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Sample records for ionic surfaces implications

  1. Surface tension of ionic liquids and ionic liquid solutions.

    PubMed

    Tariq, Mohammad; Freire, Mara G; Saramago, Benilde; Coutinho, João A P; Lopes, José N Canongia; Rebelo, Luís Paulo N

    2012-01-21

    Some of the most active scientific research fronts of the past decade are centered on ionic liquids. These fluids present characteristic surface behavior and distinctive trends of their surface tension versus temperature. One way to explore and understand their unique nature is to study their surface properties. This critical review analyses most of the surface tension data reported between 2001 and 2010 (187 references).

  2. Surface Nanocrystallization of an Ionic Liquid

    SciTech Connect

    Jeon, Yoonnam; Vaknin, David; Bu, Wei; Sung, Jaeho; Ouchi, Yukio; Sung, Woongmo; Kim, Doseok

    2012-03-26

    Surface crystallization at the vapor-liquid interface of the ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) is observed in synchrotron x-ray diffraction studies. Sharp Bragg reflections emerge in grazing-angle x-ray diffraction patterns 37 C above the bulk melting temperature, indicating the presence of a long-range ordered phase at the surface in coexistence with the bulk parent liquid. The unique structure of the vapor-liquid interface where butyl chains attached to the cations are expelled to the vapor side facilitates interionic electrostatic interactions that lead to the crystallization. Our results demonstrate the complexity of ionic-liquid structure with their tendency to spontaneously phase separate into nanodomains with finite correlation lengths in coexistence with the liquid phase. By virtue of interfacial boundary conditions, these nanodomains grow laterally to form quasi-two-dimensional crystals.

  3. Influence of the ionic liquid/gas surface on ionic liquid chemistry.

    PubMed

    Lovelock, Kevin R J

    2012-04-21

    Applications such as gas storage, gas separation, NP synthesis and supported ionic liquid phase catalysis depend upon the interaction of different species with the ionic liquid/gas surface. Consequently, these applications cannot proceed to the full extent of their potential without a profound understanding of the surface structure and properties. As a whole, this perspective contains more questions than answers, which demonstrates the current state of the field. Throughout this perspective, crucial questions are posed and a roadmap is proposed to answer these questions. A critical analysis is made of the field of ionic liquid/gas surface structure and properties, and a number of design rules are mined. The effects of ionic additives on the ionic liquid/gas surface structure are presented. A possible driving force for surface formation is discussed that has, to the best of my knowledge, not been postulated in the literature to date. This driving force suggests that for systems composed solely of ions, the rules for surface formation of dilute electrolytes do not apply. The interaction of neutral additives with the ionic liquid/gas surface is discussed. Particular attention is focussed upon H(2)O and CO(2), vital additives for many applications of ionic liquids. Correlations between ionic liquid/gas surface structure and properties, ionic liquid surfaces plus additives, and ionic liquid applications are given.

  4. Surface modification using ionic liquid ion beams

    NASA Astrophysics Data System (ADS)

    Takaoka, Gikan H.; Hamaguchi, Takuya; Takeuchi, Mitsuaki; Ryuto, Hiromichi

    2014-12-01

    We developed an ionic liquid (IL) ion source using 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) and produced IL ion beams by applying a high electric field between the tip and the extractor. Time-of-flight measurements showed that small cluster and fragment ions were contained in the positive and negative ion beams. The positive and negative cluster ions were deposited on Si(1 0 0) substrates. X-ray photoelectron spectroscopy measurements showed that the composition of the deposited layers was similar to that of an IL solvent. This suggests that a cation (A+) or an anion (B-) was attached to an IL cluster (AB)n, resulting in the formation of positive cluster ions (AB)nA+ or negative cluster ions (AB)nB-, respectively. The surfaces of the IL layers deposited on Si(1 0 0) substrates were flat at an atomic level for positive and negative cluster ion irradiation. Moreover, the contact angles of the deposited layers were similar to that of the IL solvent. Thus, surface modification of Si(1 0 0) substrates was successfully demonstrated with BMIM-PF6 cluster ion beams.

  5. Ionic conductivity on a wetting surface.

    PubMed

    Skinner, Brian; Loth, M S; Shklovksii, B I

    2009-10-01

    Recent experiments measuring the electrical conductivity of DNA molecules highlight the need for a theoretical model of ion transport along a charged surface. Here we present a simple theory based on the idea of unbinding of ion pairs. The strong humidity dependence of conductivity is explained by the decrease in the electrostatic self-energy of a separated pair when a layer of water (with high dielectric constant) is adsorbed to the surface. We compare our prediction for conductivity to experiment and discuss the limits of its applicability.

  6. Ionic surface active compounds in atmospheric aerosols.

    PubMed

    Sukhapan, Jariya; Brimblecombe, Peter

    2002-04-27

    Surfactants in the atmosphere have several potential roles in atmospheric chemistry. They can form films on aqueous surfaces, which lowers the surface tension and possibly delays water evaporation and gaseous transportation across the aqueous interface. They can also increase the solubility of organic compounds in the aqueous phase. Recently, the decrease of surface tension in cloud growing droplets has been suggested as relevant to increases in the number of droplets of smaller size, potentially enhancing cloud albedo. Natural surfactants in the lung aid gas transfer and influence the dissolution rate of aerosol particles, so surfactants in atmospheric aerosols, once inhaled, may interact with pulmonary surfactants. Ambient aerosols were collected from the edge of Norwich, a small city in a largely agricultural region of England, and analysed for surfactants. Methylene blue, a conventional dye for detecting anionic surfactants, has been used as a colorimetric agent. The concentration of surfactants expressed as methylene blue active substances (MBAS) is in the range of 6-170 pmol m(-3)(air). A negative correlation with chloride aerosol indicates that these surfactants are probably not the well-known surfactants derived from marine spray. A more positive correlation with aerosol nitrate and gaseous NOx supports an association with more polluted inland air masses. The surfactants found in aerosols seem to be relatively strong acids, compared with weaker acids such as the long-chain carboxylic acids previously proposed as atmospheric surfactants. Surfactants from the oxidation of organic materials (perhaps vegetation- or soil-derived) seem a likely source of these substances in the atmosphere.

  7. Corrosion prevention of magnesium surfaces via surface conversion treatments using ionic liquids

    DOEpatents

    Qu, Jun; Luo, Huimin

    2016-09-06

    A method for conversion coating a magnesium-containing surface, the method comprising contacting the magnesium-containing surface with an ionic liquid compound under conditions that result in decomposition of the ionic liquid compound to produce a conversion coated magnesium-containing surface having a substantially improved corrosion resistance relative to the magnesium-containing surface before said conversion coating. Also described are the resulting conversion-coated magnesium-containing surface, as well as mechanical components and devices containing the conversion-coated magnesium-containing surface.

  8. Orientational ordering of ionic liquids near a charged mica surface.

    PubMed

    Payal, Rajdeep Singh; Balasubramanian, Sundaram

    2012-05-14

    The self-assembly of ions in room-temperature ionic liquids adsorbed on a mica surface is studied using molecular dynamics simulations. Four liquids from the 1-methyl,n-alkylimidazolium bis(trifluoromethylsulfonyl)imide ([C(n)mim][NTf(2)]) family are investigated, where n ranges between 2 and 8. Cations with ethyl or butyl groups are found to orient with the hydrocarbon tails lying parallel to the surface, while the hexyl and octyl tails of cations are observed to be oriented perpendicular to it. The crossover in the orientational preference matches recent observations of surface forces of these liquids.

  9. A smart surface with switchable wettability by an ionic liquid.

    PubMed

    Chang, Li; Liu, Hongliang; Ding, Yi; Zhang, Jiajing; Li, Li; Zhang, Xiqi; Liu, Mingzhu; Jiang, Lei

    2017-02-28

    Smart control of surface wettability by ionic liquids (ILs) is significant for designing IL-related intelligent materials and devices. Herein, we present mixed molecular brushes comprised of poly(phenylethyl methacrylate) and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (PPhEtMA-co-PFDMS) grafted surfaces that are capable of dynamically regulating 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm][NTf2]) wettability. (1)H NMR and quartz crystal microbalance characterization demonstrate that the wettability changes result from a temperature-dominated cation-π interaction between [EMIm][NTf2] and PPhEtMA-co-PFDMS brushes.

  10. Dynamics and Interactions in Room Temperature Ionic Liquids, Surfaces and Interfaces

    DTIC Science & Technology

    2016-01-13

    AFRL-AFOSR-VA-TR-2016-0067 Dynamics and Interactions in Room Temperature Ionic Liquids, Surfaces and Interfaces Michael Fayer LELAND STANFORD JUNIOR...2016 4. TITLE AND SUBTITLE Dynamics and Interactions in Room Temperature Ionic Liquids, Surfaces and Interfaces 5a. CONTRACT NUMBER 5b. GRANT...were performed. Room temperature ionic liquids were also investigated. Room temperature ionic liquids (RTIL) are intrinsically interesting because

  11. Surface confined ionic liquid as a stationary phase for HPLC

    SciTech Connect

    Wang, Qian; Baker, Gary A; Baker, Sheila N; Colon, Luis

    2006-01-01

    Trimethoxysilane ionosilane derivatives of room temperature ionic liquids based on alkylimidazolium bromides were synthesized for attachment to silica support material. The derivatives 1-methyl-3-(trimethoxysilylpropyl)imidazolium bromide and 1-butyl-3-(trimethoxysilylpropyl)imidazolium bromide were used to modify the surface of 3 {micro}m diameter silica particles to act as the stationary phase for HPLC. The modified particles were characterized by thermogravimetric analysis (TGA) and {sup 13}C and {sup 29}Si NMR spectroscopies. The surface modification procedure rendered particles with a surface coverage of 0.84 {micro}mol m{sup -2} for the alkylimidazolium bromide. The ionic liquid moiety was predominantly attached to the silica surface through two siloxane bonds of the ionosilane derivative (63%). Columns packed with the modified silica material were tested under HPLC conditions. Preliminary evaluation of the stationary phase for HPLC was performed using aromatic carboxylic acids as model compounds. The separation mechanism appears to involve multiple interactions including ion exchange, hydrophobic interaction, and other electrostatic interactions.

  12. Imidazolium-based ionic liquids grafted on solid surfaces.

    PubMed

    Xin, Bingwei; Hao, Jingcheng

    2014-01-01

    Supported ionic liquids (SILs), which refer to ionic liquids (ILs) immobilized on supports, are among the most important derivatives of ILs. The immobilization process of ILs can transfer their desired properties to substrates. Combination of the advantages of ILs with those of support materials will derive novel performances while retaining properties of both moieties. SILs have been widely applied in almost all of fields involving ILs, and have brought about drastic expansion of the ionic liquid area. As green media in organic catalytic reactions, based on utilizing the ability of ILs to stabilize the catalysts, they have many advantages over free ILs, including avoiding the leaching of ILs, reducing their amount, and improving the recoverability and reusability of both themselves and catalysts. This has critical significance from both environmental and economical points of view. As novel functional materials in surface science and material chemistry, SILs are ideal surface modifying agents. They can modify and improve the properties of solids, such as wettability, lubricating property, separation efficiency and electrochemical response. With the achievements in the field of ILs, using magnetic nanoparticles (MNPs) to SILs has drawn increasing attention in catalytic reactions and separation technologies, and achieved substantial progress. The combination of MNPs and ILs renders magnetic SILs, which exhibit the unique properties of ILs as well as facile separation by an external magnetic field. In this article, we focus on imidazolium-based ILs covalently grafted to non-porous and porous inorganic materials. The excellent stability and durability of this kind of SILs offer a great advantage compared with free ILs and IL films physically adsorbed on substrates without covalent bonds. Including examples from our own research, we overview mainly the applications and achievements of covalent-linked SILs in catalytic reactions, surface modification, separation

  13. Fine tuning the ionic liquid-vacuum outer atomic surface using ion mixtures.

    PubMed

    Villar-Garcia, Ignacio J; Fearn, Sarah; Ismail, Nur L; McIntosh, Alastair J S; Lovelock, Kevin R J

    2015-03-28

    Ionic liquid-vacuum outer atomic surfaces can be created that are remarkably different from the bulk composition. In this communication we demonstrate, using low-energy ion scattering (LEIS), that for ionic liquid mixtures the outer atomic surface shows significantly more atoms from anions with weaker cation-anion interactions (and vice versa).

  14. 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.

  15. Noncovalent interactions in halogenated ionic liquids: theoretical study and crystallographic implications.

    PubMed

    Li, Haiying; Lu, Yunxiang; Wu, Weihong; Liu, Yingtao; Peng, Changjun; Liu, Honglai; Zhu, Weiliang

    2013-03-28

    In recent years, several specific imidazolium-based ionic liquids with halogen substituents on the imidazole ring as well as on the alkyl chains have been reported. In this work, noncovalent interactions in four halogenated ionic liquids, i.e. 2-bromo-/iodo- and 4,5-dibromo-/diiodo-1,3-dimethylimidazolium trifluoromethanesulfonates, were systematically investigated using density functional theory calculations. The structural and energetic properties of the ion pairs for such ionic liquids have been fully examined and compared with the non-halogenated ones. It was found that C-X···O halogen bonds, C-H···O hydrogen bonds, and electrostatic interactions with the anion located over the imidazole ring in the ion pairs. In addition, the structures and energetics of two ion pairs for such ionic liquids were also explored to reproduce experimental observations. The halogen-bonded ring structures and the conformers with the concurrent C-H···O and C-X···O contacts were predicted, consistent with the X-ray crystal structures of corresponding organic salts. Finally, the implications of the observed structural and energetic features of ion pairs on the design of halogen-bonding ionic liquids were discussed. The results presented herein should provide useful information in the development of novel halogenated ionic liquids used for specific tasks ranging from organic synthesis to gas absorption.

  16. Fluorination effects on the thermodynamic, thermophysical and surface properties of ionic liquids

    PubMed Central

    Reis, P. M.; Carvalho, P. J.; Lopes-da-Silva, J. A.; Esperança, J. M. S. S.; Araújo, J. M. M.; Rebelo, L. P. N.; Freire, M. G.; Pereiro, A. B.

    2016-01-01

    This paper reports the thermal, thermodynamic, thermophysical and surface properties of eight ionic liquids with fluorinated alkyl side chain lengths equal or greater than four carbon atoms. Melting and decomposition temperatures were determined together with experimental densities, surface tensions, refractive indices, dynamic viscosities and ionic conductivities in a temperature interval ranging from 293.15 to 353.15 K. The surface properties of these fluorinated ionic liquids were discussed and several thermodynamic functions, as well as critical temperatures, were estimated. Coefficients of isobaric thermal expansion, molecular volumes and free volume effects were calculated from experimental values of density and refractive index and compared with previous data. Finally, Walden plots were used to evaluate the ionicity of the investigated ionic liquids. PMID:27642190

  17. Effect of UV exposure on the surface chemistry of wood veneers treated with ionic liquids

    NASA Astrophysics Data System (ADS)

    Patachia, Silvia; Croitoru, Catalin; Friedrich, Christian

    2012-07-01

    In this paper, the influence of four types of imidazolium-based ionic liquids (ILs) on the chemical alteration of the surface of wood veneers exposed to 254 nm UV irradiation have been studied by using image analysis, Fourier transform infrared spectroscopy and surface energy calculation. The wood treated with ionic liquids showed better stability to UV light, as demonstrated by the low lignin, carbonyl index and cellulose crystallinity index variation, as well as very small color modification of the surface with the increase of the UV exposure period, by comparing to non-treated wood. The results show that the tested ionic liquids could be effective as UV stabilizers.

  18. Robust surface nano-architecture by alkali-carboxylate ionic bonding.

    PubMed

    Skomski, Daniel; Abb, Sabine; Tait, Steven L

    2012-08-29

    Ionic bonding in supramolecular surface networks is a promising strategy to self-assemble nanostructures from organic building blocks with atomic precision. However, sufficient thermal stability of such systems has not been achieved at metal surfaces, likely due to partial screening of the ionic interactions. We demonstrate excellent stability of a self-assembled ionic network on a metal surface at elevated temperatures. The structure is characterized directly by atomic resolution scanning tunneling microscopy (STM) experiments conducted at 165 °C showing intact domains. This robust nanometer-scale structure is achieved by the on-surface reaction of a simple and inexpensive compound, sodium chloride, with a model system for carboxylate interactions, terephthalic acid (TPA). Rather than distinct layers of TPA and NaCl, angle resolved X-ray photoelectron spectroscopy experiments indicate a replacement reaction on the Cu(100) surface to form Na-carboxylate ionic bonds. Chemical shifts in core level electron states confirm a direct interaction and a +1 charge state of the Na. High-temperature STM imaging shows virtually no fluctuation of Na-TPA island boundaries, revealing a level of thermal stability that has not been previously achieved in noncovalent organic-based nanostructures at surfaces. Comparable strength of intermolecular ionic bonds and intramolecular covalent bonds has been achieved in this surface system. The formation of these highly ordered structures and their excellent thermal stability is dependent on the interplay of adsorbate-substrate and ionic interactions and opens new possibilities for ionic self-assemblies at surfaces with specific chemical function. Robust ionic surface structures have potential uses in technologies requiring high thermal stability and precise ordering through self-assembly.

  19. Surface-functionalized ionic liquid crystal-supported ionic liquid phase materials: ionic liquid crystals in mesopores.

    PubMed

    Kohler, Florian T U; Morain, Bruno; Weiss, Alexander; Laurin, Mathias; Libuda, Jörg; Wagner, Valentin; Melcher, Berthold U; Wang, Xinjiao; Meyer, Karsten; Wasserscheid, Peter

    2011-12-23

    The influence of confinement on the ionic liquid crystal (ILC) [C(18)C(1)Im][OTf] is studied using differential scanning calorimetry (DSC), polarized optical microscopy (POM), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The ILC studied is supported on Si-based powders and glasses with pore sizes ranging from 11 to 50 nm. The temperature of the solid-to-liquid-crystalline phase transition seems mostly unaffected by the confinement, whereas the temperature of the liquid-crystalline-to-liquid phase transition is depressed for smaller pore sizes. A contact layer with a thickness in the order of 2 nm is identified. The contact layer exhibits a phase transition at a temperature 30 K lower than the solid-to-liquid-crystalline phase transition observed for the neat ILC. For applications within the "supported ionic liquid phase (SILP)" concept, the experiments show that in pores of diameter 50 nm a pore filling of α>0.4 is sufficient to reproduce the phase transitions of the neat ILC.

  20. 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.

  1. Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

    PubMed

    Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

    2016-05-02

    Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

  2. Probing the interaction of ionic liquids with graphene using surface-enhanced Raman spectroscopy

    DOE PAGES

    Mahurin, Shannon Mark; Dai, Sheng; Surwade, Sumedh P.; ...

    2015-12-17

    We report an in situ measurement of the interaction of an imidazolium-based room temperature ionic liquid with both pure silver and a graphene-over-silver electrode under an applied electrochemical potential. At a negative applied potential, overall signal intensity increased indicating enhanced ionic liquid concentration at both silver and graphene electrodes. Vibrational modes associated with the imidazolium ring exhibited greater intensity enhancements and larger peak shifts compared with the anion indicating that the cation adsorbs with the ring and alkyl chain parallel to the electrode surface for both silver and graphene. In contrast to the silver, the surface enhanced Raman spectra ofmore » the ionic liquid near graphene showed shifts in the cation peaks even at no applied potential because of the strong π–π interaction between the ionic liquid and the graphene. Furthermore, the intensity of the graphene peak decreased in the presence of ionic liquid possibly due to the interaction between the ionic liquid and graphene. In conclusion, these results illustrate the effectiveness of surface-enhanced Raman spectroscopy to investigate electrolyte interactions with graphene at the liquid/electrode interface.« less

  3. Probing the interaction of ionic liquids with graphene using surface-enhanced Raman spectroscopy

    SciTech Connect

    Mahurin, Shannon Mark; Dai, Sheng; Surwade, Sumedh P.; Crespo, Marcos

    2015-12-17

    We report an in situ measurement of the interaction of an imidazolium-based room temperature ionic liquid with both pure silver and a graphene-over-silver electrode under an applied electrochemical potential. At a negative applied potential, overall signal intensity increased indicating enhanced ionic liquid concentration at both silver and graphene electrodes. Vibrational modes associated with the imidazolium ring exhibited greater intensity enhancements and larger peak shifts compared with the anion indicating that the cation adsorbs with the ring and alkyl chain parallel to the electrode surface for both silver and graphene. In contrast to the silver, the surface enhanced Raman spectra of the ionic liquid near graphene showed shifts in the cation peaks even at no applied potential because of the strong π–π interaction between the ionic liquid and the graphene. Furthermore, the intensity of the graphene peak decreased in the presence of ionic liquid possibly due to the interaction between the ionic liquid and graphene. In conclusion, these results illustrate the effectiveness of surface-enhanced Raman spectroscopy to investigate electrolyte interactions with graphene at the liquid/electrode interface.

  4. New Alkylether-Thiazolium Room-Temperature Ionic Liquid Lubricants: Surface Interactions and Tribological Performance.

    PubMed

    Espinosa, Tulia; Sanes, José; Bermúdez, María-Dolores

    2016-07-20

    The use of newly synthesized alkylether-thiazolium ionic liquids as lubricants is described for the first time. Two ionic liquids composed of a thiazolium cation and a bis(trifluoromethanesulfonyl)amide ([Th][Tf2N]) or dicyanamide ([Th][(NC)2N]) anion have been studied, and their tribological behavior has been compared with that of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([Im][Tf2N]) in pin-on-disk tests using sapphire balls against AISI 52100 or AISI 316L steels. All ionic liquids show higher contact angles on AISI 316L steel than on AISI 52100, the lowest values found for ([Im][Tf2N]) on both steel surfaces. AISI 52100 shows similar friction coefficients for all lubricants, and negligible wear rates for the ionic liquids containing the bis(trifluoromethanesulfonyl)amide anion. Immersion tests show no corrosion of AISI 52100 in imidazolium or thiazolium bis(trifluoromethanesulfonyl)amide ionic liquids. AISI 316L shows similar friction coefficients for both bis(trifluoromethanesulfonyl)amide ionic liquids, but the lowest wear rate is obtained for [Th][Tf2N]. An increase in friction coefficient and wear rate is observed for thiazolium dicyanamide. This increase is related to a tribocorrosion process due to decomposition of the thiazolium cation. XPS shows the formation of iron sulfide on the wear track on AISI 316L after lubrication with thiazolium dicyanamide. No tribocorrosion processes take place for the [Tf2N] ionic liquids.

  5. Geometric quantization of curvature energy in equipotential surfaces of ionic crystals

    NASA Astrophysics Data System (ADS)

    Gandy, Paul J. F.; Klinowski, Jacek

    2002-06-01

    The curvature energies of triply periodic minimal surfaces (TPMS) and zero equipotential surfaces (ZEPS) of ionic crystals are both quantized with the Euler-Poincaré characteristic as the "quantum number," and the curvature energy of the TPMS larger than that of the corresponding ZEPS. Quantization is imposed by the charge-defined metric.

  6. Achieving enhanced ionic mobility in nanoporous silica by controlled surface interactions.

    PubMed

    Garaga, Mounesha Nagendrachar; Aguilera, Luis; Yaghini, Negin; Matic, Aleksandar; Persson, Michael; Martinelli, Anna

    2017-02-22

    We report a strategy to enhance the ionic mobility in an emerging class of gels, based on robust nanoporous silica micro-particles, by chemical functionalization of the silica surface. Two very different ionic liquids are used to fill the nano-pores of silica at varying pore filling factors, namely one aprotic imidazolium based (1-methyl-3-hexylimidazolium bis(trifluoromethanesulfonyl)imide, C6C1ImTFSI), and one protic ammonium based (diethylmethylammonium methanesulfonate, DEMAOMs) ionic liquid. Both these ionic liquids display higher ionic mobility when confined in functionalized silica as compared to untreated silica nano-pores, an improvement that is more pronounced at low pore filling factors (i.e. in the nano-sized pore domains) and observed in the whole temperature window investigated (i.e. from -10 to 140 °C). Solid-state NMR, diffusion NMR and dielectric spectroscopy concomitantly demonstrate this effect. The origin of this enhancement is explained in terms of weaker intermolecular interactions and a consequent flipped-ion effect at the silica interface strongly supported by 2D solid-state NMR experiments. The possibility to significantly enhance the ionic mobility by controlling the nature of surface interactions is extremely important in the field of materials science and highlights these structurally tunable gels as promising solid-like electrolytes for use in energy relevant devices. These include, but are not limited to, Li-ion batteries and proton exchange membrane (PEM) fuel cells.

  7. Chemical Reactivity as a Probe of Ionic-Liquid Surfaces

    DTIC Science & Technology

    2009-04-30

    Fernandez de la Mora, and M. Gamero-Castaño, J. Appl. Phys., 2003, 94, 3599. 10 N. V. Plechkova and K. R. Seddon , Chem. Soc. Rev., 2008, 37, 123. 11 G ...Costen and Kenneth G McKendrick* School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UK k.g.mckendrick@hw.ac.uk...synthesizing the ionic liquids for these experiments. REFERENCES 1 J. D. Holbrey and K. R. Seddon , Clean Products and Processes, 1999, 1, 223. 2

  8. Charging of ionic liquid surfaces under X-ray irradiation: the measurement of absolute binding energies by XPS.

    PubMed

    Villar-Garcia, Ignacio J; Smith, Emily F; Taylor, Alasdair W; Qiu, Fulian; Lovelock, Kevin R J; Jones, Robert G; Licence, Peter

    2011-02-21

    Ionic liquid surfaces can become electrically charged during X-ray photoelectron spectroscopy experiments, due to the flux of photoelectrons leaving the surface. This causes a shift in the measured binding energies of X-ray photoelectron peaks that depends on the magnitude of the surface charging. Consequently, a charge correction method is required for ionic liquids. Here we demonstrate the nature and extent of surface charging in ionic liquids and model it using chronopotentiometry. We report the X-ray photoelectron spectra for a range of imidazolium based ionic liquids and investigate the use of long alkyl chains (C(n)H(2n+1), n ≥ 8) and the imidazolium nitrogen, both of which are part of the ionic liquid chemical structure, as internal references for charge correction. Accurate and reproducible binding energies are obtained which allow comparisons to be made across ionic liquid-based systems.

  9. Surface-active ionic liquids in catalysis: Impact of structure and concentration on the aerobic oxidation of octanol in water.

    PubMed

    Cognigni, Alice; Kampichler, Sebastian; Bica, Katharina

    2017-04-15

    We present design and synthesis of surface-active ionic liquids for the application in micellar catalysis. A series of 1-methyl-3-dodecylimidazolium based ionic liquids with variable core structures including dicationic and zwitterionic ones was synthesized and characterized. These surface-active ionic liquids where applied in the aerobic oxidation of aliphatic alcohols to carbonyl compounds. A strong dependence on the ionic liquid concentration and structure was identified, which is in accordance with the concepts of micellar catalysis. Optimum conditions for the oxidation of 1-octanol could be identified, and the use of surface-active ionic liquids strongly improved the reaction performance compared to pure water. Under optimized conditions, it was possible to isolate up to 75% of octanoic acid using only small amounts of surface-active ionic liquid in a 0.05mM solution in water without further ligands.

  10. Magadiite Templated High Surface Area Graphene-Type Carbons from Metal-Halide based Ionic Liquids

    SciTech Connect

    Fulvio, Pasquale F; Hillesheim, Patrick C; Bauer, John C; Mahurin, Shannon Mark; Dai, Sheng; Arend, Nikolas

    2013-01-01

    Freestanding silicon films with a thickness ranging from 1 nm to several micrometers were prepared by Cat-CVD onto ionic liquid ([BMIM][BF4]) surfaces for the first time. The films, obtained without a solid substrate, can be facilely characterized by TEM and AFM to study the film formation and growth process.

  11. Accelerated CO2 transport on surface of AgO nanoparticles in ionic liquid BMIMBF4

    NASA Astrophysics Data System (ADS)

    Ji, Dahye; Kang, Yong Soo; Kang, Sang Wook

    2015-11-01

    The AgO nanoparticles were utilized for a CO2 separation membrane. The AgO nanoparticles were successfully generated in ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate (BMIMBF4) by favorable interaction between the surface of particles and the counteranion of BMIMBF4. The generated AgO nanoparticles were confirmed by TEM, and the average size was 20 nm. Coordinative interactions of dissociated AgO particles with BMIM+BF4- were investigated by FT-Raman spectroscopy. When the ionic liquid BMIMBF4 containing AgO nanoparticles was utilized as a CO2 separation membrane, the separation performance was largely enhanced.

  12. Accelerated CO2 transport on surface of AgO nanoparticles in ionic liquid BMIMBF4

    PubMed Central

    Ji, Dahye; Kang, Yong Soo; Kang, Sang Wook

    2015-01-01

    The AgO nanoparticles were utilized for a CO2 separation membrane. The AgO nanoparticles were successfully generated in ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate (BMIMBF4) by favorable interaction between the surface of particles and the counteranion of BMIMBF4. The generated AgO nanoparticles were confirmed by TEM, and the average size was 20 nm. Coordinative interactions of dissociated AgO particles with BMIM+BF4− were investigated by FT-Raman spectroscopy. When the ionic liquid BMIMBF4 containing AgO nanoparticles was utilized as a CO2 separation membrane, the separation performance was largely enhanced. PMID:26549605

  13. Ionic Behavior in Highly Concentrated Aqueous Solutions Nanoconfined between Discretely Charged Silicon Surfaces.

    PubMed

    Qiu, Yinghua; Ma, Jian; Chen, Yunfei

    2016-05-17

    Through molecular dynamics simulations considering thermal vibration of surface atoms, ionic behaviors in concentrated NaCl solutions confined between discretely charged silicon surfaces have been investigated. The electric double layer structure was found to be sensitive to the density and distribution of surface charges. Due to the discreteness of the surface charge, a slight charge inversion appeared which depended on the surface charge density, bulk concentration, and confinement. In the nanoconfined NaCl solutions concentrated from 0.2 to 4.0 M, the locations of accumulation layers for Na(+) and Cl(-) ions remained stable, but their peak values increased. The higher the concentration was, the more obvious the charge inversion appeared. In 4.0 M NaCl solution, Na(+) and Cl(-) ions show obvious alternating layered distributions which may correspond to the solidification found in experiments. By changing surface separation, the confinement had a large effect on the ionic distribution. As both surfaces approached each other, many ions and water molecules were squeezed out of the confined space. Two adjacent layers in ion or water distribution profiles can be forced closer to each other and merge together. From ionic hydration analysis, the coordination number of Na(+) ions in highly confined space was much lower than that in the bulk.

  14. Peculiar surface behavior of some ionic liquids based on active pharmaceutical ingredients.

    PubMed

    Restolho, José; Mata, José Luis; Saramago, Benilde

    2011-02-21

    The ionic liquids based on biologically active cations and anions, commonly designated by ionic liquids based on active pharmaceutical ingredients (ILs-APIs), are interesting compounds for use in pharmaceutical applications. Lidocaine docusate, ranitidine docusate, and didecyldimethylammonium ibuprofen are examples of promising ILs-APIs that were recently synthesized. They were submitted to biological testing and calorimetric measurements, but nothing is known about their surface properties. In this work, we measured the surface tension and the contact angles on both hydrophilic and hydrophobic surfaces in a temperature range as wide as possible. Based on the wettability data, the polarity fractions were estimated using the Fowkes theory. The peculiar surface behavior observed was tentatively attributed to the presence of mesophases.

  15. Effect of cation symmetry on the organization of ionic liquids near a charged mica surface.

    PubMed

    Payal, Rajdeep Singh; Balasubramanian, Sundaram

    2014-07-16

    Atomistic molecular dynamics simulations have been carried out to understand the effect of the symmetry of cations on the microscopic organization of ionic liquids near a charged mica surface. Ionic liquids with a 1,3-alkylimidazolium ([C(n)C(m)im](+)) cation and a bis(trifluoromethylsulfonyl)imide ([NTf2](-)) anion were investigated. Apart from symmetry, the length of the alkyl group attached to the cation is found to crucially determine the ion structure near the solid surface. In the first adsorbed layer, the ring planes of cations with shorter alkyl groups (less than four carbon atoms) are oriented either parallel or perpendicular to the surface. However, cations with longer alkyl tails are exclusively observed to have their ring planes parallel to the mica surface. The alkyl groups too show a similar dependence of their orientation on the tail length. Further, symmetric cations with alkyl groups of intermediate length are more highly structured at the interface than their asymmetric counterparts.

  16. Effect of surface bilayer charges on the magnetic field around ionic channels

    NASA Astrophysics Data System (ADS)

    Gomes Soares, Marília Amável; Cortez, Celia Martins; Oliveira Cruz, Frederico Alan de; Silva, Dilson

    2017-01-01

    In this work, we present a physic-mathematical model for representing the ion transport through membrane channels, in special Na+ and K+-channels, and discuss the influence of surface bilayer charges on the magnetic field behavior around the ionic current. The model was composed of a set of equations, including: a nonlinear differential Poisson-Boltzmann equation which usually allows to estimate the surface potentials and electric potential profile across membrane; equations for the ionic flux through channel and the ionic current density based on Armstrong's model for Na+ and K+ permeability and other Physics concepts; and a magnetic field expression derived from the classical Ampère equation. Results from computational simulations using the finite element method suggest that the ionic permeability is strongly dependent of surface bilayer charges, the current density through a K+-channel is very less sensible to temperature changes than the current density through a Na+- channel, active Na+-channels do not directly interfere with the K+-channels around, and vice-versa, since the magnetic perturbation generated by an active channel is of short-range.

  17. Surface active complexes formed between keratin polypeptides and ionic surfactants.

    PubMed

    Pan, Fang; Lu, Zhiming; Tucker, Ian; Hosking, Sarah; Petkov, Jordan; Lu, Jian R

    2016-12-15

    Keratins are a group of important proteins in skin and hair and as biomaterials they can provide desirable properties such as strength, biocompatibility, and moisture regaining and retaining. The aim of this work is to develop water-soluble keratin polypeptides from sheep wool and then explore how their surface adsorption behaves with and without surfactants. Successful preparation of keratin samples was demonstrated by identification of the key components from gel electrophoresis and the reproducible production of gram scale samples with and without SDS (sodium dodecylsulphate) during wool fibre dissolution. SDS micelles could reduce the formation of disulphide bonds between keratins during extraction, reducing inter-molecular crosslinking and improving keratin polypeptide solubility. However, Zeta potential measurements of the two polypeptide batches demonstrated almost identical pH dependent surface charge distributions with isoelectric points around pH 3.5, showing complete removal of SDS during purification by dialysis. In spite of different solubility from the two batches of keratin samples prepared, very similar adsorption and aggregation behavior was revealed from surface tension measurements and dynamic light scattering. Mixing of keratin polypeptides with SDS and C12TAB (dodecyltrimethylammonium bromide) led to the formation of keratin-surfactant complexes that were substantially more effective at reducing surface tension than the polypeptides alone, showing great promise in the delivery of keratin polypeptides via the surface active complexes. Neutron reflection measurements revealed the coexistence of surfactant and keratin polypeptides at the interface, thus providing the structural support to the observed surface tension changes associated with the formation of the surface active complexes.

  18. Ionic liquids influence on the surface properties of electron beam irradiated wood

    NASA Astrophysics Data System (ADS)

    Croitoru, Catalin; Patachia, Silvia; Doroftei, Florica; Parparita, Elena; Vasile, Cornelia

    2014-09-01

    In this paper, the influence of three imidazolium-based ionic liquids (1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate and 1-hexyl-3-methylimidazolium chloride) on the structure and surface properties of sycamore maple (Acer pseudoplatanus) veneers submitted to electron beam irradiation with a dose of 50 kGy has been studied by using Fourier transform infrared spectroscopy, as well as image, scanning electron microscopy/SEM/EDX, atomic force microscopy and contact angle analysis. The experimental results have proven that the studied ionic liquids determine a better preservation of the structural features of wood (cellulose crystallinity index and lignin concentration on the surface) as well as some of surface properties such as surface energy, roughness, color upon irradiation with electron beam, in comparison with the reference wood, but surface composition is changed by treatment with imidazolium-based ionic liquids mainly with 1-butyl-3-methylimidazolium tetrafluoroborate. Also, under electron beam irradiation covalent bonding of the imidazolium moiety to wood determines a higher resistance to water penetration and spreading on the surface.

  19. Ionic enhancement of silica surface nanowear in electrolyte solutions.

    PubMed

    Vakarelski, Ivan U; Teramoto, Naofumi; McNamee, Cathy E; Marston, Jeremy O; Higashitani, Ko

    2012-11-20

    The nanoscale wear and friction of silica and silicon nitride surfaces in aqueous electrolyte solutions were investigated by using sharp atomic force microscope (AFM) cantilever tips coated with silicon nitride. Measurements were carried out in aqueous solutions of varying pH and in monovalent and divalent cation chloride and nitrate solutions. The silica surface was shown to wear strongly in solutions of high pH (≈11.0), as expected, but the presence of simple cations, such as Cs(+) and Ca(2+), was shown to dramatically effect the wear depth and friction force for the silica surface. In the case of monovalent cations, their hydration enthalpies correlated well with the wear and friction. The weakest hydrated cation of Cs(+) showed the most significant enhancement of wear and friction. In the case of divalent cations, a complex dependence on the type of cation was found, where the type of anion was also seen to play an important role. The CaCl(2) solution showed the anomalous enhancement of wear depth and friction force, although the solution of Ca(NO(3))(2) did not. The present results obtained with an AFM tip were also compared with previous nanotribology studies of silica surfaces in electrolyte solutions, and possible molecular mechanisms as to why cations enhance the wear and friction were also discussed.

  20. Influence of substituents and functional groups on the surface composition of ionic liquids.

    PubMed

    Kolbeck, Claudia; Niedermaier, Inga; Deyko, Alexey; Lovelock, Kevin R J; Taccardi, Nicola; Wei, Wei; Wasserscheid, Peter; Maier, Florian; Steinrück, Hans-Peter

    2014-04-01

    We have performed a systematic study addressing the surface behavior of a variety of functionalized and non-functionalized ionic liquids (ILs). From angle-resolved X-ray photoelectron spectroscopy, detailed conclusions on the surface enrichment of the functional groups and the molecular orientation of the cations and anions is derived. The systems include imidazolium-based ILs methylated at the C2 position, a phenyl-functionalized IL, an alkoxysilane-functionalized IL, halo-functionalized ILs, thioether-functionalized ILs, and amine-functionalized ILs. The results are compared with the results for corresponding non-functionalized ILs where available. Generally, enrichment of the functional group at the surface is only observed for systems that have very weak interaction between the functional group and the ionic head groups.

  1. Surface structure determinations of crystalline ionic thin films grown on transition metal single crystal surfaces by low energy electron diffraction

    SciTech Connect

    Roberts, Joel Glenn

    2000-05-01

    The surface structures of NaCl(100), LiF(100) and alpha-MgCl2(0001) adsorbed on various metal single crystals have been determined by low energy electron diffraction (LEED). Thin films of these salts were grown on metal substrates by exposing the heated metal surface to a molecular flux of salt emitted from a Knudsen cell. This method of investigating thin films of insulators (ionic salts) on a conducting substrate (metal) circumvents surface charging problems that plagued bulk studies, thereby allowing the use of electron-based techniques to characterize the surface.

  2. Neptunium (V) Adsorption to a Halophilic Bacterium Under High Ionic Strength Conditions: A Surface Complexation Modeling Approach

    SciTech Connect

    Ams, David A

    2012-06-11

    Rationale for experimental design: Np(V) -- important as analog for Pu(V) and for HLW scenarios; High ionic strength -- relevant to salt-based repositories such as the WIPP; Halophilic microorganisms -- representative of high ionic strength environments. For the first time showed: Significant adsorbant to halophilic microorganisms over entire pH range under high ionic strength conditions; Strong influence of ionic strength with increasing adsorption with increasing ionic strength (in contrast to trends of previous low ionic strength studies); Effect of aqueous Np(V) and bacterial surface site speciation on adsorption; and Developed thermodynamic models that can be incorporated into geochemical speciation models to aid in the prediction of the fate and transport of Np(V) in more complex systems.

  3. Equilibrium and stability of polarization in ultrathin ferroelectric films with ionic surface compensation

    NASA Astrophysics Data System (ADS)

    Stephenson, G. Brian; Highland, Matthew J.

    2011-08-01

    Thermodynamic theory is developed for the ferroelectric phase transition of an ultrathin film in equilibrium with a chemical environment that supplies ionic species to compensate its surface. Equations of state and free energy expressions are developed based on Landau-Ginzburg-Devonshire theory, using electrochemical equilibria to provide ionic compensation boundary conditions. Calculations are presented for a monodomain PbTiO3 (001) film coherently strained to SrTiO3 with its exposed surface and its electronically conducting bottom electrode in equilibrium with a controlled oxygen partial pressure. The stability and metastability boundaries of phases of different polarization are determined as a function of temperature, oxygen partial pressure, and film thickness. Phase diagrams showing polarization and internal electric field are presented. At temperatures below a thickness-dependent Curie point, high or low oxygen partial pressure stabilizes positive or negative polarization, respectively. Results are compared to the standard cases of electronic compensation controlled by either an applied voltage or charge across two electrodes. Ionic surface compensation through chemical equilibrium with an environment introduces new features into the phase diagram. In ultrathin films, a stable nonpolar phase can occur between the positive and negative polar phases when varying the external chemical potential at fixed temperature, under conditions where charged surface species are not present in sufficient concentration to stabilize a polar phase.

  4. Long range electrostatic forces in ionic liquids.

    PubMed

    Gebbie, Matthew A; Smith, Alexander M; Dobbs, Howard A; Lee, Alpha A; Warr, Gregory G; Banquy, Xavier; Valtiner, Markus; Rutland, Mark W; Israelachvili, Jacob N; Perkin, Susan; Atkin, Rob

    2017-01-19

    Ionic liquids are pure salts that are liquid under ambient conditions. As liquids composed solely of ions, the scientific consensus has been that ionic liquids have exceedingly high ionic strengths and thus very short Debye screening lengths. However, several recent experiments from laboratories around the world have reported data for the approach of two surfaces separated by ionic liquids which revealed remarkable long range forces that appear to be electrostatic in origin. Evidence has accumulated demonstrating long range surface forces for several different combinations of ionic liquids and electrically charged surfaces, as well as for concentrated mixtures of inorganic salts in solvent. The original interpretation of these forces, that ionic liquids could be envisioned as "dilute electrolytes," was controversial, and the origin of long range forces in ionic liquids remains the subject of discussion. Here we seek to collate and examine the evidence for long range surface forces in ionic liquids, identify key outstanding questions, and explore possible mechanisms underlying the origin of these long range forces. Long range surface forces in ionic liquids and other highly concentrated electrolytes hold diverse implications from designing ionic liquids for energy storage applications to rationalizing electrostatic correlations in biological self-assembly.

  5. Nanoscale Lubrication of Ionic Surfaces Controlled via a Strong Electric Field

    NASA Astrophysics Data System (ADS)

    Strelcov, Evgheni; Kumar, Rajeev; Bocharova, Vera; Sumpter, Bobby G.; Tselev, Alexander; Kalinin, Sergei V.

    2015-01-01

    Frictional forces arise whenever objects around us are set in motion. Controlling them in a rational manner means gaining leverage over mechanical energy losses and wear. This paper presents a way of manipulating nanoscale friction by means of in situ lubrication and interfacial electrochemistry. Water lubricant is directionally condensed from the vapor phase at a moving metal-ionic crystal interface by a strong confined electric field, thereby allowing friction to be tuned up or down via an applied bias. The electric potential polarity and ionic solid solubility are shown to strongly influence friction between the atomic force microscope (AFM) tip and salt surface. An increase in friction is associated with the AFM tip digging into the surface, whereas reducing friction does not influence its topography. No current flows during friction variation, which excludes Joule heating and associated electrical energy losses. The demonstrated novel effect can be of significant technological importance for controlling friction in nano- and micro-electromechanical systems.

