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Sample records for polymeric ionic exchangers

  1. Preparation of anion-exchangeable polymer vesicles through the self-assembly of hyperbranched polymeric ionic liquids.

    PubMed

    Fan, Yujiao; Zhang, Dapeng; Wang, Jie; Jin, Haibao; Zhou, Yongfeng; Yan, Deyue

    2015-04-28

    This work reports the self-assembly of anion-exchangeable vesicles from an amphiphilic hyperbranched polymeric ionic liquid (HBPIL). By a simple one-step anion exchange with methyl orange, the obtained HBPILs could self-assemble into pH-indicative and colorful vesicles in water with color changes directly visible to the naked eye in response to solution pH. In addition, by another step of anion exchange with bovine serum albumin (BSA), the BSA-coated vesicles could also be readily prepared. PMID:25813408

  2. Sulfonated Polymerized Ionic Liquid Block Copolymers.

    PubMed

    Meek, Kelly M; Elabd, Yossef A

    2016-07-01

    The successful synthesis of a new diblock copolymer, referred to as sulfonated polymerized ionic liquid (PIL) block copolymer, poly(SS-Li-b-AEBIm-TFSI), is reported, which contains both sulfonated blocks (sulfonated styrene: SS) and PIL blocks (1-[(2-acryloyloxy)ethyl]-3-butylimidazolium: AEBIm) with both mobile cations (lithium: Li(+) ) and mobile anions (bis(trifluoromethylsulfonyl)imide: TFSI(-) ). Synthesis consists of polymerization via reversible addition-fragmentation chain transfer, followed by post-functionalization reactions to covalently attach the imidazolium cations and sulfonic acid anions to their respective blocks, followed by ion exchange metathesis resulting in mobile Li(+) cations and mobile TFSI(-) anions. Solid-state films containing 1 m Li-TFSI salt dissolved in ionic liquid result in an ion conductivity of >1.5 mS cm(-1) at 70 °C, where small-angle X-ray scattering data indicate a weakly ordered microphase-separated morphology. These results demonstrate a new ion-conducting block copolymer containing both mobile cations and mobile anions. PMID:27125600

  3. Effect of Electric Field Alignment on Morphology and Ionic Conductivity of Polymerized Ionic Liquid Block Copolymers

    NASA Astrophysics Data System (ADS)

    Sharick, Sharon; Nykaza, Jacob; Elabd, Yossef A.; Winey, Karen I.

    2014-03-01

    Polymerized ionic liquid (PIL) block copolymers are appealing for numerous electrochemical applications, including solid polymer electrolyte membranes for batteries and anion exchange membranes for fuel cells. The extent to which the reduced segmental motion caused by the non-conducting polymer segments and grain boundaries between block copolymer microdomains are detrimental to ionic conductivity is unknown. Increased long-range morphological order and connectivity of PIL microdomains are key to understanding the ion transport mechanism and may improve the ionic conductivity of PIL block copolymers. The effect of electric field on the morphology and ionic conductivity of poly(styrene- b-1-[2-(methacryloyloxy)ethyl]-3-butylimidazolium-bis(trifluoromethanesulfonyl)imide)) (PS- b-PMEBIm-TFSI) will be discussed as a function of microdomain orientation. Electric field is used to increase the perpendicular orientation of ion-conducting pathways with respect to the electrodes. The morphology and ionic conductivity were characterized by small-angle X-ray scattering and electrochemical impedance spectroscopy, respectively. The ionic conductivity of unoriented and oriented block copolymers will be compared to the PIL homopolymer, PMEBIm-TFSI, using the Sax and Ottino model.

  4. Morphology and charge transport in ammonium based polymerized ionic liquids

    NASA Astrophysics Data System (ADS)

    Heres, Maximilian; Minutolo, Joseph; Shamblin, Jacob; Long, Maik; Berdzinski, Stefan; Stremel, Veronika; Sangoro, Joshua

    2015-03-01

    Ionic conduction, structural dynamics and morphology in a series of ammonium based polymerized ionic liquids are investigated using broadband dielectric spectroscopy, temperature-modulated differential scanning calorimetry, and neutron as well as x-ray scattering techniques. The dielectric spectra are dominated on the low frequency regime by electrode polarization while hopping conduction is the underlying mechanism at higher frequencies. At their respective calorimetric glass transition temperatures, a strong correlation between the morphology and ionic conductivity is found. These results are discussed within the recent approaches proposed to explain the decoupling of charge transport from structural dynamics. UT/ORNL Science Alliance.

  5. Electrical Impedance of Ionic Polymeric Metal Composites

    NASA Technical Reports Server (NTRS)

    Leary, S.; Bar-Cohen, Y.

    1999-01-01

    In recent years the use of ionic polymer metal composites such as Nafion-based platinum ionomers have emerged as electroactive polymer materials with great potential for robotics and other applications. An effective activation of these materials requires understanding of their mechanism of operation. Generally, the material needs to be maintained hydrated to assure its electromechanical activity. To allow the control of the response of the material, a study is underway to investigate the electrical response. Particular emphasis is placed on possible electrochemical reactions and deviations from linear dielectric behavior. Currently, efforts are made to determine the necessary drive characteristics of the source to allow low power operation (< or = 1.0 W) of the material as an actuator.

  6. Ionic Block Copolymers for Anion Exchange Membranes

    NASA Astrophysics Data System (ADS)

    Tsai, Tsung-Han; Herbst, Dan; Giffin, Guinevere A.; di Noto, Vito; Witten, Tom; Coughlin, E. Bryan

    2013-03-01

    Anion exchange membrane (AEM) fuel cells have regained interest because it allows the use of non-noble metal catalysts. Until now, most of the studies on AEM were based on random polyelectrolytes. In this work, Poly(vinylbenzyltrimethylammonium bromide)-b- (methylbutylene) ([PVBTMA][Br]-b-PMB) was studied by SAXS, TEM and dielectric spectroscopy to understand the fundamental structure-conductivity relationship of ion transport mechanisms within well-ordered block copolymers. The ionic conductivity and the formation of order structure were dependent on the casting solvent. Higher ion exchange capacity (IEC) of the membranes showed higher conductivity at as IEC values below 1.8mmol/g, as above this, the ionic conductivity decreases due to more water uptake leading to dilution of charge density. The humidity dependence of morphology exhibited the shifting of d-spacing to higher value and the alteration in higher characteristic peak of SAXS plot as the humidity increase from the dry to wet state. This phenomenon can be further explained by a newly developed polymer brush theory. Three ionic conduction pathways with different conduction mechanism within the membranes can be confirmed by broadband electric spectroscopy. US Army MURI (W911NF1010520)

  7. Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups

    SciTech Connect

    Fan, Fei; Wang, Yangyang; Hong, Tao; Heres, Maximilian F; Saito, Tomonori; Sokolov, Alexei P

    2015-01-01

    Polymerized ionic liquids (PolyILs) are promising candidates for energy storage and electrochemical devices applications. Understanding their ionic transport mechanism is the key for designing highly conductive PolyILs. By using broadband dielectric spectroscopy (BDS), rheology, and differential scanning calorimetry (DSC), a systematic study has been carried out to provide a better understanding of the ionic transport mechanism in PolyILs with different pendant groups. The variation of pendant groups results in different dielectric, mechanical, and thermal properties of these PolyILs. The Walden plot analysis shows that the data points for all these PolyILs fall above the ideal Walden line, and the deviation from the ideal line increases upon approaching the glass transition temperature (Tg). The conductivity for these PolyILs at their Tgs are much higher than the usually reported value 10 15 S/cm for polymer electrolytes, in which the ionic transport is closely coupled to the segmental dynamics. These results indicate a decoupling of ionic conductivity from the segmental relaxation in these materials. The degree of decoupling increases with the increase of the fragility of polymer segmental relaxation. We relate this observation to a decrease in polymer packing efficiency with an increase in fragility.

  8. Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups

    DOE PAGESBeta

    Fan, Fei; Wang, Yangyang; Hong, Tao; Heres, Maximilian F; Saito, Tomonori; Sokolov, Alexei P

    2015-01-01

    Polymerized ionic liquids (PolyILs) are promising candidates for energy storage and electrochemical devices applications. Understanding their ionic transport mechanism is the key for designing highly conductive PolyILs. By using broadband dielectric spectroscopy (BDS), rheology, and differential scanning calorimetry (DSC), a systematic study has been carried out to provide a better understanding of the ionic transport mechanism in PolyILs with different pendant groups. The variation of pendant groups results in different dielectric, mechanical, and thermal properties of these PolyILs. The Walden plot analysis shows that the data points for all these PolyILs fall above the ideal Walden line, and the deviationmore » from the ideal line increases upon approaching the glass transition temperature (Tg). The conductivity for these PolyILs at their Tgs are much higher than the usually reported value 10 15 S/cm for polymer electrolytes, in which the ionic transport is closely coupled to the segmental dynamics. These results indicate a decoupling of ionic conductivity from the segmental relaxation in these materials. The degree of decoupling increases with the increase of the fragility of polymer segmental relaxation. We relate this observation to a decrease in polymer packing efficiency with an increase in fragility.« less

  9. Correlating morphology to dc conductivity in polymerized ionic liquids

    NASA Astrophysics Data System (ADS)

    Iacob, Ciprian; Matusmoto, Atsushi; Inoue, Tadashi; Runt, James

    Polymerized ionic liquids (PILs) combine the attractive mechanical characteristics of polymers and unique physico-chemical properties of low molecular weight ionic liquids in the same material. PILs have shown remarkable advantages when employed in electrochemical devices such as dye-sensitized solar cells and lithium batteries, among others. Understanding their ionic transport mechanism is the key for designing highly conductive PILs. In the current study, the correlation between morphology and charge transport in two homologous series of PILs with systematic variation of the alkyl chain length and anions is investigated using broadband dielectric spectroscopy, rheology, differential scanning calorimetry and X-ray scattering. As the alkyl chain length increases, the backbone-to-backbone separation increases, and dc-conductivity consequently decreases. The cations dominate structural dynamics since they are attached to the polymer chains, while the anions are smaller and more mobile ionic species thereby controlling the ionic conductivity. Further interpretation of decoupling of dc conductivity from the segmental relaxation enabled the correlation between polymer morphology and dc conductivity. Supported by the National Science Foundation, Polymers Program.

  10. Tuning the ionic conductivity in protic polymerized ionic liquid homo, random, and block copolymers

    NASA Astrophysics Data System (ADS)

    Evans, Christopher; Segalman, Rachel; UCSB Team

    2015-03-01

    Proton conducting membranes are of interest for a number of energy applications including use in fuel cells and artificial photosynthesis systems. We have synthesized a new class of protic polymerized ionic liquids (PILs) based on imidazolium cations which exhibit high conductivities in the solid state. In contrast to previous imidazolium based PILs, the ionic liquid moiety is attached via a carbon on the imidazole thus leaving the two nitrogens available to act as a proton donor/acceptor. The conductivies of these protic PILs, measured by dielectric spectroscopy, are orders of magnitude higher than the analogous non-protic PILs at a given distance above (Tg). These high conductivities are the result of a strong contribution from proton motion. A series of random and block copolymers containing the polymerized ionic liquid monomer and a non-ionic comonomer were also investigated to determine the role of comonomer on the conductivity of these materials. It was found that methyl acrylate, which has a low glass transition temperature and high dielectric constant, can result in improvements of ionic conductivity. Studies using solid state NMR are underway to understand the role of protons and mobile anions in controlling the overall conductivity of these materials.

  11. Synthesis of polymeric nanoparticles containing reduced graphene oxide nanosheets stabilized by poly(ionic liquid) using miniemulsion polymerization.

    PubMed

    Tokuda, Masayoshi; Yamane, Mitsuyoshi; Thickett, Stuart C; Minami, Hideto; Zetterlund, Per B

    2016-05-01

    Polymeric nanoparticles containing reduced graphene oxide (rGO) nanosheets have been prepared by aqueous miniemulsion radical polymerization of methyl methacrylate (MMA) utilizing poly(ionic liquid) (PIL) as stabilizer to effectively disperse the rGO nanosheets in the monomer phase. The PIL that gave the best results in terms of rGO dispersibility was a block copolymer of the ionic liquid monomer 1-(2-methacryloyloxyethyl)-3-butylimidazolium bis(trifluoromethanesulfonyl)amide ([Mbim][TFSA]) and MMA, the concept being that the MMA units impart solubility in the MMA monomer droplets whereas the IL units act as adsorption sites for rGO. The rGO dispersibility in vinyl monomer was demonstrated to be superior using the above PIL block copolymer compared to the corresponding statistical copolymer or PIL homopolymer. Overall, the approach developed demonstrates how PILs can be employed to conveniently switch (turn ON/OFF) the dispersibility of PIL/rGO via anion exchange reactions, which can be an efficient strategy for synthesis of polymer/rGO nanocomposite materials. PMID:27021557

  12. Versatile cation transport in imidazolium based polymerized ionic liquids

    NASA Astrophysics Data System (ADS)

    Evans, Christopher; Segalman, Rachel

    Polymerized ionic liquids (PIL) with tethered imidazolium groups are able to conduct a diverse array of cations relevant for energy applications. The well-known complexation of imidazolium with transition metals is exploited to bind ions such as H +, Li+, Cu2+, and Ni2+ by doping the neutral PIL with the appropriate Cation-TFSI- salt. Conductivities were first determined via AC impedance indicating that H+ salts lead to the highest conductivity (due to low ion mass and potential Grotthus mechanism) followed by Cu2+, Li+, Ag+, and Ni2+. The equilibrium constant for imidazolium complexation is larger for Cu2+ relative to Li-, Ag-, and Ni-imidazolium complexes leading to greater salt dissociation and higher conductivities. For LiTFSI and CuTFSI2 salts, metallic lithium or copper electrodes were employed in battery cells to pass a steady DC current and confirm that the cations are in fact carrying current. Interestingly, the divalent Cu2+ also ionically crosslinks the polymer leading to a plateau in the viscosity. Thus, divalent ions provide an unique route to high conductivity, high modulus polymeric electrolytes. Future studies involving ZnTFSI2 and MgTFSI2 for battery applications are proposed to examine how versatile the PIL platform is for cation transport.

  13. Morphology and Ionic Conductivity of Humidity-Responsive Polymerized Ionic Liquid Block Copolymers

    NASA Astrophysics Data System (ADS)

    Sharick, Sharon; Meek, Kelly; Ye, Yuesheng; Elabd, Yossef A.; Winey, Karen I.

    2014-03-01

    We present the ionic conductivity and morphology of humidity-responsive polymerized ionic liquid block copolymers (PIL BCPs), poly(methyl methacrylate- b-1-[2-(methacryloyloxy)ethyl]-3-butylimidazolium-X), where X is a bromide (Br) or hydroxide (OH) anion, as a function of relative humidity (RH), temperature, and PIL composition (ϕPIL) . PIL BCPs were characterized by in situ small-angle X-ray scattering and electrochemical impedance spectroscopy. These PIL BCPs have microphase separated morphologies and long-range order increases as ϕPIL increases. Notably, ionic conductivity increases 3 to 4 orders of magnitude when RH increases from 30 to 90 percent. When ϕPIL is greater than 0.37, BCP ionic conductivity approaches or exceeds that of the homopolymer, suggesting that the dynamics in PIL microdomains mimic the homopolymer and long-range order aids ion transport. Moreover, over 60 percent of the BCP is nonconductive without a penalty in ion transport. When ϕPIL is less than 0.37, BCP conductivity is 1 to 2 orders of magnitude less than the homopolymer and non-conductive PMMA segments dominate ion transport, as expected. Ionic conductivities at 80 °C, 90 percent RH, are 7.6 mS/cm for the Br-containing BCP with ϕPIL = 0.53 and 25.0 mS/cm for the OH-containing BCP with ϕPIL = 0.50.

  14. Anisotropic microporous supports impregnated with polymeric ion-exchange materials

    DOEpatents

    Friesen, Dwayne; Babcock, Walter C.; Tuttle, Mark

    1985-05-07

    Novel ion-exchange media are disclosed, the media comprising polymeric anisotropic microporous supports containing polymeric ion-exchange or ion-complexing materials. The supports are anisotropic, having small exterior pores and larger interior pores, and are preferably in the form of beads, fibers and sheets.

  15. Anisotropic microporous supports impregnated with polymeric ion-exchange materials

    DOEpatents

    Friesen, D.; Babcock, W.C.; Tuttle, M.

    1985-05-07

    Novel ion-exchange media are disclosed, the media comprising polymeric anisotropic microporous supports containing polymeric ion-exchange or ion-complexing materials. The supports are anisotropic, having small exterior pores and larger interior pores, and are preferably in the form of beads, fibers and sheets. 5 figs.

  16. Polymeric Ionic Networks with High Charge Density: Solid-like Electrolytes in Lithium Metal Batteries

    DOE PAGESBeta

    Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; Fang, Youxing; Veith, Gabriel M.; Sun, Xiao-Guang; Dai, Sheng

    2015-11-02

    Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10-3 S cm-1 at 22 °C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.

  17. Polymeric Ionic Networks with High Charge Density: Solid-like Electrolytes in Lithium Metal Batteries

    SciTech Connect

    Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; Fang, Youxing; Veith, Gabriel M.; Sun, Xiao-Guang; Dai, Sheng

    2015-11-02

    Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10-3 S cm-1 at 22 °C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.

  18. Polymerized Ionic Networks with High Charge Density: Quasi-Solid Electrolytes in Lithium-Metal Batteries.

    PubMed

    Zhang, Pengfei; Li, Mingtao; Yang, Bolun; Fang, Youxing; Jiang, Xueguang; Veith, Gabriel M; Sun, Xiao-Guang; Dai, Sheng

    2015-12-22

    Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10(-3) S cm(-1) at 22°C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes. PMID:26523468

  19. Ion transport and softening in a polymerized ionic liquid

    DOE PAGESBeta

    Kumar, Rajeev; Bocharova, Vera; Strelcov, Evgheni; Tselev, Alexander; Kravchenko, Ivan I.; Berdzinski, Stefan; Strehmel, Veronika; Ovchinnikova, Olga S.; Minutolo, Joseph A.; Sangoro, Joshua R.; et al

    2014-11-13

    Polymerized ionic liquids (PolyILs) are promising materials for various solid state electronic applications such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting electrochemical cells, and electrochromic devices. However, fundamental understanding of interconnection between ionic transport and mechanical properties in PolyILs is far from complete. In this paper, local charge transport and structural changes in films of a PolyIL are studied using an integrated experiment-theory based approach. Experimental data for the kinetics of charging and steady state current–voltage relations can be explained by taking into account the dissociation of ions under an applied electric field (known as themore » Wien effect). Onsager's theory of the Wien effect coupled with the Poisson–Nernst–Planck formalism for the charge transport is found to be in excellent agreement with the experimental results. The agreement between the theory and experiments allows us to predict structural properties of the PolyIL films. We have observed significant softening of the PolyIL films beyond certain threshold voltages and formation of holes under a scanning probe microscopy (SPM) tip, through which an electric field was applied. Finally, the observed softening is explained by the theory of depression in glass transition temperature resulting from enhanced dissociation of ions with an increase in applied electric field.« less

  20. Ion transport and softening in a polymerized ionic liquid

    SciTech Connect

    Kumar, Rajeev; Bocharova, Vera; Strelcov, Evgheni; Tselev, Alexander; Kravchenko, Ivan I.; Berdzinski, Stefan; Strehmel, Veronika; Ovchinnikova, Olga S.; Minutolo, Joseph A.; Sangoro, Joshua R.; Agapov, Alexander L.; Sokolov, Alexei P.; Kalinin, Sergei V.; Sumpter, Bobby G.

    2014-11-13

    Polymerized ionic liquids (PolyILs) are promising materials for various solid state electronic applications such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting electrochemical cells, and electrochromic devices. However, fundamental understanding of interconnection between ionic transport and mechanical properties in PolyILs is far from complete. In this paper, local charge transport and structural changes in films of a PolyIL are studied using an integrated experiment-theory based approach. Experimental data for the kinetics of charging and steady state current–voltage relations can be explained by taking into account the dissociation of ions under an applied electric field (known as the Wien effect). Onsager's theory of the Wien effect coupled with the Poisson–Nernst–Planck formalism for the charge transport is found to be in excellent agreement with the experimental results. The agreement between the theory and experiments allows us to predict structural properties of the PolyIL films. We have observed significant softening of the PolyIL films beyond certain threshold voltages and formation of holes under a scanning probe microscopy (SPM) tip, through which an electric field was applied. Finally, the observed softening is explained by the theory of depression in glass transition temperature resulting from enhanced dissociation of ions with an increase in applied electric field.

  1. Ion transport and softening in a polymerized ionic liquid

    NASA Astrophysics Data System (ADS)

    Kumar, Rajeev; Bocharova, Vera; Strelcov, Evgheni; Tselev, Alexander; Kravchenko, Ivan I.; Berdzinski, Stefan; Strehmel, Veronika; Ovchinnikova, Olga S.; Minutolo, Joseph A.; Sangoro, Joshua R.; Agapov, Alexander L.; Sokolov, Alexei P.; Kalinin, Sergei V.; Sumpter, Bobby G.

    2014-12-01

    Polymerized ionic liquids (PolyILs) are promising materials for various solid state electronic applications such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting electrochemical cells, and electrochromic devices. However, fundamental understanding of interconnection between ionic transport and mechanical properties in PolyILs is far from complete. In this work, local charge transport and structural changes in films of a PolyIL are studied using an integrated experiment-theory based approach. Experimental data for the kinetics of charging and steady state current-voltage relations can be explained by taking into account the dissociation of ions under an applied electric field (known as the Wien effect). Onsager's theory of the Wien effect coupled with the Poisson-Nernst-Planck formalism for the charge transport is found to be in excellent agreement with the experimental results. The agreement between the theory and experiments allows us to predict structural properties of the PolyIL films. We have observed significant softening of the PolyIL films beyond certain threshold voltages and formation of holes under a scanning probe microscopy (SPM) tip, through which an electric field was applied. The observed softening is explained by the theory of depression in glass transition temperature resulting from enhanced dissociation of ions with an increase in applied electric field.Polymerized ionic liquids (PolyILs) are promising materials for various solid state electronic applications such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting electrochemical cells, and electrochromic devices. However, fundamental understanding of interconnection between ionic transport and mechanical properties in PolyILs is far from complete. In this work, local charge transport and structural changes in films of a PolyIL are studied using an integrated experiment-theory based approach

  2. High-flux ionic diodes, ionic transistors and ionic amplifiers based on external ion concentration polarization by an ion exchange membrane: a new scalable ionic circuit platform.

    PubMed

    Sun, Gongchen; Senapati, Satyajyoti; Chang, Hsueh-Chia

    2016-04-01

    A microfluidic ion exchange membrane hybrid chip is fabricated using polymer-based, lithography-free methods to achieve ionic diode, transistor and amplifier functionalities with the same four-terminal design. The high ionic flux (>100 μA) feature of the chip can enable a scalable integrated ionic circuit platform for micro-total-analytical systems. PMID:26960551

  3. Irreversible thermochromic behavior in gold and silver nanorod/polymeric ionic liquid nanocomposite films.

    PubMed

    Tollan, Christopher M; Marcilla, Rebeca; Pomposo, Jose A; Rodriguez, Javier; Aizpurua, Javier; Molina, Jon; Mecerreyes, David

    2009-02-01

    The novel application of gold and silver nanorods as irreversible thermochromic dyes in polymeric ionic liquid (PIL) nanocomposites is proposed here. These materials have been synthesized by anion exchange of an imidazolium-based PIL in a solution that also contained gold nanorods. This resulted in the entrapment of the nanoobjects within a solid polymer precipitate. In this article, the effect of the temperature was studied in relation to the change of shape and, consequently, color of the gold or silver nanorods within the films. For the nanocomposites studied here, a maximum of two visual thermochromic transitions was observed for gold nanorods and up to three transitions were observed for silver nanorods. PMID:20353222

  4. Applications of room temperature ionic liquids in interfacial polymerization

    NASA Astrophysics Data System (ADS)

    Zhu, Lining

    2006-12-01

    Room temperature ionic liquids (ILs), with their unique physical and chemical properties, have been of great interest in various areas of chemical science and engineering during the last decade. In this dissertation, polyurea and polyamide films with surface nanostructures were synthesized by interfacial polymerization (IP) with ILs without stirring. Both polymers were prepared at the interface between n-hexane and a series of 1-alkyl-3-methylimidazolium ILs. Nanoporous or nanofibrous polymer morphologies with various sizes ranging from 50 to 500 nm and geometries, depending on the ILs used, were observed by scanning electron microscopy (SEM). A correlation length of ˜20nm and a suppression of three-dimensional (3-D) crystalline structure of the polyurea were found by small angle X-ray scattering (SAXS) and X-ray diffraction (XRD), respectively. FTIR spectra showed no significant changes in the chemical composition of the polymer by the employment of ILs. The peculiar nanostructure of the polymer could be ascribed to the intermolecular interactions between the ILs and the polymer, which affected the development of the polymer morphology. The polyamides prepared with ILs showed larger intrinsic viscosities, and consequently higher molecular weights, compared to the one prepared without ILs; this could be due to the prevention of the side reaction between sebacoyl chloride and water. The enhancement of the molecular weight renders a better thermal stability to the polyamide film, as revealed by thermogravimetric analysis (TGA) which showed a higher decomposition temperature. Coating of fine particulates with polyurea by IP has been developed. With increasing stirring speed in the coating process, a decreased mean particle size and a narrower particle size distribution, as well as a lower coating weight percentage were found by particle size analysis and TGA, respectively. A Porous coating layer was formed in the IP coating in the presence of ILs. The reaction

  5. Deposition of polymeric perfluored thin films in proton ionic membranes by plasma processes

    NASA Astrophysics Data System (ADS)

    Polak, Peter Lubomir; Mousinho, Ana Paula; Ordonez, Nelson; da Silva Zambom, Luis; Mansano, Ronaldo Domingues

    2007-10-01

    In this work the surfaces of polymeric membranes based on Nafion (proton conducting material), used in proton exchange membranes fuel cells (PEMFC) had been modified by plasma deposition of perfluored polymers, in order to improve its functioning in systems of energy generation (fuel cells). The deposition increases the chemical resistance of the proton ionic polymers without losing the electrical properties. The processing of the membranes also reduces the permeability of the membranes to the alcohols (methanol and ethanol), thus preventing poisoning of the fuel cell. The processing of the membranes of Nafion was carried through in a system of plasma deposition using a mixture of CF 4 and H 2 gases. The plasma processing was made mainly to increase the chemical resistance and result in hydrophobic surfaces. The Fourier transformed infrared (FTIR) technique supplies a spectrum with information about the CF n bond formation. Through the Rutherford back scattering (RBS) technique it was possible to verify the deposition rate of the polymeric layer. The plasma process with composition of 60% of CF 4 and 40% of H 2 presented the best deposition rate. By the spectrum analysis for the optimized configuration, it was possible to verify that the film deposition occurred with a thickness of 90 nm, and fluorine concentration was nearly 30%. Voltammetry made possible to verify that the fluorination increases the membranes chemical resistance, improving the stability of Nafion, becoming an attractive process for construction of fuel cells.

  6. Novel double-confined polymeric ionic liquids as sorbents for solid-phase microextraction with enhanced stability and durability in high-ionic-strength solution.

    PubMed

    Feng, Juanjuan; Sun, Min; Xu, Lili; Wang, Shuai; Liu, Xia; Jiang, Shengxiang

    2012-12-14

    Because of the occurrence of ion exchange between high-ionic-strength solution and anions of polymeric ionic liquids (PILs), PILs based solid-phase microextraction (SPME) fibers were rarely used in direct immersion mode to high-salt-added samples. In this work, a novel double-confined PIL sorbent was prepared by co-polymerization of cation and anion of 1-vinyl-3-octylimidzaolium p-styrenesulfonate (VOIm(+)SS(-)). The poly(VOIm(+)-SS(-)) was chemically bonded onto functionalized stainless steel wire via surface radical chain-transfer reaction. Stability of poly(VOIm(+)-SS(-)) in high-ionic-strength solution was investigated and compared with that of poly(1-vinyl-3-octylimidzaolium benzenesulfonate) (poly(VOIm(+)BS(-))) by elemental analysis of sulfur element, and results turned out that the poly(VOIm(+)-SS(-)) was more stable. Coupled to gas chromatography (GC), the poly(VOIm(+)-SS(-)) fiber was used to extract three sorts of compounds including anilines, phenols and phthalate esters in aqueous solution. The as-established method showed good linearity, low detection limits, and acceptable repeatability. The direct immersion SPME-GC method was applied to determine the model phthalate esters in bottled mineral water. The determination results were satisfactory. PMID:23127811

  7. Ionic-polymeric models and the amphoteric behavior of water in silicate melts

    NASA Astrophysics Data System (ADS)

    Moretti, R.

    2012-04-01

    In silicate melts it is almost impossible to readily distinguish solute and solvent like in aqueous solutions. The anionic framework of silicate melts, in fact, makes solute and solvents so intimately related that one cannot identify a solvation shell and identify directly, from structural studies, the complexes needed to define acid-base reactions. Therefore, the distinction between solute and solvent becomes blurred in systems such as silicate melts, because speciation is not only complex but changes with the marked depolymerization of the silicate framework that obtains from pure SiO2 to metal-oxide rich compositions. These features do not allow proper understanding of the actual physico-chemical role of many species detected by conventional techniques, a fact which can lead to confusing notation. However, these may not be serious limits to account correctly for the acid-base reactions that take place in every kind of magmatic setting, provided a 'syntax' describing the effective interactions among significative cationic and anionic entities. In particular, the syntax for acid-base exchanges is needed such that constituting oxides (i.e. chemical components) can be treated independently of (but not necessarily extraneous to) structural features in defining such entities. So-called ionic-polymeric models highlight the mutual correspondence between polymerization and acid-base properties of dissolved oxides through the Lux-Flood formalism for molten oxides. They thus provide the syntax to write chemical exchanges, but have no pretension to structural description. In fact the concept of melt polymerization is used to identify basic anions and cations that can be used, along with their formal charge, to describe effectively acid-base interactions taking place in melts. In this respect, an example is given by the description of the amphoteric behavior of water dissolved on melts, hence water autoprotolysis. Although it exerts a profound influence on properties of

  8. Ion-trapping and end-capping in ionic polymerizations

    SciTech Connect

    Penczek, S.

    1993-12-31

    Ion-trapping, developed in this laboratory, involves both vinyl and ring-opening polymerizations, anionic and cationic. Originally it was elaborated for cationic ring-opening polymerization and involved reaction of phosphines (mostly triphenylphosphine) with onium ions, like oxonium ions in the polymerization of cyclic ethers. The same method has more recently been used for the cationic polymerization of vinyl ethers, allowing not only to determine the total concentration of the growing species by {sup 31}P-NMR but also to study the stereochemistry of the chain end by the same method. In the anionic ring-opening polymerization diphenylchlorophosphate was applied. It reacts quantitatively with alcoholate, thiolate, and carboxylate anions. More recently diphenylchlorophosphine was successfully used to determine the concentration and structure of the chain ends in the anionic polymerization of styrene, butadiene, isoprene as well as their mixtures.

  9. Release of Small Polyuronides from Nitella Cell Walls during Ionic Exchange

    PubMed Central

    Gillet, Claude; Cambier, Pierre; Liners, Françoise

    1992-01-01

    Mono-divalent ion exchange in isolated cell walls of Nitella flexilis (L.) Ag. induces a marked loss of wall polymers and a decrease in the wall cationic exchange capacity. These data correlate with the replacement in the walls of adsorbed Mn2+ by Na+ ions. Boiling wall samples in methanol for 1 h or keeping the ionic solutions chilled to 4°C does not inhibit the cell wall polymer leakage but modifies the kinetics both of the ionic exchange and of the released polymers. These data are more compatible with physical rather than enzymic induced processes. The extracted polymers in the successively renewed NaCl solutions initially belong to the wall protein and pectin fractions and mainly to pectic fractions subsequently. Determination of the average degree of polymerization shows that the average molecular size of the lost acidic polysaccharides increases with extraction time up an average polymerization degree of 25. Enzyme-linked immunosorbent assay inhibition tests show the presence of homopolymer blocks equal to or higher than 10 in the released polymer fragments. Compositional analysis of released polysaccharides suggests that the pectin lost by action of monovalent ions was largely composed of rhamnogalacturonans whose acidic residue fraction is approximately 60% in association with galactose chains. Small quantities of glucuronylated xylans are also found. PMID:16653066

  10. Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids

    SciTech Connect

    Fan, Fei; Wang, Weiyu; Holt, Adam P; Feng, Hongbo; Uhrig, David; Lu, Xinyi; Hong, Tao; Wang, Yangyang; Kang, Nam-Goo; Mays, Jimmy; Sokolov, Alexei P

    2016-01-01

    The unique properties of ionic liquids (ILs) have made them promising candidates for electrochemical applications. Polymerization of the corresponding ILs results in a new class of materials called polymerized ionic liquids (PolyILs). Though PolyILs offer the possibility to combine the high conductivity of ILs and the high mechanical strength of polymers, their conductivities are typically much lower than that of the corresponding small molecule ILs. In the present work, seven PolyILs were synthesized having degrees of polymerization ranging from 1 to 333, corresponding to molecular weights (MW) from 482 to 160 400 g/mol. Depolarized dynamic light scattering, broadband dielectric spectroscopy, rheology, and differential scanning calorimetry were employed to systematically study the influence of MW on the mechanism of ionic transport and segmental dynamics in these materials. The modified Walden plot analysis reveals that the ion conductivity transforms from being closely coupled with structural relaxation to being strongly decoupled from it as MW increases.

  11. Charge transport and structural dynamics in ultra-thin films of polymerized ionic liquids

    NASA Astrophysics Data System (ADS)

    Heres, Maximilian; Cosby, Tyler; Berdzinski, Stefan; Strehmel, Veronica; Benson, Roberto; Sangoro, Joshua

    Ion conduction and structural dynamics in a series of ultra-thin films of imidazolium based polymerized ionic liquids are investigated using broadband dielectric spectroscopy, atomic force microscopy, and ellipsometry. No alteration in the characteristic charge transport rate is observed between bulk sample and films as thin as 12nm. These results are discussed within the recent approaches proposed to explain the confinement effects on structural dynamics in polymers and low molecular weight ionic liquids. NSF DRM Polymers Program.

  12. Polymerization process for carboxyl containing polymers utilizing oil soluble ionic surface active agents

    SciTech Connect

    Uebele, C.E.; Ball, L.E.; Jorkasky, R.J. II; Wardlow, E. Jr.

    1987-09-08

    This patent describes a method for polymerizing olefinically unsaturated carboxylic acid monomers containing at least one activated carbon to carbon olefinic double bond and at least one carboxyl group. The monomers are polymerized in an organic media consisting essentially of organic liquids, in the presence of free radical forming catalysts and at least one oil soluble ionic surface active agent selected from the group consisting of: (a) anionic surface active agents; (b) cationic surface active agents; and (c) amphoteric surface active agents.

  13. Unusual ionic behavior in microemulsion-polymerized membranes

    SciTech Connect

    Ong, C.L.; Gan, L.M.; Ong, C.K.; Chan, H.S.O.; Xu, G.

    1999-09-09

    Ion-containing membranes have attracted much attention recently, because of their potential applications in sensors, batteries, and fuel cells. The polymer-based membranes can offer advantages of reduced thickness, weight, and higher ionic conductivity. In addition, the mechanical flexibility of the polymers enables solid-state cells to be designed with optimized electrode/electrolyte interface as they can be readily shaped into any desired configuration. Some unusual ionic conducting phenomena were observed from ion-containing microemulsion membranes. Contrary to conventional wisdom, it was found that under the same ionic concentration, large ions exhibit higher mobilities than smaller ones. They are possibly explained by the existence of hydration shells, which eventually made the lighter cations larger. This is further supported by the sharp conductivity drop when the system was cooled below the freezing point of water. In addition, conductivity drop at higher ionic concentration was also observed.

  14. Polymeric nanocomposite proton exchange membranes prepared by radiation-induced polymerization for direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Kim, Young-Seok; Seo, Kwang-Seok; Choi, Seong-Ho

    2016-01-01

    The vinyl group-modified montmorillonite clay (F-MMT), vinyl group-modified graphene oxide (F-GO), and vinyl group-modified multi-walled carbon nanotube (F-MWNT) were first prepared by ion exchange reaction of 1-[(4-ethylphenyl)methyl]-3-butyl-imidazolium chloride in order to use the materials for protection against methanol cross-over in direct methanol fuel cell (DMFC) membrane. Then polymeric nanocomposite membranes with F-MMT, F-GO, and F-MWNT were prepared by the solvent casting method after radiation-induced polymerization of vinyl monomers in water-methanol mixture solvents. The proton conductivity, water uptake, ion-exchange capacity, methanol permeability, and DMFC performance of the polymeric nanocomposite membranes with F-MMT, F-GO, and F-MWNT were evaluated.

  15. Facile synthesis of a novel polymeric ionic liquid gel and its excellent performance for hexavalent chromium removal.

    PubMed

    Wang, Shuojue; Ma, Hui-Ling; Peng, Jing; Zhang, Youwei; Chen, Jian; Wang, Liangliang; Xu, Ling; Li, Jiuqiang; Zhai, Maolin

    2015-04-28

    A novel polymeric ionic liquid gel (PIL gel) was simply synthesized by γ-radiation-induced polymerization of ionic liquid monomer 1-allyl-3-vinylimidazolium chloride and crosslinking at ambient temperature without any additives. By changing the radiation dose, the properties of the resulting gel including the gel fraction, crosslinking density and equilibrium degree of swelling were optimized. The resulting PIL gel exhibited a superior adsorption ability toward Cr(vi) in aqueous solutions with a broad pH range (1-7) through anion exchange. It was found that the adsorption kinetics followed the pseudo-second-order model. The adsorption of Cr(vi) by the PIL gel obeyed the Langmuir isotherm equation with a theoretical maximum adsorption capacity of 283 mg g(-1), twice the highest value for ionic liquid-based adsorbents that have been reported. In addition, the PIL gel could be recovered using a NaCl solution or a NaOH solution without much decreasing the adsorption capacity. This work paves the way for the scale-up production of PIL gels using the radiation technique for potential application in heavy metal removal. PMID:25811404

  16. Analysis of beer volatiles by polymeric imidazolium-solid phase microextraction coatings: Synthesis and characterization of polymeric imidazolium ionic liquids.

    PubMed

    González-Álvarez, Jaime; Blanco-Gomis, Domingo; Arias-Abrodo, Pilar; Pello-Palma, Jairo; Ríos-Lombardía, Nicolás; Busto, Eduardo; Gotor-Fernández, Vicente; Gutiérrez-Álvarez, María Dolores

    2013-08-30

    Two polymeric ionic liquids, 3-(but-3″-en-1″-yl)-1-[2'-hydroxycyclohexyl]-1H-imidazol-3-ium bis(trifluoromethanesulfonyl)imide (IL-1) and 1-(2'-hydroxycyclohexyl)-3-(4″-vinylbenzyl)-1H-imidazol-3-ium bis(trifluoromethylsulfonyl)imide (IL-2), have been synthesized by a free radical polymerization reaction and used as coatings for solid-phase microextraction (SPME). These new fibers exhibit good film stability, high thermal stability (270-290°C) and long lifetimes, and are used for the extraction of volatile compounds in lemon beer using gas chromatography separation and flame ionization detection. The scanning electron micrographs of the fiber surface revealed a polymeric ionic liquid (PIL) film, which is distributed homogeneously on the fiber. The developed PIL fiber showed good linearity between 50 and 2000μg/L with regression coefficients in the range of 0.996-0.999. The relative standard deviations (RSD) obtained in the peak area were found to vary between 1% and 12%, which assured that adequate repeatability was achieved. The spiked recoveries for three beer samples ranged from 78.4% to 123.6%. Experimental design has been employed in the optimization of extraction factors and robustness assessment. The polymeric IL-1 butenyl fiber showed a greater efficiency compared to the PDMS-DVB (65μm) and CAR-PDMS (75μm) for the extraction of all of the analytes studied. PMID:23891206

  17. MINOR ACTINIDE SEPARATIONS USING ION EXCHANGERS OR IONIC LIQUIDS

    SciTech Connect

    Hobbs, D.; Visser, A.; Bridges, N.

    2011-09-20

    This project seeks to determine if (1) inorganic-based ion exchange materials or (2) electrochemical methods in ionic liquids can be exploited to provide effective Am and Cm separations. Specifically, we seek to understand the fundamental structural and chemical factors responsible for the selectivity of inorganic-based ion-exchange materials for actinide and lanthanide ions. Furthermore, we seek to determine whether ionic liquids can serve as the electrolyte that would enable formation of higher oxidation states of Am and other actinides. Experiments indicated that pH, presence of complexants and Am oxidation state exhibit significant influence on the uptake of actinides and lanthanides by layered sodium titanate and hybrid zirconium and tin phosphonate ion exchangers. The affinity of the ion exchangers increased with increasing pH. Greater selectivity among Ln(III) ions with sodium titanate materials occurs at a pH close to the isoelectric potential of the ion exchanger. The addition of DTPA decreased uptake of Am and Ln, whereas the addition of TPEN generally increases uptake of Am and Ln ions by sodium titanate. Testing confirmed two different methods for producing Am(IV) by oxidation of Am(III) in ionic liquids (ILs). Experimental results suggest that the unique coordination environment of ionic liquids inhibits the direct electrochemical oxidation of Am(III). The non-coordinating environment increases the oxidation potential to a higher value, while making it difficult to remove the inner coordination of water. Both confirmed cases of Am(IV) were from the in-situ formation of strong chemical oxidizers.

  18. Free Radical Polymerization of Styrene and Methyl Methacrylate in Various Room Temperature Ionic Liquids

    SciTech Connect

    Zhang, Hongwei; Hong, Kunlun; Mays, Jimmy

    2005-01-01

    Conventional free radical polymerization of styrene and methyl methacrylate was carried out in various room temperature ionic liquids (RTILs). The RTILs used in this research encompass a wide range of cations and anions. Typical cations include imidazolium, phosphonium, pyridinium, and pyrrolidinium; typical anions include amide, borate, chloride, imide, phosphate, and phosphinate. Reactions are faster and polymers obtained usually have higher molecular weights when compared to polymerizations carried out in volatile organic solvents under the same conditions. This shows that rapid rates of polymerization and high molecular weights are general features of conventional radical polymerizations in RTILs. Attempts to correlate the polarities and viscosities of the RTILs with the polymerization behavior fail to yield discernible trends.

  19. Graphene/Ionic liquid composite films and ion exchange.

    PubMed

    Mo, Yufei; Wan, Yunfang; Chau, Alicia; Huang, Fuchuan

    2014-01-01

    Wettability of graphene is adjusted by the formation of various ionic surfaces combining ionic liquid (IL) self-assembly with ion exchange. The functionalized ILs were designed and synthesized with the goal of obtaining adjustable wettability. The wettability of the graphene surface bearing various anions was measured systematically. The effect of solvent systems on ion exchange ratios on the graphene surface has also been investigated. Meanwhile, the mechanical properties of the graphene/IL composite films were investigated on a nanometer scale. The elasticity and adhesion behavior of the thin film was determined with respected to the indentation deformation by colloid probe nanoindentation method. The results indicate that anions played an important role in determining graphene/IL composite film properties. In addition, surface wetting and mechanics can be quantitatively determined according to the counter-anions on the surface. This study might suggest an alternate way for quantity detection of surface ions by surface force. PMID:24970602

  20. Graphene/Ionic Liquid Composite Films and Ion Exchange

    NASA Astrophysics Data System (ADS)

    Mo, Yufei; Wan, Yunfang; Chau, Alicia; Huang, Fuchuan

    2014-06-01

    Wettability of graphene is adjusted by the formation of various ionic surfaces combining ionic liquid (IL) self-assembly with ion exchange. The functionalized ILs were designed and synthesized with the goal of obtaining adjustable wettability. The wettability of the graphene surface bearing various anions was measured systematically. The effect of solvent systems on ion exchange ratios on the graphene surface has also been investigated. Meanwhile, the mechanical properties of the graphene/IL composite films were investigated on a nanometer scale. The elasticity and adhesion behavior of the thin film was determined with respected to the indentation deformation by colloid probe nanoindentation method. The results indicate that anions played an important role in determining graphene/IL composite film properties. In addition, surface wetting and mechanics can be quantitatively determined according to the counter-anions on the surface. This study might suggest an alternate way for quantity detection of surface ions by surface force.

  1. Graphene/Ionic Liquid Composite Films and Ion Exchange

    PubMed Central

    Mo, Yufei; Wan, Yunfang; Chau, Alicia; Huang, Fuchuan

    2014-01-01

    Wettability of graphene is adjusted by the formation of various ionic surfaces combining ionic liquid (IL) self-assembly with ion exchange. The functionalized ILs were designed and synthesized with the goal of obtaining adjustable wettability. The wettability of the graphene surface bearing various anions was measured systematically. The effect of solvent systems on ion exchange ratios on the graphene surface has also been investigated. Meanwhile, the mechanical properties of the graphene/IL composite films were investigated on a nanometer scale. The elasticity and adhesion behavior of the thin film was determined with respected to the indentation deformation by colloid probe nanoindentation method. The results indicate that anions played an important role in determining graphene/IL composite film properties. In addition, surface wetting and mechanics can be quantitatively determined according to the counter-anions on the surface. This study might suggest an alternate way for quantity detection of surface ions by surface force. PMID:24970602

  2. Thiophene-based ionic liquids: synthesis, physical properties, self-assembly and oxidative polymerization.

    SciTech Connect

    Burns, C. T.; Lee, S.; Seifert, S.; Firestone, M. A.

    2008-07-01

    Preparation and polymerization of methylimidazolium-based ionic liquids (ILs) that incorporate a thiophene moiety at the terminus of a C{sub 10} alkyl chain are described. Both a bromide and nitrate salt of the amphiphilic thiophene IL self-assembles in water (albeit the nitrate to a lesser extent), adopting columnar mesophases. Polarized optical microscopy and small-angle X-ray scattering (SAXS) studies show that at low water content the IL-water binary mixtures form liquid crystalline mesophases possessing significant short-range ordering due to strong {pi} interactions between adjacent thiophene moieties. At higher water content, the short-range ordering is lost, but long-range ordering persists up to ca. 45% (w/w) water. The chemical oxidative coupling of the nitrate monomer yields a highly water-soluble polymer. Electrochemical studies show that the polymer possesses a high oxidation potential (1.95 V) and thus, is resistant to chemical doping. In dilute aqueous solution, electronic absorption spectroscopy and X-ray scattering show the polymer adopts a random, coil-like conformational state. Slight improvement in the polymer conformation can be achieved by exchange of the counter anion.

  3. Advance workflow in lipoproteomics via polymeric ion exchanger.

    PubMed

    Javeed, Rabia; Jabeen, Fahmida; Saeed, Hira; Najam-ul-Haq, Muhammad

    2015-03-17

    A workflow is designed for the analysis of lipoproteins, high density lipoproteins (HDL), apoproteins, and lipid fraction, employing an organic polymeric anion exchanger through the enrichment of lipoproteins/peptides from serum. Polymeric separation media are chemically stable over the wide pH range. Poly(GMA/DVB), poly(GMA/EGDMA), and poly(GPE/DVB) are synthesized by radical polymerization, derivatized as strong anion exchangers, and used for lipoproteins enrichment. Lipoprotein's surface is covered by phospholipids, having phosphate groups, therefore lipoproteins are enriched by the interaction of anion exchanger with the phosphate groups and eluted at the pH of 7.5. HDL are further isolated by precipitating the very low-density lipoproteins (VLDL) and low-density lipoproteins (LDL) with phosphotungstic acid as precipitating reagent, followed by delipidation via liquid/liquid extraction. Apolipoproteins profiling is done by MALDI-MS, and lipids are analyzed using gold nanoparticles in the LDI-MS process. This study introduces a lipoproteomics work flow in separation science which analyses the intact lipoproteins. Furthermore, solid phase extraction (SPE)-based methodology is reported for the first time in lipoproteomics. Use of organic polymers, high reproducibility, detailed analysis of lipoproteins, apoproteins/peptides, and lipids from the single serum sample are the distinctive features of this workflow. Being biomarkers of numerous diseases, lipoproteins have clinical significance, and this workflow can be used at diagnostic and therapeutic levels. PMID:25674923

  4. Thermally Stimulated Discharge Current Analysis of Polymeric Solid-State Ionic Conductors

    NASA Astrophysics Data System (ADS)

    Xu, Haisheng; Gu, Qingchao; Fan, Maosen; Yang, Changzheng

    1997-06-01

    Thermally Stimulated Discharge Current (TSDC) analysis was used to study the electrical properties of two systems of polymeric solid-state ionic conductors. One system consisted of LiClO4 doped polyethylene glycol polyurethaneureas (PEUU) characterized by bi-ionic conduction and the other system was based on a sulfonated polyethylene oxide polyurethane ionomer (SPUI) characterized by a single-ion transport mechanism. TSDC spectra of the PEUU as well as SPUI matrices showed four peaks (, , , and ). These peaks are found to be related to the local motion of polyether soft segments, glass transition, Maxwell-Wagner-Sillars interfacial polarization and transport of charged ionic species, respectively. The discharge currents without polarization varying with temperature for both, the PEUU-LiClO4 complex and SPUI, are also measured. These curves of discharge current show only one peak which is attributed to transport of charged ionic species. The temperature range in which the discharge current exhibits a steep increase is consistent with the temperature range in which a turning point appears on the plot of lg i versus 1000/T obtained by ac impedance analysis. The experimental results demonstrate that the TSDC analysis is a valuable tool for studying polymeric solid-state ionic conductors.

  5. Preparation of poly(acrylic acid) particles by dispersion polymerization in an ionic liquid.

    PubMed

    Minami, Hideto; Kimura, Akira; Kinoshita, Keigo; Okubo, Masayoshi

    2010-05-01

    Poly(acrylic acid) (PAA) particles were successfully prepared by dispersion polymerization of acrylic acid in ionic liquid, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoro-methanesulfonyl)amide ([DEME][TFSA]) at 70 degrees C with low hydrolysis grade (35.4%) poly(vinyl alcohol) as stabilizer. Interestingly, the PAA particles were easily extracted as particle state with water. Thus, the PAA particles had a cross-linked structure during the polymerization without cross-linker. Moreover, it was also noted that the cross-linking density of the PAA particles could be controlled by thermal treatment at various temperatures in [DEME][TFSA] utilizing the advantages of nonvolatility and high thermal stability of the ionic liquid. PMID:20043688

  6. Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids

    DOE PAGESBeta

    Fan, Fei; Wang, Weiyu; Holt, Adam P.; Feng, Hongbo; Uhrig, David; Lu, Xinyi; Hong, Tao; Wang, Yangyang; Kang, Nam-Goo; Mays, Jimmy; et al

    2016-06-07

    The unique properties of ionic liquids (ILs) have made them promising candidates for electrochemical applications. Polymerization of the corresponding ILs results in a new class of materials called polymerized ionic liquids (PolyILs). Though PolyILs offer the possibility to combine the high conductivity of ILs and the high mechanical strength of polymers, their conductivities are typically much lower than that of the corresponding small molecule ILs. In this study, seven PolyILs were synthesized having degrees of polymerization ranging from 1 to 333, corresponding to molecular weights (MW) from 482 to 160 400 g/mol. Depolarized dynamic light scattering, broadband dielectric spectroscopy, rheology,more » and differential scanning calorimetry were employed to systematically study the influence of MW on the mechanism of ionic transport and segmental dynamics in these materials. Finally, the modified Walden plot analysis reveals that the ion conductivity transforms from being closely coupled with structural relaxation to being strongly decoupled from it as MW increases.« less

  7. Polymerized ionic liquid diblock copolymers: impact of water/ion clustering on ion conductivity.

    PubMed

    Nykaza, Jacob R; Ye, Yuesheng; Nelson, Rachel L; Jackson, Aaron C; Beyer, Frederick L; Davis, Eric M; Page, Kirt; Sharick, Sharon; Winey, Karen I; Elabd, Yossef A

    2016-01-28

    Herein, we examine the synergistic impact of both ion clustering and block copolymer morphology on ion conductivity in two polymerized ionic liquid (PIL) diblock copolymers with similar chemistries but different side alkyl spacer chain lengths (ethyl versus undecyl). When saturated in liquid water, water/ion clusters were observed only in the PIL block copolymer with longer alkyl side chains (undecyl) as evidenced by both small-angle neutron scattering and intermediate-angle X-ray scattering, i.e., water/ion clusters form within the PIL microdomain under these conditions. The resulting bromide ion conductivity in the undecyl sample was higher than the ethyl sample (14.0 mS cm(-1)versus 6.1 mS cm(-1) at 50 °C in liquid water) even though both samples had the same block copolymer morphology (lamellar) and the undecyl sample had a lower ion exchange capacity (0.9 meq g(-1)versus 1.4 meq g(-1)). No water/ion clusters were observed in either sample under high humidity or dry conditions. The resulting ion conductivity in the undecyl sample with lamellar morphology was significantly higher in the liquid water saturated state compared to the high humidity state (14.0 mS cm(-1)versus 4.2 mS cm(-1)), whereas there was no difference in ion conductivity in the ethyl sample when comparing these two states. These results show that small chemical changes to ion-containing block copolymers can induce water/ion clusters within block copolymer microdomains and this can subsequently have a significant effect on ion transport. PMID:26575014

  8. Ionic resistance and permselectivity tradeoffs in anion exchange membranes.

    PubMed

    Geise, Geoffrey M; Hickner, Michael A; Logan, Bruce E

    2013-10-23

    Salinity gradient energy technologies, such as reverse electrodialysis (RED) and capacitive mixing based on Donnan potential (Capmix CDP), could help address the global need for noncarbon-based energy. Anion exchange membranes (AEMs) are a key component in these systems, and improved AEMs are needed in order to optimize and extend salinity gradient energy technologies. We measured ionic resistance and permselectivity properties of quaternary ammonium-functionalized AEMs based on poly(sulfone) and poly(phenylene oxide) polymer backbones and developed structure-property relationships between the transport properties and the water content and fixed charge concentration of the membranes. Ion transport and ion exclusion properties depend on the volume fraction of water in the polymer membrane, and the chemical nature of the polymer itself can influence fine-tuning of the transport properties to obtain membranes with other useful properties, such as chemical and dimensional stability. The ionic resistance of the AEMs considered in this study decreased by more than 3 orders of magnitude (i.e., from 3900 to 1.6 Ω m) and the permselectivity decreased by 6% (i.e., from 0.91 to 0.85) as the volume fraction of water in the polymer was varied by a factor of 3.8 (i.e., from 0.1 to 0.38). Water content was used to rationalize a tradeoff relationship between the permselectivity and ionic resistance of these AEMs whereby polymers with higher water content tend to have lower ionic resistance and lower permselectivity. The correlation of ion transport properties with water volume fraction and fixed charge concentration is discussed with emphasis on the importance of considering water volume fraction when interpreting ion transport data. PMID:24040962

  9. Chain exchange kinetics of block copolymer micelles in ionic liquids

    NASA Astrophysics Data System (ADS)

    Ma, Yuanchi; Lodge, Timothy

    The chain exchange kinetics of block copolymer micelles has been studied using time-resolved small-angle neutron scattering (TR-SANS), a key tool in determining the average micelle composition in contrast-matched solvents. In this work, PMMA-block-PnBMA was selected as the model block copolymer, which has a LCST behavior in the common ionic liquids, [EMIM][TFSI] and [BMIM][TFSI]. We examined the chain exchange kinetics of three PMMA-block-PnBMA copolymers, with identical PMMA block length (MPMMA = 25000) and different PnBMA block lengths (MPnBMA = 24000, 35000 and 53000); the Flory-Huggins interaction parameter (χ) between the core (PnBMA) and the solvent were varied by mixing [EMIM][TFSI] and [BMIM][TFSI] in different ratios. We found that the relaxation of the initial segregation of h- and d- micelles followed the same form with the time as previously developed by our group. Assuming that single chain expulsion is the rate limiting step, the thermal barrier was found to depend linearly on the core block length (Ncore) . Furthermore, the effect of χ on the chain exchange kinetics will also be discussed.

  10. Optimizing the electrochemical performance of imidazolium-based polymeric ionic liquids by varying tethering groups

    NASA Astrophysics Data System (ADS)

    Jia, Zhe

    Increasing efforts have been made in the area of sustainable alternative energy devices in the past few decades in order to develop high efficiency, low-cost electrochemical devices with sufficient long-term stability. Due to the drawbacks of conventional organic liquid electrolytes, such as leakage, volatility, flammability, and toxicity, the synthesis of solvent-free electrolyte materials has been studied world-wide. Among all the alternatives, polymer electrolytes are of great interest and have attracted many research groups. Solid-state polymer electrolytes and in particular, polymer ionic liquids (PILs), considered to be promising candidates, have been under studied widely. Ionic Liquids (ILs), defined as organic/inorganic salts with m.p. lower than 100 °C, offer good chemical stability, low flammability, negligible vapor pressure and high ionic conductivity. PILs, as the polymerized state of ILs, not only present some of the unique properties of ILs, but also benefit from the intrinsic properties of polymers, such as better thermal and chemical stability, enhanced mechanical properties, and tunable solution properties. The constrained structure of PILs may help to overcome fabrication and leakage problems associated with simple liquid electrolytes, but typically also leads to lower ionic conductivity. Once polymerized, the ionic conductivity of PILs drops substantially, usually by several orders of magnitude compared to the corresponding monomers. Therefore, to improve PILs chain mobilitiy is crucial. Previous studies suggest that a flexible tethering group should make the polymer backbone less rigid and increase electrolyte ion mobility. To investigate how tethering groups affect both electrochemical performance and physical properties of free ILs and PILs, we first report the synthesis and characterization of a novel class of imidazolium (Im) based IL model compounds and their corresponding PILs. Poly(ethylene oxide)s (PEOs), considered to be promising

  11. Ionic Liquids and New Proton Exchange Membranes for Fuel Cells

    NASA Technical Reports Server (NTRS)

    Belieres, Jean-Philippe

    2004-01-01

    There is currently a great surge of activity in fuel cell research as laboratories across the world seek to take advantage of the high energy capacity provided by &el cells relative to those of other portable electrochemical power systems. Much of this activity is aimed at high temperature fie1 cells, and a vital component of such &el cells must be the availability of a high temperature stable proton-permeable membrane. NASA Glenn Research Center is greatly involved in developing this technology. Other approaches to the high temperature fuel cell involve the use of single- component or almost-single-component electrolytes that provide a path for protons through the cell. A heavily researched case is the phosphoric acid fuel cell, in which the electrolyte is almost pure phosphoric acid and the cathode reaction produces water directly. The phosphoric acid fie1 cell delivers an open circuit voltage of 0.9 V falling to about 0.7 V under operating conditions at 170 C. The proton transport mechanism is mainly vehicular in character according to the viscosity/conductance relation. Here we describe some Proton Transfer Ionic Liquids (PTILs) with low vapor pressure and high temperature stability that have conductivities of unprecedented magnitude for non-aqueous systems. The first requirement of an ionic liquid is that, contrary to experience with most liquids consisting of ions, it must have a melting point that is not much above room temperature. The limit commonly suggested is 100 C. PTILs constitute an interesting class of non-corrosive proton-exchange electrolyte, which can serve well in high temperature (T = 100 - 250 C) fuel cell applications. We will present cell performance data showing that the open circuit voltage output, and the performance of a simple H2(g)Pt/PTIL/Pt/O2(g) fuel cell may be superior to those of the equivalent phosphoric acid electrolyte fuel cell both at ambient temperature and temperatures up to and above 200 C. My work at NASA Glenn Research

  12. An Aqueous Thermodynamic Model for Polymerized Silica Species to High Ionic Strength

    SciTech Connect

    Felmy, Andrew R.; Cho, Herman M.; Rustad, James R.; Mason, Marvin J.

    2001-06-01

    The development of an aqueous thermodynamic model for polymerized silica species is presented which is valid to high ionic strengths and high dissolved silica concentration ({approx}0.1m) at low temperature (22-25 C). The model is based upon the equations of Pitzer and has been parameterized from solubility, electromotive force (emf), and nuclear magnetic resonance (NMR) data. The description of the silica speciation reactions at high dissolved silica and basic conditions (pH > 10) required the inclusion of monomeric, dimeric, trimeric (linear, cyclic and substituted), tetrameric (linear and cyclic) and hexameric (prismatic) species. The standard state equilibrium constants for the formation of these species, as well as the necessary Pitzer ion-interaction parameters to describe the ionic strength dependence of the formation reactions were determined.

  13. Polymer electrolytes containing guanidinium-based polymeric ionic liquids for rechargeable lithium batteries

    NASA Astrophysics Data System (ADS)

    Li, Mingtao; Yang, Li; Fang, Shaohua; Dong, Siming; Hirano, Shin-ichi; Tachibana, Kazuhiro

    2011-10-01

    The electrochemical properties of solvent-free, quaternary polymer electrolytes based on a novel polymeric ionic liquid (PIL) as polymer host and incorporating 1g13TFSI ionic liquid, LiTFSI salt and nano-scale silica are reported. The PIL-LiTFSI-1g13TFSI-SiO2 electrolyte membranes are found to be chemically stable even at 80 °C in contact with lithium anode and thermally stable up to 320 °C. Particularly, the quaternary polymer electrolytes exhibit high lithium ion conductivity at high temperature, wide electrochemical stability window, time-stable interfacial resistance values and good lithium stripping/plating performance. Batteries assembled with the quaternary polymer electrolyte at 80 °C are capable to deliver 140 mAh g-1 at 0.1C rates with very good capacity retention.

  14. Solvent tunable optical properties of a polymerized vinyl- and thienyl-substituted ionic liquid.

    SciTech Connect

    Becht, G. A.; Lee, S.; Seifert, S.; Firestone, M. A.

    2010-09-16

    Thermal free radical polymerization of a self-assembled, bifunctional imidazolium-based ionic liquid (IL) monomer bearing both vinyl and thienyl groups is reported. FT-IR spectroscopy proves that the polymerization occurs through both the vinyl and thienyl groups. The polymer is resistant to swelling in water and common organic solvents. The as-synthesized polymer can be readily chemically doped and de-doped. Small-angle X-ray scattering studies indicate that the dried polymer adopts a weakly ordered lamellar structure. The p-doped, ethanol-solvated polymer undergoes a structural conversion to a nonlamellar phase. The absorption and photoluminescence spectra can be modulated in both the neutral (thiophene) and p-doped states depending on whether the polymer is dry or ethanol-solvated. The results demonstrate the possibility of incorporating solvent responsive optical characteristics in a {pi}-conjugated polymer.

  15. Conductivity Scaling Relationships in Nanostructured Membranes based on Protic Polymerized Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Sanoja, Gabriel; Lynd, Nathaniel; Segalman, Rachel

    2015-03-01

    Nanostructured membranes based on protic polymerized ionic liquids are of great interest for a variety of electrochemical applications. Understanding the relationship between composition, structure, and ionic conductivity for these materials is essential for designing novel membranes with improved properties. In this work, we explore the effect of volume fraction of ionic liquid on conductivity, σ using a model system composed of poly[isoprene-block-(ethylene oxide-stat-histamine glycidyl ether) diblock copolymers [PI- b - P(EO-stat-HGE)] and the resulting [PI- b - P(EO-stat-IL)] obtained after treatment with trifluoroacetic acid. These materials self-assemble into lamellar structures with volume fractions of ionic liquid ranging from 0.50 to 0.90 as demonstrated by SAXS. PI- b - P(EO-stat-IL) membranes exhibit conductivities up to 4 x 10-3 S/cm at room temperature. In addition, PI- b - P(EO-stat-IL) based membranes have lower water uptake (λ = 8-10) in comparison with most proton conducting membranes reported elsewhere. The low λ in these membranes might translate into a stronger effect of morphology on transport properties. Joint Center for Artificial Photosynthesis.

  16. Trading polymeric microspheres: exchanging DNA molecules via microsphere interaction.

    PubMed

    Morimoto, Nobuyuki; Muramatsu, Kanna; Nomura, Shin-ichiro M; Suzuki, Makoto

    2015-04-01

    A new class of artificial molecular transport system is constructed by polymeric microspheres. The microspheres are prepared by self-assembly of poly(ethylene glycol)-block-poly(3-dimethyl(methacryloyloxyethyl)ammonium propane sulfonate), PEG-b-PDMAPS, by intermolecular dipole-dipole interaction of sulfobetaine side chains in water. Below the upper critical solution temperature (UCST) of PEG-b-PDMAPS, the microspheres (∼1μm) interact with other microspheres by partial and transit fusion. In order to apply the interaction between microspheres, a 3'-TAMRA-labeled single-stranded DNA oligomer (ssDNA) is encapsulated into a PEG-b-PDMAPS microsphere by thermal treatment. The exchange of ssDNA between microspheres is confirmed by fluorescence resonance energy transfer (FRET) quenching derived from double-stranded formation with complementary 5'-BHQ-2-labeled ssDNA encapsulated in PEG-b-PDMAPS microspheres. The exchange rate of ssDNA is controllable by tuning the composition of the polymer. The contact-dependent transport of molecules can be applied in the areas of microreactors, sensor devices, etc. PMID:25731098

  17. Fabrication of core-shell structured magnetic nanocellulose base polymeric ionic liquid for effective biosorption of Congo red dye.

    PubMed

    Beyki, Mostafa Hossein; Bayat, Mehrnoosh; Shemirani, Farzaneh

    2016-10-01

    Ionic liquids are considered to be a class of environmentally friendly compounds as combination of them with bioresource polymeric substances such as; cellulose, constitute emerging coating materials. Biosorption by polymeric ionic liquids exhibits an attractive green way that involves low cost and irrespective of toxicity. As a result, a novel polymeric ionic liquid has been developed by the reaction of one step synthesized Fe3O4-cellulose nanohybrid, epichlorohydrin and 1-methylimidazole and employed as a green sorbent for efficient biosorption of Congo red dye. Effective parameters on dye removing as well as their interactions were determined with response surface methodology (RSM). Congo red adsorption showed fast equilibrium time (11min) with maximum uptake of 131mgg(-1). Isotherm study revealed that Langmuir adsorption model can better describe dye adsorption behavior. Regeneration of the sorbent was performed with a mixture of methanol-acetone-NaOH (3.0molL(-1)) solution. PMID:27372013

  18. Innovative Poly(Ionic Liquid)s by the Polymerization of Deep Eutectic Monomers.

    PubMed

    Isik, Mehmet; Ruiperez, Fernando; Sardon, Haritz; Gonzalez, Alba; Zulfiqar, Sonia; Mecerreyes, David

    2016-07-01

    The incorporation of ionic liquid (IL) chemistry into functional polymers has extended the properties and applications of polyelectrolytes. However, ILs are expensive due to the presence of fluorinated anions or complicated synthetic steps which limit their technological viability. Here, we show a new family of poly(ionic liquid)s (PILs) which are based in cheap and renewable chemicals and involves facile synthetic approaches. Thus, deep eutectic monomers (DEMs) are prepared for the first time by using quaternary ammonium compounds and various hydrogen bond donors such as citric acid, terephthalic acid or an amidoxime. The deep eutectic formation is made through a simple mixing of the ingredients. Differential scanning calorimetry, nuclear magnetic resonance (NMR) and computational studies reveal the formation of the DEMs due to the ionic interactions. The resulting DEMs are liquid which facilitates their polymerization using mild photopolymerization or polycondensation strategies. Spectroscopic characterizations reveal the successful formation of the polymers. By this way, a new family of PILs can be synthesized which can be used for different applications. As an example, the polymers show promising performance as solid CO2 sorbents. Altogether the deep eutectic monomer route can lead to non-toxic, cheap and easy-to-prepare alternatives to current PILs for different applications. PMID:26954303

  19. Immobilizing Cr3+ with SO3H-functionalized solid polymeric ionic liquids as efficient and reusable catalysts for selective transformation of carbohydrates into 5-hydroxymethylfurfural.

