC was subsequently formulated into a mucoadhesive vaginal film using GRaS excipients and evaluated for spermicidal and microbicidal activities (in vitro), and contraceptive efficacy in rabbits. PPC remained fully active in quick-dissolving, mucoadhesive vaginal-film formulation, and these PPC-films significantly reduced pregnancy and fertility rates in rabbits. The films released ?90% of PPC in simulated vaginal fluid (pH 4.2) at 37°C in 5 minutes, in vitro. We have thus discovered a common target (reactive thiols) on chiefly-anaerobic, redox-sensitive cells like sperm and Trichomonas, which is susceptible to designed chemical interference for prophylactic contraception. The active thiol in PPC inactivates sperm and Trichomonas via interference with crucial sulfhydryl-disulfide based reactions, e.g. hexokinase activation in human sperm. In comparison to non-specific surfactant action of OTC spermicide nonoxynol-9, the action of thiol-active PPC is apparently much more specific, potent and safe. PPC presents a proof-of-concept for prophylactic contraception via manipulation of thiols in vagina for selective targeting of sperm and Trichomonas, and qualifies as a promising lead for the development of dually protective vaginal-contraceptive.

Jain, Ashish; Verma, Vikas; Sharma, Vikas; Kushwaha, Bhavana; Lal, Nand; Kumar, Lalit; Rawat, Tara; Dwivedi, Anil K.; Maikhuri, Jagdamba P.; Sharma, Vishnu L.; Gupta, Gopal