  6. Nanoscale lubrication of ionic surfaces controlled via a strong electric field

    SciTech Connect

    Strelcov, Evgheni; Bocharova, Vera; Sumpter, Bobby G.; Tselev, Alexander; Kalinin, Sergei V.; Kumar, Rajeev

    2015-01-27

    Frictional forces arise whenever objects around us are set in motion. Controlling them in a rational manner means gaining leverage over mechanical energy losses and wear. This paper presents a way of manipulating nanoscale friction by means of in situ lubrication and interfacial electrochemistry. Water lubricant is directionally condensed from the vapor phase at a moving metal-ionic crystal interface by a strong confined electric field, thereby allowing friction to be tuned up or down via an applied bias. The electric potential polarity and ionic solid solubility are shown to strongly influence friction between the atomic force microscope (AFM) tip and salt surface. An increase in friction is associated with the AFM tip digging into the surface, whereas reducing friction does not influence its topography. No current flows during friction variation, which excludes Joule heating and associated electrical energy losses. Lastly, the demonstrated novel effect can be of significant technological importance for controlling friction in nano- and micro-electromechanical systems.

  7. Positron annihilation in the near surface of room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Hirade, T.; O’Rourke, B. E.; Kobayashi, Y.

    2017-01-01

    Positronium (Ps; a bound state of an electron and a positron) formation in insulating materials is explained by the spur reaction model. According to the model, electron and/or positron mobility affects the yield of Ps formation. A vertical slow positron beam was used to investigate the surface of a room temperature ionic liquid, N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA-TFSI). Measurement of positron lifetimes indicated a higher Ps formation probability in near surface of TMPA-TFSI than in the bulk. This result suggests that the electron (and positron) mobility in the near surface may be larger than that in the bulk. Moreover, the longest annihilation lifetime of triplet Ps (ortho-Ps) in the near surface was found to be shorter than that measured in the bulk liquid. Ortho-Ps lifetimes in liquids are well correlated with the surface tension with a shorter lifetime corresponding to higher surface tension. The higher Ps formation yield and the shorter ortho-Ps annihilation lifetime were probably caused by the layered structure in near surface of TMPA-TFSI. A vertical slow positron beam is a strong tool to investigate the surface of room temperature ionic liquids.

  8. Surface segregation in binary mixtures of imidazolium-based ionic liquids

    NASA Astrophysics Data System (ADS)

    Souda, Ryutaro

    2010-09-01

    Surface composition of binary mixtures of room-temperature ionic liquids has been investigated using time-of-flight secondary ion mass spectrometry at room temperature over a wide composition range. The imidazolium cations with longer aliphatic groups tend to segregate to the surface, and a bis(trifluoromethanesulfonyl)imide anion (Tf 2N -) is enriched at the surface relative to hexafluorophosphate (PF 6-). The surface of an equimolar mixture of Li[Tf 2N] and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF 6]) has a nominal composition of [bmim][Tf 2N] because of surface segregation and ligand exchange. The surface segregation of cations and anions is likely to result from alignment of specific ligand-exchanged molecules at the topmost surface layer to exclude more hydrophobic part of the molecules.

  9. Immobilization of enzymes using non-ionic colloidal liquid aphrons (CLAs): Surface and enzyme effects.

    PubMed

    Ward, Keeran; Xi, Jingshu; Stuckey, David C

    2015-12-01

    The use of non-ionic colloidal liquid aphrons (CLAs) as a support for enzyme immobilisation was investigated. Formulation required the mixing of an aqueous-surfactant solution with a relatively non-polar solvent-surfactant solution, forming a solvent droplet surrounded by a thin stabilised aqueous film (soapy shell). Studies utilising anionic surfactants have showed increased retention, however, very little have been understood about the forces governing immobilisation. This study seeks to determine the effects of enzyme properties on CLA immobilisation by examining a non-ionic/non-polar solvent system comprised of two non-ionic surfactants, Tween 20 and 80, mineral oil and the enzymes lipase, aprotinin and α-chymotrypsin. From these results it was deduced that hydrophobic interactions strongly governed immobilisation. Confocal Scanning Laser Microscopy (CSLM) revealed that immobilisation was predominantly achieved by surface adsorption attributed to hydrophobic interactions between the enzyme and the CLA surface. Enzyme surface affinity was found to increase when added directly to the formulation (pre-manufacture addition), as opposed to the bulk continuous phase (post-manufacture addition), with α-chymotrypsin and aprotinin being the most perturbed, while lipase was relatively unaffected. The effect of zeta potential on immobilisation showed that enzymes adsorbed better closer to their pI, indicating that charge minimisation was necessary for immobilisation. Finally, the effect of increasing enzyme concentration in the aqueous phase resulted in an increase in adsorption for all enzymes due to cooperativity between protein molecules, with saturation occurring faster at higher adsorption rates.

  10. Surface-modified silica colloidal crystals: nanoporous films and membranes with controlled ionic and molecular transport.

    PubMed

    Zharov, Ilya; Khabibullin, Amir

    2014-02-18

    Nanoporous membranes are important for the study of the transport of small molecules and macromolecules through confined spaces and in applications ranging from separation of biomacromolecules and pharmaceuticals to sensing and controlled release of drugs. For many of these applications, chemists need to gate the ionic and molecular flux through the nanopores, which in turn depends on the ability to control the nanopore geometry and surface chemistry. Most commonly used nanoporous membrane materials are based on polymers. However, the nanostructure of polymeric membranes is not well-defined, and their surface is hard to modify. Inorganic nanoporous materials are attractive alternatives for polymers in the preparation of nanoporous membranes. In this Account, we describe the preparation and surface modification of inorganic nanoporous films and membranes self-assembled from silica colloidal spheres. These spheres form colloidal crystals with close-packed face centered cubic lattices upon vertical deposition from colloidal solutions. Silica colloidal crystals contain ordered arrays of interconnected three dimensional voids, which function as nanopores. We can prepare silica colloidal crystals as supported thin films on various flat solid surfaces or obtain free-standing silica colloidal membranes by sintering the colloidal crystals above 1000 °C. Unmodified silica colloidal membranes are capable of size-selective separation of macromolecules, and we can surface-modify them in a well-defined and controlled manner with small molecules and polymers. For the surface modification with small molecules, we use silanol chemistry. We grow polymer brushes with narrow molecular weight distribution and controlled length on the colloidal nanopore surface using atom transfer radical polymerization or ring-opening polymerization. We can control the flux in the resulting surface-modified nanoporous films and membranes by pH and ionic strength, temperature, light, and small molecule

  11. Ions-induced nanostructuration: effect of specific ionic adsorption on hydrophobic polymer surfaces.

    PubMed

    Siretanu, Igor; Chapel, Jean-Paul; Bastos-González, Delfi; Drummond, Carlos

    2013-06-06

    The effect of surface charges on the ionic distribution in close proximity to an interface has been extensively studied. On the contrary, the influence of ions (from dissolved salts) on deformable interfaces has been barely investigated. Ions can adsorb from aqueous solutions on hydrophobic surfaces, generating forces that can induce long-lasting deformation of glassy polymer films, a process called ion-induced polymer nanostructuration, IPN. We have found that this process is ion-specific; larger surface modifications are observed in the presence of water ions and hydrophobic and amphiphilic ions. Surface structuration is also observed in the presence of certain salts of lithium. We have used streaming potential and atomic force microscopy to study the effect of dissolved ions on the surface properties of polystyrene films, finding a good correlation between ionic adsorption and IPN. Our results also suggest that the presence of strongly hydrated lithium promotes the interaction of anions with polystyrene surfaces and more generally with hydrophobic polymer surfaces, triggering then the IPN process.

  12. Surface-Induced Changes in the Thermochromic Transformation of an Ionic Liquid Cobalt Thiocyanate Complex

    PubMed Central

    2017-01-01

    We demonstrate that a thermodynamic complex equilibrium within an ionic liquid film can be significantly influenced by the presence of the liquid–vacuum interface. Using surface-sensitive X-ray photoelectron spectroscopy, we find that the temperature-driven transition from the blue-colored tetrahedral [Co(II) (NCS)4]2– to the red-colored octahedral [Co(II) (NCS)6]4– complex already occurs within the outermost nanometers at around +4 °C as compared with −25 °C in the bulk. This thermochromic transformation in the near-surface region goes along with a loss in preferential surface orientation of free [SCN]− anions and with a pronounced decrease in the complex density; both effects are attributed to the formation of a weakly bound solvation shell around the [Co(II) (NCS)6]4– anion, leading to an effective complex dilution. Our results are not only relevant for high-surface area thin film systems, such as in sensor and catalysis applications, but also shed light on the role of ionic liquid surfaces in particular and liquid surfaces in general. PMID:28212033

  13. Surface-Induced Changes in the Thermochromic Transformation of an Ionic Liquid Cobalt Thiocyanate Complex.

    PubMed

    May, Benjamin; Hönle, Michael; Heller, Bettina; Greco, Francesco; Bhuin, Radha; Steinrück, Hans-Peter; Maier, Florian

    2017-02-23

    We demonstrate that a thermodynamic complex equilibrium within an ionic liquid film can be significantly influenced by the presence of the liquid-vacuum interface. Using surface-sensitive X-ray photoelectron spectroscopy, we find that the temperature-driven transition from the blue-colored tetrahedral [Co(II) (NCS)4](2-) to the red-colored octahedral [Co(II) (NCS)6](4-) complex already occurs within the outermost nanometers at around +4 °C as compared with -25 °C in the bulk. This thermochromic transformation in the near-surface region goes along with a loss in preferential surface orientation of free [SCN](-) anions and with a pronounced decrease in the complex density; both effects are attributed to the formation of a weakly bound solvation shell around the [Co(II) (NCS)6](4-) anion, leading to an effective complex dilution. Our results are not only relevant for high-surface area thin film systems, such as in sensor and catalysis applications, but also shed light on the role of ionic liquid surfaces in particular and liquid surfaces in general.

  14. Ionic strength and pH as control parameters for spontaneous surface oscillations.

    PubMed

    Kovalchuk, N M; Pimienta, V; Tadmouri, R; Miller, R; Vollhardt, D

    2012-05-01

    A system far from equilibrium, where the surfactant transfer from a small drop located in the aqueous bulk to the air-water interface results in spontaneous nonlinear oscillations of surface tension, is theoretically and experimentally considered. The oscillations in this system are the result of periodically arising and terminating Marangoni instability. The surfactant under consideration is octanoic acid, the dissociated form of which is much less surface-active than the protonated form. Numerical simulations show how the system behavior can be controlled by changes in pH and ionic strength of the aqueous phase. The results of numerical simulations are in good agreement with experimental data.

  15. Physically and chemically stable ionic liquid-infused textured surfaces showing excellent dynamic omniphobicity

    SciTech Connect

    Miranda, Daniel F.; Urata, Chihiro; Masheder, Benjamin; Dunderdale, Gary J.; Hozumi, Atsushi; Yagihashi, Makoto

    2014-05-01

    A fluorinated and hydrophobic ionic liquid (IL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, effectively served as an advantageous lubricating liquid for the preparation of physically and chemically stable omniphobic surfaces based on slippery liquid-infused porous surfaces. Here, we used particulate microstructures as supports, prepared by the chemical vapor deposition of 1,3,5,7-tetramethylcyclotetrasiloxane and subsequent surface modification with (3-aminopropyl)triethoxysilane. Confirmed by SEM and contact angle measurements, the resulting IL-infused microtextured surfaces are smooth and not only water but also various low surface tension liquids can easily slide off at low substrate tilt angles of <5°, even after exposure to high temperature, vacuum, and UV irradiation.

  16. Controlling adsorption and passivation properties of bovine serum albumin on silica surfaces by ionic strength modulation and cross-linking.

    PubMed

    Park, Jae Hyeon; Sut, Tun Naw; Jackman, Joshua A; Ferhan, Abdul Rahim; Yoon, Bo Kyeong; Cho, Nam-Joon

    2017-03-15

    Understanding the physicochemical factors that influence protein adsorption onto solid supports holds wide relevance for fundamental insights into protein structure and function as well as for applications such as surface passivation. Ionic strength is a key parameter that influences protein adsorption, although how its modulation might be utilized to prepare well-coated protein adlayers remains to be explored. Herein, we investigated how ionic strength can be utilized to control the adsorption and passivation properties of bovine serum albumin (BSA) on silica surfaces. As protein stability in solution can influence adsorption kinetics, the size distribution and secondary structure of proteins in solution were first characterized by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), and circular dichroism (CD) spectroscopy. A non-monotonic correlation between ionic strength and protein aggregation was observed and attributed to colloidal agglomeration, while the primarily α-helical character of the protein in solution was maintained in all cases. Quartz crystal microbalance-dissipation (QCM-D) experiments were then conducted in order to track protein adsorption onto silica surfaces as a function of ionic strength, and the measurement responses indicated that total protein uptake at saturation coverage is lower with increasing ionic strength. In turn, the QCM-D data and the corresponding Voigt-Voinova model analysis support that the surface area per bound protein molecule is greater with increasing ionic strength. While higher protein uptake under lower ionic strengths by itself did not result in greater surface passivation under subsequent physiologically relevant conditions, the treatment of adsorbed protein layers with a gluteraldehyde cross-linking agent stabilized the bound protein in this case and significantly improved surface passivation. Collectively, our findings demonstrate that ionic strength modulation influences BSA adsorption

  17. Life Sciences Implications of Lunar Surface Operations

    NASA Technical Reports Server (NTRS)

    Chappell, Steven P.; Norcross, Jason R.; Abercromby, Andrew F.; Gernhardt, Michael L.

    2010-01-01

    The purpose of this report is to document preliminary, predicted, life sciences implications of expected operational concepts for lunar surface extravehicular activity (EVA). Algorithms developed through simulation and testing in lunar analog environments were used to predict crew metabolic rates and ground reaction forces experienced during lunar EVA. Subsequently, the total metabolic energy consumption, the daily bone load stimulus, total oxygen needed, and other variables were calculated and provided to Human Research Program and Exploration Systems Mission Directorate stakeholders. To provide context to the modeling, the report includes an overview of some scenarios that have been considered. Concise descriptions of the analog testing and development of the algorithms are also provided. This document may be updated to remain current with evolving lunar or other planetary surface operations, assumptions and concepts, and to provide additional data and analyses collected during the ongoing analog research program.

  18. Fabrication of high performance surface enhanced Raman scattering substrates by a solid-state ionics method.

    PubMed

    Xu, Dapeng; Dong, Zhanmin; Sun, Jia-Lin

    2012-03-30

    Silver nanostructures were prepared by a solid-state ionics method using fast ionic conductor RbAg(4)I(5) films under a direct current electric field (DCEF). The surface morphology of the silver nanostructures grown under different constant current fields was characterized by scanning electron microscopy (SEM). Rhodamine 6G (R6G) aqueous solutions were used as probe molecules to detect the Raman enhancement performance of the silver nanostructure substrates. The effect of external electric field current intensity on the surface morphology of the silver nanostructures during the preparation was studied in detail. The enhancement effect of the silver nanostructure surface enhanced Raman scattering (SERS) substrates with different surface morphologies toward R6G was determined. We found that disordered silver nanowires (DSNW), ordered silver nanowires (OSNW), densely arranged silver nanobamboo arrays (SNBA) and compactly arranged silver nanobud clusters (SNBC) were respectively obtained when the constant current intensity was 3 μA, 5 μA, 8 μA and 12 μA under the same vacuum evaporation plating conditions. The limiting concentrations of R6G for these SERS substrates were found to be 10(-7) mol l(-1), 10(-13) mol l(-1), 10(-13) mol l(-1) and 10(-16) mol l(-1), respectively.

  19. On the interfacial behavior of ionic liquids: surface tensions and contact angles.

    PubMed

    Restolho, José; Mata, José L; Saramago, Benilde

    2009-12-01

    In this work the liquid/vapour and the solid/liquid interfaces of a series of ionic liquids: 1-ethyl-3-methylpyridinium ethyl sulfate, [EMPy][EtSO4], 1-ethyl-3-methylimidazolium ethyl sulfate, [EMIM][EtSO4], 1-ethanol-3-methylimidazolium tetrafluoroborate, [C2OHMIM][BF4], 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF4], and 1-octyl-3-methylimidazolium tetrafluoroborate, [OMIM][BF4], were investigated. The surface tension was measured in a wide temperature range, (298-453) K. The contact angles were determined on substrates of different polarities. Both on the polar (glass) and the non-polar substrates ((poly-(tetrafluoroethylene) and poly-(ethylene)), the liquids with maximum and minimum surface tensions lead, respectively, to the highest and the lowest contact angles. The dispersive, gamma(L)(d), and non-dispersive, gamma(L)(nd), components of the liquid surface tension, gamma(L), were calculated from the contact angles on the non-polar substrates using the Fowkes approach. The polarity fraction, gamma(L)(nd)/gamma(L), was compared with the polarity parameter, k, obtained from the fitting of the surface tension vs. temperature data to the Eötvös equation. Good agreement was found for the extreme cases: [OMIM][BF4] exhibits the lowest polarity and [BMIM][BF4], the highest. When compared with the polarity fractions of standard liquids considered as "polar" liquids, the ionic liquids studied may be considered as moderately polar.

  20. Thermodynamic Control of Two-Dimensional Molecular Ionic Nanostructures on Metal Surfaces

    DOE PAGES

    Jeon, Seokmin; Doak, Peter W.; Sumpter, Bobby G.; ...

    2016-07-26

    Bulk molecular ionic solids exhibit fascinating electronic properties, including electron correlations, phase transitions and superconducting ground states. In contrast, few of these phenomena have so far been observed in low-dimensional molecular structures, including thin films, nanoparticles and molecular blends, not in the least because most of such structures have so far been composed of nearly closed-shell molecules. It is therefore desirable to develop low-dimensional molecular structures of ionic molecules toward fundamental studies and potential applications. Here we present detailed analysis of monolayer-thick structures of the canonical TTF-TCNQ (tetrathiafulvalene 7,7,8,8-tetracyanoquinodimethane) system grown on low-index gold and silver surfaces. The most distinctivemore » property of the epitaxial growth is the wide abundance of stable TTF/TCNQ ratios, in sharp contrast to the predominance of 1:1 ratio in the bulk. We propose the existence of the surface phase-diagram that controls the structures of TTF-TCNQ on the surfaces, and demonstrate phase-transitions that occur upon progressively increasing the density of TCNQ while keeping the surface coverage of TTF fixed. Based on direct observations, we propose the binding motif behind the stable phases and infer the dominant interactions that enable the existence of the rich spectrum of surface structures. Finally, we also show that the surface phase diagram will control the epitaxy beyond monolayer coverage. Multiplicity of stable surface structures, the corollary rich phase diagram and the corresponding phase-transitions present an interesting opportunity for low-dimensional molecular systems, particularly if some of the electronic properties of the bulk can be preserved or modified in the surface phases.« less

  1. Thermodynamic Control of Two-Dimensional Molecular Ionic Nanostructures on Metal Surfaces

    SciTech Connect

    Jeon, Seokmin; Doak, Peter W.; Sumpter, Bobby G.; Ganesh, Panchapakesan; Maksymovych, Petro

    2016-07-26

    Bulk molecular ionic solids exhibit fascinating electronic properties, including electron correlations, phase transitions and superconducting ground states. In contrast, few of these phenomena have so far been observed in low-dimensional molecular structures, including thin films, nanoparticles and molecular blends, not in the least because most of such structures have so far been composed of nearly closed-shell molecules. It is therefore desirable to develop low-dimensional molecular structures of ionic molecules toward fundamental studies and potential applications. Here we present detailed analysis of monolayer-thick structures of the canonical TTF-TCNQ (tetrathiafulvalene 7,7,8,8-tetracyanoquinodimethane) system grown on low-index gold and silver surfaces. The most distinctive property of the epitaxial growth is the wide abundance of stable TTF/TCNQ ratios, in sharp contrast to the predominance of 1:1 ratio in the bulk. We propose the existence of the surface phase-diagram that controls the structures of TTF-TCNQ on the surfaces, and demonstrate phase-transitions that occur upon progressively increasing the density of TCNQ while keeping the surface coverage of TTF fixed. Based on direct observations, we propose the binding motif behind the stable phases and infer the dominant interactions that enable the existence of the rich spectrum of surface structures. Finally, we also show that the surface phase diagram will control the epitaxy beyond monolayer coverage. Multiplicity of stable surface structures, the corollary rich phase diagram and the corresponding phase-transitions present an interesting opportunity for low-dimensional molecular systems, particularly if some of the electronic properties of the bulk can be preserved or modified in the surface phases.

  2. Transport Properties of Hydrogen-Terminated Silicon Surface Controlled by Ionic-Liquid Gating

    NASA Astrophysics Data System (ADS)

    Sasama, Yosuke; Yamaguchi, Takahide; Tanaka, Masashi; Takeya, Hiroyuki; Takano, Yoshihiko

    2017-01-01

    We fabricated electric double-layer transistors on the hydrogen-terminated (111)-oriented surface of non-doped silicon using ionic liquid as a gate dielectric. We introduced hole carriers into silicon with the application of a negative gate voltage. The sheet resistance of silicon was controlled by more than three orders of magnitude at 220 K by changing the gate voltage. The temperature dependence of sheet resistance became weak as the gate voltage was increased, suggesting the approach to an insulator-metal transition.

  3. Straightforward approach to graft bioactive polysaccharides onto polyurethane surfaces using an ionic liquid

    NASA Astrophysics Data System (ADS)

    Bigot, Sandra; Louarn, Guy; Kébir, Nasreddine; Burel, Fabrice

    2014-09-01

    Surface properties directly affect the performance of a material in a biological environment. In this study, the goal was to develop a simple procedure allowing the grafting of antibacterial polysaccharides onto biomedical grade polyurethanes (e.g. Tecothane®). Thus, a straightforward chemical pathway involving an isothiocyanate-alcohol reaction in an ionic liquid (IL) was developed. PU isothiocyanted surfaces (PU-NCS) were first prepared by reacting p-phenylene diisothiocyanate with the surface urethane groups. Then, unmodified bioactive seaweed polysaccharides were directly grafted onto the surface, in mild conditions. The selected IL, i.e. 1-ethyl-3-methyl imidazolium phosphate, was of particular interest since this liquid worked as solvent for p-phenylene diisothiocyanate and the polysaccharides and as catalyst for the grafting reactions. Successful grafting of the different polysaccharides was attested by changes in the surface functional groups, using X-ray photoelectron spectroscopy (XPS). Atomic force microscopy (AFM) showed that polysaccharide grafting, slightly increased the surface roughness from 1.9 to more than 7 nm. Contact angle with water decreased from 88° (for native PU) to around 75° after polysaccharide grafting, attesting a more hydrophilic surface. This procedure would be transposed to the grafting onto PU surfaces of any macromolecule of interest bearing hydroxyl, thiol or amine groups.

  4. Nanoscale lubrication of ionic surfaces controlled via a strong electric field

    DOE PAGES

    Strelcov, Evgheni; Bocharova, Vera; Sumpter, Bobby G.; ...

    2015-01-27

    Frictional forces arise whenever objects around us are set in motion. Controlling them in a rational manner means gaining leverage over mechanical energy losses and wear. This paper presents a way of manipulating nanoscale friction by means of in situ lubrication and interfacial electrochemistry. Water lubricant is directionally condensed from the vapor phase at a moving metal-ionic crystal interface by a strong confined electric field, thereby allowing friction to be tuned up or down via an applied bias. The electric potential polarity and ionic solid solubility are shown to strongly influence friction between the atomic force microscope (AFM) tip andmore » salt surface. An increase in friction is associated with the AFM tip digging into the surface, whereas reducing friction does not influence its topography. No current flows during friction variation, which excludes Joule heating and associated electrical energy losses. Lastly, the demonstrated novel effect can be of significant technological importance for controlling friction in nano- and micro-electromechanical systems.« less

  5. Improving the thermostability of a methyl parathion hydrolase by adding the ionic bond on protein surface.

    PubMed

    Su, Yidan; Tian, Jian; Wang, Ping; Chu, Xiaoyu; Liu, Guoan; Wu, Ningfeng; Fan, Yunliu

    2011-10-01

    The thermostability of the methyl parathion hydrolase (MPH_OCH) from Ochrobactrum sp. M231 was improved using site-directed mutagenesis. Two prolines (Pro76 and Pro78) located on the protein surface were selected for mutations after inspection of the sequence alignment of MPH_OCH and OPHC2, a thermostable organophosphorus hydrolase from Pseudomonas pseudoalcaligenes C2-1. The temperature of the double-point mutant (P76D/P78K) at which the mutant lost 50% of its activity (T50) was approximately 68 °C, which is higher than that of WT enzyme (64 °C), P76D (67 °C), and P78K (59 °C). Structural analysis of P76D/P78K indicated that the substituted residues (Asp76 and Lys78) could generate an ionic bond and increase the structural electrostatic energy, which could then increase the stability of the protein. These results also suggest that the thermal stability of proteins could be improved by adding the ionic bond on protein surface.

  6. Contact angle hysteresis on superhydrophobic surfaces: an ionic liquid probe fluid offers mechanistic insight.

    PubMed

    Krumpfer, Joseph W; Bian, Pei; Zheng, Peiwen; Gao, Lichao; McCarthy, Thomas J

    2011-03-15

    Silicon/silicon dioxide surfaces containing 3 μm (width) × 6 μm (length) × 40 μm (height) staggered rhombus posts were prepared using photolithography and hydrophobized using a perfluoroalkyl-containing monofunctional silane. These surfaces exhibit water contact angles of θ(A)/θ(R) = 169°/156°. Water drops come to rest on a carefully aligned horizontal sample but roll when the surface is tilted slightly. No visible trail or evidence of water "left behind" at the receding edge of the drop is apparent on surfaces that water drops have rolled on or on samples removed from water through the air-water interface. When dimethylbis(β-hydroxyethyl)ammonium methanesulfonate (N(+)S(-), a nonvolatile ionic liquid) is used as the liquid probe fluid (instead of water), contact angles of θ(A)/θ(R) = 164°/152° are observed and ∼3-μm-diameter sessile drops are visible (by scanning electron microscopy - SEM) on the top of every post of a sample drawn out of this liquid. We interpret the formation of these sessile microdrops as arising from microcapillary bridge failure that occurs during receding events and emphasize that the capillary bridges rupture in primarily a tensile failure mode. Smaller sessile drops could be prepared using mixtures of water and N(+)S(-). Microdroplets of N(+)S(-) were also observed to form selectively at particular features on surfaces containing square holes separated by ridges. This suggests that pinning sites can be identified using microscopy and this ionic liquid probe fluid.

  7. The behavior of internal surfaces of cleavage in ionic crystals under thermoelectric influence

    NASA Astrophysics Data System (ADS)

    Karyev, Leonid; Zanina, Anna; Feodorov, Victor

    2016-01-01

    The behavior of internal surfaces of cleavage fracture in ionic crystals under complex thermoelectric effect was investigated. The experiment was carried out in case of normal and parallel orientation of the electric field lines to the investigated surface. Our basic research method lies in simultaneous influence of thermal and electric fields on the crystal. In case of normal orientation of electric field lines to the crack surface the formation of dislocation rosettes in temperature range of impurity conduction was observed. In the temperature range of intrinsic conduction authors detected the formation of single crystal outgrowths on the positively charged surface. The shape of rosettes and outgrowths depends on their relative location to the crack tip. When outgrowth reaches the opposite negatively charged surface it forms a bridge between cleavage shores. In these areas the restoration of continuity was observed. In case of parallel orientation of electric field lines to the surface authors observed the appearance of a new phase in the form of a jelly-like substance on the crack surface. The crack faces had a closing tendency due to the directed diffusion of cations to the crack edges.

  8. Ionic liquid ultrathin films at the surface of Cu(100) and Au(111)

    NASA Astrophysics Data System (ADS)

    Biedron, Aleksandra B.; Garfunkel, Eric L.; Castner, Edward W.; Rangan, Sylvie

    2017-02-01

    Monolayer to multilayer ultrathin films of the ionic liquid (IL) 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)amide have been prepared on Au(111) and Cu(100) surfaces using physical vapor deposition. The ion-surface interactions are studied using a combination of scanning tunnel microscopy, as well as ultraviolet and x-ray photoemission spectroscopies. It is found that the IL does not decompose at the surface of the metals, and that the IL interaction with the Cu(100) surface is much stronger than with the Au(111) surface. As a consequence, STM imaging at room temperature results in more stable imaging at the monolayer coverage on Cu(100) than on Au(111), and work function measurements indicate a large interface dipole upon deposition of a monolayer of IL on Cu. Additional IL depositions on the two surfaces result in two distinct behaviors for the IL core levels: a gradual energy shift of the core levels on Au and a set of two well defined monolayer and multilayer core level components found at fixed energies on Cu, due to the formation of a tightly bound monolayer. Finally, it is proposed that the particularly strong cation-Cu interaction leads to stabilization of the anion and prevents its decomposition at the surface of Cu(100).

  9. Surface modification of MoS2 nanoparticles with ionic liquid-ligands: towards highly dispersed nanoparticles.

    PubMed

    Osim, Wilton; Stojanovic, Anja; Akbarzadeh, Johanna; Peterlik, Herwig; Binder, Wolfgang H

    2013-10-18

    Highly dispersible MoS2 nanoparticles have been prepared via surface-modification using a novel tetraethylene glycol-based ionic liquid containing a chelating moiety attached to the cation. The choice of the respective ligand enables the generation of highly dispersible MoS2 nanoparticles with either polar, hydrophobic or "amphiphilic" surfaces, forming highly stable dispersions or microemulsions.

  10. Clean surface processing of rubrene single crystal immersed in ionic liquid by using frequency modulation atomic force microscopy

    SciTech Connect

    Yokota, Yasuyuki; Hara, Hisaya; Morino, Yusuke; Bando, Ken-ichi; Imanishi, Akihito; Fukui, Ken-ichi; Uemura, Takafumi; Takeya, Jun

    2014-06-30

    Surface processing of a rubrene single crystal immersed in ionic liquids is valuable for further development of low voltage transistors operated by an electric double layer. We performed a precise and clean surface processing based on the tip-induced dissolution of rubrene molecules at the ionic liquid/rubrene single crystal interfaces by using frequency modulation atomic force microscopy. Molecular resolution imaging revealed that the tip-induced dissolution proceeded via metastable low density states derived from the anisotropic intermolecular interactions within the crystal structure.

  11. Surface Tensions of Ionic Liquids: Non-Regular Trend Along the Number of Cyano Groups.

    PubMed

    Almeida, Hugo F D; Carvalho, Pedro J; Kurnia, Kiki A; Lopes-da-Silva, José A; Coutinho, João A P; Freire, Mara G

    2016-02-15

    Ionic liquids (ILs) with cyano-functionalized anions are a set of fluids that are still poorly characterized despite their remarkably low viscosities and potential applications. Aiming at providing a comprehensive study on the influence of the number of -CN groups through the surface tension and surface organization of ILs, the surface tensions of imidazolium-based ILs with cyano-functionalized anions were determined at atmospheric pressure and in the (298.15 to 343.15) K temperature range. The ILs investigated are based on 1-alkyl-3-methylimidazolium cations (alkyl = ethyl, butyl and hexyl) combined with the [SCN](-), [N(CN)2](-), [C(CN)3](-) and [B(CN)4](-)anions. Although the well-known trend regarding the surface tension decrease with the increase of the size of the aliphatic moiety at the cation was observed, the order obtained for the anions is more intricate. For a common cation and at a given temperature, the surface tension decreases according to: [N(CN)2](-) > [SCN](-) > [C(CN)3](-) > [B(CN)4](-). Therefore, the surface tension of this homologous series does not decrease with the increase of the number of -CN groups at the anion as has been previously shown by studies performed with a more limited matrix of ILs. A maximum in the surface tension and critical temperature was observed for [N(CN)2]-based ILs. Furthermore, a minimum in the surface entropy, indicative of a highly structured surface, was found for the same class of ILs. All these evidences seem to be a result of stronger hydrogen-bonding interactions occurring in [N(CN)2]-based ILs, when compared with the remaining CN-based counterparts, and as sustained by cation-anion interaction energies derived from the Conductor Like Screening Model for Real Solvents (COSMO-RS).

  12. Surface Tensions of Ionic Liquids: Non-Regular Trend Along the Number of Cyano Groups

    PubMed Central

    Almeida, Hugo F. D.; Carvalho, Pedro J.; Kurnia, Kiki A.; Lopes-da-Silva, José A.; Coutinho, João A. P.; Freire, Mara G.

    2016-01-01

    Ionic liquids (ILs) with cyano-functionalized anions are a set of fluids that are still poorly characterized despite their remarkably low viscosities and potential applications. Aiming at providing a comprehensive study on the influence of the number of –CN groups through the surface tension and surface organization of ILs, the surface tensions of imidazolium-based ILs with cyano-functionalized anions were determined at atmospheric pressure and in the (298.15 to 343.15) K temperature range. The ILs investigated are based on 1-alkyl-3-methylimidazolium cations (alkyl = ethyl, butyl and hexyl) combined with the [SCN]-, [N(CN)2]−, [C(CN)3]− and [B(CN)4]-anions. Although the well-known trend regarding the surface tension decrease with the increase of the size of the aliphatic moiety at the cation was observed, the order obtained for the anions is more intricate. For a common cation and at a given temperature, the surface tension decreases according to: [N(CN)2]- > [SCN]- > [C(CN)3]- > [B(CN)4]-. Therefore, the surface tension of this homologous series does not decrease with the increase of the number of –CN groups at the anion as has been previously shown by studies performed with a more limited matrix of ILs. A maximum in the surface tension and critical temperature was observed for [N(CN)2]-based ILs. Furthermore, a minimum in the surface entropy, indicative of a highly structured surface, was found for the same class of ILs. All these evidences seem to be a result of stronger hydrogen-bonding interactions occurring in [N(CN)2]-based ILs, when compared with the remaining CN-based counterparts, and as sustained by cation-anion interaction energies derived from the Conductor Like Screening Model for Real Solvents (COSMO-RS). PMID:27642224

  13. Determination of Surface Charge of Titanium Dioxide (Anatase) at High Ionic Strength

    NASA Astrophysics Data System (ADS)

    Schoonen, M. A.; Strongin, D. R.

    2014-12-01

    Charge development on mineral surfaces is an important control on the fate of minor and trace elements in a wide range of environments, including in possible radioactive waste repositories. Formation waters have often a high ionic strength. In this study, we determined the zeta potential (ζ) of anatase in potassium chloride solutions with concentrations up to 3M (25°C). The zeta potential is the potential at the hydrodynamic shear plane. In this study, we made use of the electro-acoustic effect. This effect is based on the development of a measureable potential/current when the electrical double layer outside the shearplane is separated from a charged particle through rapid oscillation induced by a sound wave. The advantage of this type of measurement is that the particles are not subjected to a high electric field (common to typical zeta potential measurements), which leads to electrode reactions and a shift of solution pH. Measurements were collected by subtracting the ion vibration current (IVI) due to the presence of potassium and chloride ions from the CVI. The correction is necessary for measurements in solutions with I > 0.25 M. This subtraction was done at each of the measurement conditions by centrifuging the slurrly, measuring the IVI of the supernatant, reconstituting the slurry, and then measuring CVI of the slurry. Subtraction of IVI at each condition is critical because IVI changes with pH and accounts for most of raw signal. The results show that the anatase isoelectric point shifts from a pH ~6.5 to a value of ~4.5 at 1M KCl. At ionic strength in excess of 1 M KCl, the surface appears to be slightly negatively charged accross the pH range accessible by this technique (pH 2.5-10). The loss of an isoelectric point suggests that KCl is no longer an indifferent electrolyte at 1 M KCl and higher. The results are in disagreement with earlier measurements in which anatase was shown to have a positive charge at high ionic strength across the pH scale. The

  14. Surface functionalization of cellulose nanocrystals with polymeric ionic liquids during phase transfer.

    PubMed

    Huang, Shuohan; Wang, Xinhang; Shen, Jiahao; Wu, Routeng; Zhao, Hualei; Wang, Yanping; Wang, Yimin; Xia, Yumin

    2017-02-10

    In this study, the cellulose nanocrystals (CNCs) were prepared by method of acid hydrolysis, while the polymeric ionic liquid (PIL) [PEP-MIM]DBS was synthesized by epichlorohydrin, o-phthalic anhydride as well as N-methylimidazole then anion exchanged by sodium dodecyl benzene sulfonate. It was demonstrated that [PEP-MIM]DBS could modify CNCs by non-covalent interaction to change its surface properties, such as amphiphilicity. The chemical structure of the composite CNCs/[PEP-MIM]DBS was characterized via FTIR, (13)C NMR, TGA, XRD, etc. Moreover, the properties and applications were characterized through a series of dispersion experiments, contact angle tests, FE-SEM, etc. This study showed that the PIL-modification improved the dispersion of CNCs in non-polar organic solvents with their chemical structure integrated.

  15. Fabrication of Localized Surface Plasmon Resonance Fiber Probes Using Ionic Self-Assembled Gold Nanoparticles

    PubMed Central

    Wan, Miao; Luo, Pengfei; Jin, Jiayi; Xing, Jiong; Wang, Zhiyong; Wong, Stephen T. C.

    2010-01-01

    An nm-thickness composite gold thin film consisting of gold nanoparticles and polyelectrolytes is fabricated through ionic self-assembled multilayers (ISAM) technique and is deposited on end-faces of optical fibers to construct localized surface plasmon resonance (LSPR) fiber probes. We demonstrate that the LSPR spectrum induced by ISAM gold films can be fine-tuned through the ISAM procedure. We investigate variations of reflection spectra of the probe with respect to the layer-by-layer adsorption of ISAMs onto end-faces of fibers, and study the spectral variation mechanism. Finally, we demonstrated using this fiber probe to detect the biotin-streptavidin bioconjugate pair. ISAM adsorbed on optical fibers potentially provides a simple, fast, robust, and low-cost, platform for LSPR biosensing applications. PMID:22163561

  16. Grafting of ionic liquids on stainless steel surface for antibacterial application.

    PubMed

    Pang, Li Qing; Zhong, Li Juan; Zhou, Hui Fang; Wu, Xue E; Chen, Xiao Dong

    2015-02-01

    Stainless steel (SS) is favored for many uses due to its excellent chemical resistance, thermal stability and mechanical properties. Biofilms can be formed on stainless steel and may lead to serious hygiene problems and economic losses in many areas, e.g. food processing, public infrastructure and healthcare. For the first time, our work endeavored to make SS having antibacterial properties, ionic liquids (ILs) were grafted on SS surface via silane treatment followed by thiol-ene click reaction. The chemical structure and composition of the ILs grafted stainless-steel coupon surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. The antibacterial activity has been investigated, and the results showed that the ILs grafted SS surface exhibited significant antibacterial effects against Gram-negative Escherichia coli. Additionally, the results obtained here indicated that the ILs used here having bromide anion showed much better antibacterial activity against E. coli than the corresponding ILs with tetrafluoroborate and hexafluorophosphate as anions. These results obtained here can help to design novel and more efficient stainless steel having antibacterial surface.

  17. Surface structure of an ionic liquid with high-resolution Rutherford backscattering spectroscopy

    NASA Astrophysics Data System (ADS)

    Nakajima, K.; Ohno, A.; Suzuki, M.; Kimura, K.

    2009-02-01

    The surface of an ionic liquid, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide ([TMPA] [TFSI]), is observed by high-resolution Rutherford backscattering spectroscopy (HRBS). The composition depth profiles are derived from the observed HRBS spectra through spectrum simulation. The observed composition is in good agreement with the stoichiometric composition at depths larger than ∼1 nm. The observed composition profiles, however, show pronounced structures at the surface. Fluorine profile has a sharp peak at ∼0.1 nm and a broad peak at ∼1.0 nm. The sulfur profile also has a peak at ∼0.35 nm. These results indicate that the molecules show preferred orientations at the surface. From the observed profiles, it was concluded that the C1 conformer of the [TFSI] anion is dominant over the C2 conformer at the surface in contrast to bulk, where the C2 conformer is known to be dominant. It was also found that C1 conformers are oriented with their CF3 groups pointing toward the vacuum in the outermost molecular layer.

  18. Surface tension of room temperature ionic liquids measured by dynamic light scattering.

    PubMed

    Osada, R; Hoshino, T; Okada, K; Ohmasa, Y; Yao, M

    2009-05-14

    Using dynamic light scattering techniques, we obtained the surface tension sigma, surface excess entropy S(sigma), surface excess enthalpy H(sigma), and viscosity eta for the following seven room temperature ionic liquids in a wide temperature range from 30 to around 140 degrees C: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide, N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium hexafluorophosphate, and 1-octyl-3-methyl imidazolium hexafluorophosphate. We have found that sigma increases systematically with decreasing the anion size and the alkyl side chain length. On the other hand, S(sigma) and eta increase with decreasing the anion size but decrease with decreasing the alkyl chain length. H(sigma) seems to decrease with increasing the anion size, but it has no clear dependence on the alkyl chain length. We discuss the bulk and surface properties, referring to the Coulomb interactions and van der Waals interactions.

  19. Surface tension of room temperature ionic liquids measured by dynamic light scattering

    NASA Astrophysics Data System (ADS)

    Osada, R.; Hoshino, T.; Okada, K.; Ohmasa, Y.; Yao, M.

    2009-05-01

    Using dynamic light scattering techniques, we obtained the surface tension σ, surface excess entropy S(σ), surface excess enthalpy H(σ), and viscosity η for the following seven room temperature ionic liquids in a wide temperature range from 30 to around 140 °C: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide, N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium hexafluorophosphate, and 1-octyl-3-methyl imidazolium hexafluorophosphate. We have found that σ increases systematically with decreasing the anion size and the alkyl side chain length. On the other hand, S(σ) and η increase with decreasing the anion size but decrease with decreasing the alkyl chain length. H(σ) seems to decrease with increasing the anion size, but it has no clear dependence on the alkyl chain length. We discuss the bulk and surface properties, referring to the Coulomb interactions and van der Waals interactions.

  20. Influence of trehalose on the interaction of curcumin with surface active ionic liquid micelle and its vesicular aggregate composed of a non-ionic surfactant sorbitan stearate

    NASA Astrophysics Data System (ADS)

    Roy, Arpita; Dutta, Rupam; Sarkar, Nilmoni

    2016-11-01

    The present investigation unravels the effect of trehalose on 1-hexadecyl-3-methylimidazolium chloride ([C16mim]Cl), a cationic surface active ionic liquid (SAIL) micelle and SAIL ([C16mim]Cl)-nonionic surfactant (Sorbitan Stearate, Span 60) based vesicles. The influence of trehalose on size and morphology of the aggregates has been investigated using dynamic light scattering (DLS) and transmission electron microscopic (TEM) measurements. Besides, we have studied the dynamic properties of curcumin inside these aggregates using fluorescence spectroscopic based techniques. The results revealed that trehalose molecules play crucial role in modulation of the photophysical properties of curcumin in these organized assemblies.

  1. Surface Modification of Poly(dimethylsiloxane) Using Ionic Complementary Peptides to Minimize Nonspecific Protein Adsorption.