    PubMed

    Li, Hu; Zhang, Qiuyun; Liu, Xiaofang; Chang, Fei; Zhang, Yuping; Xue, Wei; Yang, Song

    2013-09-01

    A series of functional polymeric ionic liquids (FPILs) were prepared by coupling of SO3H-functionalized polymeric ionic liquids with different counterpart anions containing or excluding CrCl3·6H2O, and characterized by SEM, FT-IR, XRD, NH3-TPD, TG, melting point, ICP-AES, and TEM. The catalytic activity of the prepared solid FPILs was investigated for the conversion of biomass including fructose, glucose and cellulose into 5-hydroxymethylfurfural (HMF) with the presence of DMSO-mediated solvents, successively producing moderate to excellent yields of HMF under atmospheric pressure. The FPILs catalysts developed in this study present improved performance on fructose-to-HMF conversion over other solid catalysts, such as functional ionic liquids supported by silica, metal oxides and strong acid ion exchange resin catalysts, and can be very easily recycled at least five times without significant loss of activity. In addition, a kinetic analysis was carried out to illustrate the formation of HMF. PMID:23850822

  20. Ionic polymer metal composite actuators employing irradiation-crosslinked sulfonated poly(styrene-ran-ethylene) as ion-exchange membranes

    NASA Astrophysics Data System (ADS)

    Wang, Xuanlun; Cheng, Tai-Hong; Xu, Liang; Oh, Il-Kwon

    2009-07-01

    Ionic polymer metal composites (IPMC) are soft polymeric smart materials having large displacement at low voltage in moist environments or water. This type of actuators consists of an ionic membrane and noble metal electrodes plated on both surfaces. The ion-exchange membrane, Nafion, remains as the benchmark for a majority of research and development in IPMC technology. In this research, we employed sulfonated poly(styrene-ran-ethylene) (SPSE) that is crosslinked by UV irradiation as a novel ionic membrane. The crosslinking reaction between polymer matrix and crosslinking agent was proved by FTIR analysis. The sulfonic acid groups were stable during the UV irradiation crosslinking process. Water uptake, ion exchange capacity, and sulfonation degree are characterized for both pure SPSE and crosslinked SPSE membrane. The bending responses of SPSE actuators under both direct current (DC) and alternating current (AC) excitations were investigated. The voltage-current behaviors of the actuators under AC excitations are also measured. Results showed the crosslinked SPSE actuators have better electromechanical performance than that of pure SPSE actuator with regard to tip displacement.

  1. Polymeric ionic liquid-plastic crystal composite electrolytes for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Li, Xiaowei; Zhang, Zhengxi; Li, Sijian; Yang, Li; Hirano, Shin-ichi

    2016-03-01

    In this work, composite polymer electrolytes (CPEs), that is, 80%[(1-x)PIL-(x)SN]-20%LiTFSI, are successfully prepared by using a pyrrolidinium-based polymeric ionic liquid (P(DADMA)TFSI) as a polymer host, succinonitrile (SN) as a plastic crystal, and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as a lithium salt. XRD and DSC measurements confirm that the as-obtained CPEs have amorphous structures. The 80%[50%PIL-50%SN]-20%LiTFSI (50% SN) electrolyte reveals a high room temperature ionic conductivity of 5.74 × 10-4 S cm-1, a wide electrochemical window of 5.5 V, as well as good mechanical strength with a Young's modulus of 4.9 MPa. Li/LiFePO4 cells assembled with the 50% SN electrolyte at 0.1C rate can deliver a discharge capacity of about 150 mAh g-1 at 25 °C, with excellent capacity retention. Furthermore, such cells are able to achieve stable discharge capacities of 131.8 and 121.2 mAh g-1 at 0.5C and 1.0C rate, respectively. The impressive findings demonstrate that the electrolyte system prepared in this work has great potential for application in lithium ion batteries.

  2. Ionic liquid based polymeric liposomes: A stable and biocompatible soft platform for bioelectrochemistry.

    PubMed

    Tian, Yanping; Xia, Jiarui; Zhang, Ling; Zhang, Junhui; Jiang, Yi; Zhang, Yao; Yang, Lini; Zhang, Qian; Xia, Lixin

    2016-10-01

    Polymeric liposomes (denoted as ILs-polysomes) are a biocompatible and conductive nanomaterial, which was first utilised as the electrode material for immobilising and biosensing redox enzyme horseradish peroxide (HRP). The morphology and surface property of IL-polysomes was characterised and systematically compared with unpolymerised ionic liquid based liposomes (denoted as ILs-liposomes). Differing from IL-liposomes, IL-polysomes preserves their original morphology and bilayer membrane structure on glassy carbon (GC) electrodes due to the cross-linking of polymerised lipids, thus exhibiting excellent stability and specific biocompability. Because of the existence of imidazolium ionic liquid moieties on the outer surface, IL-polysomes displays a positive charge in aqueous solution, leading to oppositely charged HRP self-assembling onto the vesicles to form HRP/IL-polysomes/PVA/GC electrodes. Owing to the combined merits of ILs and liposomes, electron transfer between HRP-Fe(III)/Fe(II) redox couples of immobilised enzymes and GC electrodes can be achieved. Therefore, HRP/IL-polysomes/PVA/GC electrodes exhibited good electrocatalytic performance toward the electrocatalysis of H2O2. Accordingly, IL-polysomes could act as an efficient charged platform for the self-assembled redox enzymes to realise direct electrochemistry. IL-polysomes have a promising application in the fabrication of third-generation electrochemical biosensors. PMID:27196632

  3. Theoretical studies on CO2 capture behavior of quaternary ammonium-based polymeric ionic liquids.

    PubMed

    Wang, Tao; Ge, Kun; Chen, Kexian; Hou, Chenglong; Fang, Mengxiang

    2016-05-14

    Quaternary ammonium-based polymeric ionic liquids (PILs) are novel CO2 sorbents as they have high capacity, high stability and high binding energy. Moreover, the binding energy of ionic pairs to CO2 is tunable by changing the hydration state so that the sorbent can be regenerated through humidity adjustment. In this study, theoretical calculations were conducted to reveal the mechanism of the humidity swing CO2 adsorption, based on model compounds of quaternary ammonium cation and carbonate anions. The electrostatic potential map demonstrates the anion, rather than the cation, is chemically preferential for CO2 adsorption. Further, the proton transfer process from water to carbonate at the sorbent interface is successfully depicted with an intermediate which has a higher energy state. By determining the CO2 adsorption energy and activation energy at different hydration states, it is discovered that water could promote CO2 adsorption by reducing the energy barrier of proton transfer. The adsorption/desorption equilibrium would shift to desorption by adding water, which constitutes the theoretical basis for humidity swing. By analyzing the hydrogen bonding and structure of the water molecules, it is interesting to find that the CO2 adsorption weakens the hydrophilicity of the sorbent and results in release of water. The requirement of latent heat for the phase change of water could significantly reduce the heat of adsorption. The special "self-cooling" effect during gas adsorption can lower the temperature of the sorbent and benefit the adsorption isotherms. PMID:27115032

  4. Thin liquid films from aqueous solutions of non-ionic polymeric surfactants.

    PubMed

    Exerowa, Dotchi; Platikanov, Dimo

    2009-01-01

    The conditions of formation and stability of foam, emulsion, and wetting films from aqueous solutions of non-ionic polymeric surfactants have been established. Two types of polymeric surfactants - PEO-PPO-PEO three-block copolymers (A-B-A type) and hydrophobically modified inulin graft polymer (AB(n) type) - have been explored. Information about surface forces and nanoscale phenomena in aqueous films containing polymeric surfactants was obtained using the micro-interferometric technique and the Thin Liquid Film-Pressure Balance Technique. Two types of surface forces, which determine the stability of the foam and emulsion films, have been distinguished, namely: DLVO-forces at low electrolyte concentrations and non-DLVO-forces at high electrolyte concentrations. Non-DLVO-forces are steric surface forces of the brush-to-brush and loop-to-loop interaction type according to De Gennes. A substantial difference in the behavior of these two film types has been established and in the case of O/W emulsion films transitions to Newton black film (NBF) have been observed. These films are very stable and so are the respective emulsions. In contrast the wetting films are relatively thicker compared to emulsion films, and their thickness depends on the concentration of the AB(n) polymeric surfactant. The steric repulsion of the loops and tails of the polymeric surfactant determine the film thickness of wetting films on a hydrophilic solid surface. For solid surfaces with different degrees of hydrophobicity the wetting films are stable only at high polymer concentrations and low degree of hydrophobicity. Otherwise the films are unstable and rupture. Two types of bilayer emulsion films have been distinguished for the first time. One type is related to the brush-to-brush or loop-to-loop interactions according to De Gennes. The other type is a NBF where the forces are also steric between strongly hydrated brush and loops but they are short-range forces acting in a two

  5. Conductive polymeric ionic liquids for electroanalysis and solid-phase microextraction.

    PubMed

    Young, Joshua A; Zhang, Cheng; Devasurendra, Amila M; Tillekeratne, L M Viranga; Anderson, Jared L; Kirchhoff, Jon R

    2016-03-01

    Three novel electropolymerizable thiophene-based ionic liquids (ILs) were synthesized and characterized as potential candidates for developing selective extraction media for chemical analysis. Electropolymerization of the bis[(trifluoromethyl)sulfonyl]imide ([NTf2](-)) analogs successfully produced uniform polymeric thin-films on macro- and microelectrode substrates from both vinyl and methylimidazolium IL monomer derivatives. The resultant conducting polymer IL (CPIL) films were characterized by electrochemical methods and found to exhibit attractive behavior towards anionic species while simultaneously providing an exclusion barrier toward cationic species. Thermogravimetric analysis of the thiophene-based IL monomers established a high thermal stability, particularly for the methylimidazolium IL, which was stable until temperatures above 350 °C. Subsequently, the methylimidazolium IL was polymerized on 125 μm platinum wires and utilized for the first time as a sorbent coating for headspace solid-phase microextraction (HS-SPME). The sorbent coating was easily prepared in a reproducible manner, provided high thermal stability, and allowed for the gas chromatographic analysis of polar analytes. The normalized response of the poly[thioph-C6MIm][NTf2]-based sorbent coating exhibited higher extraction efficiency compared to an 85 μm polyacrylate fiber and excellent fiber-to-fiber reproducibility. Therefore, the electropolymerizable thiophene-based ILs were found to be viable new materials for the preparation of sorbent coatings for HS-SPME. PMID:26873467

  6. Crosslinked polymeric ionic liquids as solid-phase microextraction sorbent coatings for high performance liquid chromatography.

    PubMed

    Yu, Honglian; Merib, Josias; Anderson, Jared L

    2016-03-18

    Neat crosslinked polymeric ionic liquid (PIL) sorbent coatings for solid-phase microextraction (SPME) compatible with high-performance liquid chromatography (HPLC) are reported for the first time. Six structurally different PILs were crosslinked to nitinol supports and applied for the determination of select pharmaceutical drugs, phenolics, and insecticides. Sampling conditions including sample solution pH, extraction time, desorption solvent, desorption time, and desorption solvent volume were optimized using design of experiment (DOE). The developed PIL sorbent coatings were stable when performing extractions under acidic pH and remained intact in various organic desorption solvents (i.e., methanol, acetonitrile, acetone). The PIL-based sorbent coating polymerized from the IL monomer 1-vinyl-3-(10-hydroxydecyl) imidazolium chloride [VC10OHIM][Cl] and IL crosslinker 1,12-di(3-vinylbenzylimidazolium) dodecane dichloride [(VBIM)2C12] 2[Cl] exhibited superior extraction performance compared to the other studied PILs. The extraction efficiency of pharmaceutical drugs and phenolics increased when the film thickness of the PIL-based sorbent coating was increased while many insecticides were largely unaffected. Satisfactory analytical performance was obtained with limits of detection (LODs) ranging from 0.2 to 2 μg L(-1) for the target analytes. The accuracy of the analytical method was examined by studying the relative recovery of analytes in real water samples, including tap water and lake water, with recoveries varying from 50.2% to 115.9% and from 48.8% to 116.6%, respectively. PMID:26896916

  7. Controlled nanopatterning of a polymerized ionic liquid in a strong electric field

    DOE PAGESBeta

    Bocharova, Vera; Agapov, Alexander L.; Tselev, Alexander; Kumar, Rajeev; Berdzinski, Stefan; Strehmel, Veronika; Kisliuk, Alexander; Kravchenko, Ivan I.; Sumpter, Bobby G.; Sokolov, Alexei P.; et al

    2014-12-17

    Nanolithography has become a driving force in advancements of the modern day's electronics, allowing for miniaturization of devices and a steady increase of the calculation, power, and storage densities. Among various nanofabrication approaches, scanning probe techniques, including atomic force microscopy (AFM), are versatile tools for creating nanoscale patterns utilizing a range of physical stimuli such as force, heat, or electric field confined to the nanoscale. In this study, the potential of using the electric field localized at the apex of an AFM tip to induce and control changes in the mechanical properties of an ion containing polymer—a polymerized ionic liquidmore » (PolyIL)—on a very localized scale is explored. In particular, it is demonstrated that by means of AFM, one can form topographical features on the surface of PolyIL-based thin films with a significantly lower electric potential and power consumption as compared to nonconductive polymer materials. Lastly,, by tuning the applied voltage and ambient air humidity, control over dimensions of the formed structures is reproducibly achieved.« less

  8. Controlled nanopatterning of a polymerized ionic liquid in a strong electric field

    SciTech Connect

    Bocharova, Vera; Agapov, Alexander L.; Tselev, Alexander; Kumar, Rajeev; Berdzinski, Stefan; Strehmel, Veronika; Kisliuk, Alexander; Kravchenko, Ivan I.; Sumpter, Bobby G.; Sokolov, Alexei P.; Kalinin, Sergei V.; Strelcov, Evgheni; Collins, Liam

    2014-12-17

    Nanolithography has become a driving force in advancements of the modern day's electronics, allowing for miniaturization of devices and a steady increase of the calculation, power, and storage densities. Among various nanofabrication approaches, scanning probe techniques, including atomic force microscopy (AFM), are versatile tools for creating nanoscale patterns utilizing a range of physical stimuli such as force, heat, or electric field confined to the nanoscale. In this study, the potential of using the electric field localized at the apex of an AFM tip to induce and control changes in the mechanical properties of an ion containing polymer—a polymerized ionic liquid (PolyIL)—on a very localized scale is explored. In particular, it is demonstrated that by means of AFM, one can form topographical features on the surface of PolyIL-based thin films with a significantly lower electric potential and power consumption as compared to nonconductive polymer materials. Lastly,, by tuning the applied voltage and ambient air humidity, control over dimensions of the formed structures is reproducibly achieved.

  9. Ethanol enhanced in vivo gene delivery with non-ionic polymeric micelles inhalation.

    PubMed

    Chao, Yen-Chin; Chang, Shwu-Fen; Lu, Shao-Chun; Hwang, Tzyh-Chang; Hsieh, Wei-Hsien; Liaw, Jiahorng

    2007-03-12

    Modifications of both carriers and host barriers have been investigated for efficient inhalation gene delivery to lung. Here we used a biocompatible, non-ionic poly(ethyleneoxide)-poly(propyleneoxide)-poly(ethyleneoxide) (PEO-PPO-PEO) polymeric micelles (PM) as a carrier and combined it with ethanol to enhance membrane penetration of delivered DNA. The inhalation delivery with six 100 microg doses of pCMV-Lac Z with PM co-formulated with 10%-40% ethanol to nude mice in 2 days at 8 h interval was performed. The beta-galatosidase (beta-Gal) activity was assessed using chlorophenol red-beta-d galactopyranoside (CPRG) and X-gal staining for quantitative and qualitative analysis in tissues. The results showed that beta-Gal activity was significantly increased by 38% in lung around bronchioles when inhalation with PM and 10% ethanol was given. The 10% ethanol also increased the intracellular apparent permeability by 42% in stomach and by 141% in intestine at 48 h after the first dosage of delivery. Also delivery of DNA encoding a functional human cystic fibrosis transmembrane protein (CFTR) using the same inhalation delivery method co-formulated with 10% ethanol, an increased expression of CFTR in lung was detected by immunostaining. We concluded that 10% ethanol co-formulated with the PM system could enhance inhaled gene delivery to airway and gastrointestinal (GI) tract. PMID:17258837

  10. Ring-opening graft polymerization of propylene carbonate onto xylan in an ionic liquid.

    PubMed

    Zhang, Xueqin; Chen, Mingjie; Liu, Chuanfu; Zhang, Aiping; Sun, Runcang

    2015-01-01

    The amidine organocatalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is an effective nucleophilic catalyst. Biocomposites with tuneable properties were successfully synthesized by ring-opening graft polymerization (ROGP) of propylene carbonate (PC) onto xylan using DBU as a catalyst in the ionic liquid (IL) 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The effects of reaction temperature, reaction time and the molar ratio of PC to anhydroxylose units (AXU) in xylan were investigated. The physico-chemical properties of xylan-graft-poly(propylene carbonate) (xylan-g-PPC) copolymers were characterised by FT-IR, NMR, TGA/DTG, AFM and tensile analysis. The FT-IR and NMR results indicated the successful attachment of PPC onto xylan. TGA/DTG suggested the increased thermal stability of xylan after the attachment of PPC side chains. AFM analysis revealed details about the molecular aggregation of xylan-g-PPC films. The results also showed that with the increased DS of xylan-g-PPC copolymers, the tensile strength and Young's modulus of the films decreased, while the elongation at break increased. PMID:25853319

  11. Biocatalytic synthesis of polymeric nanowires by micellar templates of ionic surfactants

    SciTech Connect

    Nazari, K.; Adhami, F.; Najjar-Safari, A.; Salmani, S.; Mahmoudi, A.

    2011-07-15

    Highlights: {yields} Soft-template production of polyguaiacol nanowire was done by peroxidase enzyme. {yields} Main advantage of this simple method is producing soluble encapsulated nanowires. {yields} Nanowire can be easily precipitated and separated by dilution with distilled water. {yields} Size tuned templates of sodium decyl sulfate (d = 2.7 nm) gave nanowires with d = 2-4 nm. {yields} Dried surfactant-coated wires recover freshly on specified and desired applications. -- Abstract: Micelle-templated polyguaiacol nanowires were successfully prepared via polymerization oxidation of guaiacol (o-methoxy phenol) by peroxidase enzyme in the presence of hydrogen peroxide at mild reaction conditions. The dimensions of the prepared nanowires were controlled by tuning the size and shape of the micelle structure via changing and controlling the type, chain length and molar concentrations of the ionic surfactant. The progress of the reaction and estimation of the size of soft micellar templates were followed by UV-Vis spectroscopy and dynamic light scattering (DLS). The resulting micelle encapsulated or purified polyguaiacol nanowires were characterized using transmission electron microscopy (TEM).

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

    PubMed

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

    2011-12-20

    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

  13. Ionic strength-dependent changes in tentacular ion exchangers with variable ligand density. I. Structural properties.

    PubMed

    Bhambure, Rahul; Gillespie, Christopher M; Phillips, Michael; Graalfs, Heiner; Lenhoff, Abraham M

    2016-09-01

    The ligand density critically affects the performance of ion-exchange resins in such measures as the adsorption capacity and transport characteristics. However, for tentacular and other polymer-modified exchangers, the mechanistic basis of the effect of ligand density on performance is not yet fully understood. In this study we map the ionic strength-dependent structural changes in tentacular cation exchangers with variable ligand densities as the basis for subsequent investigation of effects on functional properties. Inverse size-exclusion chromatography (ISEC), scanning electron microscopy (SEM) and small-angle x-ray scattering (SAXS) were used to assess the effect of ionic strength on the pore size and intraparticle architecture of resin variants with different ligand densities. Comparison of ISEC and cryo-SEM results shows a considerable reduction in average pore size with increasing ligand density; these methods also confirm an increase of average pore size at higher ionic strengths. SAXS analysis of ionic strength-dependent conformational changes in the grafted polyelectrolyte layer shows a characteristic ionomer peak at values of the scattering vector q (0.1-0.2Å(-1)) that depend on the ligand density and the ionic strength of the solution. This peak attribution reflects nanoscale changes in the structure of the grafted polyelectrolyte chains that can in turn be responsible for observed pore-size changes in the resins. Finally, salt breakthrough experiments confirm a stronger Donnan exclusion effect on pore accessibility for small ions in the high ligand density variant. PMID:27544749

  14. Anion exchange membrane prepared from simultaneous polymerization and quaternization of 4-vinyl pyridine for non-aqueous vanadium redox flow battery applications

    NASA Astrophysics Data System (ADS)

    Maurya, Sandip; Shin, Sung-Hee; Sung, Ki-Won; Moon, Seung-Hyeon

    2014-06-01

    A simple, single step and environmentally friendly process is developed for the synthesis of anion exchange membrane (AEM) by simultaneous polymerization and quaternization, unlike the conventional membrane synthesis which consists of separate polymerization and quaternization step. The membrane synthesis is carried out by dissolving polyvinyl chloride (PVC) in cyclohexanone along with 4-vinyl pyridine (4VP) and 1,4-dibromobutane (DBB) in the presence of thermal initiator benzoyl peroxide, followed by film casting to get thin and flexible AEMs. The membrane properties such as ion exchange capacity, ionic conductivity and swelling behaviour are tuned by varying the degree of crosslinking. These AEMs exhibit low vanadium permeability, while retaining good dimensional and chemical stability in an electrolyte solution, making them appropriate candidates for non-aqueous vanadium acetylacetonate redox flow battery (VRFB) applications. The optimized membrane displays ion exchange capacity and ionic conductivity of 2.0 mequiv g-1 and 0.105 mS cm-1, respectively, whereas the efficiency of 91.7%, 95.7% and 87.7% for coulombic, voltage and energy parameter in non-aqueous VRFB, respectively. This study reveals that the non-aqueous VRFB performance is greatly influenced by membrane properties; therefore the optimal control over the membrane properties is advantageous for the improved performance.

  15. Correlating Humidity-Dependent Ionically Conductive Surface Area with Transport Phenomena in Proton-Exchange Membranes

    SciTech Connect

    He, Qinggang; Kusoglu, Ahmet; Lucas, Ivan T.; Clark, Kyle; Weber, Adam Z.; Kostecki, Robert

    2011-08-01

    The objective of this effort was to correlate the local surface ionic conductance of a Nafion? 212 proton-exchange membrane with its bulk and interfacial transport properties as a function of water content. Both macroscopic and microscopic proton conductivities were investigated at different relative humidity levels, using electrochemical impedance spectroscopy and current-sensing atomic force microscopy (CSAFM). We were able to identify small ion-conducting domains that grew with humidity at the surface of the membrane. Numerical analysis of the surface ionic conductance images recorded at various relative humidity levels helped determine the fractional area of ion-conducting active sites. A simple square-root relationship between the fractional conducting area and observed interfacial mass-transport resistance was established. Furthermore, the relationship between the bulk ionic conductivity and surface ionic conductance pattern of the Nafion? membrane was examined.

  16. Conductivity Scaling Relationships of Nanostructured Membranes based on Hydrated Protic Polymerized Ionic Liquids: Effect of Domain Spacing

    NASA Astrophysics Data System (ADS)

    Sanoja, Gabriel; Popere, Bhooshan; Beckingham, Bryan; Evans, Christopher; Lynd, Nathaniel; Segalman, Rachel

    Elucidating the relationship between chemical structure, morphology, and ionic conductivity is essential for designing novel materials for electrochemical applications. In this work, the effect of lamellar domain spacing (d) on ionic conductivity (σ) is investigated for a model system of hydrated block copolymer based on a protic polymerized ionic liquid. We present a strategy that allows for the synthesis of a well-defined series of narrowly dispersed PS- b - PIL with constant volume fraction of ionic liquid moieties (fIL ~ 0.39). These materials self-assemble into ordered lamellar morphologies with variable domain spacing (23-59 nm) as demonstrated by SAXS. PS- b - PIL membranes exhibit ionic conductivities above 10-4 S/cm at room temperature, which are independent of domain spacing. The conductivity scaling relationship demonstrated in this work suggests that a mechanically robust membrane can be designed without compromising its ability to transport ions. In addition, PIL-based membranes exhibit lower water uptake (λ = 10) in comparison with many proton-conducting systems reported elsewhere. The low water content of these materials makes them promising candidates for solar-fuels electrochemical devices.

  17. Influence of Ionic Liquids on the Selectivity of Ion Exchange-Based Polymer Membrane Sensing Layers.

    PubMed

    Mendecki, Lukasz; Callan, Nicole; Ahern, Meghan; Schazmann, Benjamin; Radu, Aleksandar

    2016-01-01

    The applicability of ion exchange membranes is mainly defined by their permselectivity towards specific ions. For instance, the needed selectivity can be sought by modifying some of the components required for the preparation of such membranes. In this study, a new class of materials -trihexyl(tetradecyl)phosphonium based ionic liquids (ILs) were used to modify the properties of ion exchange membranes. We determined selectivity coefficients for iodide as model ion utilizing six phosphonium-based ILs and compared the selectivity with two classical plasticizers. The dielectric properties of membranes plasticized with ionic liquids and their response characteristics towards ten different anions were investigated using potentiometric and impedance measurements. In this large set of data, deviations of obtained selectivity coefficients from the well-established Hofmeister series were observed on many occasions thus indicating a multitude of applications for these ion-exchanging systems. PMID:27438837

  18. Influence of Ionic Liquids on the Selectivity of Ion Exchange-Based Polymer Membrane Sensing Layers

    PubMed Central

    Mendecki, Lukasz; Callan, Nicole; Ahern, Meghan; Schazmann, Benjamin; Radu, Aleksandar

    2016-01-01

    The applicability of ion exchange membranes is mainly defined by their permselectivity towards specific ions. For instance, the needed selectivity can be sought by modifying some of the components required for the preparation of such membranes. In this study, a new class of materials –trihexyl(tetradecyl)phosphonium based ionic liquids (ILs) were used to modify the properties of ion exchange membranes. We determined selectivity coefficients for iodide as model ion utilizing six phosphonium-based ILs and compared the selectivity with two classical plasticizers. The dielectric properties of membranes plasticized with ionic liquids and their response characteristics towards ten different anions were investigated using potentiometric and impedance measurements. In this large set of data, deviations of obtained selectivity coefficients from the well-established Hofmeister series were observed on many occasions thus indicating a multitude of applications for these ion-exchanging systems. PMID:27438837

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

    PubMed Central

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

    2015-01-01

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

  20. Polymeric ionic liquid and carbon black composite as a reusable supporting electrolyte: modification of the electrode surface.

    PubMed

    Yoo, Seung Joon; Li, Long-Ji; Zeng, Cheng-Chu; Little, R Daniel

    2015-03-16

    One of the major impediments to using electroorganic synthesis is the need for large amounts of a supporting electrolyte to ensure the passage of charge. Frequently this causes separation and waste problems. To address these issues, a polymeric ionic liquid-Super P carbon black composite has been formulated. The system enables electrolyses to be performed without adding an additional supporting electrolyte, and its efficient recovery and reuse. In addition, the ability of the composite to modify the electrode surface in situ leads to improved kinetics. A practical consequence is that one can decrease catalyst loading without sacrificing efficiency. PMID:25619992

  1. Ionic Liquid-Based Polymer Electrolytes via Surfactant-Assisted Polymerization at the Plasma-Liquid Interface.

    PubMed

    Tran, Quoc Chinh; Bui, Van-Tien; Dao, Van-Duong; Lee, Joong-Kee; Choi, Ho-Suk

    2016-06-29

    We first report an innovative method, which we refer to as interfacial liquid plasma polymerization, to chemically cross-link ionic liquids (ILs). By this method, a series of all-solid state, free-standing polymer electrolytes is successfully fabricated where ILs are used as building blocks and ethylene oxide-based surfactants are employed as an assisted-cross-linking agent. The thickness of the films is controlled by the plasma exposure time or the ratio of surfactant to ILs. The chemical structure and properties of the polymer electrolyte are characterized by scanning electron microscopy (SEM), Fourier transformation infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and electrochemical impedance spectroscopy (EIS). Importantly, the underlying polymerization mechanism of the cross-linked IL-based polymer electrolyte is studied to show that fluoroborate or halide anions of ILs together with the aid of a small amount of surfactants having ethylene oxide groups are necessary to form cross-linked network structures of the polymer electrolyte. The ionic conductivity of the obtained polymer electrolyte is 2.28 × 10(-3) S·cm(-1), which is a relatively high value for solid polymer electrolytes synthesized at room temperature. This study can serve as a cornerstone for developing all-solid state polymer electrolytes with promising properties for next-generation electrochemical devices. PMID:27281115

  2. Polymeric ionic liquid coatings versus commercial solid-phase microextraction coatings for the determination of volatile compounds in cheeses.

    PubMed

    Trujillo-Rodríguez, María J; Yu, Honglian; Cole, William T S; Ho, Tien D; Pino, Verónica; Anderson, Jared L; Afonso, Ana M

    2014-04-01

    The extraction performance of four polymeric ionic liquid (PIL)-based solid-phase microextraction (SPME) coatings has been studied and compared to that of commercial SPME coatings for the extraction of 16 volatile compounds in cheeses. The analytes include 2 free fatty acids, 2 aldehydes, 2 ketones and 10 phenols and were determined by headspace (HS)-SPME coupled to gas chromatography (GC) with flame-ionization detection (FID). The PIL-based coatings produced by UV co-polymerization were more efficient than PIL-based coatings produced by thermal AIBN polymerization. Partition coefficients of analytes between the sample and the coating (Kfs) were estimated for all PIL-based coatings and the commercial SPME fiber showing the best performance among the commercial fibers tested: carboxen-polydimethylsyloxane (CAR-PDMS). For the PIL-based fibers, the highest K(fs) value (1.96 ± 0.03) was obtained for eugenol. The normalized calibration slope, which takes into account the SPME coating thickness, was also used as a simpler approximate tool to compare the nature of the coating within the determinations, with results entirely comparable to those obtained with estimated K(fs) values. The PIL-based materials obtained by UV co-polymerization containing the 1-vinyl-3-hexylimidazolium chloride IL monomer and 1,12-di(3-vinylimiazolium)dodecane dibromide IL crosslinker exhibited the best performance in the extraction of the select analytes from cheeses. Despite a coating thickness of only 7 µm, this copolymeric sorbent coating was capable of quantitating analytes in HS-SPME in a 30 to 2000 µg L(-1) concentration range, with correlation coefficient (R) values higher than 0.9938, inter-day precision values (as relative standard deviation in %) varying from 6.1 to 20%, and detection limits down to 1.6 µg L(-1). PMID:24607122

  3. Mechanisms of metal ion transfer into room-temperature ionic liquids : the role of anion exchange.

    SciTech Connect

    Jensen, M. P.; Neuefeind, J.; Beitz, J. V.; Skanthakumar, S.; Soderholm, L.; Chemistry

    2003-12-17

    The structure and stoichiometry of the lanthanide(III) (Ln) complexes with the ligand 2-thenoyltrifluoroacetone (Htta) formed in a biphasic aqueous room-temperature ionic liquid system have been studied by complementary physicochemical methods. Equilibrium thermodynamics, optical absorption and luminescence spectroscopies, high-energy X-ray scattering, EXAFS, and molecular dynamics simulations all support the formation of anionic Nd(tta){sub 4}{sup -} or Eu(tta){sub 4}{sup -} complexes with no water coordinated to the metal center in 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (C{sub 4}mim{sup +}Tf{sub 2}N{sup -}), rather than the hydrated, neutral complexes, M(tta){sub 3}(H{sub 2}O){sub n} (n = 2 or 3), that form in nonpolar molecular solvents, such as xylene or chloroform. The presence of anionic lanthanide complexes in C{sub 4}mim{sup +}Tf{sub 2}N{sup -} is made possible by the exchange of the ionic liquid anions into the aqueous phase for the lanthanide complex. The resulting complexes in the ionic liquid phase should be thought of as weak C{sub 4}mim{sup +}Ln(tta){sub 4}{sup -} ion pairs which exert little influence on the structure of the ionic liquid phase.

  4. Ionic polymer-metal composite actuators employing sulfonated poly (styrene-ethylene-butylene-styrene) as ionic-exchange membranes

    NASA Astrophysics Data System (ADS)

    Wang, Xuan-Lun; Oh, Il-Kwon; Lu, Jun; Ju, Jin-Hun; Lee, Sun-Woo

    2007-07-01

    There is growing interest in biomimetic motions by employing ionic polymer-metal composites (IPMCs) as the candidates for the fabrication of artificial muscle. However, the membrane materials currently used in IPMC actuators have been limited to a few commercially available perfluorinated ionic polymers, such as Nafion, and they suffer from several shortcomings among which their high cost presents a major obstacle for wide application. With excellent proton conductivity and high water uptake capacity, commercially available Sulfonated poly (styrene-ethylene-butylene-styrene) (SEBS) of low cost has been investigated for many years as a fuel cell membrane. Herein, we report the preparation of a novel IPMC actuator based on the sulfonated SEBS (SSEBS) membrane. The platinum electrodes of the SEBS actuators were obtained with electroless plating procedure, and the cation exchange with lithium was performed by soaking the composite membranes into a 1.5N LiCl solution. The surface and cross-sectional morphologies of the SSEBS actuators were observed by using scanning electron microscopy (SEM), which revealed that the platinum layer up to 8µm was deposited on the top and bottom surfaces of the SSEBS membrane. The electromechanical bending responses were investigated under alternating current excitations with various driving frequencies and voltage amplitudes, which showed high electrical strains under sinusoidal signal. The effect of the membrane thickness on the performance of the actuators was also addressed in this presentation. This kind of IPMC has great potentials for the applications in biomimetic sensors and actuators, which can be utilized to mimic the locomotion of fish and insects and can be applied to micro-robots and bio-medical devices as well.

  5. A mechanism for enhancing ionic accessibility into selective ion exchange resins

    SciTech Connect

    Alexandratos, S.D.; Shelley, C.A.; Horwitz, E.P.; Chiarizia, R.

    1998-07-01

    A bifunctional monophosphonic/sulfonic acid ion exchange resin with high capacity has been synthesized. Metal ion studies have been carried out with europium, americium, and ferric nitrate in solutions of varying acidity, with and without sodium nitrate added. The bifunctional resin complexes far higher levels of Eu(III) from 0.5 and 1 N nitric acid than the monofunctional phosphonic acid resin. It is postulated that the sulfonic acid ligand provides an access mechanism for the metal ions into the polymer matrix by hydrating the matrix and preventing its collapse in high ionic strength solutions thus allowing for rapid ionic complexation by the selective phosphonic acid ligands. The bifunctional monophosphonic/sulfonic acid resin has both ligands bound to a polystyrene support. It complexes higher levels of metal ions than a comparable resin differing only by having the monophosphonic acid ligand directly bound to the C-C backbone. Results are compared to a diphosphonic/sulfonic acid resin.

  6. Chemical immobilization of crosslinked polymeric ionic liquids on nitinol wires produces highly robust sorbent coatings for solid-phase microextraction.

    PubMed

    Ho, Tien D; Toledo, Bruna R; Hantao, Leandro W; Anderson, Jared L

    2014-09-16

    Super elastic nitinol (NiTi) wires were exploited as highly robust supports for three distinct crosslinked polymeric ionic liquid (PIL)-based coatings in solid-phase microextraction (SPME). The oxidation of NiTi wires in a boiling (30%w/w) H2O2 solution and subsequent derivatization in vinyltrimethoxysilane (VTMS) allowed for vinyl moieties to be appended to the surface of the support. UV-initiated on-fiber copolymerization of the vinyl-substituted NiTi support with monocationic ionic liquid (IL) monomers and dicationic IL crosslinkers produced a crosslinked PIL-based network that was covalently attached to the NiTi wire. This alteration alleviated receding of the coating from the support, which was observed for an analogous crosslinked PIL applied on unmodified NiTi wires. A series of demanding extraction conditions, including extreme pH, pre-exposure to pure organic solvents, and high temperatures, were applied to investigate the versatility and robustness of the fibers. Acceptable precision of the model analytes was obtained for all fibers under these conditions. Method validation by examining the relative recovery of a homologous group of phthalate esters (PAEs) was performed in drip-brewed coffee (maintained at 60 °C) by direct immersion SPME. Acceptable recoveries were obtained for most PAEs in the part-per-billion level, even in this exceedingly harsh and complex matrix. PMID:25150693

  7. Force optimization of ionic polymeric platinum composite artificial muscles by means of an orthogonal array manufacturing method

    NASA Astrophysics Data System (ADS)

    Rashid, Tariq; Shahinpoor, Mohsen

    1999-05-01

    Ionic polymer platinum composite (IPPC) artificial muscles have been the subject of research activities at AMRI (Artificial Muscle Research Institute) and have been identified as smart intelligent material. The potential for such artificial muscles is so vast that muscles of different enhanced characteristics will be required in the future to accomplish different desired tasks. However the immediate challenges are to identify, control and enhance different desired characteristics of artificial muscles (IPPC). One important milestone that may be regarded, as the most critical one is to enhance force produced by these artificial muscles. Obviously force enhancement if successful may put these artificial muscles into one-to-one competition against the available line of traditional force actuators which fall in the same category. In order to experimentally approach the process of optimizing the force output of ionic polymeric platinum composite (IPPC) artificial muscles, an orthogonal array method was used to identify potential specific manufacturing procedures. These sets of procedures will eventually be helpful to identify the different desired characteristics of manufactured artificial muscles. One manufactured artificial muscles are tested for force outputs, the best ones would then be easily traced back to manufacturing procedure and will be further enhanced up to the desired levels by further refining the underlying manufacturing procedures. The measure chosen for optimization process was basically the force generated by a specific piece of muscle of specific geometry.

  8. Electro-thermo-mechanics of spring-loaded contractile fiber bundles with applications to ionic polymeric gel and SMA actuators

    SciTech Connect

    Shahinpoor, M.; Wang, G.; Mojarrad, M.

    1994-12-31

    Intelligent material systems and structures have become important in recent years due to some potential engineering applications. Accordingly, based on such materials, structures and their integration with appropriate sensors and actuators, novel applications, useful for a large number of engineering applications have emerged. Here, a mathematical model is presented for the dynamic response of contractile fiber bundles embedded in or around elastic springs that are either linear helical compression springs or hyperelastic springs such as rubber-like materials. The fiber bundle is assumed to consist of a parallel array of contractile fibers made from either contractile polymeric muscles such as polyacrylic acid plus sodium acrylate cross-linked with bisacrylamide (PAAM) or polyacrylonitrile (PAN) fibers. The proposed model considers the electrically or pH-induced contraction of the fibers which may include resistive heating of the fiber in case of shape-memory alloys. The theory then branches out to two different description of such processes for ionic polymeric gel fiber bundles and shape-memory alloy fiber bundles.

  9. Stable Deep Doping of Vapor-Phase Polymerized Poly(3,4-ethylenedioxythiophene)/Ionic Liquid Supercapacitors.

    PubMed

    Karlsson, Christoffer; Nicholas, James; Evans, Drew; Forsyth, Maria; Strømme, Maria; Sjödin, Martin; Howlett, Patrick C; Pozo-Gonzalo, Cristina

    2016-08-23

    Liquid-solution polymerization and vapor-phase polymerization (VPP) have been used to manufacture a series of chloride- and tosylate-doped poly(3,4-ethylenedioxythiophene) (PEDOT) carbon paper electrodes. The electrochemistry, specific capacitance, and specific charge were determined for single electrodes in 1-ethyl-3-methylimidazolium dicyanamide (emim dca) ionic liquid electrolyte. VPP-PEDOT exhibits outstanding properties with a specific capacitance higher than 300 F g(-1) , the highest value reported for a PEDOT-based conducting polymer, and doping levels as high as 0.7 charges per monomer were achieved. Furthermore, symmetric PEDOT supercapacitor cells with the emim dca electrolyte exhibited a high specific capacitance (76.4 F g(-1) ) and high specific energy (19.8 Wh kg(-1) ). A Ragone plot shows that the VPP-PEDOT cells combine the high specific power of conventional ("pure") capacitors with the high specific energy of batteries, a highly sought-after target for energy storage. PMID:27325487

  10. Crystalline, Glassy and Polymeric Electrolytes:. Similarities and Differences in Ionic Transport Mechanisms

    NASA Astrophysics Data System (ADS)

    Souquet, Jean Louis

    2006-06-01

    Ionocovalent crystals or glasses as well as molten salts or salt polymer complexes are currently studied as electrolytes for high energy density batteries. Their large Red/Ox stability range results from their thermodynamic or kinetic characteristics. For all these electrolytes, charge carriers are the consequence of local deviations from electroneutrality, identified as point defects for ionic crystals or partial dissociation in disordered structures. The charge carriers formation derives from a similar activated process. The main difference comes from the migration process, which depends on the dynamic properties of the surrounding medium. When the structural relaxation time is large, an activated process, mainly enthalpic, prevails for charge carriers migration. It is the usual case for ionic crystals or glasses. In the liquid or overcooled liquid states, the structural relaxation time of the medium is shorter that the time required for the activated migration process to occur and a local reorganization of the medium vanishes the energy barrier and provides the free volume necessary to ionic migration. In that case, the migration is mainly an entropic process. The configurational entropy necessary to this process decreases with temperature and vanishes at the so called ideal glass transition temperature which can be estimated by extrapolation of the transport properties or of the thermodynamic characteristics of the medium. However, at the experiment time scale, this configurational entropy disappears at a somewhat higher temperature, the glass transition temperature at which the structural relaxation time corresponds to the measurement time. Some glass forming ionic melts studied in a large temperature scale, over and below the glass transition temperature, evidence the two, enthalpic and entropic, migration mechanisms, allowing the determination of the thermodynamic characteristics of the charge carriers formation and migration. Some recent results indicate

  11. Tunable ionic transport for a triangular nanochannel in a polymeric nanofluidic system.

    PubMed

    Kim, Bumjoo; Heo, Joonseong; Kwon, Hyukjin J; Cho, Seong J; Han, Jongyoon; Kim, Sung Jae; Lim, Geunbae

    2013-01-22

    Recently, tremendous engineering applications utilizing new physics of nanoscale electrokinetics have been reported and their basic fundamentals are actively researched. In this work, we first report a simple and economic but reliable nanochannel fabrication technique, leading to a heterogeneously charged triangular nanochannel. The nanochannel utilized the elasticity of PDMS when it bonded with a micrometer-scale structure on a substrate. Second, we successfully demonstrated novel ionic transportations by tweaking the micrometer structures: (1) the transition of nonlinear ionic conductance depending on the nanochannel properties and (2) the ionic field-effect transistor. Nanochannel conductance has two distinguishable nonlinear regimes called the "surface-charge-governed" and the "geometry-governed" regime and its only individual overlooks were frequently reported. However, the transition between two regimes by adjusting nanochannel properties has not been reported due to the difficulty of functional nanochannel fabrication. In addition, a gate voltage was comfortably applied to the triangular nanochannel so that the field-effect ion transportation was reliably achieved. Therefore, presenting triangular nanochannels have critical advantages over its heterogeneous and tunable surface properties and thus, could be an effective means as an active fundamental to control and manipulate the ion-electromigration through a nanofluidic system. PMID:23244067

  12. Ion distribution in quaternary-ammonium-functionalized aromatic polymers: effects on the ionic clustering and conductivity of anion-exchange membranes.

    PubMed

    Weiber, E Annika; Jannasch, Patric

    2014-09-01

    A series of copoly(arylene ether sulfone)s that have precisely two, three, or four quaternary ammonium (QA) groups clustered directly on single phenylene rings along the backbone are studied as anion-exchange membranes. The copolymers are synthesized by condensation polymerizations that involve either di-, tri-, or tetramethylhydroquinone followed by virtually complete benzylic bromination using N-bromosuccinimide and quaternization with trimethylamine. This synthetic strategy allows excellent control and systematic variation of the local density and distribution of QA groups along the backbone. Small-angle X-ray scattering of these copolymers shows extensive ionic clustering, promoted by an increasing density of QA on the single phenylene rings. At an ion-exchange capacity (IEC) of 2.1 meq g(-1), the water uptake decreases with the increasing local density of QA groups. Moreover, at moderate IECs at 20 °C, the Br(-) conductivity of the densely functionalized copolymers is higher than a corresponding randomly functionalized polymer, despite the significantly higher water uptake of the latter. Thus, the location of multiple cations on single aromatic rings in the polymers facilitates the formation of a distinct percolating hydrophilic phase domain with a high ionic concentration to promote efficient anion transport, despite probable limitations by reduced ion dissociation. These findings imply a viable strategy to improve the performance of alkaline membrane fuel cells. PMID:25044778

  13. Influence of Ionic Inorganic Solutes on Self-Assembly and Polymerization Processes Related to Early Forms of Life: Implications for a Prebiotic Aqueous Medium

    NASA Astrophysics Data System (ADS)

    Monnard, Pierre-Alain; Apel, Charles L.; Kanavarioti, Anastassia; Deamer, David W.

    2002-06-01

    A commonly accepted view is that life began in a marine environment, which would imply the presence of inorganic ions such as Na+, Cl-, Mg2+, Ca2+, and Fe2+. We have investigated two processes relevant to the origin of life - membrane self-assembly and RNA polymerization - and established that both are adversely affected by ionic solute concentrations much lower than those of contemporary oceans. In particular, monocarboxylic acid vesicles, which are plausible models of primitive membrane systems, are completely disrupted by low concentrations of divalent cations, such as magnesium and calcium, and by high sodium chloride concentrations as well. Similarly, a nonenzymatic, nontemplated polymerization of activated RNA monomers in ice/eutectic phases (in a solution of low initial ionic strength) yields oligomers with >80% of the original monomers incorporated, but polymerization in initially higher ionic strength aqueous solutions is markedly inhibited. These observations suggest that cellular life may not have begun in a marine environment because the abundance of ionic inorganic solutes would have significantly inhibited the chemical and physical processes that lead to self-assembly of more complex molecular systems.

  14. Investigation of ionic conductivity of polymeric electrolytes based on poly (ether urethane) networks using positron probe

    NASA Astrophysics Data System (ADS)

    Peng, Z. L.; Wang, B.; Li, S. Q.; Wang, S. J.; Liu, H.; Xie, H. Q.

    1994-10-01

    Positron-lifetime measurements have been made for poly (ether urethane) undoped and doped with [LiClO 4]/[Unit]=0.05 in the temperature range of 120-340 K. The measured lifetime spectra were resolved into three components. The lifetime and the intensity of orthopositronium were used to evaluate the amount of the free volume in poly (ether urethane). It was found that the variation of ionic conductivity with temperature and salt concentration can be rationalised in terms of free volume consideration.

  15. Separation of phenolic acids from natural plant extracts using molecularly imprinted anion-exchange polymer confined ionic liquids.

    PubMed

    Bi, Wentao; Tian, Minglei; Row, Kyung Ho

    2012-04-01

    Polymer-confined ionic liquids were used for the separation of phenolic acids from natural plant extract by utilizing an anion-exchange mechanism. They were synthesized using molecular imprinting technique to reduce non-directional ion-ion interactions during anion-exchange and other interactions with interference substances that could decrease selectivity. A suitable sorbent for phenolic acid separation could be identified based on the adsorption behaviors of phenolic acids on different polymer-confined ionic liquids. Thus, the developed ionic liquid-based molecularly imprinted anion-exchange polymer (IMAP) achieved high recovery rates by solid-phase extraction of phenolic acids from Salicornia herbacea L. extract: 90.1% for protocatechuic acid, 95.5% for ferulic acid and 96.6% for caffeic acid. Moreover, the phenolic acids were separable from each other by repeated solid phase extraction cycles. The proposed method could be used to separate other phenolic acids or organic acids from complex samples. PMID:21903215

  16. Antimony(V) removal from water by hydrated ferric oxides supported by calcite sand and polymeric anion exchanger.

    PubMed

    Miao, Yangyang; Han, Feichao; Pan, Bingcai; Niu, Yingjie; Nie, Guangze; Lv, Lu

    2014-02-01

    We fabricated and characterized two hybrid adsorbents originated from hydrated ferric oxides (HFOs) using a polymeric anion exchanger D201 and calcite as host. The resultant adsorbents (denoted as HFO-201 and IOCCS) were employed for Sb(V) removal from water. Increasing solution pH from 3 to 9 apparently weakened Sb(V) removal by both composites, while increasing temperature from 293 to 313 K only improved Sb(V) uptake by IOCCS. HFO-201 exhibited much higher capacity for Sb(V) than for IOCCS in the absence of other anions in solution. Increasing ionic strength from 0.01 to 0.1 mol/L NaNO3 would result in a significant drop of the capacity of HFO-201 in the studied pH ranges; however, negligible effect was observed for IOCCS under similar conditions. Similarly, the competing chloride and sulfate pose more negative effect on Sb(V) adsorption by HFO-201 than by IOCCS, and the presence of silicate greatly decreased their adsorption simultaneously, while calcium ions were found to promote the adsorption of both adsorbents. XPS analysis further demonstrated that preferable Sb(V) adsorption by both hybrids was attributed to the inner sphere complexation of Sb(V) and HFO, and Ca(II) induced adsorption enhancement possibly resulted from the formation of HFO-Ca-Sb complexes. Column adsorption runs proved that Sb(V) in the synthetic water could be effectively removed from 30 microg/L to below 5 microg/L (the drinking water standard regulated by China), and the effective treatable volume of IOCCS was around 6 times as that of HFO-201, implying that HFO coatings onto calcite might be a more effective approach than immobilization inside D201. PMID:25076522

  17. Water uptake, ionic conductivity and swelling properties of anion-exchange membrane

    SciTech Connect

    Duan, QJ; Ge, SH; Wang, CY

    2013-12-01

    Water uptake, ionic conductivity and dimensional change of the anion-exchange membrane made by Tokuyama Corporation (A201 membrane) are investigated at different temperatures and water activities. Specifically, the amount of water taken up by membranes exposed to water vapor and membranes soaked in liquid water is determined. The water uptake of the A201 membrane increases with water content as well as temperature. In addition, water sorption data shows Schroeder's paradox for the AEMs investigated. The swelling properties of the A201 membrane exhibit improved dimensional stability compared with Nafion membrane. Water sorption of the A201 membrane occurs with a substantial negative excess volume of mixing. The threshold value of hydrophilic fraction in the A201 membrane for ionic conductivity is around 0.34, above which, the conductivity begins to rise quickly. This indicates that a change in the connectivity of the hydrophilic domains occurs when hydrophilic fraction approaches 0.34. (C) 2013 Elsevier B.V. All rights reserved.

  18. Ligand exchange in ionic systems and its effect on silver nucleation and growth.

    PubMed

    Abbott, Andrew P; Azam, Muhammad; Frisch, Gero; Hartley, Jennifer; Ryder, Karl S; Saleem, Saima

    2013-10-28

    The electrodeposition of metals from ionic solutions is intrinsically linked to the reactivity of the solute ions. When metal salts dissolve, the exchange of the anion with the molecular and ionic components from solution affects the speciation and therefore the characteristics of metal reduction. This study investigates the nucleation mechanism, deposition kinetics, metal speciation and diffusion coefficients of silver salts dissolved in Deep Eutectic Solvents. The electrochemical reduction of AgCl, AgNO3 and Ag2O is studied in 1 : 2 choline chloride : ethylene glycol and 1 : 2 choline chloride : urea. Cyclic voltammetry is used to evaluate electrochemical kinetics. Detailed analysis of chronoamperometric data shows that silver deposits form via multiple 3D nucleation with mass transport controlled hemispherical growth. The nucleation mechanism was found to be potential dependent, varying from progressive to instantaneous as the reduction potential becomes more cathodic. Diffusion coefficients are determined using three different methods. Trends are rationalised in terms of solvent viscosity and silver speciation analysis with EXAFS. The morphology of electroreduced silver is investigated with scanning electron microscopy and shows that deposits from the urea based liquid form more dense morphologies than those from the ethylene glycol based liquid. PMID:24019028

  19. Plasma graft-polymerization for synthesis of highly stable hydroxide exchange membrane

    NASA Astrophysics Data System (ADS)

    Hu, Jue; Zhang, Chengxu; Jiang, Lin; Fang, Shidong; Zhang, Xiaodong; Wang, Xiangke; Meng, Yuedong

    2014-02-01

    A novel plasma graft-polymerization approach is adopted to prepare hydroxide exchange membranes (HEMs) using cardo polyetherketone powders (PEK-C) and vinylbenzyl chloride. The benzylic chloromethyl groups can be successfully introduced into the PEK-C polymer matrix via plasma graft-polymerization. This approach enables a well preservation in the structure of functional groups and formation of a highly cross-linked structure in the membrane, leading to an improvement on the stability and performance of HEMs. The chemical stabilities, including alkaline and oxidative stability, are evaluated under severe conditions by measuring hydroxide conductivity and weight changes during aging. The obtained PGP-NOH membrane retains 86% of the initial hydroxide conductivity in 6 mol L-1 KOH solution at 60 °C for 120 h, and 94% of the initial weight in 3 wt% H2O2 solution at 60 °C for 262 h. The PGP-NOH membrane also possesses excellent thermal stability (safely used below 120 °C), alcohol resistance (ethanol permeability of 6.6 × 10-11 m2 s-1 and diffusion coefficient of 3.7 × 10-13 m2 s-1), and an acceptable hydroxide conductivity (8.3 mS cm-1 at 20 °C in deionized water), suggesting a good candidate of PGP-NOH membrane for HEMFC applications.

  20. Biofouling on polymeric heat exchanger surfaces with E. coli and native biofilms.

    PubMed

    Pohl, S; Madzgalla, M; Manz, W; Bart, H J

    2015-01-01

    The biofouling affinity of different polymeric surfaces (polypropylene, polysulfone, polyethylene terephthalate, and polyether ether ketone) in comparison to stainless steel (SS) was studied for the model bacterium Escherichia coli K12 DSM 498 and native biofilms originating from Rhine water. The biofilm mass deposited on the polymer surfaces was minimized by several magnitudes compared to SS. The cell count and the accumulated biomass of E. coli on the polymer surfaces showed an opposing linear trend. The promising low biofilm formation on the polymers is attributed to the combination of inherent surface properties (roughness, surface energy and hydrophobicity) when compared to SS. The fouling characteristics of E. coli biofilms show good conformity with the more complex native biofilms investigated. The results can be utilized for the development of new polymer heat exchangers when using untreated river water as coolant or for other processes needing antifouling materials. PMID:26479780

  1. Swelling and Shrinking Properties of Thermo-Responsive Polymeric Ionic Liquid Hydrogels with Embedded Linear pNIPAAM

    PubMed Central

    Gallagher, Simon; Florea, Larisa; Fraser, Kevin J.; Diamond, Dermot

    2014-01-01

    In this study, varying concentrations of linear pNIPAAM have been incorporated for the first time into a thermo-responsive polymeric ionic liquid (PIL) hydrogel, namely tributyl-hexyl phosphonium 3-sulfopropylacrylate (P-SPA), to produce semi-interpenetrating polymer networks. The thermal properties of the resulting hydrogels have been investigated along with their thermo-induced shrinking and reswelling capabilities. The semi-interpenetrating networks (IPN) hydrogels were found to have improved shrinking and reswelling properties compared with their PIL counterpart. At elevated temperatures (50–80 °C), it was found that the semi-IPN with the highest concentration of hydrophobic pNIPAAM exhibited the highest shrinking percentage of ~40% compared to the conventional P-SPA, (27%). This trend was also found to occur for the reswelling measurements, with semi-IPN hydrogels producing the highest reswelling percentage of ~67%, with respect to its contracted state. This was attributed to an increase in water affinity due to the presence of hydrophilic pNIPAAM. Moreover, the presence of linear pNIPAAM in the polymer matrix leads to improved shrinking and reswelling response compared to the equivalent PIL. PMID:24681582

  2. Swelling and shrinking properties of thermo-responsive polymeric ionic liquid hydrogels with embedded linear pNIPAAM.

    PubMed

    Gallagher, Simon; Florea, Larisa; Fraser, Kevin J; Diamond, Dermot

    2014-01-01

    In this study, varying concentrations of linear pNIPAAM have been incorporated for the first time into a thermo-responsive polymeric ionic liquid (PIL) hydrogel, namely tributyl-hexyl phosphonium 3-sulfopropylacrylate (P-SPA), to produce semi-interpenetrating polymer networks. The thermal properties of the resulting hydrogels have been investigated along with their thermo-induced shrinking and reswelling capabilities. The semi-interpenetrating networks (IPN) hydrogels were found to have improved shrinking and reswelling properties compared with their PIL counterpart. At elevated temperatures (50-80 °C), it was found that the semi-IPN with the highest concentration of hydrophobic pNIPAAM exhibited the highest shrinking percentage of ~40% compared to the conventional P-SPA, (27%). This trend was also found to occur for the reswelling measurements, with semi-IPN hydrogels producing the highest reswelling percentage of ~67%, with respect to its contracted state. This was attributed to an increase in water affinity due to the presence of hydrophilic pNIPAAM. Moreover, the presence of linear pNIPAAM in the polymer matrix leads to improved shrinking and reswelling response compared to the equivalent PIL. PMID:24681582

  3. The effect of cation structure on the mesophase architecture of self-assembled and polymerized imidazolium-based ionic liquids.

    SciTech Connect

    Batra, D.; Seifert, S.; Firestone, M. A.; Materials Science Division

    2007-01-01

    The binary phase behavior of a series of imidazolium-based ionic liquids (ILs) has been investigated. In particular, the effect of two structural modifications of the imidazolium cation, alkyl chain length, and the introduction of a polymerizable acryloyl group at the alkyl chain terminus, has been studied using small angle X-ray scattering. Upon increasing water content, the non-polymerizable IL, 1-decyl-3-methylimidazolium chloride, adopts mesophase structures of predominately two-dimensional (2D) hexagonal symmetry, including structures intermediate in character between lamellae and 2D hexagonal micelles. Introduction of a photopolymerizable acryloyl functional group to form 1-(10-(acryloyloxy)decyl)-3-methylimidazolium chloride produces a rod-coil IL cation that yields self-assembled mesophases in which the formation of tetragonal morphologies is favored. Covalent linking of the IL cations by UV-induced polymerization converts the lyotropic mesophase into three-dimensional biocontinuous chemical gels. Reducing the alkyl chain length, as in the polymerizable IL cation 1-(8-(acryloyloxy)octyl)-3-methylimidazolium chloride, severely reduces the self-assembled mesophase order, and triggers the formation of only weakly ordered one-dimensional lamellar structures.

  4. Hollow fiber membrane-coated functionalized polymeric ionic liquid capsules for direct analysis of estrogens in milk samples.

    PubMed

    Feng, Juanjuan; Sun, Min; Bu, Yanan; Luo, Chuannan

    2016-02-01

    Protein removal process is always time-consuming for the analysis of milk samples. In this work, hollow fiber membrane-coated functionalized polymeric ionic liquid (HF-PIL) capsules were synthesized and used as solid-phase microextraction (SPME) sorbent for direct analysis of estrogens in milk samples. The functionalized PIL monolith sorbent was obtained by copolymerization between 1-(3-aminopropyl)-3-(4-vinylbenzyl)imidazolium 4-styrenesulfonate IL monomer and 1,6-di(3-vinylimidazolium) hexane bishexafluorophosphate IL-crosslinking agent. A group of four capsules were installed as SPME device, to determine four kinds of estrogens (estrone, diethylstilbestrol, hexestrol, and 17α-ethynylestradiol) in milk samples, coupled to high performance liquid chromatography. Extraction and desorption conditions were optimized to get satisfactory extraction efficiency. Good linearity was obtained in the range of 5-200 μg L(-1). The limits of detection were 1 μg L(-1) for diethylstilbestrol and 2 μg L(-1) for 17α-ethynylestradiol, estrone, and hexestrol. The present method was applied to analyze the model analytes in different milk samples. Relative recoveries were in the range of 85.5-112%. The HF-PIL SPME capsules showed satisfactory extraction efficiency and high resistance to sample matrix interference. PMID:26753984

  5. Increase of ionic conductivity in the microporous lithosilicate RUB-29 by Na-ion exchange processes

    NASA Astrophysics Data System (ADS)

    Park, S.-H.; Senyshyn, A.; Paulmann, C.

    2007-12-01

    The ionic conductivity in the zeolite-like lithosilicate RUB-29 (Cs 14Li 24[Li 18Si 72O 172]·14H 2O [S.-H. Park, J.B. Parise, H. Gies, H. Liu, C.P. Grey, B.H. Toby, J. Am. Chem. Soc. 122 (2000) 11023-11024]) increases via simple ion-exchange processes, in particular when Na cations replace a part of Cs + and Li + of the material. The resulting ionic conductivity value of 3.2×10 -3 S cm -1 at 885 K is about two orders higher than that for the original material [S.-H. Park, J.B. Parise, M.E. Franke, T. Seydel, C. Paulmann, Micropor. Mesopor. Mater., in print ( doi:10.1016/j.micromeso.2007.03.040 available online since April 19, 2007)]. The structural basis of a Na +-exchanged RUB-29 sample (Na-RUB-29) at 673 K could be elucidated by means of neutron powder diffraction. Rietveld refinements confirmed the replacement of Na + for both parts of Cs and Li cations, agreeing with idealized cell content, Na 8Cs 8Li 40Si 72O 172. As a result of the incorporation of Na + in large pores, the number of Li + vacancies in dense Li 2O-layers of the structure could increase. This can be one of the main reasons for the improved conductivity in Na-RUB-29. In addition, mobile Na cations may also contribute to the conductivity in Na-RUB-29 as continuous scattering length densities were found around the sites for Na in difference Fourier map.

  6. Imidazolium-Based Polymeric Materials as Alkaline Anion-Exchange Fuel Cell Membranes

    NASA Technical Reports Server (NTRS)

    Narayan, Sri R.; Yen, Shiao-Ping S.; Reddy, Prakash V.; Nair, Nanditha

    2012-01-01

    Polymer electrolyte membranes that conduct hydroxide ions have potential use in fuel cells. A variety of polystyrene-based quaternary ammonium hydroxides have been reported as anion exchange fuel cell membranes. However, the hydrolytic stability and conductivity of the commercially available membranes are not adequate to meet the requirements of fuel cell applications. When compared with commercially available membranes, polystyrene-imidazolium alkaline membrane electrolytes are more stable and more highly conducting. At the time of this reporting, this has been the first such usage for imidazolium-based polymeric materials for fuel cells. Imidazolium salts are known to be electrochemically stable over wide potential ranges. By controlling the relative ratio of imidazolium groups in polystyrene-imidazolium salts, their physiochemical properties could be modulated. Alkaline anion exchange membranes based on polystyrene-imidazolium hydroxide materials have been developed. The first step was to synthesize the poly(styrene-co-(1-((4-vinyl)methyl)-3- methylimidazolium) chloride through a free-radical polymerization. Casting of this material followed by in situ treatment of the membranes with sodium hydroxide solutions provided the corresponding hydroxide salts. Various ratios of the monomers 4-chloromoethylvinylbenzine (CMVB) and vinylbenzine (VB) provided various compositions of the polymer. The preferred material, due to the relative ease of casting the film, and its relatively low hygroscopic nature, was a 2:1 ratio of CMVB to VB. Testing confirmed that at room temperature, the new membranes outperformed commercially available membranes by a large margin. With fuel cells now in use at NASA and in transportation, and with defense potential, any improvement to fuel cell efficiency is a significant development.

  7. Electroactive polymeric sensors in hand prostheses: bending response of an ionic polymer metal composite.

    PubMed

    Biddiss, Elaine; Chau, Tom

    2006-07-01

    In stark contrast to the inspiring functionality of the natural hand, limitations of current upper limb prostheses stemming from marginal feedback control, challenges of mechanical design, and lack of sensory capacity, are well-established. This paper provides a critical review of current sensory systems and the potential of a selection of electroactive polymers for sensory applications in hand prostheses. Candidate electroactive polymers are reviewed in terms of their relevant advantages and disadvantages, together with their current implementation in related applications. Empirical analysis of one of the most novel electroactive polymers, ionic polymer metal composites (IPMC), was conducted to demonstrate its potential for prosthetic applications. With linear responses within the operating range typical of hand prostheses, bending angles, and bending rates were accurately measured with 4.4+/-2.5 and 4.8+/-3.5% error, respectively, using the IPMC sensors. With these comparable error rates to traditional resistive bend sensors and a wide range of sensitivities and responses, electroactive polymers offer a promising alternative to more traditional sensory approaches. Their potential role in prosthetics is further heightened by their flexible and formable structure, and their ability to act as both sensors and actuators. PMID:16260170

  8. Effect of confinement on ionic liquid molecules in porous polymeric network

    NASA Astrophysics Data System (ADS)

    Raut, Prasad; Yuan, Shichen; Miyoshi, Toshikazu, , Dr.; Jana, Sadhan, , Dr.

    Ionic liquids (ILs) have attractive physicochemical properties but their room temperature liquid state necessitates pairing of IL with other solid, porous materials for fabrication of devices. Such materials are called ionogels. Loading of bulky IL molecules in the pores can dramatically affect the physical properties as function of the pore surface chemistry, pore size, and IL polarity. In this study porous syndiotactic polystyrene (sPS) network was made via thermos-reversible gelation. 1-Butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) is incorporated into the pores of sPS. DSC study and the temperature dependence of 13C-CPMAS NMR show that on confinement; the melting point of PYR14TFSI contained in the ionogel increased in comparison to the bulk PYR14TFSI. At room temperature, WAXD study of the ionogels showed diffraction pattern for PYR14TFSI in nanopores, correspondingly 1H NOESY experiments show strong non-bonded cation-cation correlation in ionogels. The results for the bulk IL does not show non-bonded correlation at room temperature, this increment of local order in ionogel might be the results of crystallization of IL molecules in confined geometry.