    PubMed

    Yu, Xiaoling; Xiao, Junzhu; Dang, Fuquan

    2015-06-02

    Poly(dimethylsiloxane) (PDMS) has become a widely used material for microfluidic and biological applications. However, PDMS has unacceptably high levels of nonspecific protein adsorption, which significantly lowers the performance of PDMS-based microfluidic chips. Most existing methods to reduce protein fouling of PDMS are to make the surface more hydrophilic by surface oxidization, polymer grafting, and physisorbed coatings. These methods suffer from the relatively short-term stability, the multistep complex treatment procedure, or the insufficient adsorption reduction. Herein, we developed a novel and facile modification method based on self-assembled peptides with well-tailored amino acid composition and sequence, which can also interact strongly with the PDMS surface in the same way as proteins, for suppressing the nonspecific protein fouling and improving the biocompatibility of PDMS-based microfluidic chips. We first demonstrated that an ionic complementary peptide, EAR16-II with a sequence of [(Ala-Glu-Ala-Glu-Ala-Arg-Ala-Arg)2], can readily self-assemble into an amphipathic film predominantly composed of tightly packed β-sheets on the native hydrophobic and plasma-oxidized hydrophilic PDMS surfaces upon low concentrations of carbohydrates. The self-assembled EAR16-II amphipathic film exposed its hydrophobic side to the solution and thus rendered the PDMS surface hydrophobic with water contact angles (WCAs) of around 110.0°. However, the self-assembled EAR16-II amphipathic film exhibited excellent protein-repelling and blood compatibility properties comparable to or better than those obtained with previously reported methods. A schematic model has been proposed to explain the interactions of EAR16-II with the PDMS surface and the antifouling capability of EAR16-II coatings at a molecular level. The current work will pave the way to the development of novel coating materials to address the nonspecific protein adsorption on PDMS, thereby broadening the

  2. Carbon dioxide capture by an amine functionalized ionic liquid: fundamental differences of surface and bulk behavior.

    PubMed

    Niedermaier, Inga; Bahlmann, Matthias; Papp, Christian; Kolbeck, Claudia; Wei, Wei; Krick Calderón, Sandra; Grabau, Mathias; Schulz, Peter S; Wasserscheid, Peter; Steinrück, Hans-Peter; Maier, Florian

    2014-01-08

    Carbon dioxide (CO2) absorption by the amine-functionalized ionic liquid (IL) dihydroxyethyldimethylammonium taurinate at 310 K was studied using surface- and bulk-sensitive experimental techniques. From near-ambient pressure X-ray photoelectron spectroscopy at 0.9 mbar CO2, the amount of captured CO2 per mole of IL in the near-surface region is quantified to ~0.58 mol, with ~0.15 mol in form of carbamate dianions and ~0.43 mol in form of carbamic acid. From isothermal uptake experiments combined with infrared spectroscopy, CO2 is found to be bound in the bulk as carbamate (with nominally 0.5 mol of CO2 bound per 1 mol of IL) up to ~2.5 bar CO2, and as carbamic acid (with nominally 1 mol CO2 bound per 1 mol IL) at higher pressures. We attribute the fact that at low pressures carbamic acid is the dominating species in the near-surface region, while only carbamate is formed in the bulk, to differences in solvation in the outermost IL layers as compared to the bulk situation.

  3. Electrostatics in ionic solution : work and energy, charge regulation, and in homogeneous surfaces

    NASA Astrophysics Data System (ADS)

    Boon, N. J. H.

    2012-01-01

    This thesis concerns the electrostatic properties of charged objects that are immersed into an ionic solvent, for example water with dissolved salt. Typically, the ions inside such a solvent form layers of countercharge close to the charged objects, causing `screening' of the charges. By employing Density Functional Theory (DFT) one is able integrate out the degrees of freedom of the ions and find relations that describe the effective electrostatic properties of the charged objects. One finds that for a large parameter regime the electrostatic potential everywhere in the solvent should satisfy the well established Poisson-Boltzmann equation. We study the electrostatic capacity of porous electrodes in salt water, and derive a method to reversibly extract electric energy from salinity gradients that occur for example at an estuary where sea- and river water meet. However, in the main part of this thesis we consider charged colloidal particles, and study the effect of internal porosity as well as heterogeneities in the surface-charge density (patchy particles) on colloid-colloid interactions. In a far-field analysis we derive equations that describe these interactions for particles with nonvanishing multipole moments, for example `Janus' colloids with a strong dipole component. If such particles locally have a high surface charge density, then the nonlinear dependence of the counterion density on the local charge density leads to a generalisation of charge renormalisation from purely monopolar to dipolar, quadrupolar, etc., including `mode couplings'. In a more detailed approach, which turns out to be important for colloidal particles at smaller distances from each other, we consider the chemical processes that lead to surface charge, and specify a parameter regime in which charging can be described by a single `chargeability' parameter. As we show in this thesis, the phase diagrams we obtain within this regime have many similarities with a `constant surface potential

  4. Genetic Modification of the Penicillin G Acylase Surface To Improve Its Reversible Immobilization on Ionic Exchangers▿

    PubMed Central

    Montes, Tamara; Grazú, Valeria; López-Gallego, Fernando; Hermoso, Juan A.; García, Jose L.; Manso, Isabel; Galán, Beatriz; González, Ramón; Fernández-Lafuente, Roberto; Guisán, José M.

    2007-01-01

    A new mutant of the industrial enzyme penicillin G acylase (PGA) from Escherichia coli has been designed to improve its reversible immobilization on anionic exchangers (DEAE- or polyethyleneimine [PEI]-coated agarose) by assembling eight new glutamic residues distributed homogeneously through the enzyme surface via site-directed mutagenesis. The mutant PGA is produced and processed in vivo as is the native enzyme. Moreover, it has a similar specific activity to and shows the same pH activity profile as native PGA; however, its isoelectric point decreased from 6.4 to 4.3. Although the new enzyme is adsorbed on both supports, the adsorption was even stronger when supports were coated with PEI, allowing us to improve the enzyme stability in organic cosolvents. The use of restrictive conditions during the enzyme adsorption on anionic exchangers (pH 5 and high ionic strength) permitted us to still further increase the strength of adsorption and the enzyme stability in the presence of organic solvents, suggesting that these conditions allow the penetration of the enzyme inside the polymeric beds, thus becoming fully covered with the polymer. After the enzyme inactivation, it can be desorbed to reuse the support. The possibility to improve the immobilization properties on an enzyme by site-directed mutagenesis of its surface opens a promising new scenario for enzyme engineering. PMID:17098917

  5. Effect of Ionic Strength on Initial Interactions of Escherichia coli with Surfaces, Studied On-Line by a Novel Quartz Crystal Microbalance Technique

    PubMed Central

    Otto, Karen; Elwing, Hans; Hermansson, Malte

    1999-01-01

    A novel quartz crystal microbalance (QCM) technique was used to study the adhesion of nonfimbriated and fimbriated Escherichia coli mutant strains to hydrophilic and hydrophobic surfaces at different ionic strengths. This technique enabled us to measure both frequency shifts (Δf), i.e., the increase in mass on the surface, and dissipation shifts (ΔD), i.e., the viscoelastic energy losses on the surface. Changes in the parameters measured by the extended QCM technique reflect the dynamic character of the adhesion process. We were able to show clear differences in the viscoelastic behavior of fimbriated and nonfimbriated cells attached to surfaces. The interactions between bacterial cells and quartz crystal surfaces at various ionic strengths followed different trends, depending on the cell surface structures in direct contact with the surface. While Δf and ΔD per attached cell increased for nonfimbriated cells with increasing ionic strengths (particularly on hydrophobic surfaces), the adhesion of the fimbriated strain caused only low-level frequency and dissipation shifts on both kinds of surfaces at all ionic strengths tested. We propose that nonfimbriated cells may get better contact with increasing ionic strengths due to an increased area of contact between the cell and the surface, whereas fimbriated cells seem to have a flexible contact with the surface at all ionic strengths tested. The area of contact between fimbriated cells and the surface does not increase with increasing ionic strengths, but on hydrophobic surfaces each contact point seems to contribute relatively more to the total energy loss. Independent of ionic strength, attached cells undergo time-dependent interactions with the surface leading to increased contact area and viscoelastic losses per cell, which may be due to the establishment of a more intimate contact between the cell and the surface. Hence, the extended QCM technique provides new qualitative information about the direct contact

  6. Surface structured platinum electrodes for the electrochemical reduction of carbon dioxide in imidazolium based ionic liquids.

    PubMed

    Hanc-Scherer, Florin A; Montiel, Miguel A; Montiel, Vicente; Herrero, Enrique; Sánchez-Sánchez, Carlos M

    2015-10-07

    The direct CO2 electrochemical reduction on model platinum single crystal electrodes Pt(hkl) is studied in [C2mim(+)][NTf2(-)], a suitable room temperature ionic liquid (RTIL) medium due to its moderate viscosity, high CO2 solubility and conductivity. Single crystal electrodes represent the most convenient type of surface structured electrodes for studying the impact of RTIL ion adsorption on relevant electrocatalytic reactions, such as surface sensitive electrochemical CO2 reduction. We propose here based on cyclic voltammetry and in situ electrolysis measurements, for the first time, the formation of a stable adduct [C2mimH-CO2(-)] by a radical-radical coupling after the simultaneous reduction of CO2 and [C2mim(+)]. It means between the CO2 radical anion and the radical formed from the reduction of the cation [C2mim(+)] before forming the corresponding electrogenerated carbene. This is confirmed by the voltammetric study of a model imidazolium-2-carboxylate compound formed following the carbene pathway. The formation of that stable adduct [C2mimH-CO2(-)] blocks CO2 reduction after a single electron transfer and inhibits CO2 and imidazolium dimerization reactions. However, the electrochemical reduction of CO2 under those conditions provokes the electrochemical cathodic degradation of the imidazolium based RTIL. This important limitation in CO2 recycling by direct electrochemical reduction is overcome by adding a strong acid, [H(+)][NTf2(-)], into solution. Then, protons become preferentially adsorbed on the electrode surface by displacing the imidazolium cations and inhibiting their electrochemical reduction. This fact allows the surface sensitive electro-synthesis of HCOOH from CO2 reduction in [C2mim(+)][NTf2(-)], with Pt(110) being the most active electrode studied.

  7. Effects of Electrode Surface Morphology on the Transduction of Ionic Polymer-Metal Composites

    NASA Astrophysics Data System (ADS)

    Palmre, Viljar

    Ionic polymer-metal composites (IPMCs) are innovative smart materials that exhibit electromechanical and mechanoelectrical transduction (conversion of electrical input into mechanical deformation and vice versa). Due to low driving voltage (< 5 V) and ability to operate in aqueous environment, IPMCs are attractive for developing soft actuators and sensors for underwater robots and medical devices. This dissertation focuses on investigating the effects of electrode surface morphology in the transduction of Pt and Pd-Pt electrodes-based IPMCs, with the aim to improve the electrode surface design and thereby enhance the transduction performance of the material. Firstly, the synthesis techniques are developed to control and manipulate the surface structure of the mentioned electrodes through the electroless plating process. Using these techniques, IPMCs with different electrode surface structures are fabricated. The changes in the electrode surface morphology and the resulting effects on the material's electromechanical, mechanoelectrical, electrochemical and mechanical properties area examined and analyzed. This study shows that increasing the impregnation-reduction cycles under appropriate conditions leads to the formation and growth of platinum nanoparticles with sharp tips and edges---called Pt nanothorn assemblies---at the polymer-electrode interface. IPMCs designed with such nanostructured Pt electrodes are first to be reported. The experiments demonstrate that the formation and growth of Pt nanothorn assemblies at the electrode interface increases considerably the total transported charge during the transduction, thereby increasing significantly the displacement and blocking force output of IPMC. The improvement of the mentioned electromechanical properties was 3--5 times, depending on the input voltage and frequency used. Also, the peak mechanoelectrically induced voltage increased somewhat, although the overall effect of the surface structure was relatively

  8. A step toward the development of high-temperature stable ionic liquid-in-oil microemulsions containing double-chain anionic surface active ionic liquid.

    PubMed

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

    2013-06-20

    Owing to their fascinating properties and wide range of potential applications, interest in nonaqueous microemulsions has escalated in the past decade. In the recent past, nonaqueous microemulsions containing ionic liquids (ILs) have been utilized in performing chemical reactions, preparation of nanomaterials, synthesis of nanostructured polymers, and drug delivery systems. The most promising fact about IL-in-oil microemulsions is their high thermal stability compared to that of aqueous microemulsions. Recently, surfactant-like properties of surface active ionic liquids (SAILs) have been used for preparation of microemulsions with high-temperature stability and temperature insensitivity. However, previously described methods present a limited possibility of developing IL-in-oil microemulsions with a wide range of thermal stability. With our previous work, we introduced a novel method of creating a huge number of IL-in-oil microemulsions (Rao, V. G.; Ghosh, S.; Ghatak, C.; Mandal, S.; Brahmachari, U.; Sarkar, N. J. Phys. Chem. B2012, 116, 2850-2855), composed of a SAIL as a surfactant, room-temperature ionic liquids as a polar phase, and benzene as a nonpolar phase. The use of benzene as a nonpolar solvent limits the application of the microemulsions to temperatures below 353 K. To overcome this limitation, we have synthesized N,N-dimethylethanolammonium 1,4-bis(2-ethylhexyl) sulfosuccinate (DAAOT), which was used as a surfactant. DAAOT in combination with isopropyl myristate (IPM, as an oil phase) and ILs (as a polar phase) produces a huge number of high-temperature stable IL-in-oil microemulsions. By far, this is the first report of a huge number of high-temperature stable IL-in-oil microemulsions. In particular, we demonstrate the wide range of thermal stability of [C6mim][TF2N]/DAAOT/IPM microemulsions by performing a phase behavior study, dynamic light scattering measurements, and (1)H NMR measurements and by using coumarin-480 (C-480) as a fluorescent probe

  9. Study of surface interactions of ionic liquids with aluminium alloys in corrosion and erosion corrosion processes

    NASA Astrophysics Data System (ADS)

    Bermúdez, María-Dolores; Jiménez, Ana-Eva; Martínez-Nicolás, Ginés

    2007-06-01

    Surface interactions of alkylimidazolium ionic liquids (ILs) with aluminium alloy Al 2011 have been studied by immersion tests in seven neat ILs [1- n-alkyl-3-methylimidazolium X - (X = BF 4; n = 2 (IL1), 6 (IL2), 8 (IL3). X = CF 3SO 3; n = 2 (IL4). X = (4-CH 3C 6H 4SO 3); n = 2 (IL5). X = PF 6; n = 6 (IL6)] and 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide (IL7)]. Immersion tests for Al 2011 have also been carried out in 1 wt.% and 5 wt.% solutions of 1-ethyl,3-methylimidazolium tetrafluoroborate (IL1) in water. No corrosion of Al 2011 by neat ILs is observed. The highest corrosion rate for Al 2011 in water is observed in the presence of a 5 wt.% IL1 due to hydrolysis of the anion with hydrogen evolution and formation of aluminium fluoride. Erosion-corrosion processes have been studied for three aluminium alloys (Al 2011, Al 6061 and Al 7075) in a 90 wt.% IL1 solution in water in the presence of α-alumina particles. The erosion-corrosion rates are around 0.2 mm/year or lower, and increase with increasing copper content to give a corrosion resistance order of Al 6061 > Al 7075 > Al 2011. Results are discussed on the basis of scanning electron microscopy (SEM) observations, energy dispersive spectroscopy (EDS) analysis, X-ray diffraction (XRD) patterns and X-ray photoelectron spectroscopy (XPS) determinations.

  10. Linear and Star Poly(ionic liquid) Assemblies: Surface Monolayers and Multilayers.

    PubMed

    Erwin, Andrew J; Xu, Weinan; He, Hongkun; Matyjaszewski, Krzysztof; Tsukruk, Vladimir V

    2017-04-04

    The surface morphology and organization of poly(ionic liquid)s (PILs), poly[1-(4-vinylbenzyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] are explored in conjunction with their molecular architecture, adsorption conditions, and postassembly treatments. The formation of stable PIL Langmuir and Langmuir-Blodgett (LB) monolayers at the air-water and air-solid interfaces is demonstrated. The hydrophobic bis(trifluoromethylsulfonyl)imide (Tf2N(-)) is shown to be a critical agent governing the assembly morphology, as observed in the reversible condensation of LB monolayers into dense nanodroplets. The PIL is then incorporated as an unconventional polyelectrolyte component in the layer-by-layer (LbL) films of hydrophobic character. We demonstrate that the interplay of capillary forces, macromolecular mobility, and structural relaxation of the polymer chains influence the dewetting mechanisms in the PIL multilayers, thereby enabling access to a diverse set of highly textured, porous, and interconnected network morphologies for PIL LbL films that would otherwise be absent in conventional LbL films. Their compartmentalized internal structure is relevant to molecular separation membranes, ultrathin hydrophobic coatings, targeted cargo delivery, and highly conductive films.

  11. Ionic adsorption on the brucite (0001) surface: A periodic electrostatic embedded cluster method study

    NASA Astrophysics Data System (ADS)

    Makkos, Eszter; Kerridge, Andrew; Austin, Jonathan; Kaltsoyannis, Nikolas

    2016-11-01

    Density functional theory (DFT) at the generalised gradient approximation level is employed within the periodic electrostatic embedded cluster method (PEECM) to model the brucite (0001) surface. Three representative studies are then used to demonstrate the reliability of the PEECM for the description of the interactions of various ionic species with the layered Mg(OH)2 structure, and its performance is compared with periodic DFT, an approach known to be challenging for the adsorption of charged species. The adsorption energies of a series of s block cations, including Sr2+ and Cs+ which are known to coexist with brucite in nuclear waste storage ponds, are well described by the embedded cluster model, provided that basis sets of triple-zeta quality are employed for the adsorbates. The substitution energies of Ca2+ and Sr2+ into brucite obtained with the PEECM are very similar to periodic DFT results, and comparison of the approaches indicates that two brucite layers in the quantum mechanical part of the PEECM are sufficient to describe the substitution. Finally, a detailed comparison of the periodic and PEECM DFT approaches to the energetic and geometric properties of differently coordinated Sr[(OH)2(H2O)4] complexes on brucite shows an excellent agreement in adsorption energies, Sr-O distances, and bond critical point electron densities (obtained via the quantum theory of atoms-in-molecules), demonstrating that the PEECM can be a useful alternative to periodic DFT in these situations.

  12. Preparation and evaluation of surface-bonded tricationic ionic liquid silica as stationary phases for high-performance liquid chromatography.

    PubMed

    Qiao, Lizhen; Shi, Xianzhe; Lu, Xin; Xu, Guowang

    2015-05-29

    Two tricationic ionic liquids were prepared and then bonded onto the surface of supporting silica materials through "thiol-ene" click chemistry as new stationary phases for high-performance liquid chromatography. The obtained columns of tricationic ionic liquids were evaluated respectively in the reversed-phase liquid chromatography (RPLC) mode and hydrophilic interaction liquid chromatography (HILIC) mode, and possess ideal column efficiency of 80,000 plates/m in the RPLC mode with naphthalene as the test solute. The tricationic ionic liquid stationary phases exhibit good hydrophobic and shape selectivity to hydrophobic compounds, and RPLC retention behavior with multiple interactions. In the HILIC mode, the retention and selectivity were evaluated through the efficient separation of nucleosides and bases as well as flavonoids, and the typical HILIC retention behavior was demonstrated by investigating retention changes of hydrophilic solutes with water volume fraction in mobile phase. The results show that the tricationic ionic liquid columns possess great prospect for applications in analysis of hydrophobic and hydrophilic samples.

  13. Heterogeneous nucleation from a supercooled ionic liquid on a carbon surface

    NASA Astrophysics Data System (ADS)

    He, Xiaoxia; Shen, Yan; Hung, Francisco R.; Santiso, Erik E.

    2016-12-01

    Classical molecular dynamics simulations were used to study the nucleation of the crystal phase of the ionic liquid [dmim+][Cl-] from its supercooled liquid phase, both in the bulk and in contact with a graphitic surface of D = 3 nm. By combining the string method in collective variables [Maragliano et al., J. Chem. Phys. 125, 024106 (2006)], with Markovian milestoning with Voronoi tessellations [Maragliano et al., J. Chem. Theory Comput. 5, 2589-2594 (2009)] and order parameters for molecular crystals [Santiso and Trout, J. Chem. Phys. 134, 064109 (2011)], we computed minimum free energy paths, the approximate size of the critical nucleus, the free energy barrier, and the rates involved in these nucleation processes. For homogeneous nucleation, the subcooled liquid phase has to overcome a free energy barrier of ˜85 kcal/mol to form a critical nucleus of size ˜3.6 nm, which then grows into the monoclinic crystal phase. This free energy barrier becomes about 42% smaller (˜49 kcal/mol) when the subcooled liquid phase is in contact with a graphitic disk, and the critical nucleus formed is about 17% smaller (˜3.0 nm) than the one observed for homogeneous nucleation. The crystal formed in the heterogeneous nucleation scenario has a structure that is similar to that of the bulk crystal, with the exception of the layers of ions next to the graphene surface, which have larger local density and the cations lie with their imidazolium rings parallel to the graphitic surface. The critical nucleus forms near the graphene surface separated only by these layers of ions. The heterogeneous nucleation rate (˜4.8 × 1011 cm-3 s-1) is about one order of magnitude faster than the homogeneous rate (˜6.6 × 1010 cm-3 s-1). The computed free energy barriers and nucleation rates are in reasonable agreement with experimental and simulation values obtained for the homogeneous and heterogeneous nucleation of other systems (ice, urea, Lennard-Jones spheres, and oxide glasses).

  14. Surface tension of binary mixtures of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids: experimental measurements and soft-SAFT modeling.

    PubMed

    Oliveira, M B; Domínguez-Pérez, M; Freire, M G; Llovell, F; Cabeza, O; Lopes-da-Silva, J A; Vega, L F; Coutinho, J A P

    2012-10-11

    Ionic liquids have attracted a large amount of interest in the past few years. One approach to better understand their peculiar nature and characteristics is through the analysis of their surface properties. Some research has provided novel information on the organization of pure ionic liquids at the vapor-liquid interface; yet, a systematic study on the surface properties of mixtures of ionic liquids and their organization at the surface has not previously been carried out in the literature. This work reports, for the first time, a comprehensive analysis of the surface organization of mixtures of ionic liquids constituted by 1-alkyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide ionic liquids, [C(n)mim][NTf(2)]. The surface tension of mixtures composed of [C(4)mim][NTf(2)] + [C(n)mim][NTf(2)] (n = 1, 2, 5, 6, 8, and 10) was experimentally determined, at 298.2 K and atmospheric pressure, in the whole composition range. From the experimental data, the surface tension deviations and the relative Gibbs adsorption isotherms were estimated showing how the surface composition of an ionic liquid mixture differs from that of the liquid bulk and that the surface is enriched by the ionic liquid with the longest alkyl chain length. Finally, the soft-SAFT equation of state coupled with the density gradient theory (DGT) was used, for the first time, to successfully reproduce the surface tension experimental data of binary mixtures of ionic liquids using a molecular-based approach. In addition, the DGT was used to compute the density profiles of the two components across the interface, confirming the experimental results for the components distribution at the bulk and at the vapor-liquid interface.

  15. Systematic analysis of silver nanoparticle ionic dissolution by tangential flow filtration: toxicological implications.

    PubMed

    Maurer, Elizabeth I; Sharma, Monita; Schlager, John J; Hussain, Saber M

    2014-11-01

    In the field of toxicology of nanomaterials, scientists have not clearly determined if the observed toxicological events are due to the nanoparticles (NPs) themselves or the dissolution of ions released into the biophysiological environment or both phenomenon participate in combination based upon their bioregional and temporal occurrence during exposure conditions. Consequently, research involving the toxicological analysis of silver NPs (Ag-NPs) has shifted towards assessment of 'nanosized' silver in comparison to its solvated 'ionic' counterpart. Current literature suggests that dissolution of ions from Ag-NPs may play a key role in toxicity; however, the present assessment methodology to separate ions from NPs still requires improvement before a definitive cause of toxicity can be determined. Recently, centrifugation-based techniques have been employed to obtain solvated ions from the NP solution, but this approach leads to NP agglomeration, making further toxicological analysis difficult to assess. Additionally, extremely small NPs are retained in the supernatant even after ultracentrifugation, leading to incomplete separation of ions from their respective NPs. To address these complex toxicology issues we applied enhanced separation techniques with the aim to study levels of ions originating from the Ag-NP using separation by a recirculating tangential flow filtration system. This system uses a unique diffusion-driven filtration method that retains large particles within the continuous flow path, while allowing the solution (ions) to pass through molecular filters by lateral diffusion separation. Use of this technique provides reproducible NP separation from their solvated ions which permits for further quantification using an inductively coupled plasma mass spectrometry or comparison use in bioassay exposures to biological systems. In this study, we thoroughly characterised NPs in biologically relevant solutions to understand the dissolution of Ag-NPs (10 and

  16. Does the influence of substituents impact upon the surface composition of pyrrolidinium-based ionic liquids? An angle resolved XPS study.

    PubMed

    Men, Shuang; Hurisso, Bitu Birru; Lovelock, Kevin R J; Licence, Peter

    2012-04-21

    The surface chemistry of a series of four pyrrolidinium based ionic liquids, [C(n)C(1)Pyrr][Tf(2)N] where n = 4-10, is investigated by angle resolved X-ray photoelectron spectroscopy (ARXPS). The importance of sample purity is demonstrated and the stability of the ionic liquids under X-ray irradiation investigated. It is apparent that the surface chemistry and orientation is broadly analogous to that of similar imidazolium-based systems.

  17. Self-assembled thin film of imidazolium ionic liquid on a silicon surface: Low friction and remarkable wear-resistivity

    NASA Astrophysics Data System (ADS)

    Gusain, Rashi; Kokufu, Sho; Bakshi, Paramjeet S.; Utsunomiya, Toru; Ichii, Takashi; Sugimura, Hiroyuki; Khatri, Om P.

    2016-02-01

    Imidazolium-hexafluorophosphate (ImPF6) ionic liquid thin film is prepared on a silicon surface using 3-chloropropyltrimethoxysilane as a bifunctional chemical linker. XPS result revealed the covalent grafting of ImPF6 thin film on a silicon surface. The atomic force microscopic images demonstrated that the ImPF6 thin film is composed of nanoscopic pads/clusters with height of 3-7 nm. Microtribological properties in terms of coefficient of friction and wear-resistivity are probed at the mean Hertzian contact pressure of 0.35-0.6 GPa under the rotational sliding contact. The ImPF6 thin film exhibited low and steady coefficient of friction (μ = 0.11) along with remarkable wear-resistivity to protect the underlying silicon substrate. The low shear strength of ImPF6 thin film, the covalent interaction between ImPF6 ionic liquid thin film and underlying silicon substrate, and its regular grafting collectively reduced the friction and improved the anti-wear property. The covalently grafted ionic liquid thin film further shows immense potential to expand the durability and lifetime of M/NEMS based devices with significant reduction of the friction.

  18. High surface area electrodes in ionic polymer transducers: numerical and experimental investigations of the chemo-electric behavior

    NASA Astrophysics Data System (ADS)

    Akle, Barbar J.; Wallmersperger, Thomas; Akle, Etienne; Leo, Donald J.

    2008-03-01

    Ionomeric polymer transducers have received considerable attention in the past ten years due to their ability to generate large bending strain and moderate stress at low applied voltages. Ionic polymer transducers consist of an ionomer, usually Nafion, sandwiched between two electrically conductive electrodes. Recently, a novel fabrication technique denoted as the direct assembly process (DAP) enabled controlled electrode architecture in ionic polymer transducers. A DAP transducer usually consists of two high surface area electrodes made of uniform distributed particles sandwiching an ionomer membrane. Further enhancements to the DAP enabled sub-micron control of the electrode architecture. In this study a previously developed finite element model, capable of simulating ionic polymer transducers with high surface area electrodes is used to study the effect of electrode architecture on the actuation performance due to a unit volt step input. Four architectures are considered: Agglomerate, Gradient, Random, and Lines. The four architectures are simulated for low particle loading and high particle loading. The agglomerate presents the case of badly dispersed metal particles in the electrode. Simulation results demonstrate that particle aggregation reduces the actuation performance on an IPT. The Gradient simulates an IPT built using an Impregnation-Reduction method. The Gradient is compared to a randomly distributed electrode which represents an IPT built using the DAP method. Simulation results demonstrate that the DAP built IPT outperforms the one built using the impregnation-reduction method. Finally line architecture is simulated and results demonstrate that it outperforms random architecture especially at high particle loading.

  19. Electrochemical Deposition of Niobium onto the Surface of Copper Using a Novel Choline Chloride-Based Ionic Liquid

    SciTech Connect

    Wixtroma, Alex I.; Buhlera, Jessica E.; Reece, Charles E.; Abdel-Fattah, Tarek M.

    2013-06-01

    Recent research has shown that choline chloride-based solutions can be used to replace acid-based electrochemical polishing solutions. In this study niobium metal was successfully deposited on the surface of copper substrate via electrochemical deposition using a novel choline chloride-based ionic liquid. The niobium metal used for deposition on the Cu had been dissolved in the solution from electrochemical polishing of a solid niobium piece prior to the deposition. The visible coating on the surface of the Cu was analyzed using scanning electron microscopy (SEM) and electron dispersive x-ray spectroscopy (EDX). This deposition method effectively recycles previously dissolved niobium from electrochemical polishing.

  20. Synthesis and micellar properties of surface-active ionic liquids: 1-alkyl-3-methylimidazolium chlorides.

    PubMed

    El Seoud, Omar A; Pires, Paulo Augusto R; Abdel-Moghny, Thanaa; Bastos, Erick L

    2007-09-01

    A series of surface-active ionic liquids, RMeImCl, has been synthesized by the reaction of purified 1-methylimidazole and 1-chloroalkanes, RCl, R=C(10),C(12),C(14), and C(16), respectively. Adsorption and aggregation of these surfactants in water have been studied by surface tension measurement. Additionally, solution conductivity, electromotive force, fluorescence quenching of micelle-solubilized pyrene, and static light scattering have been employed to investigate micelle formation. The following changes resulted from an increase in the length of R: an increase of micelle aggregation number; a decrease of: minimum area/surfactant molecule at solution/air interface; critical micelle concentration, and degree of counter-ion dissociation. Theoretically-calculated aggregation numbers and those based on quenching of pyrene are in good agreement. Gibbs free energies of adsorption at solution/air interface, DeltaG(ads)(0), and micelle formation in water, DeltaG(mic)(0), were calculated, and compared to those of three surfactant series, alkylpyridinium chlorides, RPyCl, alkylbenzyldimethylammonium chlorides, RBzMe(2)Cl, and benzyl(3-acylaminoethyl)dimethylammonium chlorides, R(')AEtBzMe(2)Cl, respectively. Contributions to the above-mentioned Gibbs free energies from surfactant methylene groups (in the hydrophobic tail) and the head-group were calculated. For RMeImCl, the former energy is similar to that of other cationic surfactants. The corresponding free energy contribution of the head-group to DeltaG(mic)(0) showed the following order: RPyCl approximately RBzMe(2)Cl>RMeImCl>R(')AEtBzMe(2)Cl. The head-groups of the first two surfactant series are more hydrophobic than the imidazolium ring of RMeImCl, this should favor their aggregation. Micellization of RMeImCl, however, is driven by a relatively strong hydrogen-bonding between the chloride ion and the hydrogens in the imidazolium ring, in particular the relatively acidic H2. This interaction more than compensates for

  1. Effect of alkyl chain length and hydroxyl group functionalization on the surface properties of imidazolium ionic liquids.

    PubMed

    Pensado, Alfonso S; Costa Gomes, Margarida F; Canongia Lopes, José N; Malfreyt, Patrice; Pádua, Agílio A H

    2011-08-14

    Properties of the surface of ionic liquids, such as surface tension, ordering, and charge and density profiles, were studied using molecular simulation. Two types of modification in the molecular structure of imidazolium cations were studied: the length of the alkyl side chain and the presence of a polar hydroxyl group at the end of the side chain. Four ionic liquids were considered: 1-ethyl-3-methylimidazolium tetrafluoroborate, [C(2)C(1)im][BF(4)]; 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate, [C(2)OHC(1)im][BF(4)]; 1-octyl-3-methylimidazolium tetrafluoroborate, [C(8)C(1)im][BF(4)] and 1-(8-hydroxyoctyl)-3-methylimidazolium tetrafluoroborate, [C(8)OHC(1)im][BF(4)]. The surface tension was calculated using both mechanical and thermodynamic definitions, with consistent treatment of the long-range corrections. The simulations reproduce the available experimental values of surface tension with a maximum deviation of ±10%. This energetic characterization of the interface is completed by microscopic structural analysis of orientational ordering at the interface and density profiles along the direction normal to the interface. The presence of the hydroxyl group modifies the local structure at the interface, leading to a less organized liquid phase. The results allow us to relate the surface tension to the structural ordering at the liquid-vacuum interface.

  2. Ionic fluids in lubrication of aluminium-steel contacts. Surface and tribochemical interactions

    NASA Astrophysics Data System (ADS)

    Jimenez Ballesta, Ana Eva

    Room-temperature ionic liquids (ILs) are high performance fluids with a wide thermal stability range. They are being studied as new lubricants in a variety of sliding contacts. One of their more interesting tribological applications is that of steel-aluminium lubrication. In this work we study the influence of the lateral alkyl chain length and of the anion on the lubricating ability of six imidazolium ILs, a pyridinium and a phosphonium derivative. For first time, these ILs have been studied as neat lubricants and as 1wt.% base oil additives in variable conditions of velocity, load and temperature in pin-on-disk tests for AISI 52100 steel-ASTM 2011 aluminium contacts. In this work we present the first study of ILs as lubricants under extreme temperature conditions. The tribological performance of ILs has been compared with that of a mineral oil and of a synthetic ester. Under these conditions, ILs show lower friction and wear values than conventional oils at all temperatures. As 1wt.% additives, the conditions of optimum lubrication and the transitions between regimes and lubrication mechanisms have been determined. We have also studied the performance of ILs as 1wt.% additives of the synthetic oil. A relationship between additive polarity and wear index has been established. If the more soluble phosphonium IL additive is used, no friction or wear reduction takes place due to competition between solvation and adsorption processes. Electronic microscopy (SEM), energy dispersive (EDS) and X-ray photoelectron (XPS) spectroscopies have been used to study the wear mechanisms and tribochemical processes that take place in the contact. Finally, we have studied the performance of three aluminium alloys in corrosion and erosion-corrosion tests. In immersion tests with free-water ILs, the aluminium alloy 2011 shows a good resistance to corrosion, but dilution of 1-ethyl, 3-methylimidazolium tetrafluoroborate in water produces the hydrolysis of the anion and the corrosion of

  3. Effect of surface charge density and electro-osmotic flow on ionic current in a bipolar nanopore fluidic diode

    NASA Astrophysics Data System (ADS)

    Pal Singh, Kunwar; Kumar, Manoj

    2011-10-01

    We have simulated bipolar nanopore fluidic diodes for different values of surface charge densities, electrolyte concentrations, and thickness of transition zone. Nanopore enrichment leads to increased nanopore conductivity with the surface charge density at low electrolyte concentrations. Potential drop across the nanopore and electric field inside the nanopore decreases. Forward current and ionic current rectification peaks for a specific value of surface charge density. Even though the electro-osmotic current component remains small as compared to other components, its non-inclusion in the modeling leads to serious errors in the solutions. Significant ion current rectification can be obtained even if transition zone between oppositely charged zones is not narrow. The effect of the surface charge is screened by counterions at higher electrolyte concentrations, which leads to reduced electrolyte polarization and a decrease in the ion current rectification.

  4. Self-assembly of new surface active ionic liquids based on Aerosol-OT in aqueous media.

    PubMed

    Rao, K Srinivasa; Gehlot, Praveen Singh; Trivedi, Tushar J; Kumar, Arvind

    2014-08-15

    New anionic ionic liquid surfactants have been synthesized by replacing the sodium cation of Aerosol-OT (sodium dioctylsulfosuccinate, [Na]AOT) with various biocompatible moieties, such as 1-butyl-3-methyl imidazolium ([C4mim]), proliniumisopropylester ([ProC3]), cholinium ([Cho]), and guanidinium ([Gua]). The Aerosol-OT derived ionic liquids (AOT-ILs) were found fairly soluble in water and formed vesicles above a critical vesicle concentration (CVC) which depended upon the nature of cation, and followed the order: [ProC3]<[C4mim]<[Gua]<[Cho]surface tension (ST), isothermal titration calorimetry (ITC), conductivity, dynamic light scattering (DLS), nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM). Unlike other AOT-ILs, a structural transformation has been observed for [C4mim]AOT above CVC, because of certain amphiphilic character in the cation [C4mim]. Thermodynamic parameters calculated from ITC and conductivity techniques revealed that the vesicle formation process is entropy driven for [C4mim]AOT, whereas the process is both enthalpy and entropy driven for other AOT-ILs. In order to check the versatility of synthesized AOT-ILs we have tested their dissolution behavior in a different class of ionic liquids. All the AOT-ILs were found fairly soluble in the hydrophilic IL, ethanolammonium formate (EOAF), whereas only [C4mim]AOT and [ProC3]AOT were found soluble in hydrophobic IL, [C4mim]Tf2N. Such combinations can have potential for construction of stable colloidal formulations or microemulsions in ionic liquid media.

  5. A paradoxical method for NAD+/NADH accumulation on an electrode surface using a hydrophobic ionic liquid.

    PubMed

    Masuda, Miyuki; Motoyama, Yusuke; Kuwahara, Jun; Nakamura, Nobuhumi; Ohno, Hiroyuki

    2013-01-15

    In this communication, we describe a novel and facile method for the immobilization of NAD(+)/NADH on an electrode surface using a hydrophobic ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][Tf(2)N]). By taking advantage of the insolubility of NAD(+)/NADH in hydrophobic ionic liquids, it is expected that NAD(+)/NADH can be retained on the electrode's surface. Alcohol dehydrogenase (ADH) and NAD(+)/NADH were immobilized with a gelatin hydrogel on an electrode that was modified with an electropolymerized ruthenium complex containing 5-amino-1,10-phenanthroline (pAPRu) as a mediator for NADH oxidation. The (ADH, NAD(+))/pAPRu-immobilized electrode exhibited the electrocatalytic oxidation of ethanol in [C4mim][Tf(2)N]. The obtained catalytic current in [C4mim][Tf(2)N] was comparable to that in buffer solution containing NAD(+). It was confirmed by UV-vis spectroscopy that NAD(+) did not dissolve in the [C4mim][Tf(2)N] and was retained on the electrode's surface. Furthermore, we succeeded in constructing an ethanol/O(2) biofuel cell comprised of an (ADH, NAD(+))/pAPRu anode and a bilirubin oxidase cathode using [C4mim][Tf(2)N] as an electrolyte.

  6. Surface history of Mercury - Implications for terrestrial planets

    NASA Technical Reports Server (NTRS)

    Murray, B. C.; Strom, R. G.; Trask, N. J.; Gault, D. E.

    1975-01-01

    A plausible surface history of Mercury is presented which is suggested by Mariner 10 television pictures. Five periods are postulated which are delineated by successive variations in the modification of the surface by external and internal processes: accretion and differentiation, terminal heavy bombardment, formation of the Caloris basin, flooding of that basin and other areas, and light cratering accumulated on the smooth plains. Each period is described in detail; the overall history is compared with the surface histories of Venus, Mars, and the moon; and the implications of this history for earth are discussed. It is tentatively concluded that: Mercury is a differentiated planet most likely composed of a large iron core enclosed by a relatively thin silicate layer; heavy surface bombardment occurred about four billion years ago, which probably affected all the inner planets, and was followed by a period of volcanic activity; no surface modifications caused by tectonic, volcanic, or atmospheric processes took place after the volcanic period.

  7. Electrochemical deposition of conducting polymer coatings on magnesium surfaces in ionic liquid

    PubMed Central

    Luo, Xiliang; Cui, Xinyan Tracy

    2012-01-01

    A conducting polymer based smart coating for magnesium (Mg) implants that can both improve the corrosion resistance of Mg and release drug in a controllable way is reported. As the ionic liquid is a highly conductive and stable solvent with a very wide electrochemical window, the conducting polymer coatings can be directly electrodeposited on the active metal Mg in ionic liquid at mild conditions, and Mg is considerably stable during the electrodeposition. The electrodeposited Poly(3,4-ethylenedioxythiophene) (PEDOT) coatings on Mg are uniform and can significantly improve the corrosion resistance of Mg. In addition, the PEDOT coatings can load the anti-inflammatory drug dexamethasone during the electrodeposition which can be subsequently released upon electric stimulation. PMID:20832505

  8. Exact exchange-correlation potential of an ionic Hubbard model with a free surface

    PubMed Central

    Brosco, V.; Ying, Z.-J.; Lorenzana, J.

    2013-01-01

    In Kohn-Sham density functional theory (DFT) the interacting electron problem is mapped into a noninteracting problem in an effective potential vKS. It is known that the charge gap of the interacting system is different from the gap of the effective problem due to a jump Δxc in vKS when an electron is added but its magnitude and its role in the ubiquitous discrepancy between the experimental gaps and approximate DFT computations is poorly understood. Here we compute the exact vKS of a strongly interacting one-dimensional lattice model which can be driven from an ionic to a Mott insulating state. Presence of a “vacuum” region allows to determine the absolute value of vKS. We show that in the ionic regime Δxc is determined by nearest-neighbor interaction, while in the Mott regime Δxc is determined by on-site Hubbard interaction. PMID:23838813

  9. A novel surface-confined glucaminium-based ionic liquid stationary phase for hydrophilic interaction/anion-exchange mixed-mode chromatography.

    PubMed

    Qiao, Lizhen; Wang, Shuangyuan; Li, Hua; Shan, Yuanhong; Dou, Abo; Shi, Xianzhe; Xu, Guowang

    2014-09-19

    Glucaminium-based ionic liquids are a new class of recently developed ionic liquids and prepared by functionalizing the amine group of N-methyl-d-glucamine, which renders them good hydrophilicity due to the presence of the glucose structure and charged quaternary ammonium group. In the present study, a glucaminium-based ionic liquid N,N-diallyl-N-methyl-d-glucaminium bromide was synthesized and subsequently bonded to the surface of 3-mercaptopropyl modified silica materials through "thiol-ene" click chemistry. The obtained stationary phase was characterized by elemental analysis and infrared spectroscopy, and then packed as a HPLC column. A mixture of five nucleosides was used to characterize the separation performance of the obtained column under HILIC mode and the column efficiency was determined with cytidine as the test solute, reaching 80,000plates/m. Then, the retention behavior was evaluated by investigating the effect of various chromatographic factors on retention of different types of solutes, and the results revealed that the developed surface-confined glucaminium-based ionic liquid stationary phase exhibited a hydrophilic interaction/anion-exchange mixed-mode retention mechanism. Finally, two mixtures of nucleotides and flavonoids were separated on the glucaminium-based ionic liquid column, respectively under hydrophilic interaction and hydrophilic interaction/anion-exchange mixed-mode chromatography. In conclusion, the multimodal retention capabilities of the glucaminium-based ionic liquid column could offer a wider range of retention behavior and flexible selectivity toward polar and hydrophilic compounds.

  10. Deposition of molybdenum carbide on the surface of diamonds by electrolysis of ionic melts

    SciTech Connect

    Shapoval, V.I.; Kushkhov, Kh.B.; Malyshev, V.V.; Vesna, V.T.; Maslov, V.P.

    1986-12-01

    The use of metallized diamonds in cutting tools considerably improves their performance and service life and thereby results in the reduced consumption of this mineral. The authors of this paper investigate the kinetics of the electrochemical deposition of molybdenum carbide on diamond from ionic melts of molybdenum oxide and lithium carbonate, the dependence of this process on temperature, current density, and deposition duration, and the interrelations of the deposition parameters with the wear and fracture properties of the diamonds. The results of fracture and compression tests are given.

  11. Influences of Surface and Ionic Properties on Electricity Generation of an Active Transducer Driven by Water Motion.

    PubMed

    Park, Junwoo; Yang, YoungJun; Kwon, Soon-Hyung; Kim, Youn Sang

    2015-02-19

    In this Letter, we discuss the surface, ionic properties, and scale-up potential of an active transducer that generated electricity from natural water motion. When a liquid contacts a solid surface, an electrical double layer (EDL) is always formed at the solid/liquid interface. By modulating the EDL, the active transducer could generate a peak voltage of ∼3 V and a peak power of ∼5 μW. Interestingly, there were specific salinities of solution droplets that showed maximum performance and different characteristics according to the ions' nature. Analyzing the results macroscopically, we tried to figure out the origins of the active transducing precipitated by ions dynamics. Also, we demonstrated the scale-up potential for practical usage by multiple electrode design.

  12. Surface effects on the structure and mobility of the ionic liquid C6C1ImTFSI in silica gels.

    PubMed

    Nayeri, Moheb; Aronson, Matthew T; Bernin, Diana; Chmelka, Bradley F; Martinelli, Anna

    2014-08-14

    We report on how the dynamical and structural properties of the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (C6C1ImTFSI) change upon different degrees of confinement in silica gels. The apparent diffusion coefficients of the individual ions are measured by (1)H and (19)F pulsed field gradient nuclear magnetic resonance (PFG-NMR) spectroscopy, while the intermolecular interactions in the ionogels are elucidated by Raman spectroscopy. In addition, the local structure of the ionic liquid at the silica interface is probed by solid-state NMR spectroscopy. Importantly, we extend this study to a wider range of ionic liquid-to-silica molar ratios (x) than has been investigated previously, from very low (high degree of confinement) to very high (liquid-like gels) ionic liquid contents. Diffusion NMR measurements indicate that a solvation shell, with a significantly lower mobility than the bulk ionic liquid, forms at the silica interface. Additionally, the diffusion of the C6C1Im(+) and TFSI(-) ions decreases more rapidly below an observed molar ratio threshold (x < 1), with the intrinsic difference in the self-diffusion coefficient between the cation and anion becoming less pronounced. For ionic liquid molar ratio of x < 1, Raman spectroscopy reveals a different conformational equilibrium for the TFSI(-) anions compared to the bulk ionic liquid, with an increased population of the cisoid isomers with respect to the transoid. Concomitantly, at these high degrees of confinement the TFSI(-) anion experiences stronger ion-ion interactions as indicated by the evolution of the TFSI(-) characteristic vibrational mode at ∼740 cm(-1). Furthermore, solid-state 2D (29)Si{(1)H} HETCOR NMR measurements establish the interactions of the ionic liquid species with the silica surface, where the presence of adsorbed water results in weaker interactions between (29)Si surface moieties and the hydrophobic alkyl protons of the cationic C6C1Im(+) molecules.

  13. The radiation of surface wave energy: Implications for volcanic tremor

    NASA Astrophysics Data System (ADS)

    Haney, M. M.; Denolle, M.; Lyons, J. J.; Nakahara, H.

    2015-12-01

    The seismic energy radiated by active volcanism is one common measurement of eruption size. For example, the magnitudes of individual earthquakes in volcano-tectonic (VT) swarms can be summed and expressed in terms of cumulative magnitude, energy, or moment release. However, discrepancies exist in current practice when treating the radiated energy of volcano seismicity dominated by surface waves. This has implications for volcanic tremor, since eruption tremor typically originates at shallow depth and is made up of surface waves. In the absence of a method to compute surface wave energy, estimates of eruption energy partitioning between acoustic and seismic waves typically assume seismic energy is composed of body waves. Furthermore, without the proper treatment of surface wave energy, it is unclear how much volcanic tremor contributes to the overall seismic energy budget during volcanic unrest. To address this issue, we derive, from first principles, the expression of surface wave radiated energy. In contrast with body waves, the surface wave energy equation is naturally expressed in the frequency domain instead of the time domain. We validate our result by reproducing an analytical solution for the radiated power of a vertical force source acting on a free surface. We further show that the surface wave energy equation leads to an explicit relationship between energy and the imaginary part of the surface wave Green's tensor at the source location, a fundamental property recognized within the field of seismic interferometry. With the new surface wave energy equation, we make clear connections to reduced displacement and propose an improved formula for the calculation of surface wave reduced displacement involving integration over the frequency band of tremor. As an alternative to reduced displacement, we show that reduced particle velocity squared is also a valid physical measure of tremor size, one based on seismic energy rate instead of seismic moment rate. These

  14. Protein imprinted ionic liquid polymer on the surface of multiwall carbon nanotubes with high binding capacity for lysozyme.

    PubMed

    Yuan, Shifang; Deng, Qiliang; Fang, Guozhen; Wu, Jianhua; Li, Wangwang; Wang, Shuo

    2014-06-01

    In this research, ionic liquid as functional monomer to prepare molecularly imprinted polymers for protein recognition was for the first time demonstrated, in which, 1-vinyl-3-butylimidazolium chloride was selected as functional monomer, acrylamide as co-functional monomer and lysozyme (Lyz) as template protein to synthesize imprinted polymers on the surface of multiwall carbon nanotubes in aqueous medium. The results indicated that ionic liquid was helpful to improve binding capacity of imprinted polymers, which had a maximum binding capacity of 763.36 mg/g in the optimum adsorption conditions. The prepared imprinted polymers had a fast adsorption rate and a much higher adsorption capacity than the corresponding non-imprinted polymers, with the difference in adsorption capacity up to 258.31 mg/g. The obtained polymer was evaluated by Lyz, bovine serum albumin (BSA), bovine hemoglobin (BHb), equine myoglobin (MB) and cytochrome c (Cyt c). The selectivity factor (β) for Lyz/BSA, Lyz/Mb, Lyz/BHb, and Lyz/Cyt c were 7.17, 2.12, 1.76 and 1.57, respectively, indicating the imprinted polymers had a good selectivity. Easy preparation of the imprinted polymers as well as high ability and selectivity to adsorb template proteins makes this polymer attractive and broadly applicable in biomacromolecular separation, biotechnology and sensors.

  15. Surface structures of equimolar mixtures of imidazolium-based ionic liquids using high-resolution Rutherford backscattering spectroscopy

    NASA Astrophysics Data System (ADS)

    Nakajima, Kaoru; Oshima, Shinichi; Suzuki, Motofumi; Kimura, Kenji

    2012-11-01

    Surface structures of equimolar mixtures of imidazolium-based ionic liquids (ILs) having a common cation (1-butyl-3-methylimidazolium ([C4MIM]) or 1-hexyl-3-methylimidazolium ([C6MIM])) and different anions (bis(trifluoromethanesulfonyl)imide ([TFSI]), hexafluorophosphate ([PF6]) or chlorine) are studied using high-resolution Rutherford backscattering spectroscopy (HRBS). Both cations and anions have the same preferential orientations at the surface as in the pure ILs. In the mixture, the larger anion is located shallower than the smaller anion. The [TFSI] anion is slightly enriched at the surface relative to [PF6] with coverage of ~ 60% for the equimolar mixtures of [C4(6)MIM] [TFSI] and [C4(6)MIM] [PF6]. No surface segregation is observed for [C6MIM] [TFSI]0.5[Cl]0.5 and [C6MIM] [PF6]0.5[Cl]0.5. These results are different from the recent TOF-SIMS measurement where very strong surface segregation of [TFSI] was concluded for the mixture of [C4MIM] [TFSI] and [C4MIM] [PF6].

  16. Asteroid surface materials - Mineralogical characterizations and cosmological implications

    NASA Technical Reports Server (NTRS)

    Gaffey, M. J.; Mccord, T. B.

    1977-01-01

    The theoretical basis for the interpretation of diagnostic spectral features is examined and previous characterizations of asteroid surface materials are considered. A summary is provided of results reported by Gaffey and McCord (1977) who have utilized the most sophisticated interpretive techniques available to interpret the spectral reflectance data of about 65 asteroids for mineralogic and petrologic information. Cosmological implications related to the study of asteroid surface materials are also considered, taking into account source bodies for the meteorites, postaccretionary thermal history, significant factors of asteroid thermal history, and the Apollo and Amor asteroids. It is found that the asteroids exhibit surface materials made up of assemblages of meteoritic minerals. The relative abundance of meteorite types reaching the earth's surface is very different from the population of mineralogic types on asteroid surfaces. The earth-crossing or -approaching asteroids apparently derive from a restricted source region or population which is very strongly depleted in the C2-like assemblages that dominate the belt as a whole.

  17. Impact of Environmental Conditions (pH, Ionic Strength, And Electrolyte Type) On The Surface Charge And Aggregation Of Silver Nanoparticles Suspensions

    EPA Science Inventory

    The impact of capping agents and environmental conditions (pH, ionic strength, and background electrolytes) on surface charge and aggregation potential of silver nanoparticles (AgNPs) suspensions were investigated. Capping agents are chemicals used in the synthesis of nanopartic...

  18. Adsorption of a Textile Dye on Commercial Activated Carbon: A Simple Experiment to Explore the Role of Surface Chemistry and Ionic Strength

    ERIC Educational Resources Information Center

    Martins, Angela; Nunes, Nelson

    2015-01-01

    In this study, an adsorption experiment is proposed using commercial activated carbon as adsorbent and a textile azo dye, Mordant Blue-9, as adsorbate. The surface chemistry of the activated carbon is changed through a simple oxidation treatment and the ionic strength of the dye solution is also modified, simulating distinct conditions of water…

  19. Roles of ionic strength and biofilm roughness on adhesion kinetics of Escherichia coli onto groundwater biofilm grown on PVC surfaces.

    PubMed

    Janjaroen, Dao; Ling, Fangqiong Q; Ling, Fangqiong; Monroy, Guillermo; Derlon, Nicolas; Morgenroth, Eberhard; Mogenroth, Eberhard; Boppart, Stephen A; Liu, Wen-Tso; Nguyen, Thanh H

    2013-05-01

    Mechanisms of Escherichia coli attachment on biofilms grown on PVC coupons were investigated. Biofilms were grown in CDC reactors using groundwater as feed solution over a period up to 27 weeks. Biofilm physical structure was characterized at the micro- and meso-scales using Scanning Electron Microscopy (SEM) and Optical Coherence Tomography (OCT), respectively. Microbial community diversity was analyzed with Terminal Restricted Fragment Length Polymorphism (T-RFLP). Both physical structure and microbial community diversity of the biofilms were shown to be changing from 2 weeks to 14 weeks, and became relatively stable after 16 weeks. A parallel plate flow chamber coupled with an inverted fluorescent microscope was also used to monitor the attachment of fluorescent microspheres and E. coli on clean PVC surfaces and biofilms grown on PVC surfaces for different ages. Two mechanisms of E. coli attachment were identified. The adhesion rate coefficients (kd) of E. coli on nascent PVC surfaces and 2-week biofilms increased with ionic strength. However, after biofilms grew for 8 weeks, the adhesion was found to be independent of solution chemistry. Instead, a positive correlation between kd and biofilm roughness as determined by OCT was obtained, indicating that the physical structure of biofilms could play an important role in facilitating the adhesion of E. coli cells.

  20. Roles of ionic strength and biofilm roughness on adhesion kinetics of Escherichia coli onto groundwater biofilm grown on PVC surfaces

    PubMed Central

    Janjaroen, Dao; Ling, Fangqiong; Monroy, Guillermo; Derlon, Nicolas; Mogenroth, Eberhard; Boppart, Stephen A.; Liu, Wen-Tso; Nguyen, Thanh H.

    2013-01-01

    Mechanisms of Escherichia coli attachment on biofilms grown on PVC coupons were investigated. Biofilms were grown in CDC reactors using groundwater as feed solution over a period up to 27 weeks. Biofilm physical structure was characterized at the micro- and meso-scales using Scanning Electron Microscopy (SEM) and Optical Coherence Tomography (OCT), respectively. Microbial community diversity was analyzed with Terminal Restricted Fragment Length Polymorphism (T-RFLP). Both physical structure and microbial community diversity of the biofilms were shown to be changing from 2 weeks to 14 weeks, and became relatively stable after 16 weeks. A parallel plate flow chamber coupled with an inverted fluorescent microscope was also used to monitor the attachment of fluorescent microspheres and E. coli on clean PVC surfaces and biofilms grown on PVC surfaces for different ages. Two mechanisms of E. coli attachment were identified. The adhesion rate coefficients (kd) of E. coli on nascent PVC surfaces and 2-week biofilms increased with ionic strength. However, after biofilms grew for 8 weeks, the adhesion was found to be independent of solution chemistry. Instead, a positive correlation between kd and biofilm roughness as determined by OCT was obtained, indicating that the physical structure of biofilms could play an important role in facilitating the adhesion of E. coli cells. PMID:23497979

  1. A comprehensive physics-based model encompassing variable surface resistance and underlying physics of ionic polymer-metal composite actuators

    NASA Astrophysics Data System (ADS)

    Shen, Qi; Palmre, Viljar; Stalbaum, Tyler; Kim, Kwang J.

    2015-09-01

    The ionic polymer-metal composite (IPMC) is an emerging smart material in actuation and sensing applications, such as artificial muscles, underwater actuators, and advanced medical devices. However, the effect of the change in surface electrode properties on the actuating of IPMC has not been well studied. To address this problem, we theoretically predict and experimentally investigate the dynamic electro-mechanical response of the IPMC thin-strip actuator. A model of the IPMC actuator is proposed based on the Poisson-Nernst-Planck equations for ion transport and charge dynamics in the polymer membrane, while a physical model for the change of surface resistance of the electrodes of the IPMC due to deformation is also incorporated. By incorporating these two models, a complete, dynamic, physics-based model for IPMC actuators is presented. To verify the model, IPMC samples were prepared and experiments were conducted. The results show that the theoretical model can accurately predict the actuating performance of IPMC actuators over a range of dynamic conditions. Additionally, the charge dynamics inside the polymer during the oscillation of the IPMC is presented. It is also shown that the charge at the boundary mainly affects the induced stress of the IPMC. The current study is beneficial for the comprehensive understanding of the surface electrode effect on the performance of IPMC actuators.

  2. High surface area electrodes in ionic polymer transducers: Numerical and experimental investigations of the electro-chemical behavior

    NASA Astrophysics Data System (ADS)

    Akle, Barbar J.; Habchi, Wassim; Wallmersperger, Thomas; Akle, Etienne J.; Leo, Donald J.

    2011-04-01

    Ionomeric polymer transducer (IPT) is an electroactive polymer that has received considerable attention due to its ability to generate large bending strain (>5%) and moderate stress at low applied voltages (±2 V). Ionic polymer transducers consist of an ionomer, usually Nafion, sandwiched between two electrically conductive electrodes. A novel fabrication technique denoted as the direct assembly process (DAP) enabled controlled electrode architecture in ionic polymer transducers. A DAP built transducer consists of two high surface area electrodes made of electrically conducting particles uniformly distributed in an ionomer matrix sandwiching an ionomer membrane. The purpose of this paper is to investigate and simulate the effect of these high surface area particles on the electro-chemical response of an IPT. Theoretical investigations as well as experimental verifications are performed. The model used consists of a convection-diffusion equation describing the chemical field as well as a Poisson equation describing the electrical field. The two-dimensional model incorporates highly conductive particles randomly distributed in the electrode area. Traditionally, these kinds of electrodes were simulated with boundary conditions representing flat electrodes with a large dielectric permittivity at the polymer boundary. This model enables the design of electrodes with complicated geometrical patterns. In the experimental section, several transducers are fabricated using the DAP process on Nafion 117 membranes. The architecture of the high surface area electrodes in these samples is varied. The concentration of the high surface area RuO2 particles is varied from 30 vol% up to 60 vol% at a fixed thickness of 30 μm, while the overall thickness of the electrode is varied from 10 μm up to 40 μm at a fixed concentration of 45%. The flux and charge accumulation in the materials are measured experimentally and compared to the results of the numerical simulations. Trends of

  3. Ionic Referencing in Surface Plasmon Microscopy: Visualization of the Difference in Surface Properties of Patterned Monomolecular Layers.

    PubMed

    Nizamov, Shavkat; Scherbahn, Vitali; Mirsky, Vladimir M

    2017-04-04

    An approach for visualization of patterned monomolecular layers in surface plasmon microscopy (SPM) is suggested. The development of hidden image in SPM is achieved by referencing of images obtained in the presence of electrolytes with a high molar refraction of either anions or cations. A formation of diffuse layer near the charged surface areas leads to the redistribution of ions. The ratio of SPM images allows one to visualize this redistribution and to distinguish surface areas with different properties. The approach is unobtrusive and robust; it can be used with most surface plasmon resonance (SPR) imaging instruments.

  4. Effect of dynamic diffusion of air, nitrogen, and helium gaseous media on the microhardness of ionic crystals with juvenile surfaces

    NASA Astrophysics Data System (ADS)

    Klyavin, O. V.; Fedorov, V. Yu.; Chernov, Yu. M.; Shpeizman, V. V.

    2015-09-01

    The load dependences of the microhardness of surface layers of NaCl and LiF ionic single crystals with juvenile surfaces and surfaces exposed to air for a long time measured in the air, nitrogen, and helium gaseous media have been investigated. It has been found that there is a change in the sign of the derivative of the microhardness as a function of the load for LiF crystals indented in helium and after their aging in air, as well as a weaker effect of the nitrogen and air gaseous media on the studied dependences as compared to NaCl crystals. It has also been found that, after the aging of the surface of NaCl crystals in air, there is a change in the sign of the derivative of the microhardness in the nitrogen and air gaseous media, as well as a pronounced change in the microhardness as a function of the time of aging the samples in air as compared to the weaker effect of the gaseous medium for LiF crystals. The obtained data have been analyzed in terms of the phenomenon of dislocation-dynamic diffusion of particles from the external medium into crystalline materials during their plastic deformation along the nucleating and moving dislocations. It has been shown that this phenomenon affects the microhardness through changes in the intensity of dislocation multiplication upon the formation of indentation rosettes in different gaseous media. The performed investigation of the microhardness of the juvenile surface of NaCl and LiF crystals in different gaseous media has revealed for the first time a different character of dislocation-dynamic diffusion of these media in a "pure" form.

  5. Ionic liquid assisted chemical strategy to TiO2 hollow nanocube assemblies with surface-fluorination and nitridation and high energy crystal facet exposure for enhanced photocatalysis.

    PubMed

    Yu, Shengli; Liu, Baocang; Wang, Qin; Gao, Yuxi; Shi, Ying; Feng, Xue; An, Xiaoting; Liu, Lixia; Zhang, Jun

    2014-07-09

    Realization of anionic nonmetal doping and high energy crystal facet exposure in TiO2 photocatalysts has been proven to be an effective approach for significantly improving their photocatalytic performance. A facile strategy of ionic liquid assisted etching chemistry by simply hydrothermally etching hollow TiO2 spheres composed of TiO2 nanoparticles with an ionic liquid of 1-butyl-3-methylimidazolium tetrafluoroborate without any other additives is developed to create highly active anatase TiO2 nanocubes and TiO2 nanocube assemblies. With this one-pot ionic liquid assisted etching process, the surface-fluorination and nitridation and high energy {001} crystal facets exposure can be readily realized simultaneously. Compared with the benchmark materials of P25 and TiO2 nanostructures with other hierarchical architectures of hollow spheres, flaky spheres, and spindles synthesized by hydrothermally etching hollow TiO2 spheres with nonionic liquid of NH4F, the TiO2 nanocubes and TiO2 nanocube assemblies used as efficient photocatalysts show super high photocatalytic activity for degradation of methylene blue, methyl orange, and rhodamine B, due to their surface-fluorination and nitridation and high energy crystal facet exposure. The ionic liquid assisted etching chemistry is facile and robust and may be a general strategy for synthesizing other metal oxides with high energy crystal facets and surface doping for improving photocatalytic activity.

  6. Molecular dynamics simulations of the liquid surface of the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide: structure and surface tension.

    PubMed

    Sanmartín Pensado, Alfonso; Malfreyt, Patrice; Pádua, Agílio A H

    2009-11-05

    Molecular dynamics simulations of the liquid-vacuum interface of the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide were performed with an all-atom force field. Structural properties of the interface, such as orientational ordering and density profiles, were calculated. The hexyl side chain of the cation is likely to protrude outward from the surface layer. There is a region with enhanced density from that of the bulk where the cation preferably slants with the imidazolium ring tending to be perpendicular to the interface. The surface tensions are calculated using mechanical and thermodynamic definitions via profiles along the direction normal to the interface. We also discuss the different contributions to the surface tension due to the repulsion-dispersion and electrostatic interactions. The use of local pressure profiles provides an explanation to the systematic problems encountered by several researchers to obtain accurate values of the surface tension at low temperature. Even when macroscopically the system looks in equilibrium, locally this is not accomplished.

  7. System-dependent dispersion coefficients for the DFT-D3 treatment of adsorption processes on ionic surfaces.

    PubMed

    Ehrlich, Stephan; Moellmann, Jonas; Reckien, Werner; Bredow, Thomas; Grimme, Stefan

    2011-12-09

    Dispersion-corrected density functional theory calculations (DFT-D3) were performed for the adsorption of CO on MgO and C(2) H(2) on NaCl surfaces. An extension of our non-empirical scheme for the computation of atom-in-molecules dispersion coefficients is proposed. It is based on electrostatically embedded M(4)X(4) (M=Na, Mg) clusters that are used in TDDFT calculations of dynamic dipole polarizabilities. We find that the C(MM)(6) dispersion coefficients for bulk NaCl and MgO are reduced by factors of about 100 and 35 for Na and Mg, respectively, compared to the values of the free atoms. These are used in periodic DFT calculations with the revPBE semi-local density functional. As demonstrated by calculations of adsorption potential energy curves, the new C(6) coefficients lead to much more accurate energies (E(ads)) and molecule-surface distances than with previous DFT-D schemes. For NaCl/C(2) H(2) we obtained at the revPBE-D3(BJ) level a value of E(ads) =-7.4 kcal mol(-1) in good agreement with experimental data (-5.7 to -7.1 kcal mol(-1)). Dispersion-uncorrected DFT yields an unbound surface state. For the MgO/CO system, the computed revPBE-D3(BJ) value of E(ads) =-4.1 kcal mol(-1) is also in reasonable agreement with experimental results (-3.0 kcal mol(-1)) when thermal corrections are taken into account. Our new dispersion correction also improves computed lattice constants of the bulk systems significantly compared to plain DFT or previous DFT-D results. The extended DFT-D3 scheme also provides accurate non-covalent interactions for ionic systems without empirical adjustments and is suggested as a general tool in surface science.

  8. Surface coating from phosphonate ionic liquid electrolyte for the enhancement of the tribological performance of magnesium alloy.

    PubMed

    Jiménez, Ana Eva; Rossi, Antonella; Fantauzzi, Marzia; Espinosa, Tulia; Arias-Pardilla, Joaquin; Martínez-Nicolás, Ginés; Bermúdez, María-Dolores

    2015-05-20

    A chronoamperometric method has been applied for the growth of a surface coating on AZ31B magnesium alloy, using the imidazolium alkylphosphonate room-temperature ionic liquid 1-ethyl-3-methylimidazolium ethylphosphonate ([EMIM][EtPO3H]) as electrolyte. A surface coating layer is obtained after 4 h under a constant voltage bias of -0.8 V with respect to the standard electrode. The coating nucleation and growth process correlates well with a 3D progressive mechanism. X-ray photoelectron spectrometry (XPS) analysis of [EMIM][EtPO3H] shows new P 2p and O 1s peaks after its use as electrolyte, as a consequence of reaction between the phosphonate anion and the magnesium substrate. Angle-resolved XPS (ARXPS) analysis of [EMIM][EtPO3H] did not show any change in the composition of the surface before and after chronoamperometry, since the sampling depth (1.5 nm at the highest emission angle) is larger than the cation and anion sizes (ca. 7 and 5 Å, respectively). Characterization of the coating was made by scanning electron microscopy (SEM), focussed ion beam SEM, energy dispersive X-ray spectroscopy, XPS, and ARXPS. FIB-SEM shows that the coating presents a mean thickness of 374 (±36) nm and contains magnesium and aluminum phosphates. Linear reciprocating tribological tests under variable load show that the presence of the coating can reduce friction coefficients of the coated AZ31B against steel up to 32% and wear rates up to 90%, with respect to the uncoated alloy.

  9. Holey graphene nanosheets with surface functional groups as high-performance supercapacitors in ionic-liquid electrolyte.

    PubMed

    Yang, Cheng-Hsien; Huang, Po-Ling; Luo, Xu-Feng; Wang, Chueh-Han; Li, Chi; Wu, Yi-Hsuan; Chang, Jeng-Kuei

    2015-05-22

    Pores and surface functional groups are created on graphene nanosheets (GNSs) to improve supercapacitor properties in a butylmethylpyrrolidinium-dicyanamide (BMP-DCA) ionic liquid (IL) electrolyte. The GNS electrode exhibits an optimal capacitance of 330 F g(-1) and a satisfactory rate capability within a wide potential range of 3.3 V at 25 °C. Pseudocapacitive effects are confirmed using X-ray photoelectron spectroscopy. Under the same conditions, carbon nanotube and activated carbon electrodes show capacitances of 80 and 81 F g(-1) , respectively. Increasing the operation temperature increases the conductivity and decreases the viscosity of the IL electrolyte, further improving cell performance. At 60 °C, a symmetric-electrode GNS supercapacitor with the IL electrolyte is able to deliver maximum energy and power densities of 140 Wh kg(-1) and 52.5 kW kg(-1) (based on the active material on both electrodes), respectively, which are much higher than the 20 Wh kg(-1) and 17.8 kW kg(-1) obtained for a control cell with a conventional organic electrolyte.

  10. Energetic atomic and ionic oxygen textured optical surfaces for blood glucose monitoring

    NASA Technical Reports Server (NTRS)

    Banks, Bruce A. (Inventor)

    2007-01-01

    Disclosed is a method and the resulting product thereof comprising a solid light-conducting fiber with a point of attachment and having a textured surface site consisting a textured distal end prepared by being placed in a vacuum and then subjected to directed hyperthermal beams comprising oxygen ions or atoms. The textured distal end comprises cones or pillars that are spaced upon from each other by less than 1 micron and are extremely suitable to prevent cellular components of blood from entering the valleys between the cones or pillars so as to effectively separate the cellular components in the blood from interfering with optical sensing of the glucose concentration for diabetic patients.

  11. Layering and shear properties of an ionic liquid, 1-ethyl-3-methylimidazolium ethylsulfate, confined to nano-films between mica surfaces.

    PubMed

    Perkin, Susan; Albrecht, Tim; Klein, Jacob

    2010-02-14

    We report high-resolution measurements of the forces between two atomically smooth solid surfaces across a film of 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid, for film thickness down to a single ion diameter. For films thinner than approximately 2 nm oscillatory structural forces are observed as the surface separation decreases and pairs of ion layers are squeezed out of the film. Strikingly, measurements of the shear stress of the ionic liquid film reveal low friction coefficients which are 1-2 orders of magnitude smaller than for analogous films of non-polar molecular liquids, including standard hydrocarbon lubricants, up to ca. 1 MPa pressure. We attribute this to the geometric and charge characteristics of the ionic liquid: the irregular shapes of the ions lead to a low shear stress, while the strong coulombic interactions between the ions and the charged confining surfaces lead to a robust film which is maintained between the shearing surfaces when pressure is applied across the film.

  12. Tuning high-harmonic generation by controlled deposition of ultrathin ionic layers on metal surfaces

    NASA Astrophysics Data System (ADS)

    Aguirre, Néstor F.; Martín, Fernando

    2016-12-01

    High-harmonic generation (HHG) from semiconductors and insulators has become a very active area of research due to its great potential for developing compact HHG devices. Here we show, that by growing monolayers (ML) of insulators on single-crystal metal surfaces, one can tune the harmonic spectrum by just varying the thickness of the ultrathin layer, rather than the laser properties. This is shown from numerical solutions of the time-dependent Schrödinger equation for Cu(111)/n -ML NaCl systems (n =1 -50 ) based on realistic potentials. Remarkably, the harmonic cutoff increases linearly with n and as much as an order of magnitude when going from n =1 to 30, while keeping the laser intensity low and the wavelength in the near-infrared range. The origin of this behavior is twofold: the initial localization of electrons in a Cu-surface state and the reduction of electronic "friction" when moving from the essentially discrete energy spectrum associated with a few-ML system to the continuous spectrum (bands) inherent in extended periodic systems. Our findings are valid for both few- and multicycle IR pulses and wavelengths ˜1 -2 μ m .

  13. Electrodes patterning on ionic polymer metal composite for making smooth surface on tunable mirrors

    NASA Astrophysics Data System (ADS)

    Cheng, Wei; Su, Guo-Dung J.

    2012-10-01

    Deformable mirror is a very important reflective component in optical system, which can vary the focal length while the surface deform. Nowadays several type of material were used as deformable mirror, such as liquid lens and MEMS deformable mirror. MEMS deformable mirror have been developed in our group and shows the potential. However, the problem of high actuation voltage is not easy to solve. In this thesis, we proposed using low voltage applied material, which is called Ioic-Polymer Metal Composite (IPMC) with the advantage of low applied voltage but high actuation performance. Arbitrary-shaped electrode IPMC was successfully fabricated by simply covering a shadow mask during electroless plating. Maximum central displacement of ellipsoid-shaped electrode IPMC can be achieved up to 350 μm under 2.5 volts applied. We believe this technique can be used in optical system as a deformable mirror in the future.

  14. Energetic Atomic and Ionic Oxygen Textured Optical Surfaces for Blood Glucose Monitoring

    NASA Technical Reports Server (NTRS)

    Banks, Bruce A. (Inventor)

    2007-01-01

    Disclosed is a method and the resulting product thereof comprising a solid light-conducting fiber with a point of attachment and having a textured surface site consisting of a textured distal end prepared by being placed in a vacuum and then subjected to directed hyperthermal beams comprising oxygen ions or atoms. The textured distal end comprises cones or pillars that are spaced upon from each other by less than 1 micron and are extremely suitable to prevent cellular components of blood from entering the valleys between the cones or pillars so as to effectively separate the cellular components in the blood from interfering with optical sensing of the glucose concentration for diabetic patients.

  15. The liquid surface of chiral ionic liquids as seen from molecular dynamics simulations combined with intrinsic analysis

    NASA Astrophysics Data System (ADS)

    Lísal, Martin

    2013-12-01

    We present molecular-level insight into the liquid/gas interface of two chiral room-temperature ionic liquids (RTILs) derived from 1-n-butyl-3-methylimidazolium bromide ([bmim][Br]); namely, (R)-1-butyl-3-(3-hydroxy-2-methylpropyl)imidazolium bromide (hydroxypropyl) and 1-butyl-3-[(1R)-nopyl]imidazolium bromide (nopyl). We use our currently developed force field which was validated against the experimental bulk density, heat of vaporization, and surface tension of [bmim][Br]. The force field for the RTILs adopts the Chemistry at Harvard Molecular Mechanics (CHARMM) parameters for the intramolecular and repulsion-dispersion interactions along with the reduced partial atomic charges based on ab initio calculations. The net charges of the ions are around ±0.8e, which mimic the anion to cation charge transfer and many-body effects. Molecular dynamics simulations in the slab geometry combined with the intrinsic interface analysis are employed to provide a detailed description of the RTIL/gas interface in terms of the structural and dynamic properties of the interfacial, sub-interfacial, and central layers at a temperature of 300 K. The focus is on the comparison of the liquid/gas interface for the chiral RTILs with the interface for parent [bmim][Br]. The structure of the interface is elucidated by evaluating the surface roughness, intrinsic atomic density profiles, and orientation ordering of the cations. The dynamics of the ions at the interfacial region is characterized by computing the survival probability, and normal and lateral self-diffusion coefficients in the layers.

  16. The liquid surface of chiral ionic liquids as seen from molecular dynamics simulations combined with intrinsic analysis

    SciTech Connect

    Lísal, Martin

    2013-12-07

    We present molecular-level insight into the liquid/gas interface of two chiral room-temperature ionic liquids (RTILs) derived from 1-n-butyl-3-methylimidazolium bromide ([bmim][Br]); namely, (R)-1-butyl-3-(3-hydroxy-2-methylpropyl)imidazolium bromide (hydroxypropyl) and 1-butyl-3-[(1R)-nopyl]imidazolium bromide (nopyl). We use our currently developed force field which was validated against the experimental bulk density, heat of vaporization, and surface tension of [bmim][Br]. The force field for the RTILs adopts the Chemistry at Harvard Molecular Mechanics (CHARMM) parameters for the intramolecular and repulsion-dispersion interactions along with the reduced partial atomic charges based on ab initio calculations. The net charges of the ions are around ±0.8e, which mimic the anion to cation charge transfer and many-body effects. Molecular dynamics simulations in the slab geometry combined with the intrinsic interface analysis are employed to provide a detailed description of the RTIL/gas interface in terms of the structural and dynamic properties of the interfacial, sub-interfacial, and central layers at a temperature of 300 K. The focus is on the comparison of the liquid/gas interface for the chiral RTILs with the interface for parent [bmim][Br]. The structure of the interface is elucidated by evaluating the surface roughness, intrinsic atomic density profiles, and orientation ordering of the cations. The dynamics of the ions at the interfacial region is characterized by computing the survival probability, and normal and lateral self-diffusion coefficients in the layers.

  17. Electropolishing of stainless steels in a choline chloride based ionic liquid: an electrochemical study with surface characterisation using SEM and atomic force microscopy.

    PubMed

    Abbott, Andrew P; Capper, Glen; McKenzie, Katy J; Glidle, Andrew; Ryder, Karl S

    2006-09-28

    We have studied the anodic dissolution (electropolishing) of various stainless steel alloys in an ionic liquid comprising a 2 : 1 stoichiometric mix of ethylene glycol (EG) and choline chloride. We have used a combination of electrochemical and spectroscopic methods together with in situ liquid probe microscopy. We discuss the role and influence of the surface oxide passivation layer, characterized here by X-ray photoelectron spectroscopy (XPS) and linear sweep voltammetry, on the polishing process. We address the question of dealloying during the polish in order to contribute to our understanding of the viability of the ionic liquid as a replacement industrial electropolishing medium; the current commercial process uses a corrosive mixture of phosphoric and sulfuric acids. Also, we present data from ex situ and in situ liquid AFM studies giving both a qualitative and quantitative insight into the nature and scale of morphological changes at the steel surface during the polishing process.

  18. Daylight-driven photocatalytic degradation of ionic dyes with negatively surface-charged In2S3 nanoflowers: dye charge-dependent roles of reactive species

    NASA Astrophysics Data System (ADS)

    Ge, Suxiang; Cai, Lejuan; Li, Dapeng; Fa, Wenjun; Zhang, Yange; Zheng, Zhi

    2015-12-01

    Even though dye degradation is a successful application of semiconductor photocatalysis, the roles of reactive species in dye degradation have not received adequate attention. In this study, we systematically investigated the degradation of two cationic dyes (rhodamine B and methylene blue) and two anionic dyes (methyl orange and orange G) over negatively surface-charged In2S3 nanoflowers synthesized at 80 °C under indoor daylight lamp irradiation. It is notable to find In2S3 nanoflowers were more stable in anionic dyes degradation compared to that in cationic dyes removal. The active species trapping experiments indicated photogenerated electrons were mainly responsible for cationic dyes degradation, but holes were more important in anionic dyes degradation. A surface-charge-dependent role of reactive species in ionic dye degradation was proposed for revealing such interesting phenomenon. This study would provide a new insight for preparing highly efficient daylight-driven photocatalyst for ionic dyes degradation.

  19. NMR, surface tension and conductance study to investigate host-guest inclusion complexes of three sequential ionic liquids with β-cyclodextrin in aqueous media

    NASA Astrophysics Data System (ADS)

    Barman, Siti; Ekka, Deepak; Saha, Subhadeep; Roy, Mahendra Nath

    2016-08-01

    Host-guest inclusion complexes of three sequential cationic room temperature surface active ionic liquids, benzyltrialkylammonium chloride [(C6H5CH2)N(CnH2n+1)3Cl; where n = 1, 2, 4] with β-cyclodextrin in aqueous media have been studied using surface tension, conductance and NMR spectroscopy. All the studies have suggested that the hydrophobic benzyl group of ionic liquids is encapsulated inside into the cavity of β-cyclodextrin and played a crucial role in supporting the formation of inclusion complexes. The variation of the thermodynamic parameters with guest size, shape is used to draw inferences about contributions to the overall binding by means of the driving forces, viz., hydrophobic effect, steric hindrance, van der Waal force, and electrostatic force.

  20. Impact of nanoscale surface heterogeneity on precursor film growth and macroscopic spreading of [Rmim][NTf2] ionic liquids on mica.

    PubMed

    Wang, Zhantao; Priest, Craig

    2013-09-10

    The connection between the interfacial properties of ionic liquids and their wetting behavior has been studied very little to date and not at all on heterogeneous surfaces. Therefore, we have investigated the static and dynamic wetting for a family of ionic liquids, 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, [Rmim][NTf2], on mica, where R represents an ethyl, butyl, or hexyl alkyl chain on the imidazolium ring. Spreading is impacted greatly by a precursor film that forms on both homogeneous and heterogeneous mica surfaces. Macroscopically, the initial viscous spreading of the ionic liquid droplet on bare mica occurs within seconds but is then followed by a very slow relaxation that can be closely correlated with the typical time-scales of the precursor film growth. The contact angle for [emim][NTf2] and [bmim][NTf2] relaxes from about 40° to 23° over 30 and 90 min, respectively. For [hmim][NTf2], the process takes approximately 24 h and approaches complete wetting. The thickness of the precursor films for [emim][NTf2], [bmim][NTf2], and [hmim][NTf2] were 0.53, 0.65, and 1.0 nm, respectively, according to atomic force microscopy (AFM). These values are consistent with a monolayer of ionic liquid cations on mica, rather than ion pairs. A monolayer of octadecylphosphonic acid (OPA) on mica prevents both the formation of a precursor film and the relaxation of the contact angle. However, only a partial surface coverage of ~60% OPA is required to have the same effect. Quenching of precursor film formation (and associated contact angle relaxation) is due to an increasingly connected network of OPA regions that closes the nanoscale paths of bare mica on which the precursor film can develop via surface diffusion.

  1. Halogen-free ionic liquid as an additive in zinc(II)-selective electrode: surface analyses as correlated to the membrane activity.

    PubMed

    Al-Asousi, Maryam F; Shoukry, Adel F; Bu-Olayan, Abdul Hadi

    2012-05-30

    Two conventional Zn(II) polyvinyl chloride (PVC) membrane electrodes have been prepared and characterized. They were based on dibenzo-24-crown-8 (DBC) as a neutral carrier, dioctyl phthalate (DOP) as a plasticizer, and potassium tetrakis (p-chlorophenyl) borate, KTpClPB or the halogen-free ionic liquid, tetraoctylammonium dodecylbenzene sulfonate [TOA][DBS] as an additive. The use of ionic liquid has been found to enhance the selectivity of the sensor. For each electrode, the surfaces of two membranes were investigated using X-ray photoelectron, ion-scattering spectroscopy and atomic force microscopy. One of the two membranes was conditioned by soaking it for 24 h in a 1.0×10(-3) M Zn(NO(3))(2) solution and the second was soaked in bi-distilled water for the same interval (24 h). Comparing the two surfaces indicated the following: (a) the high selectivity in case of using [TOA][DBS] as an additive is due to the extra mediation caused by the ionic liquid and (b) the working mechanism of the electrode is based on phase equilibrium at the surface of the membrane associated with ion transport through the bulk of the membrane.

  2. Implications of the Differential Toxicological Effects of III-V Ionic and Particulate Materials for Hazard Assessment of Semiconductor Slurries.

    PubMed

    Jiang, Wen; Lin, Sijie; Chang, Chong Hyun; Ji, Zhaoxia; Sun, Bingbing; Wang, Xiang; Li, Ruibin; Pon, Nanetta; Xia, Tian; Nel, André E

    2015-12-22

    Because of tunable band gaps, high carrier mobility, and low-energy consumption rates, III-V materials are attractive for use in semiconductor wafers. However, these wafers require chemical mechanical planarization (CMP) for polishing, which leads to the generation of large quantities of hazardous waste including particulate and ionic III-V debris. Although the toxic effects of micron-sized III-V materials have been studied in vivo, no comprehensive assessment has been undertaken to elucidate the hazardous effects of submicron particulates and released III-V ionic components. Since III-V materials may contribute disproportionately to the hazard of CMP slurries, we obtained GaP, InP, GaAs, and InAs as micron- (0.2-3 μm) and nanoscale (<100 nm) particles for comparative studies of their cytotoxic potential in macrophage (THP-1) and lung epithelial (BEAS-2B) cell lines. We found that nanosized III-V arsenides, including GaAs and InAs, could induce significantly more cytotoxicity over a 24-72 h observation period. In contrast, GaP and InP particulates of all sizes as well as ionic GaCl3 and InCl3 were substantially less hazardous. The principal mechanism of III-V arsenide nanoparticle toxicity is dissolution and shedding of toxic As(III) and, to a lesser extent, As(V) ions. GaAs dissolves in the cell culture medium as well as in acidifying intracellular compartments, while InAs dissolves (more slowly) inside cells. Chelation of released As by 2,3-dimercapto-1-propanesulfonic acid interfered in GaAs toxicity. Collectively, these results demonstrate that III-V arsenides, GaAs and InAs nanoparticles, contribute in a major way to the toxicity of III-V materials that could appear in slurries. This finding is of importance for considering how to deal with the hazard potential of CMP slurries.

  3. The squid preparation as a general model for ionic and metabolic Na+/Ca2+ exchange interactions: physiopathological implications.

    PubMed

    DiPolo, R; Beaugé, L

    2007-03-01

    We propose an integrated kinetic model for the squid nerve Na+/Ca2+ exchanger based on experimental evidences obtained in dialyzed axons. This model satisfactorily explains the interrelationship between ionic (Na+(i)-H+(i)-Ca2+(i)) and metabolic (ATP, phosphoarginine (PA)) regulation of the exchanger. Data in dialyzed axons show that the Ca(i)-regulatory site located in the large intracellular loop plays a central role in the modulation by ATP by antagonizing the inhibitory Na+(i)-H+(i) synergism. We have used the Na(o)/Na(i) exchange mode to unequivocally measure the affinity of the Ca(i)-regulatory site. This allowed us to separate Ca(i)-regulatory from Ca(i)-transport sites and to estimate their respective affinities. In this work we show for the first time that under conditions of saturation of the Ca(i)-regulatory site (10 microM Ca2+(i), pH(i) 8.0), ATP have no effect on the Ca(i)-transport site. In addition, we have expanded our equilibrium kinetic model of ionic and metabolic interactions to a complete exchange cycle (circular model). This model, in which the Ca(i)-regulatory site plays a central role, accounts for the decrease in Na(i) inactivation, at high pH(i), high Ca2+(i,) and MgATP. Furthermore, the model also predicts the net Ca2+ movements across the exchanger based on the exchanger complexes redistribution both during physiological and pathological conditions (ischemia).

  4. Phase boundaries, structural characteristics, and NMR spectra of ionic liquid-in-oil microemulsions containing double chain surface active ionic liquid: a comparative study.

    PubMed

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

    2013-02-07

    A method developed for the first time, to create a huge number of ionic liquid (IL)-in-oil microemulsions has been discussed in our earlier publication (Rao, V. G.; Ghosh, S.; Ghatak, C.; Mandal, S.; Brahmachari, U.; Sarkar, N. J. Phys. Chem. B 2012, 116, 2850-2855). Here, we present facile methods to adjust the structural parameters of microemulsions using different ionic liquids (ILs) as additives (polar phase). We have characterized ILs/[C(4)mim][AOT]/benzene ternary system by performing a phase behavior study, dynamic light scattering (DLS) measurements, and (1)H NMR measurements. The IL loading capacity of microemulsions (area of single phase region) (i) increases with increase in alkyl chain length of cation of ILs and follows the trend [C(6)mim][TF(2)N] > [C(4)mim][TF(2)N] > [C(2)mim][TF(2)N], (ii) increases with decrease in cation anion interaction strength of added ILs and follows the trend [C(4)mim][TF(2)N] > [C(4)mim][PF(6)] > [C(4)mim][BF(4)]. So depending on the IL used, the amount of IL within the core of microemulsions can be easily manipulated to directly affect the size of aggregates in microemulsions. The size increase with increasing R value (R value is defined as the molar ratio of RTILs to [C(4)mim][AOT]) was found to be maximum in the case of [C(2)mim][TF(2)N]/[C(4)mim][AOT]/benzene microemulsions and follows the trend [C(2)mim][TF(2)N] > [C(4)mim][TF(2)N] > [C(6)mim][TF(2)N]. However, the size increase was almost the same with increase in R value in the case of ILs with different anions. The most promising fact about IL-in-oil microemulsions is their high thermal stability compared to that of aqueous microemulsions, so we investigated the effect of temperature on size of aggregates in microemulsions at R = 1.0. It is evident from dynamic light scattering measurements that the aggregates in microemulsions remain monodisperse in nature with increasing temperature, and in all the cases, the size of aggregates in microemulsions decreases with

  5. Cigarette Smoke Toxins Deposited on Surfaces: Implications for Human Health

    PubMed Central

    Martins-Green, Manuela; Adhami, Neema; Frankos, Michael; Valdez, Mathew; Goodwin, Benjamin; Lyubovitsky, Julia; Dhall, Sandeep; Garcia, Monika; Egiebor, Ivie; Martinez, Bethanne; Green, Harry W.; Havel, Christopher; Yu, Lisa; Liles, Sandy; Matt, Georg; Destaillats, Hugo; Sleiman, Mohammed; Gundel, Laura A.; Benowitz, Neal; Jacob, Peyton; Hovell, Melbourne; Winickoff, Jonathan P.; Curras-Collazo, Margarita

    2014-01-01

    Cigarette smoking remains a significant health threat for smokers and nonsmokers alike. Secondhand smoke (SHS) is intrinsically more toxic than directly inhaled smoke. Recently, a new threat has been discovered – Thirdhand smoke (THS) – the accumulation of SHS on surfaces that ages with time, becoming progressively more toxic. THS is a potential health threat to children, spouses of smokers and workers in environments where smoking is or has been allowed. The goal of this study is to investigate the effects of THS on liver, lung, skin healing, and behavior, using an animal model exposed to THS under conditions that mimic exposure of humans. THS-exposed mice show alterations in multiple organ systems and excrete levels of NNAL (a tobacco-specific carcinogen biomarker) similar to those found in children exposed to SHS (and consequently to THS). In liver, THS leads to increased lipid levels and non-alcoholic fatty liver disease, a precursor to cirrhosis and cancer and a potential contributor to cardiovascular disease. In lung, THS stimulates excess collagen production and high levels of inflammatory cytokines, suggesting propensity for fibrosis with implications for inflammation-induced diseases such as chronic obstructive pulmonary disease and asthma. In wounded skin, healing in THS-exposed mice has many characteristics of the poor healing of surgical incisions observed in human smokers. Lastly, behavioral tests show that THS-exposed mice become hyperactive. The latter data, combined with emerging associated behavioral problems in children exposed to SHS/THS, suggest that, with prolonged exposure, they may be at significant risk for developing more severe neurological disorders. These results provide a basis for studies on the toxic effects of THS in humans and inform potential regulatory policies to prevent involuntary exposure to THS. PMID:24489722

  6. A Self-Consistent Charge-Embedding Methodology for ab initio Qantum Chemical Custer Modeling of Ionic Solids and Surfaces: Application to the (001) Surface of Hematite

    SciTech Connect

    Batista, Enrique; Friesner, Richard A.