  9. Separation of proteins by cation-exchange sequential injection chromatography using a polymeric monolithic column.

    PubMed

    Masini, Jorge Cesar

    2016-02-01

    Since sequential injection chromatography (SIC) emerged in 2003, it has been used for separation of small molecules in diverse samples, but separations of high molar mass compounds such as proteins have not yet been described. In the present work a poly(glycidyl methacrylate-co-ethylene dimethacrylate) (GMA-co-EDMA) monolithic column was prepared by free radical polymerization inside a 2.1-mm-i.d. activated fused silica-lined stainless steel tubing and modified with iminodiacetic acid (IDA). The column was prepared from a mixture of 24% GMA, 16% EDMA, 20% cyclohexanol, and 40% 1-dodecanol (all% as w/w) containing 1% of azobisisobutyronitrile (AIBN) (in relation to monomers). Polymerization was done at 60 °C for 24 h. The polymer was modified with 1.0 M IDA (in 2 M Na2CO3, pH 10.5) at 80 °C for 16 h. Separation of myoglobin, ribonuclease A, cytochrome C, and lysozyme was achieved at pH 7.0 (20 mM KH2PO4/K2HPO4) using a salt gradient (NaCl). Myoglobin was not retained, and the other proteins were separated by a gradient of NaCl created inside the holding coil (4 m of 0.8-mm-i.d. PTFE tubing) by sequential aspiration of 750 and 700 μL of 0.2 and 0.1 M NaCl, respectively. As the flow was reversed toward the column (5 μL s(-1)) the interdispersion of these solutions created a reproducible gradient which separated the proteins in 10 min, with the following order of retention: ribonuclease A < cytochrome C < lysozyme. The elution order was consistent with a cation-exchange mechanism as the retention increased with the isoelectric points. PMID:26677024

  10. Electrodialysis of Sulfuric Acid with Cation-Exchange Membranes Prepared by Electron-Beam-Induced Graft Polymerization

    NASA Astrophysics Data System (ADS)

    Asari, Yuki; Shoji, Nobuyoshi; Miyoshi, Kazuyoshi; Umeno, Daisuke; Saito, Kyoichi

    Strongly acidic cation-exchange membranes were prepared by the electron-beam-induced graft polymerization of glycidyl methacrylate onto a high-density polyethylene film with a thickness of 35 μm and the subsequent conversion of the resulting epoxy group into a sulfonic acid group. The resulting cation-exchange membranes with various ion-exchange capacities or sulfonic acid group densities ranging from 1.9 to 2.7 mmol/g were applied to the enrichment of 0.50 mol/L sulfuric acid by electrodialysis. Concentrated sulfuric acids at concentrations of 1.4 to 2.9 mol/L were obtained in the concentrate chamber during the electrodialysis operated at 30 mA/cm2 and 298 K, using a pair of this cation-exchange membrane and a commercially available anion-exchange membrane.

  11. Effects of experimental conditions on extraction yield of extracellular polymeric substances by cation exchange resin.

    PubMed

    Cho, Jinwoo; Hermanowicz, Slawomir W; Hur, Jin

    2012-01-01

    Effects of experimental conditions on the yield of extracellular polymeric substances (EPSs) extraction by cation exchange resin (CER) were investigated using activated sludge flocs. The experimental variables included resin dose, extraction time, sample dilution, and storage time. An empirical model was proposed to describe the kinetics of extraction process. The extraction yield increases with the extraction time and CER dose until it reached the maximum amount of EPS extraction. The maximum yield of EPS was affected as well by the sample dilution, exhibiting a decreasing trend with increasing dilution factor. It was also found that the amount of EPS extracted from a raw sample depends on the storage time. Once EPS was extracted from the sample, however, the EPS keeps its original quantity under storage at 4°C. Based on the model, the maximum amount of EPS extraction and yield rate could be estimated for different conditions. Comparing the model parameters allows one to quantitatively compare the extraction efficiencies under various extracting conditions. Based on the results, we recommend the original sample should be diluted with the volume ratio of above 1:2 and a raw sample should be treated quickly to prevent the reduction of sample homogeneity and original integrity. PMID:22919352

  12. A cation exchange model to describe Cs+ sorption at high ionic strength in subsurface sediments at Hanford site, USA.

    PubMed

    Liu, Chongxuan; Zachara, John M; Smith, Steve C

    2004-02-01

    A theoretical and experimental study of cation exchange in high ionic strength electrolytes was performed using pristine subsurface sediments from the U.S. Department of Energy Hanford site. These sediments are representative of the site contaminated sediments impacted by release of high level waste (HLW) solutions containing 137Cs+ in NaNO3 brine. The binary exchange behavior of Cs+-Na+, Cs+-K+, and Na+-K+ was measured over a range in electrolyte concentration. Vanselow selectivity coefficients (Kv) that were calculated from the experimental data using Pitzer model ion activity corrections for aqueous species showed monotonic increases with increasing electrolyte concentrations. The influence of electrolyte concentration was greater on the exchange of Na+-Cs+ than K+-Cs+, an observation consistent with the differences in ion hydration energy of the exchanging cations. A previously developed two-site ion exchange model [Geochimica et Cosmochimica Acta 66 (2002) 193] was modified to include solvent (water) activity changes in the exchanger phase through application of the Gibbs-Duhem equation. This water activity-corrected model well described the ionic strength effect on binary Cs+ exchange, and was extended to the ternary exchange system of Cs+-Na+-K+ on the pristine sediment. The model was also used to predict 137Cs+ distribution between sediment and aqueous phase (Kd) beneath a leaked HLW tank in Hanfordd's S-SX tank using the analytical aqueous data from the field and the binary ion exchange coefficients for the pristine sediment. The Kd predictions closely followed the trend in the field data and were improved by consideration of water activity effects that were considerable in certain regions of the vadose zone plume. PMID:14734247

  13. A cation exchange model to describe Cs + sorption at high ionic strength in subsurface sediments at Hanford site, USA

    NASA Astrophysics Data System (ADS)

    Liu, Chongxuan; Zachara, John M.; Smith, Steve C.

    2004-02-01

    A theoretical and experimental study of cation exchange in high ionic strength electrolytes was performed using pristine subsurface sediments from the U.S. Department of Energy Hanford site. These sediments are representative of the site contaminated sediments impacted by release of high level waste (HLW) solutions containing 137Cs + in NaNO 3 brine. The binary exchange behavior of Cs +-Na +, Cs +-K +, and Na +-K + was measured over a range in electrolyte concentration. Vanselow selectivity coefficients ( Kv) that were calculated from the experimental data using Pitzer model ion activity corrections for aqueous species showed monotonic increases with increasing electrolyte concentrations. The influence of electrolyte concentration was greater on the exchange of Na +-Cs + than K +-Cs +, an observation consistent with the differences in ion hydration energy of the exchanging cations. A previously developed two-site ion exchange model [Geochimica et Cosmochimica Acta 66 (2002) 193] was modified to include solvent (water) activity changes in the exchanger phase through application of the Gibbs-Duhem equation. This water activity-corrected model well described the ionic strength effect on binary Cs + exchange, and was extended to the ternary exchange system of Cs +-Na +-K + on the pristine sediment. The model was also used to predict 137Cs + distribution between sediment and aqueous phase ( Kd) beneath a leaked HLW tank in Hanfordd's S-SX tank using the analytical aqueous data from the field and the binary ion exchange coefficients for the pristine sediment. The Kd predictions closely followed the trend in the field data and were improved by consideration of water activity effects that were considerable in certain regions of the vadose zone plume.

  14. Hydroxyl-Exchanged Nanoporous Ionic Copolymer toward Low-Temperature Cycloaddition of Atmospheric Carbon Dioxide into Carbonates.

    PubMed

    Guo, Zengjing; Cai, Xiaochun; Xie, Jingyan; Wang, Xiaochen; Zhou, Yu; Wang, Jun

    2016-05-25

    An ionic copolymer catalyst with nanopores, large surface area, high ionic density, and superior basicity was prepared via the radical copolymerization of amino-functionalized ionic liquid bromide and divinylbenzene, followed with a hydroxyl exchange for removing bromonium. Evaluated in chemical fixation of CO2 with epoxides into cyclic carbonates in the absence of any solvent and basic additive, the nanoporous copolymer catalyst showed high and stable activity, superior to various control catalysts including the halogen-containing analogue. Further, high yields were obtained over a wide scope of substrates including aliphatic long carbon-chain alkyl epoxides and internal epoxide, even under atmospheric pressure and less than 100 °C for the majority of the substrates. On the basis of in situ Fourier transform infrared (FT-IR) investigation and density functional theory (DFT) calculation for the reaction intermediates, we proposed a possible reaction mechanism accounting for the superior catalytic activity of the ionic copolymer. The specifically prepared ionic copolymer material of this work features highly stable, noncorrosive, and sustainable catalysis and, thus, may be a new possibility for efficient chemical fixation of CO2 since it is an environmentally friendly, metal-free solid catalyst. PMID:27142654

  15. Study of Np(V) Sorption by Ionic Exchange on Na, K, Ca and Mg-Montmorillonite

    NASA Astrophysics Data System (ADS)

    Benedicto, A.; Begg, J.; Zhao, P.; Kersting, A. B.; Zavarin, M.

    2012-12-01

    The transport behavior of actinides in soil and ground water are highly influenced by clay minerals due to their ubiquity in the environment, reactivity and colloidal properties. Neptunium(V) has been introduced in the environment as a result of nuclear weapons testing [e.g. 1, 2] and is a radionuclide of potential interest for safety assessment of high level radioactive waste disposal because its long half-life and high toxicity [3]. Surface complexation and ionic exchange have been identified as Np(V) sorption mechanisms onto montmorillonite. At pH below 5, Np(V) sorption is mainly attributed to ionic exchange. This study examines Np(V) ion exchange on Na, K, Ca and Mg forms of montmorillonite. Experiments were carried out using 237Np concentrations between 2 x 10-8 M and 5 x 10-6 M at three different ionic strengths 0.1, 0.01 and 0.001M. The pH was maintained at 4.5. Np(V) sorption to montmorillonite homoionized with monovalent cations (Na and K) demonstrated a markedly different behavior to that observed for montmorillonite homoionized with divalent cations (Ca and Mg). Np sorption to Na and K-montmorillonite was greater than Np sorption to Ca and Mg-montmorillonite. Isotherms with Na and K-montmorillonite showed a strong dependence on ionic strength: the percentage of Np adsorbed was near zero at 0.1M ionic strength, but increased to 30% at 0.001 M ionic strength. This suggests ionic exchange is the main Np adsorption mechanism under the experimental conditions investigated. Dependence on ionic strength was not observed in the Np sorption isotherms for Ca and Mg-montmorillonite indicating a low exchange capacity between Np and divalent cations. Modeling of the sorption experimental data will allow determination of the Na+↔NpO2+ and K+↔NpO2+ ionic exchange constants on montmorillonite. References: [1] A. R. Felmy; K. J. Cantrell; S. D. Conradson, Phys. Chem. Earth 2010, 35, 292-297 [2] D. K. Smith; D. L. Finnegan; S. M. Bowen, J. Environ. Radioact. 2003, 67

  16. In-situ graft-polymerization preparation of cation-exchange supermacroporous cryogel with sulfo groups in glass columns.

    PubMed

    Yao, Kejian; Yun, Junxian; Shen, Shaochuan; Chen, Fang

    2007-07-20

    Graft polymerization of monomer chains with expected functional groups onto the matrix pore surfaces by initiator is an effective approach for introducing ion-exchange groups to cryogel matrix to get anion- or cation-exchange supermacroporous cryogels. In this work, a novel cation-exchange cryogel with sulfo binding groups was prepared by grafting of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSA) onto polyacrylamide-based cryogels in glass columns. The grafting polymerization was achieved in an in-situ manner which was performed by pumping the initiator and the reactive solution of graft monomer with sulfo binding groups directly through a cryogel bed pre-produced in a glass column under frozen condition. The axial liquid dispersion characteristics within the monolithic cryogel beds before and after the in-situ polymerization were compared by measuring residence time distributions (RTDs) at various liquid flow rates using tracer pulse-response method. Microstructure morphology of pores within cryogels was analyzed by scanning electron microscopy (SEM). Chromatography of lysozyme was carried out to reveal the protein breakthrough and elution characteristics in the obtained cryogel beds. PMID:17517417

  17. Click Chemistry Finds Its Way in Constructing an Ionic Highway in Anion-Exchange Membrane.

    PubMed

    Ge, Qianqian; Ran, Jin; Miao, Jibin; Yang, Zhengjin; Xu, Tongwen

    2015-12-30

    To find the way to construct an ionic highway in anion-exchange membranes (AEMs), a series of side-chain-type alkaline polymer electrolytes (APEs) based on poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) polymer backbones were synthesized via Cu(I)-catalyzed click chemistry. The resulting triazole groups and quaternary ammonium (QA) groups facilitate the formation of a continuous hydrogen bond network, which will lead to high hydroxide conductivity according to Grotthuss-type mechanism. Microphase separation induced by long alkyl side chains contributes at the same time to further improving the hydroxide conductivity of the resultant AEMs. Hydroxide conductivity as high as 52.8 mS/cm is obtained for membrane TA-14C-1.21 (IEC = 1.21 mmol/g) with the longest pendant chain at 30 °C, and the conductivity can be increased to 140 mS/cm when the temperature was increased to 80 °C. Moreover, the corresponding water uptake is only 8.6 wt % at 30 °C. In the meantime, the membrane properties can be tuned by precisely regulating the hydrophilic/hydrophobic ratio in the cationic head groups. Compared with AEMs containing triazole and quaternized trimethylammonium head groups, enhanced dimensional stability and mechanical properties are obtained by tuning side-chain chemistry. However, the alkaline stability of the membrane is not as stable as anticipated, probably because of the existence of the triazole ring. Further study will be focused on increasing the alkali stability of the membrane. We envisage that the side-chain-type APEs meditated by click chemistry bearing long hydrophobic side chains pendant to the cationic head groups hold promise as a novel AEMs material. PMID:26645427

  18. Atmospheric Ionic Deposition in Tropical Sites of Central Sulawesi Determined by Ion Exchange Resin Collectors and Bulk Water Collector.

    PubMed

    Köhler, S; Jungkunst, H F; Gutzler, C; Herrera, R; Gerold, G

    2012-09-01

    In the light of global change, the necessity to monitor atmospheric depositions that have relevant effects on ecosystems is ever increasing particularly for tropical sites. For this study, atmospheric ionic depositions were measured on tropical Central Sulawesi at remote sites with both a conventional bulk water collector system (BWS collector) and with a passive ion exchange resin collector system (IER collector). The principle of IER collector to fix all ionic depositions, i.e. anions and cations, has certain advantages referring to (1) post-deposition transformation processes, (2) low ionic concentrations and (3) low rainfall and associated particulate inputs, e.g. dust or sand. The ionic concentrations to be measured for BWS collectors may easily fall below detection limits under low deposition conditions which are common for tropical sites of low land use intensity. Additionally, BWS collections are not as independent from the amount of rain fallen as are IER collections. For this study, the significant differences between both collectors found for nearly all measured elements were partly correlated to the rainfall pattern, i.e. for calcium, magnesium, potassium and sodium. However, the significant differences were, in most cases, not highly relevant. More relevant differences between the systems were found for aluminium and nitrate (434-484 %). Almost five times higher values for nitrate clarified the advantage of the IER system particularly for low deposition rate which is one particularity of atmospheric ionic deposition in tropical sites of extensive land use. The monthly resolution of the IER data offers new insights into the temporal distribution of annual ionic depositions. Here, it did not follow the tropical rain pattern of a drier season within generally wet conditions. PMID:22865942

  19. The configuration exchanging theory for transport properties and glass formation temperature of ionic liquids.

    PubMed

    Hu, Yu-Feng; Zhang, Xian-Ming; Qi, Jian-Guang; Yin, Liu-Yi

    2015-11-28

    Understanding molecular motion in terms of molecular structure is an important issue for microscopic understanding of the nature of transport properties and glass transition, and for design of structured materials to meet specific demands in various applications. Herein, a novel molecular mechanism is proposed to connect macroscopic motion in ionic liquids with molecular structure via conformational conversions of the constituent ions or of the cation-anion pairs. New equations for description of relaxation time, diffusion coefficient, molar conductivity, and viscosity of ionic liquids are established. The equation parameters, which were determined from the temperature dependent heat capacities, self-diffusion coefficients, molar conductivities, and viscosities of typical ionic liquids, were used to produce predictions for the corresponding properties of other ionic liquids and for the glass transition temperatures of representative ionic liquids. All predictions are in nice agreements with the experimental results. PMID:26627962

  20. Molecularly imprinted electrochemical sensing interface based on in-situ-polymerization of amino-functionalized ionic liquid for specific recognition of bovine serum albumin.

    PubMed

    Wang, Yanying; Han, Miao; Liu, Guishen; Hou, Xiaodong; Huang, Yina; Wu, Kangbing; Li, Chunya

    2015-12-15

    A molecularly imprinted polymer film was in situ polymerized on a carboxyl functionalized multi-walled carbon nanotubes modified glassy carbon electrode surface under room temperature. This technique provides a promising imprinting approach for protein in an aqueous solution using 3-(3-aminopropyl)-1-vinylimidazolium tetrafluoroborate ionic liquid as functional monomer, N, N'-methylenebisacrylamide as crossing linker, ammonium persulfate and N,N,N',N'-tetramethylethylenediamine as initiator, and bovine serum albumin (BSA) as template. The molecularly imprinted polymerized ionic liquid film shows enhanced accessibility, high specificity and sensitivity towards BSA. Electrochemical sensing performance of the imprinted sensor was thoroughly investigated using K3Fe[CN]6/K4Fe[CN]6 as electroactive probes. Under optimal conditions, the current difference before and after specific recognition of BSA was found linearly related to its concentration in the range from 1.50×10(-9) to 1.50×10(-6) mol L(-1). The detection limit was calculated to be 3.91×10(-10) mol L(-1) (S/N=3). The practical application of the imprinted sensor was demonstrated by determining BSA in liquid milk samples. PMID:26232004

  1. Comparison between polymerized ionic liquids synthesized using chain-growth and step-growth mechanisms used as stationary phase in gas chromatography.

    PubMed

    Roeleveld, Kevin; David, Frank; Lynen, Frédéric

    2016-06-17

    In this study the merits of polymerized imidazolium based ionic liquid (PIL) stationary phases obtained via condensation and free radical polymerizations are compared as stationary phases in gas chromatography (GC). Poly(1-vinyl-3-butyl-imidazolium - bis(trifluoromethane)sulfonamide) (poly(ViC4Im(+) NTf2(-))) was obtained via a chain-growth mechanism while poly(propylimidazolium-NTf2) (poly(C3Im(+) NTf2(-))) was synthesized via a step-growth polymerization. The thermal stability of both polymers was assessed using thermal gravimetric analysis and compared with bleeding profiles obtained from the statically coated GC columns (30m×0.25mm×0.25μm). The performance was compared to what could be obtained on commercially available 1,5-di(2,3-dimethylimidazolium)pentane(2+) 2NTf2(-) (SLB-IL111) ionic liquid based columns. It was observed that the step-growth polymer was more thermally stable, up to 325°C, while the chain-growth polymer showed initial degradation at 250°C. Both polymers allowed reaching minimal plate heights of 0.400-0.500mm for retained solutes such as benzaldehyde, acetophenone, 1-methylnaphthalene and aniline. Assessment of the McReynolds constants illustrated that the polarity of the step-growth polymer was similar to the SLB-IL111 column, while displaying improved column stability. The PIL phases and particularly the so far little studied condensation based polymer shows particular retention and satisfactory column performance for polar moieties such as esters, amine and carbonyl functionalities. PMID:27189433

  2. Ionic polymer-metal composite actuators obtained from radiation-grafted cation- and anion-exchange membranes.

    PubMed

    Park, Jong Hyuk; Han, Man Jae; Song, Dae Seock; Jho, Jae Young

    2014-12-24

    Two series of ionic polymer-metal composites (IPMCs), one cationic and one anionic, are designed and prepared from radiation-grafted ion-exchange membranes. Through examination of the properties of the membranes synthesized from the two grafting monomers and the two base polymers, acrylic acid-grafted poly(vinylidene fluoride-co-hexafluoropropylene) and quarternized 4-vinylpyridine-grafted poly(ethylene-co-tetrafluoroethylene) with the appropriate amount of ionic groups are employed for the fabrication of cation and anion IPMCs, respectively. The bending displacement of the cation IPMC is comparable to Nafion-based IPMC under direct- and alternating-current voltage, but back-relaxation is not observed. The actuation performance of the anion IPMC is highly improved over those reported earlier in the literature for the other anion IPMCs. PMID:25420910

  3. Ionic Polymer-Metal Composites (IPMCs) with Various Ion Exchange Membranes and Their Potential Use in IPMC Applications

    NASA Astrophysics Data System (ADS)

    Park, Jiyeon

    Ionic polymer metal composites (IPMCs) have been widely studied and drawn great attention for the last several years in robotics and medical fields due to their great potential as actuators, artificial muscles, and more. Each part of an IPMC is important, but the role of ionic exchange membrane should be emphasized because, after all, it is where ions migrate when voltage is applied to produce motion. So far, most researches have been done on IPMCs made with commercially available ionic exchange membranes such as Nafion or Flemion. In this thesis, the research is mainly focused on fabricating IPMCs with several other ionic exchange membranes that are commercially available and characterization of optical, physical, and electromechanical properties of those IPMCs. Five different ion exchange membranes of DuPont (N115), Golden Energy Fuel Cells Inc (GEFC-700)., fuMA Tech (F-14100), Membranes International Inc. (CMI-7000S) and University of Nevada Las Vegas (19-PSU-S1) are the chosen membranes. N115, GEFC-700, and F-14100 have the same structure. CMI-7000S is a reinforced membrane by mixing fibers with the ion exchange membrane. 19-PSU-S1 is a membrane that was made at UNLV for fuel cell application. The physical properties of the ionic exchange membranes were studied by examining water uptake. The thermal analysis also was carried out with Differential Scanning Calorimetry (DSC). Water uptake and ion exchange capacities were measured to confirm the physical properties of IPMCs. The structure of the IPMCs was observed under Scanning Electron Microscopy (SEM). The structures of fabricated IPMCs were observed by SEM and DSC. Capacitance was also measured by drawing impedance curves. Young's modulus (E) was measured to determine the stiffness of each IPMC. Lastly, bending actuation test was carried out to observe the actual performance of each IPMC in water. The water uptake of all IPMCs is less than 40%. 19-PSU-S1 absorbed the most water (35.2 %) and CMI-7000S absorbed

  4. Effect of the phorbol ester 12-O-tetradecanoylphorbol-13-acetate (TPA) upon membrane ionic exchanges in sea urchin eggs

    SciTech Connect

    Ciapa, B.; Payan, P. ); Allemand, D. )

    1989-12-01

    The effect of TPA (12-O-tetradecanoylphorbol-13-acetate) upon ionic exchanges was investigated in eggs of the sea urchin Arbacia lixula. Ouabain-sensitive {sup 86}Rb uptake and amiloride-sensitive {sup 24}Na influx were dramatically stimulated after TPA addition, indicating an enhancement of total ionic permeabilities. Stimulation by TPA of both Na{sup +}/H{sup +} and Na{sup +}/K{sup +} exchanges was canceled by amiloride, suggesting that activation of protein kinase C elicits, via Na{sup +}/H{sup +} activity, stimulation of the sodium pump. However, TPA did not stimulate sodium pump activity and Na{sup +}/H{sup +} exchange at the same rate as fertilization, probably because of an absence of calcium-dependent events. Further fertilization of TPA pretreated eggs triggered an enhancement of sodium pump activity when the TPA treatment duration did not exceed 10 minutes. It is suggested that TPA activates preexisting transporting mechanisms in plasma membranes of unfertilized eggs (Na{sup +} stat, pH stat).

  5. Investigation of the enantioselectivity of tetramethylammonium L-hydroxyproline ionic liquid as a novel chiral ligand in ligand-exchange CE and ligand-exchange MEKC.

    PubMed

    Liu, Ruijuan; Du, Yingxiang; Chen, Jiaquan; Zhang, Qi; Du, Shuaijing; Feng, Zijie

    2015-01-01

    Chiral ionic liquids (ILs) have drawn more and more attention in separation science; however, only a few papers focused on the application of chiral ILs as chiral ligands in LE-CE. In this article, a novel amino acid ionic liquid (AAIL), tetramethylammonium L-hydroxyproline ([TMA][L-OH-Pro]), was first applied as a chiral ligand to evaluate its enantioselectivity towards several aromatic amino acids in ligand-exchange capillary electrophoresis (LE-CE) and ligand-exchange micellar electrokinetic capillary chromatography (LE-MEKC). In the LE-CE system, excellent separations were achieved for tryptophan (Rs = 3.03) and 3, 4-dihydroxyphenylalanine (DOPA) (Rs = 4.35). Several parameters affecting the enantioseparation were systematically investigated, including AAIL concentration, type and concentration of central metal ion, buffer pH, as well as applied voltage. The optimum separation was obtained with 60 mM AAIL containing 30 mM Cu (II) at pH 4.5. Additionally, an LE-MEKC system was established to further study the enantioselectivity of [TMA][L-OH-Pro] towards selected analytes. As observed, the separations of the enantiomers of tryptophan, phenylalanine, and histidine were all improved compared to the LE-CE system. The results indicated that the application of AAILs as chiral ligands is a promising method in chiral separation science. PMID:25399872

  6. Diacetylenes with Ionic-Liquid-Like Substituents: Associating a Polymerizing Cation with a Polymerizing Anion in a Single Precursor for the Synthesis of N-Doped Carbon Materials.

    PubMed

    Fahsi, Karim; Dumail, Xavier; Dutremez, Sylvain G; van der Lee, Arie; Vioux, André; Viau, Lydie

    2016-01-26

    Imidazolium- and benzimidazolium-substituted diacetylenes with bromide or nitrogen-rich dicyanamide and tricyanomethanide anions were synthesized and used as precursors for the preparation of N-doped carbon materials. On pyrolysis under argon at 800 °C both halide precursors afforded graphite-like structures with nitrogen contents of about 8.5%. When the dicyanamide and tricyanomethanide precursors were thermolyzed at the same temperature, graphite-like structures were obtained that exhibit nitrogen contents in the range 17-20 wt%; thereby, the benefit of associating a polymerizing cation with a polymerizing anion in a single precursor was demonstrated. On pyrolysis at 1100 °C the nitrogen contents of the latter pyrolysates remain high (ca. 6 wt%). Adsorption measurements with krypton at 77 K indicated that the materials are nonporous. The highest electrical conductivity was observed for a pyrolysate with one of the lowest nitrogen contents, which also has the highest degree of graphitization. Thus, the quest for N-rich carbons with high electrical conductivities should include both maximization of the nitrogen content and optimization of the degree of graphitization. Crystallographic investigation of the precursors and spectroscopic characterization of the pyrolysates prepared by heating at 220 °C indicate that construction of the final carbon framework does not involve the intermediate formation of a polydiacetylene. PMID:26695842

  7. Fabrication of an ionic liquid-based macroporous polymer monolithic column via atom transfer radical polymerization for the separation of small molecules.

    PubMed

    Zhang, Hang; Bai, Ligai; Wei, Zhen; Liu, Sha; Liu, Haiyan; Yan, Hongyuan

    2016-03-01

    A polymer monolithic column was prepared in a stainless steel column (50×4.6mm i.d.) via atom transfer radical polymerization technique using triallyl isocyanurate and ionic liquid (1-allyl-3-methylimidazolium chloride) as co-monomers, ethylene dimethacrylate as cross linking agent, polyethylene glycol 200, 1,4-butanediol, and N, N- dimethylformamide as porogen system, CCl4 as initiator, and FeCl2 as catalyst. The optimized polymer columns were characterized by scanning electron microscope, nitrogen adsorption-desorption instrument, mercury intrusion porosimetry, infrared spectrometer, and thermogravimetric analysis technique. Respectively, all of these factors above could illustrate that the optimized columns had relative uniform macroporous structure and high thermal stability. A series of basic and acidic small molecules, isomers, and homologues were used to evaluate the performance of these monoliths and enhanced column efficiency was obtained. PMID:26717814

  8. Ionically conductive thin polymer films prepared by plasma polymerization; Preparation and characterization of ultrathin films having fixed sulfonic acid groups with only one mobile species

    SciTech Connect

    Ogumi, Z.; Uchimoto, Y.; Takehara, Z. ); Foulkes, F.R. . Dept. of Chemical Engineering and Applied Chemistry)

    1990-01-01

    Ultrathin solid polymer electrolyte membranes containing sulfonic ester groups were prepared by polymerization of methyl benzenesulfonate and octamethylcyclotetrasiloxane in a glow discharge plasma. The sulfonic ester groups of the plasma polymer were transformed to lithium sulfonate groups by treatment with lithium iodide. Hybridization of this plasma polymer containing the lithium sulfonate groups with poly(ethylene oxide) (average Mw 300) resulted in the formation of a single lithium ion conductive film. The hybrid polymer electrolyte films were about 1 {mu}m thick, pinhole-free, adherent to various substrates, and showed ionic conductivities at 60{degrees}C of the order of 10{sup {minus} 6} S cm{sup {minus} 1} (10{sup 2} {Omega} cm{sup 2} resistance per unit area of as-prepared solid polymer electrolyte). This material shows promise for electrochemical applications such as all solid-state lithium batteries, sensors, and electrochemical display devices.

  9. Preparation of a polymeric ionic liquid-based adsorbent for stir cake sorptive extraction of preservatives in orange juices and tea drinks.

    PubMed

    Chen, Lei; Huang, Xiaojia

    2016-04-15

    In this study, a new polymeric ionic liquid-based adsorbent was prepared and used as the extraction medium of stir cake sorptive extraction (SCSE) of three organic acid preservatives, namely, p-hydroxybenzoic acid, sorbic acid and cinnamic acid. The adsorbent was synthesized by the copolymerization of 1-ally-3-vinylimidazolium chloride (AV) and divinylbenzene (DVB) in the presence of a porogen solvent containing 1-propanol and 1,4-butanediol. The effect of the content of monomer and the porogen solvent in the polymerization mixture on the extraction performance was investigated thoroughly. The adsorbent was characterized by infrared spectroscopy, elemental analysis, scanning electron microscopy and mercury intrusion porosimetry. To obtain the optimal extraction conditions of SCSE/AVDVB for target analytes, key parameters including desorption solvent, adsorption and desorption time, ionic strength and pH value in sample matrix were studied in detail. The results showed that under the optimized conditions, the SCSE/AVDVB could extract the preservatives effectively through multiply interactions. At the same time, a simple and sensitive method by combining SCSE/AVDVB and high-performance liquid chromatography with diode array detection was developed for the simultaneous analysis of the target preservatives in orange juices and tea drinks. Low limits of detection (S/N = 3) and quantification limits (S/N = 10) of the proposed method for the target analytes were achieved within the range of 0.012-0.23 μg/L and 0.039-0.42 μg/L, respectively. The precision of the proposed method was evaluated in terms of intra- and inter-assay variability calculated as relative standard deviation (RSD), and it was found that the values were all below 10%. Finally, the proposed method was used to detect preservatives in different orange juice and tea drink samples successfully. The recoveries were in the range of 71.9-116%, and the RSDs were below 10% in the all cases. PMID:27016436

  10. Theoretical and computational studies of renewable energy materials: Room temperature ionic liquids and proton exchange membranes

    NASA Astrophysics Data System (ADS)

    Feng, Shulu

    2011-12-01

    Two kinds of renewable energy materials, room temperature ionic liquids (RTILs) and proton exchange membranes (PEMs), especially Nafion, are studied by computational and theoretical approaches. The ultimate purpose of the present research is to design novel materials to meet the future energy demands. To elucidate the effect of alkyl side chain length and anion on the structure and dynamics of the mixtures, molecular dynamics (MD) simulations of three RTILs/water mixtures at various water mole fractions: 1-butyl-3-methylimidazolium (BMIM+)/BF4-, 1-octyl-3-methylimidazolium (OMIM+)/BF4-, and OMIM +/Cl- are performed. Replacing the BMIM + cation with OMIM+ results in stronger aggregation of the cations as well as a slower diffusion of the anions, and replacing the BF4- anion with Cl- alters the water distribution at low water mole fractions and slows diffusion of the mixtures. Potential experimental manifestations of these behaviors in both cases are provided. Proton solvation properties and transport mechanisms are studied in hydrated Nafion, by using the self-consistent multistate empirical valence bond (SCI-MS-EVB) method. It is found that by stabilizing a more Zundel-like (H5O 2+) structure in the first solvation shells, the solvation of excess protons, as well as the proton hydration structure are both influenced by the sulfonate groups. Hydrate proton-related hydrogen bond networks are observed to be more stable than those with water alone. In order to characterize the nature of the proton transport (PT), diffusive motion, Arrhenius activation energies, and transport pathways are calculated and analyzed. Analysis of diffusive motion suggests that (1) a proton-hopping mechanism dominates the proton transport for the studied water loading levels and (2) there is an obvious degree of anti-correlation between the proton hopping and the vehicular transport. The activation energy drops rapidly with an increasing water content when the water loading level is smaller

  11. Selective extraction of metal ions with polymeric extractants by ion exchange/redox

    DOEpatents

    Alexandratos, Spiro D.

    1987-01-01

    The specification discloses a method for the extraction of metal ions having a reduction potential of above about +0.3 from an aqueous solution. The method includes contacting the aqueous solution with a polymeric extractant having primary phosphinic acid groups, secondary phosphine oxide groups, or both phosphinic acid and phosphine oxide groups.

  12. Development of a functionalized polymeric ionic liquid monolith for solid-phase microextraction of polar endocrine disrupting chemicals in aqueous samples coupled to high-performance liquid chromatography.

    PubMed

    Feng, Juanjuan; Sun, Min; Bu, Yanan; Luo, Chuannan

    2015-09-01

    Ionic liquids (ILs) have been efficiently used as a "designer sorbent" in sample preparation. A novel 1-(3-aminopropyl)-3-(4-vinylbenzyl)imidazolium 4-styrenesulfonate IL monomer was synthesized and copolymerized with 1,6-di(3-vinylimidazolium) hexane bishexafluorophosphate IL as cross-linking agent to prepare a cross-linked polymeric ionic liquids (PILs) monolith. Coupled to high-performance liquid chromatography (HPLC), the PILs monolith was used as a solid-phase microextraction (SPME) sorbent to extract some polar endocrine disrupting chemical (EDCs) such as estrogens, bisphenol A, and phthalate esters in aqueous samples. Preparation and extraction conditions were investigated and optimized to obtain satisfactory extraction efficiency. Limits of detection (LODs) of the proposed method for three steroid estrogens and bisphenol A were 0.25 and 0.2 μg L(-1), respectively, which were lower than or comparable to some other sample preparation methods. Intra- and inter-day repeatability for all the analytes was 2.2-12%. The monolith-to-monolith repeatability was 7.4-15%. The extraction performance of the method for analysis of target estrogens in treated domestic wastewater was investigated and compared with a dispersive liquid-liquid microextraction (DLLME) method. The proposed SPME method provided better sensitivity and higher resistance to matrix interferences. PMID:26220716

  13. A comparison study of ionic polymer-metal composites (IPMCs) fabricated with Nafion and other ion exchange membranes

    NASA Astrophysics Data System (ADS)

    Park, Jiyeon; Palmre, Viljar; Kim, Kwang; Shin, Dongsuk; Kim, Daniel H.; Yim, Woosoon; Bae, Chulsung

    2013-04-01

    Ionic polymer-metal composites (IPMCs) have been and still are one of the best candidates with great potential to be used as actuators and sensors particularly in bioengineering where the environmental conditions are in an aqueous medium. Each component of an IPMC is important. However, the ion exchange membrane should be more emphasized because it is where ions migrate when electrical stimulation is applied and eventually it produces deformation of the IPMC. So far, the most commonly used ion exchange membrane is Nafion and many studies have been conducted with it for IPMC applications. There are a number of other commercially available ion exchange membranes now, but only a few studies have been done on those membranes to be used in IPMC applications. In this study, four commercially available membranes, (1) Nafion N115 (DuPont), (2) CMI7000S (Membranes International Inc.), (3) F-14100 (fumatech), (4) GEFC-700 (Golden Energy Fuel Cell) were selected and fabricated in IPMCs and their potentials as actuators were examined by conducting various characterizations such as water uptake, ion exchange capacity, SEM, DSC, blocking force and bending displacement.

  14. Facile preparation of organic-inorganic hybrid polymeric ionic liquid monolithic column with a one-pot process for protein separation in capillary electrochromatography.

    PubMed

    Liu, Cuicui; Deng, Qiliang; Fang, Guozhen; Feng, Xue; Qian, Hailong; Wang, Shuo

    2014-11-01

    An organic-inorganic hybrid monolithic column based on 1-vinyl-3-dodecylimidazolium bromide (VC12Im(+)Br(-)) has been prepared in a single step by combining radical copolymerization with a non-hydrolytic sol-gel (NHSG) process. The NHSG process was significantly shortened to 6 h by using formic acid as catalyst. For comparison, we also prepared polymeric ionic liquid (PIL) monolithic columns by hydrolytic sol-gel and organic polymeric process, respectively. The resulting monolithic columns were characterized by Fourier transform infrared spectra, scanning electron microscopy, and Brunauer-Emmett-Teller. Under the capillary electrochromatography mode, these columns were applied to separate alkylbenzenes, anilines, and proteins, respectively. The results indicated that the NHSG-based hybrid PIL monolithic column exhibited the highest column efficiency among the three types of columns; organic solvent, commonly required by the traditional columns to achieve satisfactory separation efficiency for proteins, was absent in the NHSG-based hybrid PIL monolithic column because of the biocompatibility of the VC12Im(+)Br(-), which was beneficial to analysis of protein containing samples. In order to demonstrate its application potential, the developed NHSG-based hybrid PIL monolithic column was also employed to separate egg white sample. PMID:25277101

  15. One-Pot Synthesis of Double Poly(Ionic Liquid) Block Copolymers by Cobalt-Mediated Radical Polymerization-Induced Self-Assembly (CMR-PISA) in Water.

    PubMed

    Cordella, Daniela; Debuigne, Antoine; Jérôme, Christine; Kochovski, Zdravko; Taton, Daniel; Detrembleur, Christophe

    2016-07-01

    Amphiphilic double poly(ionic liquid) (PIL) block copolymers are directly prepared by cobalt-mediated radical polymerization induced self-assembly (CMR-PISA) in water of N-vinyl imidazolium monomers carrying distinct alkyl chains. The cobalt-mediated radical polymerization of N-vinyl-3-ethyl imidazolium bromide (VEtImBr) is first carried out until high conversion in water at 30 °C, using an alkyl bis(acetylacetonate)cobalt(III) adduct as initiator and controlling agent. The as-obtained hydrophilic poly(N-vinyl-3-ethyl imidazolium bromide) (PVEtImBr) is then used as a macroinitiator for the CMR-PISA of N-vinyl-3-octyl imidazolium bromide (VOcImBr). Self-assembly of the amphiphilic PVEtImBr-b-PVOcImBr block copolymer, i.e., of PIL-b-PIL-type, rapidly takes place in water, forming polymer nanoparticles consisting of a hydrophilic PVEtImBr corona and a hydrophobic PVOcImBr core. Preliminary investigation into the effect of the size of the hydrophobic block on the dimension of the nanoparticles is also described. PMID:26991998

  16. Sorption of chlorimuron-ethyl on montmorillonite clays: effects of exchangeable cations, pH, and ionic strength.

    PubMed

    Ren, Wenjie; Teng, Ying; Zhou, Qixing; Paschke, Albrecht; Schüürmann, Gerrit

    2014-10-01

    Sorption interaction of chlorimuron-ethyl with montmorillonite clays was investigated under varied types of exchangeable cation, pH, and ionic strength conditions. Chlorimuron-ethyl sorption on bentonites exhibited pronounced cation dependency, and the sorption ability increased as the sequence Ca(2+)- < Na(+)- < Al(3+)- < Fe(3+)-bentonite, due to different sorption mechanisms, whereas the cation dependency was influenced by the clay type and much weaker for montmorillonites. The decrease of pH at the range of 4.0-6.0 prominently increased sorption of chlorimuron-ethyl on all cation-exchanged montmorillonite clays, and nearly a neglected sorption (about 2 %) can be observed at pH over 7.0. In the presence of CaCl2, sorption of chlorimuron-ethyl on Fe(3+)-bentonite was promoted because of complexion of Ca(2+) and the surface of Fe(3+)-bentonite. However, as the concentration of CaCl2 increased, chlorimuron-ethyl sorption on Ca(2+)- and Fe(3+)-exchanged bentonite decreased, suggesting that Ca bridging was not the prevailing mechanism for sorption of chlorimuron-ethyl on these clays. Furthermore, chlorimuron-ethyl sorption was relatively sensitive to pH, and the change of pH may obscure effect of other factors on the sorption, so it was quite necessary to control pH at a constant value when the effect of other factor was being studied. PMID:25028319

  17. Balance between the physical diffusion and the exchange reaction on binary ionic liquid electrolyte for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Hao, Feng; Lin, Hong; Zhang, Jing; Li, Jianbao

    A comprehensive characterizations of viscosities, conductivities, triiodide diffusion coefficients, charge-transfer resistances and photovoltaic performance of a potential dye-sensitized solar cell (DSC) electrolyte systems based on binary ionic liquid (IL) mixtures, namely, 1-ethyl-3-methylimidazolium dicyanamide (EMIDCA)/1-methyl-3-propylimidazolium iodide (PMII) with a fixed iodine concentration at varying EMIDCA volume fraction are investigated in the present study. Viscosity and conductivity values are accurately correlated with regard to temperature and EMIDCA volume fraction. The triiodide diffusion coefficients, the predominant electrolyte parameter for limitation of DSC efficiency, are determined by symmetrical cell methods. The physical diffusion and exchange reactions between the iodide and triiodide dominate the apparent triiodide diffusion coefficients at different range of EMIDCA volume fraction. A balance between the viscosity-dependent physical diffusion and the exchange reactions can get at an optimal volume percents of EMIDCA. Impedance spectroscopy and photovoltaic results both support the existence of an optimized binary IL electrolyte composition. Hence, for optimizing an IL-based electrolyte in regards to triiodide transport, a low viscosity is not the exclusive crucial factor since exchange reactions transport effects also play an important role to resolve the diffusion limitation of DSC efficiency.

  18. Novel ion-exchange membranes for electrodialysis prepared by radiation-induced graft polymerization

    SciTech Connect

    Tsuneda, Satoshi; Saito, Kyoichi; Misuhara, Hisashi; Sugo, Takanobu

    1995-11-01

    Ion-exchange membranes have been used to concentrate seawater to produce salt as well as to desalinate brackish water to render it potable. Also, the interest in applications of ion-exchange membranes as separators for electrodialytic desalination of bioproducts and separators in hydrogen-oxygen fuel cells has been growing. Novel ion-exchange membranes containing sulfonic acid (SO{sub 3}H) and trimethyl ammonium [N(CH{sub 3}){sub 3}] groups were prepared by a simple method of radiation-induced cografting of sodium styrene sulfonate (SSS) with acrylic acid (AAc) and vinyl benzyl trimethyl ammonium chloride (VBTAC) with 2-hydroxyethyl methacrylate (HEMA), onto a polyethylene film with a thickness of 50 {micro}m. The high density graft chain was introduced throughout the polyethylene film. The maximum cation- and anion-exchange capacities of the resultant membranes were 2.5 and 1.3 mol/kg, receptively. These membranes exhibited an electrical resistance one order lower than commercially available ion-exchange membranes; for example, 12 h cografting provided cation- and anion-exchange membranes whose electrical resistances in a 0.5 M NaCl solution were 0.25 and 0.85 {Omega} cm{sup 2}, respectively. From the evaluation of electrodialytic desalination in a batch mode, using a pair of the graft-type ion-exchange membranes, the time required to achieve 99.5% desalination of the initial 0.5 M NaCl solutions was reduced to 85% comparing with that of the commercial ion-exchange membranes.

  19. Desalination by electrodialysis with the ion-exchange membrane prepared by radiation-induced graft polymerization

    NASA Astrophysics Data System (ADS)

    Choi, Seong-Ho; Han Jeong, Young; Jeong Ryoo, Jae; Lee, Kwang-Pill

    2001-01-01

    Ion-exchange membranes modified with the triethylamine [-N(CH 2CH 3) 3] and phosphoric acid (-PO 3 H) groups were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto the polyolefin nonwavon fabric (PNF) and subsequent chemical modification of poly(GMA) graft chains. The physical and chemical properties of the GMA-grafted PNF and the PNF modified with ion-exchange groups were investigated by SEM, XPS, TGA, and DSC. Furthermore, electrochemical properties such as specific electric resistance, transport number of K +, and desalination were examined. The grafting yield increased with increasing reaction time and reaction temperature. The maximum grafting yield was obtained with 40% (vol.%) monomer concentration in dioxane at 60°C. The content of the cation- and anion-exchange group increased with increasing grafting yield. Electrical resistance of the PNF modified with TEA and -PO 3 H group decreased, while the water uptake (%) increased with increasing ion-exchange group capacities. Transport number of the PNF modified with ion-exchange group were the range of ca. 0.82-0.92. The graft-type ion-exchange membranes prepared by radiation-induced graft copolymerization were successfully applied as separators for electrodialysis.

  20. The influence of particle size and AgNO3 concentration in the ionic exchange process on the fungicidal action of antimicrobial glass.

    PubMed

    Mendes, E; Piletti, R; Barichello, T; Oliveira, C M; Kniess, C T; Angioletto, E; Riella, H G; Fiori, M A

    2012-08-01

    Antimicrobial materials have long been used as an effective means of reducing the risks posed to humans by fungi, bacteria and other microorganisms. These materials are essential in environments where cleanliness, comfort and hygiene are the predominate concerns. This work presents preliminary results for the development of a fungicidal vitreous material that is produced by the incorporation of a silver ionic specimen through ionic exchange reactions. Silver ions were incorporated into powdered glass via ionic exchange in an ionic medium containing silver species with different concentrations of AgNO3. The fungicidal efficiency of the samples was studied as a function of the AgNO3 concentration and the particle size of the glass using the agar diffusion test for the microbiological analysis of the fungus species Candida albicans. The samples were examined by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The experimental results showed that the fungicidal effect was dependent on the AgNO3 concentration in the ionic exchange medium but was not dependent on the particle size of the glass. PMID:24364954

  1. Isothermal and non-isothermal crystallization kinetics of PVA + ionic liquid [BDMIM][BF4]-based polymeric films

    NASA Astrophysics Data System (ADS)

    Saroj, A. L.; Chaurasia, S. K.; Kataria, Shalu; Singh, R. K.

    2016-06-01

    The effect of ionic liquid (IL), 1-butyl-2,3-dimethylimidazolium tetrafluoroborate [BDMIM][BF4], on crystallization behavior of poly(vinyl alcohol) (PVA) has been studied by isothermal and non-isothermal differential scanning calorimetry techniques. The PVA + IL based polymer electrolyte films have been prepared using solution casting technique. To describe the isothermal and non-isothermal crystallization kinetics, several kinetic equations have been employed on PVA + IL based films. There is strong dependence of the peak crystallization temperature (Tc), relative degree of crystallity (Xt), half-time of crystallization (t1/2), crystallization rate constants (Avrami Kt and Tobin AT), and Avrami (n) and Tobin (nT) exponents on the cooling rate and IL loading.

  2. Molecular interactions in the ionic liquid emim acetate and water binary mixtures probed via NMR spin relaxation and exchange spectroscopy.

    PubMed

    Allen, Jesse J; Bowser, Sage R; Damodaran, Krishnan

    2014-05-01

    Interactions of ionic liquids (ILs) with water are of great interest for many potential IL applications. 1-Ethyl-3-methylimidazolium (emim) acetate, in particular, has shown interesting interactions with water including hydrogen bonding and even chemical exchange. Previous studies have shown the unusual behavior of emim acetate when in the presence of 0.43 mole fraction of water, and a combination of NMR techniques is used herein to investigate the emim acetate-water system and the unusual behavior at 0.43 mole fraction of water. NMR relaxometry techniques are used to describe the effects of water on the molecular motion and interactions of emim acetate with water. A discontinuity is seen in nuclear relaxation behavior at the concentration of 0.43 mole fraction of water, and this is attributed to the formation of a hydrogen bonded network. EXSY measurements are used to determine the exchange rates between the H2 emim proton and water, which show a complex dependence on the concentration of the mixture. The findings support and expand our previous results, which suggested the presence of an extended hydrogen bonding network in the emim acetate-water system at concentrations close to 0.50 mole fraction of H2O. PMID:24654003

  3. Chaotic behavior of ion exchange phenomena in polymer gel electrolytes through irradiated polymeric membrane

    NASA Astrophysics Data System (ADS)

    Rawat, Sangeeta; Saha, Barnamala; Prasad, Awadhesh; Chandra, Amita

    2012-05-01

    A desktop experiment has been done to show the nonlinearity in the I-V characteristics of an ion conducting electrochemical micro-system. Its chaotic dynamics is being reported for the first time which has been captured by an electronic circuit. Polyvinylidene fluoride-co-hexafluoropropene (PVdF-HFP) gel electrolyte comprising of a combination of plasticizers (ethylene carbonate and propylene carbonate) and salts have been prepared to study the exchange of ions through porous polyethylene terephthalate (PET) membranes. The nonlinearity of this system is due to the ion exchange of the polymer gel electrolytes (PGEs) through a porous membrane. The different regimes of spiking and non-spiking chaotic motions are being presented. The possible applications are highlighted.

  4. A highly selective voltammetric sensor for nanomolar detection of mercury ions using a carbon ionic liquid paste electrode impregnated with novel ion imprinted polymeric nanobeads.

    PubMed

    Bahrami, Azam; Besharati-Seidani, Abbas; Abbaspour, Abdolkarim; Shamsipur, Mojtaba

    2015-03-01

    This work reports the preparation of a voltammetric sensor for selective recognition and sensitive determination of mercury ions using a carbon ionic liquid paste electrode (CILE) impregnated with novel Hg(2+)-ion imprinted polymeric nanobeads (IIP) based on dithizone, as a suitable ligand for complex formation with Hg(2+) ions. The differential pulse anodic stripping voltammetric technique was employed to investigate the performance of the prepared IIP-CILE for determination of hazardous mercury ions. The designed modified electrode revealed linear responses in the ranges of 0.5nM-10nM and 0.08μM-2μM with a limit of detection of 0.1nM (S/N=3). It was found that the peak currents of the modified electrode for Hg(2+) ions were at a maximum value in phosphate buffer of pH4.5. The optimized preconcentration potential and accumulation time were to be -0.9V and 35s, respectively. The applicability of the proposed sensor to mercury determination in waste water samples is reported. PMID:25579915

  5. Free volume and ionic conductivity of poly(ether urethane)-LiClO4 polymeric electrolyte studied by positron annihilation

    NASA Astrophysics Data System (ADS)

    Peng, Z. L.; Wang, B.; Li, S. Q.; Wang, S. J.

    1995-01-01

    The positron lifetime spectra and ionic conductivity have been measured for poly(ether urethane)-LiClO4 polymeric electrolyte as a function of temperature. The glass transition temperature T(sub g), free-volume V(sub f), and fractional free-volume f were derived from the positron annihilation parameters. A correlation between fractional free-volume f(T) and conductivity sigma above T(sub g), log(sigma/sigma(T(sub g))) = C(sub 1)(f(T) - f(T(sub g)))/f(T), was first experimentally confirmed using measured positron annihilation results. The comparison of the value of the obtained constant C(sub 1) with the universal values for the segmental diffusion of amorphous polymers indicated that the critical free volume required for the ion transport is much smaller than that required for polymer chain segment mobility. Carrier transport and the segmental motion are discussed in terms of the free-volume theory.

  6. A chemometric approach toward the detection and quantification of coffee adulteration by solid-phase microextraction using polymeric ionic liquid sorbent coatings.

    PubMed

    Toledo, Bruna R; Hantao, Leandro W; Ho, Tien D; Augusto, Fabio; Anderson, Jared L

    2014-06-13

    Solid-phase microextraction (SPME) using cross-linked polymeric ionic liquid (PIL)-based sorbent coatings was used to extract volatile aroma-related compounds from coffee samples. Several PIL-based coatings were screened alongside a commercial poly(acrylate) (PA) SPME coating. The best performing PIL-based SPME fiber, poly(1-vinyl-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonylimide]) with 50% (w/w) 1,12-di(3-vinylbenzylimidazolium)dodecane dibis[(trifluoromethyl)sulfonyl]imide incorporated cross-linker, was used to isolate the volatile fraction of Arabica coffee. To illustrate the importance of trace analyte isolation, a method for the detection and quantification of coffee adulteration is described. Chromatographic profiles obtained by gas chromatography/mass spectrometry (GC/MS) were used to create the chemometric model. Partial least squares (PLS) regression was employed to correlate the aroma-related chemical fingerprint to the degree of adulteration. The proposed method successfully detected fraud down to 1% (w/w) of adulterant and accurately determined the degree of coffee adulteration (i.e, root mean square error of calibration and prediction of 0.54% and 0.83% (w/w), respectively). Finally, important aroma-related compounds including furans, methoxyphenols, pyrazines, and ketones were identified. PMID:24786655

  7. Sensitive determination of estrogens in environmental waters treated with polymeric ionic liquid-based stir cake sorptive extraction and liquid chromatographic analysis.

    PubMed

    Chen, Lei; Mei, Meng; Huang, Xiaojia; Yuan, Dongxing

    2016-05-15

    A simple, sensitive and environmentally friendly method using polymeric ionic liquid-based stir cake sorptive extraction followed by high performance liquid chromatography with diode array detection (HPLC/DAD) has been developed for efficient quantification of six selected estrogens in environmental waters. To extract trace estrogens effectively, a poly (1-ally-3-vinylimidazolium chloride-co-ethylene dimethacrylate) monolithic cake was prepared and used as the sorbent of stir cake sorptive extraction (SCSE). The effects of preparation conditions of sorbent and extraction parameters of SCSE for estrogens were investigated and optimized. Under optimal conditions, the developed method showed satisfactory analytical performance for targeted analytes. Low limits of detection (S/N=3) and quantification limits (S/N=10) were achieved within the range of 0.024-0.057µg/L and 0.08-0.19µg/L, respectively. Good linearity of method was obtained for analytes with the correlation coefficients (R(2)) above 0.99. At the same time, satisfactory method repeatability and reproducibility was achieved in terms of intra- and inter-day precisions, respectively. Finally, the established SCSE-HPLC/DAD method was successfully applied for the determination of estrogens in different environmental water samples. Recoveries obtained for the determination of estrogens in spiked samples ranged from 71.2% to 108%, with RSDs below 10% in all cases. PMID:26992499

  8. Determination of polychlorinated biphenyls in ocean water and bovine milk using crosslinked polymeric ionic liquid sorbent coatings by solid-phase microextraction.

    PubMed

    Joshi, Manishkumar D; Ho, Tien D; Cole, William T S; Anderson, Jared L

    2014-01-01

    Crosslinked polymeric ionic liquid (PIL)-based sorbent coatings were employed in the extraction of 21 polychlorinated biphenyls (PCBs) from ocean water and bovine milk using solid-phase microextraction (SPME). The extraction temperature, time, and concentration of sodium chloride added to the matrix were optimized in order to determine the best extraction conditions for the extraction of PCBs. The analytical performance of the crosslinked PIL-based SPME fibers was compared with a commercial 7 µm polydimethylsiloxane (PDMS) fiber using gas chromatography (GC) employing an electron capture detector (ECD) and mass spectrometric detection (MS). Higher sensitivities for PCBs were achieved using PIL-based fibers when compared to PDMS fiber due to the incorporation of benzyl moieties into the PIL structures. The limits of detection (LOD) for all PCBs were determined to be in the low ng L(-1) range using the three studied coatings. Recovery studies were performed for PCBs in ocean water and bovine milk to validate the applicability of the current SPME method. PMID:24274285

  9. Graphene oxide reinforced polymeric ionic liquid monolith solid-phase microextraction sorbent for high-performance liquid chromatography analysis of phenolic compounds in aqueous environmental samples.

    PubMed

    Sun, Min; Bu, Yanan; Feng, Juanjuan; Luo, Chuannan

    2016-01-01

    A graphene oxide reinforced polymeric ionic liquids monolith was obtained by copolymerization of graphene oxide doped 1-(3-aminopropyl)-3-(4-vinylbenzyl)imidazolium 4-styrenesulfonate monomer and 1,6-di-(3-vinylimidazolium) hexane bihexafluorophosphate cross-linking agent. Coupled to high-performance liquid chromatography, the monolith was used as a solid-phase microextraction sorbent to analyze several phenolic compounds in aqueous samples. Under the optimized extraction and desorption conditions, linear ranges were 5-400 μg/L for 3-nitrophenol, 2-nitrophenol, and 2,5-dichlorophenol and 2-400 μg/L for 4-chlorophenol, 2-methylphenol, and 2,4,6-trichlorophenol (R(2) = 0.9973-0.9988). The limits of detection were 0.5 μg/L for 3-nitrophenol and 2-nitrophenol and 0.2 μg/L for the rest of the analytes. The proposed method was used to determine target analytes in groundwater from an industrial park and river water. None of the analytes was detected. Relative recoveries were in the range of 75.5-113%. PMID:26519095

  10. Independent control of the shape and composition of ionic nanocrystals through sequential cation exchange reactions

    SciTech Connect

    Luther, Joseph Matthew; Zheng, Haimei; Sadtler, Bryce; Alivisatos, A. Paul

    2009-07-06

    Size- and shape-controlled nanocrystal growth is intensely researched for applications including electro-optic, catalytic, and medical devices. Chemical transformations such as cation exchange overcome the limitation of traditional colloidal synthesis, where the nanocrystal shape often reflects the inherent symmetry of the underlying lattice. Here we show that nanocrystals, with established synthetic protocols for high monodispersity, can be templates for independent composition control. Specifically, controlled interconversion between wurtzite CdS, chalcocite Cu2S, and rock salt PbS occurs while preserving the anisotropic dimensions unique to the as-synthesized materials. Sequential exchange reactions between the three sulfide compositions are driven by the disparate solubilites of the metal ion exchange pair in specific coordinating molecules. Starting with CdS, highly anisotropic PbS nanorods are created, which serve as an important material for studying strong 2-dimensional quantum confinement, as well as for optoelectronic applications. Furthermore, interesting nanoheterostructures of CdS|PbS are obtained by precise control over ion insertion and removal.

  11. Air supply using an ionic wind generator in a proton exchange membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Kwon, Kilsung; Li, Longnan; Park, Byung Ho; Lee, Seung Jun; Kim, Daejoong

    2015-06-01

    A new air supply is demonstrated for a portable polymer electrolyte membrane fuel cell (PEMFC). The air supply is an ionic wind generator (IWG) with a needle-to-cylinder configuration. The IWG supplies air to the portable PEMFC owing to momentum transfer to the air by charged molecules generated by the corona discharge from a high applied potential. There is no difference in the performance of the PEMFC when compressed air and the IWG are used as the air supply. For the varying interelectrode distance, IWG performance is varied and measured in terms of the flow rate and current. At the interelectrode distance of 9.0 mm, the air flow rate is a suitable for the portable PEMFC with low power consumption. When the IWG is used to supply air to the portable PEMFC, it is found that the flow rate per unit power consumed decreases with the applied voltage, the gross power generation monotonously increases with the applied voltage, and the highest net power (268 mW) is obtained at the applied voltage of 8.5 kV. The parasitic power ratio reaches a minimum value of ∼0.06 with the applied IWG voltage of 5.5 kV.

  12. An investigation of the structure-property relationships in ionic polymer polymer composites (IP2Cs) manufactured by polymerization in situ of PEDOT/PSS on Nafion®117

    NASA Astrophysics Data System (ADS)

    Di Pasquale, G.; Graziani, S.; Messina, F. G.; Pollicino, A.; Puglisi, R.; Umana, E.

    2014-03-01

    Ionic polymer polymer composites (IP2Cs) are all-organic electroactive polymers (EAPs) that show sensing and actuation capabilities when a deformation or a voltage is applied, respectively. They are fabricated starting from an ionic polymer coated on both sides with a conducting polymer as electrode element. In this work, poly(3,4-ethylendioxytiophene)-poly-(styrenesulfonate) (PEDOT/PSS) has been polymerized directly on Nafion®117 membrane and devices have been manufactured varying the polymerization time. Water and ethylene glycol (EG) have been used as solvents. The obtained IP2Cs have been characterized using thermal and mechanical analyses and electromechanically tested. The results have shown that in IP2Cs manufactured by polymerization in situ the PEDOT/PSS layer adheres very strongly on the Nafion®117 film, improving the possibility of rehydrating the devices after use. Moreover, taking into account that the different polymerization times influence the uniformity of the surface of the organic electrode and, consequently, both device stiffness and electrode conductivity, the structure-property relationships of the obtained devices have been investigated. The influence of the different solvents inside the devices has also been studied when IP2Cs have been used as actuators or sensors. Reported results show that it is possible to modulate the performances of IP2Cs by varying some manufacture parameters and the solvent.

  13. Characterization of self-assembled functional polymeric nanostructures: I. magnetic nanostructures from metallopolymers II. Zwitterionic polymer vesicles in ionic liquid

    NASA Astrophysics Data System (ADS)

    Maddikeri, Raghavendra Raj

    matrix is confined between the non-magnetic cylinders, had second highest and lamellar morphology with least confinement among BCPs, exhibited lowest coercivity. The proposed hypothesis was further tested by systematically varying the dipolar interactions between the SPM cobalt nanoparticles by reducing the density of cobalt within the cylindrical domains and varying the dimensions of the cylindrical domains (i.e. diameter). A series of novel ferrocene-cobalt containing block copolymers were developed and cobalt density within the cylindrical domains of BCP was varied by changing the chemical composition of the metal functionalized block. Further, the diameter of the cylindrical domains was varied by varying the molecular weight of the cobalt-containing BCPs. These studies allowed us to understand the fundamental correlations between the self-assembled nanostructures and their macroscopic magnetic properties. In the second part of the thesis, a novel amphiphilic block copolymer (ABC), composed of a hydrophilic zwitterionic block and a hydrophobic PS block, was synthesized by ROMP. The formation of zwitterionic vesicles in an ionic liquid, as well as in PBS buffer, was confirmed by TEM and DLS characterization. The dispersion of vesicles within ionic liquid enabled the usage of conventional, room temperature TEM to visualize them in their solution state. This technique of materials characterization could be extended for the visualization of other hydrophilic soft matter.

  14. Sustainable polymerizations in recoverable microemulsions.

    PubMed

    Chen, Zhenzhen; Yan, Feng; Qiu, Lihua; Lu, Jianmei; Zhou, Yinxia; Chen, Jiaxin; Tang, Yishan; Texter, John

    2010-03-16

    Free radical and atom-transfer radical polymerizations were conducted in monomer/ionic liquid microemulsions. After the polymerization and isolation of the resultant polymers, the mixture of the catalyst and ionic liquids (surfactant and continuous phase) can be recovered and reused, thereby dramatically improving the environmental sustainability of such chemical processing. The addition of monomer to recovered ionic liquid mixtures regenerates transparent, stable microemulsions that are ready for the next polymerization cycle upon addition of initiator. The method combines the advantages of IL recycling and microemulsion polymerization and minimizes environmental disposable effects from surfactants and heavy metal ions. PMID:20170175

  15. Preparation of high-capacity, weak anion-exchange membranes by surface-initiated atom transfer radical polymerization of poly(glycidyl methacrylate) and subsequent derivatization with diethylamine

    NASA Astrophysics Data System (ADS)

    Qian, Xiaolei; Fan, Hua; Wang, Chaozhan; Wei, Yinmao

    2013-04-01

    Ion-exchange membrane is of importance for the development of membrane chromatography. In this work, a high-capacity anion-exchange membrane was prepared by grafting of glycidyl methacrylate (GMA) onto the surface of regenerated cellulose (RC) membranes via surface-initiated atom transfer radical polymerization (SI-ATRP) and subsequent derivatization with diethylamine. Attenuated total reflectance Fourier-transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to characterize changes in the chemical functionality, surface topography and pore morphology of the modified membranes. The static capacity of the prepared anion-exchange membrane was evaluated with bovine serum albumin (BSA) as a model protein. The results indicated that the anion-exchange membrane which could reach a maximum capacity of 96 mg/mL for static adsorption possesses a higher adsorption capacity, and the adsorption capacity increases with the polymerization time. The effect of pH and salt concentration confirmed that the adsorption of BSA followed ion-exchange mechanism. The established method would have potential application in the preparation of anion-exchange membrane.

  16. Beneficial phosphate recovery from reverse osmosis (RO) concentrate of an integrated membrane system using polymeric ligand exchanger (PLE).

    PubMed

    Kumar, Manish; Badruzzaman, Mohammad; Adham, Samer; Oppenheimer, Joan

    2007-05-01

    Phosphorus (P) discharge to surface water is a major environmental problem. Wastewater treatment is targeted towards removal of this nutrient to prevent degradation of surface water. Integrated membrane systems (IMS) are increasingly being considered for wastewater reclamation, and provide excellent removal of P compounds. However, reverse osmosis (RO), which forms an integral part of these IMSs, concentrates most dissolved substances including P-species such as phosphates in the RO waste stream. In this study, removal of phosphate from this stream using polymeric ligand exchange (PLE) resins was investigated. Further, the possibility of phosphate recovery through struvite (MgNH(4)PO(4).6H(2)O) precipitation was tested. Struvite has been promoted as a slow release fertilizer in recent years. This study demonstrates that PLEs can be successfully used to remove phosphate from RO-concentrate, and to recover more than 85% of the adsorbed phosphorus from the exhausted media and precipitated as a beneficial product (struvite). The approach, presented in this study, suggests advantages of providing economic benefit from a waste product (RO) while avoiding phosphorus discharge to the environment. PMID:17379269

  17. Single-Site Heterogeneous Catalysts for Olefin Polymerization Enabled by Cation Exchange in a Metal-Organic Framework.

    PubMed

    Comito, Robert J; Fritzsching, Keith J; Sundell, Benjamin J; Schmidt-Rohr, Klaus; Dincă, Mircea

    2016-08-17

    The manufacture of advanced polyolefins has been critically enabled by the development of single-site heterogeneous catalysts. Metal-organic frameworks (MOFs) show great potential as heterogeneous catalysts that may be designed and tuned on the molecular level. In this work, exchange of zinc ions in Zn5Cl4(BTDD)3, H2BTDD = bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin) (MFU-4l) with reactive metals serves to establish a general platform for selective olefin polymerization in a high surface area solid promising for industrial catalysis. Characterization of polyethylene produced by these materials demonstrates both molecular and morphological control. Notably, reactivity approaches single-site catalysis, as evidenced by low polydispersity indices, and good molecular weight control. We further show that these new catalysts copolymerize ethylene and propylene. Uniform growth of the polymer around the catalyst particles provides a mechanism for controlling the polymer morphology, a relevant metric for continuous flow processes. PMID:27443860

  18. Coordination Chemistry Inside Polymeric Nanoreactors: Interparticle Metal Exchange and Ionic Compound Vectorization in Phosphine-Functionalized Amphiphilic Polymer Latexes.

    PubMed

    Chen, Si; Gayet, Florence; Manoury, Eric; Joumaa, Ahmad; Lansalot, Muriel; D'Agosto, Franck; Poli, Rinaldo

    2016-04-25

    Stable latexes of hierarchically organized core-cross-linked polymer micelles that are functionalized at the core with triphenylphosphine (TPP@CCM) have been investigated by NMR spectroscopic analysis at both natural (ca. pH 5) and strongly basic (pH 13.6) pH values after core swelling with toluene. The core-shell interface structuring forces part of the hydrophilic poly(ethylene oxide) (PEO) chains to reside inside the hydrophobic core at both pH values. Loading the particle cores with [Rh(acac)(CO)2 ] (acac=acetylacetonate) at various Rh/P ratios yielded polymer-supported [Rh(acac)(CO)(TPP)] (TPP=triphenylphosphine). The particle-to-particle rhodium migration is very fast at natural pH, but slows down dramatically at high pH, whereas the size distribution of the nanoreactors remains unchanged. The slow migration at pH 13.6 leads to the generation of polymer-anchored [Rh(OH)(CO)(TPP)2 ], which is also generated immediately upon the addition of NaOH to the particles with a [Rh(acac)(CO)] loading of 50 %. Similarly, treatment of the same particles with NaCl yielded polymer-anchored [RhCl(CO)(TPP)2 ]. Interparticle coupling occurs during these rapid processes. These experiments prove that the major contribution to metal migration is direct core-core contact. The slow migration at the high pH value, however, must result from a pathway that does not involve core-core contact. The facile penetration of the polymer cores by NaOH and NaCl results from the presence of shell-linked poly(ethylene oxide) methyl ether functions both outside and inside the polymer core-shell interface. PMID:27001452

  19. Structural basis of thymosin-β4/profilin exchange leading to actin filament polymerization

    PubMed Central

    Xue, Bo; Leyrat, Cedric; Grimes, Jonathan M.; Robinson, Robert C.