    2002-07-16

    To ab initio simulate an ionic crystal using a cluster of atoms, one must surround that cluster with point charges. These point charges add the effect of the electrostatic potential of the rest of the crystal on the electronic structure of the quantum cluster. The value of the point charges has to be chosen to reproduce the crystal field in the region of the cluster. In this work, a method to compute the necessary point charges is presented. The algorithm to choose the point charges is an extension of the one presented by Derenzo et al. [J. Chem. Phys. 2000, 112, 2074]. The method consists of a self-consistent loop, fitting in each iteration the value of the point charges to reproduce the electrostatic field, calculated from the quantum simulation, in the region of the cluster. This method was then applied to the study of the (001) basal surface of hematite, R-Fe2O3. As the cluster size is systematically increased, it is shown that to fully converge the electrostatic effect on the electronic structure of the cluster, clusters of the order of 60 atoms are necessary. As a convergence parameter for the cluster to the bulk behavior, we used the ionization energy of the cluster. In the limit of an infinite cluster, we obtained the work function of hematite to be 5.6 eV.

  7. Ionic liquids in tribology.

    PubMed

    Minami, Ichiro

    2009-06-24

    Current research on room-temperature ionic liquids as lubricants is described. Ionic liquids possess excellent properties such as non-volatility, non-flammability, and thermo-oxidative stability. The potential use of ionic liquids as lubricants was first proposed in 2001 and approximately 70 articles pertaining to fundamental research on ionic liquids have been published through May 2009. A large majority of the cations examined in this area are derived from 1,3-dialkylimidazolium, with a higher alkyl group on the imidazolium cation being beneficial for good lubrication, while it reduces the thermo-oxidative stability. Hydrophobic anions provide both good lubricity and significant thermo-oxidative stability. The anions decompose through a tribochemical reaction to generate metal fluoride on the rubbed surface. Additive technology to improve lubricity is also explained. An introduction to tribology as an interdisciplinary field of lubrication is also provided.

  8. New chemical approach to obtain dense layer phosphate-based ionic conductor coating on negative electrode material surface: Synthesis way, outgassing and improvement of C-rate capability

    NASA Astrophysics Data System (ADS)

    Fleutot, Benoit; Davoisne, Carine; Gachot, Grégory; Cavalaglio, Sébastien; Grugeon, Sylvie; Viallet, Virginie

    2017-04-01

    Li4Ti5O12 (LTO) based batteries have severe gassing behavior during charge/discharge and storage process, due to interfacial reactions between active material and electrolyte solution. In the same time, the electronic and ionic conductivity of pristine LTO is very poor and induces the use of nanoparticles which increase the outgassing phenomena. The coating of LTO particles could be a solution. For this the LTO spinel particles are modified with ionic conductor Li3PO4 coating using a spray-drying method. For the first time a homogeneous thin dense layer phosphate based conductor is obtained without nanoparticles, as a thin film material. It is so possible to study the influence of ionic conductor deposited on the negative electrode material on performances by the controlled layer thickness. This coating was characterized by XRD, SEM, XPS and TEM. The electrochemical performance of Li3PO4 coated Li4Ti5O12 is improved at high C-rate by the surface modification (improvement of 30 mAh g-1 at 5 C-rate compared to pristine LTO for 5 nm of coating), inducing by a modification of surface energy. An optimum coating thickness was studied. This type of coating allows a significant decrease of outgassing phenomena due the conformal coating and opens the way to a great number of studies and new technologies.

  9. p-Si(1 1 1):H/ionic liquid interface investigated through a combination of electrochemical measurements and reflection high energy electron diffraction surface analysis in vacuum

    NASA Astrophysics Data System (ADS)

    Watanabe, Ko; Maruyama, Shingo; Matsumoto, Yuji

    2016-07-01

    A combination study of electrochemical measurements and reflection high energy electron diffraction (RHEED) surface analysis experiments in a vacuum was first demonstrated to characterize a p-Si(1 1 1):H/ionic liquid interface. Mott-Schottky plot analysis was made to successfully not only evaluate the acceptor density and flat band potential of the p-Si(1 1 1):H, but also get some insight into its surface states. Furthermore, the electric double layer capacitance and specific adsorption properties at the IL/Si(1 1 1):H interface as well as the electrochemical interface stability will be discussed in this paper.

  10. Lubrication of starch in ionic liquid-water mixtures: Soluble carbohydrate polymers form a boundary film on hydrophobic surfaces.

    PubMed

    Yakubov, Gleb E; Zhong, Lei; Li, Ming; Boehm, Michael W; Xie, Fengwei; Beattie, David A; Halley, Peter J; Stokes, Jason R

    2015-11-20

    Soluble starch polymers are shown to enhance the lubrication of ionic liquid-water solvent mixtures in low-pressure tribological contacts between hydrophobic substrates. A fraction of starch polymers become highly soluble in 1-ethyl-3-methylimidazolium acetate (EMIMAc)-water solvents with ionic liquid fraction ≥60wt%. In 65wt% EMIMAc, a small amount of soluble starch (0.33wt%) reduces the boundary friction coefficient by up to a third in comparison to that of the solvent. This low-friction is associated with a nanometre thick film (ca. 2nm) formed from the amylose fraction of the starch. In addition, under conditions where there is a mixture of insoluble starch particles and solubilised starch polymers, it is found that the presence of dissolved amylose enhances the lubrication of starch suspensions between roughened substrates. These findings open up the possibility of utilising starch biopolymers, as well as other hydrocolloids, for enhancing the performance of ionic liquid lubricants.

  11. 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…

  12. Long-range electrostatic screening in ionic liquids.

    PubMed

    Gebbie, Matthew A; Dobbs, Howard A; Valtiner, Markus; Israelachvili, Jacob N

    2015-06-16

    Electrolyte solutions with high concentrations of ions are prevalent in biological systems and energy storage technologies. Nevertheless, the high interaction free energy and long-range nature of electrostatic interactions makes the development of a general conceptual picture of concentrated electrolytes a significant challenge. In this work, we study ionic liquids, single-component liquids composed solely of ions, in an attempt to provide a novel perspective on electrostatic screening in very high concentration (nonideal) electrolytes. We use temperature-dependent surface force measurements to demonstrate that the long-range, exponentially decaying diffuse double-layer forces observed across ionic liquids exhibit a pronounced temperature dependence: Increasing the temperature decreases the measured exponential (Debye) decay length, implying an increase in the thermally driven effective free-ion concentration in the bulk ionic liquids. We use our quantitative results to propose a general model of long-range electrostatic screening in ionic liquids, where thermally activated charge fluctuations, either free ions or correlated domains (quasiparticles), take on the role of ions in traditional dilute electrolyte solutions. This picture represents a crucial step toward resolving several inconsistencies surrounding electrostatic screening and charge transport in ionic liquids that have impeded progress within the interdisciplinary ionic liquids community. More broadly, our work provides a previously unidentified way of envisioning highly concentrated electrolytes, with implications for diverse areas of inquiry, ranging from designing electrochemical devices to rationalizing electrostatic interactions in biological systems.

  13. Long-range electrostatic screening in ionic liquids

    PubMed Central

    Gebbie, Matthew A.; Dobbs, Howard A.; Valtiner, Markus; Israelachvili, Jacob N.

    2015-01-01

    Electrolyte solutions with high concentrations of ions are prevalent in biological systems and energy storage technologies. Nevertheless, the high interaction free energy and long-range nature of electrostatic interactions makes the development of a general conceptual picture of concentrated electrolytes a significant challenge. In this work, we study ionic liquids, single-component liquids composed solely of ions, in an attempt to provide a novel perspective on electrostatic screening in very high concentration (nonideal) electrolytes. We use temperature-dependent surface force measurements to demonstrate that the long-range, exponentially decaying diffuse double-layer forces observed across ionic liquids exhibit a pronounced temperature dependence: Increasing the temperature decreases the measured exponential (Debye) decay length, implying an increase in the thermally driven effective free-ion concentration in the bulk ionic liquids. We use our quantitative results to propose a general model of long-range electrostatic screening in ionic liquids, where thermally activated charge fluctuations, either free ions or correlated domains (quasiparticles), take on the role of ions in traditional dilute electrolyte solutions. This picture represents a crucial step toward resolving several inconsistencies surrounding electrostatic screening and charge transport in ionic liquids that have impeded progress within the interdisciplinary ionic liquids community. More broadly, our work provides a previously unidentified way of envisioning highly concentrated electrolytes, with implications for diverse areas of inquiry, ranging from designing electrochemical devices to rationalizing electrostatic interactions in biological systems. PMID:26040001

  14. Inelastic and Reactive Scattering Dynamics of Hyperthermal Oxygen Atoms on Ionic Liquid Surfaces: [emim][NTf{sub 2}] and [C{sub 12}mim][NTf{sub 2}

    SciTech Connect

    Wu Bohan; Zhang Jianming; Minton, Timothy K.; McKendrick, Kenneth G.; Slattery, John M.; Yockel, Scott; Schatz, George C.

    2011-05-20

    Collisions of hyperthermal oxygen atoms, with an average translational energy of 520 kJ mol{sup -1}, on continuously refreshed ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([emim][NTf{sub 2}]) and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([C{sub 12}mim][NTf{sub 2}]), were studied with the use of a beam-surface scattering technique. Time-of-flight and angular distributions of inelastically scattered O and reactively scattered OH and H{sub 2}O were collected for various angles of incidence with the use of a rotatable mass spectrometer detector. For both O and OH, two distinct scattering processes were identified, which can be empirically categorized as thermal and non-thermal. Non-thermal scattering is more probable for both O and OH products. The observation of OH confirms that at least some reactive sites, presumably alkyl groups, must be exposed at the surface. The ionic liquid with the longer alkyl chain, [C{sub 12}mim][NTf{sub 2}], is substantially more reactive than the liquid with the shorter alkyl chain, [emim][NTf{sub 2}], and proportionately much more so than would be predicted simply from stoichiometry based on the number of abstractable hydrogen atoms. Molecular dynamics models of these surfaces shed light on this change in reactivity. The scattering behavior of O is distinctly different from that of OH. However, no such differences between inelastic and reactive scattering dynamics have been seen in previous work on pure hydrocarbon liquids, in particular the benchmark, partially branched hydrocarbon, squalane (C{sub 30}H{sub 62}). The comparison between inelastic and reactive scattering dynamics indicates that inelastic scattering from the ionic liquid surfaces takes place predominantly at non-reactive sites that are effectively stiffer than the reactive alkyl chains, with a higher proportion of collisions sampling such sites for [emim][NTf{sub 2}] than for [C{sub 12}mim][NTf{sub 2}].

  15. Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

    2014-08-01

    Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses.

  16. Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

    PubMed Central

    Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

    2014-01-01

    Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses. PMID:25168309

  17. The gibbs energy, chemical potential, and state parameters of the surface of an ionic micelle in the form of an ellipsoid of revolution

    NASA Astrophysics Data System (ADS)

    Kuznetsov, V. S.; Usol'Tseva, N. V.; Blinov, A. P.

    2008-12-01

    A molecular-thermodynamic model of an ionic micelle in the form of an ellipsoid of revolution was suggested. Equations for the chemical potential of an ellipsoidal micelle, the work of transfer of ions from solution volume into the micelle, and the state parameters of the surface of the micelle (fraction of free hydrophobic surface, surface tension coefficient, and surface charge density) were obtained. The Gibbs energy, chemical potential, work of transfer, and state parameters of an ellipsoidal micelle were determined as depending on the form factor of the corresponding ellipsoid. The model was verified for the example of sodium decyl sulfate micelles. The calculated parameters were close to the thermochemical data on the asymmetrization of spherical micelles in a solution of sodium decyl sulfate. The equilibrium ion-micellar solution composition was estimated.

  18. Competitive interactions of ionic surfactants with salbutamol and bovine serum albumin: a molecular spectroscopy study with implications for salbutamol in food analysis.

    PubMed

    Zhang, Qiulan; Ni, Yongnian; Kokot, Serge

    2013-08-14

    The effect of ionic surfactants, sodium dodecyl sulfate (SDS) and N-cetyl-N,N,N-trimethylammonium bromide (CTAB), on the interaction between β-agonist salbutamol (SAL) and bovine serum albumin (BSA) was investigated with the use of fluorescence spectroscopy (FLS) and chemometrics methods [multivariate curve resolution-alternating least-squares (MCR-ALS) and parallel factor analysis algorithm (PARAFAC)]. It was found that the binding constant of SAL to BSA in the presence of CTAB was much larger than that without this ligand. The ligand/BSA stoichiometry was 4:1, that is, (CTAB)4-BSA, and was 2:1 with the ligand, that is, (SAL)2-BSA. These results were obtained from the concentration profiles extracted by MCR-ALS for all three reactants. Quantitative information on the complex CTAB-BSA-SAL species was obtained with the resolution of the excitation-emission fluorescence three-way data matrices by PARAFAC. This research has implications for the analysis of SAL in food and might be performed in laboratories associated with organizations such as the U.S. Food and Drug Administration (FDA) and the International Olympic Committee (IOC).

  19. Curvature-dependent surface energy and implications for nanostructures

    NASA Astrophysics Data System (ADS)

    Chhapadia, P.; Mohammadi, P.; Sharma, P.

    2011-10-01

    At small length scales, several size-effects in both physical phenomena and properties can be rationalized by invoking the concept of surface energy. Conventional theoretical frameworks of surface energy, in both the mechanics and physics communities, assume curvature independence. In this work we adopt a simplified and linearized version of a theory proposed by Steigmann-Ogden to capture curvature-dependence of surface energy. Connecting the theory to atomistic calculations and the solution to an illustrative paradigmatical problem of a bent cantilever beam, we catalog the influence of curvature-dependence of surface energy on the effective elastic modulus of nanostructures. The observation in atomistic calculations that the elastic modulus of bent nanostructures is dramatically different than under tension - sometimes softer, sometimes stiffer - has been a source of puzzlement to the scientific community. We show that the corrected surface mechanics framework provides a resolution to this issue. Finally, we propose an unambiguous definition of the thickness of a crystalline surface.

  20. "Practical" Electrospinning of Biopolymers in Ionic Liquids.

    PubMed

    Shamshina, Julia L; Zavgorodnya, Oleksandra; Bonner, Jonathan R; Gurau, Gabriela; Di Nardo, Thomas; Rogers, Robin D

    2017-01-10

    To address the need to scale up technologies for electrospinning of biopolymers from ionic liquids to practical volumes, a setup for the multi-needle electrospinning of chitin using the ionic liquid 1-ethyl-3-methylimidazolium acetate, [C2 mim]-[OAc], was designed, built, and demonstrated. Materials with controllable and high surface area were prepared at the nanoscale using ionic-liquid solutions of high-molecular-weight chitin extracted with the same ionic liquid directly from shrimp shells.

  1. Characterization of critical micelle concentration of ionic liquid on molecular length scale by X-ray surface scattering and spectroscopy study

    NASA Astrophysics Data System (ADS)

    Wang, Wenjie; Sung, Woongmo; Lindemann, William; Kuzmenko, Ivan; Kim, Doseok; Vaknin, David

    2013-03-01

    Ionic liquids (ILs) with long alkyl chains tend to form micelles in aqueous solutions once the critical micelle concentration (CMC) is reached, a phenomenon commonly described by the Gibbs isotherm for ionic surfactants. We report synchrotron X-ray measurements at far below, near and above the CMC of each IL of 1-dodecyl-3-methyl-imidazolium halides, [C12mim]X, (X =Cl,Br,I). Our X-ray reflectivity measurements provide the depth density profiles of the interfacial films formed by the ILs. A liquid state of the alkyl chains can also be identified by grazing incidence X-ray diffraction measurements that reveal the in-plane packing of the IL molecules. The ILs form monolayers on the aqueous surfaces and the cations [C12mim]+ bind with Cl- and I- ions with different affinity. We discuss our experimental results of surfactants surface enrichment in the context of Gibbs equations. Supported by DOE Basic Energy Sciences contract no. DE-AC02-07CH11358.

  2. Ionic Strength, Surface Charge, and Packing Density Effects on the Properties of Peptide Self-Assembled Monolayers.

    PubMed

    Leo, Norman; Liu, Juan; Archbold, Ian; Tang, Yongan; Zeng, Xiangqun

    2017-02-28

    The various environmental parameters of packing density, ionic strength, and solution charge were examined for their effects on the properties of the immobilized peptide mimotope CH19 (CGSGSGSQLGPYELWELSH) that binds with the therapeutic antibody Trastuzumab (Herceptin) on a gold substrate. The immobilization of CH19 onto gold was examined with a quartz crystal microbalance (QCM). The QCM data showed the presence of intermolecular interactions resulting in the increase of viscoelastic properties of the peptide self-assembled monolayer (SAM). The CH19 SAM was diluted with CS7 (CGSGSGS) to decrease the packing density as CH19/CS7. The packing density and ionic strength parameters were evaluated by atomic force microscopy (AFM), ellipsometry, and QCM. AFM and ellipsometry showed a distinct conformational difference between CH19 and CH19/CS7, indicating a relationship between packing density and conformational state of the immobilized peptide. The CH19 SAM thickness was 40 Å with a rough topology, while the CH19/CS7 SAM thickness was 20 Å with a smooth topology. The affinity studies showed that the affinity of CH19 and CH19/CS7 to Trastuzumab were both on the order of 10(7) M(-1) in undiluted PBS buffer, while the dilution of the buffer by 1000× increased both SAMs affinities to Trastuzumab to the order of 10(15) M(-2) and changed the binding behavior from noncooperative to cooperative binding. This indicated that ionic strength had a more pronounced effect on binding properties of the CH19 SAM than packing density. Electrochemical impedance spectroscopy (EIS) was conducted on the CH19/CS7 SAM, which showed an increase in impedance after each EIS measurement cycle. Cyclic voltammetry on the CH19/CS7 SAM decreased impedance to near initial values. The impact of the packing density, buffer ionic strength, and local charge perturbation of the peptide SAM properties was interpreted based on the titratable sites in CH19 that could participate in the proton transfer and

  3. In situ STM investigation of spinodal decomposition and surface alloying during underpotential deposition of Cd on Au(111) from an ionic liquid.

    PubMed

    Pan, Ge-Bo; Freyland, Werner

    2007-07-07

    The electrodeposition and anodic dissolution of Cd on Au(111) in an acidic chloroaluminate ionic liquid (MBIC-AlCl(3), 42 : 58 mol%) have been investigated by cyclic voltammetry and in situ STM. In the Cd underpotential deposition region, various nanostructures can be distinguished. At a potential of 0.95 V vs. Al/Al(iii), a transformation from a well ordered AlCl(4)(-) adlayer to a ( radical3 x radical19) superstructure, presumably due to Cd-AlCl(4)(-) coadsorption, is observed. Reducing the potential to 0.45 V, surface alloying of Cd and Au occurs, which is evidenced for the first time by typical spinodal structures occurring both during deposition and dissolution of the surface alloy layer having a hexagonal structure. At still lower potentials below 0.21 V, a layer-by-layer growth of bulk Cd sets in.

  4. Lattice-constant and electron-affinity effects on negative-ion conversion in atom-ionic-crystal-surface grazing scattering

    NASA Astrophysics Data System (ADS)

    Zhou, Wang; Zhou, Hu; Zhang, Meixiao; Zhou, Lihua; Li, Yuan; Li, Bowen; Chen, Ximeng

    2016-11-01

    The effects of the lattice constant and electron affinity on the negative-ion conversion of a neutral atom undergoing grazing scattering on an ionic-crystal surface over the complete velocity range were investigated. Here, a comparison of negative-ion conversion of neutral O0-KCl (100 ) , F0-KCl (100 ) , and O0-KI (100 ) surface systems shows that the pronounced difference in the efficiency of negative-ion formation between F0-KCl (100 ) and O0-KCl (100 ) is caused by the large difference in their projectile electron affinities, whereas the difference between O0-KI (100 ) and O0-KCl (100 ) is caused by the difference in their lattice constants.

  5. Surface structures of binary mixtures of imidazolium-based ionic liquids using high-resolution Rutherford backscattering spectroscopy and time of flight secondary ion mass spectroscopy.

    PubMed

    Nakajima, Kaoru; Miyashita, Motoki; Suzuki, Motofumi; Kimura, Kenji

    2013-12-14

    Surface structures of binary mixtures of imidazolium-based ionic liquids having a common anion (bis(trifluoromethanesulfonyl)imide ([TFSI]), namely [C2MIM]1-x[C10MIM]x[TFSI] (x = 0.5 and 0.1), are studied using high-resolution Rutherford backscattering spectroscopy (HRBS) and time of flight secondary ion mass spectroscopy (TOF-SIMS). Although both measurements show surface segregation of [C10MIM] the degrees of the segregation are different. The surface fraction xsurf of [C10MIM] is estimated to be 0.6 ± 0.05 and 0.18 ± 0.02 by HRBS for x = 0.5 and 0.1, respectively. On the other hand, TOF-SIMS indicates much stronger surface segregation, namely xsurf = 0.83 ± 0.03 and 0.42 ± 0.04 for x = 0.5 and 0.1, respectively. The observed discrepancy can be attributed to the difference in the probing depth between HRBS and TOF-SIMS. The observed surface segregation can be roughly explained in terms of surface tension.

  6. Surface structures of binary mixtures of imidazolium-based ionic liquids using high-resolution Rutherford backscattering spectroscopy and time of flight secondary ion mass spectroscopy

    NASA Astrophysics Data System (ADS)

    Nakajima, Kaoru; Miyashita, Motoki; Suzuki, Motofumi; Kimura, Kenji

    2013-12-01

    Surface structures of binary mixtures of imidazolium-based ionic liquids having a common anion (bis(trifluoromethanesulfonyl)imide ([TFSI]), namely [C2MIM]1-x[C10MIM]x[TFSI] (x = 0.5 and 0.1), are studied using high-resolution Rutherford backscattering spectroscopy (HRBS) and time of flight secondary ion mass spectroscopy (TOF-SIMS). Although both measurements show surface segregation of [C10MIM] the degrees of the segregation are different. The surface fraction xsurf of [C10MIM] is estimated to be 0.6 ± 0.05 and 0.18 ± 0.02 by HRBS for x = 0.5 and 0.1, respectively. On the other hand, TOF-SIMS indicates much stronger surface segregation, namely xsurf = 0.83 ± 0.03 and 0.42 ± 0.04 for x = 0.5 and 0.1, respectively. The observed discrepancy can be attributed to the difference in the probing depth between HRBS and TOF-SIMS. The observed surface segregation can be roughly explained in terms of surface tension.

  7. Synthesis, COSMO-RS analysis and optical properties of surface modified ZnS quantum dots using ionic liquids

    NASA Astrophysics Data System (ADS)

    Shahid, Robina; Muhammad, Nawshad; Gonfa, Girma; Toprak, Muhammet S.; Muhammed, Mamoun

    2015-10-01

    Zinc sulfide (ZnS) quantum dots (QDs) were synthesized using the microwave assisted ionic liquid (MAIL) route. Three ionic liquids (ILs), namely, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF4]), trihexyl(tetradecyl) phosphonium bis(trifluoromethanesulfonyl) amide ([P6,6,6,14][TSFA]) and trihexyl(tetradecyl) phosphonium chloride ([P6,6,6,14][Cl]) were used in this study. The size and structure of the QDs were characterized by high-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) pattern, respectively. The synthesized QDs were of wurtzite crystalline structure with size less than 5 nm. The QDs were more uniformly distributed while using the phosponium based ILs as a reaction medium during synthesis. The optical properties were investigated by UV-vis absorption and photoluminescence (PL) emission spectroscopy. The optical properties of QDs showed the quantum confinement effect in their absorption and the effect of cation and anion structural moiety was observed on their bandedge emission. The QDs emission intensity was measured higher for [P6,6,6,14][Cl] due to their better dispersion as well as high charge density of Cl anion. The capability of the ILs in stabilizing the QDs was interpreted by density functional theory (DFT) computations. The obtained results are in good agreement with the theoretical prediction.

  8. Practical Implications of Electron-Beam Surface Melting

    NASA Astrophysics Data System (ADS)

    Lewis, Brian G.; Strutt, Peter R.

    1982-11-01

    The use of laser/electron-beam techniques to glaze large surface areas is briefly reviewed. The properties thus obtained for a range of iron-based alloys is discussed. Recent results show that electron-beam glazing can extend the wear life of certain cemented carbide materials and preliminary results indicate that glazed tool steels show enhanced corrosion resistance.

  9. Modeling electrokinetics in ionic liquids.

    PubMed

    Wang, Chao; Bao, Jie; Pan, Wenxiao; Sun, Xin

    2017-03-17

    Using direct numerical simulations, we provide a thorough study regarding the electrokinetics of ionic liquids. In particular, modified Poisson-Nernst-Planck (MPNP) equations are solved to capture the crowding and overscreening effects characteristic of an ionic liquid. For modeling electrokinetic flows in an ionic liquid, the MPNP equations are coupled with Navier-Stokes equations to study the coupling of ion transport, hydrodynamics, and electrostatic forces. Specifically, we consider the ion transport between two parallel charged surfaces, charging dynamics in a nanopore, capacitance of electric double-layer capacitors, electro-osmotic flow in a nanochannel, electroconvective instability on a plane ion-selective surface, and electroconvective flow on a curved ion-selective surface. We also discuss how crowding and overscreening and their interplay affect the electrokinetic behaviors of ionic liquids in these application problems. This article is protected by copyright. All rights reserved.

  10. Surface active ionic liquids: study of the micellar properties of 1-(1-alkyl)-3-methylimidazolium chlorides and comparison with structurally related surfactants.

    PubMed

    Galgano, Paula D; El Seoud, Omar A

    2011-09-01

    The impetus for the increasing interest in studying surface active ionic liquids (SAILs; ionic liquids with long-chain "tails") is the enormous potential for their applications, e.g., in nanotechnology and biomedicine. The progress in these fields rests on understanding the relationship between surfactant structure and solution properties, hence applications. This need has prompted us to extend our previous study on 1-(1-hexadecyl)-3-methylimidazolium chloride to 1-(1-alkyl)-3-methylimidazolium chlorides, with alkyl chains containing 10, 12, and 14 carbons. In addition to investigating relevant micellar properties, we have compared the solution properties of the imidazolium-based surfactants with: 1-(1-alkyl)pyridinium chlorides, and benzyl (2-acylaminoethyl)dimethylammonium chlorides. The former series carries a heterocyclic ring head-group, but does not possess a hydrogen that is as acidic as H2 of the imidazolium ring. The latter series carries an aromatic ring, a quaternary nitrogen and (a hydrogen-bond forming) amide group. The properties of the imidazolium and pyridinium surfactants were determined in the temperature range from 15 to 75°C. The techniques employed were conductivity, isothermal titration calorimetry, and static light scattering. The results showed the important effects of the interactions in the interfacial region on the micellar properties over the temperature range studied.

  11. Scaling of Crack Surfaces and Implications for Fracture Mechanics

    NASA Astrophysics Data System (ADS)

    Morel, Stéphane; Schmittbuhl, Jean; Bouchaud, Elisabeth; Valentin, Gérard

    2000-08-01

    The scaling laws describing the roughness development of crack surfaces are incorporated into the Griffith criterion. We show that, in the case of a Family-Vicsek scaling, the energy balance leads to a purely elastic brittle behavior. On the contrary, it appears that an anomalous scaling reflects an R-curve behavior associated with a size effect of the critical resistance to crack growth in agreement with the fracture process of heterogeneous brittle materials exhibiting a microcracking damage.

  12. Scaling of crack surfaces and implications for fracture mechanics

    PubMed

    Morel; Schmittbuhl; Bouchaud; Valentin

    2000-08-21

    The scaling laws describing the roughness development of crack surfaces are incorporated into the Griffith criterion. We show that, in the case of a Family-Vicsek scaling, the energy balance leads to a purely elastic brittle behavior. On the contrary, it appears that an anomalous scaling reflects an R-curve behavior associated with a size effect of the critical resistance to crack growth in agreement with the fracture process of heterogeneous brittle materials exhibiting a microcracking damage.

  13. Phase transition of a binary room-temperature ionic liquid composed of bis(pentafluoroethanesulfonyl)amide salts of tetraheptylammonium and N-tetradecylisoquinolinium and its surface properties at the ionic liquid|water interface.

    PubMed

    Ishimatsu, Ryoichi; Kitazumi, Yuki; Nishi, Naoya; Kakiuchi, Takashi

    2009-07-09

    A binary room-temperature ionic liquid (RTIL) composed of bis(pentafluoroethanesulfonyl)amide (C(2)C(2)N(-)) salts of tetraheptylammonium (THpA(+)) and N-tetradecylisoquinolinium (C(14)Iq(+)) undergoes a phase transition upon increasing the mole fraction of C(14)Iq(+) (x) in the bulk RTIL. The initial decrease with x of the interfacial tension (gamma) at the interface between water (W) and the binary RTIL reaches a break point at x approximately 0.2 irrespective of the values of the phase-boundary potential. The surface tension at RTIL|air interface and the conductivity of the binary RTIL support that the break point at x = 0.2 at the RTIL|W interface is attributable to the change of the bulk property. However, unlike the micelle formation of a surfactant solution, a further increase in x gives rise to a further change in gamma. Whereas the phase transition at x = 0.2 does not depend on the applied potential (E) across the RTIL|W interface, the mode of the change in gamma at x > 0.2 strongly depends on E and the apparent deficit of C(14)Iq(+) at the interface is more pronounced when E is closer to the point of zero charge.

  14. Constraints on surface evapotranspiration: implications for modeling and observations

    NASA Astrophysics Data System (ADS)

    Gentine, P.

    2015-12-01

    The continental hydrological cycle and especially evapotranspiration are constrained by additional factors such as the energy availability and the carbon cycle. As a results trying to understand and predict the surface hydrologic cycle in isolation might be highly unreliable. We present two examples were constraints induced by 1) radiation control through cloud albedo feedback and 2) carbon control on the surface water use efficiency are essential to correctly predict the seasonal hydrologic cycle. In the first example we show that correctly modeling diurnal and seasonal convection and the associated cloud-albedo feedback (through land-atmosphere and convection-large-scale circulation feedbacks) is essential to correctly model the surface hydrologic cycle in the Amazon, and to correct biases observed in all general circulation models. This calls for improved modeling of convection to correctly predict the tropical continental hydrologic cycle.In the second example we show that typical drought index based only on energy want water availability misses vegetation physiological and carbon feedback and cannot correctly represent the seasonal cycle of soil moisture stress. The typical Palmer Drought Stress Index is shown to be incapable of rejecting water stress in the future. This calls for new drought assessment metrics that may include vegetation and carbon feedback.

  15. 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

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

    PubMed

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

    2015-12-30

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

  17. Ocean Surface Circulation with Implication for Marine Debris Distribution

    NASA Astrophysics Data System (ADS)

    Hafner, Jan; Maximenko, Nikolai; Niiler, Peter

    2010-05-01

    Modern, multi-instrumental Global Ocean Observing System (GOOS) includes satellites and in situ observations, monitoring the ocean state at the highest accuracy and resolution ever. By combining data of satellite altimetry, surface drifters, wind and gravity, ocean currents can be assessed globally and at research quality. The map of the mean surface currents shows a complex pattern of oceanic fronts and gyres. Distinct are the convergences of Ekman currents in subtropical gyres that, through the Sverdrup mechanism, are feeding anticyclonic circulation in the gyres. Drifter trajectories can also be utilized to simulate the evolution of the marine debris. Main problem is the inhomogeneous drifter data density, both due to convergence/divergence of the ocean currents and due to the drifter deployment scheme. A model constructed from statistics of the drifters exchange between small bins corrects this bias and was run from the uniform initial condition to study the fate of debris in the ocean. In addition to such actively studied debris accumulation areas as the Great Garbage Patch in the North Pacific, a new so far unrecognized, the world-strongest convergence is discovered in the South Pacific from the model solution. The same model reveals a complex pattern of convergence/divergence on the cold/warm flanks of major oceanic fronts. This pattern is studied in the framework of nonlinear interaction between Ekman drift and geostrophic baroclinic fronts outcropping at the sea surface. Results are generalized to assess the dynamics of internal Ekman layer distributed along the thermocline and controlling the secondary circulation at the fronts.

  18. Secondary craters on Europa and implications for cratered surfaces.

    PubMed

    Bierhaus, Edward B; Chapman, Clark R; Merline, William J

    2005-10-20

    For several decades, most planetary researchers have regarded the impact crater populations on solid-surfaced planets and smaller bodies as predominantly reflecting the direct ('primary') impacts of asteroids and comets. Estimates of the relative and absolute ages of geological units on these objects have been based on this assumption. Here we present an analysis of the comparatively sparse crater population on Jupiter's icy moon Europa and suggest that this assumption is incorrect for small craters. We find that 'secondaries' (craters formed by material ejected from large primary impact craters) comprise about 95 per cent of the small craters (diameters less than 1 km) on Europa. We therefore conclude that large primary impacts into a solid surface (for example, ice or rock) produce far more secondaries than previously believed, implying that the small crater populations on the Moon, Mars and other large bodies must be dominated by secondaries. Moreover, our results indicate that there have been few small comets (less than 100 m diameter) passing through the jovian system in recent times, consistent with dynamical simulations.

  19. Drainage pits in cohesionless materials: implications for surface of Phobos.

    PubMed

    Horstman, K C; Melosh, H J

    1989-09-10

    Viking orbiter images show grooves and chains of pits crossing the surface of Phobos, many of which converge toward the large crater Stickney or its antipode. Although it has been proposed that the pits and grooves are chains of secondary craters, their morphology and geometric relations suggest that they are the surface traces of fractures in the underlying solid body of Phobos. Several models have been proposed to explain the pits, of which the most plausible are gas venting and drainage of regolith into open fractures. the latter mechanism is best supported by the image data and is the mechanism studied in this investigation. Drainage pits and fissures are modeled experimentally by using two rigid substrate plates placed edge to edge and covered by uniform thicknesses of dry fragmental debris (simulated regolith). Fracture extension is simulated by drawing the plates apart, allowing drainage of regolith into the newly created void. A typical drainage experiment begins with a shallow depression on the surface of the regolith, above the open fissure. Increased drainage causes local drainage pits to form; continued drainage causes the pits to coalesce, forming a cuspate groove. The resulting experimental patterns of pits and grooves have pronounced similarities to those observed on Phobos. Characteristics such as lack of raised rims, linearity of grooves and chains of pits, uniform spacing of pits, and progression from discrete pits to cuspate grooves are the same in the experiments and on Phobos. In contrast, gas-venting pits occur in irregular chains and have raised rims. These experiments thus indicate that the Phobos grooves and pits formed as drainage structures. The pit spacing in an experiment is measured at the time that the maximum number of pits forms, prior to groove development. The average pit spacing is compared to the regolith thickness for each material. Regression line fits indicate that the average spacing of drainage pits in unconsolidated

  20. Thermal anomaly on Mimas surface: Implications on its regolith structure

    NASA Astrophysics Data System (ADS)

    Ferrari, C.; Lucas, A.

    2015-10-01

    Thanks to the Cassini CIRS infrared spectrometer,Howett et al. [1] have discovered a large scale thermal anomaly on the surface of Saturn satellite Mimas. This anomaly translates into a dichotomy in thermal inertia between leading and trailing faces of this synchronous icy satellite: the leading face (region R2) exhibits a high thermal inertia,Γ =66 ± 23 J/m 2/K/s 1/2, compared to the trailing one(region R1), where Γ < 16 J/m2/K/s1/2. The pattern appears to be well correlated with a color anomaly (Schenk et al. [2]) in visible light, also observed on other Saturn moons. It maybe due to the alter ation of their leading face by a focused bombardment of highly energetic electrons.This is thought to increase the contact between regolith grains by gluing them, improving thus the thermal conductivity or decrea sing porosity.

  1. The global topography of Mars and implications for surface evolution

    NASA Technical Reports Server (NTRS)

    Smith, D. E.; Zuber, M. T.; Solomon, S. C.; Phillips, R. J.; Head, J. W.; Garvin, J. B.; Banerdt, W. B.; Muhleman, D. O.; Pettengill, G. H.; Neumann, G. A.; Lemoine, F. G.; Abshire, J. B.; Aharonson, O.; Brown, C. D.; Hauck, S. A.; Ivanov, A. B.; McGovern, P. J.; Zwally, H. J.; Duxbury, T. C.

    1999-01-01

    Elevations measured by the Mars Orbiter Laser Altimeter have yielded a high-accuracy global map of the topography of Mars. Dominant features include the low northern hemisphere, the Tharsis province, and the Hellas impact basin. The northern hemisphere depression is primarily a long-wavelength effect that has been shaped by an internal mechanism. The topography of Tharsis consists of two broad rises. Material excavated from Hellas contributes to the high elevation of the southern hemisphere and to the scarp along the hemispheric boundary. The present topography has three major drainage centers, with the northern lowlands being the largest. The two polar cap volumes yield an upper limit of the present surface water inventory of 3.2 to 4.7 million cubic kilometers.

  2. Aqueous oxidation reaction enabled layer-by-layer corrosion of semiconductor nanoplates into single-crystalline 2D nanocrystals with single layer accuracy and ionic surface capping.

    PubMed

    Ji, Muwei; Xu, Meng; Zhang, Jun; Liu, Jiajia; Zhang, Jiatao

    2016-02-25

    A controllable aqueous oxidation reaction enabled layer-by-layer corrosion has been proposed to prepare high-quality two-dimensional (2D) semiconductor nanocrystals with single layer accuracy and well-retained hexagonal shapes. The appropriate oxidizing agent, such as H2O2, Fe(NO3)3, and HNO3, could not only corrode the layered-crystalline-structured Bi2Te3 nanoplates layer-by-layer to be a single quintuple layer, but also replace the organic barriers to be ionic ligands on the surface synergistically. AFM analysis was used to confirm the layer-by-layer exfoliation from the side to the center. Together with precise XRD, LRTEM and HRTEM characterizations, the controllable oxidation reaction enabled aqueous layer-by-layer corrosion mechanism has been studied.

  3. Enhanced super-hydrophobic and switching behavior of ZnO nanostructured surfaces prepared by simple solution--immersion successive ionic layer adsorption and reaction process.

    PubMed

    Suresh Kumar, P; Sundaramurthy, J; Mangalaraj, D; Nataraj, D; Rajarathnam, D; Srinivasan, M P

    2011-11-01

    A simple and cost-effective successive ionic layer adsorption and reaction (SILAR) method was adopted to fabricate hydrophobic ZnO nanostructured surfaces on transparent indium-tin oxide (ITO), glass and polyethylene terephthalate (PET) substrates. ZnO films deposited on different substrates show hierarchical structures like spindle, flower and spherical shape with diameters ranging from 30 to 300 nm. The photo-induced switching behaviors of ZnO film surfaces between hydrophobic and hydrophilic states were examined by water contact angle and X-ray photoelectron spectroscopy (XPS) analysis. ZnO nanostructured films had contact angles of ~140° and 160°±2 on glass and PET substrates, respectively, exhibiting hydrophobic behavior without any surface modification or treatment. Upon exposure to ultraviolet (UV) illumination, the films showed hydrophilic behavior (contact angle: 15°±2), which upon low thermal stimuli revert back to its original hydrophobic nature. Such reversible and repeatable switching behaviors were observed upon cyclical exposure to ultraviolet radiation. These biomimetic ZnO surfaces exhibit good anti-reflective properties with lower reflectance of 9% for PET substrates. Thus, the present work is significant in terms of its potential application in switching devices, solar coatings and self-cleaning smart windows.

  4. Change of electrostatic potential of mean force between two curved surfaces due to different salt composition, ion valence and size under certain ionic strength

    NASA Astrophysics Data System (ADS)

    Zhou, Shiqi

    2016-02-01

    Change of an electrostatic potential of mean force (EPMF) between two cylindrical rod surfaces with salt composition, ion valence, and ion size at a constant ionic strength of 0.3 M is studied by a classical density functional theory (CDFT) in a primitive model electrolyte solution. Several novel observations are made: (i) strength of a so-called like charge attraction (LCA) reduces in an invariable manner with the salt solution changing from single 2:1 electrolyte to mixture of 2:1 and 1:1 type electrolytes of varying concentration ratios; the change is even over entire range of the composition variation under low surface charge strength, and tends to be insensitive to the composition variation in the presence of the divalent counter-ion, and more and more drastic at a critical point the divalent counter-ion disappears, respectively, as the surface charge strength becomes big enough. (ii) Both monovalent counter-ion and co-ion diameters have only a marginal effect on both the LCA strength and equilibrium distance, and the former "abnormally" affects less than the latter. (iii) Depending on the surface charge strength considered, the divalent counter-ion diameter influences the LCA strength in solution comprised of 2:1 type and 1:1 type electrolytes, monotonously or non-monotonously. All of these findings provide forceful support for a recently proposed hydrogen-bonding style mechanism explaining the LCA.

  5. Nanoparticles in ionic liquids: interactions and organization.

    PubMed

    He, Zhiqi; Alexandridis, Paschalis

    2015-07-28

    Ionic liquids (ILs), defined as low-melting organic salts, are a novel class of compounds with unique properties and a combinatorially great chemical diversity. Ionic liquids are utilized as synthesis and dispersion media for nanoparticles as well as for surface functionalization. Ionic liquid and nanoparticle hybrid systems are governed by a combined effect of several intermolecular interactions between their constituents. For each interaction, including van der Waals, electrostatic, structural, solvophobic, steric, and hydrogen bonding, the characterization and quantitative calculation methods together with factors affecting these interactions are reviewed here. Various self-organized structures based on nanoparticles in ionic liquids are generated as a result of a balance of these intermolecular interactions. These structures, including colloidal glasses and gels, lyotropic liquid crystals, nanoparticle-stabilized ionic liquid-containing emulsions, ionic liquid surface-functionalized nanoparticles, and nanoscale ionic materials, possess properties of both ionic liquids and nanoparticles, which render them useful as novel materials especially in electrochemical and catalysis applications. This review of the interactions within nanoparticle dispersions in ionic liquids and of the structure of nanoparticle and ionic liquid hybrids provides guidance on the rational design of novel ionic liquid-based materials, enabling applications in broad areas.