    2014-01-01

    Thymosin-β4 (Tβ4) and profilin are the two major sequestering proteins that maintain the pool of monomeric actin (G-actin) within cells of higher eukaryotes. Tβ4 prevents G-actin from joining a filament, whereas profilin:actin only supports barbed-end elongation. Here, we report two Tβ4:actin structures. The first structure shows that Tβ4 has two helices that bind at the barbed and pointed faces of G-actin, preventing the incorporation of the bound G-actin into a filament. The second structure displays a more open nucleotide binding cleft on G-actin, which is typical of profilin:actin structures, with a concomitant disruption of the Tβ4 C-terminal helix interaction. These structures, combined with biochemical assays and molecular dynamics simulations, show that the exchange of bound actin between Tβ4 and profilin involves both steric and allosteric components. The sensitivity of profilin to the conformational state of actin indicates a similar allosteric mechanism for the dissociation of profilin during filament elongation. PMID:25313062

  20. Proton dynamics in sulfonated ionic salt composites: Alternative membrane materials for proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    De Almeida, N. E.; Goward, G. R.

    2014-12-01

    Hydrated Nafion, the most prevalent proton exchange membrane utilizes a vehicular mechanism for proton conduction. However, there is an increasing need for such membranes to perform under anhydrous conditions, at high temperatures, which would employ a structural transport mechanism for proton conductivity. Here, several solid-acids are characterized, both as pristine salts, and as polymer composites. Materials of interest include benzimidazolium methanesulfonate (BMSA), imidazolium methanesulfonate (IMSA), and imidazolium trifluoromethanesulfate (IFMS). The proton dynamics of these solid acids are characterized as pure salts, and as composites, embedded into porous Teflon, by solid state NMR. It was determined that spin lattice (T1) relaxation of the composites are systematically lower than that of the pure salt, indicating that local dynamics are enhanced in the composites. Spin-spin relaxation (T2∗) was measured as a function of temperature to determine the activation energy for local mobility for each salt and composite. The activation energy for local proton mobility in each salt decreased after being inserted into porous Teflon. Finally, the long-range ion transport was characterized using impedance spectroscopy. The IFMS-Teflon composite possessed the lowest activation energy for local proton mobility, the highest thermal stability, and the most favorable proton conductivity, among the investigated materials.

  1. Multifunctional Iodide-Free Polymeric Ionic Liquid for Quasi-Solid-State Dye-Sensitized Solar Cells with a High Open-Circuit Voltage.

    PubMed

    Lin, Yi-Feng; Li, Chun-Ting; Lee, Chuan-Pei; Leu, Yow-An; Ezhumalai, Yamuna; Vittal, R; Chen, Ming-Chou; Lin, Jiang-Jen; Ho, Kuo-Chuan

    2016-06-22

    A polymeric ionic liquid, poly(oxyethylene)-imide-imidazolium selenocyanate (POEI-IS), was newly synthesized and used for a multifunctional gel electrolyte in a quasi-solid-state dye-sensitized solar cell (QSS-DSSC). POEI-IS has several functions: (a) acts as a gelling agent for the electrolyte of the DSSC, (b) possesses a redox mediator of SeCN(-), which is aimed to form a SeCN(-)/(SeCN)3(-) redox couple with a more positive redox potential than that of traditional I(-)/I3(-), (c) chelates the potassium cations through the lone pair electrons of the oxygen atoms of its poly(oxyethylene)-imide-imidazolium (POEI-I) segments, and (d) obstructs the recombination of photoinjected electrons with (SeCN)3(-) ions in the electrolyte through its POEI-I segments. Thus, the POEI-IS renders a high open-circuit voltage (VOC) to the QSS-DSSC due to its functions of b-d and prolongs the stability of the cell due to its function of a. The QSS-DSSC with the gel electrolyte containing 30 wt % of the POEI-IS in liquid selenocyanate electrolyte exhibited a high VOC of 825.50 ± 3.51 mV and a high power conversion efficiency (η) of 8.18 ± 0.02%. The QSS-DSSC with 30 wt % POEI-IS retained up to 95% of its initial η after an at-rest stability test with the period of more than 1,000 h. PMID:27248206

  2. Enhanced Ionic Conductivity and Power Generation Using Ion-Exchange Resin Beads in a Reverse-Electrodialysis Stack.

    PubMed

    Zhang, Bopeng; Gao, Haiping; Chen, Yongsheng

    2015-12-15

    Reverse electrodialysis (RED) is a promising technique for harvesting energy by mixing seawater with river water. The energy production is usually limited by ionic conductivity in dilute compartments of a RED system. Novel tests were conducted in this research, which used ion-exchange resin beads (IERB) to replace nonconductive spacer fabrics in RED compartments with dilute NaCl solution in a modified stack containing Fumasep FKS and Fumasep FAS membranes. We compared the conductivity of an IERB packed bed with that of an inert glass-beads-packed bed as a control to confirm IERB's effectiveness. When applied in a RED system, IERB decreased the stack resistance by up to 40%. The maximum gross power density improved by 83% in the RED stack compared to that in a regular RED stack at 1.3 cm/s average linear flow velocity. IERB-filled stack resistance was modeled. The model results fit well with experimental data, thereby confirming the effectiveness of the new approach presented here. The net power density is also estimated based on the measured pressure drop and pumping energy model. Both gross and net power density was improved by over 75% at higher flow rate. A net power density of 0.44 W/m(2) was achieved at a cell thickness of 500 μm. To the best of our knowledge, this research is the first to study the impact of IERB on power generation and establishes a new approach to improving the power performance of a RED system. PMID:26560232

  3. Automated direct-immersion solid-phase microextraction using crosslinked polymeric ionic liquid sorbent coatings for the determination of water pollutants by gas chromatography.

    PubMed

    Cordero-Vaca, María; Trujillo-Rodríguez, María J; Zhang, Cheng; Pino, Verónica; Anderson, Jared L; Afonso, Ana M

    2015-06-01

    Four different crosslinked polymeric ionic liquid (PIL)-based sorbent coatings were evaluated in an automated direct-immersion solid-phase microextraction method (automated DI-SPME) in combination with gas chromatography (GC). The crosslinked PIL coatings were based on vinyl-alkylimidazolium- (ViCnIm-) or vinylbenzyl-alkylimidazolium- (ViBzCnIm-) IL monomers, and di-(vinylimidazolium)dodecane ((ViIm)2C12-) or di-(vinylbenzylimidazolium)dodecane ((ViBzIm)2C12-) dicationic IL crosslinkers. In addition, a PIL-based hybrid coating containing multi-walled carbon nanotubes (MWCNTs) was also studied. The studied PIL coatings were covalently attached to derivatized nitinol wires and mounted onto the Supelco assembly to ensure automation when acting as SPME coatings. Their behavior was evaluated in the determination of a group of water pollutants, after proper optimization. A comparison was carried out with three common commercial SPME fibers. It was observed that those PILs containing a benzyl group in their structures, either in the IL monomer and crosslinker (PIL-1-1) or only in the crosslinker (PIL-0-1), were the most efficient sorbents for the selected analytes. The validation of the overall automated DI-SPME-GC-flame ionization detector (FID) method gave limits of detection down to 135 μg · L(-1) for p-cresol when using the PIL-1-1 and down to 270 μg · L(-1) when using the PIL-0-1; despite their coating thickness: ~2 and ~5 μm, respectively. Average relative recoveries with waters were of 85 ± 14 % and 87 ± 15 % for PIL-1-1 and PIL-0-1, respectively. Precision values as relative standard deviation were always lower than 4.9 and 7.6 % (spiked level between 10 and 750 μg · L(-1), as intra-day precision). Graphical Abstract Automated DI-SPME-GC-FID using crosslinked-PILs sorbent coatings for the determination of waterpollutants. PMID:25925853

  4. Selective extraction of genotoxic impurities and structurally alerting compounds using polymeric ionic liquid sorbent coatings in solid-phase microextraction: Alkyl halides and aromatics.

    PubMed

    Ho, Tien D; Joshi, Manishkumar D; Silver, Mark A; Anderson, Jared L

    2012-06-01

    A series of polymeric ionic liquids (PILs) possessing varied chemical makeup and composition were applied as selective solid-phase microextraction (SPME) sorbent coatings for the analysis of genotoxic impurities (GTIs) and related structurally alerting compounds, namely, alkyl halides and aromatics. In addition to exploiting two previously synthesized PILs as selective coatings, two new PILs, namely, N,N-didecyl-N-methyl-D-glucaminium poly(2-methyl-acrylic acid 2-[1-(3-{2-[2-(3-trifluoromethanesulfonylamino-propoxy)-ethoxy]-ethoxy}-propylamino)-vinylamino]-ethyl ester) (poly([DDMGlu][MTFSI])), and poly(1-vinyl-3-propylphenylimidazolium) chloride (poly([VPPIM][Cl])), were designed, synthesized, and their selectivity examined in the extraction of the selected analytes. The glucaminium-based coating was developed to exploit the hydrogen bond-acidic hydroxyl groups within the carbohydrate moiety of the PIL in addition to dispersive capabilities resulting from the cation and anion. The poly([VPPIM][Cl]) coating was tailored to possess π-π interaction capabilities through the phenyl functionality while also containing the hydrogen bond-basic chloride anion. Calibration studies were performed via headspace extraction to determine the sensitivity and limit of detection (LOD) for all analytes with respect to each PIL-based sorbent coating and compared to the polyacrylate (PA) and polydimethylsiloxane (PDMS) sorbent coatings. PILs containing the chloride anion exhibited high selectivity for aniline-based compounds. The glucaminium-based PIL exhibited good sensitivity for larger aliphatic alkyl halides. The poly(1-4-vinylbenzyl-3-hexadecylimidazolium) bis[(trifluoromethyl)sulfonyl] imide (poly([VBHDIM][NTf₂])) PIL coating demonstrated superior selectivity for larger aliphatic/aromatic analytes. The LODs of both commercial and PIL-based coatings for the two classes of GTIs ranged from low part-per-billion (ppb) to mid part-per-trillion (ppt) levels. Recovery studies were

  5. Selective sorption of lead, cadmium and zinc ions by a polymeric cation exchanger containing nano-Zr(HPO3S)2.

    PubMed

    Zhang, Qingrui; Pan, Bingcai; Pan, Bingjun; Zhang, Weiming; Jia, Kun; Zhang, Quanxing

    2008-06-01

    A novel polymeric hybrid sorbent, namely ZrPS-001, was fabricated for enhanced sorption of heavy metal ions by impregnating Zr(HPO3S)2 (i.e., ZrPS) nanoparticles within a porous polymeric cation exchanger D-001. The immobilized negatively charged groups bound to the polymeric matrix D-001 would result in preconcentration and permeation enhancement of target metal ions prior to sequestration, and ZrPS nanoparticles are expected to sequester heavy metals selectively through an ion-exchange process. Highly effective sequestration of lead, cadmium, and zinc ions from aqueous solution can be achieved by ZrPS-001 even in the presence of competing calcium ion at concentration several orders of magnitude greater than the target species. The exhausted ZrPS-001 beads are amenable to regeneration with 6 M HCI solution for repeated use without any significant capacity loss. Fixed-bed column treatment of simulated waters containing heavy metals at high or trace levels was also performed. The content of heavy metals in treated effluent approached or met the WHO drinking water standard. PMID:18589978

  6. Development of high-productivity, strong cation-exchange adsorbers for protein capture by graft polymerization from membranes with different pore sizes

    PubMed Central

    Chenette, Heather C.S.; Robinson, Julie R.; Hobley, Eboni; Husson, Scott M.

    2012-01-01

    This paper describes the surface modification of macroporous membranes using ATRP (atom transfer radical polymerization) to create cation-exchange adsorbers with high protein binding capacity at high product throughput. The work is motivated by the need for a more economical and rapid capture step in downstream processing of protein therapeutics. Membranes with three reported nominal pore sizes (0.2, 0.45, 1.0 μm) were modified with poly(3-sulfopropyl methacrylate, potassium salt) tentacles, to create a high density of protein binding sites. A special formulation was used in which the monomer was protected by a crown ether to enable surface-initiated ATRP of this cationic polyelectrolyte. Success with modification was supported by chemical analysis using Fourier-transform infrared spectroscopy and indirectly by measurement of pure water flux as a function of polymerization time. Uniformity of modification within the membranes was visualized with confocal laser scanning microscopy. Static and dynamic binding capacities were measured using lysozyme protein to allow comparisons with reported performance data for commercial cation-exchange materials. Dynamic binding capacities were measured for flow rates ranging from 13 to 109 column volumes (CV)/min. Results show that this unique ATRP formulation can be used to fabricate cation-exchange membrane adsorbers with dynamic binding capacities as high as 70 mg/mL at a throughput of 100 CV/min and unprecedented productivity of 300 mg/mL/min. PMID:23175597

  7. Investigation of the free volume and ionic conducting mechanism of poly(ethylene oxide)-LiClO4 polymeric electrolyte by positron annihilating lifetime spectroscopy

    NASA Astrophysics Data System (ADS)

    Gong, Jing; Gong, Zhen-Li; Yan, Xiao-Li; Gao, Shu; Zhang, Zhong-Liang; Wang, Bo

    2012-10-01

    The positron annihilation lifetime and ionic conductivity are each measured as a function of organophilic rectorite (OREC) content and temperature in a range from 160 K to 300 K. According to the variation of ortho-positronium (o-Ps) lifetime with temperature, the glassy transition temperature is determined. The continuous maximum entropy lifetime (MELT) analysis clearly shows that the OREC and temperature have important effects on o-Ps lifetime and free volume distribution. The experimental results show that the temperature dependence of ionic conductivity obeys the Vogel—Tammann—Fulcher (VTF) and Williams—Landel—Ferry (WLF) equations, implying a free-volume transport mechanism. A linear least-squares procedure is used to evaluate the apparent activation energy related to the ionic transport in the VTF equation and several important parameters in the WLF equation. It is worthwhile to notice that a direct linear relationship between the ionic conductivity and free volume fraction is established using the WLF equation based on the free volume theory for nanocomposite electrolyte, which indicates that the segmental chain migration and ionic migration and diffusion could be explained by the free volume theory.

  8. Modeling cesium retention onto Na-, K- and Ca-smectite: Effects of ionic strength, exchange and competing cations on the determination of selectivity coefficients

    NASA Astrophysics Data System (ADS)

    Missana, Tiziana; Benedicto, Ana; García-Gutiérrez, Miguel; Alonso, Ursula

    2014-03-01

    Cesium (137Cs) retention onto three homoionic smectites (Na-, K- and Ca-smectite), obtained from natural Spanish FEBEX bentonite, was studied. Special emphasis was given to the analysis of non-linear sorption behaviour and the dependence of selectivity on the ionic strength. A very large set of experimental sorption data was generated from sorption tests under a wide range of pHs (2-11), ionic strengths (10-3 to 100 M), and radionuclide concentrations (10-10 to 10-3 M). The aqueous phase, in contact with the clay, was analysed to quantify the effects of the presence of trace aqueous ions on Cs retention. For all the exchanged clays, Cs sorption was non-linear and a two-site exchange model approach was adopted to interpret and model sorption data. Highly selective sites for Cs sorption (Type 1 sites, T1), resembling those present in micaceous materials, with very low capacity but controlling uptake of Cs at low concentration, were observed. The logarithm value of selectivity coefficients determined for Cs+ in respect to Na+, K+ and Ca2+ in these sites is: LogNaCsK(T1)=7.59±0.15,LogKCsK(T1)=5.15±0.15 and LogCaCsK(T1)=14.41±0.17, respectively. The exchange sites at the surface of smectite sheets (planar sites), with a capacity approximately equivalent to the cation exchange capacity (CEC) of the clay, constitute the second type of sorption sites (Type 2 sites, T2). The logarithm of the selectivity coefficients determined for Cs+ with respect to Na+, K+ and Ca2+ is: LogNaCsK(T2)=1.68±0.15,LogKCsK(T2)=1.16±0.15LogCaCsK(T2)=3.02± 0.15, respectively. The analysis of the dependence of sorption values on the ionic strength clearly indicated that for a correct interpretation of data, competition effects of trace ions in solution must be always accounted for. Data obtained in this work and performed analyses are basic to explain the behaviour of raw FEBEX bentonite, and other smectite-based clay materials, under more complex experimental conditions.

  9. Effect of water on the transport properties of protic and aprotic imidazolium ionic liquids - an analysis of self-diffusivity, conductivity, and proton exchange mechanism.

    PubMed

    Yaghini, N; Nordstierna, L; Martinelli, A

    2014-05-28

    In this paper we report on the transport properties of protic and aprotic ionic liquids of the imidazolium cation (C2C1Im(+) or C2HIm(+)) and the TFSI(-) or TfO(-) anion as a function of added water. We observe that the self-diffusion coefficient of the ionic species increases upon addition of water, and that the cation diffuses faster than the anion in the entire water concentration range investigated. We also observe that the overall increase of anionic and cationic diffusion coefficients is significant for C2HImTfO while it is rather weak for C2C1ImTFSI, the former being more hydrophilic. Moreover, the difference between cationic and anionic self-diffusivity specifically depends on the structure of the ionic liquid's ions. The degree of ion-ion association has been investigated by comparing the molar conductivity obtained by impedance measurements with the molar conductivity calculated from NMR data using the Nernst-Einstein equation. Our data indicate that the ions are partly dissociated (Λimp/ΛNMR in the range 0.45-0.75) but also that the degree of association decreases in the order C2HImTfO > C2HImTFSI ≈ C2C1ImTfO > C2C1ImTFSI. From these results, it seems that water finds different sites of interaction in the protic and aprotic ionic liquids, with a strong preference for hydrogen bonding to the -NH group (when available) and a stronger affinity to the TfO anion as compared to the TFSI. For the protic ionic liquids, the analysis of (1)H NMR chemical shifts (upon addition of H2O and D2O, respectively) indicates a water-cation interaction of hydrogen bonding nature. In addition, we could probe proton exchange between the -NH group and deuterated water for the protic cation, which occurs at a significantly faster rate if associated with the TfO anion as compared to the TFSI. PMID:24714867

  10. Determination of acrylamide in brewed coffee and coffee powder using polymeric ionic liquid-based sorbent coatings in solid-phase microextraction coupled to gas chromatography-mass spectrometry.

    PubMed

    Cagliero, Cecilia; Ho, Tien D; Zhang, Cheng; Bicchi, Carlo; Anderson, Jared L

    2016-06-01

    This study describes a simple and rapid sampling method employing a polymeric ionic liquid (PIL) sorbent coating in direct immersion solid-phase microextraction (SPME) for the trace-level analysis of acrylamide in brewed coffee and coffee powder. The crosslinked PIL sorbent coating demonstrated superior sensitivity in the extraction of acrylamide compared to all commercially available SPME coatings. A spin coating method was developed to evenly distribute the PIL coating on the SPME support and reproducibly produce fibers with a large film thickness. Ninhydrin was employed as a quenching reagent during extraction to inhibit the production of interfering acrylamide. The PIL fiber produced a limit of quantitation for acrylamide of 10μgL(-1) and achieved comparable results to the ISO method in the analysis of six coffee powder samples. PMID:27157428

  11. Phase-transfer behavior of cross-linked poly(acrylic acid) particles prepared by dispersion polymerization from ionic liquid to water.

    PubMed

    Minami, Hideto; Mizuta, Yusuke; Kimura, Akira

    2012-02-01

    The phase-transfer behavior of poly(acrylic acid) (PAA) particles from the hydrophobic ionic liquid N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)amide phase to the water phase in the particle state, which we reported previously, was examined in more detail. PAA particles were prepared in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([Bmim][TFSA]) and the organic solvent chloroform and were extracted. The transfer of PAA particles to water in the particle state was also observed in [Bmim][TFSA] systems. In contrast, the transfer phenomenon was not observed in the chloroform system. It was clarified that water/oil interfacial tension γ(wo) is an important parameter in the extraction of PAA in the particle state from the viewpoint of free energy. When the cationic surfactant tetradecyltrimethylammonium bromide, aqueous solution was used as the extraction medium, the PAA particles were extracted in the particle state from chloroform to water, in which γ(wo) became as low as that of the ionic liquid. This suggests that the phase-transfer phenomenon of PAA particles in the particle state was induced by the ionic liquid's unique property of low interfacial tension with water despite its high hydrophobic character. PMID:22235893

  12. Incorporation of multi-walled carbon nanotubes in microspheres used as anion exchange resin via suspension polymerization

    NASA Astrophysics Data System (ADS)

    Fathy, Mahmoud; Abdel Moghny, Th.; Awadallah, Ahmed E.; El-Bellihi, Abdel-Hameed A.-A.

    2014-06-01

    Amination of vinylbenzyl chloride-divinylbenzene (VBC-DVB) copolymers is an effective method for preparation of anion-exchange resins. Conventionally, the starting polymer is produced by chloromethylation of a styrene-divinylbenzene copolymer that utilizes chloromethyl methyl ether, a known carcinogen. An alterative approach is to copolymerize vinylbenzyl chloride with divinylbenzene to generate the necessary VBC-DVB. This method provides precise control over the density of the ion-exchange groups. The regiochemistry of the vinylbenzyl chloride methods was realized using solvent-ion exchange groups. These resulting anion-exchange polymers were characterized by a variety of techniques such as analytical titrations, transform infrared spectroscopy and thermal gravimetric analysis. Testing of these copolymers for breakthrough was performed. The results indicate that these anion exchangers have a meaningful increase in thermal stability over commercial anionic exchange beads. Resins containing MWCNTs achieved anion exchange capacity value of 323.6 meq/100 g over than that of copolymer resins and that useful in water desalination or treatment.

  13. White-light-exciting, layer-by-layer-assembled ZnCdHgSe quantum dots/polymerized ionic liquid hybrid film for highly sensitive photoelectrochemical immunosensing of neuron specific enolase.

    PubMed

    Yu, Xiangyang; Wang, Yanying; Chen, Xuemin; Wu, Kangbing; Chen, Danchao; Ma, Ming; Huang, Zhenjia; Wu, Wangze; Li, Chunya

    2015-04-21

    ZnCdHgSe quantum dots (QDs) functionalized with N-acetyl-l-cysteine were synthesized and characterized. Through layer-by-layer assembling, the ZnCdHgSe QDs was integrated with a polymerized 1-decyl-3-[3-pyrrole-1-yl-propyl]imidazolium tetrafluoroborate (PDPIT) ionic liquid film modified indium tin oxide (ITO) electrode to fabricated a photoelectrochemical interface for the immobilization of rabbit antihuman neuron specific enolase (anti-NSE). After being treated with glutaraldehyde vapor and bovine serum albumin successively, an anti-NSE/ZnCdHgSe QDs/PDPIT/ITO sensing platform was established. Simplely using a white-light LED as an excitation source, the immunoassay of neuron specific enolase (NSE) was achieved through monitoring the photocurrent variation. The polymerized ionic liquid film was demonstrated to be an important element to enhance the photocurrent response of ZnCdHgSe QDs. The anti-NSE/ZnCdHgSe QDs/PDPIT/ITO based immunosensor presents excellent performances in neuron specific enolase determination. The photocurrent variation before and after being interacted with NSE exhibits a good linear relationship with the logarithm of its concentration (log cNSE) in the range from 1.0 pg mL(-1) to 100 ng mL(-1). The limit of detection of this immunosensor is able to reach 0.2 pg mL(-1) (S/N = 3). The determination of NSE in clinical human sera was also demonstrated using anti-NSE/ZnCdHgSe QDs/PDPIT/ITO electrode. The results were found comparable with those obtained by using enzyme-linked immunosorbent assay method. PMID:25790014

  14. Determination of non-ionic and anionic surfactants in industrial products by separation on a weak ion-exchanger, derivatization and liquid chromatography.

    PubMed

    Ripoll-Seguer, L; Beneito-Cambra, M; Herrero-Martínez, J M; Simó-Alfonso, E F; Ramis-Ramos, G

    2013-12-13

    A method for the determination of priority surfactants, including fatty alcohol ethoxylates (FAE), alkylether sulfates (AES) and linear alkylbenzene sulfonates (LAS) is described. The samples were diluted with 50% methanol at pH 4 prior to solid-phase extraction on a weak anionic exchanger (WAX). The AES and LAS surfactant classes were retained, whereas the non-ionic components, including most FAE oligomers were eluted. After washing the WAX cartridge to remove cations, the remaining hydrophobic FAE oligomers were eluted using hot 80% methanol at pH 4 (at ca. 50°C). These two eluates were combined to constitute the non-ionic fraction. Then, AES and LAS were eluted using 80% MeOH with 3M NH3 followed by 95% methanol with 0.75M NH3. The two eluates obtained in basic media were combined to constitute the anionic fraction. The solvents were evaporated, the residues were dissolved in 1,4-dioxane, and esterification of the alcohols and transesterification of AES with phthalic anhydride was performed. Separation of the derivatized oligomers was achieved by gradient elution on a C8 column with acetonitrile/water in the presence of 0.1% acetic acid and 0.1M NaClO4. The chromatogram of the non-ionic fraction showed the peaks of the resolved FAE oligomers. The chromatogram of the anionic fraction showed the peaks of the LAS homologues well resolved from those of the AES oligomers. The method was applied to laundry and industrial cleaners, shampoos and a shower gel. PMID:24210557

  15. Non-ionic surfactant modified ligand exchange chromatography using copper (II) complex of N,N-dimethyl-L-phenylalanine as the chiral additive for enantioselective amino acids separation.

    PubMed

    Dimitrova, Pepa; Bart, Hans-Jörg

    2010-03-17

    The influence of non-ionic surfactants on the selectivity and retention in the ligand exchange chromatography for the enantioselective separation of racemic mixtures of the amino acids dl-methionine, dl-leucine, dl-valine and dl-tyrosine applying chiral mobile phases was investigated, whereas five different surfactants were tested as modifiers. The experiments were carried out using a commercially available non-chiral RP-C8 column and the copper (II) complex of N,N-dimethyl-l-phenylalanine as the chiral additive. Varying the surfactant concentrations the retention factors and the selectivity could be controlled and in general no negative influence on the separation (due to surfactant adsorption on the non-chiral stationary phase) occurred. Changing the temperature the van't Hoff plots were obtained and the thermodynamic parameters calculated. Temperature had influence on the selectivity for each surfactant and lowered the retention times as expected. PMID:20172105

  16. Ring-opening metathesis polymerization-derived large-volume monolithic supports for reversed-phase and anion-exchange chromatography of biomolecules.

    PubMed

    Bandari, Rajendar; Buchmeiser, Michael R

    2012-07-21

    Preparative-scale monolithic columns up to 433.5 mL in volume were prepared via transition metal-catalyzed ring-opening metathesis polymerization (ROMP) from norborn-2-ene (NBE) and trimethylolpropane-tris(5-norbornene-2-carboxylate) (CL) using the 1(st)-generation Grubbs initiator RuCl(2)(PCy(3))(2)(CHPh) (Cy = cyclohexyl) (1) in the presence of a macro- and microporogen, i.e. of 2-propanol and toluene. To prepare large-volume monoliths, bulk polymerizations were completed within borosilicate or PEEK column formats with diameters in the range of 3 to 49 mm. The pore structure of the large-volume monoliths was investigated by electron microscopy and inverse-size exclusion chromatography (ISEC), respectively. Monolithic columns with inner diameters (I.D.s) in the range of 10-49 mm were tested for the separation of a mixture of five proteins, i.e., insulin, cytochrome C, lysozyme, conalbumin, and β-lactoglobulin. Preparative separation of these proteins was achieved within less than 12 min in a 433.5 mL monolithic column by applying gradient elution in the RP-HPLC mode. Furthermore, weak and strong anion exchangers were prepared via post-synthesis grafting of bicyclo[2.2.1]hept-5-en-2-yl-methyl-N,N-dimethylammonium hydrochloride (4) and bicyclo[2.2.1]hept-5-en-2-ylmethyl-N,N,N-trimethylammonium iodide (5), respectively. The weak and strong anion exchangers were used for the preparative-scale separation of 5'-phosphorylated oligodeoxythymidylic acid fragments of d[pT](12-18) at pH values ranging from 5 to 9. PMID:22673214

  17. EXCHANGE

    SciTech Connect

    Boltz, J.C.

    1992-09-01

    EXCHANGE is published monthly by the Idaho National Engineering Laboratory (INEL), a multidisciplinary facility operated for the US Department of Energy (DOE). The purpose of EXCHANGE is to inform computer users about about recent changes and innovations in both the mainframe and personal computer environments and how these changes can affect work being performed at DOE facilities.

  18. Preparation of a Proton-Exchange Me mbrane with -SO3H Group Based on Polyethylene and Poly(vinylidene fluoride) Film by Radiation-Induced Graft Polymerization for Proton-Exchange Fuel Cell.

    PubMed

    Kim, Sang-Kyum; Lee, Yong-Sang; Koo, Kee-Kahb; Kim, Sang-Ho; Choi, Seong-Ho

    2015-09-01

    This paper reports the preparation of a proton-exchange membrane (PEM) with sulfonic acid (-SO3H) groups based on polyethylene (PE) films and poly(vinylidene fluoride) (PVdF) films by the radiation-induced graft polymerization (RIGP) of sodium styrene sulfonate (NaSS) in the presence of the polymerizable access agents, such as acrylic acid and pyrollidone in a methanol solution. A PEM with -SO3H based on PE and PVdF films were confirmed by ATR, XPS and contact angle measurements. The water uptake (%), graft yield (%), ion-exchange content (mmol/g), and proton conductivity (S/cm), as well as the current density (mA/cm2), and power density (mW/cm) for PEM with -SO3H groups prepared by RIGP were evaluated. The PEM prepared with the -SO3H groups based on PE and PVdF films can be used as a proton-exchange fuel cell membrane. PMID:26716266

  19. PbSe films by ion exchange of synthetic plumbonacrite layers immersed in a selenium ionic solution

    NASA Astrophysics Data System (ADS)

    Mendívil-Reynoso, T.; Ochoa-Landín, R.; Ramírez-Rodríguez, L. P.; Gutierrez-Acosta, K.; Ramírez-Bon, R.; Castillo, S. J.

    2016-06-01

    Plumbonacrite is a lead compound with chemical formula Pb10(CO3)6(OH)6O, where several groups can be substituted by ion exchange in mild conditions. Plumbonacrite layers can be deposited by means of the chemical bath deposition technique. In this work it is studied the structural and morphological evolution of a plumbonacrite layer as a function of the immersion time in an aqueous solution containing Se-2 ions. The 1.39 μm thick plumbonacrite layer was chemically deposited on a glass substrate and immersed in an aqueous solution with Se-2 ions for 10, 20, 30 and 50 min. The as grown plumbonacrite layer as well as the immersed ones were analyzed by X-rays Diffraction, Scanning Electron Microscopy and Raman Spectroscopy measurements. The results show that the plumbonacrite layer is gradually converted to PbSe one by ion exchange process, where Se-2 ions substitute the groups of plumbonacrite.

  20. Matrix-compatible sorbent coatings based on structurally-tuned polymeric ionic liquids for the determination of acrylamide in brewed coffee and coffee powder using solid-phase microextraction.

    PubMed

    Cagliero, Cecilia; Nan, He; Bicchi, Carlo; Anderson, Jared L

    2016-08-12

    Nine crosslinked polymeric ionic liquid (PIL)-based SPME sorbent coatings were designed and screened in this study for the trace level determination of acrylamide in brewed coffee and coffee powder using gas chromatography-mass spectrometry (GC-MS). The structure of the ionic liquid (IL) monomer was tailored by introducing different functional groups to the cation and the nature of the IL crosslinker was designed by altering both the structure of the cation as well as counteranions. The extraction efficiency of the new PIL coatings towards acrylamide was investigated and compared to a previously reported PIL sorbent coating. All PIL fibers exhibited excellent analytical precision and linearity. The PIL fiber coating consisting of 50% 1,12-di(3-vinylbenzylbenzimidazolium)dodecane dibis[(trifluoromethyl)sulfonyl]imide as IL crosslinker in 1-vinyl-3-(10-hydroxydecyl)imidazolium bis[(trifluoromethyl)sulfonyl]imide IL monomer resulted in a limit of quantitation of 0.5μgL(-1) with in-solution SPME sampling. The hydroxyl moiety appended to the IL cation was observed to significantly increase the sensitivity of the PIL coating toward acrylamide. The quantitation of acrylamide in brewed coffee and coffee powder was performed using the different PIL-based fibers by the method of standard addition after a quenching reaction using ninhydrin to inhibit the formation of interfering acrylamide in the GC inlet, mainly by asparagine thermal degradation. Excellent repeatability with relative standard deviations below 10% were obtained on the real coffee samples and the structure of the coatings appeared intact by scanning electron microscopy after coffee sampling proving the matrix-compatibility of the PIL sorbent coatings. PMID:27423776

  1. Utilization of highly robust and selective crosslinked polymeric ionic liquid-based sorbent coatings in direct-immersion solid-phase microextraction and high-performance liquid chromatography for determining polar organic pollutants in waters.

    PubMed

    Pacheco-Fernández, Idaira; Najafi, Ali; Pino, Verónica; Anderson, Jared L; Ayala, Juan H; Afonso, Ana M

    2016-09-01

    Several crosslinked polymeric ionic liquid (PIL)-based sorbent coatings of different nature were prepared by UV polymerization onto nitinol wires. They were evaluated in a direct-immersion solid-phase microextraction (DI-SPME) method in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The studied PIL coatings contained either vinyl alkyl or vinylbenzyl imidazolium-based (ViCnIm- or ViBCnIm-) IL monomers with different anions, as well as different dicationic IL crosslinkers. The analytical performance of these PIL-based SPME coatings was firstly evaluated for the extraction of a group of 10 different model analytes, including hydrocarbons and phenols, while exhaustively comparing the performance with commercial SPME fibers such as polydimethylsyloxane (PDMS), polyacrylate (PA) and polydimethylsiloxane/divinylbenzene (PDMS/DVB), and using all fibers under optimized conditions. Those fibers exhibiting a high selectivity for polar compounds were selected to carry out an analytical method for a group of 5 alkylphenols, including bisphenol-A (BPA) and nonylphenol (n-NP). Under optimum conditions, average relative recoveries of 108% and inter-day precision values (3 non-consecutive days) lower than 19% were obtained for a spiked level of 10µgL(-1). Correlations coefficients for the overall method ranged between 0.990 and 0.999, and limits of detection were down to 1µgL(-1). Tap water, river water, and bottled water were analyzed to evaluate matrix effects. Comparison with the PA fiber was also performed in terms of analytical performance. Partition coefficients (logKfs) of the alkylphenols to the SPME coating varied from 1.69 to 2.45 for the most efficient PIL-based fiber, and from 1.58 to 2.30 for the PA fiber. These results agree with those obtained by the normalized calibration slopes, pointing out the affinity of these PILs-based coatings. PMID:27343586

  2. Anion-exchange reactions on a robust phosphonium photopolymer for the controlled deposition of ionic gold nanoclusters.

    PubMed

    Guterman, Ryan; Hesari, Mahdi; Ragogna, Paul J; Workentin, Mark S

    2013-05-28

    UV curing (photopolymerization) is ubiquitous in many facets of industry ranging from the application of paints, pigments, and barrier coatings all the way to fiber optic cable production. To date no reports have focused on polymerizable phosphonium salts under UV irradiation, and despite this dearth of examples, they potentially offer numerous substantial advantages to traditional UV formulation components. We have generated a highly novel coating based on UV-curable trialkylacryloylphosphonium salts that allow for the fast (seconds) and straightforward preparation of ion-exchange surfaces amenable to a roll-to-roll process. We have quantified the surface charges and exploited their accessibility by employing these surfaces in an anion exchange experiment by which [Au25L18](-) (L = SCH2CH2Ph) nanocrystals can be assembled into the solid state. This unprecedented application of such surfaces offers a paradigm shift in the emerging chemistry of Au25 research where the nanocrystals remain single and intact and where the integrity of the cluster and its solution photophysical properties are resilient in the solid state. The specific loading of [Au25L18](-) on the substrates has been determined and the completely reversible loading and unloading of intact nanocrystals to and from the surface has been established. In the solid state, the assembly has an incredible mechanical resiliency, where the surface remains undamaged even when subjected to repeated Scotch tests. PMID:23472738

  3. Ionic diffusion in single crystals of vermiculite

    SciTech Connect

    Maraqah, H.R.

    1993-01-01

    Novel guest-host compounds, based on single crystal vermiculite, were synthesized by diffusive techniques through a new hydrogen vermiculite. Single crystals were chosen because of the ease of characterization. An investigation of the ion transport properties of these single crystals was done to determine the mechanism of conductivity including the predominant charge carrier. Measurements of the ionic conductivity using impedance spectroscopy and X-ray lattice parameters of the ion-exchanged samples strongly suggest that the native cations and not protons are the major current carriers. Single crystals of hydrogen vermiculite were synthesized at room temperature by ion exchange from sodium-vermiculite using 1 molar acetic acid for a one week. Subsequent ion exchange with other cations was found to be much enhanced. Thus transition metals were exchanged in about a week in contrast to the need of several months using previous methods. The ionic conductivity of hydrogen vermiculite was measured and shown to be much lower than that of many other monovalent cations in the same host lattice. Its enthalpy of motion is also much lower. These marked differences suggest that protonic species do not play a significant role in charge transport in these layered materials. These materials were characterized by x-ray powder diffraction, thermogravimetric analysis and acid-base titration. Hydrogen-vermiculite was found to react with organic bases, like methylamine, ethylamine, n-butylamine, n-hexylamine, n-octylamine, n-decylamine, aniline, acrylamide, methacrylaminde, urea, 1,10phenanthroline, and 1,1phenanthroline ferrous sulfate complex, to undergo ion exchange with metal cations like sodium, zinc, copper(II) ions and polymerization reactions could be performed in the galleries of the structure like pyrrole and aniline. Its behavior was compared with that of powdered montmorillonite.

  4. Preparation of size-controlled magnetite nanoparticles with a graphene and polymeric ionic liquid coating for the quick, easy, cheap, effective, rugged and safe extraction of preservatives from vegetables.

    PubMed

    Chen, Yaling; Cao, Shurui; Zhang, Lei; Xi, Cunxian; Li, Xianliang; Chen, Zhiqiong; Wang, Guoming

    2016-05-27

    Size-controlled magnetite nanoparticles (Fe3O4) with 200-1000nm were synthesized by co-precipitation method. Then Fe3O4@SiO2@G@PIL was synthesized and used as modified QuEChERS adsorbent for the determination of preservatives in vegetables. The size of about 200nm of Fe3O4 in Fe3O4@SiO2@G@PIL was selected as optimum size to clean-up. It not only exerted the nanometer features of magnetic nanoparticles, but also displayed the large specific surface area of graphene (G) and the solvent effects of polymeric ionic liquids (PILs). Various experimental parameters have been investigated. Under the optimized conditions, a simple, rapid and effective method for the determination of 20 preservatives residues in vegetables was established by modified QuEChERS to gas chromatography/mass spectrometry (GC-MS) analysis. The good linearity with correlation coefficients (R(2)) of 0.9972-0.9999 was obtained over the range of 0.02-2.00mg/L for 20 preservatives. The detection limits of the proposed method for 20 preservatives ranged from 0.82 to 6.64μg/kg. The adsorbent was successfully applied for extraction and determination of preservatives in vegetable samples, which thus was time-saving with keeping good clean-up performance. PMID:27109197

  5. Selective extraction and analysis of catecholamines in rat blood microdialysate by polymeric ionic liquid-diphenylboric acid-packed capillary column and fast separation in high-performance liquid chromatography-electrochemical detector.

    PubMed

    Zhou, Xinguang; Zhu, Anwei; Shi, Guoyue

    2015-08-28

    Concentration of blood catecholamines (CAs) is linked to a host of cardiovascular diseases, including hypertension and stenocardia. The matrix interferences and low concentration require tedious sample pretreatment methods before quantitative analysis by the gold standard method of high-performance liquid chromatography-electrochemical detector (HPLC-ECD). Solid phase extraction (SPE) has been widely used as the pretreatment technique. Here, a facile polymeric ionic liquid (PIL)-diphenylboric acid (DPBA)-packed capillary column was prepared to selectively extract dopamine (DA), noradrenaline (NE) and epinephrine (E) prior to their quantitative analysis by a fast separation in HPLC-ECD method, while microdialysis sampling method was applied to get the analysis sample. Parameters that influenced desorption efficiency, such as pH, salt concentration, acetonitrile content and wash time, were examined and optimized. The proposed method, combining microdialysis sampling technique, SPE and HPLC-ECD system, was successfully applied to detect CAs in rat blood microdialysate with high sensitivity and selectivity in small sample volumes (5-40μl) and a short analysis time (8min), yielding good reproducibility (RSD 6.5-7.7%) and spiked recovery (91-104.4%). PMID:26206631

  6. Radiofrequency plasma polymerized perfluoroionomer membrane materials

    SciTech Connect

    Danilich, M.J.; Gervasio, D.F.; Marchant, R.E.

    1993-12-31

    Ion exchange membranes have received considerable attention in recent years. Applications of ion exchange membranes have included such electrochemical systems as water and organic electrolyzers, redox-flow batteries, and sensors. This work is a study of radiofrequency plasma polymerization of perfluorinated acid-containing monomers and a perfluorinated {open_quotes}backbone{close_quotes} comonomer as a method for synthesizing novel polyionomer film coatings for use as membranes on electrodes and biomedical sensors. The results indicate that, by altering the deposition conditions, some control can be exercised over the retention of acid functional groups by plasma polymers. Using AC impedance measurements, the ionic conductivity of these films was found to be two to four orders of magnitude higher than their aqueous environments. In addition, several of the acid-containing plasma polymerized films were hydrophilic, having an advancing water contact angle of less than fifteen degrees. The initial results of this study have demonstrated the feasibility of using acid-containing plasma polymers as crosslinked membrane materials suitable for use with electrochemical sensors and biosensors.

  7. Two solid-phase recycling method for basic ionic liquid [C4mim]Ac by macroporous resin and ion exchange resin from Schisandra chinensis fruits extract.

    PubMed

    Ma, Chun-hui; Zu, Yuan-gang; Yang, Lei; Li, Jian

    2015-01-22

    In this study, two solid-phase recycling method for basic ionic liquid (IL) 1-butyl-3-methylimidazolium acetate ([C4mim]Ac) were studied through a digestion extraction system of extracting biphenyl cyclooctene lignans from Schisandra chinensis. The RP-HPLC detection method for [C4mim]Ac was established in order to investigate the recovery efficiency of IL. The recycling method of [C4mim]Ac is divided into two steps, the first step was the separation of lignans from the IL solution containing HPD 5000 macroporous resin, the recovery efficiency and purity of [C4mim]Ac achieved were 97.8% and 67.7%, respectively. This method cannot only separate the lignans from [C4mim]Ac solution, also improve the purity of lignans, the absorption rate of lignans in [C4mim]Ac solution was found to be higher (69.2%) than that in ethanol solution (57.7%). The second step was the purification of [C4mim]Ac by the SK1B strong acid ion exchange resin, an [C4mim]Ac recovery efficiency of 55.9% and the purity higher than 90% were achieved. Additionally, [C4mim]Ac as solvent extraction of lignans from S. chinensis was optimized, the hydrolysis temperature was 90°C and the hydrolysis time was 2h. PMID:25463641

  8. Development of new chiral ligand exchange capillary electrophoresis system with amino acid ionic liquids ligands and its application in studying the kinetics of L-amino acid oxidase.

    PubMed

    Sun, Bingbing; Mu, Xiaoyu; Qi, Li

    2014-04-22

    New kinds of amino acid ionic liquids (AAILs) with pyridinium as cations and L-lysine (L-Lys) as anion have been developed as the available chiral ligands coordinated with Zn(II) in chiral ligand-exchange capillary electrophoresis (CLE-CE). Four kinds of AAILs, including [1-ethylpyridinium][L-lysine], 1-butylpyridinium][L-lysine], [1-hexylpyridinium][L-lysine] and 1-[octylpyridinium][L-lysine], were successfully synthesized and characterized by nuclear magnetic resonance and mass spectrometry. Compared with other AAILs, the best chiral separation of Dns-D, L-amino acids could be achieved when [1-ethylpyridinium][L-lysine] was chosen as the chiral ligand. It has been found that after investigating the influence of key factors on the separation efficiency, such as pH of buffer solution, the ratio of Zn(II) to ligand and complex concentration, eight pairs of Dns-D, L-AAs enantiomers could be baseline separated and three pairs were partly separated under the optimum conditions. The proposed CLE-CE method also exhibited favorable quantitative analysis property of Dns-D, L-Met with good linearity (r(2)=0.998) and favorable repeatability (RSD≤1.5%). Furthermore, the CLE-CE system was applied in investigating the kinetic contents of L-amino acid oxidase, which implied that the proposed system has the potential in studying the enzymatic reaction mechanism. PMID:24703219

  9. An Alternative to the Ionic Model

    ERIC Educational Resources Information Center

    Sanderson, R. T.

    1975-01-01

    Describes the "coordinated polymeric model," which yields more accurate energy calculations than the "ionic model" for compounds which exhibit considerable covalency. The dichotomy between ionic and covalent bonding is thus largely broken down for solids which are nonmolecular in the crystalline state. (MLH)

  10. Polymeric microspheres

    DOEpatents

    Walt, David R.; Mandal, Tarun K.; Fleming, Michael S.

    2004-04-13

    The invention features core-shell microsphere compositions, hollow polymeric microspheres, and methods for making the microspheres. The microspheres are characterized as having a polymeric shell with consistent shell thickness.

  11. Polymeric ionic liquid modified graphene oxide-grafted silica for solid-phase extraction to analyze the excretion-dynamics of flavonoids in urine by Box-Behnken statistical design.

    PubMed

    Hou, Xiudan; Liu, Shujuan; Zhou, Panpan; Li, Jin; Liu, Xia; Wang, Licheng; Guo, Yong

    2016-07-22

    A solid-phase extraction method for the efficient analysis of the excretion-dynamics of flavonoids in urine was established and described. In this work, in situ surface radical chain-transfer polymerization and in situ anion exchange were utilized to tune the extraction performance of poly(1-vinyl-3-hexylimidazolium bromide)-graphene oxide-grafted silica (poly(VHIm(+)Br(-))@GO@Sil). Graphene oxide (GO) was first coated onto the silica using a layer-by-layer fabrication method, and then the anion of poly(VHIm(+)Br(-))@GO@Sil was changed into hexafluorophosphate (PF6(-)) by in situ anion exchange. The interaction energies between two PILs and four flavonoids were calculated with the Gaussian09 suite of programs. A Box-Behnken design was used for the optimization of four greatly influential parameters after single-factor experiments to obtain more accurate and precise results. Coupled to high performance liquid chromatography, the poly(VHIm(+)PF6(-))@GO@Sil method showed acceptable extraction recoveries for the four flavonoids, with limits of detection in the range of 0.1-0.5μgL(-1), and wide linear ranges with correlation coefficients (R) ranging from 0.9935 to 0.9987. Under the optimum conditions, the proposed method was applied to analyze the urines collected from a healthy volunteer. The excretion amount-time profiles revealed that 4-15h was the main excretion time for the detected flavonoids. The results indicated that the newly developed method offered the advantages of being feasible, green and cost-effective, and could be successfully applied to the extraction and enrichment of flavonoids in human body systems allowing the study of the metabolic kinetics. PMID:27295963

  12. Proton Conducting Polymer Membrane Using The Ionic Liquid 2-Hydroxyethylammonium Lactate For Ethanol Fuel Cells

    NASA Astrophysics Data System (ADS)

    Oliveira, L.; José, N. M.; Boaventura, J.; Iglesias, M.; Mattedi, S.

    2011-12-01

    In this work, there were developed a proton conducting polymer membrane using an ammonium based protic ionic liquid: 2-hydroxyethylamominum lactate for use in proton exchange fuel cells (PEMFC). This kind of ionic liquid has been proven to be biodegradable and they have potentially low toxicity besides low cost of preparation, simple synthesis and purification. The prepared membranes are hybrid organic-inorganic materials. The polymeric matrix is prepared with polydimethylsiloxane (PDMS) mixed with tetraethoxysilane (TEOS) in a ratio of 70/30% in weight. Then, the eletrolytical mixture containing sodium monododecylsulfate (SDS) and the ionic liquid was introduced in the lattice near the gel point, there were used different proportions of the eletrolyte from 5 to 30% in weight. The prepared membranes were characterized using infrared spectroscopy (FTIR), X-ray diffraction (DRX), termogravimetric analysis (TGA), scanning electronic microscopy (SEM) and conductivity and impedance measurements. The prepared materials are flexible, with good thermal and mechanical stability and with a great potential to be used as conducting membranes of fuel cells. The used mixture minimizes the lixiviation lost of the ionic liquid from the polymeric membrane and enhances the cell efficiency if compared with traditional synthetic membranes.

  13. Membrane separation of ionic liquid solutions

    SciTech Connect

    Campos, Daniel; Feiring, Andrew Edward; Majumdar, Sudipto; Nemser, Stuart

    2015-09-01

    A membrane separation process using a highly fluorinated polymer membrane that selectively permeates water of an aqueous ionic liquid solution to provide dry ionic liquid. Preferably the polymer is a polymer that includes polymerized perfluoro-2,2-dimethyl-1,3-dioxole (PDD). The process is also capable of removing small molecular compounds such as organic solvents that can be present in the solution. This membrane separation process is suitable for drying the aqueous ionic liquid byproduct from precipitating solutions of biomass dissolved in ionic liquid, and is thus instrumental to providing usable lignocellulosic products for energy consumption and other industrial uses in an environmentally benign manner.

  14. Ionic Liquid Crystals: Versatile Materials.

    PubMed

    Goossens, Karel; Lava, Kathleen; Bielawski, Christopher W; Binnemans, Koen

    2016-04-27

    This Review covers the recent developments (2005-2015) in the design, synthesis, characterization, and application of thermotropic ionic liquid crystals. It was designed to give a comprehensive overview of the "state-of-the-art" in the field. The discussion is focused on low molar mass and dendrimeric thermotropic ionic mesogens, as well as selected metal-containing compounds (metallomesogens), but some references to polymeric and/or lyotropic ionic liquid crystals and particularly to ionic liquids will also be provided. Although zwitterionic and mesoionic mesogens are also treated to some extent, emphasis will be directed toward liquid-crystalline materials consisting of organic cations and organic/inorganic anions that are not covalently bound but interact via electrostatic and other noncovalent interactions. PMID:27088310

  15. Improvement of the chromatographic separation performance of an imidazolium ionic liquid functionalized silica column by in situ anion-exchange with dodecyl sulfonate and dodecylbenzene sulfonate anions.

    PubMed

    Sun, Min; Feng, Juanjuan; Chen, Wenjie; Li, Leilei; Duan, Huimin; Luo, Chuannan

    2014-06-01

    The anionic part of ionic liquids can provide additional interactions during chromatographic separations. In this work, the chromatographic separation performance of a silica column functionalized with 1-propyl-3-methylimidazolium chloride ionic liquid was improved by in situ anion-exchange from chloride anions to dodecyl sulfonate anions and dodecylbenzene sulfonate anions. The separation performances of these ionic liquid functionalized phases were investigated and compared with each other using polycyclic aromatic hydrocarbons, phthalates, parabens, and phenols as model compounds. Results indicated that the new columns presented a better chromatographic separation than the original one. This was ascribed retention mechanism from organic anions. The introduction of dodecyl sulfonate anions increased the hydrophobicity of stationary phase. Furthermore, the phenyl groups of dodecylbenzene sulfonate anions could provide an enhanced selectivity to aromatic compounds such as polycyclic aromatic hydrocarbons by π-π interactions. Analysis repeatability of the new columns was satisfactory (RSD of retention time, 0.10-0.40%; RSD of peak area, 0.66-0.84%). PMID:24616155

  16. Ionic Blocks

    ERIC Educational Resources Information Center

    Sevcik, Richard S.; Gamble, Rex; Martinez, Elizabet; Schultz, Linda D.; Alexander, Susan V.

    2008-01-01

    "Ionic Blocks" is a teaching tool designed to help middle school students visualize the concepts of ions, ionic compounds, and stoichiometry. It can also assist high school students in reviewing their subject mastery. Three dimensional blocks are used to represent cations and anions, with color indicating charge (positive or negative) and size…

  17. Sterically and electrosterically stabilized emulsion polymerization. Kinetics and preparation.

    PubMed

    Capek, Ignác

    2002-10-21

    The principal subject discussed in the current paper is the radical polymerization in the aqueous emulsions of unsaturated monomers (styrene, alkyl (meth)acrylates, etc.) stabilized by non-ionic and ionic/non-ionic emulsifiers. The sterically and electrosterically stabilized emulsion polymerization is a classical method which allows to prepare polymer lattices with large particles and a narrow particle size distribution. In spite of the similarities between electrostatically and sterically stabilized emulsion polymerizations, there are large differences in the polymerization rate, particle size and nucleation mode due to varying solubility of emulsifiers in oil and water phases, micelle sizes and thickness of the interfacial layer at the particle surface. The well-known Smith-Ewart theory mostly applicable for ionic emulsifier, predicts that the number of particles nucleated is proportional to the concentration of emulsifier up to 0.6. The thin interfacial layer at the particle surface, the large surface area of relatively small polymer particles and high stability of small particles lead to rapid polymerization. In the sterically stabilized emulsion polymerization the reaction order is significantly above 0.6. This was ascribed to limited flocculation of polymer particles at low concentration of emulsifier, due to preferential location of emulsifier in the monomer phase. Polymerization in the large particles deviates from the zero-one approach but the pseudo-bulk kinetics can be operative. The thick interfacial layer can act as a barrier for entering radicals due to which the radical entry efficiency and also the rate of polymerization are depressed. The high oil-solubility of non-ionic emulsifier decreases the initial micellar amount of emulsifier available for particle nucleation, which induces non-stationary state polymerization. The continuous release of emulsifier from the monomer phase and dismantling of the non-micellar aggregates maintained a high level of

  18. Charge transport in confined ionic liquids

    NASA Astrophysics Data System (ADS)

    Sangoro, Joshua; Iacob, Ciprian; Kipnusu, Wycliffe; Kremer, Friedrich

    2011-03-01

    Charge transport and glassy dynamics in neat and polymerized ionic liquids confined in nanoporous silica are investigated in a wide frequency and temperature ranges by a combination of Broadband Dielectric Spectroscopy and Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR). By applying the Einstein-Smoluchowski relations to the dielectric spectra, diffusion coefficients are obtained in quantitative agreement with independent PFG NMR. The impact of geometrical confinement as well as the pore wall-ionic liquid interactions on the overall ionic mobility is explored for diverse categories of ionic liquids. The results are discussed within the framework of dynamic glass transition assisted charge transport in ionic liquids. Financial support from the Deutsche Forschungsgemeinschaft under the DFG SPP 1191 Priority Program on Ionic Liquids is gratefully acknowledged.

  19. Polymerization catalyst

    SciTech Connect

    Graves, V.

    1987-05-12

    A process is described for polymerizing at least one alpha olefin under conditions characteristic of Ziegler polymerization wherein the polymerization is conducted in the presence of a catalyst system which comprises: a supported catalyst prepared under anhydrous conditions by the sequential steps of: preparing a slurry of inert particulate support material; adding to the slurry a solution of an organomagnesium compound; adding to the slurry and reacting a solution of a zirconium halide compound, hafnium compound or mixtures thereof; adding to the slurry and reacting a halogenator; adding to the slurry and reacting a tetravalent titanium halide compound; and recovering solid catalyst.

  20. Polymerization catalyst

    SciTech Connect

    Graves, V.

    1986-10-21

    A process is described for polymerizing at least one alpha-olefin under conditions characteristic of Ziegler polymerization wherein the polymerization is conducted in the presence of a catalyst comprising: a supported catalyst prepared under anhydrous conditions by the steps of: (1) sequentially; (a) preparing a slurry of inert particulate support material; (b) adding to the slurry a solution of an organomagnesium compound; (c) adding to the slurry and reacting a solution of zirconium compound; and (2) thereafter; (d) adding to the slurry and reacting a halogenator; (e) adding to the slurry and reacting a tetravalent titanium compound; (f) recovering solid catalyst; and an organoaluminum compound.

  1. Polymeric nanoparticles

    PubMed Central

    Bolhassani, Azam; Javanzad, Shabnam; Saleh, Tayebeh; Hashemi, Mehrdad; Aghasadeghi, Mohammad Reza; Sadat, Seyed Mehdi

    2014-01-01

    Nanocarriers with various compositions and biological properties have been extensively applied for in vitro/in vivo drug and gene delivery. The family of nanocarriers includes polymeric nanoparticles, lipid-based carriers (liposomes/micelles), dendrimers, carbon nanotubes, and gold nanoparticles (nanoshells/nanocages). Among different delivery systems, polymeric carriers have several properties such as: easy to synthesize, inexpensive, biocompatible, biodegradable, non-immunogenic, non-toxic, and water soluble. In addition, cationic polymers seem to produce more stable complexes led to a more protection during cellular trafficking than cationic lipids. Nanoparticles often show significant adjuvant effects in vaccine delivery since they may be easily taken up by antigen presenting cells (APCs). Natural polymers such as polysaccharides and synthetic polymers have demonstrated great potential to form vaccine nanoparticles. The development of new adjuvants or delivery systems for DNA and protein immunization is an expanding research field. This review describes polymeric carriers especially PLGA, chitosan, and PEI as vaccine delivery systems. PMID:24128651

  2. Continuous elimination of Pb2+, Cu2+, Zn2+, H+ and NH4 + from acidic waters by ionic exchange on natural zeolites.

    PubMed

    Calvo, Benjamin; Canoira, Laureano; Morante, Fernando; Martínez-Bedia, José M; Vinagre, Carlos; García-González, Jerónimo-Emilio; Elsen, Jan; Alcantara, Ramon

    2009-07-30

    A study of breakthrough curves for cations usually found in acid mine drainage (Pb(2+), Cu(2+), Zn(2+) and H(+)) and municipal wastewater (NH(4)(+)) have been conducted on some natural zeolitic tuffs. The zeolitic tuffs used in this study are: three zeolitic tuffs from Cayo Formation, Guayaquil (Ecuador), characterized by X-ray diffraction as clinoptilolite (sample CLI-1) and heulandite (samples HEU-1 and HEU-2)-rich tuffs, and two zeolitic tuffs from Parnaiba Basin, Belem do Pará (Brazil), characterized as stilbite-rich tuffs (samples STI-1 and STI-2). The clinoptilolite sample CLI-1 shows an exceedingly good exchange capacities for Pb(2+) and NH(4)(+) as received, and also a very high exchange capacity for Cu(2+) and Zn(2+) when conditioned with 2M sodium chloride, with much higher values than those reported in the literature for other clinioptilolite ores. A general order of effective cation exchange capacity could be inferred from breakthrough curves on these zeolitic tuffs: CLI-1 > HEU-2 > HEU-1 > STI-2. Since it is true for most of the cations studied. PMID:19124201

  3. High temperature structural, polymeric foams from high internal emulsion polymerization

    SciTech Connect

    Hoisington, M.A.; Duke, J.R.; Apen, P.G.

    1996-02-01

    In 1982, a high internal phase emulsion (HIPE) polymerization process to manufacture microcellular, polymeric foam systems was patented by Unilever. This patent discloses a polymerization process that occurs in a water-in-oil emulsion in which the water represents at least 76% of the emulsion by volume. The oil phase consists of vinyl monomers such as styrene and acrylates that are crosslinked by divinyl monomers during polymerization. After polymerization and drying to remove the water phase, the result is a crosslinked polymer foam with an open cell microstructure that is homogeneous throughout in terms of morphology, density, and mechanical properties. Since 1982, numerous patents have examined various HIPE polymerized foam processing techniques and applications that include absorbents for body fluids, cleaning materials, and ion exchange systems. All the published HIPE polymerized foams have concentrated on materials for low temperature applications. Copolymerization of styrene with maleic anhydride and N-substituted maleimides to produce heat resistant thermoplastics has been studied extensively. These investigations have shown that styrene will free radically copolymerize with N-substituted maleimides to create an alternating thermoplastic copolymer with a Tg of approximately 200{degrees}C. However, there are many difficulties in attempting the maleimide styrene copolymerization in a HIPE such as lower polymerization temperatures, maleimide solubility difficulties in both styrene and water, and difficulty obtaining a stable HIPE with a styrene/maleimide oil phase. This work describes the preparation of copolymer foams from N-ethylmaleimide and Bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane with styrene based monomers and crosslinking agents.

  4. Ionic liquid polyoxometalates as light emitting materials

    SciTech Connect

    Ortiz-acosta, Denisse; Del Sesto, Rico E; Scott, Brian; Bennett, Bryan L; Purdy, Geraldine M; Muenchausen, Ross E; Mc Kigney, Edward; Gilbertson, Robert

    2008-01-01

    The low melting point, negligible vapor pressure, good solubility, and thermal and chemical stability make ionic liquids useful materials for a wide variety of applications. Polyoxometalates are early transition metal oxygen clusters that can be synthesized in many different sizes and with a variety of heterometals. The most attractive feature of POMs is that their physical properties, in particular electrical, magnetic, and optical properties, can be easily modified following known procedures. It has been shown that POMs can exhibit cooperative properties, as superconductivity and energy transfer. POM ionic liquids can be obtained by selecting the appropliate cation. Different alkyl ammonium and alkyl phosphonium salts are being used to produce new POM ionic liquids together with organic or inorganic luminescent centers to design light emitting materials. Ammonium and phosphonium cations with activated, polymerizable groups are being used to further polymerize the ionic liquid into transparent, solid materials with high metal density.

  5. Chain Reaction Polymerization.

    ERIC Educational Resources Information Center

    McGrath, James E.

    1981-01-01

    The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

  6. Host-guest chemistry of a water-soluble pillar[5]arene: evidence for an ionic-exchange recognition process and different complexation modes.

    PubMed

    Gómez, Borja; Francisco, Vitor; Fernández-Nieto, Fernando; Garcia-Rio, Luis; Martín-Pastor, M; Paleo, M Rita; Sardina, F Javier

    2014-09-15

    The complexation of an anionic guest by a cationic water-soluble pillararene is reported. Isothermal titration calorimetry (ITC), (1)H NMR, (1)H and (19)F DOSY, and STD NMR experiments were performed to characterize the complex formed under aqueous neutral conditions. The results of ITC and (1)H NMR analyses showed the inclusion of the guest inside the cavity of the pillar[5]arene, with the binding constant and thermodynamic parameters influenced by the counter ion of the macrocycle. NMR diffusion experiments showed that although a fraction of the counter ions are expelled from the host cavity by exchange with the guest, a complex with both counter ions and the guest inside the pillararene is formed. The results also showed that at higher concentrations of guest in solution, in addition to the inclusion of one guest molecule in the cavity, the pillararene can also form an external complex with a second guest molecule. PMID:25110897

  7. Rational design on controlled release ion-exchange polymeric microspheres and polymer-lipid hybrid nanoparticles for the delivery of water-soluble drugs through a multidisciplinary approach

    NASA Astrophysics Data System (ADS)

    Li, Yongqiang

    Sulfopropyl dextran sulfate (SP-DS) microspheres and polymer-lipid hybrid nanoparticles (PLN) for the delivery of water-soluble anticancer drugs and P-glycoprotein inhibitors were developed by our group recently and demonstrated effectiveness in local chemotherapy. To optimize the delivery performance of these particulate systems, particularly PLN, an integrated multidisciplinary approach was developed, based on an in-depth understanding of drug-excipient interactions, internal structure, drug loading and release mechanisms, and application of advanced modeling/optimization techniques. An artificial neural networks (ANN) simulator capable of formulation optimization and drug release prediction was developed. In vitro drug release kinetics of SP-DS microspheres, with various drug loading and in different release media, were predicted by ANN. The effects of independent variables on drug release were evaluated. Good modeling performance suggested that ANN is a useful tool to predict drug release from ion-exchange microspheres. To further improve the performance of PLN, drug-polymer-lipid interactions were characterized theoretically and experimentally using verapamil hydrochloride (VRP) as a model drug and dextran sulfate sodium (DS) as a counter-ion polymer. VRP-DS complexation followed a stoichiometric rule and solid-state transformation of VRP were observed. Dodecanoic acid (DA) was identified as the lead lipid carrier material. Based upon the optimized drug-polymer-lipid interactions, PLN with high drug loading capacity (36%, w/w) and sustained release without initial burst release were achieved. VRP remained amorphous and was molecularly dispersed within PLN. H-bonding contributed to the miscibility between the VRP-DS complex and DA. Drug release from PLN was mainly controlled by diffusion and ion-exchange processes. Drug loading capacity and particle size of PLN depend on the formulation factors of the weight ratio of drug to lipid and concentrations of

  8. Application of enzymes, sodium tripolyphosphate and cation exchange resin for the release of extracellular polymeric substances from sewage sludge. Characterization of the extracted polysaccharides/glycoconjugates by a panel of lectins.

    PubMed

    Wawrzynczyk, J; Szewczyk, E; Norrlöw, O; Dey, E Szwajcer

    2007-06-30

    The study describes extraction of extracellular polymeric substances (EPS) from sewage sludge by applying enzymes and enzymes combined with sodium tripolyphosphate (STPP). Additionally, a systematic study of two non-enzymatic extraction agents is described. The assessment of the released products is made by colorimetrical methods and polysaccharides/glycoconjugates identification by the interaction with four immobilized lectins. Bio-sludge from Helsingborg (Sweden) and Damhusåen (Denmark) were used as two case studies for testing enzymatic extractability and thereby to make useful prediction of sludge bio-digestibility. From Helsingborg sludge the enzymes extracted about 40% more of EPS than from Damhusåen. The polysaccharides/glycoconjugates in both sludges maintained the same level, and showed substantial different interaction motifs with lectins panel. Damhusåen enzymatic extracted EPS had an enhanced amount of suspended material that was post-hydrolysed by the use of polygalacturonase and lysozyme resulting in pectin like polymers and petiptidoglycans. Petiptidoglycan is a marker from bacterial cell debris. STPP and cation exchange resin (CER) released different quantities of EPS. The CER released polysaccharides/glycoconjugates had higher molecular weight and stronger affinity towards Concanavalin A than the one released by the action of STPP. Independent of the extraction conditions, STPP released elevated amounts of polyvalent cations and humic substances in contrast to the very low amounts of released by CER. PMID:17543410

  9. Polymer electrolyte membranes with exceptional conductivity anisotropy via holographic polymerization

    NASA Astrophysics Data System (ADS)

    Smith, Derrick M.; Cheng, Shan; Wang, Wenda; Bunning, Timothy J.; Li, Christopher Y.

    2014-12-01

    Polymer electrolyte membranes using an ionic liquid as electrolyte with an ionic conductivity anisotropy of ∼5000 have been fabricated using a holographic polymerization nanomanufacturing technique. The resultant structure is referred to as holographic polymer electrolyte membranes (hPEMs), which are comprised of alternating nanolayers of a room temperature ionic liquid and crosslinked polymer resin, confirmed under TEM imaging. These hPEMs also show no reduction in room temperature conductivity with respect to the loaded ionic liquid when characterized in the plane of ionic liquid nanolayers. At elevated temperatures with the optimal electrolyte volume loading, calculation shows that the free ion concentration is higher than the pure ionic liquid, suggesting that the photopolymer dual-functionalizes as a loadbearing scaffold and an ion-complexing agent, allowing for more ions to participate in charge transfer. These hPEMs provide a promising solution to decoupling mechanical enhancement and ion transport in polymer electrolyte membranes.

  10. Superbase-derived protic ionic liquids

    DOEpatents

    Dai, Sheng; Luo, Huimin; Baker, Gary A.

    2013-09-03

    Protic ionic liquids having a composition of formula (A.sup.-)(BH.sup.+) wherein A.sup.- is a conjugate base of an acid HA, and BH.sup.+ is a conjugate acid of a superbase B. In particular embodiments, BH.sup.+ is selected from phosphazenium species and guanidinium species encompassed, respectively, by the general formulas: ##STR00001## The invention is also directed to films and membranes containing these protic ionic liquids, with particular application as proton exchange membranes for fuel cells.

  11. Solid State Ionics 4. Proceedings of Materials Research Society Symposium, volume 369

    NASA Astrophysics Data System (ADS)

    Nazri, Gholam-Abbas; Tarascon, Jean-Marie; Schreiber, Martha

    The proceeding of the 4th Solid State Ionics symposium is presented. This first part of the proceeding deals with the chemistry and physics of insertion materials, mostly from the viewpoint of applications as cathode materials for rechargeable lithium batteries, Ni/Cd, and Ni/metal hydride systems. Crystal chemistry and electrochemistry properties of potential oxides cathodes are discussed. The second part of the proceeding deals with sol-gel process for preparation of cathode materials for lithium batteries and other applications. Novel synthetic methods of preparation of high surface area transition metal oxides are presented. The third part deals with theory of ion conduction in solids, as well as mechanisms of ion conduction in glassy and polymeric materials. Part four deals with defect chemistry in solid electrolytes and the role of defect on ionic conductivity of ceramic electrolytes. The fifth part of the proceedings deals with polymer electrolytes and electrodes. Synthesis, characterization and performance of various polymer electrolytes and electrodes are discussed. The last part of the proceedings deals with characteristics and materials aspect of ionic devices. this includes advance solid state batteries, sensors, electrochromic devices, fuel cells, and the dynamic of ion exchange in high T(c) superconductors.

  12. 3D Printing of Micropatterned Anion Exchange Membranes.

    PubMed

    Seo, Jiho; Kushner, Douglas I; Hickner, Michael A

    2016-07-01

    Micropatterned anion exchange membranes (AEMs) have been 3D printed via a photoinitiated free radical polymerization and quaternization process. The photocurable formulation, consisting of diurethane dimethacrylate (DUDA), poly(ethylene glycol) diacrylate (PEGDA), dipentaerythritol penta-/hexa- acrylate, and 4-vinylbenzyl chloride (VBC), was directly cured into patterned films using a custom 3D photolithographic printing process similar to stereolithography. Measurements of water uptake, permselectivity, and ionic resistance were conducted on the quaternized poly(DUDA-co-PEGDA-co-VBC) sample series to determine their suitability as ion exchange membranes. The water uptake of the polymers increased as the ion exchange capacity (IEC) increased due to greater quaternized VBC content. Samples with IEC values between 0.98 to 1.63 mequiv/g were synthesized by varying the VBC content from 15 to 25 wt %. The water uptake was sensitive to the PEGDA content in the network resulting in water uptake values ranging from 85 to 410 wt % by varying the PEGDA fractions from 0 to 60 wt %. The permselectivity of the AEM samples decreased from 0.91 (168 wt %, 1.63 mequiv/g) to 0.85 (410 wt %, 1.63 mequiv/g) with increasing water uptake and to 0.88 (162 wt %, 0.98 mequiv/g) with decreasing IEC. Permselectivity results were relatively consistent with the general understanding of the correlation between permselectivity, water uptake, and ion content of the membrane. Lastly, it was revealed that the ionic resistance of patterned membranes was lower than that of flat membranes with the same material volume or equivalent thickness. A parallel resistance model was used to explain the influence of patterning on the overall measured ionic resistance. This model may provide a way to maximize ion exchange membrane performance by optimizing surface patterns without chemical modification to the membrane. PMID:27218137

  13. A morpholinium ionic liquid for cellulose dissolution.

    PubMed

    Raut, Dilip G; Sundman, Ola; Su, Weiqing; Virtanen, Pasi; Sugano, Yasuhito; Kordas, Krisztian; Mikkola, Jyri-Pekka

    2015-10-01

    A series of substituted morpholinium ionic salts and allyl ammonium acetates were prepared. Amongst those, N-allyl-N-methylmorpholinium acetate ([AMMorp][OAc]) was found to dissolve cellulose readily without any pre-processing of native cellulose. At 120°C, [AMMorp][OAc] could dissolve 30 wt%, 28 wt% and 25 wt% of cellulose with degree of polymerization (DPn) - 789, 1644 and 2082 respectively, in 20 min. Importantly, SEC analysis indicated that no discernible changes occurred in terms of the degree of polymerization of the different celluloses after regeneration. Furthermore, when comparing the cellulose dissolution capability of these newly synthesized ionic liquids, it is evident that the combination of all three constituents - the morpholinium cation, the existence of an allyl group and choosing the acetate anion are essential for efficient cellulose dissolution. The structure and morphology of the regenerated cellulosic materials were characterized by SEM, XRD, TGA, CP/MAS (13)C NMR and FTIR, respectively. PMID:26076596

  14. Ionic Liquids Database- (ILThermo)

    National Institute of Standards and Technology Data Gateway

    SRD 147 Ionic Liquids Database- (ILThermo) (Web, free access)   IUPAC Ionic Liquids Database, ILThermo, is a free web research tool that allows users worldwide to access an up-to-date data collection from the publications on experimental investigations of thermodynamic, and transport properties of ionic liquids as well as binary and ternary mixtures containing ionic liquids.

  15. Simultaneous Enhancements of Conductivity and Stability for Anion Exchange Membranes (AEMs) through Precise Structure Design

    PubMed Central

    Ran, Jin; Wu, Liang; Wei, Bing; Chen, Yaoyao; Xu, Tongwen

    2014-01-01

    Polymeric materials as anion exchange membranes (AEMs) play an essential role in the field of energy and environment. The achievement of high performance AEMs by the precise manipulation of macromolecular architecture remains a daunting challenge. Herein, we firstly report a novel rod-coil graft copolymer AEM, possessing rigid hydrophobic main chains and soft hydrophilic graft chains. The low graft density, which can alleviate the adverse influences of ioinc graft chains on the main chains, was obtained by using the living polymerization technique. Consequently, the grafted ionic groups which result in the degradation of polymer backbone was decreased to a small degree. Moreover, the relatively long graft chains induced the nanophase separation between the hydrophobic polymer chains and hydrophilic graft chains, which creates a convinient pathway for high hydroxide ion mobility. Such an accurate molecular design simultaneously improves the hydroxide ion conductivity and alkaline stability as well as dimensional stability. PMID:25255843

  16. A new method for separation and determination of Cr(III) and Cr(VI) in water samples by high-performance liquid chromatography based on anion exchange stationary phase of ionic liquid modified silica.

    PubMed

    Sadeghi, Susan; Moghaddam, Ali Zeraatkar

    2015-12-01

    In this work, N-methylimidazolium-chloride ionic liquid functionalized silica was prepared and used as an anion-exchange stationary phase for separation of chromium species by high-performance liquid chromatography (HPLC) with UV detection at 200 nm. The Cr(VI) as HCr2O7(-) and chelated Cr(III) with potassium hydrogen phthalate (PHP) as Cr(PHP)2 (-) was retained on the prepared column and separated using a mobile phase composed of 5% methanol in 25 mM phosphate buffer at pH 6.5. Several variables affecting the chelation/separation steps were modeled by response surface methodology (RSM) using Box-Behnken (BBD) design. The significance of the independent variables and their interactions were tested by the analysis of variances (ANOVA) with 95% confidence limit. Under the optimized conditions, the Cr(III) and Cr(VI) anionic species were well separated with a single peak for each Cr species at retention times of 2.3 and 4.3 min, respectively. The relationship between the peak area and concentration was linear in the range of 0.025-30 for Cr(III) and 0.5-20 mg L(-1) for Cr(VI) with detection limits of 0.010 and 0.210 mg L(-1) for Cr(III) and Cr(VI), respectively. The proposed method was validated by simultaneous separation and determination of the Cr species in tap and underground water samples without impose to any pretreatment. PMID:26526699

  17. [Advances of poly (ionic liquid) materials in separation science].

    PubMed

    Liu, Cuicui; Guo, Ting; Su, Rina; Gu, Yuchen; Deng, Qiliang

    2015-11-01

    Ionic liquids, as novel ionization reagents, possess beneficial characteristics including good solubility, conductivity, thermal stability, biocompatibility, low volatility and non-flammability. Ionic liquids are attracting a mass of attention of analytical chemists. Poly (ionic liquid) materials have common performances of ionic liquids and polymers, and have been successfully applied in separation science area. In this paper, we discuss the interaction mechanisms between the poly(ionic liquid) materials and analytes including hydrophobic/hydrophilic interactions, hydrogen bond, ion exchange, π-π stacking and electrostatic interactions, and summarize the application advances of the poly(ionic liquid) materials in solid phase extraction, chromatographic separation and capillary electrophoresis. At last, we describe the future prospect of poly(ionic liquid) materials. PMID:26939357

  18. Acidic Ionic Liquids.

    PubMed

    Amarasekara, Ananda S

    2016-05-25

    Ionic liquid with acidic properties is an important branch in the wide ionic liquid field and the aim of this article is to cover all aspects of these acidic ionic liquids, especially focusing on the developments in the last four years. The structural diversity and synthesis of acidic ionic liquids are discussed in the introduction sections of this review. In addition, an unambiguous classification system for various types of acidic ionic liquids is presented in the introduction. The physical properties including acidity, thermo-physical properties, ionic conductivity, spectroscopy, and computational studies on acidic ionic liquids are covered in the next sections. The final section provides a comprehensive review on applications of acidic ionic liquids in a wide array of fields including catalysis, CO2 fixation, ionogel, electrolyte, fuel-cell, membrane, biomass processing, biodiesel synthesis, desulfurization of gasoline/diesel, metal processing, and metal electrodeposition. PMID:27175515

  19. Polymerization of perfluorobutadiene

    NASA Technical Reports Server (NTRS)

    Newman, J.; Toy, M. S.

    1970-01-01

    Diisopropyl peroxydicarbonate dissolved in liquid perfluorobutadiene is conducted in a sealed vessel at the autogenous pressure of polymerization. Reaction temperature, ratio of catalyst to monomer, and amount of agitation determine degree of polymerization and product yield.

  20. Frontal polymerizations carried out in Deep-Eutectic mixtures providing both the monomers and the polymerization medium.

    PubMed

    Mota-Morales, Josué D; Gutiérrez, María C; Sanchez, Isaac C; Luna-Bárcenas, Gabriel; del Monte, Francisco

    2011-05-14

    Deep Eutectic Solvents (DESs) based upon mixtures of Acrylic Acid (AA) or Methacrylic Acid (MAA) and Choline Chloride (CCl) demonstrated superior performance than regular organic solvents and even ionic liquids for frontal polymerizations (FPs). Full recovering of CCl after FP provided an interesting green character to the process. PMID:21455538

  1. Adsorption to goethite of extracellular polymeric substances from Bacillus subtilis

    NASA Astrophysics Data System (ADS)

    Omoike, Anselm; Chorover, Jon

    2006-02-01

    Extracellular polymeric substances (EPS) are heterogeneous biopolymers produced by Gram-negative and Gram-positive bacterial cells. Adsorption of EPS to minerals can alter the substrata physico-chemistry and influence initial bacterial adhesion processes via conditioning film formation, but the effects of solution chemistry on uptake of EPS remain poorly understood. In this study, the adsorption to goethite (α-FeOOH) of EPS isolated from the early stationary growth-phase culture of Bacillus subtilis was investigated as a function of pH and ionic strength ( I) in NaCl background electrolyte using batch studies coupled with Fourier transform infrared spectroscopy and size-exclusion high-performance liquid chromatography. Proteins, particularly those of higher molar mass, and phosphorylated macromolecules were adsorbed preferentially. Increasing solution I (1-100 mM NaCl) or pH (3.0-9.0) resulted in a decrease in the mass of EPS adsorbed. Batch studies and diffuse reflectance infrared Fourier transform spectra are consistent with ligand exchange of EPS phosphate groups for surface hydroxyls at Fe metal centers. The data indicate that both electrostatic and chemical bonding interactions contribute to selective fractionation of the EPS solution. Proteins and phosphate groups in phosphodiester bridges of nucleic acids likely play an important role in conditioning film formation at Fe oxide surfaces.

  2. Polymerization Reactor Engineering.

    ERIC Educational Resources Information Center

    Skaates, J. Michael

    1987-01-01

    Describes a polymerization reactor engineering course offered at Michigan Technological University which focuses on the design and operation of industrial polymerization reactors to achieve a desired degree of polymerization and molecular weight distribution. Provides a list of the course topics and assigned readings. (TW)

  3. Thermally Cross-Linked Anion Exchange Membranes from Solvent Processable Isoprene Containing Ionomers

    SciTech Connect

    Tsai, Tsung-Han; Ertem, S. Piril; Maes, Ashley M.; Seifert, Soenke; Herring, Andrew M; Coughlin, E. Bryan

    2015-01-28

    Random copolymers of isoprene and 4-vinylbenzyl chloride (VBCl) with varying compositions were synthesized via nitroxide-mediated polymerization. Subsequent quaternization afforded solvent processable and cross-linkable ionomers with a wide range of ion exchange capacities (IECs). Solution cast membranes were thermally cross-linked to form anion exchange membranes. Cross-linking was achieved by taking advantage of the unsaturations on the polyisoprene backbone, without added cross-linkers. A strong correlation was found between water uptake and ion conductivity of the membranes: conductivities of the membranes with IECs beyond a critical value were found to be constant related to their high water absorption. Environmentally controlled small-angle X-ray scattering experiments revealed a correlation between the average distance between ionic clusters and the ion conductivity, indicating that a well-connected network of ion clusters is necessary for efficient ion conduction and high ion conductivity.

  4. Dipyridyl-immobilized ionic liquid type hybrid silica monolith for hydrophilic interaction electrochromatography.

    PubMed

    Wang, Xiao; Zheng, Na; Huang, Yifang; Wang, Jiabin; Lin, Xucong; Xie, Zenghong

    2013-11-01

    A pyridinium-based immobilized ionic liquid type multifunctional hybrid silica monolith was prepared by the in situ polymerization of 3-chloropropyl-silica matrix and 4,4'-dipyridyl for hydrophilic interaction CEC. The obtained hybrid monolith possessed of high stable skeletal microstructures with obviously hydrophilic retention mechanism under ACN content >50% in the mobile phase. Strong and stable anodic EOF could be observed under a broad pH range from pH 3.0 to 9.0. Due to the immobilized dipyridyl groups bonded to the silica matrix surface, the resulting hydrophilic hybrid monolith possessed multiple separation interactions including hydrogen bond, π-π, and anion exchange. Excellent separations of various polar analytes including electroneutral phenols, charged acid nucleotides, and basic analytes were successfully achieved. The highest column efficiencies up to 120,000, 164,000, and 106,000 plates/m were obtained for nucleotides, nucleic acid bases, and nucleosides and nicotines, respectively. These results demonstrated that the dipyridyl-immobilized ionic liquid functionalized hybrid monolith possessed highly mechanical stability and good chromatographic performance for hydrophilic interaction electrochromatography. PMID:23925897

  5. Interpenetrating polymer network ion exchange membranes and method for preparing same

    DOEpatents

    Alexandratos, Spiro D.; Danesi, Pier R.; Horwitz, E. Philip

    1989-01-01

    Interpenetrating polymer network ion exchange membranes include a microporous polymeric support film interpenetrated by an ion exchange polymer and are produced by absorbing and polymerizing monomers within the support film. The ion exchange polymer provides ion exchange ligands at the surface of and throughout the support film which have sufficient ligand mobility to extract and transport ions across the membrane.

  6. Ionic liquid based multifunctional double network gel

    NASA Astrophysics Data System (ADS)

    Ahmed, Kumkum; Higashihara, Tomoya; Arafune, Hiroyuki; Kamijo, Toshio; Morinaga, Takashi; Sato, Takaya; Furukawa, Hidemitsu

    2015-04-01

    Gels are a promising class of soft and wet materials with diverse application in tissue engineering and bio-medical purpose. In order to accelerate the development of gels, it is required to synthesize multi-functional gels of high mechanical strength, ultra low surface friction and suitable elastic modulus with a variety of methods and new materials. Among many types of gel ionic gel made from ionic liquids (ILs) could be used for diverse applications in electrochemical devices and in the field of tribology. IL, a promising materials for lubrication, is a salt with a melting point lower than 100 °C. As a lubricant, ILs are characterized by an extremely low vapor pressure, high thermal stability and high ion conductivity. In this work a novel approach of making double network DN ionic gel using IL has been made utilizing photo polymerization process. A hydrophobic monomer Methyl methacrylate (MMA) has been used as a first network and a hydrophobic IL monomer, N,N-diethyl-N-(2-mthacryloylethyl)-N-methylammonium bistrifluoromethylsulfonyl)imide (DEMM-TFSI) has been used as a second network using photo initiator benzophenon and crosslinker triethylene glycol dimethacrylate (TEGDMA). The resulting DN ionic gel shows transparency, flexibility, high thermal stability, good mechanical toughness and low friction coefficient value which can be a potential candidate as a gel slider in different mechanical devices and can open a new area in the field of gel tribology.

  7. Application of Ionic Liquids in Pot-in-Pot Reactions.

    PubMed

    Çınar, Simge; Schulz, Michael D; Oyola-Reynoso, Stephanie; Bwambok, David K; Gathiaka, Symon M; Thuo, Martin

    2016-01-01

    Pot-in-pot reactions are designed such that two reaction media (solvents, catalysts and reagents) are isolated from each other by a polymeric membrane similar to matryoshka dolls (Russian nesting dolls). The first reaction is allowed to progress to completion before triggering the second reaction in which all necessary solvents, reactants, or catalysts are placed except for the starting reagent for the target reaction. With the appropriate trigger, in most cases unidirectional flux, the product of the first reaction is introduced to the second medium allowing a second transformation in the same glass reaction pot-albeit separated by a polymeric membrane. The basis of these reaction systems is the controlled selective flux of one reagent over the other components of the first reaction while maintaining steady-state catalyst concentration in the first "pot". The use of ionic liquids as tools to control chemical potential across the polymeric membranes making the first pot is discussed based on standard diffusion models-Fickian and Payne's models. Besides chemical potential, use of ionic liquids as delivery agent for a small amount of a solvent that slightly swells the polymeric membrane, hence increasing flux, is highlighted. This review highlights the critical role ionic liquids play in site-isolation of multiple catalyzed reactions in a standard pot-in-pot reaction. PMID:26927045

  8. Synthesis, characterization and applications of ionic supramolecular assemblies

    NASA Astrophysics Data System (ADS)

    Lin, Xinrong

    Supramolecular ionic assemblies not only provide alternatives to conventional polymers, but also introduce unique and interesting functions for the design of "smart" polymeric assemblies for use in a number of fields due to their programmable and reversible properties. Research in the area has led to an understanding of the connection between molecular contributions and macroscopic properties, as well as a range of applications from material processing/manufacuturing to energy transfer and storage. To this end, we have developed a library of charged building blocks based on ionic liquids to create functional supramolecular ionic assemblies. The polymeric ionic assemblies prepared from a di-phosphonium and poly (acrylic acid) were first studied and found to have the potential to be utilized as "smart" materials due to their ability to reversibly respond to stimuli such as temperature and pressure. With the interest of elucidating the molecular contributions to the bulk macroscopic material properties, six supramolecular assemblies were sequentially characterized in terms of thermal, rheological and X-ray studies. The effect of side alkyl chain was found to dramatically change the material properties. A second type of supramolecular assembly was investigated based on a poly-phosphonium ionic liquid, which was complexed with a number of carboxylic acids. The material properties were easily manipulated from a sticky fiber to a brittle solid by changing the composition of the carboxylic acid. A crosslinked supramolecular assembly combining ionic interactions and weak covalent bonds, specifically disulfide bonds, was next designed and characterized. The network properties could be switched between "on and off" using mild conditions. The polymeric ionic networks and their building block ionic liquids are also of interest as safe electrolytes in energy storage devices due to their non-flammability, non-volatility, etc. We have identified one ionic liquid with superior

  9. Highly conductive side chain block copolymer anion exchange membranes.

    PubMed

    Wang, Lizhu; Hickner, Michael A

    2016-06-28

    Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days. PMID:27216558

  10. Polymeric Carbon Dioxide

    SciTech Connect

    Yoo, C-S.

    1999-11-02

    Synthesis of polymeric carbon dioxide has long been of interest to many chemists and materials scientists. Very recently we discovered the polymeric phase of carbon dioxide (called CO{sub 2}-V) at high pressures and temperatures. Our optical and x-ray results indicate that CO{sub 2}-V is optically non-linear, generating the second harmonic of Nd: YLF laser at 527 nm and is also likely superhard similar to cubic-boron nitride or diamond. CO{sub 2}-V is made of CO{sub 4} tetrahedra, analogous to SiO{sub 2} polymorphs, and is quenchable at ambient temperature at pressures above 1 GPa. In this paper, we describe the pressure-induced polymerization of carbon dioxide together with the stability, structure, and mechanical and optical properties of polymeric CO{sub 2}-V. We also present some implications of polymeric CO{sub 2} for high-pressure chemistry and new materials synthesis.

  11. Ion-exchange hollow fibers

    NASA Technical Reports Server (NTRS)

    Rembaum, A.; Yen, S. P. S.; Klein, E. (Inventor)

    1976-01-01

    An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, crosslinked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

  12. Ion-exchange hollow fibers

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Klein, Elias (Inventor)

    1980-01-01

    An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, cross-linked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

  13. Ion-exchange hollow fibers

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Klein, Elias (Inventor)

    1977-01-01

    An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, cross-linked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

  14. Polymerization catalyst system

    SciTech Connect

    Graves, V.

    1986-03-25

    This patent describes a catalyst system for polymerizing at least one alpha-olefin under conditions characteristic of Ziegler polymerization. This system consists of: 1. a supported polymerization catalyst or mixture of polymerization catalysts prepared under anhydrous conditions by the sequential steps of: (a) preparing a slurry of inert particulate porous support material; (b) adding to the slurry a solution of an organomagnesium compound; (c) adding to the slurry and reacting a solution of a zirconium halide compound, hafnium compound or mixtures thereof; (d) adding to the slurry and reacting a halogenator; (e) adding to the slurry and reacting a tetravalent titanium halide compound; and (f) recovering solid catalyst component; 2. an organoaluminum compound; and 3. a promotor of chlorinated hydrocarbons having one to 20 carbon atoms.

  15. Morphology-induced low temperature conductivity in ionic liquids

    NASA Astrophysics Data System (ADS)

    Erbas, Aykut; Olvera de La Cruz, Monica; Olvera de la Cruz Team

    Ionic liquids exhibit nano-scale liquid crystalline order depending on the polymeric details of salt molecules. The resulting morphology and temperature behavior are key factors in determining the room temperature conductivity of ionic liquids. Here we discuss the phase behavior and related ionic conductivities of dry ionic liquids with volume fractions close to unity by using extensive molecular dynamics simulations. Temperature dependence, effective persistence length of tails, and excluded volume symmetry of amphiphilic ionic liquid molecules are investigated in large scale systems with short and long-range electrostatics. Our results suggest that by adjusting stiffness of the amphiphilic molecules and excluded volume interactions, lamellar or interconnected 3D phases can be obtained. Resulting phases have significant effects on the conductive properties. If there is no excluded volume asymmetry along the molecules, mostly lamellar phases with anisotropic conductivities emerge. If the excluded volume interactions become asymmetric, lamellar phases are replaced by interconnected phases consist of charged groups. Within temperature ranges that morphological phases are observed, conductivities exhibit low-temperature maxima in accord with experiments of ionic liquid-based liquid Center of Bio-inspried Energy Center (CBES).

  16. Applications of ionic liquids.

    PubMed

    Patel, Divia Dinesh; Lee, Jong-Min

    2012-06-01

    Ionic liquids have recently gained popularity in the scientific community owing to their special properties and characteristics. One of the reasons why ionic liquids have been termed "green solvents" is due to their negligible vapour pressure. Their use in electrochemical, biological and metal extraction applications is discussed. Wide research has been carried out for their use in batteries, solar panels, fuel cells, drug deliveries and biomass pretreatments. This work aims to consolidate the various findings from previous works in these areas. PMID:22711528

  17. Ionic homeostasis in brain conditioning

    PubMed Central

    Cuomo, Ornella; Vinciguerra, Antonio; Cerullo, Pierpaolo; Anzilotti, Serenella; Brancaccio, Paola; Bilo, Leonilda; Scorziello, Antonella; Molinaro, Pasquale; Di Renzo, Gianfranco; Pignataro, Giuseppe

    2015-01-01

    Most of the current focus on developing neuroprotective therapies is aimed at preventing neuronal death. However, these approaches have not been successful despite many years of clinical trials mainly because the numerous side effects observed in humans and absent in animals used at preclinical level. Recently, the research in this field aims to overcome this problem by developing strategies which induce, mimic, or boost endogenous protective responses and thus do not interfere with physiological neurotransmission. Preconditioning is a protective strategy in which a subliminal stimulus is applied before a subsequent harmful stimulus, thus inducing a state of tolerance in which the injury inflicted by the challenge is mitigated. Tolerance may be observed in ischemia, seizure, and infection. Since it requires protein synthesis, it confers delayed and temporary neuroprotection, taking hours to develop, with a pick at 1–3 days. A new promising approach for neuroprotection derives from post-conditioning, in which neuroprotection is achieved by a modified reperfusion subsequent to a prolonged ischemic episode. Many pathways have been proposed as plausible mechanisms to explain the neuroprotection offered by preconditioning and post-conditioning. Although the mechanisms through which these two endogenous protective strategies exert their effects are not yet fully understood, recent evidence highlights that the maintenance of ionic homeostasis plays a key role in propagating these neuroprotective phenomena. The present article will review the role of protein transporters and ionic channels involved in the control of ionic homeostasis in the neuroprotective effect of ischemic preconditioning and post-conditioning in adult brain, with particular regards to the Na+/Ca2+ exchangers (NCX), the plasma membrane Ca2+-ATPase (PMCA), the Na+/H+ exchange (NHE), the Na+/K+/2Cl− cotransport (NKCC) and the acid-sensing cation channels (ASIC). Ischemic stroke is the third leading

  18. Radical-Mediated Enzymatic Polymerizations

    PubMed Central

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  19. Radical-Mediated Enzymatic Polymerizations.

    PubMed

    Zavada, Scott R; Battsengel, Tsatsral; Scott, Timothy F

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes--catalytic proteins--owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol-ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  20. Advancing Polymer-Supported Ionogel Electrolytes Formed via Radical Polymerization

    NASA Astrophysics Data System (ADS)

    Visentin, Adam F.

    fabricated. In addition to developing an understanding of UV-polymerized systems, a rapid 10 to 20 second, microwave-assisted polymerization method was developed as a novel means to create ionogels. These ionogels exhibited comparable mechanical response and ionic conductivity levels to those gels fabricated by the UV method. Lastly, an EDLC prototype was fabricated using a UV-polymerized ionogel formed in situ between two high-surface area carbon electrodes. The device performance metrics were comparable to commercial EDLCs, and functioned for several thousand cycles with limited loss in capacitance.

  1. Failure Mechanisms of Hollow Fiber Supported Ionic Liquid Membranes.

    PubMed

    Zeh, Matthew; Wickramanayake, Shan; Hopkinson, David

    2016-01-01

    Hollow fiber supported ionic liquid membranes (SILMs) were tested using the bubble point method to investigate potential failure modes, including the maximum transmembrane pressure before loss of the ionic liquid from the support. Porous hollow fiber supports were fabricated with different pore morphologies using Matrimid(®) and Torlon(®) as the polymeric material and 1-hexyl-3-methylimidalzolium bis(trifluoromethylsulfonyl)imide ([C₆mim][Tf₂N]) as the ionic liquid (IL) component. Hollow fiber SILMs were tested for their maximum pressure before failure, with pressure applied either from the bore side or shell side. It was found that the membranes exhibited one or more of three different modes of failure when pressurized: liquid loss (occurring at the bubble point), rupture, and collapse. PMID:27023620

  2. Failure Mechanisms of Hollow Fiber Supported Ionic Liquid Membranes

    PubMed Central

    Zeh, Matthew; Wickramanayake, Shan; Hopkinson, David

    2016-01-01

    Hollow fiber supported ionic liquid membranes (SILMs) were tested using the bubble point method to investigate potential failure modes, including the maximum transmembrane pressure before loss of the ionic liquid from the support. Porous hollow fiber supports were fabricated with different pore morphologies using Matrimid® and Torlon® as the polymeric material and 1-hexyl-3-methylimidalzolium bis(trifluoromethylsulfonyl)imide ([C6mim][Tf2N]) as the ionic liquid (IL) component. Hollow fiber SILMs were tested for their maximum pressure before failure, with pressure applied either from the bore side or shell side. It was found that the membranes exhibited one or more of three different modes of failure when pressurized: liquid loss (occurring at the bubble point), rupture, and collapse. PMID:27023620

  3. Polymeric salt bridges for conducting electric current in microfluidic devices

    DOEpatents

    Shepodd, Timothy J.; Tichenor, Mark S.; Artau, Alexander

    2009-11-17

    A "cast-in-place" monolithic microporous polymer salt bridge for conducting electrical current in microfluidic devices, and methods for manufacture thereof is disclosed. Polymeric salt bridges are formed in place in capillaries or microchannels. Formulations are prepared with monomer, suitable cross-linkers, solvent, and a thermal or radiation responsive initiator. The formulation is placed in a desired location and then suitable radiation such as UV light is used to polymerize the salt bridge within a desired structural location. Embodiments are provided wherein the polymeric salt bridges have sufficient porosity to allow ionic migration without bulk flow of solvents therethrough. The salt bridges form barriers that seal against fluid pressures in excess of 5000 pounds per square inch. The salt bridges can be formulated for carriage of suitable amperage at a desired voltage, and thus microfluidic devices using such salt bridges can be specifically constructed to meet selected analytical requirements.

  4. Ionic liquids as novel solvents for ionic polymer transducers

    NASA Astrophysics Data System (ADS)

    Bennett, Matthew D.; Leo, Donald J.

    2004-07-01

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

  5. Grafting glycidyl methacrylate to Sepharose gel for fabricating high-capacity protein anion exchangers.

    PubMed

    Wang, Qianqian; Yu, Linling; Sun, Yan

    2016-04-22

    To develop ion exchangers of high protein adsorption capacity, we have herein introduced atom transfer radical polymerization (ATRP) method to graft glycidyl methacrylate (GMA) onto Sepharose FF gel. GMA-grafted Sepharose FF resins of four grafting densities and different grafting chain lengths were obtained by adjusting reaction conditions. The epoxy groups on the grafted chains were functionalized by modification with diethylamine (DEA), leading to the fabrication of Sepharose-based anion exchangers of 14 different grafting densities and/or grafting chain lengths. The resins were first characterized for the effects of grafting density, chain length and ionic strength on pore sizes by inverse size exclusion chromatography. Then, the resins were evaluated by adsorption equilibria of bovine serum albumin (BSA) as a function of ionic capacity (IC) (chain length) at individual grafting densities. It was observed that at each grafting density there was a specific IC value (chain length) that offered the maximum equilibrium capacity. Of the resins with maximum values at individual grafting densities, the resin of the second grafting density with an IC value of 330 mmol/L (denoted as FF-Br2-pG-D330) showed the highest capacity, 264 mg/mL, about two times higher than that of the traditional ungrafted resin Q Sepharose FF (137 mg/mL). This resin also showed the most favorable uptake kinetics among the resins of similar IC values but different grafting densities, or of the same grafting density but different IC values. Effects of ionic strength showed that the capacities of FF-Br2-pG-D330 were much higher than Q Sepharose FF at a wide range of NaCl concentrations (0-200 mmol/L), and the uptake rates of the two resins were similar in the ionic strength range. Therefore, the dynamic binding capacity values of BSA on FF-Br2-pG-D330 were much higher than Q Sepharose FF as demonstrated at different residence times and ionic strengths. Taken together, the research has proved the

  6. Polyanionic and polyzwitterionic azobenzene ionic liquid-functionalized silica materials and their chromatographic applications.

    PubMed

    Qiu, Hongdeng; Jiang, Shengxiang; Takafuji, Makoto; Ihara, Hirotaka

    2013-03-25

    New polyanionic and polyzwitterionic azobenzene ionic liquid-functionalized silica materials were designed based on the preparation of a new polymerizable azobenzene anionic monomer and either its cation-exchange with alkylimidazolium after grafting or the formation of an ionic liquid monomer pair before grafting onto silica. PMID:23417018

  7. Morphological and electromechanical characterization of ionic liquid/Nafion polymer composites

    NASA Astrophysics Data System (ADS)

    Bennett, Matthew; Leo, Donald

    2005-05-01

    Ionic liquids have shown promise as replacements for water in ionic polymer transducers. Ionic liquids are non-volatile and have a larger electrochemical stability window than water. Therefore, transducers employing ionic liquids can be operated for long periods of time in air and can be actuated with higher voltages. Furthermore, transducers based on ionic liquids do not exhibit the characteristic back relaxation that is common with water-swollen materials. However, the physics of transduction in the ionic liquid-swollen materials is not well understood. In this paper, the morphology of Nafion/ionic liquid composites is characterized using small-angle X-ray scattering (SAXS). The electromechanical transduction behavior of the composites is also investigated. For this testing, five different counterions and two ionic liquids are used. The results reveal that both the morphology and transduction performance of the composites is affected by the identity of the ionic liquid, the cation, and the swelling level of ionic liquid within the membrane. Specifically, speed of response is found to be lower for the membranes that were exchanged with the smaller lithium and potassium ions. The response speed is also found to increase with increased content of ionic liquid. Furthermore, for the two ionic liquids studied, the actuators swollen with the less viscous ionic liquid exhibited a slower response. The slower speed of response corresponds to less contrast between the ionically conductive phase and the inert phase of the polymer. This suggests that disruption of the clustered morphology in the ionic liquid-swollen membranes as compared to water-swollen membranes attenuates ion mobility within the polymer. This attenuation is attributed to swelling of the non-conductive phase by the ionic liquids.

  8. Investigation of Carbon-2 Substituted Imidazoles and Their Corresponding Ionic Liquids

    SciTech Connect

    Liao, Chen; Xiang, Zhu; Sun, Xiao-Guang; Dai, Sheng

    2011-01-01

    The functionality at the C-2 position of the imidazole ring plays a key role in defining the chemical properties of the imidazoles and their corresponding ionic liquids. Imidazoles 1 6 with different C-2 functionality were synthesized and their corresponding ionic liquids were systematically investigated. Based on their physical properties the six imidazoles can be divided into three groups. 1) The imidazoles 2 and 3 are capable of self-polymerization to form poly(ionic liquid)s, and they are characterized with a strong leaving group at the C-2 position. 2) The imidazoles 4 and 5 can form ionic liquids, but they are very sensitive to moisture. 3) The imidazoles 1 and 6 can form stable ionic liquids, and their stabilities were influenced by the electronic effects of the substituents at the C-2 position.

  9. Mesoporous and biocompatible surface active silica aerogel synthesis using choline formate ionic liquid.

    PubMed

    Meera, Kamal Mohamed Seeni; Sankar, Rajavelu Murali; Jaisankar, Sellamuthu N; Mandal, Asit Baran

    2011-09-01

    In this paper, we report the preparation and characterization of mesoporous and biocompatible transparent silica aerogel by the sol-gel polymerization of tetraethyl orthosilicate using ionic liquid. Choline cation based ionic liquid allows the silica framework to form in a non collapsing environment and controls the pore size of the gel. FT-IR spectra reveal the interaction of ionic liquid with surface -OH of the gel. DSC thermogram giving the evidence of confinement of ionic liquid within the silica matrix, which helps to avoid the shrinkage of the gel during the aging process. Nitrogen sorption measurements of gel prepared with ionic liquid exhibit a low surface area of 100.53 m2/g and high average pore size of 3.74 nm. MTT assay proves the biocompatibility and cell viability of the prepared gels. This new nanoporous silica material can be applied to immobilize biological molecules, which may retain their stability over a longer period. PMID:21565470

  10. NMR Characterization of Ionicity and Transport Properties for a Series of Diethylmethylamine Based Protic Ionic Liquids.

    PubMed

    Davidowski, Stephen K; Thompson, Forrest; Huang, Wei; Hasani, Mohammad; Amin, Samrat A; Angell, C Austen; Yarger, Jeffery L

    2016-05-12

    The ionicity and transport properties of a series of diethylmethylamine (DEMA) based protic ionic liquids (PILs) were characterized, principally utilizing nuclear magnetic resonance (NMR) spectroscopy. PILs were formed via the protonation of DEMA by an array of acids spanning a large range of acidities. A correlation between the (1)H chemical shift of the exchangeable proton and the acidity of the acid used for the synthesis of the PIL was observed. The gas phase proton affinity of the acid was found to be a better predictor of the extent of proton transfer than the commonly used aqueous ΔpKa. Pulsed field gradient (PFG) NMR was used to determine the diffusivity of the exchangeable proton in a subset of the PILs. The exchangeable proton diffuses with the acid if the PIL is synthesized with a weak acid, and with the base if a strong acid is used. The ionicity of the PILs was characterized using the Walden analysis and by comparing to the ideal Nernst-Einstein conductivity predicted from the (1)H PFG-NMR results. PMID:27088704

  11. Organocatalyzed Group Transfer Polymerization.

    PubMed

    Chen, Yougen; Kakuchi, Toyoji

    2016-08-01

    In contrast to the conventional group transfer polymerization (GTP) using a catalyst of either an anionic nucleophile or a transition-metal compound, the organocatalyzed GTP has to a great extent improved the living characteristics of the polymerization from the viewpoints of synthesizing structurally well-defined acrylic polymers and constructing defect-free polymer architectures. In this article, we describe the organocatalyzed GTP from a relatively personal perspective to provide our colleagues with a perspicuous and systematic overview on its recent progress as well as a reply to the curiosity of how excellently the organocatalysts have performed in this field. The stated perspectives of this review mainly cover five aspects, in terms of the assessment of the livingness of the polymerization, limit and scope of applicable monomers, mechanistic studies, control of the polymer structure, and a new GTP methodology involving the use of tris(pentafluorophenyl)borane and hydrosilane. PMID:27427399

  12. Electroplating Using Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Abbott, Andrew P.; Frisch, Gero; Ryder, Karl S.

    2013-07-01

    Electroplating is a key technology in many large-scale industrial applications such as corrosion-resistant and decorative coatings. Issues with current aqueous processes, such as toxicity of reagents and low current efficiencies, can often be overcome by using ionic liquids, and this approach has turned ionometallurgy into a fast-growing area of research. This review outlines the interactions in ionic liquids that are responsible for the advantageous properties of these solvents in electroplating. It summarizes recent research in which these properties have been analyzed or exploited and highlights fundamental issues in research and technology that need to be addressed.

  13. Variable Effect during Polymerization

    ERIC Educational Resources Information Center

    Lunsford, S. K.

    2005-01-01

    An experiment performing the polymerization of 3-methylthiophene(P-3MT) onto the conditions for the selective electrode to determine the catechol by using cyclic voltammetry was performed. The P-3MT formed under optimized conditions improved electrochemical reversibility, selectivity and reproducibility for the detection of the catechol.

  14. Polymerized and functionalized triglycerides

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Plant oils are useful sustainable raw materials for the development of new chemical products. As part of our research emphasis in sustainability and green polymer chemistry, we have explored a new method for polymerizing epoxidized triglycerides with the use of fluorosulfonic acid. Depending on the ...

  15. Programmable Supramolecular Polymerizations.

    PubMed

    van der Zwaag, Daan; de Greef, Tom F A; Meijer, E W

    2015-07-13

    Living large: Rational design of self-assembly pathways has been demonstrated in supramolecular polymers. By controlling the concentration of an aggregation-competent monomer through intramolecular interactions, living supramolecular polymerization conditions were achieved. This universal approach can be used to obtain aggregates of well-defined length and narrow dispersity, and allows access to new supramolecular polymer architectures. PMID:26095705

  16. Effective integrative supramolecular polymerization.

    PubMed

    Zhang, Qiwei; Tian, He

    2014-09-26

    Exercise control: By taking advantage of self-sorting processes among host-guest components, a controlled supramolecular polymerization can be realized, as demonstrated recently with the preparation of a cucurbit[n]uril-based supramolecular polymer. This method may be used for the design of more ordered supramolecular polymers from complex and discrete components. PMID:25080388

  17. Protein specific polymeric immunomicrospheres

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Dreyer, William J. (Inventor)

    1980-01-01

    Small, round, bio-compatible microspheres capable of covalently bonding proteins and having a uniform diameter below about 3500 A are prepared by substantially instantaneously initiating polymerization of an aqueous emulsion containing no more than 35% total monomer including an acrylic monomer substituted with a covalently bondable group such as hydroxyl, amino or carboxyl and a minor amount of a cross-linking agent.

  18. Fun with Ionic Compounds

    ERIC Educational Resources Information Center

    Logerwell, Mollianne G.; Sterling, Donna R.

    2007-01-01

    Ionic bonding is a fundamental topic in high school chemistry, yet it continues to be a concept that students struggle to understand. Even if they understand atomic structure and ion formation, it can be difficult for students to visualize how ions fit together to form compounds. This article describes several engaging activities that help…

  19. Synthesis of ionic liquids

    DOEpatents

    Dai, Sheng; Luo, Huimin

    2011-11-01

    Ionic compounds which are liquids at room temperature are formed by the method of mixing a neutral organic ligand with the salt of a metal cation and its conjugate anion. The liquids are hydrophobic, conductive and stable and have uses as solvents and in electrochemical devices.

  20. Synthesis of ionic liquids

    DOEpatents

    Dai, Sheng [Knoxville, TN; Luo, Huimin [Knoxville, TN

    2008-09-09

    Ionic compounds which are liquids at room temperature are formed by the method of mixing a neutral organic liqand with the salt of a metal cation and its conjugate anion. The liquids are hydrophobic, conductive and stable and have uses as solvents and in electrochemical devices.

  1. Carbenes from ionic liquids.

    PubMed

    Hollóczki, Oldamur; Nyulászi, László

    2014-01-01

    In the last decade an explosive development has been observed in the fields of both ionic liquids (ILs) as potential chemically inert solvents with many possible technical applications, and N-heterocyclic carbenes (NHCs) as catalysts with superb performance. Since the cations of many ILs can be deprotonated by strong bases yielding NHCs, this two fields are inherently connected. It has only recently been recognized that some of the commonly used basic anions of the ILs (such as acetate) are able to deprotonate azolium cations. While the resulting NHC could clearly be observed in the vapor phase, in the liquid - where the mutual electrostatic interactions within the ion network stabilize the ion pairs - the neutral NHC cannot be detected by commonly used analytical techniques; however, from these ionic liquids NHCs can be trapped, e.g., by complex formation, or more importantly these ILs can be directly used as catalysts, since the NHC content is sufficiently large for these applications. Apart from imidazole-2-ylidenes, the formation of other highly reactive neutral species ("abnormal carbenes," 2-alkylideneimidazoles, pyridine-ylidenes or pyridinium-ylides) is feasible in highly basic ionic liquids. The cross-fertilizing overlap between the two fields may provide access to a great advance in both areas, and we give an overview here on the results published so far, and also on the remaining possibilities and challenges in the concept of "carbenes from ionic liquids." PMID:23539381

  2. Extracellular polymeric substances (EPS) from aerobic granular sludges: extraction, fractionation, and anionic properties.

    PubMed

    Caudan, Cédric; Filali, Ahlem; Lefebvre, Dominique; Spérandio, Mathieu; Girbal-Neuhauser, Elisabeth

    2012-04-01

    A multi-method protocol previously proposed for the extraction of extracellular polymeric substances (EPS) from flocculated sludges was investigated on dense aerobic granules. The protocol combines mechanical disruption by sonication and chemical extraction using the Tween detergent and the cation chelator, EDTA. Polysaccharides were mainly recovered during the first sonication step while proteins were recovered all along the extractive procedure with a high prevalence in the EDTA step. These data confirmed the interest of the multi-method protocol for harvesting a diversified pool of EPS from dense granules and for fractionation of the polymers according to their physicochemical properties. In addition, the high extractability of proteins with EDTA confers a specific behavior of the aerobic granules towards the multi-method extraction protocol, supporting the idea that proteins are associated in the granule matrix through ionic interactions involving divalent cations. Analysis of the extracted EPS by anionic exchange chromatography confirmed the presence of highly anionic proteins that were specifically detected in the extracts obtained from granules. One important question is now to investigate whether these highly anionic proteins are involved in the aggregation and densification process and if their presence is related to the cohesive properties of these particles. PMID:22415780

  3. Cross-linked anion exchange membranes with pendent quaternary pyrrolidonium salts for alkaline polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Lan, Chunhua; Fang, Jun; Guan, Yingjie; Zhou, Huili; Zhao, Jinbao

    2015-11-01

    Novel anion-exchange membranes based on two kinds of pyrrolidonium type ionic liquids, N-methyl-N-vinyl-pyrrolidonium (NVMP) and N-ethyl-N-vinyl-pyrrolidonium (NVEP), have been synthesized via polymerization and crosslinking treatment, followed by membrane casting. The covalent cross-linked structures of these membranes are confirmed by FT-IR. The obtained membranes are also characterized in terms of water uptake, ion exchange capacity (IEC), ionic conductivity as well as thermal, dimensional and chemical stability. The membranes display hydroxide conductivity of above 10-2 S cm-1 at 25 °C. Excellent thermal stability with onset degradation temperature above 235 °C, good alkaline stability in 6 mol L-1 NaOH at 60 °C for 168 h and remarkable dimensional stability of the resulting membranes have been proved. H2/air single fuel cells employed membrane M3 and N3 show the open-circuit voltage (OCV) of 0.953 V and 0.933 V, and the maximum power density of 88.90 mW cm-2 and 81.90 mW cm-2 at the current density of 175 mA cm-2 and 200 mA cm-2 at 65 °C, respectively.

  4. Polymerization in emulsion microdroplet reactors

    NASA Astrophysics Data System (ADS)

    Carroll, Nick J.

    The goal of this research project is to utilize emulsion droplets as chemical reactors for execution of complex polymerization chemistries to develop unique and functional particle materials. Emulsions are dispersions of immiscible fluids where one fluid usually exists in the form of drops. Not surprisingly, if a liquid-to-solid chemical reaction proceeds to completion within these drops, the resultant solid particles will possess the shape and relative size distribution of the drops. The two immiscible liquid phases required for emulsion polymerization provide unique and complex chemical and physical environments suitable for the engineering of novel materials. The development of novel non-ionic fluorosurfactants allows fluorocarbon oils to be used as the continuous phase in a water-free emulsion. Such emulsions enable the encapsulation of almost any hydrocarbon compound in droplets that may be used as separate compartments for water-sensitive syntheses. Here, we exemplify the promise of this approach by suspension polymerization of polyurethanes (PU), in which the liquid precursor is emulsified into droplets that are then converted 1:1 into polymer particles. The stability of the droplets against coalescence upon removal of the continuous phase by evaporation confirms the formation of solid PU particles. These results prove that the water-free environment of fluorocarbon based emulsions enables high conversion. We produce monodisperse, cross-linked, and fluorescently labeled PU-latexes with controllable mesh size through microfluidic emulsification in a simple one-step process. A novel method for the fabrication of monodisperse mesoporous silica particles is presented. It is based on the formation of well-defined equally sized emulsion droplets using a microfluidic approach. The droplets contain the silica precursor/surfactant solution and are suspended in hexadecane as the continuous oil phase. The solvent is then expelled from the droplets, leading to

  5. Tuning Ion Conducting Pathways Using Holographic Polymerization

    NASA Astrophysics Data System (ADS)

    Smith, Derrick; Li, Christopher; Dong, Bin; Bunning, Timothy

    2012-02-01

    While much research has demonstrated repeatable characteristics of electrolyte membranes, the fundamentals behind the interactions during ionic diffusion in solid polymer electrolyte membranes for battery applications are not well understood, specifically the role of nanostructures, which hold the key to improving performance of energy storage devices such as fuel cells and Lithium ion batteries. The challenges in fabricating highly controlled model systems are largely responsible for the interdependent ambiguities between nanostructures and the corresponding ion conducting behavior. In this work, Holographic Polymer Electrolyte Membranes (hPEM) volume gratings comprised of alternating layers of crosslinked polymer resin and lithium ion salt were fabricated using holographic polymerization with an average d-spacing of approximately 200 nm. These one-dimensional confinement structures were used to quantitatively study the anisotropic ionic conductivity between the directions of in-plane and normal to the layers, and the unique ion conducting behavior was correlated with nanoscale phase separation. These volume gratings also offer an exciting route to fabricate multifunctional gratings for optic and sensing applications.

  6. Biocatalytic transformations in ionic liquids.

    PubMed

    van Rantwijk, Fred; Madeira Lau, Rute; Sheldon, Roger A

    2003-03-01

    Room temperature ionic liquids are non-volatile, thermally stable and highly polar; they are also moderately hydrophilic solvents. Here, we discuss their use as reaction media for biocatalysis. Enzymes of widely diverging types are catalytically active in ionic liquids or aqueous biphasic ionic liquid systems. Lipases, in particular, maintain their activity in anhydrous ionic liquid media; the (enantio)selectivity and operational stability are often better than in traditional media. The unconventional solvent properties of ionic liquids have been exploited in biocatalyst recycling and product recovery schemes that are not feasible with traditional solvent systems. PMID:12628370

  7. Metal-air cell with ion exchange material

    SciTech Connect

    Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

    2015-08-25

    Embodiments of the invention are related to anion exchange membranes used in electrochemical metal-air cells in which the membranes function as the electrolyte material, or are used in conjunction with electrolytes such as ionic liquid electrolytes.

  8. Glutathione-based zwitterionic stationary phase for hydrophilic interaction/cation-exchange mixed-mode chromatography.

    PubMed

    Shen, Aijin; Li, Xiuling; Dong, Xuefang; Wei, Jie; Guo, Zhimou; Liang, Xinmiao

    2013-11-01

    As a naturally hydrophilic peptide, glutathione was facilely immobilized onto silica surface to obtain a novel hydrophilic interaction/cation-exchange mixed-mode chromatographic stationary phase (Click TE-GSH) via copper-free "thiol-ene" click chemistry. The resulting material was characterized by solid state (13)C/CP MAS NMR and elemental analysis. The measurement of ζ-potential indicated the cation-exchange characteristics and adjustable surface charge density of Click TE-GSH material. The influence of acetonitrile content and pH value on the retention of ionic compounds was investigated for understanding the chromatographic behaviors. The results demonstrated that Click TE-GSH column could provide both hydrophilic and cation-exchange interaction. Taking advantage of the good hydrophilicity and inherent cation-exchange characteristics of Click TE-GSH material, the resolution of neutral fructosan with high degree of polymerization (DP), basic chitooligosaccharides and strongly acidic carrageenan oligosaccharides was successfully realized in hydrophilic interaction chromatography (HILIC), hydrophilic interaction/cation-exchange mixed-mode chromatography (HILIC/CEX), cation-exchange chromatography (CEX) and electrostatic repulsion/hydrophilic interaction chromatography (ERLIC). On the other hand, the separation of standard peptides varying in hydrophobicity/hydrophilicity and charge was achieved in both CEX and HILIC/CEX mode with high efficiency and distinct selectivity. To further demonstrate the versatility and applicability of Click TE-GSH stationary phase, the separation of a human serum albumin (HSA) tryptic digest was performed in HILIC/CEX mode. Peptides were adequately resolved and up to 86 HSA peptides were identified with sequence coverage of 85%. The results indicated the good potential of Click TE-GSH material in glycomics and proteomics. PMID:24075460

  9. Ion-Exchange Membranes Prepared Using Layer-by-Layer Polyelectrolyte Deposition

    PubMed Central

    Liu, Guanqing; Dotzauer, David M.; Bruening, Merlin L

    2010-01-01

    Layer-by-layer polyelectrolyte adsorption in porous polymeric membranes provides a simple way to create ion-exchange sites without greatly decreasing hydraulic permeability (<20% reduction in permeability). At 80% breakthrough, membranes coated with 3-bilayer poly(styrene sulfonate) (PSS)/polyethyleneimine (PEI) films bind 37±6 mg of negatively charged Au colloids per mL of membrane volume. The binding capacity of membranes coated with 1-bilayer films decreases in the order PSS/PEI>PSS/poly(diallyldimethyl ammonium chloride)>PSS/poly(allylamine hydrochloride). Films terminated with a polyanion present cation-exchange sites that bind lysozyme, and the lysozyme-binding capacities of (PSS/PEI)3/PSS films increase with the ionic strength of the solution from which the last PSS layer is deposited. Charge screening during deposition of the terminal PSS layer gives rise to a larger number of ion-exchange sites and lysozyme binding capacities as high as 16 mg per mL of membrane. At 10% breakthrough, a stack of 3 membranes binds 3 times as much lysozyme as a single membrane, showing that stacking is an effective way to increase capacity. PMID:20606722

  10. Dissolving Polymers in Ionic Liquids.

    NASA Astrophysics Data System (ADS)

    Hoagland, David; Harner, John

    2009-03-01

    Dissolution and phase behavior of polymers in ionic liquids have been assessed by solution characterization techniques such as intrinsic viscosity and light scattering (static and dynamic). Elevated viscosity proved the greatest obstacle. As yet, whether principles standard to conventional polymer solutions apply to ionic liquid solutions is uncertain, especially for polymers such as polyelectrolytes and hydrophilic block copolymers that may specifically interact with ionic liquid anions or cations. For flexible polyelectrolytes (polymers releasing counterions into high dielectric solvents), characterization in ionic liquids suggests behaviors more typical of neutral polymer. Coil sizes and conformations are approximately the same as in aqueous buffer. Further, several globular proteins dissolve in a hydrophilic ionic liquid with conformations analogous to those in buffer. General principles of solubility, however, remain unclear, making predictions of which polymer dissolves in which ionic liquid difficult; several otherwise intractable polymers (e.g., cellulose, polyvinyl alcohol) dissolve and can be efficiently functionalized in ionic liquids.

  11. Development of Practical Supported Ionic Liquid Membranes: A Systematic Approach

    SciTech Connect

    Luebke, D.R.; Ilconich, J.B.; Myers, C.R.; Pennline, H.W.

    2007-11-01

    Supported liquid membranes (SLMs) are a class of materials that allow the researcher to utilize the wealth of knowledge available on liquid properties to optimize membrane performance. These membranes also have the advantage of liquid phase diffusivities, which are higher than those observed in polymers and grant proportionally greater permeabilities. The primary shortcoming of the supported liquid membranes demonstrated in past research has been the lack of stability caused by volatilization of the transport liquid. Ionic liquids, which may possess high CO2 solubility relative to light gases such as H2, are excellent candidates for this type of membrane since they are stable at elevated temperatures and have negligible vapor pressure. A study has been conducted evaluating the use of a variety of ionic liquids in supported ionic liquid membranes for the capture of CO2 from streams containing H2. In a joint project, researchers at the University of Notre Dame synthesized and characterized ionic liquids, and researchers at the National Energy Technology Laboratory incorporated candidate ionic liquids into supports and evaluated membrane performance for the resulting materials. Several steps have been taken in the development of practical supported ionic liquid membranes. Proof-of-concept was established by showing that ionic liquids could be used as the transport media in SLMs. Results showed that ionic liquids are suitable media for gas transport, but the preferred polymeric supports were not stable at temperatures above 135oC. The use of cross-linked nylon66 supports was found to produce membranes mechanically stable at temperatures exceeding 300oC but CO2/H2 selectivity was poor. An ionic liquid whose selectivity does not decrease with increasing temperature was needed, and a functionalized ionic liquid that complexes with CO2 was used. An increase in CO2/H2 selectivity with increasing temperature over the range of 37 to 85oC was observed and the dominance of a

  12. Ionic contrast terahertz near field imaging

    NASA Astrophysics Data System (ADS)

    Gallot, Guilhem

    2013-09-01

    We demonstrated the direct and noninvasive imaging of functional neurons by Ionic Contrast Terahertz (ICT) near-field microscopy. This technique provides quantitative measurements of ionic concentrations in both the intracellular and extracellular compartments and opens the way to direct noninvasive imaging of neurons during electrical, toxin, or thermal stresses. Furthermore, neuronal activity results from both a precise control of transient variations in ionic conductance and a much less studied water exchange between the extracellular matrix and the intraaxonal compartment. The developed ICT technique associated with a full three-dimensional simulation of the axon-aperture near-field system allows a precise measurement of the axon geometry and therefore the direct visualization of neuron swelling induced by temperature change or neurotoxin poisoning. We also developed Terahertz Attenuated Total Reflection (ATR) devices perfectly suited for studying cell layers. Inserted in a terahertz time-domain system, and using a high resistivity low loss silicon prism to couple the terahertz wave into the sample, the detection scheme is based on the relative differential spectral phase of two orthogonal polarizations. Biological sample imaging as well as subwavelength (λ/16) longitudinal resolution are demonstrated.

  13. Thallium Transfer from Hydrochloric Acid Media into Pure Ionic Liquids.

    PubMed

    Tereshatov, Evgeny E; Boltoeva, Maria Yu; Mazan, Valerie; Volia, Merinda F; Folden, Charles M

    2016-03-10

    Pure hydrophobic ionic liquids are known to extract metallic species from aqueous solutions. In this work we have systematically investigated thallium (Tl) extraction from aqueous hydrochloric acid (HCl) solutions into six pure fluorinated ionic liquids, namely imidazolium- and pyrrolidinium-based ionic liquids with bis(trifluoromethanesulfonyl)imide and bis(fluorosulfonyl)-imide anions. The dependence of the Tl extraction efficiency on the structure and composition of the ionic liquid ions, metal oxidation state, and initial metal and aqueous acid concentrations have been studied. Tl concentrations were on the order of picomolar (analyzed using radioactive tracers) and millimolar (analyzed using inductively coupled plasma mass spectrometry). The extraction of the cationic thallium species Tl(+) is higher for ionic liquids with more hydrophilic cations, while for the TlX(z)(3-z) anionic species (where X = Cl(-) and/or Br(-)), the extraction efficiency is greater for ionic liquids with more hydrophobic cations. The highest distribution value of Tl(III) was approximately 2000. An improved mathematical model based on ion exchange and ion pair formation mechanisms has been developed to describe the coextraction of two different anionic species, and the relative contributions of each mechanism have been determined. PMID:26769597

  14. Super ionic conductive glass

    DOEpatents

    Susman, Sherman; Volin, Kenneth J.

    1984-01-01

    An ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A.sub.1+x D.sub.2-x/3 Si.sub.x P.sub.3-x O.sub.12-2x/3, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

  15. Super ionic conductive glass

    DOEpatents

    Susman, S.; Volin, K.J.

    Described is an ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A/sub 1 + x/D/sub 2-x/3/Si/sub x/P/sub 3 - x/O/sub 12 - 2x/3/, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

  16. Frontal Polymerization in Microgravity

    NASA Technical Reports Server (NTRS)

    Pojman, John A.

    1999-01-01

    Frontal polymerization systems, with their inherent large thermal and compositional gradients, are greatly affected by buoyancy-driven convection. Sounding rocket experiments allowed the preparation of benchmark materials and demonstrated that methods to suppress the Rayleigh-Taylor instability in ground-based research did not significantly affect the molecular weight of the polymer. Experiments under weightlessness show clearly that bubbles produced during the reaction interact very differently than under 1 g.

  17. Polymeric Bicontinuous Microemulsions

    NASA Astrophysics Data System (ADS)

    Bates, Frank S.; Maurer, Wayne W.; Lipic, Paul M.; Hillmyer, Marc A.; Almdal, Kristoffer; Mortensen, Kell; Fredrickson, Glenn H.; Lodge, Timothy P.

    1997-08-01

    High molecular weight block copolymers can be viewed as macromolecular surfactants when blended with thermodynamically incompatible homopolymers. This Letter describes the formation of polymeric bicontinuous microemulsions in mixtures containing a model diblock copolymer and two homopolymers. Although we attribute development of this equilibrium morphology to the effects of fluctuations, mean-field theory provides a quantitative strategy for preparing the bicontinuous state at blend compositions near an isotropic Lifshitz point.

  18. Surface polymerization agents

    SciTech Connect

    Taylor, C.; Wilkerson, C.

    1996-12-01

    This is the final report of a 1-year, Laboratory-Directed R&D project at LANL. A joint technical demonstration was proposed between US Army Missile Command (Redstone Arsenal) and LANL. Objective was to demonstrate that an unmanned vehicle or missile could be used as a platform to deliver a surface polymerization agent in such a manner as to obstruct the filters of an air-breathing mechanism, resulting in operational failure.

  19. Thermodynamic estimation: Ionic materials

    SciTech Connect

    Glasser, Leslie

    2013-10-15

    Thermodynamics establishes equilibrium relations among thermodynamic parameters (“properties”) and delineates the effects of variation of the thermodynamic functions (typically temperature and pressure) on those parameters. However, classical thermodynamics does not provide values for the necessary thermodynamic properties, which must be established by extra-thermodynamic means such as experiment, theoretical calculation, or empirical estimation. While many values may be found in the numerous collected tables in the literature, these are necessarily incomplete because either the experimental measurements have not been made or the materials may be hypothetical. The current paper presents a number of simple and relible estimation methods for thermodynamic properties, principally for ionic materials. The results may also be used as a check for obvious errors in published values. The estimation methods described are typically based on addition of properties of individual ions, or sums of properties of neutral ion groups (such as “double” salts, in the Simple Salt Approximation), or based upon correlations such as with formula unit volumes (Volume-Based Thermodynamics). - Graphical abstract: Thermodynamic properties of ionic materials may be readily estimated by summation of the properties of individual ions, by summation of the properties of ‘double salts’, and by correlation with formula volume. Such estimates may fill gaps in the literature, and may also be used as checks of published values. This simplicity arises from exploitation of the fact that repulsive energy terms are of short range and very similar across materials, while coulombic interactions provide a very large component of the attractive energy in ionic systems. Display Omitted - Highlights: • Estimation methods for thermodynamic properties of ionic materials are introduced. • Methods are based on summation of single ions, multiple salts, and correlations. • Heat capacity, entropy

  20. 3-Methylpiperidinium ionic liquids.

    PubMed

    Belhocine, Tayeb; Forsyth, Stewart A; Gunaratne, H Q Nimal; Nieuwenhuyzen, Mark; Nockemann, Peter; Puga, Alberto V; Seddon, Kenneth R; Srinivasan, Geetha; Whiston, Keith

    2015-04-28

    A wide range of room temperature ionic liquids based on the 3-methylpiperdinium cation core were produced from 3-methylpiperidine, which is a derivative of DYTEK® A amine. First, reaction with 1-bromoalkanes or 1-bromoalkoxyalkanes generated the corresponding tertiary amines (Rmβpip, R = alkyl or alkoxyalkyl); further quaternisation reactions with the appropriate methylating agents yielded the quaternary [Rmmβpip]X salts (X(-) = I(-), [CF3CO2](-) or [OTf](-); Tf = -SO2CF3), and [Rmmβpip][NTf2] were prepared by anion metathesis from the corresponding iodides. All [NTf2](-) salts are liquids at room temperature. [Rmmβpip]X (X(-) = I(-), [CF3CO2](-) or [OTf](-)) are low-melting solids when R = alkyl, but room temperature liquids upon introduction of ether functionalities on R. Neither of the 3-methylpiperdinium ionic liquids showed any signs of crystallisation, even well below 0 °C. Some related non-C-substituted piperidinium and pyrrolidinium analogues were prepared and studied for comparison. Crystal structures of 1-hexyl-1,3-dimethylpiperidinium tetraphenylborate, 1-butyl-3-methylpiperidinium bromide, 1-(2-methoxyethyl)-1-methylpiperidinium chloride and 1-(2-methoxyethyl)-1-methylpyrrolidinium bromide are reported. Extensive structural and physical data are collected and compared to literature data, with special emphasis on the systematic study of the cation ring size and/or asymmetry effects on density, viscosity and ionic conductivity, allowing general trends to be outlined. Cyclic voltammetry shows that 3-methylpiperidinium ionic liquids, similarly to azepanium, piperidinium or pyrrolidinium counterparts, are extremely electrochemically stable; the portfolio of useful alternatives for safe and high-performing electrolytes is thus greatly extended. PMID:25669485

  1. Cyclic phosphonium ionic liquids

    PubMed Central

    Mukhlall, Joshua A; Romeo, Alicia R; Gohdo, Masao; Ramati, Sharon; Berman, Marc; Suarez, Sophia N

    2014-01-01

    Summary Ionic liquids (ILs) incorporating cyclic phosphonium cations are a novel category of materials. We report here on the synthesis and characterization of four new cyclic phosphonium bis(trifluoromethylsulfonyl)amide ILs with aliphatic and aromatic pendant groups. In addition to the syntheses of these novel materials, we report on a comparison of their properties with their ammonium congeners. These exemplars are slightly less conductive and have slightly smaller self-diffusion coefficients than their cyclic ammonium congeners. PMID:24605146

  2. The influence of various cations on the catalytic properties of clays. [polymerization of alanine adenylate

    NASA Technical Reports Server (NTRS)

    Paecht-Horowitz, M.

    1978-01-01

    The polymerization of alanine adenylate in the presence of the sodium form of various clays was studied, and hectorite was found to cause more polymerization than nontronite and montmorillonite (in that order) although the differences were not great. The effect on polymerization of presaturating montmorillonite with different cations was determined. Hectorite, with increased basicity of the interspatial planes, allows polymerization of lysine, which montmorillonite does not. The general trend is that, for the same amino acid, higher degrees of polymerization are obtained when the cation in the octahedral lattice of the clay is divalent rather than trivalent. With the exchangeable cations the order is reversed, for a reason that is explained. The main role of clays in the polymerization mechanism of amino acids is concentration and neutralization of charges.

  3. Encapsulation of Ln(III) Ions/Dyes within a Microporous Anionic MOF by Post-synthetic Ionic Exchange Serving as a Ln(III) Ion Probe and Two-Color Luminescent Sensors.