  6. Identifying the ionically bound cell wall and intracellular glycoside hydrolases in late growth stage Arabidopsis stems: implications for the genetic engineering of bioenergy crops

    PubMed Central

    Wei, Hui; Brunecky, Roman; Donohoe, Bryon S.; Ding, Shi-You; Ciesielski, Peter N.; Yang, Shihui; Tucker, Melvin P.; Himmel, Michael E.

    2015-01-01

    Identifying the cell wall-ionically bound glycoside hydrolases (GHs) in Arabidopsis stems is important for understanding the regulation of cell wall integrity. For cell wall proteomics studies, the preparation of clean cell wall fractions is a challenge since cell walls constitute an open compartment, which is more likely to contain a mixture of intracellular and extracellular proteins due to cell leakage at the late growth stage. Here, we utilize a CaCl2-extraction procedure to isolate non-structural proteins from Arabidopsis whole stems, followed by the in-solution and in-gel digestion methods coupled with Nano-LC-MS/MS, bioinformatics and literature analyses. This has led to the identification of 75 proteins identified using the in-solution method and 236 proteins identified by the in-gel method, among which about 10% of proteins predicted to be secreted. Together, eight cell wall proteins, namely AT1G75040, AT5G26000, AT3G57260, AT4G21650, AT3G52960, AT3G49120, AT5G49360, and AT3G14067, were identified by the in-solution method; among them, three were the GHs (AT5G26000, myrosinase 1, GH1; AT3G57260, β-1,3-glucanase 2, GH17; AT5G49360, bifunctional XYL 1/α-L-arabinofuranosidase, GH3). Moreover, four more GHs: AT4G30270 (xyloglucan endotransferase, GH16), AT1G68560 (bifunctional α-l-arabinofuranosidase/XYL, GH31), AT1G12240 (invertase, GH32) and AT2G28470 (β-galactosidase 8, GH35), were identified by the in-gel solution method only. Notably, more than half of above identified GHs are xylan- or hemicellulose-modifying enzymes, and will likely have an impact on cellulose accessibility, which is a critical factor for downstream enzymatic hydrolysis of plant tissues for biofuels production. The implications of these cell wall proteins identified at the late growth stage for the genetic engineering of bioenergy crops are discussed. PMID:26029221

  7. Identifying the ionically bound cell wall and intracellular glycoside hydrolases in late growth stage Arabidopsis stems: Implications for the genetic engineering of bioenergy crops

    DOE PAGES

    Wei, Hui; Brunecky, Roman; Donohoe, Bryon S.; ...

    2015-05-13

    Identifying the cell wall-ionically bound glycoside hydrolases (GHs) in Arabidopsis stems is important for understanding the regulation of cell wall integrity. For cell wall proteomics studies, the preparation of clean cell wall fractions is a challenge since cell walls constitute an open compartment, which is more likely to contain a mixture of intracellular and extracellular proteins due to cell leakage at the late growth stage. Here, for this study, we utilize a CaCl2-extraction procedure to isolate non-structural proteins from Arabidopsis whole stems, followed by the in-solution and in-gel digestion methods coupled with Nano-LC-MS/MS, bioinformatics and literature analyses. This has ledmore » to the identification of 75 proteins identified using the in-solution method and 236 proteins identified by the in-gel method, among which about 10% of proteins predicted to be secreted. Together, eight cell wall proteins, namely AT1G75040, AT5G26000, AT3G57260, AT4G21650, AT3G52960, AT3G49120, AT5G49360, and AT3G14067, were identified by the in-solution method; among them, three were the GHs (AT5G26000, myrosinase 1, GH1; AT3G57260, β-1,3-glucanase 2, GH17; AT5G49360, bifunctional XYL 1/α-L-arabinofuranosidase, GH3). Moreover, four more GHs: AT4G30270 (xyloglucan endotransferase, GH16), AT1G68560 (bifunctional α-l-arabinofuranosidase/XYL, GH31), AT1G12240 (invertase, GH32) and AT2G28470 (β-galactosidase 8, GH35), were identified by the in-gel solution method only. Notably, more than half of above identified GHs are xylan- or hemicellulose-modifying enzymes, and will likely have an impact on cellulose accessibility, which is a critical factor for downstream enzymatic hydrolysis of plant tissues for biofuels production. Finally, the implications of these cell wall proteins identified at the late growth stage for the genetic engineering of bioenergy crops are discussed.« less

  8. Identifying the ionically bound cell wall and intracellular glycoside hydrolases in late growth stage Arabidopsis stems: Implications for the genetic engineering of bioenergy crops

    SciTech Connect

    Wei, Hui; Brunecky, Roman; Donohoe, Bryon S.; Ding, Shi -You; Ciesielski, Peter N.; Yang, Shihui; Tucker, Melvin P.; Himmel, Michael E.

    2015-05-13

    Identifying the cell wall-ionically bound glycoside hydrolases (GHs) in Arabidopsis stems is important for understanding the regulation of cell wall integrity. For cell wall proteomics studies, the preparation of clean cell wall fractions is a challenge since cell walls constitute an open compartment, which is more likely to contain a mixture of intracellular and extracellular proteins due to cell leakage at the late growth stage. Here, for this study, we utilize a CaCl2-extraction procedure to isolate non-structural proteins from Arabidopsis whole stems, followed by the in-solution and in-gel digestion methods coupled with Nano-LC-MS/MS, bioinformatics and literature analyses. This has led to the identification of 75 proteins identified using the in-solution method and 236 proteins identified by the in-gel method, among which about 10% of proteins predicted to be secreted. Together, eight cell wall proteins, namely AT1G75040, AT5G26000, AT3G57260, AT4G21650, AT3G52960, AT3G49120, AT5G49360, and AT3G14067, were identified by the in-solution method; among them, three were the GHs (AT5G26000, myrosinase 1, GH1; AT3G57260, β-1,3-glucanase 2, GH17; AT5G49360, bifunctional XYL 1/α-L-arabinofuranosidase, GH3). Moreover, four more GHs: AT4G30270 (xyloglucan endotransferase, GH16), AT1G68560 (bifunctional α-l-arabinofuranosidase/XYL, GH31), AT1G12240 (invertase, GH32) and AT2G28470 (β-galactosidase 8, GH35), were identified by the in-gel solution method only. Notably, more than half of above identified GHs are xylan- or hemicellulose-modifying enzymes, and will likely have an impact on cellulose accessibility, which is a critical factor for downstream enzymatic hydrolysis of plant tissues for biofuels production. Finally, the implications of these cell wall proteins identified at the late growth stage for the genetic engineering of bioenergy crops are discussed.

  9. Ionic Conductivity of Mesostructured Yttria-Stabilized Zirconia Thin Films with Cubic Pore Symmetry—On the Influence of Water on the Surface Oxygen Ion Transport.

    PubMed

    Elm, Matthias T; Hofmann, Jonas D; Suchomski, Christian; Janek, Jürgen; Brezesinski, Torsten

    2015-06-10

    Thermally stable, ordered mesoporous thin films of 8 mol % yttria-stabilized zirconia (YSZ) were prepared by solution-phase coassembly of chloride salt precursors with an amphiphilic diblock copolymer using an evaporation-induced self-assembly process. The resulting material is of high quality and exhibits a well-defined three-dimensional network of pores averaging 24 nm in diameter after annealing at 600 °C for several hours. The wall structure is polycrystalline, with grains in the size range of 7 to 10 nm. Using impedance spectroscopy, the total electrical conductivity was measured between 200 and 500 °C under ambient atmosphere as well as in dry atmosphere for oxygen partial pressures ranging from 1 to 10(-4) bar. Similar to bulk YSZ, a constant ionic conductivity is observed over the whole oxygen partial pressure range investigated. In dry atmosphere, the sol-gel derived films have a much higher conductivity, with different activation energies for low and high temperatures. Overall, the results indicate a strong influence of the surface on the transport properties in cubic fluorite-type YSZ with high surface-to-volume ratio. A qualitative defect model which includes surface effects (annihilation of oxygen vacancies as a result of water adsorption) is proposed to explain the behavior and sensitivity of the conductivity to variations in the surrounding atmosphere.

  10. Fluorescence resonance energy transfer in microemulsions composed of tripled-chain surface active ionic liquids, RTILs, and biological solvent: an excitation wavelength dependence study.

    PubMed

    Banerjee, Chiranjib; Kundu, Niloy; Ghosh, Surajit; Mandal, Sarthak; Kuchlyan, Jagannath; Sarkar, Nilmoni

    2013-08-15

    In this article we have reported the fluorescence resonance energy transfer (FRET) study in our earlier characterized surface active ionic liquids (SAILs)-containing microemulsion, i.e., N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([P13][Tf2N])/[CTA][AOT]/isopropyl myristate ([IPM]) and N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide ([N3111][Tf2N])/[CTA][AOT]/[IPM] microemulsions (Banerjee, C.; Mandal, S.; Ghosh, S.; Kuchlyan, J.; Kundu, N.; Sarkar, N. J. Phys. Chem. B 2013, 117, 3927-3934). The occurrence of effective FRET from the donor, coumarin-153 (C-153) to the acceptor rhodamine 6G (R6G) is evident from the decrease in the steady state fluorescence intensity of the donor with addition of acceptor and subsequent increase in the fluorescence intensity of the acceptor in the presence of donor. The excitation wavelength dependent FRET from C-153 to R6G has also been performed to assess the dynamic heterogeneity of these confined systems. In time-resolved experiments, the significant rise time of the acceptor in the presence of the donor further confirms the occurrence of FRET. The multiple donor-acceptor (D-A) distances, for various microemulsions, obtained from the rise times of the acceptor emission in the presence of a donor can be rationalized from the varying distribution of the donor, C-153, in the different regions of the microemulsion. Time-resolved measurement reveals that with increasing excitation wavelength from 408 to 440 nm, the contribution of the faster rise component of FRET increases significantly due to the close proximity of the C-153 and R6G in the polar region of the microemulsion where occurrence of FRET is very high. Moreover, we have also studied the FRET with variation of R (R = [room temperature ionic liquids (RTILs)]/[surfactant]) and shown that the effect of excitation wavelength on FRET is similar irrespective of R values.

  11. Surface structure of imidazolium-based ionic liquids: Quantitative comparison between simulations and high-resolution RBS measurements

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    Elemental depth profiles of 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([CnMIM][TFSI], n = 4, 6, 8) are measured using high-resolution Rutherford backscattering spectroscopy (HRBS). The profiles are compared with the results of molecular dynamics (MD) simulations. Both MD simulations and HRBS measurements show that the depth profiles deviate from the uniform stoichiometric composition in the surface region, showing preferential orientations of ions at the surface. The MD simulations qualitatively reproduce the observed HRBS profiles but the agreement is not satisfactory. The observed discrepancy is ascribed to the capillary waves. By taking account of the surface roughness induced by the capillary waves, the agreement becomes almost perfect.

  12. Analysis of passive surface-wave noise in surface microseismic data and its implications

    USGS Publications Warehouse

    Forghani-Arani, F.; Willis, M.; Haines, S.; Batzle, M.; Davidson, M.

    2011-01-01

    Tight gas reservoirs are projected to be a major portion of future energy resources. Because of their low permeability, hydraulic fracturing of these reservoirs is required to improve the permeability and reservoir productivity. Passive seismic monitoring is one of the few tools that can be used to characterize the changes in the reservoir due to hydraulic fracturing. Although the majority of the studies monitoring hydraulic fracturing exploit down hole microseismic data, surface microseismic monitoring is receiving increased attention because it is potentially much less expensive to acquire. Due to a broader receiver aperture and spatial coverage, surface microseismic data may be more advantageous than down hole microseismic data. The effectiveness of this monitoring technique, however, is strongly dependent on the signal-to-noise ratio of the data. Cultural and ambient noise can mask parts of the waveform that carry information about the subsurface, thereby decreasing the effectiveness of surface microseismic analysis in identifying and locating the microseismic events. Hence, time and spatially varying suppression of the surface-wave noise ground roll is a critical step in surface microseismic monitoring. Here, we study a surface passive dataset that was acquired over a Barnett Shale Formation reservoir during two weeks of hydraulic fracturing, in order to characterize and suppress the surface noise in this data. We apply techniques to identify the characteristics of the passive ground roll. Exploiting those characteristics, we can apply effective noise suppression techniques to the passive data. ?? 2011 Society of Exploration Geophysicists.

  13. Ionic electroactive hybrid transducers

    NASA Astrophysics Data System (ADS)

    Akle, Barbar J.; Bennett, Matthew D.; Leo, Donald J.

    2005-05-01

    Ionic electroactive actuators have received considerable attention in the past ten years. Ionic electroactive polymers, sometimes referred to as artificial muscles, have the ability to generate large bending strain and moderate stress at low applied voltages. Typical types of ionic electroactive polymer transducers include ionic polymers, conducting polymers, and carbon nanotubes. Preliminary research combining multiple types of materials proved to enhance certain transduction properties such as speed of response, maximum strain, or quasi-static actuation. Recently it was demonstrated that ionomer-ionic liquid transducers can operate in air for long periods of time (>250,000 cycles) and showed potential to reduce or eliminate the back-relaxation issue associated with ionomeric polymers. In addition, ionic liquids have higher electrical stability window than those operated with water as the solvent thereby increasing the maximum strain that the actuator can produce. In this work, a new technique developed for plating metal particulates on the surface of ionomeric materials is applied to the development of hybrid transducers that incorporate carbon nanotubes and conducting polymers as electrode materials. The new plating technique, named the direct assembly process, consists of mixing a conducting powder with an ionomer solution. This technique has demonstrated improved response time and strain output as compared to previous methods. Furthermore, the direct assembly process is less costly to implement than traditional impregnation-reduction methods due to less dependence on reducing agents, it requires less time, and is easier to implement than other processes. Electrodes applied using this new technique of mixing RuO2 (surface area 45~65m2/g) particles and Nafion dispersion provided 5x the displacement and 10x the force compared to a transducer made with conventional methods. Furthermore, the study illustrated that the response speed of the transducer is optimized

  14. Frost grain size metamorphism - Implications for remote sensing of planetary surfaces

    NASA Technical Reports Server (NTRS)

    Clark, R. N.; Fanale, F. P.; Zent, A. P.

    1983-01-01

    The effective grain size of a material on a planetary surface affects the strength of absorption features observed in the reflectance of a particulate surface. In the case of a planetary surface containing volatile ices, the absorption characteristics can change in connection with processes leading to a change in the grain size of the material. The present investigation is concerned with an evaluation regarding the occurrence of such processes and the implications for remote sensing applications. It is found that quantitative modeling of the kinetics of grain growth and destruction by thermal and nonthermal processes can provide a means to reconcile apparent optical paths in the volatile portions of planetary surfaces with the physical history of those surfaces. Attention is also given to conditions in the case of the Pluto/Triton system, Uranus and Saturnian satellites, and the Galilean system.

  15. SORPTION OF CU AND ZN TO KAOLINITE AND IRON OXIDE: EFFECTS OF HUMIC ACID AND IONIC STRENGTH AND IMPLICATIONS FOR STORMWATER RUNOFF

    EPA Science Inventory

    Heavy metals are common pollutants in wet weather flows and urban waterways. Changes in ionic strength, whether from mixing with saline waters, road salt, or from the large osmotic adjustment needed for the Microtox toxicity assay, affect the aqueous chemistry of stormwater runof...

  16. Facile Fabrication of a Silver Nanoparticle Immersed, Surface-Enhanced Raman Scattering Imposed Paper Platform through Successive Ionic Layer Absorption and Reaction for On-Site Bioassays.

    PubMed

    Kim, Wansun; Kim, Yeon-Hee; Park, Hun-Kuk; Choi, Samjin

    2015-12-23

    We introduce a novel, facile, rapid, low-cost, highly reproducible, and power-free synthesizable fabrication method of paper-based silver nanoparticle (AgNP) immersed surface-enhanced Raman scattering (SERS) platform, known as the successive ionic layer absorption and reaction (SILAR) method. The rough and porous properties of the paper led to direct synthesis of AgNPs on the surface as well as in the paper due to capillary effects, resulting in improved plasmon coupling with interparticles and interlayers. The proposed SERS platform showed an enhancement factor of 1.1 × 10(9), high reproducibility (relative standard deviation of 4.2%), and 10(-12) M rhodamine B highly sensitive detection limit by optimizing the SILAR conditions including the concentration of the reactive solution (20/20 mM/mM AgNO3/NaBH4) and the number of SILAR cycles (six). The applicability of the SERS platform was evaluated using two samples including human cervical fluid for clinical diagnosis of human papillomavirus (HPV) infection, associated with cervical cancer, and a malachite green (MG) solution for fungicide and parasiticide in aquaculture, associated with human carcinogenesis. The AgNP-immersed SERS-functionalized platform using the SILAR technique allowed for high chemical structure sensitivity without additional tagging or chemical modification, making it a good alternative for early clinical diagnosis of HPV infection and detection of MG-activated human carcinogenesis.

  17. Controlling successive ionic layer absorption and reaction cycles to optimize silver nanoparticle-induced localized surface plasmon resonance effects on the paper strip

    NASA Astrophysics Data System (ADS)

    Lee, Jae-Chul; Kim, Wansun; Park, Hun-Kuk; Choi, Samjin

    2017-03-01

    This study investigates why a silver nanoparticle (SNP)-induced surface-enhanced Raman scattering (SERS) paper chip fabricated at low successive ionic layer absorption and reaction (SILAR) cycles leads to a high SERS enhancement factor (7 × 108) with an inferior nanostructure and without generating a hot spot effect. The multi-layered structure of SNPs on cellulose fibers, verified by magnified scanning electron microscopy (SEM) and analyzed by a computational simulation method, was hypothesized as the reason. The pattern of simulated local electric field distribution with respect to the number of SILAR cycles showed good agreement with the experimental Raman intensity, regardless of the wavelength of the excitation laser sources. The simulated enhancement factor at the 785-nm excitation laser source (2.8 × 109) was 2.5 times greater than the experimental enhancement factor (1.1 × 109). A 532-nm excitation laser source exhibited the highest maximum local electric field intensity (1.9 × 1011), particularly at the interparticle gap called a hot spot. The short wavelength led to a strong electric field intensity caused by strong electromagnetic coupling arising from the SNP-induced local surface plasmon resonance (LSPR) effects through high excitation energy. These findings suggest that our paper-based SILAR-fabricated SNP-induced LSPR model is valid for understanding SNP-induced LSPR effects.

  18. Controlling successive ionic layer absorption and reaction cycles to optimize silver nanoparticle-induced localized surface plasmon resonance effects on the paper strip.

    PubMed

    Lee, Jae-Chul; Kim, Wansun; Park, Hun-Kuk; Choi, Samjin

    2017-03-05

    This study investigates why a silver nanoparticle (SNP)-induced surface-enhanced Raman scattering (SERS) paper chip fabricated at low successive ionic layer absorption and reaction (SILAR) cycles leads to a high SERS enhancement factor (7×10(8)) with an inferior nanostructure and without generating a hot spot effect. The multi-layered structure of SNPs on cellulose fibers, verified by magnified scanning electron microscopy (SEM) and analyzed by a computational simulation method, was hypothesized as the reason. The pattern of simulated local electric field distribution with respect to the number of SILAR cycles showed good agreement with the experimental Raman intensity, regardless of the wavelength of the excitation laser sources. The simulated enhancement factor at the 785-nm excitation laser source (2.8×10(9)) was 2.5 times greater than the experimental enhancement factor (1.1×10(9)). A 532-nm excitation laser source exhibited the highest maximum local electric field intensity (1.9×10(11)), particularly at the interparticle gap called a hot spot. The short wavelength led to a strong electric field intensity caused by strong electromagnetic coupling arising from the SNP-induced local surface plasmon resonance (LSPR) effects through high excitation energy. These findings suggest that our paper-based SILAR-fabricated SNP-induced LSPR model is valid for understanding SNP-induced LSPR effects.

  19. Effects of ionic strength on bacteriophage MS2 behavior and their implications for the assessment of virus retention by ultrafiltration membranes.

    PubMed

    Furiga, Aurelie; Pierre, Gwenaelle; Glories, Marie; Aimar, Pierre; Roques, Christine; Causserand, Christel; Berge, Mathieu

    2011-01-01

    Bacteriophage MS2 is widely used as a surrogate to estimate pathogenic virus elimination by membrane filtration processes used in water treatment. Given that this water technology may be conducted with different types of waters, we focused on investigating the effects of ionic strength on MS2 behavior. For this, MS2 was analyzed while suspended in solutions of various ionic strengths, first in a batch experiment and second during membrane ultrafiltration, and quantified using (i) quantitative reverse transcriptase PCR (qRT-PCR), which detects the total number of viral genomes, (ii) qRT-PCR without the RNA extraction step, which reflects only particles with a broken capsid (free RNA), and (iii) the PFU method, which detects only infectious viruses. At the beginning of the batch experiments using solutions containing small amounts of salts, losses of MS2 infectivity (90%) and broken particles (20%) were observed; these proportions did not change during filtration. In contrast, in high-ionic-strength solutions, bacteriophage kept its biological activity under static conditions, but it quickly lost its infectivity during the filtration process. Increasing the ionic strength decreased both the inactivation and the capsid breakup in the feed suspension and increased the loss of infectivity in the filtration retentate, while the numbers of MS2 genomes were identical in both experiments. In conclusion, the effects of ionic strength on MS2 behavior may significantly distort the results of membrane filtration processes, and therefore, the combination of classical and molecular methods used here is useful for an effective validation of the retention efficiency of ultrafiltration membranes.

  20. Role of specific amine surface configurations for grafted surfaces: implications for nanostructured CO2 adsorbents.

    PubMed

    Shimizu, Steven; Song, Changsik; Strano, Michael

    2011-03-15

    Amine-grafted porous materials that capture CO2 from emission streams have been considered to be potential alternatives to the more energy-intensive liquid amine systems currently employed. An underappreciated fact in the uptake mechanism of these materials is that under dry, anhydrous conditions each CO2 molecule must react with two adjacent amine groups to adsorb onto the surface, which makes the configuration of amine groups on the surface critically important. Using this chemical mechanism, we developed a semiempirical adsorption isotherm equation that allows straightforward computation of the adsorption isotherm from an arbitrary surface configuration of grafted amines for honeycomb, square, and triangular lattices. The model makes use of the fact that the distribution of amines with respect to the number of nearest neighbors, referred to as the z-histogram, along with the amine loading and equilibrium constant, uniquely determine the adsorption characteristics to a very good approximation. This model was used to predict the range of uptakes possible just through surface configuration, and it was used to fit experimental data in the literature to give a meaningful equilibrium constant and show how efficiently amines were utilized. We also demonstrate how the model can be utilized to design more efficient nanostructured adsorbents and polymer-based adsorbents. Recommendations for exploiting the role of surface configuration include the use of linear instead of branched polyamines, higher amine grafting densities, the use of flexible, less bulky, long, and rotationally free amine groups, and increased silanol densities.

  1. Charging Properties of Cassiterite (alpha-SnO2) Surfaces in NaCl and RbCl Ionic Media.

    SciTech Connect

    Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, Lukas; Wesolowski, David J

    2009-09-01

    The acid-base properties of cassiterite ({alpha}-SnO{sub 2}) surfaces at 10-50 C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH range of 4.0-4.5 under all conditions, and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical molecular dynamics (MD) simulations, was analyzed in detail, and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated that the terminal SnOH{sub 2} group is more acidic than the bridging Sn{sub 2}OH group, with protonation constants (log K{sub H}) of 3.60 and 5.13 at 25 C, respectively. This is contrary to the situation on the isostructural {alpha}-TiO{sub 2} (rutile), apparently because of the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na{sup +} and Rb{sup +}, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na{sup +} between the different complexes shows a considerable dependence on the surface charge density (pH), whereas the distribution of adsorbed Rb{sup +} is almost independent of pH. A surface complexation model (SCM) capable of accurately describing both the measured surface charge and the MD-predicted speciation of adsorbed Na{sup +}/Rb{sup +} was formulated. According to the SCM, the deprotonated terminal group (SnOH{sup -0.40}) and the protonated bridging group (Sn{sub 2}OH{sup +0.36}) dominate the surface speciation over the entire pH range of this study (2.7-10). The

  2. Charging Properties of Cassiterite (alpha-SnO2) surfaces in NaCl and RbCl Ionic Media.

    SciTech Connect

    Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, Lukas; Wesolowski, David J

    2009-09-01

    The acid-base properties of cassiterite (alpha-SnO2) surfaces at 10-50 degrees C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH range of 4.0-4.5 under all conditions, and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical molecular dynamics (MD) simulations, was analyzed in detail, and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated that the terminal SnOH2 group is more acidic than the bridging Sn2OH group, with protonation constants (log KH) of 3.60 and 5.13 at 25 degrees C, respectively. This is contrary to the situation on the isostructural alpha-TiO2 (rutile), apparently because of the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na+ and Rb+, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na+ between the different complexes shows a considerable dependence on the surface charge density (pH), whereas the distribution of adsorbed Rb+ is almost independent of pH. A surface complexation model (SCM) capable of accurately describing both the measured surface charge and the MD-predicted speciation of adsorbed Na+/Rb+ was formulated. According to the SCM, the deprotonated terminal group (SnOH(-0.40)) and the protonated bridging group (Sn2OH+0.36) dominate the surface speciation over the entire pH range of this study (2.7-10). The complexation of medium cations increases significantly with increasing

  3. Graphene and graphene oxide can "lubricate" ionic liquids based on specific surface interactions leading to improved low-temperature hypergolic performance.

    PubMed

    McCrary, Parker D; Beasley, Preston A; Alaniz, Spencer A; Griggs, Chris S; Frazier, Rachel M; Rogers, Robin D

    2012-09-24

    Space-qualified lubricants: Graphene and graphene oxide (r-GO) can strongly improve the low-temperature performance of hypergolic ionic liquids by reduction of viscosity. Key to success is to match the graphene type to the specific ionic-liquid functionality.

  4. Model for oxygen recombination on silicon-dioxide surfaces. II - Implications toward reentry heating

    NASA Technical Reports Server (NTRS)

    Jumper, E. J.; Seward, W. A.

    1992-01-01

    This paper briefly reviews the model for recombination of oxygen on a silicon-dioxide surface presented in detail in a previous paper. New data supporting the model is also presented. The ramifications of the model toward the production of excited molecular oxygen is examined as it pertains to surface heating. A reentry simulation is given and compared to STS-2 reentry data, and conclusions are drawn as to the implications of the recombination model toward reentry heating. A possible buffering of the heating above a critical temperature associated with the physics of the model is also discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

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

    PubMed

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

    2016-11-14

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

  7. Charged plate in asymmetric electrolytes: One-loop renormalization of surface charge density and Debye length due to ionic correlations

    NASA Astrophysics Data System (ADS)

    Ding, Mingnan; Lu, Bing-Sui; Xing, Xiangjun

    2016-10-01

    Self-consistent field theory (SCFT) is used to study the mean potential near a charged plate inside a m :-n electrolyte. A perturbation series is developed in terms of g =4 π κ b , where b a n d 1 /κ are Bjerrum length and bare Debye length, respectively. To the zeroth order, we obtain the nonlinear Poisson-Boltzmann theory. For asymmetric electrolytes (m ≠n ), the first order (one-loop) correction to mean potential contains a secular term, which indicates the breakdown of the regular perturbation method. Using a renormalizaton group transformation, we remove the secular term and obtain a globally well-behaved one-loop approximation with a renormalized Debye length and a renormalized surface charge density. Furthermore, we find that if the counterions are multivalent, the surface charge density is renormalized substantially downwards and may undergo a change of sign, if the bare surface charge density is sufficiently large. Our results agrees with large MC simulation even when the density of electrolytes is relatively high.

  8. Polar surface energies of iono-covalent materials: implications of a charge-transfer model tested on Li2FeSiO4 surfaces.

    PubMed

    Hörmann, Nicolas G; Groß, Axel

    2014-07-21

    The ionic compounds that are used as electrode materials in Li-based rechargeable batteries can exhibit polar surfaces that in general have high surface energies. We derive an analytical estimate for the surface energy of such polar surfaces assuming charge redistribution as a polarity compensating mechanism. The polar contribution to the converged surface energy is found to be proportional to the bandgap multiplied by the surface charge necessary to compensate for the depolarization field, and some higher order correction terms that depend on the specific surface. Other features, such as convergence behavior, coincide with published results. General conclusions are drawn on how to perform polar surface energy calculations in a slab configuration and upper boundaries of "purely" polar surface energies are estimated. Furthermore, we compare these findings with results obtained in a density functional theory study of Li(2)FeSiO(4) surfaces. We show that typical polar features are observed and provide a decomposition of surface energies into polar and local bond-cutting contributions for 29 different surfaces. We show that the model is able to explain subtle differences of GGA and GGA+U surface energy calculations.

  9. Evaluation of the hemodynamic effects of intravenous administration of ionic and nonionic contrast materials: implications for deriving physiologic measurements from computed tomography and digital cardiovascular imaging

    SciTech Connect

    Higgins, C.B.; Berber, K.H.; Mattrey, R.F.; Slutsky, R.A.

    1982-03-01

    The effects of intravenous injection of an ionic contrast material (Renografin-76 (meglumine sodium diatrizoate)) on left ventricular pressure, internal diameter, and wall thickness, and on coronary and femoral hemodynamics were compared with those of a hydrolytically stable nonionic contrast material (iohexol). Renografin-76 caused drastic biphasic changes in left ventricular pressure and dp/dt (rate of change of left ventricular pressure), and moderate changes in end systolic dimension. Iohexol caused little or no change in left ventricular pressure and dimensions. In addition, Renografin-76 caused marked arterial hypotension and large increases in coronary and femoral blood lows, while iohexol caused no significant change in arterial pressure and coronary blood flow, and a mild increase in femoral blood flow. Based on these findings, it is concluded that iohexol is preferable to standard ionic contrast material for deriving basal physiologic information from computed tomographic and digital vascular studies.

  10. Chemical interactions between the present-day Martian atmosphere and surface minerals: Implications for sample return

    NASA Technical Reports Server (NTRS)

    Prinn, Ronald; Fegley, Bruce

    1988-01-01

    Thermochemical and photochemical reactions between surface minerals and present-day atmospheric constituents are predicted to produce microscopic effects on the surface of mineral grains. Relevant reactions hypothesized in the literature include conversions of silicates and volcanic glasses to clay minerals, conversion of ferrous to ferric compounds, and formation of carbonates, nitrates, and sulfates. These types of surface-atmosphere weathering of minerals, biological potential of the surface environment, and atmospheric stability in both present and past Martian epochs. It is emphasized that the product of these reactions will be observable and interpretable on the microscopic surface layers of Martian surface rocks using modern techniques with obvious implications for sample return from Mars. Macroscopic products of chemical weathering reactions in past Martian epochs are also expected in Martian surface materials. These products are expected not only as a result of reactions similar to those proceeding today but also due to aqueous reactions in past epochs in which liquid water was putatively present. It may prove very difficult or impossible, however, to determine definitively from the relic macroscopic product alone either the exact weathering process which led to its formation of the identity of its weathering parent mineral. The enormous advantages of studying the Martian chemical weathering by investigating the microscopic products of present-day chemical reactions on sample surfaces are very apparent.

  11. Examination of 1-methylimidazole series ionic liquids in the extraction of flavonoids from Chamaecyparis obtuse leaves using a response surface methodology.

    PubMed

    Tang, Baokun; Lee, Yu Jin; Lee, Yu Ri; Row, Kyung Ho

    2013-08-15

    Ionic liquids (ILs) are a new type of reagent that has accelerated research in extraction technology. On the other hand, few studies have systematically applied 1-methylimidazole ([MIM]) series ILs to the extraction of bioactive compounds from plants. In this study, [MIM] series ILs were used to extract four bioactive flavonoids, such as dihydrokaempferol, quercitrin, amentoflavone and myricetin, from Chamaecyparis obtuse (CO) leaves. First, a screen of the extraction method and solvent revealed the [MIM] series ILs to be suitable as additives in methanol in Soxhlet extraction. Second, an examination of a range of cations and anions of [MIM] series ILs for extraction revealed 1-decyl-3-methylimidazolium bromide ([DMIM][Br]) to be the best selection as an additive in methanol for the Soxhlet extraction of flavonoids from (CO) leaves. Finally, some factors of extraction, such as temperature, time and amount of samples, were examined systematically using a response surface methodology (RSM). Based on the above optimization, 2.41, 3.47, 0.76 and 3.15mg/g of dihydrokaempferol, quercitrin, amentoflavone and myricetin, respectively, were extracted from 15g of CO leaves by 2.5mgmL(-1) of [DMIM][Br] as additives in 200mL of methanol in Soxhlet extraction at 200°C for 8h. This study highlights the potential of [MIM] series ILs as promising reagents for the extraction of bioactive compounds from plants.

  12. Effect of microwave radiation on surface charge, surface sites and ionic state of iron, and the activity of crocidolite asbestos fibres

    NASA Astrophysics Data System (ADS)

    Gulumian, M.; Pollak, H.

    1998-12-01

    Surface charge, surface sites, and the content of ferrous ions of crocidolite asbestos fibres are some of the properties which are considered to play a role in determining their activity in biological systems. Any treatment which changes these properties may therefore change their activity and subsequently increase or decrease their toxicity in biological surroundings. Surfaces of crocidolite fibres are shown to be negatively charged. In the present study, microwave radiation at 300°C was able to increase the number of positive charges within the bulk of the crocidolite fibres. In the presence of atmospheric oxygen, this increase could simultaneously reduce the hydroxyl groups on the surface of the fibres. The increase in positive charge was monitored by: (i) Mössbauer spectroscopy, where a change in the oxidation state of iron from ferrous to ferric was observed, (ii) visual microscopic observations of the irradiated fibres where there was an increase in their aggregation, and (iii) the difficulty to suspend these radiated fibres in solution. A decrease in the number of the surface hydroxyl groups on the other hand, was monitored by infrared spectroscopy. The reduction in the activity of the radiated crocidolite fibres was investigated by studying their ability to peroxidize lipids. Results have shown that changes in their surface charge, surface site and a reduction of the content of ferrous ions produce a concomitant decrease in their ability to initiate lipid peroxidation.

  13. Transition of cellulose crystalline structure and surface morphology of biomass as a function of ionic liquid pretreatment and its relation to enzymatic hydrolysis.

    PubMed

    Cheng, Gang; Varanasi, Patanjali; Li, Chenlin; Liu, Hanbin; Melnichenko, Yuri B; Simmons, Blake A; Kent, Michael S; Singh, Seema

    2011-04-11

    Cellulose is inherently resistant to breakdown, and the native crystalline structure (cellulose I) of cellulose is considered to be one of the major factors limiting its potential in terms of cost-competitive lignocellulosic biofuel production. Here we report the impact of ionic liquid pretreatment on the cellulose crystalline structure in different feedstocks, including microcrystalline cellulose (Avicel), switchgrass (Panicum virgatum), pine ( Pinus radiata ), and eucalyptus ( Eucalyptus globulus ), and its influence on cellulose hydrolysis kinetics of the resultant biomass. These feedstocks were pretreated using 1-ethyl-3-methyl imidazolium acetate ([C2mim][OAc]) at 120 and 160 °C for 1, 3, 6, and 12 h. The influence of the pretreatment conditions on the cellulose crystalline structure was analyzed by X-ray diffraction (XRD). On a larger length scale, the impact of ionic liquid pretreatment on the surface roughness of the biomass was determined by small-angle neutron scattering (SANS). Pretreatment resulted in a loss of native cellulose crystalline structure. However, the transformation processes were distinctly different for Avicel and for the biomass samples. For Avicel, a transformation to cellulose II occurred for all processing conditions. For the biomass samples, the data suggest that pretreatment for most conditions resulted in an expanded cellulose I lattice. For switchgrass, first evidence of cellulose II only occurred after 12 h of pretreatment at 120 °C. For eucalyptus, first evidence of cellulose II required more intense pretreatment (3 h at 160 °C). For pine, no clear evidence of cellulose II content was detected for the most intense pretreatment conditions of this study (12 h at 160 °C). Interestingly, the rate of enzymatic hydrolysis of Avicel was slightly lower for pretreatment at 160 °C compared with pretreatment at 120 °C. For the biomass samples, the hydrolysis rate was much greater for pretreatment at 160 °C compared with pretreatment

  14. Identification of ionic chloroacetanilide-herbicide metabolites in surface water and groundwater by HPLC/MS using negative ion spray

    USGS Publications Warehouse

    Ferrer, I.; Thurman, E.M.; Barcelo, D.

    1997-01-01

    Solid-phase extraction (SPE) was combined with high-performance liquid chromatography/high-flow pneumatically assisted electrospray mass spectrometry (HPLC/ESP/MS) for the trace analysis of oxanilic and sulfonic acids of acetochlor, alachlor, and metolachlor. The isolation procedure separated the chloroacetanilide metabolites from the parent herbicides during the elution from C18 cartridges using ethyl acetate for parent compounds, followed by methanol for the anionic metabolites. The metabolites were separated chromatographically using reversed-phase HPLC and analyzed by negative-ion MS using electrospray ionization in selected ion mode. Quantitation limits were 0.01 ??g/L for both the oxanilic and sulfonic acids based on a 100-mL water sample. This combination of methods represents an important advance in environmental analysis of chloroacetanilide-herbicide metabolites in surface water and groundwater for two reasons. First, anionic chloroacetanilide metabolites are a major class of degradation products that are readily leached to groundwater in agricultural areas. Second, anionic metabolites, which are not able to be analyzed by conventional methods such as liquid extraction and gas chromatography/mass spectrometry, are effectively analyzed by SPE and high-flow pneumatically assisted electrospray mass spectrometry. This paper reports the first HPLC/MS identification of these metabolites in surface water and groundwater.

  15. Correlations between VIMS and RADAR data over the surface of Titan: Implications for Titan's surface properties

    NASA Astrophysics Data System (ADS)

    Tosi, F.; Orosei, R.; Seu, R.; Coradini, A.; Lunine, J. I.; Filacchione, G.; Capaccioni, F.; Cerroni, P.; Flamini, E.; Brown, R. H.; Cruikshank, D. P.; Lopes, R. M.

    2010-12-01

    We present new results combining the VIMS and RADAR medium resolution data on Titan’s surface. In RADAR data we consider two geophysical quantities: the normalized backscatter cross-section obtained from the scatterometer measurement, corrected for the incidence angle, and the calibrated antenna temperature determined from the radiometer measurement, as found in publicly available data products. In VIMS data, combining spatial and spectral information, we have selected some atmospheric windows in the spectral range between 2 and 5 μm, providing the best optical depth to measure surface reflectance. The two RADAR parameters are combined with VIMS data, with estimated errors, to produce an aggregate data set, that we process using multivariate classification methods to identify homogeneous taxonomic units in the multivariate space of the samples. Such units in fact reveal compositional trends in the surface, that are likely related to different abundances of simple ices and/or hydrocarbons. Our analysis relies on the G-mode method, which has been successfully used in the past for the classification of such diverse data sets as lunar rock samples, asteroids and planetary surfaces. Due to the large number of data of Titan, the classification work proceeds in several steps. In a previous work (Tosi et al., 2010), we analyzed the data acquired in Titan flybys: T3, T4, T8, T13 and T16, covering mostly the major bright and dark features seen around the equator, combined with VIMS infrared data, in order to validate the classification method. Now we focus on flybys: T23, T25, T28, T30, and T43, covering also regions of Titan located at higher latitudes, and partly including the polar regions. The obtained results are generally in agreement with previous work devoted both to the analysis of the scatterometry data through physical models and to the correlation between SAR and radiometry data at a high resolution scale. This classification can be expanded and refined as new

  16. 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.

  17. Interactions between glycine derivatives and mineral surfaces: Implications for the origins of life on planetary surfaces

    NASA Astrophysics Data System (ADS)

    Marshall-Bowman, K. J.; Cleaves, H. J.; Sverjensky, D. A.; Hazen, R. M.

    2009-12-01

    Various mechanisms could have delivered amino acids to the prebiotic Earth (Miller and Orgel 1974). The polymerization of amino acids may have been important for the origin of life, as peptides may have been components for the first self-replicating systems (Kauffman 1971; Yao et al 1998). Though amino acid concentrations in the primitive oceans were likely too dilute for significant oligomerization to occur (Cleaves et al 2009), mineral surface adsorption may have concentrated these biomolecules (Bernal 1951; Lambert 2008). Few studies have examined the catalytic effects of mineral surfaces on aqueous peptide oligomerization or degradation. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied the reverse reaction of polymer degradation to measure potential mineral catalysis. Glycine (G) derivatives glycylglycine (GG), diketopiperazine (DKP), and glycylglycylglycine (GGG) were reacted with different minerals (calcite, hematite, montmorillonite, rutile, amorphous silica, and pyrite) in the presence of 0.05 M pH 8.1 KHCO3 buffer and 0.1 M NaCl as background electrolyte. Experiments were performed by reacting the aqueous amino acid derivative-mineral mixtures in a thermostatted oven (modified to accommodate a mechanical rotator) at 25°, 50° or 70°C. Samples were removed after 30, 60, 90, and 140 hours. Samples were then analyzed using high performance liquid chromatography to quantify the products. Besides mineral catalysis, it was determined that degradation of GGG proceeds principally via a GGG → DKP + G mechanism, rather than via GGG → GG + G. Below 70°C kinetics were generally too sluggish to detect catalytic activity over reasonable laboratory time-scales at this pH. At 70°C, pyrite was the only mineral with detectible catalytic effects on the degradation of GGG. GGG degraded ~ 1.5 - 4 x faster in the presence of pyrite than in control reactions, depending on the ratio of solution

  18. Ionic Surfactant Binding to pH-Responsive Polyelectrolyte Brush-Grafted Nanoparticles in Suspension and on Charged Surfaces.

    PubMed

    Riley, John K; An, Junxue; Tilton, Robert D

    2015-12-29

    The interactions between silica nanoparticles grafted with a brush of cationic poly(2-(dimethylamino) ethyl methacrylate) (SiO2-g-PDMAEMA) and anionic surfactant sodium dodecyl sulfate (SDS) is investigated by dynamic light scattering, electrophoretic mobility, quartz crystal microbalance with dissipation, ellipsometry, and atomic force microscopy. SiO2-g-PDMAEMA exhibits pH-dependent charge and size properties which enable the SDS binding to be probed over a range of electrostatic conditions and brush conformations. SDS monomers bind irreversibly to SiO2-g-PDMAEMA at low surfactant concentrations (∼10(-4) M) while exhibiting a pH-dependent threshold above which cooperative, partially reversible SDS binding occurs. At pH 5, SDS binding induces collapse of the highly charged and swollen brush as observed in the bulk by DLS and on surfaces by QCM-D. Similar experiments at pH 9 suggest that SDS binds to the periphery of the weakly charged and deswollen brush and produces SiO2-g-PDMAEMA/SDS complexes with a net negative charge. SiO2-g-PDMAEMA brush collapse and charge neutralization is further confirmed by colloidal probe AFM measurements, where reduced electrosteric repulsions and bridging adhesion are attributed to effects of the bound SDS. Additionally, sequential adsorption schemes with SDS and SiO2-g-PDMAEMA are used to enhance deposition relative to SiO2-g-PDMAEMA direct adsorption on silica. This work shows that the polyelectrolyte brush configuration responds in a more dramatic fashion to SDS than to pH-induced changes in ionization, and this can be exploited to manipulate the structure of adsorbed layers and the corresponding forces of compression and friction between opposing surfaces.