    PubMed

    Zhao, Shu-Na; Song, Xue-Zhi; Zhu, Min; Meng, Xing; Wu, Lan-Lan; Feng, Jing; Song, Shu-Yan; Zhang, Hong-Jie

    2015-06-26

    A new anionic framework {[Me2NH2]0.125[In0.125(H2L)0.25]⋅xDMF}n (1) with one-dimensional (1D) channels along the c axis of about 13.06×13.06 Å(2), was solvothermally synthesized and well characterized. Post-synthetic cation exchange of 1 with Eu(3+), Tb(3+), Dy(3+), Sm(3+) afforded lanthanide(III)-loaded materials, Ln(3+)@1, with different luminescent behavior, indicating that compound 1 could be used as a potential luminescent probe toward different lanthanide(III) ions. Additionally, compound 1 exhibits selective adsorption ability toward cationic dyes. Moreover, the RhB@1 realized the probing of different organic solvent molecules by tuning the energy transfer efficiency between two different emissions, especially for sensing DMF. This work highlights the practical application of luminescent guest@MOFs as sensors, and it paves the way toward other one/multi-color luminescent host-guest systems by rational selection of MOF hosts and guest chromophores with suitable emissive colors and energy levels. PMID:26013556

  4. Carbon Dioxide Separation with Supported Ionic Liquid Membranes

    SciTech Connect

    Luebke, D.R.; Ilconich, J.B.; Myers, C.R.; Pennline, H.W.

    2007-04-01

    Supported liquid membranes are a class of materials that allow the researcher to utilize the wealth of knowledge available on liquid properties as a direct guide in the development of a capture technology. These membranes also have the advantage of liquid phase diffusivities higher than those observed in polymeric membranes which grant proportionally greater permeabilities. The primary shortcoming of the supported liquid membranes demonstrated in past research has been the lack of stability caused by volatilization of the transport liquid. Ionic liquids, which possess high carbon dioxide solubility relative to light gases such as hydrogen, are an excellent candidate for this type of membrane since they have negligible vapor pressure and are not susceptible to evaporation. A study has been conducted evaluating the use of several ionic liquids, including 1-hexyl-3-methyl-imidazolium bis(trifuoromethylsulfonyl)imide, 1-butyl-3-methyl-imidazolium nitrate, and 1-ethyl-3-methyl-imidazolium sulfate in supported ionic liquid membranes for the capture of carbon dioxide from streams containing hydrogen. In a joint project, researchers at the University of Notre Dame lent expertise in ionic liquid synthesis and characterization, and researchers at the National Energy Technology Laboratory incorporated candidate ionic liquids into supports and evaluated the resulting materials for membrane performance. Initial results have been very promising with carbon dioxide permeabilities as high as 950 barrers and significant improvements in carbon dioxide/hydrogen selectivity over conventional polymers at 37C and at elevated temperatures. Results include a comparison of the performance of several ionic liquids and a number of supports as well as a discussion of innovative fabrication techniques currently under development.

  5. Stable and water-tolerant ionic liquid ferrofluids.

    PubMed

    Jain, Nirmesh; Zhang, Xiaoli; Hawkett, Brian S; Warr, Gregory G

    2011-03-01

    Ionic liquid ferrofluids have been prepared containing both bare and sterically stabilized 8-12 nm diameter superparamagnetic iron oxide nanoparticles, which remain stable for several months in both protic ethylammonium and aprotic imidazolium room-temperature ionic liquids. These ferrofluids exhibit spiking in static magnetic fields similar to conventional aqueous and nonaqueous ferrofluids. Ferrofluid stability was verified by following the flocculation and settling behavior of dilute nanoparticle dispersions. Although bare nanoparticles showed excellent stability in some ILs, they were unstable in others, and exhibited limited water tolerance. Stability was achieved by incorporating a thin polymeric steric stabilization layer designed to be compatible with the IL. This confers the added benefit of imbuing the ILF with a high tolerance to water. PMID:21338083

  6. Surface-initiated atom transfer radical polymerization from chitin nanofiber macroinitiator film.

    PubMed

    Yamamoto, Kazuya; Yoshida, Sho; Kadokawa, Jun-Ichi

    2014-11-01

    This paper reports the preparation of chitin nanofiber-graft-poly(2-hydroxyethyl acrylate) (CNF-g-polyHEA) films by surface-initiated atom transfer radical polymerization (ATRP) of HEA monomer from a CNF macroinitiator film. First, a CNF film was prepared by regeneration from a chitin ion gel with an ionic liquid. Then, acylation of the CNF surface with α-bromoisobutyryl bromide was carried out to obtain the CNF macroinitiator film having the initiating moieties (α-bromoisobutyrate group). The surface-initiated graft polymerization of HEA from the CNF macroinitiator film by ATRP was performed to produce the CNF-g-polyHEA film. The IR, XRD, and SEM measurements of the resulting film indicated the progress of the graft polymerization of HEA on surface of CNFs. The molecular weights of the grafted polyHEAs increased with prolonged polymerization times, which affected the mechanical properties of the films under tensile mode. PMID:25129725

  7. Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

    DOEpatents

    Skotheim, T.A.; Okamoto, Yoshiyuki; Lee, H.S.

    1989-11-21

    The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10[sup [minus]4] to 10[sup [minus]7] S cm[sup [minus]1] at room temperature.

  8. Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

    DOEpatents

    Skotheim, Terje A.; Okamoto, Yoshiyuki; Lee, Hung S.

    1989-01-01

    The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10.sup.-4 to 10.sup.-7 S cm.sup.-1 at room temperature.

  9. PEDOT Electrochemical Polymerization Improves Electrode Fidelity and Sensitivity

    PubMed Central

    Frost, Christopher M.; Wei, Benjamin; Baghmanli, Ziya; Cederna, Paul S.; Urbanchek, Melanie G.

    2015-01-01

    Background The goal of the authors is to restore fine motor control and sensation for high-arm amputees. They developed a regenerative peripheral nerve interface with the aim of attaining closed loop neural control by integrating directly with the amputee's residual motor and sensory peripheral nerves. PEDOT, poly(3,4-ethylenedioxythiophene), has both electrical and ionic conduction characteristics. This hybrid character could help bridge the salutatory conduction of the nervous system to an electrode. The purpose of this study was to determine whether electrodes polymerized with PEDOT have improved ability to both record and stimulate peripheral nerve action potentials. Methods Impedance spectroscopy and cyclic voltammetry were performed on electrodes before and after polymerization to measure electrode impedance and charge capacity. Both recording needle and bipolar stimulating electrodes were polymerized with PEDOT. Plain and PEDOT electrodes were tested using rat (n = 18) in situ nerve conduction studies. The peroneal nerve was stimulated using a bipolar electrode at multiple locations along the nerve. Action potentials were measured in the extensor digitorum longus muscle. Results Bench testing showed PEDOT electrodes had a higher charge capacity and lower impedance than plain electrodes, indicating significantly improved electrode fidelity. Nerve conduction testing indicated a significant reduction in the stimulus threshold for both PEDOT recording and PEDOT stimulatory electrodes when compared with plain electrodes, indicating an increase in sensitivity. Conclusions PEDOT electrochemical polymerization improves electrode fidelity. Electrodes that have been electropolymerized with PEDOT show improved sensitivity when recording or stimulating action potentials at the tissue–electrode interface. PMID:22456363

  10. Development of ionic polymer actuator arrays

    NASA Astrophysics Data System (ADS)

    Le Guilly, Marie

    Ionic polymer metal composites (IPMC) are bending type actuators which are soft, and show large deformation at low voltage. This work explored the creation of IPMC actuator arrays to take advantage of the unique features of IPMCs, in applications such as pump and valve arrays for micro-fluidic devices, microwave switch arrays etc. In the design of the arrays, the concept of integration is key, to make the actuator array reliable, compact and scalable. The arrays are created as a single physical part, by electrode patterning on the ionic polymer and material engineering. Gold chemical plating was used to create the flexible electrodes with large capacitance on Flemion and Nafion. Patterning was done with masks created in various ways. Nafion, because of its high flexibility, can be made into diaphragm actuators with very good dynamic properties. Flemion in cantilever mode was found to generate large forces without relaxation, a key feature for the design of IPMC switches and valves. A new electrode fabrication technique was developed based on plasma polymerization on an amine monomer on the membrane and subsequent self assembly of Au colloids. A 14-micron thick Flemion sample with 10 layers of 13nm diameter Au colloids showed actuation at +/-1.5V. The demonstration of actuation of IPMC with self-assembled electrodes is a milestone for the future application of IPMC to MEMS. Finally the actuation mechanisms of Nafion and Flemion were modeled. Two dominant contributions in the actuation of IPMC were considered: electro-osmosis, and equilibrium volume which can change upon cation redistribution. A large volume transition upon pH change was observed for Flemion, whereas Nafion proved indifferent to pH. It is proposed that Flemion is generally weakly ionized and has many ionic groups in acid form. Upon cation redistribution, this structure is perturbed and the ionization increases at the cathode side because of the increase in sodium concentration, leading to an increase

  11. Acrylic esters in radiation polymerization

    SciTech Connect

    Fomina, N.V.; Khoromskaya, V.A.; Shiryaeva, G.V.

    1988-03-01

    The radiation behavior of (meth)acrylic esters of varying structure was studied. It was shown that in radiation polymerization, in contrast to thermal polymerization, the structure of the ester part can significantly affect the reaction rate and capacity for polymerization in the presence of oxygen. The experimental data are explained from the point of view of consideration of nonvalence effects of the substitutent on the reactivity of the double bond.

  12. Polymerization Evaluation by Spectrophotometric Measurements.

    ERIC Educational Resources Information Center

    Dunach, Jaume

    1985-01-01

    Discusses polymerization evaluation by spectrophotometric measurements by considering: (1) association degrees and molar absorptivities; (2) association degrees and equilibrium constants; and (3) absorbance and equilibrium constants. (JN)

  13. Continuous polymerization reactor

    SciTech Connect

    Wilt, M.S.

    1986-05-06

    A method is described for contacting olefinic monomer and initiator in a continuous polymerization process comprising of the steps of: creating three turbulent zones in a vessel; introducing the olefinic monomer into a first part of the periphery of each one of the three turbulent zones; introducing the initiator into a second part of the periphery of each one of the three turbulent zones, wherein the first part of the periphery of each one of the three turbulent zones is substantially diametrically opposed to the second part of the periphery of each one of the three turbulent zones respectively.

  14. Bimorphic polymeric photomechanical actuator

    NASA Technical Reports Server (NTRS)

    Sarkisov, Sergey S. (Inventor); Curley, Michael J. (Inventor); Adamovsky, Grigory (Inventor); Sarkisov, Jr., Sergey S. (Inventor); Fields, Aisha B. (Inventor)

    2006-01-01

    A bimorphic polymeric photomechanical actuator, in one embodiment using polyvinylidene fluoride (PVDF) as a photosensitive body, transmitting light over fiber optic cables, and controlling the shape and pulse duration of the light pulse to control movement of the actuator. Multiple light beams are utilized to generate different ranges of motion for the actuator from a single photomechanical body and alternative designs use multiple light beams and multiple photomechanical bodies to provide controlled movement. Actuator movement using one or more ranges of motion is utilized to control motion to position an actuating element in three dimensional space.

  15. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Bauman, Robert

    2006-11-14

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  16. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Baumann, Robert

    2003-08-26

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  17. Living olefin polymerization processes

    DOEpatents

    Schrock, R.R.; Baumann, R.

    1999-03-30

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  18. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Baumann, Robert

    1999-01-01

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  19. Ionic versus nonionic MR imaging contrast media: operational definitions.

    PubMed

    Chang, C A; Sieving, P F; Watson, A D; Dewey, T M; Karpishin, T B; Raymond, K N

    1992-01-01

    An experimental rationale is provided to differentiate between the terms ionic and nonionic for magnetic resonance (MR) imaging contrast media such as gadodiamide and gadopentetate dimeglumine. Four independent types of physical measurements (electric conductivity, osmolality, electrophoresis, and ion exchange) were performed on a range of test compounds, including D-glucose, iohexol, gadopentetate dimeglumine, and gadodiamide. Iohexol, D-glucose, and gadodiamide are shown to be nonionic species at physiologic pH (7.4), not measurably dissociating in solution. A range of gadopentetate salts behave as electrolytes, dissociating into constituent charged ions in aqueous media. Operational definitions for the terms ionic and nonionic are provided, and the terms neutral and net zero charge are compared with nonionic for accuracy. The nomenclature nonionic and ionic is deemed appropriate for differentiating MR imaging contrast media. PMID:1623289

  20. Ionic liquids, electrolyte solutions including the ionic liquids, and energy storage devices including the ionic liquids

    SciTech Connect

    Gering, Kevin L.; Harrup, Mason K.; Rollins, Harry W.

    2015-12-08

    An ionic liquid including a phosphazene compound that has a plurality of phosphorus-nitrogen units and at least one pendant group bonded to each phosphorus atom of the plurality of phosphorus-nitrogen units. One pendant group of the at least one pendant group comprises a positively charged pendant group. Additional embodiments of ionic liquids are disclosed, as are electrolyte solutions and energy storage devices including the embodiments of the ionic liquid.

  1. Organometallic Polymeric Conductors

    NASA Technical Reports Server (NTRS)

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. The highest conductivities reported (approximately 4/Scm) were achieved with polythiophene in a polystyrene host polymer. The best films using a polyamide as base polymer were four orders of magnitude less conductive than the polystyrene films. The authors suggested that this was because polyimides were unable to swell sufficiently for infiltration of monomer as in the polystyrene. It was not clear, however, if the different conductivities obtained were merely the result of differing oxidation conditions. Oxidation time, temperature and oxidant concentration varied widely among the studies.

  2. Role of Heavy Meromyosin in Heat-Induced Gelation in Low Ionic Strength Solution Containing L-Histidine.

    PubMed

    Hayakawa, Toru; Yoshida, Yuri; Yasui, Masanori; Ito, Toshiaki; Wakamatsu, Jun-ichi; Hattori, Akihito; Nishimura, Takanori

    2015-08-01

    The gelation of myosin has a very important role in meat products. We have already shown that myosin in low ionic strength solution containing L-histidine forms a transparent gel after heating. To clarify the mechanism of this unique gelation, we investigated the changes in the nature of myosin subfragments during heating in solutions with low and high ionic strengths with and without L-histidine. The hydrophobicity of myosin and heavy meromyosin (HMM) in low ionic strength solution containing L-histidine was lower than in high ionic strength solution. The SH contents of myosin and HMM in low ionic strength solution containing l-histidine did not change during the heating process, whereas in high ionic strength solution they decreased slightly. The heat-induced globular masses of HMM in low ionic strength solution containing L-histidine were smaller than those in high ionic strength solution. These findings suggested that the polymerization of HMM molecules by heating was suppressed in low ionic strength solution containing L-histidine, resulting in formation of the unique gel. PMID:26148000

  3. Self-stabilized magnetic polymeric composite nanoparticles by emulsifier-free miniemulsion polymerization.

    PubMed

    Lu, Shulai; Ramos, Jose; Forcada, Jacqueline

    2007-12-18

    Self-stabilized magnetic polymeric composite nanoparticles (SS-MPCPs) were prepared by emulsifier-free miniemulsion polymerization using styrene (St) as a monomer, sodium p-styrenesulfonate (NaSS) as an ionic comonomer, hexadecane (HD) as a hydrophobe, and 2,2'-azodiisobutyronitrile (AIBN) as an initiator in the presence of hydrophobic magnetite particles. The hydrophobic magnetite particles with an average size of about 10 nm were prepared by the acidification of the water-based magnetite ferrofluid, previously synthesized by a chemical coprecipitation method. Some colloidal features of the synthesized SS-MPCPs were analyzed. The morphology and the particle size distributions (PSDs) of the SS-MPCPs were observed and analyzed by transmission electron microscopy (TEM). The surface charge density was determined by conductometric titration. The surface hairy layer and the colloidal stability of SS-MPCPs against different electrolytes were determined by photon correlation spectroscopy (PCS). The average Fe3O4 content of SS-MPCPs was determined by thermogravimetric analysis (TGA). Vibrating sample magnetometry (VSM) was used to analyze the magnetic properties of the SS-MPCPs under dry conditions. The results show that the encapsulation of magnetite is successful and the distribution of magnetite particles inside SS-MPCPs is mainly in the core of the particles. The best SS-MPCPs prepared had a relatively narrow PSD, exhibited superparamagnetism, and possessed some magnetic response. PMID:18031070

  4. Food and Gill Exchange of Toxic Substances

    EPA Science Inventory

    Food and Gill Exchange of Toxic Substances (FGETS) is a FORTRAN simulation model that predicts temporal dynamics of fish whole body concentration (ug chemical/(g live weight fish)) of non ionic, non metabolized, organic chemicals that are bioaccumulated from either: (a) water onl...

  5. Coating of plasma polymerized film

    NASA Technical Reports Server (NTRS)

    Morita, S.; Ishibashi, S.

    1980-01-01

    Plasma polymerized thin film coating and the use of other coatings is suggested for passivation film, thin film used for conducting light, and solid body lubrication film of dielectrics of ultra insulators for electrical conduction, electron accessories, etc. The special features of flow discharge development and the polymerized film growth mechanism are discussed.

  6. Sensitive Biological Detection with a Soluble and Stable Polymeric Paramagnetic Nano Cluster

    PubMed Central

    Kim, Benjamin; Schmieder, Anne H.; Stacy, Allen J.; Williams, Todd A.; Pan, Dipanjan

    2012-01-01

    We describe the design, synthesis and biological characterization of manganese oxocluster-based “single molecule magnets (SMMs)”. We demonstrate that polymeric micellar nanoparticles can serve as a carrier and help to stabilize delicate SMM molecules from breaking down easily and thus prevent their property loss. Concentrating thousands of Mn-clusters per micelle provided a high ionic and per-particle relaxivity allowing sensitive MR imaging in vivo. This reports one of the earliest examples of in vivo imaging of a rationally designed polymeric micelles that features SMM. PMID:22693958

  7. Degradation of Ionic Pathway in PEM Fuel Cell Cathode

    SciTech Connect

    Park, Seh Kyu; Shao, Yuyan; Wan, Haiying; Viswanathan, Vilayanur V.; Towne, Silas A.; Rieke, Peter C.; Liu, Jun; Wang, Yong

    2011-11-12

    The degradation of the ionic pathway throughout the catalyst layer in proton exchange membrane fuel cells was studied under an accelerated stress test of catalyst support (potential hold at 1.2 V). Electrochemical behaviors of the cathode based on graphitic mesoporous carbon supported Pt catalyst were examined using electrochemical impedance spectroscopy and cyclic voltammetry. Impedance data were plotted and expressed in the complex capacitance form to determine useful parameters in the transmission line model: the double-layer capacitance, peak frequency, and ionic resistance. Electrochemical surface area and hydrogen crossover current through the membrane were estimated from cyclic voltammogram, while cathode Faradaic resistance was compared with ionic resistance as a function of test time. It was observed that during an accelerated stress test of catalyst support, graphitic mesoporous carbon becomes hydrophilic which increases interfacial area between the ionomer and the catalyst up to 100 h. However, the ionic resistance in the catalyst layer drastically increases after 100 h with further carbon support oxidation. The underlying mechanism has been studied and it was found that significant degradation of ionic pathway throughout the catalyst layer due to catalyst support corrosion induces uneven hydration and mechanical stress in the ionomer.

  8. Enzyme catalysis in ionic liquids.

    PubMed

    Kragl, Udo; Eckstein, Marrit; Kaftzik, Nicole

    2002-12-01

    Ionic liquids offer new possibilities for the application of solvent engineering to biocatalytic reactions. Although in many cases ionic liquids have simply been used to replace organic solvents, they have often led to improved process performance. Unlike conventional organic solvents, ionic liquids possess no vapor pressure, are able to dissolve many compounds, and can be used to form two-phase systems with many solvents. To date, reactions involving lipases have benefited most from the use of ionic liquids, but the use of ionic liquids with other enzymes and in whole-cell processes has also been described. In some cases, remarkable results with respect to yield, (enantio)selectivity or enzyme stability were observed. PMID:12482515

  9. Ionic α-Helical Polypeptides towards Non-Viral Gene Delivery

    PubMed Central

    Zhang, Rujing; Song, Ziyuan; Yin, Lichen; Zheng, Nan; Tang, Haoyu; Lu, Hua; Gabrielson, Nathan P.; Lin, Yao; Kim, Kyung; Cheng, Jianjun

    2014-01-01

    The advent of polymeric materials has significantly promoted the development and rapid growth of various technologies in biomedical applications, such as tissue engineering and controlled drug and gene delivery. Water-soluble polypeptides bearing functional side chains and adopting stable secondary structures are a new class of functional polymeric materials of potentially broad applications in medicine and biotechnology. In this article, we summarize our recent effort on the design and synthesis of the water-soluble α-helical ionic polypeptides originally developed in our laboratory and highlight their applications in cell membrane penetration and non-viral gene/siRNA delivery. PMID:25377262

  10. Ionic Vapor Composition in Pyridinium-Based Ionic Liquids.

    PubMed

    Chaban, Vitaly V; Prezhdo, Oleg V

    2016-05-26

    Strong electrostatic interactions in ionic compounds make vaporization a complex process. The gas phase can contain a broad range of ionic clusters, and the cluster composition can differ greatly from that in the liquid phase. Room-temperature ionic liquids (RTILs) constitute a complicated case due to their ionic nature, asymmetric structure, and a huge versatility of ions and ionic clusters. This work reports vapor-liquid equilibria and vapor compositions of butylpyridinium (BPY) RTILs formed with hexafluorophosphate (PF6), trifluoromethanesulfonate (TF), and bis(trifluoromethanesulfonyl)imide (TFSI) anions. Unlike inorganic crystals, the pyridinium-based RTILs contain significant percentages of charged clusters in the vapor phase. Ion triplets and ion quadruplets each constitute up to 10% of the vapor phase composition. Triples prevail over quadruples in [BPY][PF6] due to the size difference of the cation and the anion. The percentage of charged ionic clusters in the gas phase is in inverse proportion to the mass of the anion. The largest identified vaporized ionic cluster comprises eight ions, with a formation probability below 1%. Higher temperature fosters formation of larger clusters due to an increase of the saturated vapor density. PMID:27165866

  11. Polymerization in emulsion microdroplet reactors

    NASA Astrophysics Data System (ADS)

    Carroll, Nick J.

    The goal of this research project is to utilize emulsion droplets as chemical reactors for execution of complex polymerization chemistries to develop unique and functional particle materials. Emulsions are dispersions of immiscible fluids where one fluid usually exists in the form of drops. Not surprisingly, if a liquid-to-solid chemical reaction proceeds to completion within these drops, the resultant solid particles will possess the shape and relative size distribution of the drops. The two immiscible liquid phases required for emulsion polymerization provide unique and complex chemical and physical environments suitable for the engineering of novel materials. The development of novel non-ionic fluorosurfactants allows fluorocarbon oils to be used as the continuous phase in a water-free emulsion. Such emulsions enable the encapsulation of almost any hydrocarbon compound in droplets that may be used as separate compartments for water-sensitive syntheses. Here, we exemplify the promise of this approach by suspension polymerization of polyurethanes (PU), in which the liquid precursor is emulsified into droplets that are then converted 1:1 into polymer particles. The stability of the droplets against coalescence upon removal of the continuous phase by evaporation confirms the formation of solid PU particles. These results prove that the water-free environment of fluorocarbon based emulsions enables high conversion. We produce monodisperse, cross-linked, and fluorescently labeled PU-latexes with controllable mesh size through microfluidic emulsification in a simple one-step process. A novel method for the fabrication of monodisperse mesoporous silica particles is presented. It is based on the formation of well-defined equally sized emulsion droplets using a microfluidic approach. The droplets contain the silica precursor/surfactant solution and are suspended in hexadecane as the continuous oil phase. The solvent is then expelled from the droplets, leading to

  12. Electrodialysis heterogeneous ion exchange membranes modified by SiO2 nanoparticles: fabrication and electrochemical characterization.

    PubMed

    Hosseini, S M; Ahmadi, Z; Nemati, M; Parvizian, F; Madaeni, S S

    2016-01-01

    In the current study mixed matrix heterogeneous cation exchange membranes were prepared by solution casting technique. The effect of SiO(2) nanoparticles in the polymeric solution on the physicochemical properties of prepared membranes was studied. Scanning optical microscope images showed uniform particle distribution and relatively uniform surfaces for the prepared membranes. The membrane water content was reduced by silica nanoparticles in the membranes' matrix. The membrane ion exchange capacity, membrane potential, transport number and selectivity were improved initially by an increase of SiO(2) nanoparticles concentration up to 1%wt in prepared membranes and then showed a decreasing trend with a further increase in additive ratio from 1 to 4%wt. The ionic permeability and flux were also decreased initially by an increase of silica nanoparticles concentration up to 0.5%wt in the membrane matrix and then increased again with a further increase in nanoparticles concentration from 0.5 to 4%wt. Moreover, the results exhibited that using silica nanoparticles in the membrane matrix caused an obvious decrease in areal electrical resistance. The opposite trend was found for membrane mechanical strength using SiO(2) nanoparticles. PMID:27148708

  13. Wettability by Ionic Liquids.

    PubMed

    Liu, Hongliang; Jiang, Lei

    2016-01-01

    Ionic liquids (ILs) have become particularly attractive recently because they have demonstrated themselves to be important construction units in the broad fields of chemistry and materials science, from catalysis and synthesis to analysis and electrochemistry, from functional fluids to clean energy, from nanotechnology to functional materials. One of the greatest issues that determines the performance of ILs is the wettability of correlated surfaces. In this concept article, the key developments and issues in IL wettability are surveyed, including the electrowetting of ILs in gas-liquid-solid systems and liquid-liquid-solid systems, ILs as useful probe fluids, the superwettability of Ils, and future directions in IL wettability. This should generate extensive interest in the field and encourage more scientists to engage in this area to tackle its scientific challenges. PMID:26619157

  14. Noble metal ionic catalysts.

    PubMed

    Hegde, M S; Madras, Giridhar; Patil, K C

    2009-06-16

    Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NO(x), and unburned hydrocarbons-need to be fully converted to CO(2), N(2), and H(2)O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al(2)O(3) or SiO(2) promoted by CeO(2). However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce(1-x)M(x)O(2-delta) and Ce(1-x-y)Ti(y)M(x)O(2-delta) (M = Pt, Pd, Rh; x = 0.01-0.02, delta approximately x, y = 0.15-0.25) oxides in fluorite structure. In these oxide catalysts, Pt(2+), Pd(2+), or Rh(3+) ions are substituted only to the extent of 1-2% of Ce(4+) ion. Lower-valent noble metal ion substitution in CeO(2) creates oxygen vacancies. Reducing molecules (CO, H(2), NH(3)) are adsorbed onto electron-deficient noble metal ions, while oxidizing (O(2), NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NO(x) reduction (with >80% N(2) selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO(2) or Ce(1-x)Ti(x)O(2) were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the

  15. Electrodeposition in Ionic Liquids.

    PubMed

    Zhang, Qinqin; Wang, Qian; Zhang, Suojiang; Lu, Xingmei; Zhang, Xiangping

    2016-02-01

    Due to their attractive physico-chemical properties, ionic liquids (ILs) are increasingly used as deposition electrolytes. This review summarizes recent advances in electrodeposition in ILs and focuses on its similarities and differences with that in aqueous solutions. The electrodeposition in ILs is divided into direct and template-assisted deposition. We detail the direct deposition of metals, alloys and semiconductors in five types of ILs, including halometallate ILs, air- and water-stable ILs, deep eutectic solvents (DESs), ILs with metal-containing cations, and protic ILs. Template-assisted deposition of nanostructures and macroporous structures in ILs is also presented. The effects of modulating factors such as deposition conditions (current density, current density mode, deposition time, temperature) and electrolyte components (cation, anion, metal salts, additives, water content) on the morphology, compositions, microstructures and properties of the prepared materials are highlighted. PMID:26530378

  16. Sulfonic acid catalysts prepared by radiation-induced graft polymerization

    SciTech Connect

    Mizota, Tomotoshi; Tsuneda, Satoshi; Saito, Kyoichi, Saito

    1994-09-01

    In this study, the authors prepared two variations of graft-type acid catalysts with different adjacent groups by radiation-induced graft polymerization (RIGP), and compared the hydrolytic activity of the resultant acid catalysts for methyl acetate with that of commercially available SO{sub 3}H-type ion-exchange beads with different degrees of cross-linking. 8 refs., 3 figs.

  17. A New Class of Ionic Liquids: Anion Amphiprotic Ionic Liquids.

    PubMed

    Treskow, Marcel; Pitawala, Jagath; Arenz, Sven; Matic, Aleksandar; Johansson, Patrik

    2012-08-16

    We here present a new class of protic ionic liquids, anion amphiprotic ionic liquids (AAILs). These materials are protonation equilibrium free protic ionic liquids and interesting in their own right by not following the classical Brønsted acid-base neutralization concept. Due to the very simple synthesis route applied and their stable basic chemistry, we believe in a potential use for manifold applications. This is supported by the combination of practical material properties, foremost, a general intrinsic stability versus reversal of the formation reaction toward neutral species, broad liquidus ranges, long-term thermal stabilities, high conductivities, protic characteristics, and a general stability versus water. PMID:26295756

  18. Biocompatibility of Cation Coated on Plasma-Polymerized Ti Surface

    NASA Astrophysics Data System (ADS)

    Lee, Kang; Ko, Yeong-Mu; Kim, Byung-Hoon

    2012-08-01

    In this study, we investigated the bone formation properties and cell responses on Na-, Mg-, K-, and Ca-ion-exchanged carboxyl plasma polymerized titanium (Ti) surfaces. The phase and morphologies of deposits bonelike apatite were significantly influence by the cation species. Na and Mg ions promote bonelike apatite nucleation and growth on plasma-functionalized Ti surfaces in simulated body fluid (SBF) and improves the crystallinity of the bonelike apatite deposited layer. The cell viability tests revealed significantly enhanced viability on the Ca-ion-exchanged plasma-functionalized Ti surface than on any other surface.

  19. Investigation of Four Different Laponite Clays as Stabilizers in Pickering Emulsion Polymerization.

    PubMed

    Brunier, Barthélémy; Sheibat-Othman, Nida; Chniguir, Mehdi; Chevalier, Yves; Bourgeat-Lami, Elodie

    2016-06-21

    Clay-armored polymer particles were prepared by emulsion polymerization in the presence of Laponite platelets that adsorb at the surface of latex particles and act as stabilizers during the course of the polymerization. While Laponite RDS clay platelets are most often used, the choice of the type of clay still remains an open issue that is addressed in the present article. Four different grades of Laponite were investigated as stabilizers in the emulsion polymerization of styrene. First, the adsorption isotherms of the clays, on preformed polystyrene particles, were determined by ICP-AES analysis of the residual clay in the aqueous phase. Adsorption of clay depended on the type of clay at low concentrations corresponding to adsorption as a monolayer. Adsorption of clay particles as multilayers was observed for all the grades above a certain concentration under the considered ionic strength (mainly due to the initiator ionic species). The stabilization efficiency of these clays was investigated during the polymerization reaction (free of any other stabilizer). The clays did not have the same effect on stabilization, which was related to differences in their compositions and in their adsorption isotherms. The different grades led to different polymer particles sizes and therefore to different polymerization reaction rates. Laponite RDS and S482 gave similar results, ensuring the best stabilization efficiency and the fastest reaction rate; the number of particles increased as the clay concentration increased. Stabilization with Laponite XLS gave the same particles size and number as the latter two clays at low clay concentrations, but it reached an upper limit in the number of nucleated polymer particles at higher concentrations indicating a decrease of stabilization efficiency at high concentrations. Laponite JS did not ensure a sufficient stability of the polymer particles, as the polymerization results were comparable to a stabilizer-free polymerization system

  20. Ionic dependence of sulphur mustard cytotoxicity

    SciTech Connect

    Sawyer, Thomas W. Nelson, Peggy; Bjarnason, Stephen; Vair, Cory; Shei Yimin; Tenn, Catherine; Lecavalier, Pierre; Burczyk, Andrew

    2010-09-15

    The effect of ionic environment on sulphur mustard (bis 2-chloroethyl sulphide; HD) toxicity was examined in CHO-K1 cells. Cultures were treated with HD in different ionic environments at constant osmolar conditions (320 mOsM, pH 7.4). The cultures were refed with fresh culture medium 1 h after HD exposure, and viability was assessed. Little toxicity was apparent when HD exposures were carried out in ion-free sucrose buffer compared to LC{sub 50} values of {approx} 100-150 {mu}M when the cultures were treated with HD in culture medium. Addition of NaCl to the buffer increased HD toxicity in a salt concentration-dependent manner to values similar to those obtained in culture medium. HD toxicity was dependent on both cationic and anionic species with anionic environment playing a much larger role in determining toxicity. Substitution of NaI for NaCl in the treatment buffers increased HD toxicity by over 1000%. The activity of the sodium hydrogen exchanger (NHE) in recovering from cytosolic acidification in salt-free and in different chloride salts did not correlate with the HD-induced toxicity in these buffers. However, the inhibition by HD of intracellular pH regulation correlated with its toxicity in NaCl, NaI and sucrose buffers. Analytical chemical studies and the toxicity of the iodine mustard derivative ruled out the role of chemical reactions yielding differentially toxic species as being responsible for the differences in HD toxicity observed. This work demonstrates that the early events that HD sets into motion to cause toxicity are dependent on ionic environment, possibly due to intracellular pH deregulation.

  1. Novel functionalized fluorescent polymeric nanoparticles for immobilization of biomolecules

    NASA Astrophysics Data System (ADS)

    Jain, Swati; Chattopadhyay, Sruti; Jackeray, Richa; Abid, C. K. V. Zainul; Singh, Harpal

    2013-07-01

    Novel, size controlled fluorescent polymeric nanoparticles (FPNP) were synthesized having acetoacetoxy functionality on the surface for immobilization of biomolecules which can be utilized as biomarkers and labels in fluoroimmunoassays. Core-shell nanoparticles of poly(styrene, St-methyl methacrylate, MMA-acetoacetoxy ethyl methacrylate, AAEM), stabilized by various concentrations of surfactant, sodium lauryl sulphate (SLS), were obtained by facile miniemulsion co-polymerization encapsulated with pyrene molecules in their hydrophobic core. Analytical, spectroscopic and imaging characterization techniques revealed the formation of stable, monodisperse, spherical nano sized particles exhibiting high luminescence properties. Particles with 1% SLS (S1) showed good dispersion stability and fluorescence intensity and were chosen as ideal candidates for further immobilization studies. Steady state fluorescence studies showed 10 times higher fluorescence intensity of S1 nanoparticles than that of pyrene solution in solvent-toluene at the same concentration. Environmental factors such as pH, ionic strength and time were found to have no effect on fluorescence intensity of FPNPs. Surface β-di-ketone groups were utilized for the covalent immobilization of enzyme conjugated antibodies without any activation or pre-treatment of nanoparticles.Novel, size controlled fluorescent polymeric nanoparticles (FPNP) were synthesized having acetoacetoxy functionality on the surface for immobilization of biomolecules which can be utilized as biomarkers and labels in fluoroimmunoassays. Core-shell nanoparticles of poly(styrene, St-methyl methacrylate, MMA-acetoacetoxy ethyl methacrylate, AAEM), stabilized by various concentrations of surfactant, sodium lauryl sulphate (SLS), were obtained by facile miniemulsion co-polymerization encapsulated with pyrene molecules in their hydrophobic core. Analytical, spectroscopic and imaging characterization techniques revealed the formation of stable

  2. Removal of charged micropollutants from water by ion-exchange polymers -- effects of competing electrolytes.

    PubMed

    Bäuerlein, Patrick S; Ter Laak, Thomas L; Hofman-Caris, Roberta C H M; de Voogt, Pim; Droge, Steven T J

    2012-10-15

    A wide variety of environmental compounds of concern, e.g. pharmaceuticals or illicit drugs, are acids or bases that may predominantly be present as charged species in drinking water sources. These charged micropollutants may prove difficult to remove by currently used water treatment steps (e.g. UV/H(2)O(2), activated carbon (AC) or membranes). We studied the sorption affinity of some ionic organic compounds to both AC and different charged polymeric materials. Ion-exchange polymers may be effective as additional extraction phases in water treatment, because sorption of all charged compounds to oppositely charged polymers was stronger than to AC, especially for the double-charged cation metformin. Tested below 1% of the polymer ion-exchange capacity, the sorption affinity of charged micropollutants is nonlinear and depends on the composition of the aqueous medium. Whereas oppositely charged electrolytes do not impact sorption of organic ions, equally charged electrolytes do influence sorption indicating ion-exchange (IE) to be the main sorption mechanism. For the tested polymers, a tenfold increased salt concentration lowered the IE-sorption affinity by a factor two. Different electrolytes affect IE with organic ions in a similar way as inorganic ions on IE-resins, and no clear differences in this trend were observed between the sulphonated and the carboxylated cation-exchanger. Sorption of organic cations is five fold less in Ca(2+) solutions compared to similar concentrations of Na(+), while that of anionic compounds is three fold weaker in SO(4)(2-) solutions compared to equal concentrations of Cl(-). PMID:22818952

  3. Properties of Water Confined in Ionic Liquids

    PubMed Central

    Saihara, Koji; Yoshimura, Yukihiro; Ohta, Soichi; Shimizu, Akio

    2015-01-01

    The varying states of water confined in the nano-domain structures of typical room temperature ionic liquids (ILs) were investigated by 1H NMR and by measurements of self-diffusion coefficients while systematically varying the IL cations and anions. The NMR peaks for water in BF4-based ILs were clearly split, indicating the presence of two discrete states of confined water (H2O and HOD). Proton and/or deuterium exchange rate among the water molecules was very slowly in the water-pocket. Notably, no significant changes were observed in the chemical shifts of the ILs. Self-diffusion coefficient results showed that water molecules exhibit a similar degree of mobility, although their diffusion rate is one order of magnitude faster than that of the IL cations and anions. These findings provide information on a completely new type of confinement, that of liquid water in soft matter. PMID:26024339

  4. Electroactive cellophane actuators: ionic or piezoelectric?

    NASA Astrophysics Data System (ADS)

    Je, Chung-hwan; Kim, Doyeon; Kim, Kwang Jin

    2004-07-01

    In this paper, we present a standard irreversible thermodynamic model to describe the working principle of electroactive cellophane bending actuators. Based upon the fact that cellophane possesses a number of important properties of interest including ion-exchange capability, high water absorptivity, and good permeability, under an imposed electric field across the bender the ions and conjugated solvent will create a redistribution of them within the cellophane matrix and lead to effective strain in the bender geometry. The results are compared against the available data in terms of tip displacement. Also, the effect of electrode-thickness is investigated. The present study focuses on a phenomenological description of cellulophane actuators although a piezoelectric model is not included. A study is currently under way to experimentally verify if the working principle of electroactive cellophane actuators is ionic or piezoelectric.

  5. Production of monodisperse, polymeric microspheres

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Rhim, Won-Kyu (Inventor); Hyson, Michael T. (Inventor); Chang, Manchium (Inventor)

    1990-01-01

    Very small, individual polymeric microspheres with very precise size and a wide variation in monomer type and properties are produced by deploying a precisely formed liquid monomer droplet, suitably an acrylic compound such as hydroxyethyl methacrylate into a containerless environment. The droplet which assumes a spheroid shape is subjected to polymerizing radiation such as ultraviolet or gamma radiation as it travels through the environment. Polymeric microspheres having precise diameters varying no more than plus or minus 5 percent from an average size are recovered. Many types of fillers including magnetic fillers may be dispersed in the liquid droplet.

  6. Melting line of polymeric nitrogen

    NASA Astrophysics Data System (ADS)

    Yakub, L. N.

    2013-05-01

    We made an attempt to predict location of the melting line of polymeric nitrogen using two equations for Helmholtz free energy: proposed earlier for cubic gauche-structure and developed recently for liquid polymerized nitrogen. The P-T relation, orthobaric densities and latent heat of melting were determined using a standard double tangent construction. The estimated melting temperature decreases with increasing pressure, alike the temperature of molecular-nonmolecular transition in solid. We discuss the possibility of a triple point (solid-molecular fluid-polymeric fluid) at ˜80 GPa and observed maximum of melting temperature of nitrogen.

  7. Fabrication of Poly(methyl Methacrylate) microfluidic chips by redox-initiated polymerization

    SciTech Connect

    Chen, Jiang; Lin, Yuehe; Chen, Gang

    2007-08-16

    In this report, a method based on the redox-initiated polymerization of methyl methacrylate (MMA) has been developed for the rapid fabrication of PMMA microfluidic chips.The new fabrication approach obviates the need for special equipment and significantly simplifies the process of fabricating microdevices. The attractive performance of the novel PMMA microchips has been demonstrated in connection with contactless conductivity detection for the separation and detection of ionic species.

  8. Organometallic Polymeric Conductors

    NASA Technical Reports Server (NTRS)

    Youngs, Wiley J.

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for

  9. Biological Ion Exchanger Resins

    PubMed Central

    Damadian, Raymond; Goldsmith, Michael; Zaner, K. S.

    1971-01-01

    Biological selectivity is shown to vary with medium osmotic strength and temperature. Selectivity reversals occur at 4°C and at an external osmolality of 0.800 indicating that intracellular hydration and endosolvent (intracellular water) structure are important determinants in selectivity. Magnetic resonance measurements of line width by steady-state nuclear magnetic resonance (NMR) indicate a difference in the intracellular water signal of 16 Hz between the K form and Na form of Escherichia coli, providing additional evidence that changes in the ionic composition of cells are accompanied by changes in endosolvent structure. The changes were found to be consistent with the thermodynamic and magnetic resonance properties of aqueous electrolyte solutions. Calculation of the dependence of ion-pairing forces on medium dielectric reinforces the role of endosolvent structure in determining ion exchange selectivity. PMID:4943653

  10. Dynamics of polymeric brushes: End exchange and bridging kinetics

    NASA Astrophysics Data System (ADS)

    Johner, A.; Joanny, J. F.

    1993-01-01

    We study some dynamical aspects of grafted polymer layers in a solvent. The structure of the brush is described in a θ solvent by the self-consistent mean field theory and in a good solvent using scaling laws. The Rouse-Zimm model including hydrodynamic interactions is used for the dynamic properties. A given chain end explores the entire thickness of a free grafted layer in a time Te proportional to the cube of the thickness. The exploration time is much larger than the Rouse time that characterizes the relaxation of the fluctuations of the chains conformations. In a θ-solvent we give a detailed study of the relaxation of the density of a few labeled chain ends towards its equilibrium value. The bridging kinetics between a grafting plate and a plate adsorbing the free ends is also discussed. When adsorption proceeds, an exclusion zone grows in the vicinity of the adsorbing plate. To cross the exclusion zone and adsorb, a chain end must overcome an energy barrier. The typical adsorption time is the first passage time through this barrier. Except in the very late stages where the fraction of chains η forming bridges saturates at its equilibrium value, the energy barrier against adsorption increases as a power law of η and the bridging fraction increases very slowly (logarithmically) with time. Both weak bridging where only a small fraction of chains form bridges and total bridging where all the chains form bridges are studied.

  11. Redox-active cross-linkable poly(ionic liquid)s.

    PubMed

    Sui, Xiaofeng; Hempenius, Mark A; Vancso, G Julius

    2012-03-01

    The synthesis of a new class of cross-linkable redox-responsive poly(ferrocenylsilane)-based poly(ionic liquid)s (PFS-PILs) is reported. PFS-PILs self-cross-link at low concentrations into nanogels or form macroscopic hydrogel networks at higher concentrations. PFS-PILs proved to be efficient dispersants in the microemulsion polymerization of methyl methacrylate, producing stable PFS-poly(methyl methacrylate) latex suspensions. PMID:22353019

  12. Characterization of polymeric nanomaterials using analytical ultracentrifugation.

    PubMed

    Diaz, Leosveys; Peyrot, Caroline; Wilkinson, Kevin J

    2015-06-16

    The characterization of nanomaterials represents a complex analytical challenge due to their dynamic nature (small size, high reactivity, and instability) and the low concentrations in the environment, often below typical analytical detection limits. Analytical ultracentrifugation (AUC) is especially useful for the characterization of small nanoparticles (1-10 nm), which are often the most problematic for the commonly used techniques such as electron microscopy or dynamic light scattering. In this study, small polymeric nanomaterials (allospheres) that are used commercially to facilitate the distribution of pesticides in agricultural fields were characterized under a number of environmentally relevant conditions. Under most of the studied conditions, the allospheres were shown to have a constant hydrodynamic diameter (dH) of about 7.0 nm. Only small increases in diameter were observed, either at low pH or very high ionic strength or hardness, demonstrating their high physicochemical stability (and thus high mobility in soils). Furthermore, natural organic matter had little effect on the hydrodynamic diameters of the allospheres. The concentration of the nanoparticles was an important parameter influencing their agglomeration-results obtained using dynamic light scattering at high particle concentrations showed large agglomerate sizes and significant particle losses through sedimentation, clearly indicating the importance of characterizing the nanomaterials under environmentally relevant conditions. PMID:25988704

  13. Low-noise polymeric nanomechanical biosensors

    NASA Astrophysics Data System (ADS)

    Calleja, Montserrat; Tamayo, Javier; Nordström, Maria; Boisen, Anja

    2006-03-01

    A sensor device based on a single polymer cantilever and optical readout has been developed for detection of molecular recognition reactions without the need of a reference cantilever for subtraction of unspecific signals. Microcantilevers have been fabricated in the photoresist SU-8 with one surface passivated with a thin fluorocarbon layer. The SU-8 surface is sensitized with biological receptors by applying silanization methods, whereas the fluorocarbon surface remains inert to these processes. The thermal and mechanical properties of the chosen materials allow overcoming the main limitations of gold-coated silicon cantilevers: the temperature, pH, and ionic strength cross sensitivities. This is demonstrated by comparing the response of SU-8 cantilevers and that of gold-coated silicon nitride cantilevers to variations in temperature and pH. The sensitivity of the developed polymeric nanomechanical sensor is demonstrated by real-time detection of the human growth hormone with sensitivity in differential surface stress of about 1mN /m.

  14. Design of Self-Healing Supramolecular Rubbers by Introducing Ionic Cross-Links into Natural Rubber via a Controlled Vulcanization.

    PubMed

    Xu, Chuanhui; Cao, Liming; Lin, Baofeng; Liang, Xingquan; Chen, Yukun

    2016-07-13

    Introducing ionic associations is one of the most effective approaches to realize a self-healing behavior for rubbers. However, most of commercial rubbers are nonpolar rubbers without now available functional groups to be converted into ionic groups. In this paper, our strategy was based on a controlled peroxide-induced vulcanization to generate massive ionic cross-links via polymerization of zinc dimethacrylate (ZDMA) in natural rubber (NR) and exploited it as a potential self-healable material. We controlled vulcanization process to retard the formation of covalent cross-link network, and successfully generated a reversible supramolecular network mainly constructed by ionic cross-links. Without the restriction of covalent cross-linkings, the NR chains in ionic supramolecular network had good flexibility and mobility. The nature that the ionic cross-links was easily reconstructed and rearranged facilitating the self-healing behavior, thereby enabling a fully cut sample to rejoin and retain to its original properties after a suitable self-healing process at ambient temperature. This study thus demonstrates a feasible approach to impart an ionic association induced self-healing function to commercial rubbers without ionic functional groups. PMID:27337545

  15. Influence of the ionic liquid cation on the solvent extraction of trivalent rare-earth ions by mixtures of Cyanex 923 and ionic liquids.

    PubMed

    Rout, Alok; Binnemans, Koen

    2015-01-21

    Trivalent rare-earth ions were extracted from nitric acid medium by the neutral phosphine oxide extractant Cyanex 923 into ionic liquid phases containing the bis(trifluoromethylsulfonyl)imide anion. Five different cations were considered: 1-butyl-3-methylimidazolium, 1-decyl-3-methylimidazolium, methyltributylammonium, methyltrioctylammonium and trihexyl(tetradecyl)phosphonium. The extraction behavior of neodymium(iii) was investigated as a function of various parameters: pH, extractant concentration, concentration of the neodymium(iii) ion in the aqueous feed and concentration of the salting-out agent. The loading capacity of the ionic liquid phase was studied. The extraction efficiency increased with increasing pH of the aqueous feed solution. The extraction occurred for all ionic liquids via an ion-exchange mechanism and the extraction efficiency could be related to the solubility of the ionic liquid cation in the aqueous phase: high distribution ratios for hydrophilic cations and low ones for hydrophobic cations. Addition of nitrate ions to the aqueous phase resulted in an increase in extraction efficiency for ionic liquids with hydrophobic cations due to extraction of neutral complexes. Neodymium(iii) could be stripped from the ionic liquid phase by 0.5-1.0 M nitric acid solutions and the extracting phase could be reused. The extractability of other rare earths present in the mixture was compared for the five ionic liquids. PMID:25423581

  16. Ionic liquid crosslinkers for chiral imprinted nanoGUMBOS.

    PubMed

    Hamdan, Suzana; Moore, Leonard; Lejeune, Jason; Hasan, Farhana; Carlisle, Trevor K; Bara, Jason E; Gin, D L; LaFrate, Andrew L; Noble, R D; Spivak, David A; Warner, Isiah M

    2016-02-01

    Molecularly imprinted polymers (MIPs) are an important class of selective materials for molecular specific sensors and separations. Molecular imprinting using non-covalent interactions in aqueous conditions still remains a difficult challenge due to interruption of hydrogen-bonding or electrostatic interactions water. Newly developed crosslinking ionic liquids are demonstrated herein to overcome problems of synthesizing aqueous MIPs, adding to previous examples of ionic liquids used as monomers in non-aqueous conditions or used as MIP solvents. Vinylimidazole ionic liquid crosslinkers were synthesized and subsequently explored as matrix supports for fabrication of molecularly imprinted polymeric nanoGUMBOS (nanoparticles derived from a group of uniform materials based on organic salts). Each of the four crosslinkers incorporated a unique functional spacer between the vinylimidazole groups, and the performance of the corresponding molecularly imprinted polymers was evaluated using chiral recognition as the diagnostic. High uptake values for l-tryptophan were found in the 13-87μmol/g range; and chiral recognition was determined via binding ratios of l-tryptophan over d-tryptophan that ranged from 5:1 to 13:1 for polymers made using different crosslinkers. Not only are these materials good for chiral recognition, but the results highlight the utility of these materials for imprinting aqueous templates such as biological targets for theranostic agents. PMID:26513734

  17. Partitioning of Laponite Clay Platelets in Pickering Emulsion Polymerization.

    PubMed

    Brunier, Barthélémy; Sheibat-Othman, Nida; Chevalier, Yves; Bourgeat-Lami, Elodie

    2016-01-12

    Partitioning of laponite disklike clay platelets between polymer particles and bulk aqueous phase was investigated in Pickering surfactant-free emulsion polymerization of styrene. Adsorption of laponite clay platelets plays an important role in the stabilization of this system, influencing the particle size and the number of particles, and, hence, the reaction rate. Adsorption isotherms show that, while the laponite clay platelets are almost fully exfoliated in water, they form multilayers on the surface of the polymer particles by the end of polymerization, as confirmed by transmission electron microscopy (TEM). This observation is supported by quartz crystal microbalance, conductivity, and TEM measurements, which reveal interactions between the clay and polystyrene, as a function of the ionic strength. The strong adsorption of clay platelets leaves a low residual concentration in the aqueous phase that cannot cause further nucleation of polymer particles, as demonstrated during seeded emulsion polymerization experiments in the presence of a high excess of clay. A Brunauer-Emmett-Teller (BET)-type model for laponite adsorption on polystyrene particles matches the adsorption isotherms. PMID:26653971

  18. Special Report: Solid Ionic Conductors.

    ERIC Educational Resources Information Center

    Shriver, Duward F.; Farrington, Gregory C.

    1985-01-01

    Solid ionic conductors are unusual materials that may find valuable applications in devices ranging from high-energy density batteries to lasers. The nature of these materials and their potential uses are discussed. (JN)

  19. Nonlinear ionic pulses along microtubules.

    PubMed

    Sekulić, D L; Satarić, B M; Tuszynski, J A; Satarić, M V

    2011-05-01

    Microtubules are cylindrically shaped cytoskeletal biopolymers that are essential for cell motility, cell division and intracellular trafficking. Here, we investigate their polyelectrolyte character that plays a very important role in ionic transport throughout the intra-cellular environment. The model we propose demonstrates an essentially nonlinear behavior of ionic currents which are guided by microtubules. These features are primarily due to the dynamics of tubulin C-terminal tails which are extended out of the surface of the microtubule cylinder. We also demonstrate that the origin of nonlinearity stems from the nonlinear capacitance of each tubulin dimer. This brings about conditions required for the creation and propagation of solitonic ionic waves along the microtubule axis. We conclude that a microtubule plays the role of a biological nonlinear transmission line for ionic currents. These currents might be of particular significance in cell division and possibly also in cognitive processes taking place in nerve cells. PMID:21604102

  20. Novel approaches to ionic chromatography

    SciTech Connect

    Dasgupta, P.K.

    1990-11-01

    Research during this reporting period, continued on ionic chromatography. Major progress has been made towards on-line on-demand generation of ultrapure chemicals by electrochemical means. The concentration of the generated material is governed electrochemically.

  1. Admicellar polymerization of precipated silica

    SciTech Connect

    Reynolds, J.L.; Grady, B.P.; Harwell, J.H.

    1996-10-01

    The tendency of a surfactant molecule to adsorb at a solid-liquid interface is the basis for an in situ surface modification process, termed admicellar polymerization. The four-step admicellar polymerization process includes: (1) adsorption of surfactant at the solid-liquid interface, (2) adsolubilization of monomer into the surfactant bilayer, (3) polymerization using free-radical initiators and heat, (4) removal of excess surfactant to expose the polymer modified surface. The process is used to apply polymer to precipitated silica to enhance the compatibility of the silica when added to filled rubber. The adsorption isotherms were first determined for particular surfactant/silica combinations to find the surfactant concentration that would sufficiently adsolubilize the monomer, while remaining below the critical micelle concentration. A series of experiments were then devised for the polymerization reactions in which the surfactant and monomer amounts were varied over three levels to establish the optimal combination.

  2. Polymerization of anionic wormlike micelles.

    PubMed

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles. PMID:16430253

  3. Kinetics of silica polymerization

    SciTech Connect

    Weres, O.; Yee, A.; Tsao, L.

    1980-05-01

    The polymerization of silicic acid in geothermal brine-like aqueous solutions to produce amorphous silica in colloidal form has been studied experimentally and theoretically. A large amount of high quality experimental data has been generated over the temperature rang 23 to 100{sup 0}C. Wide ranges of dissolved silica concentration, pH, and sodium chloride concentration were covered. The catalytic effects of fluoride and the reaction inhibiting effects of aluminum and boron were studied also. Two basic processes have been separately studied: the formation of new colloidal particles by the homogeneous nucleation process and the deposition of dissolved silica on pre-existing colloidal particles. A rigorous theory of the formation of colloidal particles of amorphous silica by homogeneous nucleation was developed. This theory employs the Lothe-Pound formalism, and is embodied in the computer code SILNUC which quantitatively models the homogeneous nucleation and growth of colloidal silica particles in more than enough detail for practical application. The theory and code were extensively used in planning the experimental work and analyzing the data produced. The code is now complete and running in its final form. It is capable of reproducing most of the experimental results to within experimental error. It is also capable of extrapolation to experimentally inaccessible conditions, i.e., high temperatures, rapidly varying temperature and pH, etc.

  4. Ionic Liquid Epoxy Resin Monomers

    NASA Technical Reports Server (NTRS)

    Paley, Mark S. (Inventor)

    2013-01-01

    Ionic liquid epoxide monomers capable of reacting with cross-linking agents to form polymers with high tensile and adhesive strengths. Ionic liquid epoxide monomers comprising at least one bis(glycidyl) N-substituted nitrogen heterocyclic cation are made from nitrogen heterocycles corresponding to the bis(glycidyl) N-substituted nitrogen heterocyclic cations by a method involving a non-nucleophilic anion, an alkali metal cation, epichlorohydrin, and a strong base.

  5. Hydrophobic ionic liquids

    DOEpatents

    Koch, V.R.; Nanjundiah, C.; Carlin, R.T.

    1998-10-27

    Ionic liquids having improved properties for application in non-aqueous batteries, electrochemical capacitors, electroplating, catalysis and chemical separations are disclosed. Exemplary compounds have one of the following formulas shown in a diagram wherein R{sub 1}, R{sub 2}, R{sub 3}, R{sub 4}, R{sub 5}, and R{sub 6} are either H; F; separate alkyl groups of from 1 to 4 carbon atoms, respectively, or joined together to constitute a unitary alkylene radical of from 2 to 4 carbon atoms forming a ring structure converging on N; or separate phenyl groups; and wherein the alkyl groups, alkylene radicals or phenyl groups may be substituted with electron withdrawing groups, preferably F-, Cl-, CF{sub 3}-, SF{sub 5}-, CF{sub 3}S-, (CF{sub 3}){sub 2}CHS- or (CF{sub 3}){sub 3}CS-; and X{sup {minus}} is a non-Lewis acid-containing polyatomic anion having a van der Waals volume exceeding 100 {angstrom}{sup 3}. 4 figs.

  6. Hydrophobic ionic liquids

    DOEpatents

    Koch, Victor R.; Nanjundiah, Chenniah; Carlin, Richard T.

    1998-01-01

    Ionic liquids having improved properties for application in non-aqueous batteries, electrochemical capacitors, electroplating, catalysis and chemical separations are disclosed. Exemplary compounds have one of the following formulas: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are either H; F; separate alkyl groups of from 1 to 4 carbon atoms, respectively, or joined together to constitute a unitary alkylene radical of from 2 to 4 carbon atoms forming a ring structure converging on N; or separate phenyl groups; and wherein the alkyl groups, alkylene radicals or phenyl groups may be substituted with electron withdrawing groups, preferably F--, Cl--, CF.sub.3 --, SF.sub.5 --, CF.sub.3 S--, (CF.sub.3).sub.2 CHS-- or (CF.sub.3).sub.3 CS--; and X.sup.- is a non-Lewis acid-containing polyatomic anion having a van der Waals volume exceeding 100 .ANG..sup.3.

  7. Synthesis and characterization of polyacrylonitrile nanoparticles by dispersion/emulsion polymerization process.

    PubMed

    Boguslavsky, Lior; Baruch, Sigal; Margel, Shlomo

    2005-09-01

    Polyacrylonitrile nanoparticles in sizes ranging from approximately 35 to 270 nm were prepared by dispersion/emulsion polymerization of acrylonitrile in a continuous aqueous phase in the presence of potassium persulfate as initiator and various alkyl-sulfate and sulfonate surfactants. The influence of various polymerization parameters (e.g., concentration of monomer and initiator, type and concentration of surfactant, temperature and time of polymerization, ionic strength, pH and co-solvent concentration) on the properties (e.g., size and size distribution, yield, stability, etc.) of the particles has been investigated. The polymerization of acrylonitrile may occur in two major locations: in the aqueous continuous phase (dispersion polymerization) and/or within the surfactant micelles (emulsion polymerization). A discussion concerning the role of these two mechanisms under different conditions, including comparison with previous literature, is also presented. Surface and bulk characterizations of the particles were performed by methods such as transmission and scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, zeta potential, and gravimetric measurements. PMID:16009219

  8. Investigation of microstructure and conducting mechanism of nanocomposite polymeric electrolytes with rectorite clay by PALS

    NASA Astrophysics Data System (ADS)

    Gao, S.; Gong, J.; Yan, X. L.; Xue, G. B.; Zhong, J.; Wang, B.

    2013-06-01

    Polymeric electrolytes with different modified organic nanoretorite (OREC) content have been prepared. Measurements of the structural transition, the positron annihilation lifetime, free volume and ionic conductivity as a function of the OREC content and the temperature have been performed. According to the variations of the ortho-positronium (o-Ps) lifetimes with temperature, the glass transition temperatures have been determined. A direct relationship between the ionic conductivity and the fractional free volume has been established using based on free volume theory Williams-Landel-Ferry (WLF)equations, implying a free-volume transport mechanism. Our experimental results indicated that the segmental chain motion and ionic migration and diffusion could be explained by the free volume theory.

  9. Alkaline Anion-Exchange Membranes Containing Mobile Ion Shuttles.

    PubMed

    Ge, Xiaolin; He, Yubin; Guiver, Michael D; Wu, Liang; Ran, Jin; Yang, Zhengjin; Xu, Tongwen

    2016-05-01

    A new class of alkaline anion-exchange membranes containing mobile ion shuttles is developed. It is achieved by threading ionic linear guests into poly(crown ether) hosts via host-guest molecular interaction. The thermal- and pH-triggered shuttling of ionic linear guests remarkably increases the solvation-shell fluctuations in inactive hydrated hydroxide ion complexes (OH(-) (H2 O)4 ) and accelerates the OH(-) transport. PMID:26972938

  10. Polymeric materials in Space

    NASA Astrophysics Data System (ADS)

    Skurat, Vladimir

    Paper of short review type. It is the continuation of and addition to previous review papers "V. E. Skurat. Polymers in Space. In: Encyclopedia of aerospace engineering, vol. 4, Wiley and sons, 2010; Ibid., 2012 (on line)". Following topics are considered: (1) Destruction of polymers by solar radiation with various wavelengths in different spectral regions (visible-UV, vacuum UV (VUV), deep UV, soft and hard X-rays) are discussed. In difference with common polymer photochemistry induced by UV radiation, directions of various routs of polymer phototransformations and their relative yields are greatly dependent on wavelength of light (photon energy) during illuminations in VUV, deep UV and X-ray regions. During last twenty years, intensive spacecraft investigations of solar spectrum show great periodic and spontaneous variations of radiation intensities in short-wavelengths regions - up to one - two decimal orders of magnitude for X-rays. As a result, during solar flares the absorbed dose on the polymer surfaces from X-rays can be compared with absorbed dose from VUV radiation. (2) Some new approaches to predictions of reaction efficiencies of fast orbital atomic oxygen in their interaction with polymeric materials are considered. (3) Some aspects of photocatalitic destruction of polymers in vacuum conditions by full-spectrum solar radiation are discussed. This process can take place in enamels containing semiconducting particles (TiO2, ZnO) as pigments. (4) Contamination of spacecraft surfaces from intrinsic outer atmosphere play important role not only from the point of view of deterioration of optical and thermophysical properties. Layers of SiO2 contaminations with nanometer thicknesses can greatly diminish mass losses from perfluorinated polymers under VUV irradiation.

  11. Polymeric materials for neovascularization

    NASA Astrophysics Data System (ADS)

    DeVolder, Ross John

    Revascularization therapies have emerged as a promising strategy to treat various acute and chronic wounds, cardiovascular diseases, and tissue defects. It is common to either administer proangiogenic growth factors, such as vascular endothelial growth factor (VEGF), or transplant cells that endogenously express multiple proangiogenic factors. Additionally, these strategies utilize a wide variety of polymeric systems, including hydrogels and biodegradable plastics, to deliver proangiogenic factors in a sophisticated manner to maintain a sustained proangiogenic environment. Despite some impressive results in rebuilding vascular networks, it is still a challenging task to engineer mature and functional neovessels in target tissues, because of the increasing complexities involved with neovascularization applications. To resolve these challenges, this work aims to design a wide variety of proangiogenic biomaterial systems with tunable properties used for neovascularization therapies. This thesis describes the design of several biomaterial systems used for the delivery of proangiogenic factors in neovascularization therapies, including: an electrospun/electrosprayed biodegradable plastic patch used for directional blood vessel growth (Chapter 2), an alginate-g-pyrrole hydrogel system that biochemically stimulates cellular endogenous proangiogenic factor expression (Chapter 3), an enzyme-catalyzed alginate-g-pyrrole hydrogel system for VEGF delivery (Chapter 4), an enzyme-activated alginate-g-pyrrole hydrogel system with systematically controllable electrical and mechanical properties (Chapter 5), and an alginate-g-pyrrole hydrogel that enables the decoupled control of electrical conductivity and mechanical rigidity and is use to electrically stimulate cellular endogenous proangiogenic factor expression (Chapter 6). Overall, the biomaterial systems developed in this thesis will be broadly useful for improving the quality of a wide array of molecular and cellular based

  12. Fabrication of a Multi-Walled Nanotube (MWNT) Ionic Liquid Electrode and Its Application for Sensing Phenolics in Red Wines

    PubMed Central

    Kim, Kyo-Il; Kang, Hee-Young; Lee, Jae-Chan; Choi, Seong-Ho

    2009-01-01

    A multi-walled nanotube (MWNT) ionic liquid was prepared by the immobilization of 1-butylimidazole bromide onto an epoxy group on a poly(glycidyl methacrylate)-grafted MWNT, which was synthesized by radiation-induced graft polymerization of glycidyl methacrylate onto MWNT in an aqueous solution. Subsequently, a MWNT ionic liquid electrode was fabricated by hand-casting MWNT ionic liquid, tyrosinase, and chitosan solution as a binder on indium tin oxide (ITO) glass. The sensing ranges of the MWNT ionic liquid electrode with immobilized tyrosinase was in the range of 0.01-0.08 mM in a phosphate buffer solution. The optimal conditions such as pH, temperature, and effects of different phenolic compounds were determined. The total phenolic compounds of three commercial red wines were also determined on the tyrosinase-immobilized biosensor. PMID:22399973

  13. β-Lactoglobulin (BLG) binding to highly charged cationic polymer-grafted magnetic nanoparticles: effect of ionic strength.

    PubMed

    Qin, Li; Xu, Yisheng; Han, Haoya; Liu, Miaomiao; Chen, Kaimin; Wang, Siyi; Wang, Jie; Xu, Jun; Li, Li; Guo, Xuhong

    2015-12-15

    Poly(2-(methacryloyloxy)ethyltrimethyl ammonium chloride) (PMATAC) modified magnetic nanoparticles (NPs) with a high zeta potential of ca. 50mV were synthesized by atom transfer radical polymerization (ATRP). The prepared NPs consist of a magnetic core around 13nm and a PMATAC shell around 20nm attached on the surface of magnetic nanoparticles. Thermodynamic binding parameters between β-lactoglobulin and these polycationic NPs were investigated at different ionic strengths by high-resolution turbidimetry, dynamic light scattering (DLS), and isothermal titration calorimetry (ITC). Both turbidity and ITC show that binding affinities for BLG display a non-monotonic ionic strength dependence trend and a maximum appears at ionic strength of 50mM. Such observation should arise from the coeffects of protein charge anisotropy visualized by DelPhi electrostatic modeling and the strong electrostatic repulsion among highly charged NPs at a variety of ionic strengths. PMID:26322494

  14. Enhanced ionic oxygen flow through mixed ionic-electronic conducting membranes: Directional dependence, composite construction and the partial oxidation of methane

    NASA Astrophysics Data System (ADS)

    Gerdes, Kirk R.

    Mixed Ionic-Electronic Conducting (MIEC) membranes transport ions and electrons in a crystalline matrix. Ionic transport occurs through MIEC materials in the presence of an applied ionic potential gradient. MIEC membranes form a special class of ionic conductors with primary applications as membrane separators, sensors, and components in solid oxide fuel cells. Current efforts focus on separation of oxygen from air for supply to high temperature reactions. One such reaction is the methane partial oxidation to synthesis gas (CO and H2). Certain MIEC membrane characteristics are required for a methane partial oxidation reactor: (1) the cost of the material must be economical on a tube cost per mol oxygen transported basis; (2) the membrane must be stable in steep oxygen partial pressure gradients and in the presence of reducing gases; (3) the membrane must be stable at temperatures exceeding 800°C without fracturing due to thermal stress. Two mechanisms govern the transport of oxygen through MIEC membranes: surface exchange at the MIEC/gas surface and ionic transport through the MIEC bulk. Most MIEC membranes conduct oxygen with a mixed transport mechanism, i.e., both surface exchange and bulk diffusion affect the total transport. We investigate the relative importance of bulk diffusion versus surface exchange in MIEC tubular and disk membranes made of La0.5Sr0.5Fe 0.8Ga0.2O3-delta. We propose a proof based on the currently accepted transport model for the directional dependence of ionic flow through a tubular MIEC. We qualitatively confirm directional dependence using a novel experimental system. Further, we propose a model for ionic flow in a composite membrane system consisting of a dense, tubular LSFG substrate with a thin, dense layer of SrCox Fe1-xO3-delta applied to the surface(s). Comparisons are made between the performance of the monolithic membrane tube and the layered composite membrane tube. A layered composite tubular membrane is constructed and tested

  15. Giant exchange interaction in mixed lanthanides

    PubMed Central

    Vieru, Veacheslav; Iwahara, Naoya; Ungur, Liviu; Chibotaru, Liviu F.

    2016-01-01

    Combining strong magnetic anisotropy with strong exchange interaction is a long standing goal in the design of quantum magnets. The lanthanide complexes, while exhibiting a very strong ionic anisotropy, usually display a weak exchange coupling, amounting to only a few wavenumbers. Recently, an isostructural series of mixed (Ln = Gd, Tb, Dy, Ho, Er) have been reported, in which the exchange splitting is estimated to reach hundreds wavenumbers. The microscopic mechanism governing the unusual exchange interaction in these compounds is revealed here by combining detailed modeling with density-functional theory and ab initio calculations. We find it to be basically kinetic and highly complex, involving non-negligible contributions up to seventh power of total angular momentum of each lanthanide site. The performed analysis also elucidates the origin of magnetization blocking in these compounds. Contrary to general expectations the latter is not always favored by strong exchange interaction. PMID:27087470

  16. Giant exchange interaction in mixed lanthanides

    NASA Astrophysics Data System (ADS)

    Vieru, Veacheslav; Iwahara, Naoya; Ungur, Liviu; Chibotaru, Liviu F.

    2016-04-01

    Combining strong magnetic anisotropy with strong exchange interaction is a long standing goal in the design of quantum magnets. The lanthanide complexes, while exhibiting a very strong ionic anisotropy, usually display a weak exchange coupling, amounting to only a few wavenumbers. Recently, an isostructural series of mixed (Ln = Gd, Tb, Dy, Ho, Er) have been reported, in which the exchange splitting is estimated to reach hundreds wavenumbers. The microscopic mechanism governing the unusual exchange interaction in these compounds is revealed here by combining detailed modeling with density-functional theory and ab initio calculations. We find it to be basically kinetic and highly complex, involving non-negligible contributions up to seventh power of total angular momentum of each lanthanide site. The performed analysis also elucidates the origin of magnetization blocking in these compounds. Contrary to general expectations the latter is not always favored by strong exchange interaction.

  17. Giant exchange interaction in mixed lanthanides.

    PubMed

    Vieru, Veacheslav; Iwahara, Naoya; Ungur, Liviu; Chibotaru, Liviu F

    2016-01-01

    Combining strong magnetic anisotropy with strong exchange interaction is a long standing goal in the design of quantum magnets. The lanthanide complexes, while exhibiting a very strong ionic anisotropy, usually display a weak exchange coupling, amounting to only a few wavenumbers. Recently, an isostructural series of mixed (Ln = Gd, Tb, Dy, Ho, Er) have been reported, in which the exchange splitting is estimated to reach hundreds wavenumbers. The microscopic mechanism governing the unusual exchange interaction in these compounds is revealed here by combining detailed modeling with density-functional theory and ab initio calculations. We find it to be basically kinetic and highly complex, involving non-negligible contributions up to seventh power of total angular momentum of each lanthanide site. The performed analysis also elucidates the origin of magnetization blocking in these compounds. Contrary to general expectations the latter is not always favored by strong exchange interaction. PMID:27087470

  18. Dual Ionic and Organic Nature of Ionic Liquids

    PubMed Central

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids—a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs. PMID:26782660

  19. Dual Ionic and Organic Nature of Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids—a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs.

  20. Dual Ionic and Organic Nature of Ionic Liquids.

    PubMed

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids--a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs. PMID:26782660

  1. Polymeric bicontinuous microemulsions

    NASA Astrophysics Data System (ADS)

    Krishnan, Kasiraman

    Rheology of complex fluids has been a topic of considerable interest recently. Bicontinuous microemulsions (BmuE), made by mixing appropriate amounts of oil, water and a surfactant, form a unique class of complex fluids. They possess a characteristic nanostructure consisting of undulating surfaces with vanishingly small interfacial curvature. BmuEs can also be generated in polymers by mixing appropriate amounts of two homopolymers and their corresponding diblock copolymer. The main objective of the present research is to study effects of shear on a model polymeric BmuE. Scattering is used as a predominant tool with in situ flow devices, along with optical microscopy and rheology. The model BmuE consists of a ternary blend of poly(ethyl ethylene) (PEE), poly(dimethyl siloxane) (PDMS) and a PEE-PDMS diblock copolymer. Steady shear experiments reveal four regimes as a function of shear rate. At low shear rates (regime I), Newtonian behavior is observed; there is onset of shear thinning at higher rates (regime II). In regime III, the stress is independent of shear rate, whereas it increases with shear rate once again in regime IV. Morphological characterization was carried out for each of these four regimes using scattering and microscopy, the key result being the evidence for flow-induced phase separation in regime III. Transient rheological measurements were conducted for startup and step changes in shear rate, and the BmuE exhibits features similar to worm-like micellar colloidal systems. Time-resolved light scattering and microscopy also reveal interesting characteristics. Dynamic mechanical spectroscopy indicates similarities with neat block copolymers near the order-disorder transition. The equilibrium rheological behavior is intriguing and detailed comparisons are made with Landau-Ginzburg theoretical models. Other areas of research as a part of this thesis include study of structural dynamics of BmuEs with dynamic light scattering, and the rheological

  2. Stereospecific olefin polymerization catalysts

    DOEpatents

    Bercaw, John E.; Herzog, Timothy A.

    1998-01-01

    A metallocene catalyst system for the polymerization of .alpha.-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula ##STR1## wherein: R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; R.sup.4 and R.sup.6 are substituents both having van der Waals radii larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ; R.sup.5 is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E.sup.1, E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; and the ligand may have C.sub.S or C.sub.1 -symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from .alpha.-olefin monomers.

  3. Stereospecific olefin polymerization catalysts

    DOEpatents

    Bercaw, J.E.; Herzog, T.A.

    1998-01-13

    A metallocene catalyst system is described for the polymerization of {alpha}-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula shown wherein: R{sup 1}, R{sup 2}, and R{sup 3} are independently selected from the group consisting of hydrogen, C{sub 1} to C{sub 10} alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C{sub 1} to C{sub 10} alkyls as a substituent, C{sub 6} to C{sub 15} aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R{sup 8}){sub 3} where R{sup 8} is selected from the group consisting of C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; R{sup 4} and R{sup 6} are substituents both having van der Waals radii larger than the van der Waals radii of groups R{sup 1} and R{sup 3}; R{sup 5} is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E{sup 1}, E{sup 2} are independently selected from the group consisting of Si(R{sup 9}){sub 2}, Si(R{sup 9}){sub 2}--Si(R{sup 9}){sub 2}, Ge(R{sup 9}){sub 2}, Sn(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}--C(R{sup 9}){sub 2}, where R{sup 9} is C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; and the ligand may have C{sub S} or C{sub 1}-symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from {alpha}-olefin monomers.

  4. Ionic Graphitization of Ultrathin Films of Ionic Compounds.

    PubMed

    Kvashnin, A G; Pashkin, E Y; Yakobson, B I; Sorokin, P B

    2016-07-21

    On the basis of ab initio density functional calculations, we performed a comprehensive investigation of the general graphitization tendency in rocksalt-type structures. In this paper, we determine the critical slab thickness for a range of ionic cubic crystal systems, below which a spontaneous conversion from a cubic to a layered graphitic-like structure occurs. This conversion is driven by surface energy reduction. Using only fundamental parameters of the compounds such as the Allen electronegativity and ionic radius of the metal atom, we also develop an analytical relation to estimate the critical number of layers. PMID:27333810

  5. HEAT EXCHANGER

    DOEpatents

    Fox, T.H. III; Richey, T. Jr.; Winders, G.R.

    1962-10-23

    A heat exchanger is designed for use in the transfer of heat between a radioactive fiuid and a non-radioactive fiuid. The exchanger employs a removable section containing the non-hazardous fluid extending into the section designed to contain the radioactive fluid. The removable section is provided with a construction to cancel out thermal stresses. The stationary section is pressurized to prevent leakage of the radioactive fiuid and to maintain a safe, desirable level for this fiuid. (AEC)

  6. Kinetic regimes of polyelectrolyte exchange between the adsorbed state and free solution

    NASA Astrophysics Data System (ADS)

    Sukhishvili, Svetlana A.; Granick, Steve

    1998-10-01

    We studied the exchange between the adsorbed state and free solution when polyelectrolyte chains, adsorbed to a solid surface of opposite charge, were displaced by chains of higher charge density. Metastable states of surface composition were extremely long-lived (>2-3 days). The system was a family of poly(1,4 vinyl)pyridines (PVP) with different fractions of charged segments (14%, 48%, and 98% quaternized and the same degree of polymerization); samples were exposed sequentially from aqueous D2O solution to a single silicon oxide substrate at pH where the surface carried a large negative charge (pH=9.2 or 10.5). Measurements were based on Fourier transform infrared spectroscopy in attenuated total reflection (FTIR-ATR). As a first conclusion, we found charge of adsorbed polymer to be conserved during extended exchange times, suggesting that charge at the surface (not mass adsorbed) regulated the dynamics of adsorption and desorption. Except at the highest ionic strength charge of polymer at the surface during the displacement process considerably exceeded that for the initially-adsorbed layer, suggesting an intermediate state in which newly-adsorbed chains were more extended from the surface and not yet equilibrated in their conformations. Second, we concluded that desorption was the rate-limiting step in adsorption-desorption, since the desorption rate responded more to changes of ionic strength than did the adsorption rate onto previously-adsorbed polymer. Ionic strength appeared to modulate the intensity of sticking to the surface. Third, we found that the initial stages of desorption obeyed a simple functional form, exponential in the square root of elapsed time. This is conclusively slower than a first-order kinetic process and suggests that desorption in this polyelectrolyte system was diffusion-controlled during the initial stages. It is the same functional form observed for flexible polymers in nonpolar solvents. Fourth, we concluded that at relatively low

  7. A Colorful Ion Exchange Experiment

    NASA Astrophysics Data System (ADS)

    Mendes, Adélio

    1999-11-01

    A colorful ion-exchange experiment is described. The use of a resin with an adsorbed acid-base indicator allows students to follow the progress of the ion-exchange front along the column. In parallel, students can follow the ion-exchange breakthrough curve using a continuous conductometric cell at the column outlet. In the present example, K+ (KCl) exchanges with H+ (HCl) in a strong cationic resin (Amberlite IR 120). The adsorbed indicator is methyl violet. Sorption equilibrium is favorable to the K+ ions. Monovalent ions, used in this experiment, have the disadvantage of usually being colorless (except perhaps permanganate, but this is an extremely strong oxidant which attacks the resin). On the other hand, many divalent ions are colorful but the shape of the concentration front is hard to explain qualitatively as well as quantitatively. That is because the shape of the front depends on the total ionic concentration. However, color can be introduced in a monovalent ion-exchange system by adding an appropriate acid-base indicator to the resin. The text describes this experiment qualitatively. A simplified quantitative description, using the solute movement theory, can be found online.

  8. Electronically and ionically conductive porous material and method for manufacture of resin wafers therefrom

    DOEpatents

    Lin, YuPo J.; Henry, Michael P.; Snyder, Seth W.

    2011-07-12

    An electrically and ionically conductive porous material including a thermoplastic binder and one or more of anion exchange moieties or cation exchange moieties or mixtures thereof and/or one or more of a protein capture resin and an electrically conductive material. The thermoplastic binder immobilizes the moieties with respect to each other but does not substantially coat the moieties and forms the electrically conductive porous material. A wafer of the material and a method of making the material and wafer are disclosed.

  9. Electronically and ionically conductive porous material and method for manufacture of resin wafers therefrom

    DOEpatents

    Lin, YuPo J.; Henry, Michael P.; Snyder, Seth W.

    2008-11-18

    An electrically and ionically conductive porous material including a thermoplastic binder and one or more of anion exchange moieties or cation exchange moieties or mixtures thereof and/or one or more of a protein capture resin and an electrically conductive material. The thermoplastic binder immobilizes the moieties with respect to each other but does not substantially coat the moieties and forms the electrically conductive porous material. A wafer of the material and a method of making the material and wafer are disclosed.

  10. 81891 - A New Class of Solvents for TRU Dissolution and Separation: Ionic Liquids

    SciTech Connect

    Robin D. Rogers

    2004-12-10

    Through the current EMSP funding, solvent extraction technologies based on liquid-liquid partitioning of TRU to an Ionic Liquid phase containing conventional complexants has been shown to be viable. The growing understanding of the role that the different components of an ionic liquid can have on the partitioning mechanism, and on the nature of the subsequent dissolved species indicates strongly that ionic liquids are not necessarily direct replacements for volatile or otherwise hazardous organic solvents. Separations and partitioning can be exceptionally complex with competing solvent extraction, cation, anion and sacrificial ion exchange mechanisms are all important, depending on the selection of components for formation of the ionic liquid phase, and that control of these competing mechanisms can be utilized to provide new, alternative separations schemes.

  11. Revisiting ether-derivatized imidazolium-based ionic liquids.

    PubMed

    Fei, Zhaofu; Ang, Wee Han; Zhao, Dongbin; Scopelliti, Rosario; Zvereva, Elena E; Katsyuba, Sergey A; Dyson, Paul J

    2007-08-30

    A series of ether-derivatized imidazolium halides have been prepared and characterized. Contrary to literature reports, they are all crystalline solids and have melting points well above room temperature (50-100 degrees C). Single crystals of the imidazolium salts, obtained in situ by slow cooling from their molten state to room temperature, were analyzed by X-ray crystallography, revealing various anion-cation interactions in the solid state. Exchange of the halides with [Tf(2)N]- yielded room temperature ionic liquids with viscosities that are comparable to related 1-alkyl-3-methylimidazolium ionic liquids. Density functional theory combined with IR spectroscopy has been used to analyze the role of functionalization of the imidazolium side chain on the formation of the molecular and supramolecular structure of the compounds and its possible impact on their physical properties. PMID:17676796

  12. Deciphering Physical versus Chemical Contributions to the Ionic Conductivity of Functionalized Poly(methacrylate)-Based Ionogel Electrolytes.

    PubMed

    D'Angelo, Anthony J; Grimes, Jerren J; Panzer, Matthew J

    2015-11-25

    Polymer-supported ionic liquids (ionogels) are emergent, nonvolatile electrolytes for electrochemical energy storage applications. Here, chemical and physical interactions between the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI TFSI) and three different cross-linked polymer scaffolds with varying chemical functional groups have been investigated in ionogels fabricated via in situ UV-initiated radical polymerization of methyl methacrylate (MMA), 2,2,2-trifluoroethyl methacrylate (TFEMA), or 2-(dimethylamino)ethyl methacrylate (DMAEMA) and a small amount of the cross-linker pentaerythritol tetraacrylate. Experimental findings demonstrate that the chemical functionality of the polymer side groups can significantly affect the degree of ion dissociation within the ionic liquid component of the ionogel and that the fraction of dissociated ions is the dominant factor in determining relative ionic conductivity in these materials, rather than any large differences in ion diffusivity. The MMA-based polymer scaffold exhibits a stronger attractive interaction with EMI TFSI (as evidenced by a higher activation energy of ionic conductivity) compared to the TFEMA- and DMAEMA-based scaffolds, resulting in consistently lower ionic conductivity values for MMA-based ionogels. These results may offer guidance toward the rational selection of future polymer-ionic liquid pairings in order to maximize the fraction of dissociated ions, thereby yielding highly conductive ionogel electrolytes. PMID:26528868

  13. Preparation of molecularly imprinted polymers for strychnine by precipitation polymerization and multistep swelling and polymerization and their application for the selective extraction of strychnine from nux-vomica extract powder.

    PubMed

    Nakamura, Yukari; Matsunaga, Hisami; Haginaka, Jun

    2016-04-01

    Monodisperse molecularly imprinted polymers for strychnine were prepared by precipitation polymerization and multistep swelling and polymerization, respectively. In precipitation polymerization, methacrylic acid and divinylbenzene were used as a functional monomer and crosslinker, respectively, while in multistep swelling and polymerization, methacrylic acid and ethylene glycol dimethacrylate were used as a functional monomer and crosslinker, respectively. The retention and molecular recognition properties of the molecularly imprinted polymers prepared by both methods for strychnine were evaluated using a mixture of sodium phosphate buffer and acetonitrile as a mobile phase by liquid chromatography. In addition to shape recognition, ionic and hydrophobic interactions could affect the retention of strychnine in low acetonitrile content. Furthermore, molecularly imprinted polymers prepared by both methods could selectively recognize strychnine among solutes tested. The retention factors and imprinting factors of strychnine on the molecularly imprinted polymer prepared by precipitation polymerization were 220 and 58, respectively, using 20 mM sodium phosphate buffer (pH 6.0)/acetonitrile (50:50, v/v) as a mobile phase, and those on the molecularly imprinted polymer prepared by multistep swelling and polymerization were 73 and 4.5. These results indicate that precipitation polymerization is suitable for the preparation of a molecularly imprinted polymer for strychnine. Furthermore, the molecularly imprinted polymer could be successfully applied for selective extraction of strychnine in nux-vomica extract powder. PMID:26914809

  14. Lithium ion conducting ionic electrolytes

    DOEpatents

    Angell, C.A.; Xu, K.; Liu, C.

    1996-01-16

    A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100 C or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors. 4 figs.

  15. Lithium ion conducting ionic electrolytes

    DOEpatents

    Angell, C. Austen; Xu, Kang; Liu, Changle

    1996-01-01

    A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100.degree. C. or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors.

  16. Group transfer polymerization. Mechanism revisted

    SciTech Connect

    Sogah, D.Y.

    1993-12-31

    Group Transfer Polymerization (GTP) is a living polymerization technique that allows control of characteristics of vinyl polymers, especially those derived from methacrylate monomers. Several mechanistic pathways have been proposed by different research groups. This presentation will examine the most plausible mechanisms and the evidence supporting each one. The dependence of the reaction on the type, nature and concentrations of catalysts, other additives, initiators and monomers will be discussed. The crucial role that chiral organosilicon reagents may play will be examined using a novel cyclic initiator containing 2,2`-dialkylsilyl-1,1`-binaphthyl.

  17. Deactivator for olefin polymerization catalyst

    SciTech Connect

    Rekers, L.J.; Speca, A.N.; Mayhew, H.W.

    1987-03-10

    A method is described comprising deactivating an olefin polymerization catalyst selected from the group consisting of Ziegler-Natta transition element catalysts and catalysts based on transition metal oxides by contacting the catalyst with a copolymer. The copolymer consists of an alpha-olefin having from 2 to about 12 carbon atoms and an unsaturated ester of a carboxylic acid. The deactivating copolymer is present in an amount such that the molar ratio of the unsaturated ester thereof to the sum of the transition element component of the polymerization catalyst and a cocatalyst for the transition element catalyst is in the range of between about 0.1 and about 6.

  18. On-demand photoinitiated polymerization

    DOEpatents

    Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa

    2013-12-10

    Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

  19. On-demand photoinitiated polymerization

    DOEpatents

    Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa

    2015-01-13

    Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

  20. Influence of chemical microstructure of single-ion polymeric electrolyte membranes on performance of lithium-ion batteries.

    PubMed

    Zhang, Yunfeng; Rohan, Rupesh; Cai, Weiwei; Xu, Guodong; Sun, Yubao; Lin, An; Cheng, Hansong

    2014-10-22

    A novel protocol to generate and control porosity in polymeric structures is presented for fabrication of single ion polymer electrolyte (SIPE) membranes for lithium ion batteries. A series of SIPEs with varying ratios of aliphatic and aromatic segments was successfully synthesized and subsequently blended with PVDF-HFP to fabricate membranes of various sizes of pores. The membranes were characterized using techniques including SEM, solvent uptake capacity measurement and ionic conductivity. We demonstrate that appropriate membrane porosity enhances ionic conductivity, reduces interfacial resistance between electrodes and electrolyte and ultimately boosts performance of Li-ion batteries. The implication of the structure-performance relationship for battery design is discussed. PMID:25225970

  1. Ionic conductivity studies of gel polyelectrolyte based on ionic liquid

    NASA Astrophysics Data System (ADS)

    Cha, E. H.; Lim, S. A.; Park, J. H.; Kim, D. W.; Macfarlane, D. R.

    Novel lithium polyelectrolyte-ionic liquids have been prepared and characterized of their properties. Poly(lithium 2-acrylamido-2-methyl propanesulfonate) (PAMPSLi) and its copolymer with N-vinyl formamide (VF) also has been prepared as a copolymer. 1-Ethyl-3-methylimidazolium tricyanomethanide (emImTCM) and N, N-dimethyl- N-propyl- N-butyl ammonium tricyanomethanide (N 1134TCM) which are chosen because of the same with the anion of ionic liquid were prepared. The ionic conductivity of copolymer system (PAMPSLi/PVF/emImTCM: 5.43 × 10 -3 S cm -1 at 25 °C) exhibits about over four times higher than that of homopolymer system (PAMPSLi/emImTCM: 1.28 × 10 -3 S cm -1 at 25 °C). Introduction of vinyl formamide into the copolymer type can increase the dissociation of the lithium cations from the polymer backbone. The ionic conductivity of copolymer with emImTCM (PAMPSLi/PVF/emImTCM) exhibits the higher conductivity than that of PAMPSLi/PVF/N 1134TCM (2.48 × 10 -3 S cm -1). Because of using the polymerizable anion it is seen to maintain high flexibility of imidazolium cation effectively to exhibit the higher conductivity. And also the viscosity of emImTCM (19.56 cP) is lower than that of N 1134TCM (28.61 cP). Low viscosity leads to a fast rate of diffusion of redox species.

  2. Balanced charge injection in multilayer polymer light-emitting diode with water soluble nonconjugated polymer dispersed by ionic compounds

    NASA Astrophysics Data System (ADS)

    Park, Dong-Kyu; Chun, A.-Rum; Kim, Soo-Hong; Kim, Min-Sook; Kim, Choong-Gi; Kwon, Tae-Woo; Cho, Seong-Jin; Woo, Hyung-Suk; Lee, Jae-Gyoung; Lee, Suck-Hyun; Guo, Zhi-Xin

    2007-07-01

    The authors have fabricated highly efficient polymeric light-emitting diode (PLED) from ionic compound dispersed water soluble nonconjugated polymer, polyurethane (PU), which was used as an ultrathin hole blocking and electron injection layer (HB-EIL) on the top of commercially available blue-emitting polymer, polyfluorene. The device with HB-EIL showed a maximum quantum efficiency of 1.7%, while the one without HB-EIL showed an efficiency of 0.6%. They propose that the better performance in PLED with PU layer was due to a well balanced charge injection in emitting layer after the enhanced electron injection due to ionic compound in the insulating PU layer.

  3. Polymeric additives for antistatic treatment of sheet molding composites (SMC)

    NASA Astrophysics Data System (ADS)

    Gedan-Smolka, Michaela; Schubert, Katrin; Taeger, Antje; Marks, Hagen

    2016-03-01

    Novel oligomeric/polymeric additives with ionic units were synthesized in a one pot procedure in order to enhance the specific surface resistivity of SMC-materials. In contrast to industrially used inorganic salts or carbon materials, such as carbon black or CNT's, these substances are nearly colorless and matrix compatible and, resulting from that, easy to homogenize with the SMC-matrix. Furthermore, it was found, that additives which can be covalently bonded to the matrix during the molding procedure are preferred compared to physically mixed substances. The effectiveness of chemically bonded substances regarding with the lowering of the specific surface resistivity is higher and selected additives do not change the reactivity and resulting mechanical properties of the molded material.

  4. Alkali oxide-tantalum, niobium and antimony oxide ionic conductors

    NASA Technical Reports Server (NTRS)

    Roth, R. S.; Brower, W. S.; Parker, H. S.; Minor, D. B.; Waring, J. L.

    1975-01-01

    The phase equilibrium relations of four systems were investigated in detail. These consisted of sodium and potassium antimonates with antimony oxide and tantalum and niobium oxide with rubidium oxide as far as the ratio 4Rb2O:llB2O5 (B=Nb, Ta). The ternary system NaSbO3-Sb2O4-NaF was investigated extensively to determine the actual composition of the body centered cubic sodium antimonate. Various other binary and ternary oxide systems involving alkali oxides were examined in lesser detail. The phases synthesized were screened by ion exchange methods to determine mobility of the mobility of the alkali ion within the niobium, tantalum or antimony oxide (fluoride) structural framework. Five structure types warranted further investigation; these structure types are (1) hexagonal tungsten bronze (HTB), (2) pyrochlore, (3) the hybrid HTB-pyrochlore hexagonal ordered phases, (4) body centered cubic antimonates and (5) 2K2O:3Nb2O5. Although all of these phases exhibit good ion exchange properties only the pyrochlore was prepared with Na(+) ions as an equilibrium phase and as a low porosity ceramic. Sb(+3) in the channel interferes with ionic conductivity in this case, although relatively good ionic conductivity was found for the metastable Na(+) ion exchanged analogs of RbTa2O5F and KTaWO6 pyrochlore phases.

  5. Separation of Fission Products Based on Ionic Liquids: Anion Effect

    SciTech Connect

    Luo, Huimin; Dai, Sheng; Bonnesen, Peter V.

    2004-03-28

    The applications of ionic liquids (ILs) as new separation media have been actively investigated recently. The most commonly studied class of ILs for such applications is based on dialkyl imidazolium cations. In comparison with conventional molecular solvents, ILs exhibit enhanced distribution coefficients for a number of complexing neutral ligands in extraction of metal ions from aqueous solutions. The effect of the alkyl chain length of imidazolium cations on the distribution coefficients of solvent extraction using crown ethers was the subject of a number of the previous investigations. The distribution coefficients have been found to decrease with the alkyl chain length of the IL cations. This observation implies that the extraction process also involves the exchange of the IL cations with metal ions. The longer the alkyl chain lengths of the IL cations are, the more hydrophobic the IL cations are and the more difficult to be transported into aqueous phases via ion exchange. Accordingly, the ion-exchange process is another unique property of IL-based extractions involving charged species. Here, we report the investigation about the effect of the variation of IL anions on the solvent extraction of metal ions using crown ethers as extractants. The elucidation of different solvation effects involved in ionic liquids could lead to optimized separation media for these novel solvents.

  6. Nanoparticle enhanced ionic liquid heat transfer fluids

    DOEpatents

    Fox, Elise B.; Visser, Ann E.; Bridges, Nicholas J.; Gray, Joshua R.; Garcia-Diaz, Brenda L.

    2014-08-12

    A heat transfer fluid created from nanoparticles that are dispersed into an ionic liquid is provided. Small volumes of nanoparticles are created from e.g., metals or metal oxides and/or alloys of such materials are dispersed into ionic liquids to create a heat transfer fluid. The nanoparticles can be dispersed directly into the ionic liquid during nanoparticle formation or the nanoparticles can be formed and then, in a subsequent step, dispersed into the ionic liquid using e.g., agitation.

  7. Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates

    NASA Technical Reports Server (NTRS)

    Simpson, Joycely O. (Inventor); St.Clair, Terry L. (Inventor)

    1999-01-01

    A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers. acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors, in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors. weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 1000 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

  8. Poly(ionic liquid) superabsorbent for polar organic solvents.

    PubMed

    Horne, W Jeffrey; Andrews, Mary A; Terrill, Kelsey L; Hayward, Spenser S; Marshall, Jeannie; Belmore, Kenneth A; Shannon, Matthew S; Bara, Jason E

    2015-05-01

    A simple, polymerized ionic liquid (poly(IL)) based on methylimidazolium cations tethered to a polystyrene backbone exhibits superabsorbent behavior toward polar organic solvents, most notably propylene carbonate (PC) and dimethyl sulfoxide (DMSO), wherein the poly(IL) was observed to swell more than 390 and 200 times (w/w) its original mass, yet absorbs negligible quantities of water, hexanes, and other solvents, many of which were miscible with the IL monomer. Although solubility parameters and dielectric constants are typically used to rationalize such behaviors, we find that poly(IL)-solvent compatibility is most clearly correlated to solvent dipole moment. Poly(IL) superabsorbency is not reliant upon the addition of a cross-linking agent. PMID:25893981

  9. Ionic Liquids for the Imaging of Wet Polymer Morphology

    NASA Astrophysics Data System (ADS)

    Hoagland, David; Harner, John; Bihari, Malvika

    2011-03-01

    Unlike convention aqueous and organic solvents, ionic liquids are essentially nonvolatile and thus compatible with the high vacuum environments of electron microscopy. Here is described the room temperature imaging of wet polymer systems such as patterned gels, gel networks, polymeric vesicles, and proteins. Both TEM and SEM images will be offered, along with a discussion of difficulties in applying the two techniques. Via SEM, imprinted surface structures as small as 100-300 nm can be captured for chemically crosslinked gels (polyHEMA), and via TEM, the structure of a physical gel (PEG) is viewed at the 50-to-10-nm scale, revealing network connectivity established by PEG crystallinity. Self-assembled vesicle and micelle structures will be presented for dispersed block copolymers, and the same approach will be applied toward discerning the quality of dispersion for proteins (ferritin) and other nanoparticles. Funding: UMass MRSEC.

  10. Stimuli-responsive nanoparticles from ionic cellulose derivatives

    NASA Astrophysics Data System (ADS)

    Wang, Yonggui; Heinze, Thomas; Zhang, Kai

    2015-12-01

    Stimuli-responsive nanoparticles (NPs) based on sustainable polymeric feedstock still need more exploration in comparison with NPs based on synthetic polymers. In this report, stimuli-responsive NPs from novel ionic cellulose derivatives were prepared via a facile nanoprecipitation. Cellulose 10-undecenoyl ester (CUE) with a degree of substitution (DS) of 3 was synthesized by esterification of cellulose with 10-undecenoyl chloride. Then, CUE was modified by photo-induced thiol-ene reactions, in order to obtain organo-soluble ionic cellulose derivatives with DSs of ~3, namely cellulose 11-((3-carboxyl)ethylthio)undecanoate (CUE-MPA), cellulose 11-((2-aminoethyl)thio)undecanoate (CUE-CA), cellulose 11-(2-(2-(diethylamino)ethyl)thio)undecanoate (CUE-DEAET) and cellulose 11-(2-(2-(dimethylamino)ethyl)thio)undecanoate (CUE-DMAET). CUE-MPA could be transformed into NPs with average diameters in the range of 80-330 nm, but these NPs did not show particular stimuli-responsive properties. Moreover, the dropping technique resulted in smaller NPs than a dialysis technique. Stable NPs with average diameters in the range of 90-180 nm showing pH-responsive and switchable sizes were obtained from CUE-DEAET and CUE-DMAET possessing tertiary amines using nanoprecipitation. Thus, altering the terminal functional groups will be a new approach to prepare stimuli-responsive cellulose-derived polymeric NPs.Stimuli-responsive nanoparticles (NPs) based on sustainable polymeric feedstock still need more exploration in comparison with NPs based on synthetic polymers. In this report, stimuli-responsive NPs from novel ionic cellulose derivatives were prepared via a facile nanoprecipitation. Cellulose 10-undecenoyl ester (CUE) with a degree of substitution (DS) of 3 was synthesized by esterification of cellulose with 10-undecenoyl chloride. Then, CUE was modified by photo-induced thiol-ene reactions, in order to obtain organo-soluble ionic cellulose derivatives with DSs of ~3, namely cellulose

  11. Ionic polymer metal composites with polypyrrole-silver electrodes

    NASA Astrophysics Data System (ADS)

    Cellini, F.; Grillo, A.; Porfiri, M.

    2015-03-01

    Ionic polymer metal composites (IPMCs) are a class of soft active materials that are finding increasing application in robotics, environmental sensing, and energy harvesting. In this letter, we demonstrate the fabrication of IPMCs via in-situ photoinduced polymerization of polypyrrole-silver electrodes on an ionomeric membrane. The composition, morphology, and sheet resistance of the electrodes are extensively characterized through a range of experimental techniques. We experimentally investigate IPMC electrochemistry through electrochemical impedance spectroscopy, and we propose a modified Randle's model to interpret the impedance spectrum. Finally, we demonstrate in-air dynamic actuation and sensing and assess IPMC performance against more established fabrication methods. Given the simplicity of the process and the short time required for the formation of the electrodes, we envision the application of our technique in the development of a rapid prototyping technology for IPMCs.

  12. Science exchanges

    NASA Astrophysics Data System (ADS)

    Richman, Barbara T.

    Dwindling scientific and technical exchange between the United States and the Soviet Union and prospects for enhancing such exchanges were discussed at an August 2 hearing by the Foreign Affairs Committee of the U.S. House of Representatives. The committee also heard overviews on the United States' approach to international exchange of science and technology. The hearing was the first in a series on current and future international science and technology programs.Four of eight science and technology agreements with the USSR that have expired in the last 15 months, including one on space, have not been renewed. The remaining four agreements have been extended into 1987 and 1988. Two others, including one on oceanography, are scheduled to run out in 1984.

  13. Ionic transport and electrical relaxation in glass

    NASA Astrophysics Data System (ADS)

    Moynihan, C. T.; Barkatt, A.

    1987-09-01

    The basic purpose of the work described was to achieve extensive and quantitative understanding of ionic transport processes in melts and glasses by means of a combination of experimental measurements and theoretical modeling. Two major subjects of the study were the mechanism of dielectric relaxation in ionically conducting glasses and the large retardation of ionic transport in mixed alkali systems.

  14. The hype with ionic liquids as solvents

    NASA Astrophysics Data System (ADS)

    Kunz, Werner; Häckl, Katharina

    2016-09-01

    In this mini review, we give our personal opinion about the present state of the art concerning Ionic Liquids, proposed as alternative solvents. In particular, we consider their different drawbacks and disadvantages and discuss the critical aspects of the research of Ionic Liquids as solvents. Finally, we point out some aspects on potentially promising Ionic Liquid solvents.

  15. Heat exchanger

    SciTech Connect

    Drury, C.R.

    1988-02-02

    A heat exchanger having primary and secondary conduits in heat-exchanging relationship is described comprising: at least one serpentine tube having parallel sections connected by reverse bends, the serpentine tube constituting one of the conduits; a group of open-ended tubes disposed adjacent to the parallel sections, the open-ended tubes constituting the other of the conduits, and forming a continuous mass of contacting tubes extending between and surrounding the serpentine tube sections; and means securing the mass of tubes together to form a predetermined cross-section of the entirety of the mass of open-ended tubes and tube sections.

  16. Nonlinear optical and conductive polymeric material

    DOEpatents

    Barton, Thomas J.; Ijadi-Maghsoodi, Sina; Pang, Yi

    1993-10-19

    A polymeric material which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl.sub.5 or W(CO).sub.6 /hv.

  17. Nonlinear optical and conductive polymeric material

    DOEpatents

    Barton, T.J.; Ijadi-Maghsoodi, S.; Pang, Y.

    1992-05-19

    A polymeric material which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl[sub 5] or W(CO)[sub 6]/hv.

  18. Nonlinear optical and conductive polymeric material

    DOEpatents

    Barton, T.J.; Ijadi-Maghsooodi, S; Yi Pang.

    1993-10-19

    A polymeric material is described which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl[sub 5] or W(CO)[sub 6].

  19. Nonlinear optical and conductive polymeric material

    DOEpatents

    Barton, Thomas J.; Ijadi-Maghsoodi, Sina; Pang, Yi

    1992-05-19

    A polymeric material which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl.sub.5 or W(CO).sub.6 /hv.

  20. Low vibration polymeric composite engine

    NASA Astrophysics Data System (ADS)

    Guimond, David P.; Muench, Rolf K.

    1994-12-01

    An internal combustion engine is constructed with metallic parts in its regions which are subjected to high stress (temperature, pressure) during combustion and polymeric materials in its regions which are subjected to relatively lower stresses. The integrated construction helps realize increased power densities and reductions on engine noise without compromising engine performance. V-configuration Diesel engines particularly benefit from this construction.

  1. Novel polymeric materials from triglycerides

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Triglycerides are good platforms for new polymeric products that can substitute for petroleum-based materials. As part of our research emphasis in sustainability and green polymer chemistry, we have explored a number of reactions in efforts to produce a wide range of value-added products. In this ...

  2. Supramolecular polymerization: Living it up

    NASA Astrophysics Data System (ADS)

    Würthner, Frank

    2014-03-01

    Protein fibril formation is involved in many human diseases and thus has been mechanistically elucidated in the context of understanding -- and in turn treating -- them. This biological phenomenon has now also inspired the design of a supramolecular system that undergoes living polymerization.

  3. The Viscosity of Polymeric Fluids.

    ERIC Educational Resources Information Center

    Perrin, J. E.; Martin, G. C.

    1983-01-01

    To illustrate the behavior of polymeric fluids and in what respects they differ from Newtonian liquids, an experiment was developed to account for the shear-rate dependence of non-Newtonian fluids. Background information, procedures, and results are provided for the experiment. Useful in transport processes, fluid mechanics, or physical chemistry…

  4. The absorption of polymeric composites

    NASA Astrophysics Data System (ADS)

    Řídký, R.; Popovič, M.; Rolc, S.; Drdlová, M.; Krátký, J.

    2016-06-01

    An absorption capacity of soft, viscoelastic materials at high strain rates is important for wide range of practical applications. Nowadays there are many variants of numerical models suitable for this kind of analysis. The main difficulty is in selection of the most realistic numerical model and a correct setup of many unknown material constants. Cooperation between theoretical simulations and real testing is next crucial point in the investigation process. Standard open source material database offer material properties valid for strain rates less than 250 s-1. There are experiments suitable for analysis of material properties with strain rates close to 2000 s-1. The high strain-rate characteristics of a specific porous blast energy absorbing material measured by modified Split Hopkinson Pressure Bar apparatus is presented in this study. Testing these low impedance materials using a metallic split Hopkinson pressure bar setup results in poor signal to noise ratios due to impedance mismatching. These difficulties are overcome by using polymeric Hopkinson bars. Conventional Hopkinson bar analysis cannot be used on the polymeric bars due to the viscoelastic nature of the bar material. One of the possible solution leads to complex and frequency depended Young modulus of testing bars material. This testing technique was applied to materials composed of porous glass/ceramic filler and polymeric binder, with density of 125 - 300 kg/m3 and particle size in range of 50 µm - 2 mm. The achieved material model was verified in practical application of sandwich structure includes polymeric composites under a blast test.

  5. POLYMERIC INTERFACES FOR STACK MONITORING

    EPA Science Inventory

    Research has been performed on the use of polymeric interfaces for in situ continuous stack monitoring of gaseous pollutants. Permeabilities of candidate interface materials to SO2 were measured at temperatures from ambient to 200C, and the results were used to design interfaces ...

  6. Pyrrole-Terminated Ionic Liquid Surfactant: One Molecule with Multiple Functions for Controlled Synthesis of Diverse Multispecies Co-Doped Porous Hollow Carbon Spheres.

    PubMed

    Li, Jian; Zhu, Wei; Ji, Jingwei; Wang, Peng; Lan, Yue; Gao, Ning; Yin, Xianpeng; Wang, Hui; Li, Guangtao

    2016-05-01

    Rationally and efficiently controlling chemical composition, microstructure, and morphology of carbon nanomaterials plays a crucial role in significantly enhancing their functional properties and expending their applications. In this work, a novel strategy for simultaneously controlling these structural parameters was developed on the base of a multifunctional precursor approach, in which the precursor not only serves as carbon source and structure-directing agent, but also contains two heteroatom doping sites. As exemplified by using pyrrole-terminated ionic liquid surfactant as such precursor, in conjunction with sol-gel chemistry this strategy allows for efficiently producing well-defined hollow carbon spheres with controlled microstructure and chemical compositions. Remarkably, the dual-doping sites in confined silica channels provide an exciting opportunity and flexibility to access various doped carbons through simply anion exchange or altering the used oxidative polymerization agent, especially the multispecies codoped materials by combination of the two doping modes. All the results indicate that the described strategy may open up a new avenue for efficiently synthesizing functional carbon materials with highly controllable capability. PMID:27093191

  7. Polymer-based separations: Synthesis and application of polymers for ionic and molecular recognition. Annual performance report, August 1, 1993--July 31, 1994

    SciTech Connect

    Alexandratos, S.D.

    1994-04-01

    During this period, focus was on design and synthesis of bifunctional polymers for complexing metal ions from aqueous solutions; this could provide a means for separating radioactive and toxic metal ions from contaminated waste water as well as valuable metals from dilute ore processing streams. The synthesis of bifunctional polymers required a new preparative technique; bifunctional interpenetrating polymer networks (IPN) was an important part of the studies. In the preparation, a pre-formed crosslinked polymer is contacted with a solution of monomers, and a second network was polymerized within the first. Imidazole ligands were used. A new resin, prepared with a macrocyclic sorbed within polystyrene beads modified with sulfonic acid ligands, extracted Cu(II) 10--100-fold. Maximum metal ion complexation rates depend on a balance between chemical interactions and physical parameters (matrix porosity, rigidity). A novel ion exchange resin (Diphonix{trademark}) has been produced which displays both ionic selectivity (diphosphonic acid ligands) and rapid complexation rates (sulfonic acid ligands).

  8. Fabrication and Characterization of Polysaccharide Ion Gels with Ionic Liquids and Their Further Conversion into Value-Added Sustainable Materials

    PubMed Central

    Takada, Akihiko; Kadokawa, Jun-ichi

    2015-01-01

    A review of the fabrication of polysaccharide ion gels with ionic liquids is presented. From various polysaccharides, the corresponding ion gels were fabricated through the dissolution with ionic liquids. As ionic liquids, in the most cases, 1-butyl-3-methylimidazolium chloride has been used, whereas 1-allyl-3methylimidazolium acetate was specifically used for chitin. The resulting ion gels have been characterized by suitable analytical measurements. Characterization of a pregel state by viscoelastic measurement provided the molecular weight information. Furthermore, the polysaccharide ion gels have been converted into value-added sustainable materials by appropriate procedures, such as exchange with other disperse media and regeneration. PMID:25793912

  9. Glycine Polymerization on Oxide Minerals

    NASA Astrophysics Data System (ADS)

    Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

    2016-07-01

    It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH3 + group of adsorbed Gly to the nucleophilic NH2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

  10. Automated resource-saving technology of ion-exchange water treatment

    NASA Astrophysics Data System (ADS)

    Livshits, M.

    2015-01-01

    Stable high quality of the purified water can be provided by adaptive control of water-treatment installations with the observer in a loop of the control system on the basis of observer of ion exchange processes. To obtain this goal the following problems have been solved: the hierarchic structure of water treatment system is developed; the system of water treatment quality criteria for ion exchange processes is developed; the created mathematical model of ionic exchange processes is functionally oriented to application in control system as an observer; methodologies of identification of a mathematical model of ionic exchange processes is developed; verification of the mathematical model of ionic exchange is performed on experimental-industrial basis; automatic control system of water treatment with observer in the loop is developed for low-waste installation of a heat supply system.

  11. Heat exchanger

    DOEpatents

    Daman, Ernest L.; McCallister, Robert A.

    1979-01-01

    A heat exchanger is provided having first and second fluid chambers for passing primary and secondary fluids. The chambers are spaced apart and have heat pipes extending from inside one chamber to inside the other chamber. A third chamber is provided for passing a purge fluid, and the heat pipe portion between the first and second chambers lies within the third chamber.

  12. Cesium-specific phenolic ion exchange resin

    DOEpatents

    Bibler, Jane P.; Wallace, Richard M.

    1995-01-01

    A phenolic, cesium-specific, cation exchange resin is prepared by neutralizing resorcinol with potassium hydroxide, condensing/polymerizing the resulting intermediate with formaldehyde, heat-curing the resulting polymer to effect cross-linking and grinding it to desired particle size for use. This resin will selectively and efficiently adsorb cesium ions in the presence of a high concentration of sodium ions with a low carbon to cesium ratio.

  13. Cesium-specific phenolic ion exchange resin

    DOEpatents

    Bibler, J.P.; Wallace, R.M.

    1995-08-15

    A phenolic, cesium-specific, cation exchange resin is prepared by neutralizing resorcinol with potassium hydroxide, condensing/polymerizing the resulting intermediate with formaldehyde, heat-curing the resulting polymer to effect cross-linking and grinding it to desired particle size for use. This resin will selectively and efficiently adsorb cesium ions in the presence of a high concentration of sodium ions with a low carbon to cesium ratio. 2 figs.

  14. Polymerization topochemistry of cellulose nanocrystals: a function of surface dehydration control.

    PubMed

    Tian, Chen; Fu, Shiyu; Habibi, Youssef; Lucia, Lucian A

    2014-12-01

    The activation (dehydration) of cellulose nanocrystals (CNCs) toward surface "brush" polymerization is accomplished either by freeze drying or solvent exchange. However, the question of which one of these protocols to choose over the other is generally open-ended. The current study attempts to shed light on this question by installing a standard polymer, polycaprolactone (PCL), onto the surface of both freeze-dried and solvent-exchanged CNCs by ring-opening polymerization (ROP) and examining the differences in polymerization and final product properties. The work is the first to demonstrate that the efficiency of surface polymerization and final product properties are in fact influenced by the protocols. The differences between the two sample PCL-grafted CNCs were investigated by X-ray photoelectron spectroscopy (XPS), elemental analysis, gel permeation chromatography (GPC), and contact-angle measurements. The freeze-dried samples had a significantly reduced PCL surface density. The crystallinity of the solvent-exchanged PCL-grafted CNCs (SECNC-g-PCL), however, was lower than that of either pure CNCs or freeze-dried PCL-grafted CNCs (FDCNC-g-PCL). It was determined that solvent exchange sufficiently modified the CNC surface to provide enhanced reactivity, an effect that was not as apparent for FDCNC-g-PCL. The solvent-exchanged CNCs tended to have more porous, nanotextured surfaces that were tended to be more responsive toward brush polymerization. In addition to the physical dissimilarities in surface morphology and surface accessibility contributing to topochemical differences between the two species, it was also found that the dispersibility, aggregation, and thermal stability were different. PMID:25387043

  15. Application of Ionic Liquids in Hydrometallurgy

    PubMed Central

    Park, Jesik; Jung, Yeojin; Kusumah, Priyandi; Lee, Jinyoung; Kwon, Kyungjung; Lee, Churl Kyoung

    2014-01-01

    Ionic liquids, low temperature molten salts, have various advantages manifesting themselves as durable and environmentally friendly solvents. Their application is expanding into various fields including hydrometallurgy due to their unique properties such as non-volatility, inflammability, low toxicity, good ionic conductivity, and wide electrochemical potential window. This paper reviews previous literatures and our recent results adopting ionic liquids in extraction, synthesis and processing of metals with an emphasis on the electrolysis of active/light, rare earth, and platinum group metals. Because the research and development of ionic liquids in this area are still emerging, various, more fundamental approaches are expected to popularize ionic liquids in the metal manufacturing industry. PMID:25177864

  16. Application of ionic liquids in hydrometallurgy.

    PubMed

    Park, Jesik; Jung, Yeojin; Kusumah, Priyandi; Lee, Jinyoung; Kwon, Kyungjung; Lee, Churl Kyoung

    2014-01-01

    Ionic liquids, low temperature molten salts, have various advantages manifesting themselves as durable and environmentally friendly solvents. Their application is expanding into various fields including hydrometallurgy due to their unique properties such as non-volatility, inflammability, low toxicity, good ionic conductivity, and wide electrochemical potential window. This paper reviews previous literatures and our recent results adopting ionic liquids in extraction, synthesis and processing of metals with an emphasis on the electrolysis of active/light, rare earth, and platinum group metals. Because the research and development of ionic liquids in this area are still emerging, various, more fundamental approaches are expected to popularize ionic liquids in the metal manufacturing industry. PMID:25177864

  17. Observation of ionic Coulomb blockade in nanopores

    NASA Astrophysics Data System (ADS)

    Feng, Jiandong; Liu, Ke; Graf, Michael; Dumcenco, Dumitru; Kis, Andras; di Ventra, Massimiliano; Radenovic, Aleksandra

    2016-08-01

    Emergent behaviour from electron-transport properties is routinely observed in systems with dimensions approaching the nanoscale. However, analogous mesoscopic behaviour resulting from ionic transport has so far not been observed, most probably because of bottlenecks in the controlled fabrication of subnanometre nanopores for use in nanofluidics. Here, we report measurements of ionic transport through a single subnanometre pore junction, and the observation of ionic Coulomb blockade: the ionic counterpart of the electronic Coulomb blockade observed for quantum dots. Our findings demonstrate that nanoscopic, atomically thin pores allow for the exploration of phenomena in ionic transport, and suggest that nanopores may also further our understanding of transport through biological ion channels.

  18. All-inorganic Germanium nanocrystal films by cationic ligand exchange

    DOE PAGESBeta

    Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; Anderson, Nicholas C.; Beard, Matthew C.; Neale, Nathan R.

    2016-01-21

    In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport inmore » germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.« less

  19. All-Inorganic Germanium Nanocrystal Films by Cationic Ligand Exchange.

    PubMed

    Wheeler, Lance M; Nichols, Asa W; Chernomordik, Boris D; Anderson, Nicholas C; Beard, Matthew C; Neale, Nathan R

    2016-03-01

    We introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and (1)H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport in germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications. PMID:26796765

  20. Decellular biological scaffold polymerized with PEDOT for improving peripheral nerve interface charge transfer.

    PubMed

    Frost, Christopher M; Cederna, Paul S; Martin, David C; Shim, Bong Sup; Urbanchek, Melanie G

    2014-01-01

    Regenerative peripheral nerve interfaces (RPNIs) are for signal transfer between peripheral nerves inside the body to controllers for motorized prosthetics external to the body. Within the residual limb of an amputee, surgical construction of a RPNI connects a remaining peripheral nerve and spare muscle. Nerve signals become concentrated within the RPNI. Currently metal electrodes implanted on the RPNI muscle transfer signals but scarring around metal electrodes progressively diminishes charge transfer. Engineered materials may benefit RPNI signal transfer across the neural interface if they lower the power and charge density of the biologically meaningful signals. Poly3,4-ethylenedioxythiophene (PEDOT) is known to mediate ionic potentials allowing excitation across a critical nerve gap. We hypothesize that the capacity of an interface material to conduct electron mediated current is significantly increased by polymerized coating of PEDOT. SIS was either used plain or after PEDOT coating by electrochemical polymerization. Muscle forces are a direct representation of stimulating current distribution within an RPNI. In situ muscle forces were measured for the same muscle by electrically stimulating: a) the muscle's innervating nerve, b) directly on the muscle, c) on plain SIS laid on the muscle, and d) on SIS polymerized with PEDOT laid on the muscle. Electro-chemically coating PEDOT on SIS resulted in a thin, flexible material. PEDOT coated SIS distributed electrical stimulation more efficiently than SIS alone. Conductive polymer containing biological material allowed ionic signal distribution within the RPNI like muscle at lower charge density. PMID:25569986

  1. Study of surface-bonded dicationic ionic liquids as stationary phases for hydrophilic interaction chromatography.

    PubMed

    Qiao, Lizhen; Li, Hua; Shan, Yuanhong; Wang, Shuangyuan; Shi, Xianzhe; Lu, Xin; Xu, Guowang

    2014-02-21

    In the present study, several geminal dicationic ionic liquids based on 1,4-bis(3-allylimidazolium)butane and 1,8-bis(3-allylimidazolium)octane in combination with different anions bromide and bis(trifluoromethanesulphonyl)imide were prepared and then bonded to the surface of 3-mercaptopropyl modified silica materials through the "thiol-ene" click chemistry as stationary phases for hydrophilic interaction chromatography (HILIC). Compared with their monocationic analogues, the dicationic ionic liquids stationary phases presented effective retention and good selectivity for typical hydrophilic compounds under HILIC mode with the column efficiency as high as 130,000 plates/m. Moreover, the influence of different alkyl chain spacer between dications and combined anions on the retention behavior and selectivity of the dicationic ionic liquids stationary phases under HILIC mode was displayed. The results indicated that the longer linkage chain would decrease the hydrophilicity and retention on the dicationic ionic liquid stationary phase, and while differently combined anions had no difference due to the exchangeability under the common HILIC mobile phase with buffer salt. Finally, the retention mechanism was investigated by evaluating the effect of chromatographic factors on retention, including the water content in the mobile phase, the mobile phase pH and buffer salt concentration. The results showed that the dicationic ionic liquids stationary phases presented a mixed-mode retention behavior with HILIC mechanism and anion exchange. PMID:24484692

  2. Phosphonium chloromercurate room temperature ionic liquids of variable composition.

    PubMed

    Metlen, Andreas; Mallick, Bert; Murphy, Richard W; Mudring, Anja-Verena; Rogers, Robin D

    2013-12-16

    The system trihexyl(tetradecyl)phosphonium ([P66614]Cl)/mercury chloride (HgCl2) has been investigated by varying the stoichiometric ratios from 4:1 to 1:2 (25, 50, 75, 100, 150, and 200 mol % HgCl2). All investigated compositions turn out to give rise to ionic liquids (ILs) at room temperature. The prepared ionic liquids offer the possibility to study the structurally and compositionally versatile chloromercurates in a liquid state at low temperatures in the absence of solvents. [P66614]2[HgCl4] is a simple IL with one discrete type of anion, while [P66614]{HgCl3} (with {} indicating a polynuclear arrangement) is an ionic liquid with a variety of polyanionic species, with [Hg2Cl6](2-) apparently being the predominant building block. [P66614]2[Hg3Cl8] and [P66614][Hg2Cl5] appear to be ILs at ambient conditions but lose HgCl2 when heated in a vacuum. For the liquids with the compositions 4:1 and 4:3, more than two discrete ions can be evidenced, namely, [P66614](+), [HgCl4](2-), and Cl(-) and [P66614](+), [HgCl4](2-), and the polynuclear {HgCl3}(-), respectively. The different stoichiometric compositions were characterized by (199)Hg NMR, Raman- and UV-vis spectroscopy, and cyclic voltammetry, among other techniques, and their densities and viscosities were determined. The [P66614]Cl/HgCl2 system shows similarities to the well-known chloroaluminate ILs (e.g., decrease in viscosity with increasing metal content after addition of more than 0.5 mol of HgCl2/mol [P66614]Cl, increasing density with increasing metal content, and the likely formation of polynuclear/polymeric/polyanionic species) but offer the advantage that they are air and water stable. PMID:24274831

  3. Multiscale implications of stress-induced ionic polymer transducer sensing

    NASA Astrophysics Data System (ADS)

    Zangrilli, Ursula Therese

    Ionic Polymer Transducers (IPTs) can act as both actuators and sensors. As actuators, the energy density values are much better than PZT or PVDF materials. As sensors, IPTs are extraordinarily sensitive and have the potential to be used in any mode of deformation. However, application of IPT sensors is limited because of a lack of understanding of their fundamental physics. In this work, the main focus will be to explore and develop a better understanding of how IPTs function with respect to shear deformation. In turn, the results developed here will improve upon the state of understanding of IPT sensors in general and potentially expand meaningful application opportunities. Because IPT active response is a multiscale phenomenon, this study adopts a multiscale modeling framework. Of interest are the interplay among the polymeric backbone of the ionic polymer, the diluent present in the hydrophilic regions of the polymer and the interspersed electrode particulate. To begin, this work improves upon a past multiscale modeling framework for the polymer backbone based upon Rotational Isomeric State Theory such that the effects of material anisotropy may be considered. This is potentially significant in light of the polymer manufacturing process. These modeling results are then incorporated into a model of the diluent movement within the ionic transport regions of the IPT. The electrical current predictions are based upon streaming potential theories. Finally, this model incorporates viscoelastic behavior in order to develop a better understanding of the coupling of these two systems (the polymer and the diluent) and how this coupling influence affects the expected current output over time.

  4. Design and Characterization of Styrene-Based Proton Exchange Membranes

    NASA Astrophysics Data System (ADS)

    Ebrasu, D.; Petreanu, I.; Patularu, L.; Stefanescu, I.; Valeanu, M.

    This paper deals with preparation of PEM, based on commercial block copolymer of the styrene-butadiene. The copolymer was structurally changed by sulfonation followed by cross linking, in order to design a Proton Exchange Membrane for Fuel Cells. The membranes were structural tested by FTIR Spectroscopy and Scanning Electron Microscopy. Ionic Exchange Capacity (IEC) and thermal behavior by Differential Scanning Calorimetry (DSC) were measured too.

  5. Morphology and transport in ionic membranes

    NASA Astrophysics Data System (ADS)

    Disabb-Miller, Melanie Lisa

    Ion-containing polymers for fuel cell membranes have been studied to determine the chemical structure and ion content relationship to membrane water uptake, conductivity, and morphology. Random and block copolymer proton exchange membranes (PEMs) and anion exchange membranes (AEMs) with unique properties, such as diblock and triblock copolymers, superacidic moieties, and charge-delocalized polymer-tethered Ru-complex based cations, were investigated, and new metrics were developed to analyze fundamental ion transport behavior in these polymers. The morphology of the polymer systems was examined using small angle x-ray scattering (SAXS), small angle neutron scattering (SANS), and transmission electron microscopy (TEM). By studying a number of different ion-conducting systems using multiple techniques and deep analysis of structure-property relationships, a more complete picture of the property landscape of these materials was developed. Model diblock and unique triblock copolymer systems with center-functionalized blocks based on poly(styrene), PS, and poly(hexyl methacrylate), PHMA, were synthesized via atom transfer radical polymerization (ATRP). The PS block was functionalized for backbone-independent comparisons of PEM and AEM water uptake and conductivity to provide insight in how the properties of PEMs and AEMs compare and aid in further AEM development. The ratio of the mobile ion diffusion coefficients and dilute solution ion diffusivity (D/D0) was developed as a new metric, allowing for accurate comparison of polymer systems with different ion moieties and contents. Subsequently, it was determined that block copolymer PEMs and AEMs demonstrate the same barriers to ion transport if the mobility of the charge carrier is considered.

  6. Polymeric Nanofibers in Tissue Engineering

    PubMed Central

    Dahlin, Rebecca L.; Kasper, F. Kurtis

    2011-01-01

    Polymeric nanofibers can be produced using methods such as electrospinning, phase separation, and self-assembly, and the fiber composition, diameter, alignment, degradation, and mechanical properties can be tailored to the intended application. Nanofibers possess unique advantages for tissue engineering. The small diameter closely matches that of extracellular matrix fibers, and the relatively large surface area is beneficial for cell attachment and bioactive factor loading. This review will update the reader on the aspects of nanofiber fabrication and characterization important to tissue engineering, including control of porous structure, cell infiltration, and fiber degradation. Bioactive factor loading will be discussed with specific relevance to tissue engineering. Finally, applications of polymeric nanofibers in the fields of bone, cartilage, ligament and tendon, cardiovascular, and neural tissue engineering will be reviewed. PMID:21699434

  7. Metal containing polymeric functional microspheres

    NASA Technical Reports Server (NTRS)

    Yen, Shiao-Ping S. (Inventor); Rembaum, Alan (Inventor); Molday, Robert S. (Inventor)

    1979-01-01

    Polymeric functional microspheres containing metal or metal compounds are formed by addition polymerization of a covalently bondable olefinic monomer such as hydroxyethylmethacrylate in the presence of finely divided metal or metal oxide particles, such as iron, gold, platinum or magnetite, which are embedded in the resulting microspheres. The microspheres can be covalently bonded to chemotherapeutic agents, antibodies, or other proteins providing a means for labeling or separating labeled cells. Labeled cells or microspheres can be concentrated at a specific body location such as in the vicinity of a malignant tumor by applying a magnetic field to the location and then introducing the magnetically attractable microspheres or cells into the circulatory system of the subject. Labeled cells can be separated from a cell mixture by applying a predetermined magnetic field to a tube in which the mixture is flowing. After collection of the labeled cells, the magnetic field is discontinued and the labeled sub-cell population recovered.

  8. Polymeric cationic substituted acrylamide surfactants

    SciTech Connect

    Nieh, E.C.Y.

    1983-11-15

    A new composition of matter comprises a copolymer of a surface active quaternary ammonium monomer salt and from 50 to 97% by wt of acrylamide. The new copolymers can have molecular weights substantially greater than 10,000 and still remain water soluble and surface active. Copolymers are prepared by polymerization techniques known in the art. The quaternary ammonium monomer is dispersed under inert atmosphere in aqueous solution which may additionally contain dissolved therein a low molecular weight alcohol such as ethanol, isopropanol, and the like. Acidic polymerization initiator such as the azo initiators, organic peroxides, or redox initiators such as the sulfite- persulfate system is then added in an amount calculated to yield a polymer product of desired molecular weight. (14 claims.

  9. Concurrent Covalent and Supramolecular Polymerization.

    PubMed

    Hou, Xisen; Ke, Chenfeng; Zhou, Yu; Xie, Zhuang; Alngadh, Ahmed; Keane, Denis T; Nassar, Majed S; Botros, Youssry Y; Mirkin, Chad A; Stoddart, J Fraser

    2016-08-22

    Covalent and supramolecular polymerizations, both of which offer their own unique advantages, have emerged as popular strategies for making artificial materials. Herein, we describe a concurrent covalent and supramolecular polymerization strategy-namely, one which utilizes 1) a bis-azide-functionalized diazaperopyrenium dication that undergoes polymeriation covalently with a bis-alkyne-functionalized biphenyl derivative in one dimension as a result of a rapid and efficient β-cyclodextrin(CD)-accelerated, cucurbit[6]uril(CB)-templated azide-alkyne cycloaddition, while 2) the aromatic core of the dication is able to dimerize in a criss-cross fashion by dint of π-π interactions, enabling simultaneous supramolecular assembly, resulting in an extended polymer network in an orthogonal dimension. PMID:27338246

  10. Performances and mechanistic investigations of a triphosphine trioxide/ionic liquid system for rare earth extraction.

    PubMed

    Turgis, R; Arrachart, G; Dubois, V; Dourdain, S; Virieux, D; Michel, S; Legeai, S; Lejeune, M; Draye, M; Pellet-Rostaing, S

    2016-01-21

    The extraction of rare earth elements (REEs) from nitric acid solution with a triphosphine trioxide (TPO) is presented. Performances of such a ligand in ionic liquids vs. a classical solvent (benzyl ether) are compared. TPO seems to be 10 to 100 times more efficient when it is dissolved in ionic media whatever the concentration of nitric acid involved. Mechanistic investigations reveal that cation exchange classically observed in ionic liquids is not consistent with the experimental data. Moreover, clear differences in the TPO/Ln complexes between classical and ionic media are highlighted. A stable complex of 1 lanthanide for 3 TPO is formed in an ionic liquid whereas a complex of 1 lanthanide for 6 to 9 TPO is formed in benzyl ether. Back extraction is also studied and good recovery of REEs could be obtained. The TPO/ionic liquid system shows remarkable performances i.e. efficiency and selectivity towards lanthanides in a simulated leaching solution of a Nd/Fe/B/Dy magnet. PMID:26673884

  11. Externally Wetted Ionic Liquid Thruster

    NASA Astrophysics Data System (ADS)

    Lozano, P.; Martinez-Sanchez, M.; Lopez-Urdiales, J. M.

    2004-10-01

    This paper presents initial developments of an electric propulsion system based on ionic liquid ion sources (ILIS). Propellants are ionic liquids, which are organic salts with two important characteristics; they remain in the liquid state at room temperature and have negligible vapor pressure, thus allowing their use in vacuum. The working principles of ILIS are similar to those of liquid metal ion sources (LMIS), in which a Taylor cone is electrostatically formed at the tip of an externally wetted needle while ions are emitted directly from its apex. ILIS have the advantage of being able to produce negative ions that have similar masses than their positive counterparts with similar current levels. This opens up the possibility of achieving plume electrical neutrality without electron emitters. The possible multiplexing of these emitters is discussed in terms of achievable thrust density for applications other than micro-propulsion.

  12. Quantized ionic conductance in nanopores

    SciTech Connect

    Zwolak, Michael; Lagerqvist, Johan; Di Ventra, Massimilliano

    2009-01-01

    Ionic transport in nanopores is a fundamentally and technologically important problem in view of its ubiquitous occurrence in biological processes and its impact on DNA sequencing applications. Using microscopic calculations, we show that ion transport may exhibit strong non-liDearities as a function of the pore radius reminiscent of the conductance quantization steps as a function of the transverse cross section of quantum point contacts. In the present case, however, conductance steps originate from the break up of the hydration layers that form around ions in aqueous solution. Once in the pore, the water molecules form wavelike structures due to multiple scattering at the surface of the pore walls and interference with the radial waves around the ion. We discuss these effects as well as the conditions under which the step-like features in the ionic conductance should be experimentally observable.

  13. Radiation-hardened polymeric films

    DOEpatents

    Arnold, C. Jr.; Hughes, R.C.; Kepler, R.G.; Kurtz, S.R.

    1984-07-16

    The radiation-induced conductivity of polymeric dielectrics with low electronic mobility is reduced by doping with electron donor or electron acceptor compounds at a level of 10/sup 15/ to 10/sup 21/ molecules of dopant/cm/sup 3/. Polyesters, polyolefins, perfluoropolyolefins, vinyl polymers, vinylidene polymers, polycarbonates, polysulfones and polyimides can benefit from such a treatment. Usable dopants include 2,4,7-trinitro-9-fluorenone, tetracyanethylene, 7,7,8,8-tetracyanoquinodimethane, m-dinitrobenzene, 2-isopropylcarbazole, and triphenylamine.

  14. Electrochemical polymerization of pyrrole derivatives

    SciTech Connect

    Inagaki, T.; Hunter, M.; Yang, X.Q.; Skotheim, T.A.; Lee, H.S.; Okamoto, Y.

    1988-01-01

    Electrochemical copolymerization of pyrrole and 3-(6-ferrocenyl-6-hydroxyhexyl)pyrrole (P-Fc) yields a ferrocene functionalized polypyrrole with a controlled amount of ferrocene functionalization. Similarly, copolymers of pyrrole and 3-(4-(2,5- dimethoxyphenyl)butyl)pyrrole (P-MP) can be made by electrochemical polymerization and converted to the copolymers containing pH dependent electroactive hydroquinone moieties. 16 refs., 6 figs.

  15. Radiation-hardened polymeric films

    DOEpatents

    Arnold, Jr., Charles; Hughes, Robert C.; Kepler, R. Glen; Kurtz, Steven R.

    1986-01-01

    The radiation-induced conductivity of polymeric dielectrics with low electronic mobility is reduced by doping with electron donor or electron acceptor compounds at a level of 10.sup.15 to 10.sup.21 molecules of dopant/cm.sup.3. Polyesters, polyolefins, perfluoropolyolefins, vinyl polymers, vinylidene polymers, polycarbonates, polysulfones and polyimides can benefit from such a treatment. Usable dopants include 2,4,7-trinitro-9-fluorenone, tetracyanethylene, 7,7,8,8-tetracyanoquinodimethane, m-dinitrobenzene, 2-isopropylcarbazole, and triphenylamine.