  19. Hot surface ionic line emission and cold K-inner shell emission from petawatt-laser irradiated Cu foil targets

    SciTech Connect

    Theobald, W; Akli, K; Clarke, R; Delettrez, J A; Freeman, R R; Glenzer, S; Green, J; Gregori, G; Heathcote, R; Izumi, N; King, J A; Koch, J A; Kuba, J; Lancaster, K; MacKinnon, A J; Key, M; Mileham, C; Myatt, J; Neely, D; Norreys, P A; Park, H; Pasely, J; Patel, P; Regan, S P; Sawada, H; Shepherd, R; Snavely, R; Stephens, R B; Stoeckl, C; Storm, M; Zhang, B; Sangster, T C

    2005-12-13

    A hot, T{sub e} {approx} 2- to 3-keV surface plasma was observed in the interaction of a 0.7-ps petawatt laser beam with solid copper-foil targets at intensities >10{sup 20} W/cm{sup 2}. Copper K-shell spectra were measured in the range of 8 to 9 keV using a single-photon-counting x-ray CCD camera. In addition to K{sub {alpha}} and K{sub {beta}} inner-shell lines, the emission contained the Cu He{sub {alpha}} and Ly{sub {alpha}} lines, allowing the temperature to be inferred. These lines have not been observed previously with ultrafast laser pulses. For intensities less than 3 x 10{sup 18} W/cm{sup 2}, only the K{sub {alpha}} and K{sub {beta}} inner-shell emissions are detected. Measurements of the absolute K{sub {alpha}} yield as a function of the laser intensity are in agreement with a model that includes refluxing and confinement of the suprathermal electrons in the target volume.

  20. A sol-gel derived pH-responsive bovine serum albumin molecularly imprinted poly(ionic liquids) on the surface of multiwall carbon nanotubes.

    PubMed

    Liu, Mingming; Pi, Jiangyan; Wang, Xiaojie; Huang, Rong; Du, Yamei; Yu, Xiaoyang; Tan, Wenfeng; Liu, Fan; Shea, Kenneth J

    2016-08-17

    A pH-responsive surface molecularly imprinted poly(ionic liquids) (MIPILs) was prepared on the surface of multiwall carbon nanotubes (MWCNTs) by a sol-gel technique. The material was synthesized using a 3-aminopropyl triethoxysilane modified multiwall carbon nanotube (MWCNT-APTES) as the substrate, bovine serum albumin (BSA) as the template molecule, an alkoxy-functionalized IL 1-(3-trimethoxysilyl propyl)-3-methyl imidazolium chloride ([TMSPMIM]Cl) as both the functional monomer and the sol-gel catalyst, and tetraethoxysilane (TEOS) as the crosslinking agent. The molecular interaction between BSA and [TMSPMIM]Cl was quantitatively evaluated by UV-vis spectroscopy prior to polymerization so as to identify an optimal template/monomer ratio and the most suitable pH value for the preparation of the MWCNTs@BSA-MIPILs. This strategy was found to be effective to overcome the problems of trial-and-error protocol in molecular imprinting. The optimum synthesis conditions were as follows: template/monomer ratio 7:20, crosslinking agent content 2.0-2.5 mL, temperature 4 °C and pH 8.9 Tris-HCl buffer. The influence of incubation pH on adsorption was also studied. The result showed that the imprinting effect and selectivity improved significantly with increasing incubation pH from 7.7 to 9.9. This is mainly because the non-specific binding from electrostatic and hydrogen bonding interactions decreased greatly with the increase of pH value, which made the specific binding affinity from shape selectivity strengthened instead. The polymers synthesized under the optimal conditions were then characterized by BET surface area measurement, FTIR, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The adsorption capacity, imprinting effect, selective recognition and reusability were also evaluated. The as-prepared MWCNTs@BSA-MIPILs were also found to have a number of advantages including high surface area (134.2 m(2) g(-1)), high adsorption capacity (55.52

  1. Ionic Liquid-Based Microemulsions in Catalysis.

    PubMed

    Hejazifar, Mahtab; Earle, Martyn; Seddon, Kenneth R; Weber, Stefan; Zirbs, Ronald; Bica, Katharina

    2016-12-16

    The design and properties of surface-active ionic liquids that are able to form stable microemulsions with heptane and water are presented, and their promise as reaction media for thermomorphic palladium-catalyzed cross-coupling reactions is demonstrated.

  2. Process optimization studies of 10-Hydroxycamptothecin (HCPT)-loaded folate-conjugated chitosan nanoparticles by SAS-ionic crosslink combination using response surface methodology (RSM)

    NASA Astrophysics Data System (ADS)

    Zhao, Xiuhua; Jiang, Ru; Zu, Yuangang; Wang, Ying; Zhao, Qi; Zu, Baishi; Zhao, Dongmei; Wang, Meixiang; Sun, Zhiqiang

    2012-01-01

    10-Hydroxycamptothecin (HCPT) is a well-established topoisomerase I inhibitor of a broad spectrum of cancers. However, poor aqueous solubility, low instability, and toxicity to normal tissues have limited its clinical development. A novel HCPT-containing drug carrier system was developed to overcome these disadvantages. The response surface methodology was used to optimize the process of preparing HCPT-chitosan nanoparticles (HCPT-CSNPs) by the SAS-ionic crosslink (supercritical antisolvent SAS) combination method; the resulting HCPT-CSNPs were then conjugated with folate for specific targeting. A central composite design, composed of four independent variables, namely, chitosan concentration, TPP concentration, HCPT nanoparticle concentration, and crosslink time, was applied in the modeling process. The mean particle size and drug entrapment efficiency (DEE) of HCPT-CSNPs were chosen as response variables. The interactive effects of the four independent variables on the response variables were also studied. Nanoparticle characteristics such as morphology, DEE, and mean particle size were investigated. The optimum conditions for preparing HCPT-CSNPs were determined as follows: folate-coupled chitosan concentration 2.46 mg/ml, TPP concentration 7.73 mg/ml, HCPT nanoparticle concentration 0.48 mg/ml, and crosslinking time 47.4 min. Optimum conditions for preparing desired HCPT-CSNPs with a mean particle size of 173.5 nm and entrapment efficiency of 77.3% were obtained. The resulting folate-conjugated HCPT-CSNPs (FA-HCPT-CSNPs) reveal that the amount of folate conjugation was 197.64 mg/g CS. FA-HCPT-CSNPs used in drug carrier systems could have potential value in HCPT-sensitive tumors.

  3. On the characterization of host-guest complexes: surface tension, calorimetry, and molecular dynamics of cyclodextrins with a non-ionic surfactant.

    PubMed

    Piñeiro, Angel; Banquy, Xavier; Pérez-Casas, Silvia; Tovar, Edgar; García, Abel; Villa, Alessandra; Amigo, Alfredo; Mark, Alan E; Costas, Miguel

    2007-05-03

    Three host-guest systems have been characterized using surface tension (sigma), calorimetry, and molecular dynamics simulations (MD). The hosts were three native cyclodextrins (CD) and the guest the non-ionic carbohydrate surfactant octyl-beta-d-glucopyranoside. It is shown that, for any host-guest system, a rough screening of the most probable complex stoichiometries can be obtained in a model free form, using only calorimetric data. The sigma data were analyzed using a model that includes a newly proposed adsorption isotherm. The equilibrium constants for several stoichiometries were simultaneously obtained through fitting the sigma data. For alpha- and beta-CD, the predominant species is 1:1 and to a lesser extent 2:1, disregarding the existence of the 1:2. For gamma-CD, the 1:2 species dominates, the other two being also present. In an attempt to confirm these results, 10 ns MD simulations for each CD were performed using seven different starting conformations. The MD stable conformations agree with the results found from the experimental data. In one case, the spontaneous dissociation-formation of a complex was observed. Analysis of the trajectories indicates that hydrophobic interactions are primarily responsible for the formation and stability of the inclusion complexes. For the 2:1 species, intermolecular H-bonds between CD molecules result in a tight packed structure where their original truncated cone shape is lost in favor of a cylindrical geometry. Together, the results clearly demonstrate that the often used assumption of considering only a 1:1 species is inappropriate.

  4. Probing the Interaction between a DNA Nucleotide (Adenosine-5'-Monophosphate Disodium) and Surface Active Ionic Liquids by Rotational Relaxation Measurement and Fluorescence Correlation Spectroscopy.

    PubMed

    Roy, Arpita; Banerjee, Pavel; Dutta, Rupam; Kundu, Sangita; Sarkar, Nilmoni

    2016-10-02

    This article demonstrates the interaction of a deoxyribonucleic acid (DNA) nucleotide, adenosine-5'-monophosphate disodium (AMP) with a cationic surface active ionic liquid (SAIL) 1-dodecyl-3-methylimidazoium chloride (C12mimCl) and an anionic SAIL, 1-butyl-3-methylimidazolium n-octylsulfate ([C4mim][C8SO4]). Dynamic light scattering (DLS) measurements and 1H NMR (nuclear magnetic resonance) studies indicate that substantial interaction is taking place among the DNA nucleotide, AMP and the SAILs. Moreover, cryogenic transmission electron microscopy (cryo-TEM) suggests that SAILs containing micellar assemblies are transformed into larger micellar assemblies in presence of DNA nucleotide. Additionally, the rotational motion of two oppositely charged molecules, Rhodamine 6G perchlorate (R6G) and Fluorescein sodium salt (Fl-Na) have been monitored in these aggregates. The rotational motion of R6G and Fl-Na differs significantly between SAILs micelles, and SAILs-AMP containing larger micellar aggregates. The effect of negatively charged DNA nucleotide (AMP) addition into the cationic and anionic SAILs is more prominent for the cationic charged molecule R6G than that of anionic probe Fl-Na due to the favourable electrostatic interaction between the AMP and cationic R6G. Moreover, the influence of the anionic DNA nucleotide on the cationic and anionic SAIL micelles is monitored through the variation of the lateral diffusion motion of oppositely charged probe molecules (R6G and Fl-Na) inside these aggregates. This variation in diffusion coefficient values also suggests that interaction pattern of these oppositely charged probes are different within the SAILs-nucleotide containing aggregates. Therefore, both rotational and translational diffusion measurements confirm that the DNA nucleotide (AMP) renders more rigid microenvironment within the micellar solution of SAILs.

  5. Quantized friction across ionic liquid thin films

    NASA Astrophysics Data System (ADS)

    Smith, Alexander M.; Lovelock, Kevin R. J.; Gosvami, Nitya Nand; Welton, Tom; Perkin, Susan

    Ionic liquids, salts in the liquid state under ambient conditions, are of great interest as precision lubricants. Ionic liquids form layered structures at surfaces, yet it is not clear how this nano-structure relates to their lubrication properties. We measured the friction force between atomically smooth solid surfaces across ionic liquid films of controlled thickness in terms of the number of ion layers. Multiple friction-load regimes emerge, each corresponding to a different number of ion layers in the film. In contrast to molecular liquids, the friction coefficients differ for each layer due to their varying composition.

  6. Quantized friction across ionic liquid thin films.

    PubMed

    Smith, Alexander M; Lovelock, Kevin R J; Gosvami, Nitya Nand; Welton, Tom; Perkin, Susan

    2013-10-07

    Ionic liquids - salts in the liquid state under ambient conditions - are of great interest as precision lubricants. Ionic liquids form layered structures at surfaces, yet it is not clear how this nano-structure relates to their lubrication properties. We measured the friction force between atomically smooth solid surfaces across ionic liquid films of controlled thickness in terms of the number of ion layers. Multiple friction-load regimes emerge, each corresponding to a different number of ion layers in the film. In contrast to molecular liquids, the friction coefficients differ for each layer due to their varying composition.

  7. Ionic contamination detection. Final report

    SciTech Connect

    Benkovich, M.G.

    1994-04-01

    The effectiveness of Meter A and B for detecting ionic contamination was evaluated and compared on the following types of samples: (1) copper panels, (2) printed wiring boards with through-hold components (lCs), (3) printed wiring boards with surface-mounted components, and (4) mixed-technology printed wiring boards (both through-hole and surface-mount components). The extraction efficiency of the two meters was calculated

  8. The effect of ionic strength on the adsorption of H{sup +}, Cd{sup 2+}, Pb{sup 2+}, and Cu{sup 2+} by Bacillus subtilis and Bacillus licheniformis: A surface complexation model

    SciTech Connect

    Daughney, C.J.; Fein, J.B.

    1998-02-01

    To quantify metal adsorption onto bacterial surfaces, recent studies have applied surface complexation theory to model the specific chemical and electrostatic interactions occurring at the solution-cell wall interface. However, to date, the effect of ionic strength on these interactions has not been investigated. In this study, the authors perform acid-base titrations of suspensions containing Bacillus subtilis or Bacillus licheniformis in 0.01 or 0.1 M NaNO{sub 3}, and they evaluate the constant capacitance and basic Stern double-layer models for their ability to describe ionic-strength-dependent behavior. The constant capacitance model provides the best description of the experimental data. The constant capacitance model parameters vary between independently grown bacterial cultures, possibly due to cell wall variation arising from genetic exchange during reproduction. The authors perform metal-B. subtilis and metal-B. licheniformis adsorption experiments using Cd, Pb, and Cu, and they solve for stability constants describing metal adsorption onto distinct functional groups on the bacterial cell walls. They find that these stability constants vary substantially but systematically between the two bacterial species at the two different ionic strengths.

  9. Seasonal variability of ionic concentrations in surface snow and elution processes in snow-firn packs at the PGPI site on Ürümqi glacier No. 1, eastern Tien Shan, China

    NASA Astrophysics Data System (ADS)

    Li, Zhongqin; Edwards, Ross; Mosley-Thompson, E.; Wang, Feiteng; Dong, Zhibao; You, Xiaoni; Li, Huilin; Li, Chuanjin; Zhu, Yuman

    To investigate the effects of both non-meltwater and meltwater-related post-depositional processes on chemical species within the snow-firn pack, a research program, the Program for Glacier Processes Investigation, was initiated in July 2002 by the Tien Shan Glaciological Station, Chinese Academy of Sciences. The seasonal variability of the ionic concentrations in surface snow samples and ion elution behavior in the snow-firn pack were assessed from surface samples collected year-round and 1011 samples collected from a snow pit at weekly intervals from September 2003 through September 2004. The results indicate that elevated ionic concentrations in spring and summer result from Asian dust-storm-derived aerosol input and other aerosols entrained in precipitation. Potential sources of these chemical species are explored using correlation and factor analyses. The elution sequence through the snow-firn pack was determined to be SO42- > Ca2+ > Na+ > NO3- > Cl- > K+ > Mg2+ > NH4+. The elution of ions at the sampling site was found to be driven primarily by air temperature and became evident when a diurnal mean temperature of -3.6°C was attained. At 0.3°C all of the year-round new ionic input was leached from the snow.

  10. Surface-active ionic liquids in micellar catalysis: impact of anion selection on reaction rates in nucleophilic substitutions† †Electronic supplementary information (ESI) available: Formulae for calculating aggregation parameters and fitting of kinetic constants and copies of NMR spectra. See DOI: 10.1039/c6cp00493h Click here for additional data file.

    PubMed Central

    Cognigni, Alice; Gaertner, Peter; Zirbs, Ronald; Peterlik, Herwig; Prochazka, Katharina; Schröder, Christian

    2016-01-01

    A series of surface-active ionic liquids based on the 1-dodecyl-3-methylimidazolium cation and different anions such as halides and alkylsulfates was synthesized. The aggregation behavior of these ionic liquids in water was characterized by surface tension, conductivity measurements and UV-Vis spectroscopy in order to determine the critical micelle concentration (CMC) and to provide aggregation parameters. The determination of surface activity and aggregation properties of amphiphilic ionic liquids was accompanied by SAXS studies on selected surface-active ionic liquids. The application of these surface-active ionic liquids with different anions was tested in nucleophilic substitution reactions for the degradation of organophosphorus compounds. Kinetic studies via UV-Vis spectrophotometry showed a strong acceleration of the reaction in the micellar system compared to pure water. In addition, an influence of the anion was observed, resulting in a correlation between the anion binding to the micelle and the reaction rate constants, indicating that the careful choice of the surface-active ionic liquid can considerably affect the outcome of reactions. PMID:27121134

  11. Effect of Imidazolium-Based Surface-Active Ionic Liquids on the Orientation of Liquid Crystals at Various Fluid/Liquid Crystal Interfaces.

    PubMed

    Tian, Tongtong; Hu, Qiongzheng; Wang, Yi; Gao, Yan'an; Yu, Li

    2016-11-15

    A series of imidazolium-based surface-active ionic liquids (IM-SAILs), viz., single-chained IM-SAILs, 1-alkyl-3-methylimidazolium bromide ([Cnmim]Br, n = 12, 14, 16), 1-dodecyl-3-methylimidazolium salicylate ([C12mim]Sal), 1-dodecyl-3-methylimidazolium 3-hydroxy-2-naphthoate ([C12mim]HNC), 1-dodecyl-3-methylimidazolium cinnamate ([C12mim]CA), 1-dodecyl-3-methylimidazolium para-hydroxy-cinnamate ([C12mim]PCA), gemini IM-SAIL, and 1,2-bis(3-dodecylimidazolium-1-yl)ethane bromide ([C12-2-C12im]Br2), along with three short-chained ionic liquids (ILs) [ethylammonium nitrate (EAN), propylammonium nitrate (PAN), and butylammonium nitrate (BAN)] were synthesized and applied to nematic liquid crystal (LC)/fluid interfaces. First, we evaluated the influence of the length and number of aliphatic chains as well as the counterion in the IM-SAIL structures on the anchoring of LCs at the aqueous/LC interface. It was observed that the threshold concentration of [Cnmim]Br (n = 12, 14, 16) decreased with the increase in aliphatic chain length. And double-chained [C12-2-C12im]Br2 has a far lower threshold concentration than single-chained [C12mim]Br. But the alteration of counterions (e.g., Br(-) and aromatic counterions) scarcely affected the anchoring of LCs at the interface. Second, we investigated the alignment of LCs at the diverse IL/LC interfaces in the presence of IM-SAILs. It is found that the variations in both aliphatic chain length and number can remarkably change the trigger points of the orientational transition of LCs at the EAN/LC interface. Specifically, with a slight increase in the alkyl chain length of short-chained ILs, as the fluid medium, the orientation of LCs varied tremendously at the IL/LC interface. Therefore, the higher threshold concentration of IM-SAILs and the corresponding greater stability in the optical appearance of LCs at the EAN/LC interface compared to that of the aqueous/LC interface can be ascribed to the discrepancy in the microstructure of

  12. 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.

  13. Long-term changes in net radiation at the Earth's surface: uncertainties and implications

    NASA Astrophysics Data System (ADS)

    Sheffield, Justin; Coccia, Gabriele; Siemann, Amanda; Wood, Eric

    2014-05-01

    Net radiation at the earth's surface plays a key role in terrestrial water, energy and carbon fluxes, but there is large uncertainty in its variation over decadal time scales. Globally, surface and satellite measurements indicate global dimming in solar radiation over many regions since the mid-20th century and then brightening over recent decades due to changes in cloudiness and aerosols. Changes in longwave radiation are driven by long-term increases in greenhouse gases and inter-annual variations in short-lived constituents such as dust and black carbon. These increases are partially offset, however, by increases in surface temperature. Current estimates of these components of the net radiation balance from satellite remote sensing are inconsistent because of inhomogeneities from changes in satellites, sensor calibration, retrieval algorithms, and so on, in addition to systematic biases. Estimates from direct ground observations are hampered by sparse spatial networks and often short-term records, and estimates based on denser networks of meteorological data are affected by errors in empirical radiation models. Some of the largest uncertainties are in the characterization of the global distribution and temporal changes in surface shortwave albedo and infrared emissivity, especially in regions with seasonal and patchy snow cover. This paper presents comparisons of legacy satellite-derived datasets (e.g. ISCCP, GEWEX/SRB) and recently developed datasets based on updated algorithms and homogenized data sources (e.g. NASA Princeton-Measures, HIRS) in the context of long-term changes in the net radiation balance at the earth's surface. We compare these with ground observations and empirical estimates based on meteorological data from in-situ sources and reanalysis. In particular we focus on the uncertainties in the magnitude and variation in surface albedo and emissivity, and their contribution to uncertainties in net radiation. We discuss the implications of these

  14. Thermally induced stresses in boulders on airless body surfaces: Implications for breakdown

    NASA Astrophysics Data System (ADS)

    Molaro, Jamie; Byrne, Shane

    2016-10-01

    granular disintegration. These two mechanisms likely work together to hasten disaggregation of the near-surface.We will present results for boulder stresses on the Moon and other airless bodies, and discuss implications for breakdown on these surfaces.

  15. Highly reversible lithium metal secondary battery using a room temperature ionic liquid/lithium salt mixture and a surface-coated cathode active material.

    PubMed

    Seki, Shiro; Kobayashi, Yo; Miyashiro, Hajime; Ohno, Yasutaka; Usami, Akira; Mita, Yuichi; Watanabe, Masayoshi; Terada, Nobuyuki

    2006-02-07

    For the purpose of realizing high-voltage, high-capacity, long-life and safe rechargeable batteries, a lithium secondary battery that uses high-voltage stable ZrO2-coated LiCoO2 cathode powder and a nonvolatile high-safety room temperature ionic liquid was fabricated.

  16. Ion Exchange and Antibiofouling Properties of Poly(ether sulfone) Membranes Prepared by the Surface Immobilization of Brønsted Acidic Ionic Liquids via Double-Click Reactions.

    PubMed

    Yi, Zhuan; Liu, Cui-Jing; Zhu, Li-Ping; Xu, You-Yi

    2015-07-28

    Brønsted acidic ionic liquids (BAILs) are unique ionic liquids that display chemical structures similar to zwitterions, and they were typically used as solvents and catalysts. In this work, an imidazole-based BAIL monolayer was fabricated onto poly(ether sulfone) (PES) membranes via surface clicking reactions, and the multifunctionality, including ion exchange and biofouling resistance to proteins and bacteria, was demonstrated, which was believed to be one of few works in which BAIL had been considered to be a novel fouling resistance layer for porous membranes. The successful immobilization of the BAILs onto a membrane surface was confirmed by X-ray photoelectron spectroscopy analysis, contact angle measurement, and ζ potential determination. The results from Raman spectroscopy showed that, as a decisive step prior to zwitterion, the BAIL was deprotonated in aqueous solution, and biofouling resistance to proteins and bacteria was found. However, BAIL displayed ion exchange ability at lower pH, and surface hydrophilicity/hydrophobicity of membranes could be tuned on purpose. Our results have demonstrated that the BAIL grafted onto membranes will not only act as an antibiofouling barrier like zwitterions but also provide a platform for surface chemical tailoring by ion exchange, the property of which will become especially important in acidic solutions where the fouling resistance performances of zwitterions are greatly weakened.

  17. Understanding global cycling of atmosphere-surface exchangeable pollutants and its implications

    NASA Astrophysics Data System (ADS)

    Selin, N. E.; Giang, A.; Song, S.; Pike-thackray, C.; Friedman, C. L.

    2014-12-01

    We combine modeling approaches with data analysis to provide quantitative constraints on the global biogeochemical cycling of pollutants such as mercury (Hg) and persistent organic pollutants (POPs). These pollutants, released by human activities, continue to cycle between land, ocean, and atmosphere surfaces, extending their effective lifetimes in the environment. Measurement data are limited for all of these substances, providing few constraints on the magnitude of surface-atmosphere fluxes and thus the timescales of their cycling. This limits our ability to trace emissions to impacts for these substances, particularly in the context of both ongoing policies and climate change. We present a suite of modeling and analysis tools, including uncertainty analysis, that can provide quantitative constraints on cycling for these data-limited problems, and we illustrate their applicability through examples of Hg and selected POPs. Specifically, we summarize recent insights from inverse modeling of mercury, polynomial chaos-based methods for PAHs. Finally, we assess how uncertainty in timescales affects the entire emissions-to-impacts pathway for atmosphere-surface exchangeable pollutants. We discuss the implications of this analysis for policies under the Stockholm and Minamata Conventions.

  18. New and revised 14C dates for Hawaiian surface lava flows: Paleomagnetic and geomagnetic implications

    USGS Publications Warehouse

    Pressline, N.; Trusdell, F.A.; Gubbins, David

    2009-01-01

    Radiocarbon dates have been obtained for 30 charcoal samples corresponding to 27 surface lava flows from the Mauna Loa and Kilauea volcanoes on the Island of Hawaii. The submitted charcoal was a mixture of fresh and archived material. Preparation and analysis was undertaken at the NERC Radiocarbon Laboratory in Glasgow, Scotland, and the associated SUERC Accelerator Mass Spectrometry facility. The resulting dates range from 390 years B.P. to 12,910 years B.P. with corresponding error bars an order of magnitude smaller than previously obtained using the gas-counting method. The new and revised 14C data set can aid hazard and risk assessment on the island. The data presented here also have implications for geomagnetic modelling, which at present is limited by large dating errors. Copyright 2009 by the American Geophysical Union.

  19. Surface-enhanced Raman spectroscopy at single-molecule scale and its implications in biology.

    PubMed

    Wang, Yuling; Irudayaraj, Joseph

    2013-02-05

    Single-molecule (SM) spectroscopy has been an exciting area of research offering significant promise and hope in the field of sensor development to detect targets at ultra-low levels down to SM resolution. To the experts and developers in the field of surface-enhanced Raman spectroscopy (SERS), this has often been a challenge and a significant opportunity for exploration. Needless to say, the opportunities and excitement of this multidisciplinary area impacts span the fields of physics, chemistry and engineering, along with a significant thrust in applications constituting areas in medicine, biology, environment and agriculture among others. In this review, we will attempt to provide a quick snapshot of the basics of SM-SERS, nanostructures and devices that can enable SM Raman measurement. We will conclude with a discussion on SERS implications in biomedical sciences.

  20. The effects of non-ionic polymeric surfactants on the cleaning of biofouled hydrogel materials.

    PubMed

    Guan, Allan; Li, Zhenyu; Phillips, K Scott

    2015-01-01

    Block co-polymer surfactants have been used for cleaning hydrogel medical devices that contact the body (e.g., contact lenses) because of their biocompatibility. This work examined the relationship between concentration and detergency of two non-ionic polymeric surfactants (Pluronic F127 and Triton X-100) for cleaning protein soil, with anionic surfactants (sodium dodecyl sulfate and sodium laureth sulfate) as positive controls. Surface plasmon resonance was used to quantify removal of simulated tear soil from self-assembled monolayer surfaces, and a microplate format was used to study the removal of fluorescently labeled soil proteins from contact lenses. While detergency increased as a function of concentration for anionic surfactants, it decreased with concentration for the two polymeric surfactants. The fact that the protein detergency of some non-ionic polymeric surfactants did not increase with concentration above the critical micelle concentration could have implications for optimizing the tradeoff between detergency and biocompatibility.

  1. Fluctuating hydrodynamics for ionic liquids

    NASA Astrophysics Data System (ADS)

    Lazaridis, Konstantinos; Wickham, Logan; Voulgarakis, Nikolaos

    2017-04-01

    We present a mean-field fluctuating hydrodynamics (FHD) method for studying the structural and transport properties of ionic liquids in bulk and near electrified surfaces. The free energy of the system consists of two competing terms: (1) a Landau-Lifshitz functional that models the spontaneous separation of the ionic groups, and (2) the standard mean-field electrostatic interaction between the ions in the liquid. The numerical approach used to solve the resulting FHD-Poisson equations is very efficient and models thermal fluctuations with remarkable accuracy. Such density fluctuations are sufficiently strong to excite the experimentally observed spontaneous formation of liquid nano-domains. Statistical analysis of our simulations provides quantitative information about the properties of ionic liquids, such as the mixing quality, stability, and the size of the nano-domains. Our model, thus, can be adequately parameterized by directly comparing our prediction with experimental measurements and all-atom simulations. Conclusively, this work can serve as a practical mathematical tool for testing various theories and designing more efficient mixtures of ionic liquids.

  2. Halogen bonding interactions between brominated ion pairs and CO2 molecules: implications for design of new and efficient ionic liquids for CO2 absorption.

    PubMed

    Zhu, Xiang; Lu, Yunxiang; Peng, Changjun; Hu, Jun; Liu, Honglai; Hu, Ying

    2011-04-14

    In recent years, several novel halogenated liquids with characteristics of ionic liquids (ILs) were reported. To explore their performance in the absorption of CO(2), in this work, quantum chemical calculations at DFT level have been carried out to investigate halogen bonding interactions between experimentally available brominated ion pairs and CO(2) molecules. It is shown that, as compared to B3LYP, the functional PBE yields geometrical and energetic data more close to those of MP2 for cation-CO(2) systems. The cation of brominated ILs under study can interact with CO(2) molecules through Br···O interactions, possibly making an important impact on the physical solubility of CO(2) in brominated ILs. The optimized geometries of the complexes of the ion pair with CO(2) molecules are quite similar to those of the corresponding complexes of the cation, especially for the essentially linear C-Br···O contacts. However, much weaker halogen bonds are predicted in the former systems, as indicated by the longer intermolecular distances and the smaller interaction energies. Charges derived from NBO analysis reveal the origin of the different optimized conformations and halogen bonding interactions for the CO(2) molecule. Based on the electrostatic potential results, the substitution of hydrogen atoms with fluorine atoms constituting the cation is then applied to enhance halogen bond strength. The QTAIM analysis further validates the existence of halogen bonding interaction in all complexes. The topological properties at the halogen bond critical points indicate that the Br···O interactions in the complexes are basically electrostatic in nature and belong to conventional weak halogen bonds. This study would be helpful for designing new and effective ILs for CO(2) physical absorption.

  3. Ionic Conduction in Nanocrystalline Materials

    DTIC Science & Technology

    2000-02-10

    photo- largely due to oxygen desorption from particle voltaic cells and as the photocatalyst in water surfaces. The latter interpretation...and Tuller [22] prepared dense (-95%) temperature, where bulk reduction was observed. At compacts of TiO2 with the anatase phase. The lower... TiO2 , evidence preparation. is mixed. Nanocrystalline rutile appears to exhibit higher ionic conductivity than single crystal rutile while

  4. Adsorption of CO on oxide and water ice surfaces - Implications for the Martian atmosphere

    NASA Technical Reports Server (NTRS)

    Leu, M.-T.; Blamont, J. E.; Anbar, A. D.; Keyser, L. F.; Sander, S. P.

    1992-01-01

    The adsorption of carbon monoxide (CO) on water ice and on the oxides Fe2O3, Fe3O4, Al2O3, SiO2, CaO, MgO, and TiO2 (rutile and anatase) has been investigated in a flow reactor. A mass spectrometer was employed as a detector to monitor the temporal concentrations of CO. Adsorption coefficients as large as 1 x 10 exp -4 were measured for CO on TiO2 solids in helium at 196 K. The fractional surface coverage for CO on TiO2 solids in helium was also determined to be approximately 10 percent at 196 K. The upper limits of the fractional surface coverage for the other oxides (Fe2O3, Fe3O4, Al2O3, SiO2, CaO, and MgO) and water ice were also measured to be less than 1 percent. The implications for the stability of CO2 in the Martian atmosphere and the 'CO hole' observed by the Phobos/ISM experiment are discussed.

  5. Radicals in ionic liquids.

    PubMed

    Strehmel, Veronika

    2012-05-14

    Stable radicals and recombination of photogenerated lophyl radicals are investigated in ionic liquids. The 2,2,6,6-tetramethylpiperidine-1-yloxyl derivatives contain various substituents at the 4-position to the nitroxyl group, including hydrogen-bond-forming or ionic substituents that undergo additional interactions with the individual ions of the ionic liquids. Some of these spin probes contain similar ions to ionic liquids to avoid counter-ion exchange with the ionic liquid. Depending on the ionic liquid anion, the Stokes-Einstein theory or the Spernol-Gierer-Wirtz theory can be applied to describe the temperature dependence of the average rotational correlation time of the spin probe in the ionic liquids. Furthermore, the spin probes give information about the micropolarity of the ionic liquids. In this context the substituent at the 4-position to the nitroxyl group plays a significant role. Covalent bonding of a spin probe to the imidazolium ion results in bulky spin probes that are strongly immobilized in the ionic liquid. Furthermore, lophyl radical recombination in the dark, which is chosen to understand the dynamics of bimolecular reactions in ionic liquids, shows a slow process at longer timescale and a rise time at a shorter timescale. Although various reactions may contribute to the slower process during lophyl radical recombination, it follows a second-order kinetics that does not clearly show solvent viscosity dependence. However, the rise time, which may be attributed to radical pair formation, increases with increasing solvent viscosity.

  6. High-Surface-Area CO2 Sponge: High Performance CO2 Scrubbing Based on Hollow Fiber-Supported Designer Ionic Liquid Sponges

    SciTech Connect

    2010-09-01

    IMPACCT Project: The team from ORNL and Georgia Tech is developing a new technology that will act like a sponge, integrating a new, alcohol-based ionic liquid into hollow fibers (magnified image, right) to capture CO2 from the exhaust produced by coal-fired power plants. Ionic liquids, or salts that exist in liquid form, are promising materials for carbon capture and storage, but their tendency to thicken when combined with CO2 limits their efficiency and poses a challenge for their development as a cost-effective alternative to current-generation solutions. Adding alcohol to the mix limits this tendency to thicken in the presence of CO2 but can also make the liquid more likely to evaporate, which would add significantly to the cost of CO2 capture. To solve this problem, ORNL is developing new classes of ionic liquids with high capacity for absorbing CO2. ORNL’s sponge would reduce the cost associated with the energy that would need to be diverted from power plants to capture CO2 and release it for storage.

  7. Fundamental studies of the chemisorption of organosulfur compounds on Au(111). Implications for molecular self-assembly on gold surfaces

    SciTech Connect

    Nuzzo, R.G.; Zegarski, B.R.; Dubois, L.H.

    1987-02-04

    Studies of the adsorption of methanethiol and dimethyl disulfide on an Au(111) surface under UHV conditions are described. Both adsorbates bind strongly, with the bonding of the disulfide being greatly favored. It is found that, under these conditions, the disulfide bond is dissociated to give a stable surface thiolate. Adsorption of methanethiol does not involve cleavage of the S-H bond. The implications of these results for solution adsorption experiments and the thermodynamics characterizing monolayer formation are discussed.

  8. Stimulus-responsive Au@(MeO2MAx-co-OEGMAy) nanoparticles stabilized by non-DLVO interactions: implications of ionic strength and copolymer (x:y) fraction on aggregation kinetics.

    PubMed

    Gambinossi, Filippo; Chanana, Munish; Mylon, Steven E; Ferri, James K

    2014-02-25

    Functionalized nanoparticles can assist in stabilizing fluid-fluid interfaces; however, developing and applying the appropriate surface modification presents a challenge because successful application of these nanomaterials for biotechnological, food processing, and environmental applications requires their long-term stability in elevated ionic strength media. This work studies stimulus responsive polymeric materials based on random copolymers of di(ethylene glycol) methyl ether methacrylate (x = MeO2MA) and oligo(ethylene glycol) methyl ether methacrylate (y= OEGMA) which, when grafted to gold nanoparticles, show significant, tunable, colloidal stability. The nanoparticles Au@(MeO2MAx-co-OEGMAy) display tunable, reversible aggregation that is highly dependent on the (x:y) ratio and ionic strength. Effects of these parameters on the initial rate constant of aggregation (k11) are studied by time-resolved dynamic light scattering (TR-DLS) experiments. At the same nanoparticle concentration, a strong sensitivity to salt concentration is observed. Over less than 300 mM increase in NaCl concentration, we observed a two-order of magnitude increase in aggregation rate constants, 4.2 × 10(-20) < k11 < 1.8 × 10(-18) m(3)s(-1). Additionally, for the same gold nanoparticles, a higher fraction of OEGMA requires a higher salt concentration to induce aggregation. A linear relationship between the critical NaCl coagulation concentration (CCC) and the copolymer composition is observed. Analysis of the experimental data with an extended Derjaguin-Landau-Verwey-Overbeek (xDLVO) theory that includes hydration and osmotic forces is used to explain the stability of these systems. We find the hydration pressure, 2.4 < P(h,0) < 7.2 MPa, scales linearly both with the osmotic pressure and the OEGMA monomer concentration (5 < y < 20%). Specific knowledge of P(h,0)(y, C(NaCl)) enables design of both aggregation kinetics and stability as a function of the copolymer ratio and external

  9. Unravelling the secrets of Cs controlled secondary ion formation: Evidence of the dominance of site specific surface chemistry, alloying and ionic bonding

    NASA Astrophysics Data System (ADS)

    Wittmaack, Klaus

    2013-03-01

    implantation can be evaluated as a function of Cs coverage. The summarised results imply that secondary ions are commonly not formed by charge transfer between an escaping atom and the electronic system of the sample but are already emitted as ions. The probability of ion formation appears to be controlled by the local ionic character of the alkali-target atom bonds, i.e., by the difference in electronegativity between the involved elements as well as by the electron affinity and the ionisation potential of the departing atom. This idea is supported by the finding that Si- yields exhibit the same very strong dependence on Cs coverage as Si+ and O- yields on the oxygen fraction in oxygen loaded Si. Most challenging to theoreticians is the finding that the ionisation probability is independent of the emission velocity of sputtered ions. This phenomenon cannot be rationalised along established routes of thinking. Different concepts need to be explored. An old, somewhat exotic idea takes account of the heavy perturbation created for a very short period of time at the site of ion emission (dynamic randomisation). Molecular dynamics simulations are desirable to clarify the issue. Ultimately it may be possible to describe all phenomena of enhanced or suppressed secondary ion formation, produced either by surface loading with alkali atoms or by enforced surface oxidation, on the basis of a single universal model. There is plenty of room for exciting new studies.

  10. Unravelling the secrets of Cs controlled secondary ion formation: Evidence of the dominance of site specific surface chemistry, alloying and ionic bonding

    NASA Astrophysics Data System (ADS)

    Wittmaack, Klaus

    2013-03-01

    implantation can be evaluated as a function of Cs coverage.The summarised results imply that secondary ions are commonly not formed by charge transfer between an escaping atom and the electronic system of the sample but are already emitted as ions. The probability of ion formation appears to be controlled by the local ionic character of the alkali-target atom bonds, i.e., by the difference in electronegativity between the involved elements as well as by the electron affinity and the ionisation potential of the departing atom. This idea is supported by the finding that Si- yields exhibit the same very strong dependence on Cs coverage as Si+ and O- yields on the oxygen fraction in oxygen loaded Si. Most challenging to theoreticians is the finding that the ionisation probability is independent of the emission velocity of sputtered ions. This phenomenon cannot be rationalised along established routes of thinking. Different concepts need to be explored. An old, somewhat exotic idea takes account of the heavy perturbation created for a very short period of time at the site of ion emission (dynamic randomisation). Molecular dynamics simulations are desirable to clarify the issue. Ultimately it may be possible to describe all phenomena of enhanced or suppressed secondary ion formation, produced either by surface loading with alkali atoms or by enforced surface oxidation, on the basis of a single universal model. There is plenty of room for exciting new studies.

  11. The effects of steam on the surface properties of palygorskite: Implications for palygorskite-water interactions

    NASA Astrophysics Data System (ADS)

    Kadakia, Abhy

    decreased by 40-50% after steam treatment. The reduced affinity for water and EGME may represent a reduced affinity for polar molecules in general. These results, particularly the XPS spectra and the observed large changes in rheological properties, suggest that steam altered the H + ion environment and/or concentration on palygorskite's surface. Exposing palygorskite to steam may have significant implications for its industrial applications, adversely affecting some applications and enhancing others.

  12. The flexible structure of the K24S28 region of Leucine-Rich Amelogenin Protein (LRAP) bound to apatites as a function of surface type, calcium, mutation, and ionic strength.

    PubMed

    Lu, Jun-Xia; Burton, Sarah D; Xu, Yimin S; Buchko, Garry W; Shaw, Wendy J

    2014-01-01

    Leucine-Rich Amelogenin Protein (LRAP) is a member of the amelogenin family of biomineralization proteins, proteins which play a critical role in enamel formation. Recent studies have revealed the structure and orientation of the N- and C-terminus of LRAP bound to hydroxyapatite (HAP), a surface used as an analog of enamel. The structure of one region, K24 to S28, was found to be sensitive to phosphorylation of S16, the only naturally observed site of serine phosphorylation in LRAP, suggesting that K24S28 may sit at a key region of structural flexibility and play a role in the protein's function. In this work, we investigated the sensitivity of the structure and orientation of this region when bound to HAP as a function of several factors which may vary during enamel formation to influence structure: the ionic strength (0.05, 0.15, 0.2 M), the calcium concentration (0.07 and 0.4 mM), and the surface to which it is binding [HAP and carbonated apatite (CAP), a more direct mimic of enamel]. A naturally occurring mutation found in amelogenin (T21I) was also investigated. The structure in the K24S28 region of the protein was found to be sensitive to these conditions, with the CAP surface and excess Ca(2+) (8:1 [Ca(2+)]:[LRAP-K24S28(+P)]) resulting in a tighter helix, while low ionic strength relaxed the helical structure. Higher ionic strength and the point mutation did not result in any structural change in this region. The distance of the backbone of K24 from the surface was most sensitive to excess Ca(2+) and in the T21I-mutation. Collectively, these data suggest that phosphorylated LRAP is able to accommodate structural changes while maintaining its interaction with the surface, and provides further evidence of the structural sensitivity of the K24S28 region, a sensitivity that may contribute to function in biomineralization.

  13. The flexible structure of the K24S28 region of Leucine-Rich Amelogenin Protein (LRAP) bound to apatites as a function of surface type, calcium, mutation, and ionic strength

    SciTech Connect

    Lu, Junxia; Burton, Sarah D.; Xu, Yimin; Buchko, Garry W.; Shaw, Wendy J.

    2014-07-11

    Leucine-Rich Amelogenin Protein (LRAP) is a member of the amelogenin family of biomineralization proteins, proteins which play a critical role in enamel formation. Recent studies have revealed the structure and orientation of the N- and C-terminus of LRAP bound to hydroxyapatite (HAP), a surface used as an analog of enamel. The structure of one region, K24 to S28, was found to be sensitive to phosphorylation of S16, the only naturally observed site of serine phosphorylation in LRAP, suggesting that the residues from K24 to S28 may sit at a key region of structural flexibility and play a role in the protein’s function. In this work, we investigated the sensitivity of the structure and orientation of this region when bound to HAP as a function of several factors which may vary during enamel formation to influence structure: the ionic strength (0.05 M, 0.15 M, 0.2 M), the calcium concentration (0.07 mM and 0.4 mM), and the surface to which it is binding (HAP and carbonated apatite (CAP), a more direct mimic of enamel). A naturally occurring mutation found in amelogenin (T21I), was also investigated. The structure in the K24S28 region of the protein was found to be sensitive to these conditions, with the CAP surface and excess Ca2+ (8:1 [Ca2+]:[LRAP-K24S28(+P)]) resulting in a much tighter helix, while low ionic strength relaxed the helical structure. Higher ionic strength and the point mutation did not result in any structural change in this region. The distance of the backbone of K24 from the surface was most sensitive to excess Ca2+ and in the T21I-mutation. Collectively, these data suggest that the protein is able to accommodate structural changes while maintaining its interaction with the surface, and provides further evidence of the structural sensitivity of the K24 to S28 region, a sensitivity that may contribute to function in biomineralization. This research was supported by NIH-NIDCR Grant DE-015347. The research was performed at the Pacific Northwest

  14. Application of response surface methodology for optimization of ionic liquid-based dispersive liquid-liquid microextraction of cadmium from water samples.

    PubMed

    Rajabi, M; Kamalabadi, M; Jamali, M R; Zolgharnein, J; Asanjarani, N

    2013-06-01

    A new, rapid, and simple method for the determination of cadmium in water samples was developed using ionic liquid-based dispersive liquid-liquid microextraction (IL-DLLME) coupled to flame atomic absorption spectrometry (FAAS). In the proposed approach, 2-(5-boromo-2-pyridylazo)-5-(diethyamino) phenol was used as a chelating agent and 1-hexyl-3-methylimidazolium bis(trifluoro methylsulfonyl)imide and acetone were selected as extraction and dispersive solvents, respectively. Sample pH, concentration of chelating agent, amount of ionic liquid (extraction solvent), disperser solvent volume, extraction time, salt effect, and centrifugation speed were selected as interested variables in IL-DLLME process. The significant variables affecting the extraction efficiency were determined using a Placket-Burman design. Thereafter, the significant variables were optimized using a Box-Behnken design and the quadratic model between the dependent and the independent variables was built. The optimum experimental conditions obtained from this statistical evaluation included: pH: 6.7; concentration of chelating agent: 1.1 10(-) (3) mol L(-1); and ionic liquid: 50.0 mg. Under the optimum conditions, the preconcentration factor obtained was 100. Calibration graph was linear in the range of 0.2-60 µg L(-1) with correlation coefficient of 0.9992. The limit of detection was 0.06 µg L(-) (1), which is lower than other reported approaches applied to the determination of cadmium using FAAS. The relative SD (n = 8) was 2.4%. The proposed method was successfully applied to the determination of trace amounts of cadmium in the real water samples with satisfactory results.