  16. Alcohol polymerization using electron emission

    NASA Astrophysics Data System (ADS)

    Matsuura, Hiroshi; Tanikawa, Tamio; Takaba, Hiromitsu; Fujiwara, Yutaka

    2004-04-01

    We report a means of instantaneous alcohol polymerization using electron emission at room temperature. We selected 1-butanol as a source of alcohol polymer. A 1-butanol molecule has a simple molecular structure and is a good candidate for analyzing reaction mechanisms. Direct electron emission onto the surface of volatile 1-butanol prevented intense discharge and gently composed 1-butanol-polymer at room temperature in air. The strategy enabled exciting liquids and instantaneously composing new materials at room temperature.

  17. [Ion specificity during ion exchange equilibrium in natural clinoptilolite].

    PubMed

    He, Yun-Hua; Li, Hang; Liu, Xin-Min; Xiong, Hai-Ling

    2015-03-01

    Zeolites have been widely applied in soil improvement and environment protection. The study on ion specificity during ion exchange equilibrium is of important significance for better use of zeolites. The maximum adsorption capacities of alkali ions during ion exchange equilibrium in the clinoptilolite showed obvious specificity. For alkali metal ions with equivalent valence, the differences in adsorption capacity increased with the decrease of ionic concentration. These results cannot be well explained by the classical theories including coulomb force, ionic size, hydration, dispersion force, classic induction force and surface complexation. We found that the coupling of polarization effects resulted from the quantum fluctuation of diverse alkali metal ions and electric field near the zeolite surface should be the primary reason for specific ion effect during ion exchange in zeolite. The result of this coupling effect was that the difference in the ion dipole moment increased with the increase of surface potential, which further expanded the difference in the adsorption ability between zeolite surface and ions, resulting in different ion exchange adsorption ability at the solid/liquid interface. Due to the high surface charge density of zeolite, ionic size also played an important role in the distribution of ions in the double diffuse layer, which led to an interesting result that distinct differences in exchange adsorption ability of various alkali metal ions were only detected at high surface potential (the absolute value was greater than 0.2 V), which was different from the ion exchange equilibrium result on the surface with low charge density. PMID:25929073

  18. Composite plasma polymerized sulfonated polystyrene membrane for PEMFC

    SciTech Connect

    Nath, Bhabesh Kumar; Khan, Aziz; Chutia, Joyanti

    2015-10-15

    Highlights: • Methyl methane sulfonate (MMS) is used as the sulfonating agent. • The proton conductivity of the membrane is found to be 0.141 S cm{sup −1}. • Power density of fuel cell with styrene/MMS membrane is 0.5 W cm{sup −2}. • The membrane exhibits thermal stability up to 140 °C. - Abstract: This work presents the introduction of an organic compound methyl methane sulfonate (MMS) for the first time in fabrication of polystyrene based proton exchange membrane (PEM) by plasma polymerization process. The membrane is fabricated by co-polymerizing styrene and MMS in capacitively coupled continuous RF plasma. The chemical composition of the plasma polymerized polymer membrane is investigated using Fourier Transform Infrared Spectroscopy which reveals the formation of composite structure of styrene and MMS. The surface morphology studied using AFM and SEM depicts the effect of higher partial pressure of MMS on surface topography of the membrane. The proton transport property of the membrane studied using electrochemical impedance spectroscopy shows the achievement of maximum proton conductivity of 0.141 S cm{sup −1} which is comparable to Nafion 117 membrane. Fuel cell performance test of the synthesized membrane shows a maximum power density of 500 mW cm{sup −2} and current density of 0.62 A cm{sup −2} at 0.6 V.

  19. Effects of solution conditions on the physicochemical properties of stratification components of extracellular polymeric substances in anaerobic digested sludge.

    PubMed

    Yuan, Dongqin; Wang, Yili

    2013-01-01

    The composition and effects of solution conditions on the physicochemical properties of the stratification components of extracellular polymeric substances (EPS) in anaerobic digested sludge were determined. The total EPS in anaerobic digested sludge were extracted by the cation exchange resin method. Another EPS extraction method, the centrifugation and sonication technique was employed to stratify the EPS into three fractions: slime, loosely bound (LB)-EPS, and tightly bound (TB)-EPS from the outside to the inside of the anaerobic digested sludge. Proteins and polysaccharides were dispersed uniformly across the different EPS fractions, and humic-like substances were mainly partitioned in the slime, with TB-EPS second. Protein was the major constituent of the LB-EPS and TB-EPS, and the corresponding ratios ranged from 54.0% to 65.6%. The hydrophobic part in the EPS chemical components was primarily comprised of protein and DNA, while the hydrophilic part was mainly composed of polysaccharide. In the slime, the hydrophobic values of several EPS chemical components (protein, polysaccharide, humic-like substances and DNA) were all below 50%. The protein/polysaccharide ratio had a significant influence on the Zeta potentials and isoelectric point values of the EPS: the greater the protein/polysaccharide ratio of the EPS was, the greater the Zeta potential and the higher the isoelectric point value were. All Zeta potentials of the EPS showed a decreasing trend with increasing pH. The corresponding isoelectric point values (pH) were 2.8 for total EPS, 2.2 for slime, 2.7 for LB-EPS, and 2.6 for TB-EPS. As the ionic strength increased, the Zeta potentials sharply increased and then gradually became constant without charge reversal. In addition, as the temperature increased (< 40 degrees C), the apparent viscosity of the EPS decreased monotonically and then gradually became stable between 40 and 60 degrees C. PMID:23586310

  20. Two Photon Polymerization of Ormosils

    NASA Astrophysics Data System (ADS)

    Matei, A.; Zamfirescu, M.; Jipa, F.; Luculescu, C.; Dinescu, M.; Buruiana, E. C.; Buruiana, T.; Sima, L. E.; Petrescu, S. M.

    2010-10-01

    In this work, 3D structures of hybrid polymers—ORMOSILS (organically modified silicates) were produced via Two Photon Polymerization (2PP) of hybrid methacrylates based on silane derivates. Synthetic routes have been used to obtain series of hybrid monomers, their structure and purity being checked by NMR Spectroscopy and Fourier Transform Infrared Spectroscopy. Two photon polymerization method (a relatively new technology which allows fast micro and nano processing of three-dimensional structures with application in medical devices, tissue scaffolds, photonic crystals etc) was used for monomers processing. As laser a Ti: Sapphire laser was used, with 200 fs pulse duration and 2 kHz repetition rate, emitting at 775 nm. A parametric study on the influence of the processing parameters (laser fluence, laser scanning velocity, photo initiator) on the written structures was carried out. The as prepared polymeric scaffolds were tested in mesenchymal stem cells and fibroblasts cell cultures, with the aim of further obtaining bone and dermal grafts. Cells morphology, proliferation, adhesion and alignment were analyzed for different experimental conditions.

  1. Ionic Liquids to Replace Hydrazine

    NASA Technical Reports Server (NTRS)

    Koelfgen, Syri; Sims, Joe; Forton, Melissa; Allan, Barry; Rogers, Robin; Shamshina, Julia

    2011-01-01

    A method for developing safe, easy-to-handle propellants has been developed based upon ionic liquids (ILs) or their eutectic mixtures. An IL is a binary combination of a typically organic cation and anion, which generally produces an ionic salt with a melting point below 100 deg C. Many ILs have melting points near, or even below, room temperature (room temperature ionic liquids, RTILs). More importantly, a number of ILs have a positive enthalpy of formation. This means the thermal energy released during decomposition reactions makes energetic ILs ideal for use as propellants. In this specific work, to date, a baseline set of energetic ILs has been identified, synthesized, and characterized. Many of the ILs in this set have excellent performance potential in their own right. In all, ten ILs were characterized for their enthalpy of formation, density, melting point, glass transition point (if applicable), and decomposition temperature. Enthalpy of formation was measured using a microcalorimeter designed specifically to test milligram amounts of energetic materials. Of the ten ILs characterized, five offer higher Isp performance than hydrazine, ranging between 10 and 113 seconds higher than the state-of-the-art propellant. To achieve this level of performance, the energetic cations 4- amino-l,2,4-triazolium and 3-amino-1,2,4-triazolium were paired with various anions in the nitrate, dicyanamide, chloride, and 3-nitro-l,2,4-triazole families. Protonation, alkylation, and butylation synthesis routes were used for creation of the different salts.

  2. Revealing ionic motion molecular solids

    NASA Astrophysics Data System (ADS)

    Thurzo, I.; Zahn, D. R. T.

    2006-01-01

    Thin films of mixed valence semiconductor copper-tetracyano-quinodimethane (Cu-TCNQ) and small molecule tris(8-hydroxyquinolinato)aluminum (Alq3) were investigated by current-voltage (I-V) and admittance (C-V,G-V) techniques in single-layer configuration with different combinations of electrodes. The predicted hysteresis of I-V curves and nearly constant loss (NCL) could be observed for both materials. When cycling devices between negative and positive biases, slowly decaying ionic transient currents interfere with steady-state currents and point to unidirectional motions of the ionic species with subsequent redox reaction at one of the electrodes. Plotting the frequency f dependence of the equivalent parallel capacitance at zero bias as log10 C(0) versus log10(f), the dielectric behavior of Cu-TCNQ and Alq3 complies with the effective-medium model for NCL in ionic conductors [J. R. Macdonald J. Appl. Phys. 94, 558 (2003)]. It also holds for a similar plot of the equivalent parallel zero-bias conductance G(0). The nature of the revealed mobile ions is discussed with emphasis on their sources.

  3. Modelling Mixed Bed Ion Exchange Kinetics for Removal of Trace Levels of Divalent Cations in Ultrapure Water

    SciTech Connect

    B. Widman

    2003-01-01

    Ion exchanger resin fluid film mass transfer coefficients and the ionic diffusivities from which they are derived are often measured by use of ion exchange resin columns. Such tests, usually run dynamically using short resin beds, are often performed using relatively high (ppm) concentrations of ions to accurately measure output concentrations as a function of flow rate. The testing described herein was performed to determine fluid film ionic diffusivities for cationic concentrations typical of ultrapure water ({le}ppb levels) containing ppm levels of ammonia. Effective ionic diffusivities at these low ionic concentrations and high pHs were needed to complete a computer model (SIMIX) to be used in ion exchange simulations. SIMIX is a generalized multicomponent ion exchange model designed to simulate the removal of divalent cations from ultrapure water.

  4. Radiation Chemistry and Photochemistry of Ionic Liquids

    SciTech Connect

    Wishart, J.F.; Takahaski, K.

    2010-12-01

    As our understanding of ionic liquids and their tunable properties has grown, it is possible to see many opportunities for ionic liquids to contribute to the sustainable use of energy. The potential safety and environmental benefits of ionic liquids, as compared to conventional solvents, have attracted interest in their use as processing media for the nuclear fuel cycle. Therefore, an understanding of the interactions of ionizing radiation and photons with ionic liquids is strongly needed. However, the radiation chemistry of ionic liquids is still a relatively unexplored topic although there has been a significant increase in the number of researchers in the field recently. This article provides a brief introduction to ionic liquids and their interesting properties, and recent advances in the radiation chemistry and photochemistry of ionic liquids. In this article, we will mainly focus on excess electron dynamics and radical reaction dynamics. Because solvation dynamics processes in ionic liquids are much slower than in molecular solvents, one of the distinguishing characteristics is that pre-solvated electrons play an important role in ionic liquid radiolysis. It will be also shown that the reaction dynamics of radical ions is significantly different from that observed in molecular solvents because of the Coulombic screening effects and electrostatic interactions in ionic liquids.

  5. Simultaneous bench scale production of dissolving grade pulp and valuable hemicelluloses from softwood kraft pulp by ionic liquid extraction.

    PubMed

    Laine, Christiane; Asikainen, Sari; Talja, Riku; Stépán, Agnes; Sixta, Herbert; Harlin, Ali

    2016-01-20

    Ionic liquid extraction of wood pulp has been highlighted as a highly potential new process for dissolving pulp production. Coproduction with a polymeric hemicellulose fraction was demonstrated in bench scale from softwood kraft pulp using extraction with the ionic liquid 1-ethyl-3-methylimidazolium acetate (EMIM OAc) and water. In total, the recovered pulp and hemicellulose fraction together yielded 95.5 wt.% of the pulp input. The extracted pulp had a remarkably high purity with an R18-value of 97.8%. The hemicellulose fraction consisted of galactoglucomannan, arabinoxylan and some cellulose and was precipitated from the ionic liquid-water mixture. After hydroxypropylation of the hemicellulose fraction, films were prepared and barrier and strength properties were compared to films from other polysaccharides. Reduced oxygen and water vapor permeation and good strength properties were demonstrated when compared to corresponding films from hydroxypropylated xylan from cold caustic extraction. The films have potential for applications in food packaging and edible films. PMID:26572370

  6. Ultrasound-Mediated Polymeric Micelle Drug Delivery.

    PubMed

    Xia, Hesheng; Zhao, Yue; Tong, Rui

    2016-01-01

    The synthesis of multi-functional nanocarriers and the design of new stimuli-responsive means are equally important for drug delivery. Ultrasound can be used as a remote, non-invasive and controllable trigger for the stimuli-responsive release of nanocarriers. Polymeric micelles are one kind of potential drug nanocarrier. By combining ultrasound and polymeric micelles, a new modality (i.e., ultrasound-mediated polymeric micelle drug delivery) has been developed and has recently received increasing attention. A major challenge remaining in developing ultrasound-responsive polymeric micelles is the improvement of the sensitivity or responsiveness of polymeric micelles to ultrasound. This chapter reviews the recent advance in this field. In order to understand the interaction mechanism between ultrasound stimulus and polymeric micelles, ultrasound effects, such as thermal effect, cavitation effect, ultrasound sonochemistry (including ultrasonic degradation, ultrasound-initiated polymerization, ultrasonic in-situ polymerization and ultrasound site-specific degradation), as well as basic micellar knowledge are introduced. Ultrasound-mediated polymeric micelle drug delivery has been classified into two main streams based on the different interaction mechanism between ultrasound and polymeric micelles; one is based on the ultrasound-induced physical disruption of the micelle and reversible release of payload. The other is based on micellar ultrasound mechanochemical disruption and irreversible release of payload. PMID:26486348

  7. Gallium and indium complexes containing the bis(imino)phenoxide ligand: synthesis, structural characterization and polymerization studies.

    PubMed

    Ghosh, Swarup; Gowda, Ravikumar R; Jagan, Rajamony; Chakraborty, Debashis

    2015-06-14

    A series of gallium and indium complexes containing a bis(imino)phenolate ligand framework were synthesized and completely characterized with different spectroscopic techniques. The molecular structures of a few complexes were determined using single crystal X-ray diffraction studies. These compounds were found to be extremely active towards the bulk ring opening polymerization (ROP) of lactides yielding polymers with high number average molecular weight (Mn) and controlled molecular weight distributions (MWDs). The neutral complexes produce isotactic enriched poly(lactic acid) (PLA) from rac-lactide (rac-LA) under melt conditions, whereas the ionic complex produces atactic PLA. The polymerizations are controlled, as evidenced by the narrow molecular distribution (MWDs) of the isolated polymers in addition to the linear nature of number average molecular weight (Mn) versus conversion plots with variations in monomer to catalyst ratios. The kinetic and mechanistic studies associated with these polymerizations have been performed. PMID:25977999

  8. Chemically modified polymeric resins for high performance liquid chromatography, solid-phase extraction and organic separation by LC and GC

    SciTech Connect

    Sun, Jeffrey Jiafang.

    1991-08-06

    Polystyrene divinylbenzene resins were chemically modified by introduction of various functional groups, which included polar, non-polar, ionic and metallic groups. These chemically modified polymeric resins were used successfully for high performance liquid chromatography, solid phase extraction and some special applications in liquid and gas chromatography. The introduced functional groups offer an additional selectivity parameter for liquid chromatographic separation. The polar derivatized polymeric resins dramatically increased the recoveries of solid phase extraction, especially for polar compounds. The sulfonated polystyrene resins were used for separation of neutral and basic compounds as well as basic and weaker basic compounds. The sulfonated non-porous resin was used amine abstracter and the polymeric-mercuric resin was used as mercaptan abstracter in capillary gas chromatograph. The researches in this dissertation has shown the very promising applications of polystyrene divinylbenzene resin in chromatographic field. 58 refs., 34 figs., 28 tabs.

  9. Polymerization in the gas phase, in clusters, and on nanoparticle surfaces.

    PubMed

    El-Shall, M Samy

    2008-07-01

    Gas phase and cluster experiments provide unique opportunities to quantitatively study the effects of initiators, solvents, chain transfer agents, and inhibitors on the mechanisms of polymerization. Furthermore, a number of important phenomena, unique structures, and novel properties may exist during gas-phase and cluster polymerization. In this regime, the structure of the growing polymer may change dramatically and the rate coefficient may vary significantly upon the addition of a single molecule of the monomer. These changes would be reflected in the properties of the oligomers deposited from the gas phase. At low pressures, cationic and radical cationic polymerizations may proceed in the gas phase through elimination reactions. In the same systems at high pressure, however, the ionic intermediates may be stabilized, and addition without elimination may occur. In isolated van der Waals clusters of monomer molecules, sequential polymerization with several condensation steps can occur on a time scale of a few microseconds following the ionization of the gas-phase cluster. The cluster reactions, which bridge gas-phase and condensed-phase chemistry, allow examination of the effects of controlled states of aggregation. This Account describes several examples of gas-phase and cluster polymerization studies where the most significant results can be summarized as follows: (1) The carbocation polymerization of isobutene shows slower rates with increasing polymerization steps resulting from entropy barriers, which could explain the need for low temperatures for the efficient propagation of high molecular weight polymers. (2) Radical cation polymerization of propene can be initiated by partial charge transfer from an ionized aromatic molecule such as benzene coupled with covalent condensation of the associated propene molecules. This novel mechanism leads exclusively to the formation of propene oligomer ions and avoids other competitive products. (3) Structural information

  10. The advantage of polymer addition to a non-ionic oil in water microemulsion for the dermal delivery of progesterone.

    PubMed

    Biruss, Babette; Valenta, Claudia

    2008-02-12

    The influence of progesterone on the physicochemical behaviour of the o/w microemulsion consisting of the non-ionic surfactant polyoxyethylene-10-dodecyl ether, tributyrin and water was investigated. Thereby no significant influence could be detected in terms of droplet size, zeta potential, conductivity and pH by progesterone. However the chemical stability of progesterone was insufficient during the storage of 6 months. Therefore, two different polymeric agents, named silicon dioxide and polymeric emulsifier, were added to the progesterone containing microemulsions. These polymers increased the chemical stability of progesterone significantly. Moreover the polymeric additives improved the skin permeation 1.24- and 1.63-fold and decreased the skin retention in relation to the pure microemulsion. The polymer-stabilized progesterone microemulsions are interesting vehicles for skin application of progesterone. PMID:17869457

  11. Heat-Exchange Fluids for Sulfuric Acid Vaporizers

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.; Petersen, G. R.

    1982-01-01

    Some fluorine-substituted organic materials meet criteria for heat-exchange fluids in contact with sulfuric acid. Most promising of these are perfluoropropylene oxide polymers with degree of polymerization (DP) between 10 and 50. It is desirable to have DP in high range because vapor pressure of material decreases as DP increases, and high-DP liquids have lower loss due to vaporization.

  12. Nanopatterned Protein Films Directed by Ionic Complexation with Water-Soluble Diblock Copolymers

    PubMed Central

    Kim, Bokyung; Lam, Christopher N.; Olsen, Bradley D.

    2014-01-01

    The use of ionic interactions to direct both protein templating and block copolymer self-assembly into nanopatterned films with only aqueous processing conditions is demonstrated using block copolymers containing both thermally responsive and pH responsive blocks. Controlled reversible addition-fragmentation chain-transfer (RAFT) polymerization is employed to synthesize poly(N-isopropylacrylamide-b-2-(dimethylamino)ethyl acrylate) (PNIPAM-b-PDMAEA) diblock copolymers. The pH-dependent ionic complexation between the fluorescent protein, mCherry, and the ionic PDMAEA block is established using dynamic light scattering (DLS) and UV-Vis spectroscopy. DLS shows that the size of the resulting coacervate micelles depends strongly on pH, while UV-Vis spectroscopy shows a correlation between the protein’s absorption maximum and the ionic microenvironment. Zeta potential measurements clearly indicate the ionic nature of the complex-forming interactions. Spin casting was used to prepare nanostructured films from the protein-block copolymer coacervates. After film formation, the lower critical solution temperature (LCST) of the PNIPAM blocks allows the nanomaterial to be effectively immobilized in aqueous environments at physiological temperatures, enabling potential use as a controlled protein release material or polymer matrix for protein immobilization. At pH 9.2 and 7.8, the release rates are at least 10 times faster than that at pH 6.4 due to weaker interaction between protein and PNIPAM-b-PDMAEA (PND) diblock copolymer. Due to the ionic environment in which protein is confined, the majority of the protein (80%) remains active, independent of pH, even after having been dehydrated in vacuum and confined in the films. PMID:24904186

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  14. Heat exchanger

    DOEpatents

    Brackenbury, Phillip J.

    1986-04-01

    A heat exchanger comparising a shell attached at its open end to one side of a tube sheet and a detachable head connected to the other side of said tube sheet. The head is divided into a first and second chamber in fluid communication with a nozzle inlet and nozzle outlet, respectively, formed in said tube sheet. A tube bundle is mounted within said shell and is provided with inlets and outlets formed in said tube sheet in communication with said first and second chambers, respectively.

  15. Anhydrous Proton Conducting Polymer Electrolyte Membranes via Polymerization-Induced Microphase Separation.

    PubMed

    Chopade, Sujay A; So, Soonyong; Hillmyer, Marc A; Lodge, Timothy P

    2016-03-01

    Solid-state polymer electrolyte membranes (PEMs) exhibiting high ionic conductivity coupled with mechanical robustness and high thermal stability are vital for the design of next-generation lithium-ion batteries and high-temperature fuel cells. We present the in situ preparation of nanostructured PEMs incorporating a protic ionic liquid (IL) into one of the domains of a microphase-separated block copolymer created via polymerization-induced microphase separation. This facile, one-pot synthetic strategy transforms a homogeneous liquid precursor consisting of a poly(ethylene oxide) (PEO) macro-chain-transfer agent, styrene and divinylbenzene monomers, and protic IL into a robust and transparent monolith. The resulting PEMs exhibit a bicontinuous morphology comprising PEO/protic IL conducting pathways and highly cross-linked polystyrene (PS) domains. The cross-linked PS mechanical scaffold imparts thermal and mechanical stability to the PEMs, with an elastic modulus approaching 10 MPa at 180 °C, without sacrificing the ionic conductivity of the system. Crucially, the long-range continuity of the PEO/protic IL conducting nanochannels results in an outstanding ionic conductivity of 14 mS/cm at 180 °C. We posit that proton conduction in the protic IL occurs via the vehicular mechanism and the PEMs exhibit an average proton transference number of 0.7. This approach is very promising for the development of high-temperature, robust PEMs with excellent proton conductivities. PMID:26927732

  16. Characterization of ionic permeability and water vapor transmission rate of polymers used for implantable electronics.

    PubMed

    Kirsten, Sabine; Schubert, Martin; Uhlemann, Jürgen; Wolter, Klaus-Jurgen

    2014-01-01

    Biocompatible polymers used as encapsulation and packaging materials for implantable electronic devices have to comply with numerous requirements. Especially their barrier properties against water molecules and ions are of particular interest regarding the reliability of the encapsulation as well as functional integrity of the electronic components since water and ions on the circuit board may evoke corrosion, leakage current and finally the failure of the device. This paper describes a measurement setup to investigate the ionic permeability under in vitro conditions of polymeric membranes manufactured from various biocompatible polymers. Ionic permeability and water vapor transmission rate representing the barrier properties of these membranes were investigated. First results were obtained for polyimide, silicone, polyether ether ketone and polyamide, whereas polyimide evinced the best properties. PMID:25571499

  17. Preparation of corn starch-g-polystyrene copolymer in ionic liquid: 1-ethyl-3-methylimidazolium acetate.

    PubMed

    Men, Yongjun; Du, Xiyan; Shen, Jianan; Wang, Leli; Liu, Zhengping

    2015-05-01

    The copolymer of starch grafted with polystyrene (starch-g-PS) was synthesized with high grafting percentage by utilizing the ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM]Ac) as solvent and potassium persulfate as initiator. The effect of various parameters upon the polymerization were studied including: initiator concentration, styrene:starch weight ratio, the reaction time and temperature. Grafting percentages were calculated using an FT-IR calibration method, with values up to 114%. The resulting copolymer was characterized using FT-IR, SEM, WAXD and TGA, which demonstrated that polystyrene side chains were evenly distributed on the starch backbone. Our results indicate that ionic liquid dissolution of starch, prior to polystyrene grafting, is a versatile methodology for the synthesis of amphiphilic, polysaccharide-based graft copolymers, having high grafting percent. PMID:25659709

  18. Structure of highly rigid ionic polymers from single molecules to membranes

    NASA Astrophysics Data System (ADS)

    He, Lilin; Cornelius, Christopher J.

    2005-03-01

    The structure of ionic polymers in solutions and in their solid state is governed by the segregation to hydrophilic and hydrophobic regions. Very rigid backbones with persistence lengths much larger than the size of the monomer limit the segregation affecting the resulting structure and dynamics of the polymers. Using a newly synthesized para phenylene based sulfonated polymer with a potential to serve as a polymeric electrolytic membrane for fuel cell applications, we followed the structure of highly rigid ionic polymers from a single molecule to a water swollen membranes using small angle neutron scattering and AFM/TEM techniques. AFM and TEM images show that the dry membranes have domains with a diameter from 30 nm to 70nm. Small angle neutron scattering probes the smaller structure in the membranes from dry to swollen states. Fitting to Teubner-Strey model of SANS data indicates the bi-continuous phases were formed with water and ethanol despite the rigidity of the backbone.

  19. Crosslinked polymer gel electrolytes based on polyethylene glycol methacrylate and ionic liquid for lithium battery applications

    SciTech Connect

    Liao, Chen; Sun, Xiao-Guang; Dai, Sheng

    2013-01-01

    Gel polymer electrolytes were synthesized by copolymerization polyethylene glycol methyl ether methacrylate with polyethylene glycol dimethacrylate in the presence of a room temperature ionic liquid, methylpropylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPY TFSI). The physical properties of gel polymer electrolytes were characterized by thermal analysis, impedance spectroscopy, and electrochemical tests. The ionic conductivities of the gel polymer electrolytes increased linearly with the amount of MPPY TFSI and were mainly attributed to the increased ion mobility as evidenced by the decreased glass transition temperatures. Li||LiFePO4 cells were assembled using the gel polymer electrolytes containing 80 wt% MPPY TFSI via an in situ polymerization method. A reversible cell capacity of 90 mAh g 1 was maintained under the current density of C/10 at room temperature, which was increased to 130 mAh g 1 by using a thinner membrane and cycling at 50 C.

  20. Polymerization rate and mechanism of ultrasonically initiated emulsion polymerization of n-butyl acrylate.

    PubMed

    Xia, Hesheng; Wang, Qi; Liao, Yongqin; Xu, Xi; Baxter, Steven M; Slone, Robert V; Wu, Shuguang; Swift, Graham; Westmoreland, David G

    2002-07-01

    The factors affecting the induction period and polymerization rate in ultrasonically initiated emulsion polymerization of n-butyl acrylate (BA) were investigated. The induction period takes only an instant in ultrasonically initiated emulsion polymerization of BA without any added initiator by enhancing the N2 flow rate. Increasing temperature, power output and SDS concentration, decreasing the monomer concentration results in further decreasing induction period and enhanced polymerization rate. Under optimized reaction conditions the conversion of BA reaches 92% in 11 min. The polymerization rate can be controlled by varying reaction parameters. The apparatus of ultrasonically initiated semi-continuous and continuous emulsion polymerization were set up and the feasibility was first studied. Based on the experimental results, a free radical polymerization mechanism for ultrasonically initiated emulsion polymerization was proposed, including the sources of the radicals, the process of radical formation, the locus of polymerization and the polymerization process. Compared with conventional emulsion polymerization, where the radicals come from thermal decomposition of a chemical initiator, ultrasonically initiated emulsion polymerization has attractive features such as no need for a chemical initiator, lower reaction temperature, faster polymerization rate, and higher molecular weight of the polymer prepared. PMID:12154689

  1. A multifunctional azobenzene-based polymeric adsorbent for effective water remediation

    NASA Astrophysics Data System (ADS)

    Wan, Decheng; Chen, Feng; Geng, Qingrui; Lu, Hang; Willcock, Helen; Liu, Qiuming; Wang, Fangyingkai; Zou, Kaidian; Jin, Ming; Pu, Hongting; Du, Jianzhong

    2014-12-01

    The efficient removal of trace carcinogenic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs) and ionic dyes, from water is an important technical challenge. We report a highly effective recyclable multifunctional azobenzene (AZ)-based silica-supported polymeric adsorbent which can simultaneously remove both PAHs and anionic dyes from water to below parts per billion (ppb) level based on multiple interactions such as the hydrophobic effect, π-π stacking and electrostatic interactions, thus providing a new strategy for designer water remediation materials.

  2. A multifunctional azobenzene-based polymeric adsorbent for effective water remediation

    PubMed Central

    Wan, Decheng; Chen, Feng; Geng, Qingrui; Lu, Hang; Willcock, Helen; Liu, Qiuming; Wang, Fangyingkai; Zou, Kaidian; Jin, Ming; Pu, Hongting; Du, Jianzhong

    2014-01-01

    The efficient removal of trace carcinogenic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs) and ionic dyes, from water is an important technical challenge. We report a highly effective recyclable multifunctional azobenzene (AZ)-based silica-supported polymeric adsorbent which can simultaneously remove both PAHs and anionic dyes from water to below parts per billion (ppb) level based on multiple interactions such as the hydrophobic effect, π–π stacking and electrostatic interactions, thus providing a new strategy for designer water remediation materials. PMID:25465671

  3. Internal Morphology-Controllable Self-Assembly in Poly(Ionic Liquid) Nanoparticles.

    PubMed

    Zhang, Weiyi; Kochovski, Zdravko; Lu, Yan; Schmidt, Bernhard V K J; Antonietti, Markus; Yuan, Jiayin

    2016-08-23

    Precise control of the interior and outer shapes of polymer nanoparticles has found broad interest in nanosciences, for example, in fundamental studies of their physical properties, colloidal behavior, and corresponding applications. Realizing such control below the 50 nm scale (i.e., a size scale close to individual polymer chains) requires accurate manipulation of polymerization techniques and a judicious choice of the chemical structure in monomers and/or polymers. Here, we constructed a series of well-defined sub-50 nm homopolymer nanoparticles with controllable shape and highly ordered, complex internal structures with sub-5 nm domain spacings, starting from 1-vinyl-1,2,4-triazolium-type ionic liquids in a one-pot dispersion polymerization. With cryogenic electron microscopy and tomography, a morphological evolution of particle shape and interior at this extremely small size end, unusual for polymer colloids, was identified and investigated in detail. PMID:27501014

  4. Enzyme catalysis with small ionic liquid quantities.

    PubMed

    Fischer, Fabian; Mutschler, Julien; Zufferey, Daniel

    2011-04-01

    Enzyme catalysis with minimal ionic liquid quantities improves reaction rates, stereoselectivity and enables solvent-free processing. In particular the widely used lipases combine well with many ionic liquids. Demonstrated applications are racemate separation, esterification and glycerolysis. Minimal solvent processing is also an alternative to sluggish solvent-free catalysis. The method allows simplified down-stream processing, as only traces of ionic liquids have to be removed. PMID:21107639

  5. Early Events in Ionic Liquid Radiation Chemistry

    SciTech Connect

    Wishart, J.F.; Cook, A.; Rimmer, R.D.; Gohdo, M.

    2010-09-14

    Ionic liquids are interesting and useful materials whose solvation time scales are up to thousands of times longer than in conventional solvents. The extended lifetimes of pre-solvated electrons and other energetic species in ionic liquids has profound consequences for the radiolytic product distributions and reactivity patterns. We use a newly developed, multiplexed variation of pulse-probe spectroscopy to measure the kinetics of the early dynamical and reactive events in ionic liquids.

  6. Sorption of tellurium ion from aqueous solutions by anion-exchangers and amphoteric ion-exchangers

    SciTech Connect

    Dreipa, E.F.; Pakholkov, V.S.; Luk'yanov, S.A.

    1981-10-20

    Sorption of tellurium from solutions of telluric acid under dynamic and static conditions by anion-exchangers and amphoteric ion-exchangers containing various ionic groups was studied and the influence of the ion form, pH of the medium, presence of electrolytes, and the H/sub 6/TeO/sub 6/ concentration in the original solutions was determined. The mechanism of sorption of tellurium (VI) by anion-exchangers was deduced from sorption and IR-spectroscopic data. Differences in the behavior of tellurium and selenium were used for separating these elements in 0.05 N H/sub 2/SeO/sub 4/ + 0.05 N H/sub 6/TeO/sub 6/ solution of pH = 1.0 with the aid of EDE-10P anion-exchange resin.

  7. Utilizing advanced polymerization techniques for simplifying polymer grafting from silica colloidal crystal substrates

    NASA Astrophysics Data System (ADS)

    Yerneni, Charu K.

    Polyacrylamide has been well established as a biocompatible material when Polyacrylamide gel electrophoresis (PAGE) came into existence in the 1960s. Under aqueous buffer conditions it becomes non-adsorptive to proteins and due to its molecular level pore forming nature could be used in size based biomolecule separations. Since then considerable research has been done to explore the non-adsorptive nature of polyacrylamide on a platform or substrate. Attempts were made to grow polyacrylamide chains from silica as a substrate which can then be used in various protein separation techniques. Based on an ionic polymerization method which was used for gel casting in PAGE, polymers were grown on silica gel. Though considerable thickness could be achieved, polymerization was not just confined to the surface. Therefore a rigid polymer brush layer could not be achieved. Atom transfer radical polymerization (ATRP) method showed the solution to this problem. Polymer brush layers with acceptable thickness could now be achieved for growing polyacrylamide from silica gel. Yet it still suffered from several disadvantages such as the need of an inert atmosphere for polymerization and limited thickness. Many developments have taken place in the past decade which led to improvements in substrate and polymerization methods. This research used non porous sub-micron silica as the substrate and AGET ATRP (Activator generated electron transfer atom transfer radical polymerization) for surface grafting polyacrylamide. Non porous submicron silica has been shown to be a better stationary phase substrate for protein separations than conventional substrates. AGET ATRP enables polymerization to be performed under ambient conditions and in water based solutions which gives thicknesses much higher than conventional ATRP. Data from various analytical techniques showed that within the experimental range the polymerization is linear and has decent control. This means silica nanoparticles coated with

  8. 2,5-Dihydroxybenzoic acid butylamine and other ionic liquid matrixes for enhanced MALDI-MS analysis of biomolecules.

    PubMed

    Mank, Marko; Stahl, Bernd; Boehm, Günther

    2004-05-15

    The performance of the new ionic liquid MALDI-MS matrix 2,5-dihydroxybenzoic acid butylamine (DHBB) was assessed and compared to results obtained with the ionic liquid MALDI-MS matrixes alpha-cyano-4-hydroxycinnamic acid butylamine (CHCAB), 3,5-dimethoxycinnamic acid triethylamine (SinTri), and the frequently used solid MALDI matrixes 2,5-dihydroxybenzoic acid (DHB) and alpha-cyano-4-hydroxycinnamic acid (CHCA). The vacuum-stable, liquid consistency of ionic liquid matrix sample preparations considerably enhanced MALDI-MS analysis in terms of shot-to-shot reproducibility. Consequently, relative standard deviations serving as a measure for reproducibility of intensity-values acquired from 90 different spots on one MALDI-MS preparation were approximately one-half as high when solid DHB was replaced by the ionic liquid DHBB and eight times lower after exchange of solid CHCA by ionic liquid CHCAB. Interestingly, the ionic liquid MALDI matrix DHBB conserved the broad applicability of its solid analogue DHB, reduced MALDI induced fragmentation of monosialylated glycans and gangliosides, and was the superior ionic liquid matrix for MALDI-MS analysis of oligosaccharides and polymers, such as poly(ethylene glycol). It also worked well with glycoconjugates, peptides, and proteins; however, the tendency of DHBB to form multiple alkali adduct ions with peptides and proteins made CHCAB the ionic liquid matrix of choice for peptides. SinTri was the best ionic liquid matrix for proteins of high molecular weight, such as IgG. Furthermore, it was demonstrated for the first time that solvent properties and MALDI matrix properties of ionic liquids, such as DHBB, can be combined to enable fast, direct screening of an enzymatic reaction. This was proven by the desialylation of sialylactose with sialidase from Clostridium perfringens in the presence of diluted aqueous DHBB and subsequent direct MALDI-MS analysis of the reaction mixture. PMID:15144208

  9. Anionic polymerization of azo substituted methacrylates

    SciTech Connect

    Dimov, D.K.; Dalton, L.R.; Hogen-Esch, T.E.

    1993-12-31

    The anionic polymerization of 4-phenylazophenyl methacrylate (PAM) and 6-(4-phenylazophenoxy)-hexyl methacrylate (PAHM) initiated by {open_quotes}living{close_quotes} PMMA with lithium counterion was studied in THF at {minus}78{degrees}C. The polymerization of PAM was prevented by a side termination reaction. The polymerization of PAHM proceeded smoothly to furnish PMMA/azopolymer block copolymers. The process showed features typical of {open_quotes}living{close_quotes} anionic polymerization. No phase transitions could be detected by DSC to prove liquid crystalline mesophase formation by the block copolymers.

  10. Ketoprofen as a photoinitiator for anionic polymerization.

    PubMed

    Wang, Yu-Hsuan; Wan, Peter

    2015-06-01

    A new photoinitiating system for anionic polymerization of acrylates based on the efficient photodecarboxylation of Ketoprofen (1) and the related derivatives 3 and 4 that generate the corresponding carbanion intermediates is presented. Carbanion intermediates are confirmed by deuterium incorporation in the trapped Michael adducts and by spectroscopic detection using laser flash photolysis (LFP). This novel anionic initiating system features excitation in the near UV and visible regions, potential characteristics of photocontrolled living polymerization, and metal-free photoinitiators generated from photoexcitation, different from typical anionic polymerization where the polymerizations are initiated by heat and strong base containing alkali metals. PMID:25917384

  11. Ionic self-assembly affords mesoporous ionic networks by crosslinking linear polyviologens with polyoxometalate clusters.

    PubMed

    Chen, Guojian; Hou, Wei; Li, Jing; Wang, Xiaochen; Zhou, Yu; Wang, Jun

    2016-03-21

    Ionic-bonded mesoporous ionic networks were prepared by the ionic self-assembly of polyoxometalate (POM) clusters with linear cationic polyviologens in water. The POM-enriched PMIN-2(V) possesses a high surface area up to 120 m(2) g(-1), exhibiting superior non-noble metal heterogeneous catalytic performance in the ambient aerobic selective oxidation of 5-hydroxymethylfurfural. PMID:26898883

  12. Electrically controlled polymeric gel actuators

    DOEpatents

    Adolf, Douglas B.; Shahinpoor, Mohsen; Segalman, Daniel J.; Witkowski, Walter R.

    1993-01-01

    Electrically controlled polymeric gel actuators or synthetic muscles capable of undergoing substantial expansion and contraction when subjected to changing pH environments, temperature, or solvent. The actuators employ compliant containers for the gels and their solvents. The gels employed may be cylindrical electromechanical gel fibers such as polyacrylamide fibers or a mixture of poly vinyl alcohol-polyacrylic acid arranged in a parallel aggregate and contained in an electrolytic solvent bath such as salt water. The invention includes smart, electrically activated devices exploiting this phenomenon. These devices are capable of being manipulated via active computer control as large displacement actuators for use in adaptive structure such as robots.

  13. Electrically controlled polymeric gel actuators

    DOEpatents

    Adolf, D.B.; Shahinpoor, M.; Segalman, D.J.; Witkowski, W.R.

    1993-10-05

    Electrically controlled polymeric gel actuators or synthetic muscles are described capable of undergoing substantial expansion and contraction when subjected to changing pH environments, temperature, or solvent. The actuators employ compliant containers for the gels and their solvents. The gels employed may be cylindrical electromechanical gel fibers such as polyacrylamide fibers or a mixture of poly vinyl alcohol-polyacrylic acid arranged in a parallel aggregate and contained in an electrolytic solvent bath such as salt water. The invention includes smart, electrically activated devices exploiting this phenomenon. These devices are capable of being manipulated via active computer control as large displacement actuators for use in adaptive structure such as robots. 11 figures.

  14. Ionene modified small polymeric beads

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor)

    1977-01-01

    Linear ionene polyquaternary cationic polymeric segments are bonded by means of the Menshutkin reaction (quaternization) to biocompatible, extremely small, porous particles containing halide or tertiary amine sites which are centers for attachment of the segments. The modified beads in the form of emulsions or suspensions offer a large, positively-charged surface area capable of irreversibly binding polyanions such as heparin, DNA, RNA or bile acids to remove them from solution or of reversibly binding monoanions such as penicillin, pesticides, sex attractants and the like for slow release from the suspension.

  15. Molecularly Regulated Reversible DNA Polymerization.

    PubMed

    Chen, Niancao; Shi, Xuechen; Wang, Yong

    2016-06-01

    Natural polymers are synthesized and decomposed under physiological conditions. However, it is challenging to develop synthetic polymers whose formation and reversibility can be both controlled under physiological conditions. Here we show that both linear and branched DNA polymers can be synthesized via molecular hybridization in aqueous solutions, on the particle surface, and in the extracellular matrix (ECM) without the involvement of any harsh conditions. More importantly, these polymers can be effectively reversed to dissociate under the control of molecular triggers. Since nucleic acids can be conjugated with various molecules or materials, we anticipate that molecularly regulated reversible DNA polymerization holds potential for broad biological and biomedical applications. PMID:27100911

  16. Polymerized nanotube structures new zeolites?

    NASA Astrophysics Data System (ADS)

    Chernozatonskii, Leonid A.

    1998-11-01

    Polymers of single-wall carbon nanotubes - possible new zeolites - are modeled by molecular mechanics (MM2 calculation method). The polymerization at issue occurs by bonding of 6 sp 3 atomic pairs in each nanotube unit cell with similar atomic pairs located on 6 neighboring tubes like 2+2 cycloaddition in a rhombic two-dimensional C 60 polymer. It is shown these bonding in armchair ( n, n) SWNT ropes ( n=6, 8, 10, 12) changes positive radial curvature of tube segments to a negative one.

  17. Computational studies of polymeric systems

    NASA Astrophysics Data System (ADS)

    Carrillo, Jan-Michael Y.

    Polymeric systems involving polyelectrolytes in surfaces and interfaces, semiflexible polyelectrolytes and biopolymers in solution, complex polymeric systems that had applications in nanotechnology were modeled using coarse grained molecular dynamics simulation. In the area of polyelectrolytes in surfaces and interfaces, the phenomena of polyelectrolyte adsorption at oppositely charge surface was investigated. Simulations found that short range van der Waals interaction was a major factor in determining morphology and thickness of the adsorbed layer. Hydrophobic polyelectrolytes adsorbed in hydrophobic surfaces tend to be the most effective in forming multi-layers because short range attraction enhances the adsorption process. Adsorbed polyelectrolytes could move freely along the surface which was in contrast to polyelectrolyte brushes. The morphologies of hydrophobic polyelectrolyte brushes were investigated and simulations found that brushes had different morphologies depending on the strength of the short range monomer-monomer attraction, electrostatic interaction and counterion condensation. Planar polyelectrolyte brushes formed: (1) vertically oriented cylindrical aggregates, (2) maze-like aggregate structures, or (3) thin polymeric layer covering a substrate. While, the spherical polyelectrolyte brushes could be in any of the previous morphologies or be in a micelle-like conformation with a dense core and charged corona. In the area of biopolymers and semiflexible polyelectrolytes in solution, simulations demonstrated that the bending rigidity of these polymers was scale-dependent. The bond-bond correlation function describing a chain's orientational memory could be approximated by a sum of two exponential functions manifesting the existence of the two characteristic length scales. The existence of the two length scales challenged the current practice of describing chain stretching experiments using a single length scale. In the field of nanotechnology

  18. Marketing NASA Langley Polymeric Materials

    NASA Technical Reports Server (NTRS)

    Flynn, Diane M.

    1995-01-01

    A marketing tool was created to expand the knowledge of LaRC developed polymeric materials, in order to facilitate the technology transfer process and increase technology commercialization awareness among a non-technical audience. The created brochure features four materials, LaRC-CP, LaRC-RP46, LaRC-SI, and LaRC-IA, and highlights their competitive strengths in potential commercial applications. Excellent opportunities exist in the $40 million per year microelectronics market and the $6 billion adhesives market. It is hoped that the created brochure will generate inquiries regarding the use of the above materials in markets such as these.

  19. Minimizing back exchange in the hydrogen exchange-mass spectrometry experiment.

    PubMed

    Walters, Benjamin T; Ricciuti, Alec; Mayne, Leland; Englander, S Walter

    2012-12-01

    The addition of mass spectrometry (MS) analysis to the hydrogen exchange (HX) proteolytic fragmentation experiment extends powerful HX methodology to the study of large biologically important proteins. A persistent problem is the degradation of HX information due to back exchange of deuterium label during the fragmentation-separation process needed to prepare samples for MS measurement. This paper reports a systematic analysis of the factors that influence back exchange (solution pH, ionic strength, desolvation temperature, LC column interaction, flow rates, system volume). The many peptides exhibit a range of back exchange due to intrinsic amino acid HX rate differences. Accordingly, large back exchange leads to large variability in D-recovery from one residue to another as well as one peptide to another that cannot be corrected for by reference to any single peptide-level measurement. The usual effort to limit back exchange by limiting LC time provides little gain. Shortening the LC elution gradient by 3-fold only reduced back exchange by ~2%, while sacrificing S/N and peptide count. An unexpected dependence of back exchange on ionic strength as well as pH suggests a strategy in which solution conditions are changed during sample preparation. Higher salt should be used in the first stage of sample preparation (proteolysis and trapping) and lower salt (<20 mM) and pH in the second stage before electrospray injection. Adjustment of these and other factors together with recent advances in peptide fragment detection yields hundreds of peptide fragments with D-label recovery of 90% ± 5%. PMID:22965280

  20. Quantized ionic conductance in nanopores.

    PubMed

    Zwolak, Michael; Lagerqvist, Johan; Di Ventra, Massimiliano

    2009-09-18

    Ionic transport in nanopores is a fundamentally and technologically important problem in view of its occurrence in biological processes and its impact on novel DNA sequencing applications. Using molecular dynamics simulations we show that ion transport may exhibit strong nonlinearities as a function of the pore radius reminiscent of the conductance quantization steps as a function of the transverse cross section of quantum point contacts. In the present case, however, conductance steps originate from the break up of the hydration layers that form around ions in aqueous solution. We discuss this phenomenon and the conditions under which it should be experimentally observable. PMID:19792463

  1. Stabilization of extracellular polymeric substances ( Bacillus subtilis) by adsorption to and coprecipitation with Al forms

    NASA Astrophysics Data System (ADS)

    Mikutta, Robert; Zang, Ulrich; Chorover, Jon; Haumaier, Ludwig; Kalbitz, Karsten

    2011-06-01

    Extracellular polymeric substances (EPS) are continuously produced by bacteria during their growth and metabolism. In soils, EPS are bound to cell surfaces, associated with biofilms, or released into solution where they can react with other solutes and soil particle surfaces. If such reaction results in a decrease in EPS bioaccessibility, it may contribute to stabilization of microbial-derived organic carbon (OC) in soil. Here we examined: (i) the chemical fractionation of EPS produced by a common Gram positive soil bacterial strain ( Bacillus subtilis) during reaction with dissolved and colloidal Al species and (ii) the resulting stabilization against desorption and microbial decay by the respective coprecipitation (with dissolved Al) and adsorption (with Al(OH) 3(am)) processes. Coprecipitates and adsorption complexes obtained following EPS-Al reaction as a function of pH and ionic strength were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The stability of adsorbed and coprecipitated EPS against biodegradation was assessed by mineralization experiments for 1100 h. Up to 60% of the initial 100 mg/L EPS-C was adsorbed at the highest initial molar Al:C ratio (1.86), but this still resulted only in a moderate OC mass fraction in the solid phase (17 mg/g Al(OH) 3(am)). In contrast, while coprecipitation by Al was less efficient in removing EPS from solution (maximum values of 33% at molar Al:C ratios of 0.1-0.2), the OC mass fraction in the solid product was substantially larger than that in adsorption complexes. Organic P compounds were preferentially bound during both adsorption and coprecipitation. Data are consistent with strong ligand exchange of EPS phosphoryl groups during adsorption to Al(OH) 3(am), whereas for coprecipitation weaker sorption mechanisms are also involved. X-ray photoelectron analyses indicate an intimate mixing of EPS with Al in the coprecipitates, which is not observed in the case

  2. Electrical resistance and transport numbers of ion-exchange membranes used in electrodialytic soil remediation

    SciTech Connect

    Hansen, H.K.; Ottosen, L.M.; Villumsen, A.

    1999-08-01

    Electrodialytic soil remediation is a recently developed method to decontaminate heavy metal polluted soil using ion-exchange membranes. In this method one side of the ion-exchange membrane is in direct contact with the polluted soil. It is of great importance to known if this contact with the soil causes damage to the membrane. This work presents the result of transport number and electrical resistance measurements done on four sets of ion-exchange membranes (Ionics, Inc CR67 HMR412 cation-exchange membranes and Ionics, Inc AR204 SXZR anion-exchange membranes), which have been used in four different electrodialytic soil remediation experiments. The experiments showed that after the use in electrodialytic soil remediation, the ion-exchange membranes had transport numbers in the same magnitude as new membranes. The electrical resistance for six membranes did not differ from that of new membranes, whereas two membranes showed a slightly increased resistance.

  3. Active musculoskeletal structures equipped with a circulatory system and a network of ionic polymeric gel muscles

    SciTech Connect

    Shahinpoor, M.; Mojarrad, M.

    1994-12-31

    Presented are descriptions of design and fabrication of an active musculoskeletal structure composed of an artificial human skeleton of 5.3 feet in height. This skeletal structure is further equipped with an artificial heart in the form of a multi-channel computer-controlled fluid pump. The fluid pump may be programmed to selectively pump either an acid, a base or de-ionized water to a network of veins that feed a network of pairs of antagonist contractile synthetic muscles. These muscles are manufactured in the laboratory from polyacrylonitrile (PAN) fiber bundles that are specially designed and packaged inside flexible, hyperelastic latex membranes. Each pair of muscles act as a pair of antagonist actuator similar to the biceps and triceps muscles of the human arm. The initial fabrication indicates that it is possible to dynamically control such active musculoskeletal structures. A model is also presented for the dynamic control of such antagonist muscles. The model is intended to be used to study the human musculoskeletal dynamics.

  4. Nanomechanical testing of polymeric nanofibers

    NASA Astrophysics Data System (ADS)

    Tan, E. P. S.; Lim, C. T.

    2005-04-01

    Biodegradable polymeric nanofibrous scaffold comprises individual nanofibers where their stiffnesses can promote or undermine the various cellular functions as well as structural integrity of the scaffold. As such, there is a need to investigate the nanomechanical properties of these individual nanofibers. However, conducting mechanical tests of individual fibers at the nanometer scale can pose great challenges and difficulties. Here, we present novel techniques to perform nanomechanical testing of individual polymeric nanofibers. For demonstration of the nano tensile tests, polycaprolactone (PCL) nanofibers were produced via electrospinning. These fibers were deposited across two parallel edges of a cardboard frame so that a single nanofiber can be isolated for tensile test using a nano tensile tester. For nanoscale three-point bend test, a Poly (L-lactic acid) (PLLA) nanofiber was suspended across a microsized groove etched on a silicon wafer. An atomic force microscope (AFM) tip was then used to apply a point load on the mid-span of the suspended fiber. Beam bending theory was then used to calculate the elastic modulus of the nanofiber. For nanoindentation test, a PLLA nanofiber was deposited on a mica substrate and an AFM tip used to indent the nanofiber. Modified Hertz theory for normal contact was then used to evaluate the elastic modulus of the nanofiber.

  5. Ionic effects on spindle adaptation

    PubMed Central

    Husmark, I.; Ottoson, D.

    1971-01-01

    1. Effects of changes in ionic environment on the receptor potential were studied in isolated frog spindle. Particular attention was focused on the action of potassium removal on the early adaptive decline of the response. 2. Removal of potassium caused a reduction and final disappearance of the dynamic overshoot of the receptor potential. The static phase of the response was also reduced although to less extent. The repolarization phase of the response following release of phasic or maintained stretch was greatly prolonged. 3. Increased potassium concentration caused a reduction of the response, but did not change its general time course. The amount of reduction was related to the potassium concentration. 4. Removal of sodium caused a marked diminution of the response, the static phase being in general more affected than the dynamic phase. 5. It is suggested that the effects of potassium removal are caused by a delay in sodium inactivation and a partial depolarization of the endings. It is concluded that the greater part of the early adaptation of the spindle proper may be attributed to ionic mechanisms in the transducer membrane. PMID:4256546

  6. Ionic liquid tunes microemulsion curvature.

    PubMed

    Liu, Liping; Bauduin, Pierre; Zemb, Thomas; Eastoe, Julian; Hao, Jingcheng

    2009-02-17

    Middle-phase microemulsions formed from cationic dioctadecyldimethylammonium chloride (DODMAC), anionic sodium dodecylsulfate (SDS), n-butanol, and n-heptane were studied. An ionic liquid (IL), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), was employed as the electrolyte in the aqueous media instead of inorganic salts usually used in microemulsion formulation. Studies have been carried out as a function of the concentrations of [bmim][BF4], n-butanol, total surfactant (cDODMAC+SDS), and temperature on the phase behavior and the ultralow interfacial tensions in which the anionic component is present in excess in the catanionic film. Ultralow interfacial tension measurements confirmed the formation of middle-phase microemulsions and the necessary conditions for stabilizing middle-phase microemulsions. Electrical conductivity, small-angle X-ray scattering (SAXS), and small-angle neutron scattering (SANS) experiments were also performed, indicating that the typical heptane domain size has an average radius of 360 A and the ionic liquid induces softening of the charged catanionic film. Most interestingly, the IL concentration (cIL) is shown to act as an effective interfacial curvature-control parameter, representing a new approach to tuning the formulation of microemulsions and emulsions. The results expand the potential uses of ILs but also point to the design of new ILs that may achieve superefficient control over interfacial and self-assembly systems. PMID:19161325

  7. Segmented heat exchanger

    DOEpatents

    Baldwin, Darryl Dean; Willi, Martin Leo; Fiveland, Scott Byron; Timmons, Kristine Ann

    2010-12-14

    A segmented heat exchanger system for transferring heat energy from an exhaust fluid to a working fluid. The heat exchanger system may include a first heat exchanger for receiving incoming working fluid and the exhaust fluid. The working fluid and exhaust fluid may travel through at least a portion of the first heat exchanger in a parallel flow configuration. In addition, the heat exchanger system may include a second heat exchanger for receiving working fluid from the first heat exchanger and exhaust fluid from a third heat exchanger. The working fluid and exhaust fluid may travel through at least a portion of the second heat exchanger in a counter flow configuration. Furthermore, the heat exchanger system may include a third heat exchanger for receiving working fluid from the second heat exchanger and exhaust fluid from the first heat exchanger. The working fluid and exhaust fluid may travel through at least a portion of the third heat exchanger in a parallel flow configuration.

  8. Ionic liquid-in-oil microemulsions.

    PubMed

    Eastoe, Julian; Gold, Sarah; Rogers, Sarah E; Paul, Alison; Welton, Tom; Heenan, Richard K; Grillo, Isabelle

    2005-05-25

    Phase stability and small-angle neutron scattering (SANS) data show that surfactant-stabilized nanodomains of a typical ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF4]) may be dispersed by the nonionic surfactant Triton-X100 in cyclohexane. Analyses of these SANS data are consistent with the formation of ionic liquid-in-oil microemulsion droplets. PMID:15898765

  9. Engineered microorganisms having resistance to ionic liquids

    DOEpatents

    Ruegg, Thomas Lawrence; Thelen, Michael P.

    2016-03-22

    The present invention provides for a method of genetically modifying microorganisms to enhance resistance to ionic liquids, host cells genetically modified in accordance with the methods, and methods of using the host cells in a reaction comprising biomass that has been pretreated with ionic liquids.

  10. Ultraviolet photoinitiated on-fiber copolymerization of ionic liquid sorbent coatings for headspace and direct immersion solid-phase microextraction.

    PubMed

    Ho, Tien D; Yu, Honglian; Cole, William T S; Anderson, Jared L

    2012-11-01

    A high-throughput method for the production of solid-phase microextraction (SPME) sorbent coatings via ultraviolet (UV) photoinitiated copolymerization of ionic liquid (IL) monomers on a fused silica support is described. The copolymerization of monocationic and dicationic IL cross-linkers was performed "on-fiber" using UV initiated free radical polymerization. Mixtures composed of various amounts of the IL cross-linker, UV initiator (DAROCUR 1173), and IL monomer were dip-coated onto an etched and derivatized fused silica support and placed in a high-capacity UV reactor. The method requires no organic dispersive solvent and is much more rapid compared to traditional methods in which polymeric ionic liquid (PIL) sorbent coatings are prepared by 2,2'-azobis(2-methylpropionitrile) (AIBN)-initiated polymerization. Two ionic liquid-based cross-linkers, namely, 1,8-di (3-vinylimidazolium) octane dibromide ([(VIM)(2)C(8)] 2[Br]) and 1,12-di (3-vinylimidazolium) dodecane dibromide ([(VIM)(2)C(12)] 2[Br]), were copolymerized with an ionic liquid monomer, 1-vinyl-3-hexylimidazolium chloride ([VHIM][Cl]), to produce polar cross-linked PIL-based SPME sorbent coatings. The cross-linking and immobilization of these coatings make them particularly applicable in direct immersion SPME. The coatings were applied in the extraction of polar analytes, including alcohols, aldehydes, and esters, from aqueous solutions using headspace and direct immersion SPME gas chromatography mass spectrometry (GC/MS). Compared to linear PIL-based sorbent coatings containing the same anions, the cross-linked PIL-based coatings exhibited higher thermal stability and lower bleed, making them ideal for GC/MS. Recovery experiments were performed in deionized, well, and river water. The structural integrity of the sorbent coatings, as well as their analytical precision, was not diminished after 90 extractions from complex samples using headspace and direct immersion SPME. PMID:22991947

  11. Chromatographic evaluation of reversed-phase/anion-exchange/cation-exchange trimodal stationary phases prepared by electrostatically driven self-assembly process.

    PubMed

    Liu, Xiaodong; Pohl, Christopher; Woodruff, Andrew; Chen, Jinhua

    2011-06-01

    This work describes chromatographic properties of reversed-phase/cation-exchange/anion-exchange trimodal stationary phases. These stationary phases were based on high-purity porous spherical silica particles coated with nano-polymer beads using an electrostatically driven self-assembly process. The inner-pore area of the material was modified covalently with an organic layer that provided both reversed-phase and anion-exchange properties while the outer surface was coated with nano-sized polymer beads with strong cation-exchange characteristics. This design ensured spatial separation of the anion-exchange and the cation-exchange regions, and allowed reversed-phase, anion-exchange and cation-exchange retention mechanisms to function simultaneously. Chromatographic evaluation of ions and small molecules suggested that retention of ionic analytes was influenced by the ionic strength, pH, and mobile phase organic solvent content, and governed by both ion-exchange and hydrophobic interactions. Meanwhile, neutral analytes were retained by hydrophobic interaction and was mainly affected by mobile phase organic solvent content. Depending on the specific application, selectivity could be optimized by adjusting the anion-exchange/cation-exchange capacity ratio (selectivity), which was achieved experimentally by using porous silica particles with different surface areas. PMID:21530974

  12. Spring-loaded polymeric gel actuators

    DOEpatents

    Shahinpoor, M.

    1995-02-14

    Spring-loaded electrically controllable polymeric gel actuators are disclosed. The polymeric gels can be polyvinyl alcohol, polyacrylic acid, or polyacrylamide, and are contained in an electrolytic solvent bath such as water plus acetone. The action of the gel is mechanically biased, allowing the expansive and contractile forces to be optimized for specific applications. 5 figs.

  13. Polymeric Additives For Graphite/Epoxy Composites

    NASA Technical Reports Server (NTRS)

    Kourtides, D. A.; Nir, Z.

    1990-01-01

    Report describes experimental studies of properties of several graphite/epoxy composites containing polymeric additives as flexibilizing or toughening agents. Emphasizes effects of brominated polymeric additives (BPA's) with or without carboxy-terminated butadiene acrylonitrile rubber. Reviews effects of individual and combined additives on fracture toughnesses, environmental stabilities, hot/wet strengths, thermomechanical behaviors, and other mechanical properties of composites.

  14. Radiation polymerization of diethyl fumarate [rapid communication

    NASA Astrophysics Data System (ADS)

    Alkassiri, Haroun

    2005-05-01

    Diethyl fumarate (DEF) has been polymerized by gamma irradiation using doses in the range 50-300 kGy, and in this dose range the polymerization yield increased almost linearly. The polymer has a glass transition temperature of about -20 °C, softening point about 15 °C, and decomposition temperature 300 °C.

  15. Spring-loaded polymeric gel actuators

    DOEpatents

    Shahinpoor, Mohsen

    1995-01-01

    Spring-loaded electrically controllable polymeric gel actuators are disclosed. The polymeric gels can be polyvinyl alcohol, polyacrylic acid, or polyacrylamide, and are contained in an electrolytic solvent bath such as water plus acetone. The action of the gel is mechanically biased, allowing the expansive and contractile forces to be optimized for specific applications.

  16. The use of ionic liquids based on choline chloride for metal deposition: A green alternative?

    PubMed

    Haerens, Kurt; Matthijs, Edward; Chmielarz, Andrzej; Van der Bruggen, Bart

    2009-08-01

    Ionic liquids are studied intensively for different applications. They tend to be denoted as "green solvents", largely because of their low vapour pressure. In recent years toxicity and biotoxicity of ionic liquids have also been investigated, which proved that not all of these are "green". In this paper the use of ionic liquids based on choline chloride and ethylene glycol in electrochemistry is discussed in the context of their use as green solvents. Due to their low toxicity and ready biodegradability, these deep eutectic solvents are promising for the electrodeposition of metals. The influence of the use of these liquids as metal deposition baths on the waste water is investigated. Drag-out was found to be the most influencing parameter on the environmental impact of the process, as it is three times higher compared to classical solutions due to the higher viscosity of the ionic liquid. There are no major changes needed in the rinsing configuration of classic electroplating plants, and ion exchange to remove the metal out of the waste water was not hindered by the presence of the ionic liquid. The formation of by-products during the deposition of metals has to be further investigated and evaluated in consideration of the environmental impact. PMID:19523749

  17. Kinetics and mass spectrometric measurements of myoglobin unfolding in aqueous ionic liquid solutions.

    PubMed

    Miller, Miranda C; Hanna, Sylvia L; DeFrates, Kelsey G; Fiebig, Olivia C; Vaden, Timothy D

    2016-04-01

    Recent studies have characterized the effects of aqueous ionic liquids on myoglobin unfolding for the broader purposes of understanding their effects on protein structures, stabilities, and ultimately biocompatibilities for future applications. Here, we investigated the effects of four different ionic liquids (ILs) on the thermal stability, unfolding kinetics, and tertiary shape of myoglobin. We compared results for four different ILs: 1-butyl-3-methyl imidazolium tetrafluoroborate (BMIBF4); 1-butyl-3-methyl pyrrolidinium tetrafluoroborate (PyrrBF4); 1-ethyl-3-methyl imidazolium acetate (EMIAc); and tetramethylguanidinium acetate (TMGAc). Results showed that ILs accelerate myoglobin unfolding kinetics both through aqueous solution ionic strength effects and ionic liquid-specific effects. Arrhenius plots of observed rate constants reveal that some ILs lower the energy barrier to unfolding, possibly by destabilizing the native protein state. The magnitude of these ionic liquid effects correlates with their effects on protein thermodynamic stabilities. Hydrogen-deuterium exchange (HDX) experiments using ESI-MS showed that myoglobin exhibits a more open, and presumably less stable, tertiary shape in aqueous IL solutions. Overall, BMIBF4 and TMGAc exhibit the strongest effect on the myoglobin stability, unfolding rate, and tertiary structure while PyrrBF4 and EMIAc have weaker effects under our experimental conditions. PMID:26751398

  18. Strong Ionic Hydrogen Bonding Causes a Spectral Isotope Effect in Photoactive Yellow Protein

    PubMed Central

    Kaledhonkar, Sandip; Hara, Miwa; Stalcup, T. Page; Xie, Aihua; Hoff, Wouter D.

    2013-01-01

    Standard hydrogen bonds are of great importance for protein structure and function. Ionic hydrogen bonds often are significantly stronger than standard hydrogen bonds and exhibit unique properties, but their role in proteins is not well understood. We report that hydrogen/deuterium exchange causes a redshift in the visible absorbance spectrum of photoactive yellow protein (PYP). We expand the range of interpretable isotope effects by assigning this spectral isotope effect (SIE) to a functionally important hydrogen bond at the active site of PYP. The inverted sign and extent of this SIE is explained by the ionic nature and strength of this hydrogen bond. These results show the relevance of ionic hydrogen bonding for protein active sites, and reveal that the inverted SIE is a novel, to our knowledge, tool to probe ionic hydrogen bonds. Our results support a classification of hydrogen bonds that distinguishes the properties of ionic hydrogen bonds from those of both standard and low barrier hydrogen bonds, and show how this classification helps resolve a recent debate regarding active site hydrogen bonding in PYP. PMID:24314088

  19. Lithium-Air and ionic Liquids

    SciTech Connect

    Kellar, Michael

    2015-09-01

    The final portion of this project was accomplished at Sandia National Labs, Livermore, with the overall goal being to optimize lithium-air cells with an ionic liquid electrolyte. Both of these are potential future routes for lithium-ion technology. Lithiumair presents the advantage of higher gravimetric energy density, and ionic liquids present the advantage of greater hydrophobicity and much lower volatility, along with a larger window of electrochemical stability. Ionic liquids however have several drawbacks for the battery industry. Currently they are not as cost effective as many organic solvents. Additionally, because of the added viscosity of ionic interactions compared to the typical dipole interactions of a solvent, the ionic conductivity is lower than for common organic solvents.

  20. Ionic liquid incorporating thiosalicylate for metal removal

    NASA Astrophysics Data System (ADS)

    Wilfred, Cecilia Devi; Mustafa, Fadwa Babiker; Romeli, Fatimah Julia

    2012-09-01

    Ionic liquids are a class of organic molten salts "designer solvents" that are composed totally of anions (inorganic and organic polyatomic) and organic cations. The replacement of volatile organic solvents from a separation process is of utmost importance since the use of a large excess of these solvents is hazardous and creates ecological problem. The new method for metal ion extraction is by using task-specific ionic liquids such as ionic liquids which incorporate thiosalicylate functionality. This paper looks at producing a new cluster of ionic liquids which incorporates thiosalicylate with pyridinium cation. Its thermophysical properties such as density and viscosity in single and binary mixtures are studied. The ionic liquids' capability in metal removal processes is evaluated.