  15. Diverse policy implications for future ozone and surface UV in a changing climate

    NASA Astrophysics Data System (ADS)

    Butler, A. H.; Daniel, J. S.; Portmann, R. W.; Ravishankara, A. R.; Young, P. J.; Fahey, D. W.; Rosenlof, K. H.

    2016-06-01

    Due to the success of the Montreal Protocol in limiting emissions of ozone-depleting substances, concentrations of atmospheric carbon dioxide, nitrous oxide, and methane will control the evolution of total column and stratospheric ozone by the latter half of the 21st century. As the world proceeds down the path of reducing climate forcing set forth by the 2015 Conference of the Parties to the United Nations Framework Convention on Climate Change (COP 21), a broad range of ozone changes are possible depending on future policies enacted. While decreases in tropical stratospheric ozone will likely persist regardless of the future emissions scenario, extratropical ozone could either remain weakly depleted or even increase well above historical levels, with diverse implication for ultraviolet (UV) radiation. The ozone layer’s dependence on future emissions of these gases creates a complex policy decision space for protecting humans and ecosystems, which includes unexpected options such as accepting nitrous oxide emissions in order to maintain historical column ozone and surface UV levels.

  16. 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.

  17. Temperature-dependent electronic and vibrational structure of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide room-temperature ionic liquid surface: a study with XPS, UPS, MIES, and HREELS.

    PubMed

    Krischok, S; Eremtchenko, M; Himmerlich, M; Lorenz, P; Uhlig, J; Neumann, A; Ottking, R; Beenken, W J D; Höfft, O; Bahr, S; Kempter, V; Schaefer, J A

    2007-05-10

    The near-surface structure of the room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide has been investigated as a function of temperature between 100 and 620 K. We used a combination of photoelectron spectroscopies (XPS and UPS), metastable induced electron spectroscopy (MIES), and high-resolution electron energy loss spectroscopy (HREELS). The valence band and HREELS spectra are interpreted on the basis of density functional theory (DFT) calculations. At room temperature, the most pronounced structures in the HREELS, UPS, and MIES spectra are related to the CF3 group in the anion. Spectral changes observed at 100 K are interpreted as a change of the molecular orientation at the outermost surface, when the temperature is lowered. At elevated temperatures, early volatilization, starting at 350 K, is observed under reduced pressure.

  18. Kinetics and mechanism of oxygen reduction in a protic ionic liquid.

    PubMed

    Walsh, Darren A; Ejigu, Andinet; Smith, Joshua; Licence, Peter

    2013-05-28

    The oxygen reduction reaction (ORR) has been studied at Pt surfaces in the protic ionic liquid diethylmethylammonium trifluoromethanesulfonate. Water content measurements suggested that the ORR proceeded in the ionic liquid predominantly via a 4-electron reduction to water. A mechanistic analysis using rotating ring-disk electrode (RRDE) voltammetry confirmed that negligible amounts of hydrogen peroxide were formed during the ORR. A kinetic analysis of the ORR was performed using rotating disk electrode (RDE) voltammetry and the importance of correcting for ohmic (iR) drop prior to performing kinetic measurements in the ionic liquid is demonstrated. A Tafel analysis of the RDE voltammetry data revealed a change in the ORR Tafel slope from 70 mV per decade at low ORR overpotentials to 117 mV per decade at high overpotentials, and the reason for this change is discussed. The change in the Tafel slope for the ORR with increasing overpotential meant that the exchange current density for the ORR varied from 0.007 nA cm(-2) to 10 nA cm(-2), depending on the applied potential. Finally, the implications of these results for the development of protic ionic liquid fuel cells are discussed.

  19. Electron-transfer reactions of cobalt(III) complexes. 1. The kinetic investigation of the reduction of various surfactant cobalt(III) complexes by iron(II) in surface active ionic liquids.

    PubMed

    Nagaraj, Karuppiah; Senthil Murugan, Krishnan; Thangamuniyandi, Pilavadi; Sakthinathan, Subramanian

    2015-05-15

    The kinetics of outer sphere electron transfer reaction of surfactant cobalt(III) complex ions, cis-[Co(en)2(C12H25NH2)2](3+) (1), cis-[Co(dp)2(C12H25NH2)2](3+) (2), cis-[Co(trien)(C12H25NH2)2](3+) (3), cis-[Co(bpy)2(C12H25NH2)2](3+) (4) and cis-[Co(phen)2(C12H25NH2)2](3+) (5) (en: ethylenediamine, dp: diaminopropane, trien : triethylenetetramine, bpy: 2,2'-bipyridyl, phen: 1,10-phenanthroline and C12H25NH2 : dodecylamine) have been interrogated by Fe(2+) ion in ionic liquid (1-butyl-3-methylimidazoliumbromide) medium at different temperatures (298, 303, 308, 313, 318 and 323K) by the spectrophotometry method under pseudo first order conditions using an excess of the reductant. Experimentally the reactions were found to be of second order and the electron transfer as outer sphere. The second order rate constant for the electron transfer reaction in ionic liquids was found to increase with increase in the concentration of all these surfactant cobalt(III) complexes. Among these complexes (from en to phen ligand), complex containing the phenanthroline ligand rate is higher compared to other complexes. By assuming the outer sphere mechanism, the results have been explained based on the presence of aggregated structures containing cobalt(III) complexes at the surface of ionic liquids formed by the surfactant cobalt(III) complexes in the reaction medium. The activation parameters (enthalpy of activation ΔH(‡) and entropy of activation ΔS(‡)) of the reaction have been calculated which substantiate the kinetics of the reaction.

  20. Estimating dermal transfer of copper particles from the surfaces of pressure-treated lumber and implications for exposure.

    PubMed

    Platten, William E; Sylvest, Nicholas; Warren, Casey; Arambewela, Mahendranath; Harmon, Steve; Bradham, Karen; Rogers, Kim; Thomas, Treye; Luxton, Todd Peter

    2016-04-01

    Lumber pressure-treated with micronized copper was examined for the release of copper and copper micro/nanoparticles using a surface wipe method to simulate dermal transfer. In 2003, the wood industry began replacing CCA treated lumber products for residential use with copper based formulations. Micronized copper (nano to micron sized particles) has become the preferred treatment formulation. There is a lack of information on the release of copper, the fate of the particles during dermal contact, and the copper exposure level to children from hand-to-mouth transfer. For the current study, three treated lumber products, two micronized copper and one ionic copper, were purchased from commercial retailers. The boards were left to weather outdoors for approximately 1year. Over the year time period, hand wipe samples were collected periodically to determine copper transfer from the wood surfaces. The two micronized formulations and the ionic formulation released similar levels of total copper. The amount of copper released was high initially, but decreased to a constant level (~1.5mgm(-2)) after the first month of outdoor exposure. Copper particles were identified on the sampling cloths during the first two months of the experiment, after which the levels of copper were insufficient to collect interpretable data. After 1month, the particles exhibited minimal changes in shape and size. At the end of 2-months, significant deterioration of the particles was evident. Based on the wipe sample data, a playground visit may result in a potential exposure to 2.58mg of copper, which is near or exceeds the daily tolerable upper intake limits for children under the age of 8, if completely ingested through hand-to-mouth transfer. While nanoparticles were found, there is not enough information to estimate the exposure from the released particles due to a lack of published literature on copper carbonate.

  1. Widespread Surface Weathering on Early Mars: possible implication on the Past Climate

    NASA Astrophysics Data System (ADS)

    Loizeau, Damien; Carter, John; Mangold, Nicolas; Poulet, François; Rossi, Angelo P.; Allemand, Pascal; Lozac'h, Loïc; Quantin, Cathy; Bibring, Jean-Pierre

    2015-04-01

    The recent discovery of widespread hydrous clays on Mars with OMEGA/Mars Express and CRISM/MRO indicates that diverse and widespread aqueous environments existed on Mars, from the surface to kilometric depths [1, 2]. The study of the past habitability and past climates of the planet requires assessing the importance of sustained surface water vs. subsurface water in its aqueous history. Vertical sequences of Al-rich clays on top of Fe/Mg-rich clays in the top tens of meters of the surface are identified on Mars [3-6] (see figure 1) and interpreted as possible weathering profiles, similar to cases of pedogenesis on Earth (e.g. [7, 8]). A global study of these clay sequences has recently been published by Carter et al. [9]. This following work presents detailed geological analysis, performed for each identified candidate, in order to constrain their age and origin. With the increasing availability of CTX and HiRISE stereoimages, we investigate the thickness of the altered sequences, the age of the altered units and the different geological contexts to further understand the weathering process(es), and their possible implication on the past climate. The types of geologic settings where the interpreted weathering profiles are observed are much varied: from basin floor to plateaus, in apparent massive rocks to finely layered rocks. Besides, the number and variety of sequences is/was likely larger. However, in term of chronology, the alteration seems to have stopped in a relatively limited period of time for the studied cases, between 3.8 and 3.6 Ga. This would point to a formation due to a global process that enabled liquid water at the surface and pedogenesis in various regions, on various terrains, from late Noachian to early Hesperian. This global process would imply regular, widely distributed ice or precipitations in large regions of Mars at that time. If weathering occurred before that time, during the early or middle Noachian, the sequences may have been erased

  2. Optimization of Ionic Liquid Based Simultaneous Ultrasonic- and Microwave-Assisted Extraction of Rutin and Quercetin from Leaves of Velvetleaf (Abutilon theophrasti) by Response Surface Methodology

    PubMed Central

    Zhao, Chunjian; Lu, Zhicheng; He, Xin; Li, Zhao; Shi, Kunming; Yang, Lei; Fu, Yujie; Zu, Yuangang

    2014-01-01

    An ionic liquids based simultaneous ultrasonic and microwave assisted extraction (ILs-UMAE) method has been proposed for the extraction of rutin (RU), quercetin (QU), from velvetleaf leaves. The influential parameters of the ILs-UMAE were optimized by the single factor and the central composite design (CCD) experiments. A 2.00 M 1-butyl-3-methylimidazolium bromide ([C4mim]Br) was used as the experimental ionic liquid, extraction temperature 60°C, extraction time 12 min, liquid-solid ratio 32 mL/g, microwave power of 534 W, and a fixed ultrasonic power of 50 W. Compared to conventional heating reflux extraction (HRE), the RU and QU extraction yields obtained by ILs-UMAE were, respectively, 5.49 mg/g and 0.27 mg/g, which increased, respectively, 2.01-fold and 2.34-fold with the recoveries that were in the range of 97.62–102.36% for RU and 97.33–102.21% for QU with RSDs lower than 3.2% under the optimized UMAE conditions. In addition, the shorter extraction time was used in ILs-UMAE, compared with HRE. Therefore, ILs-UMAE was a rapid and an efficient method for the extraction of RU and QU from the leaves of velvetleaf. PMID:25243207

  3. Modeling of ionic liquids

    NASA Astrophysics Data System (ADS)

    Tatlipinar, Hasan

    2017-02-01

    Ionic liquids are very important entry to industry and technology. Because of their unique properties they may classified as a new class of materials. IL usually classified as a high temperature ionic liquids (HTIL) and room temperature ionic liquids (RTIL). HTIL are molten salts. There are many research studies on molten salts such as recycling, new energy sources, rare elements mining. RTIL recently become very important in daily life industry because of their "green chemistry" properties. As a simple view ionic liquids consist of one positively charged and one negatively charged components. Because of their Coulombic or dispersive interactions the local structure of ionic liquids emerges. In this presentation the local structural properties of the HTIL are discussed via correlation functions and integral equation theories. RTIL are much more difficult to do modeling, but still general consideration for the modeling of the HTIL is valid also for the RTIL.

  4. Potentiostat for Characterizing Microstructures at Ionic Liquid/Electrode Interfaces

    DTIC Science & Technology

    2015-10-10

    systems via simultaneous electrochemical and spectroscopic studies. These data are pertinent to understanding the microscopic (molecular and ionic...characterize ionic liquid-based (IL-based) electrolyte systems via simultaneous electrochemical and spectroscopic studies. These data are pertinent to...spectrometer to perform surface enhanced infrared absorption (SEIRA) spectroscopy with electrochemical control. The multichannel instrument has also

  5. Employing ionic liquids to deposit cellulose on PET fibers.

    PubMed

    Textor, Torsten; Derksen, Leonie; Gutmann, Jochen S

    2016-08-01

    Several ionic liquids are excellent solvents for cellulose. Starting from that finishing of PET fabrics with cellulose dissolved in ionic liquids like 1-ethyl-3-methyl imidazolium acetate, diethylphosphate and chloride, or the chloride of butyl-methyl imidazolium has been investigated. Finishing has been carried out from solutions of different concentrations, using microcrystalline cellulose or cotton and by employing different cross-linkers. Viscosity of solutions has been investigated for different ionic liquids, concentrations, cellulose sources, linkers and temperatures. Since ionic liquids exhibit no vapor pressure, simple pad-dry-cure processes are excluded. Before drying the ionic liquid has to be removed by a rinsing step. Accordingly rinsing with fresh ionic liquid followed by water or the direct rinsing with water have been tested. The amount of cellulose deposited has been investigated by gravimetry, zinc chloride iodine test as well as reactive dyeing. Results concerning wettability, water up-take, surface resistance, wear-resistance or washing stability are presented.

  6. Tuning Hydrated Nanoceria Surfaces: Experimental/Theoretical Investigations of Ion Exchange and Implications in Organic and Inorganic Interactions

    PubMed Central

    Vincent, Abhilash; Inerbaev, Talgat M.; Babu, Suresh; Karakoti, Ajay S.; Self, William T.; Masunov, Artëm E.; Seal, Sudipta

    2010-01-01

    Long term stability and surface properties of colloidal nanoparticles have significance in many applications. Here, surface charge modified hydrated cerium oxide nanoparticles (CNPs, also known as nanoceria) are synthesized and their dynamic ion exchange interactions with the surrounding medium are investigated in detail. Time dependent Zeta (ζ) potential (ZP) variations of CNPs are demonstrated as a useful characteristic for optimizing their surface properties. The surface charge reversal of CNPs observed with respect to time, concentration, temperature and doping is correlated to the surface modification of CNPs in aqueous solution and the ion exchange reaction between the surface protons (H+) and the neighboring hydroxyls ions (OH−). Using density functional theory (DFT) calculations, we have demonstrated that the adsorption of H+ ions on the CNP surface is kinetically more favorable while the adsorption of OH− ions on CNPs is thermodynamically more favorable. The importance of selecting CNPs with appropriate surface charges and the implications of dynamic surface charge variations are exemplified with applications in microelectronics and biomedical.\\ PMID:20131920

  7. The bounding-surfaces record of a barrier spit from Huangqihai Lake, North China: implications for coastal barrier boundary hierarchy

    NASA Astrophysics Data System (ADS)

    Shan, Xin; Yu, Xinghe; Clift, Peter D.; Wang, Tianyi; Tan, Chengpeng; Jin, Lina

    2016-09-01

    Ground-penetrating radar and trenching studies of a barrier spit on the north shore of Huangqihai Lake were made, that reveal important implications for the coastal washover barrier boundary hierarchy and interpretations of this depositional record. A four-fold hierarchy bounding-surface model, representing different levels of impact and genesis, is defined. Each level of the hierarchy is enclosed by a distinct kind of surface characterized by different ground-penetrating radar reflection features, sedimentary characteristics (color, grain size, sorting, rounding and sedimentary structures) and origin. We suggest that this hierarchical model can be applied to any coastal washover barrier deposits.

  8. On the implications of the Surface Water and Ocean Topography (SWOT) mission for hydrologic science and applications (Invited)

    NASA Astrophysics Data System (ADS)

    Lettenmaier, D. P.

    2010-12-01

    The SWOT mission will provide surface water elevation and extent information with unprecedented accuracy and spatial resolution globally. All of the implications of thedata that SWOT will produce for the hydrologic science and applications communities are not yet apparent. The SWOT data will, however, certainly offer groundbreaking opportunities for estimation of two key terms in the land surface water budget: surface water storage (in almost all water bodies with surface area exceeding about 1 km2) and derived discharge for many of the world’s large rivers (widths greater than roughly 100-250 m). Among just a few of the science questions that the observations should allow us to address are a) what are the dynamics of floods and overbank flows in large rivers? b) what is the contribution of long-term, seasonal, and interannual storage in reservoirs, lakes, and wetlands to sea level? c) what is the magnitude of surface water storage changes at seasonal to decadal time scales and continental spatial scales relative to soil moisture and groundwater? d) what will be the implications of SWOT-based estimates of reservoir storage and storage change to the management of transboundary rivers? These quite likely are among just a few of the questions that SWOT will help elucidate. Others no doubt will arise from creative analyses of SWOT data in combination with data from other missions I conclude with a discussion of mechanisms that will help foster a community to investigate these and other questions, and the implications of a SWOT data policy.

  9. 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.

  10. Mantle viscosity stratification and flow geometry - Implications for surface motions on earth and Venus

    NASA Technical Reports Server (NTRS)

    Kiefer, Walter S.

    1993-01-01

    For a fixed heat flow, the surface flow velocity of a convecting layer is not strongly sensitive to the variation of viscosity as a function of depth. Thus, the inferred absence of a low viscosity asthenosphere on Venus can not account for the limited surface motions there. The surface velocity is dependent on the convective geometry. Cartesian geometry convection can produce large surface velocities if the high viscosity surface layer is broken in places by weak zones. On the other hand, a high viscosity surface layer may inhibit the development of large surface velocities in axisymmetric convection.

  11. Effects of surface roughening of Nafion 117 on the mechanical and physicochemical properties of ionic polymer-metal composite (IPMC) actuators

    NASA Astrophysics Data System (ADS)

    Wang, Yanjie; Zhu, Zicai; Liu, Jiayu; Chang, Longfei; Chen, Hualing

    2016-08-01

    In this paper, the surface of a Nafion membrane was roughened by the sandblasting method, mainly considering the change of sandblasting time and powder size. The roughened surfaces were characterized in terms of their topography from the confocal laser scanning microscope (CLSM) and SEM. The key surface parameters, such as Sa (the arithmetical mean deviation of the specified surface profile), SSA (the surface area ratio before and after roughening) and the area measurement on the histogram from the CLSM images, were extracted and evaluated from the roughened membranes. Also, the detailed change in surface and interfacial electrodes were measured and discussed together with the surface resistance, equivalent modulus, capacitance and performances of IPMC actuators based on the roughened membranes. The results show that a suitable sandblasting condition, resulting in the decrease in the bending stiffness and the increase in the interface area closely related to the capacitance, can effectively increase the electromechanical responses of IPMCs. Although the surface roughening by sandblasting caused a considerable lowering of mechanical strength, it was very effective for enlarging the interfacial area between Nafion membrane and the electrode layers, and for forming a penetrated electrode structure, which facilitated improvement of the surface resistance and capacitance characteristics of IPMCs. In this work, a quantitative relationship was built between the topography of Nafion membrane surface and electromechanical performance of IPMCs by means of sandblasting.

  12. Study on analysis of ionic wind for heat transfer enhancement .

    NASA Astrophysics Data System (ADS)

    Ko, Han Seo; Shin, Dong Ho

    2016-11-01

    Local heat transfer technology was investigated using ionic wind generation in this study. Characteristics of ionic wind using wire and plate electrodes were studied by experimental and numerical methods. A particle image velocitimetry (PIV) test was conducted for a study of a boundary layer controlled by the ionic wind on the heated surface in the wind tunnel. It was found that the coulombic force consistently acted on the surface to reduce the effect of the viscous boundary layer. The boundary layer was formed on the heated surface and controlled by the ionic wind regardless of the Reynolds number of the bulk flow. The heat transfer coefficient increased and decreased, 11% and 19% in average on the heated surface by the ionic wind, for the condition of lower (100 200) and higher (2500 3500) Reynolds numbers of the bulk flow, respectively. It was concluded that the ionic wind can be used for enhancing the convection heat transfer rate or insulating the local surface according to its operating condition. The results of the local heat transfer controlled by the ionic wind were applied for the heat exchanger and the performance was confirmed by the experimental and numerical methods.

  13. Ionic Liquid-Based Microemulsions in Catalysis

    PubMed Central

    2016-01-01

    The design and properties of surface-active ionic liquids that are able to form stable microemulsions with heptane and water are presented, and their promise as reaction media for thermomorphic palladium-catalyzed cross-coupling reactions is demonstrated. PMID:27978714

  14. Ionic electrostatic excitations along biological membranes

    NASA Astrophysics Data System (ADS)

    Moradi, Afshin

    2011-02-01

    A theoretical analysis of ionic electrostatic excitations of a charged biological membrane is presented within the framework of the fluid theory for surface ions inside and outside the cell, in conjunction with the Poisson's equation. General expressions of dispersion relations are obtained for electrostatic oscillations of intrinsic cellular with different shapes and symmetries.

  15. Micro-porous surfaces in controlled drug delivery systems: design and evaluation of diltiazem hydrochloride controlled porosity osmotic pump using non-ionic surfactants as pore-former.

    PubMed

    Adibkia, Khosro; Ghanbarzadeh, Saeed; Shokri, Mohammad Hosein; Arami, Zahra; Arash, Zeinab; Shokri, Javad

    2014-06-01

    The major problem associated with conventional drug delivery systems is unpredictable plasma concentrations. The aim of this study was to design a controlled porosity osmotic pump (CPOP) of diltiazem hydrochloride to deliver the drug in a controlled manner. CPOP tablets were prepared by incorporation of drug in the core and subsequent coating with cellulose acetate as semi-permeable membrane. Non-ionic surfactants were applied as pore-formers as well. The effect of pore-formers concentration on the in vitro release of diltiazem was also studied. The formulations were compared based on four comparative parameters, namely, total drug released after 24 h (D24 h), lag-time (tL), squared correlation coefficient of zero order equation (RSQzero) and mean percent deviation from zero order kinetic (MPDzero). Results of scanning electron microscopy studies exhibited formation of pores in the membrane from where the drug release occurred. It was revealed that drug release rate was directly proportional to the concentration of the pore-formers. The value of D24 h in the formulations containing Tween 80 (10%) and Brij 35 (5%) were found to be more than 94.9%, and drug release followed zero order kinetic (RSQzero > 0.99 and MPDzero < 8%) with acceptable tL (lower than 1 h).

  16. Unravelling nanoconfined films of ionic liquids

    SciTech Connect

    Lee, Alpha A.; Vella, Dominic; Goriely, Alain; Perkin, Susan

    2014-09-07

    The confinement of an ionic liquid between charged solid surfaces is treated using an exactly solvable 1D Coulomb gas model. The theory highlights the importance of two dimensionless parameters: the fugacity of the ionic liquid, and the electrostatic interaction energy of ions at closest approach, in determining how the disjoining pressure exerted on the walls depends on the geometrical confinement. Our theory reveals that thermodynamic fluctuations play a vital role in the “squeezing out” of charged layers as the confinement is increased. The model shows good qualitative agreement with previous experimental data, with all parameters independently estimated without fitting.

  17. Are Ionic Liquids Chemically Stable?

    PubMed

    Wang, Binshen; Qin, Li; Mu, Tiancheng; Xue, Zhimin; Gao, Guohua

    2017-02-27

    Ionic liquids have attracted a great deal of interest in recent years, illustrated by their applications in a variety of areas involved with chemistry, physics, biology, and engineering. Usually, the stabilities of ionic liquids are highlighted as one of their outstanding advantages. However, are ionic liquids really stable in all cases? This review covers the chemical stabilities of ionic liquids. It focuses on the reactivity of the most popular imidazolium ionic liquids at structural positions, including C2 position, N1 and N3 positions, and C4 and C5 positions, and decomposition on the imidazolium ring. Additionally, we discuss decomposition of quaternary ammonium and phosphonium ionic liquids and hydrolysis and nucleophilic reactions of anions of ionic liquids. The review aims to arouse caution on potential decomposition of ionic liquids and provides a guide for better utilization of ionic liquids.

  18. The action of alcohols and other non-ionic surface active substances on the sodium current of the squid giant axon.

    PubMed Central

    Haydon, D A; Urban, B W

    1983-01-01

    The effects of several n-alkanols and n-alkyl oxyethylene alcohols, methyl octanoate, glycerol 1-monooctanoate and dioctanoyl phosphatidylcholine on the ionic currents and electrical capacity of the squid giant axon membrane have been examined. The peak inward current in voltage-clamped axons was reduced reversibly by each substance. For n-pentanol to n-decanol the concentrations required to suppress the peak inward current by 50% were determined. From these data, it was estimated that the standard free energy per CH2 for adsorption to the site of action was -3.04 kJ mole-1, as compared with -3.11 kJ mole-1 for adsorption into phospholipid bilayers or an n-alkane/aqueous solution interface. The membrane capacity at 100 kHz was not greatly by any of the test substances at concentrations which reduced the inward current by 50%. Na currents under voltage clamp were recorded in intracellularly perfused axons before, during and sometimes after exposure to the test substances and the records were fitted with equations similar to those proposed by Hodgkin & Huxley (1952). Shifts in the curves of the steady-state activation and inactivation parameters (m infinity and h infinity) against membrane potential, changes in the peak heights of the activation and inactivation time constants (tau m and tau h) and reductions in the maximum Na conductance (gNa) have been tabulated. All of the test substances shifted the voltage dependence of the steady-state activation in the depolarizing direction and lowered the peak time constants for both activation and inactivation. The origins of these effects, and of the differences in the present results from those of the hydrocarbons (Haydon & Urban, 1983), have been discussed in terms of the physico-chemical properties of the two groups of substances and with reference to their effects on artificial membranes. PMID:6312030

  19. Reactive uptake of ozone at simulated leaf surfaces: Implications for 'non-stomatal' ozone flux

    NASA Astrophysics Data System (ADS)

    Cape, J. Neil; Hamilton, Richard; Heal, Mathew R.

    The reaction of ozone (O 3) with α-pinene has been studied as a function of temperature and relative humidity and in the presence of wax surfaces that simulate a leaf surface. The objective was to determine whether the presence of a wax surface, in which α-pinene could dissolve and form a high surface concentration, would lead to enhanced reaction with O 3. The reaction of O 3 itself with the empty stainless steel reactor and with aluminium and wax surfaces demonstrated an apparent activation energy of around 30 kJ mol -1 for all the surfaces, similar to that observed in long-term field measurements of O 3 fluxes to vegetation. However, the absolute reaction rate was 14 times greater for aluminium foil and saturated hydrocarbon wax surfaces than for stainless steel, and a further 5 times greater for beeswax than hydrocarbon wax. There was no systematic dependence on either relative or absolute humidity for these surface reactions over the range studied (20-100% RH). Reaction of O 3 with α-pinene occurred at rates close to those predicted for the homogeneous gas-phase reaction, and was similar for both the empty reactor and in the presence of wax surfaces. The hypothesis of enhanced reaction at leaf surfaces caused by enhanced surface concentrations of α-pinene was therefore rejected. Comparison of surface decomposition reactions on different surfaces as reported in the literature with the results obtained here demonstrates that the loss of ozone at the earth's surface by decomposition to molecular oxygen (i.e. without oxidative reaction with a substrate) can account for measured 'non-stomatal' deposition velocities of a few mm s -1. In order to quantify such removal, the effective molecular surface area of the vegetation/soil canopy must be known. Such knowledge, combined with the observed temperature-dependence, provides necessary input to global-scale models of O 3 removal from the troposphere at the earth's surface.

  20. Ionic Liquid Ordering at an Oxide Surface†

    PubMed Central

    Wagstaffe, Michael; Jackman, Mark J.; Syres, Karen L.; Generalov, Alexander

    2016-01-01

    Abstract The interaction of the ionic liquid [C4C1Im][BF4] with anatase TiO2, a model photoanode material, has been studied using a combination of synchrotron radiation photoelectron spectroscopy and near‐edge X‐ray absorption fine structure spectroscopy. The system is of interest as a model for fundamental electrolyte–electrode and dye‐sensitized solar cells. The initial interaction involves degradation of the [BF4]− anion, resulting in incorporation of F into O vacancies in the anatase surface. At low coverages, [C4C1Im][BF4] is found to order at the anatase(101) surface via electrostatic attraction, with the imidazolium ring oriented 32±4° from the anatase TiO2 surface. As the coverage of ionic liquid increases, the influence of the oxide surface on the topmost layers is reduced and the ordering is lost. PMID:27458919

  1. Surface-attached cells, biofilms and biocide susceptibility: implications for hospital cleaning and disinfection.

    PubMed

    Otter, J A; Vickery, K; Walker, J T; deLancey Pulcini, E; Stoodley, P; Goldenberg, S D; Salkeld, J A G; Chewins, J; Yezli, S; Edgeworth, J D

    2015-01-01

    Microbes tend to attach to available surfaces and readily form biofilms, which is problematic in healthcare settings. Biofilms are traditionally associated with wet or damp surfaces such as indwelling medical devices and tubing on medical equipment. However, microbes can survive for extended periods in a desiccated state on dry hospital surfaces, and biofilms have recently been discovered on dry hospital surfaces. Microbes attached to surfaces and in biofilms are less susceptible to biocides, antibiotics and physical stress. Thus, surface attachment and/or biofilm formation may explain how vegetative bacteria can survive on surfaces for weeks to months (or more), interfere with attempts to recover microbes through environmental sampling, and provide a mixed bacterial population for the horizontal transfer of resistance genes. The capacity of existing detergent formulations and disinfectants to disrupt biofilms may have an important and previously unrecognized role in determining their effectiveness in the field, which should be reflected in testing standards. There is a need for further research to elucidate the nature and physiology of microbes on dry hospital surfaces, specifically the prevalence and composition of biofilms. This will inform new approaches to hospital cleaning and disinfection, including novel surfaces that reduce microbial attachment and improve microbial detachment, and methods to augment the activity of biocides against surface-attached microbes such as bacteriophages and antimicrobial peptides. Future strategies to address environmental contamination on hospital surfaces should consider the presence of microbes attached to surfaces, including biofilms.

  2. Chemistry of Frozen NaCl and MgSO4 Brines - Implications for Surface Expression of Europa's Ocean Composition

    NASA Astrophysics Data System (ADS)

    Johnson, P. V.; Hodyss, R. P.; Choukroun, M.; Vu, T. H.

    2015-12-01

    The composition of Europa's subsurface ocean is a critical determinant of its habitability, but current analysis of the ocean composition is limited to its expression on the Europan surface. While there is observational evidence indicating that ocean materials make their way to the surface, our understanding of the chemical processes that can alter this material under Europan surface conditions is limited. We present experimental data on the chemistry of mixed solutions of NaCl and MgSO4 as they are frozen to 100 K, replicating the conditions that may occur when subsurface ocean fluids are emplaced onto Europa's surface. Confocal micro-Raman spectroscopy is used to study the formation of salts during the freezing process, and the interaction of ions in the frozen brines. Our data indicate that mixed aqueous solutions of NaCl and MgSO4 form Na2SO4 and MgCl2 preferentially when frozen, rather than making NaCl and MgSO4 precipitates. The detection of epsomite (MgSO4Ÿ•7H2O) on Europa's surface may therefore imply an ocean composition relatively low in sodium, unless radiolytic chemistry converts MgCl2 to MgSO4 as suggested by Hand and Brown 2013 (ApJ 145 110). These results have important implications for the interpretation of remote sensing data of Europa's surface.

  3. Water Contaminant Mitigation in Ionic Liquid Propellant

    NASA Technical Reports Server (NTRS)

    Conroy, David; Ziemer, John

    2009-01-01

    Appropriate system and operational requirements are needed in order to ensure mission success without unnecessary cost. Purity requirements applied to thruster propellants may flow down to materials and operations as well as the propellant preparation itself. Colloid electrospray thrusters function by applying a large potential to a room temperature liquid propellant (such as an ionic liquid), inducing formation of a Taylor cone. Ions and droplets are ejected from the Taylor cone and accelerated through a strong electric field. Electrospray thrusters are highly efficient, precise, scaleable, and demonstrate low thrust noise. Ionic liquid propellants have excellent properties for use as electrospray propellants, but can be hampered by impurities, owing to their solvent capabilities. Of foremost concern is the water content, which can result from exposure to atmosphere. Even hydrophobic ionic liquids have been shown to absorb water from the air. In order to mitigate the risks of bubble formation in feed systems caused by water content of the ionic liquid propellant, physical properties of the ionic liquid EMI-Im are analyzed. The effects of surface tension, material wetting, physisorption, and geometric details of the flow manifold and electrospray emitters are explored. Results are compared to laboratory test data.

  4. The Development of Surface Roughness and Implications for Cellular Attachment in Biomedical Applications

    NASA Technical Reports Server (NTRS)

    Banks, Bruce; Miller, Sharon; deGroh, Kim; Chan, Amy; Sahota, Mandeep

    2001-01-01

    The application of a microscopic surface texture produced by ion beam sputter texturing to the surfaces of polymer implants has been shown to result in significant increases in cellular attachment compared to smooth surface implants in animal studies. A collaborative program between NASA Glenn Research Center and the Cleveland Clinic Foundation has been established to evaluate the potential for improving osteoblast attachment to surfaces that have been microscopically roughened by atomic oxygen texturing. The range of surface textures that are feasible depends upon both the texturing process and the duration of treatment. To determine whether surface texture saturates or continues to increase with treatment duration, an effort was conducted to examine the development of surface textures produced by various physical and chemical erosion processes. Both experimental tests and computational modeling were performed to explore the growth of surface texture with treatment time. Surface texturing by means of abrasive grit blasting of glass, stainless steel, and polymethylmethacry I ate surfaces was examined to measure the growth in roughness with grit blasting duration by surface profilometry measurements. Laboratory tests and computational modeling was also conducted to examine the development of texture on Aclar(R) (chlorotfifluoroethylene) and Kapton(R) polyimide, respectively. For the atomic oxygen texturing tests of Aclar(R), atomic force microscopy was used to measure the development of texture with atomic oxygen fluence. The results of all the testing and computational modeling support the premise that development of surface roughness obeys Poisson statistics. The results indicate that surface roughness does not saturate but increases as the square root of the treatment time.

  5. Stretchable, transparent, ionic conductors.

    PubMed

    Keplinger, Christoph; Sun, Jeong-Yun; Foo, Choon Chiang; Rothemund, Philipp; Whitesides, George M; Suo, Zhigang

    2013-08-30

    Existing stretchable, transparent conductors are mostly electronic conductors. They limit the performance of interconnects, sensors, and actuators as components of stretchable electronics and soft machines. We describe a class of devices enabled by ionic conductors that are highly stretchable, fully transparent to light of all colors, and capable of operation at frequencies beyond 10 kilohertz and voltages above 10 kilovolts. We demonstrate a transparent actuator that can generate large strains and a transparent loudspeaker that produces sound over the entire audible range. The electromechanical transduction is achieved without electrochemical reaction. The ionic conductors have higher resistivity than many electronic conductors; however, when large stretchability and high transmittance are required, the ionic conductors have lower sheet resistance than all existing electronic conductors.

  6. Importance of bulk states for the electronic structure of semiconductor surfaces: implications for finite slabs

    NASA Astrophysics Data System (ADS)

    Sagisaka, Keisuke; Nara, Jun; Bowler, David

    2017-04-01

    We investigate the influence of slab thickness on the electronic structure of the Si(1 0 0)- p(2× 2 ) surface in density functional theory (DFT) calculations, considering both density of states and band structure. Our calculations, with slab thicknesses of up to 78 atomic layers, reveal that the slab thickness profoundly affects the surface band structure, particularly the dangling bond states of the silicon dimers near the Fermi level. We find that, to precisely reproduce the surface bands, the slab thickness needs to be large enough to completely converge the bulk bands in the slab. In the case of the Si(1 0 0) surface, the dispersion features of the surface bands, such as the band shape and width, converge when the slab thickness is larger than 30 layers. Complete convergence of both the surface and bulk bands in the slab is only achieved when the slab thickness is greater than 60 layers.

  7. Polymerizable ionic liquid crystals.

    PubMed

    Jazkewitsch, Olga; Ritter, Helmut

    2009-09-17

    Polymerizable vinylimidazolium ionic liquids (ILs) that contain mesogenic coumarin and biphenyl units, respectively, have been synthesized. The N-alkylation of N-vinylimidazole with bromoalkylated mesogenic units 7-(6-bromohexyloxy)coumarin (1) and 4,4'-bis(6-bromohexyloxy)biphenyl (2) was then carried out. The thermal behavior of the obtained ILs 3 and 4 was investigated by differential scanning calorimetry and polarizing optical microscopy. These measurements showed that the attached mesogenic units induce the self-assembly of ILs and, therefore, the occurrence of liquid crystalline phases. Subsequently, the ionic liquid crystals (ILCs) 3 and 4 were polymerized by a free-radical mechanism.

  8. Communication: Salt-induced water orientation at a surface of non-ionic surfactant in relation to a mechanism of Hofmeister effect

    SciTech Connect

    Hishida, Mafumi; Kaneko, Yohei; Okuno, Masanari; Yamamura, Yasuhisa; Ishibashi, Taka-aki; Saito, Kazuya

    2015-05-07

    The behavior of water molecules at the surface of nonionic surfactant (monomyristolein) and effects of monovalent ions on the behavior are investigated using the heterodyne-detected vibrational sum frequency generation spectroscopy. It is found that water molecules at the surface are oriented with their hydrogen atoms pointing to the bulk, and that the degree of orientation depends on the anion strongly but weakly on the cation. With measured surface potentials in those saline solutions, it is concluded that the heterogeneous distribution of anions and cations in combination with the nonionic surfactant causes the water orientation. This heterogeneous distribution well explains the contrasting order of anions and cations with respect to the ion size in the Hofmeister series.

  9. Ionic liquids in chemical engineering.

    PubMed

    Werner, Sebastian; Haumann, Marco; Wasserscheid, Peter

    2010-01-01

    The development of engineering applications with ionic liquids stretches back to the mid-1990s when the first examples of continuous catalytic processes using ionic liquids and the first studies of ionic liquid-based extractions were published. Ever since, the use of ionic liquids has seen tremendous progress in many fields of chemistry and engineering, and the first commercial applications have been reported. The main driver for ionic liquid engineering applications is to make practical use of their unique property profiles, which are the result of a complex interplay of coulombic, hydrogen bonding and van der Waals interactions. Remarkably, many ionic liquid properties can be tuned in a wide range by structural modifications at their cation and anion. This review highlights specific examples of ionic liquid applications in catalysis and in separation technologies. Additionally, the application of ionic liquids as working fluids in process machines is introduced.

  10. Modifications of microvascular EC surface modulate phototoxicity of a porphycene anti-ICAM-1 immunoconjugate; therapeutic implications

    PubMed Central

    Rosàs, Elisabet; Santomá, Pablo; Duran-Frigola, Miquel; Hernandez, Bryan; Llinàs, Maria C.; Ruiz-González, Rubén; Nonell, Santi; Sánchez-García, David; Edelman, Elazer R.; Balcells, Mercedes

    2013-01-01

    Inflammation and shear stress can upregulate expression of cellular adhesion molecules in endothelial cells (EC). The modified EC surface becomes a mediating interface between the circulating blood elements and the endothelium, and grants opportunity for immunotherapy. In photodynamic therapy (PDT), immunotargeting might overcome the lack of selectivity of currently used sensitizers. In this study, we hypothesized that differential ICAM-1 expression modulates the effects of a drug targeted to surface ICAM-1. A novel porphycene-anti-ICAM-1 conjugate was synthesized and applied to treat endothelial cells from macro and microvasculature. Results show that the conjugate induces phototoxicity in inflamed, but not in healthy, microvascular EC. Conversely, macrovascular EC exhibited phototoxicity regardless of their state. These findings have two major implications; the relevance of ICAM-1 as a modulator of drug effects in microvasculature, and the potential of the porphycene bioconjugate as a promising novel PDT agent. PMID:23844929

  11. Effect of protic ionic liquid nanostructure on phospholipid vesicle formation.

    PubMed

    Bryant, Saffron J; Wood, Kathleen; Atkin, Rob; Warr, Gregory G

    2017-02-15

    The formation of bilayer-based lyotropic liquid crystals and vesicle dispersions by phospholipids in a range of protic ionic liquids has been investigated by polarizing optical microscopy using isothermal penetration scans, differential scanning calorimetry, and small angle X-ray and neutron scattering. The stability and structure of both lamellar phases and vesicle dispersions is found to depend primarily on the underlying amphiphilic nanostructure of the ionic liquid itself. This finding has significant implications for the use of ionic liquids in soft and biological materials and for biopreservation, and demonstrates how vesicle structure and properties can be controlled through selection of cation and anion. For a given ionic liquid, systematic trends in bilayer thickness, chain-melting temperature and enthalpy increase with phospholipid acyl chain length, paralleling behaviour in aqueous systems.

  12. Models of Martian Hydrothermal Circulation and Ice Melt with Implications for Surface Feature Formation

    NASA Astrophysics Data System (ADS)

    Craft, K. L.; Lowell, R. P.; Kraal, E.

    2011-03-01

    Here we investigate the amount of fluid provided to the martian surface by dike- and sill-driven hydrothermal systems with overlying ice layers. The resulting fluid flow rates are then compared to model estimates for formation of surface features on Mars.

  13. Implications of surface noise for the motional coherence of trapped ions

    NASA Astrophysics Data System (ADS)

    Talukdar, I.; Gorman, D. J.; Daniilidis, N.; Schindler, P.; Ebadi, S.; Kaufmann, H.; Zhang, T.; Häffner, H.

    2016-04-01

    Electric noise from metallic surfaces is a major obstacle towards quantum applications with trapped ions due to motional heating of the ions. Here, we discuss how the same noise source can also lead to pure dephasing of motional quantum states. The mechanism is particularly relevant at small ion-surface distances, thus imposing a constraint on trap miniaturization. By means of a free induction decay experiment, we measure the dephasing time of the motion of a single ion trapped 50 μ m above a Cu-Al surface. From the dephasing times we extract the integrated noise below the secular frequency of the ion. We find that none of the most commonly discussed surface noise models for ion traps describes both the observed heating as well as the measured dephasing satisfactorily. Thus, our measurements provide a benchmark for future models for the electric noise emitted by metallic surfaces.

  14. Ceres: predictions for near-surface water ice stability and implications for plume generating processes

    USGS Publications Warehouse

    Titus, Timothy N.

    2015-01-01

    This paper will constrain the possible sources and processes for the formation of recently observed H2O vapor plumes above the surface of the dwarf planet Ceres. Two hypotheses have been proposed: (1) cryovolcanism where the water source is the mantle and the heating source is still unknown or (2) comet-like sublimation where near-surface water ice is vaporized by seasonally increasing solar insolation. We test hypothesis #2, comet-like near-surface sublimation, by using a thermal model to examine the stability of water-ice in the near surface. For a reasonable range of physical parameters (thermal inertia, surface roughness, slopes), we find that water ice is only stable at latitudes higher than ~40-60 degrees. These results indicate that either (a) the physical properties of Ceres are unlike our expectations or (b) an alternative to comet-like sublimation, such as the cryovolcanism hypothesis, must be invoked.

  15. Effects of Film Elasticity and Surface Forces on the Stability of Foams and Lamellae Films in the Presence of Non-ionic Surfactants

    NASA Astrophysics Data System (ADS)

    Wang, Liguang; Yoon, Roe-Hoan

    2008-07-01

    This paper describes the basic factors affecting the stability of the foam films produced in the presence of nonionic surfactants such as n-pentanol, n-octanol, methyl isobutyl carbinol (MIBC), and polypropylene glycol (PPG). We used a model developed by Wang and Yoon (Colloids and Surfaces A: Physicochem. Eng. Aspects 282-283, 84-91 (2006)) to calculate the Gibbs elasticity of the lamellae films. In addition, we used the thin film pressure balance (TFPB) technique to measure film thicknesses. The results were used to determine the disjoining pressures in the thin lamellae (foam) films formed between air bubbles, which are relevant forces governing the final drainage stage of foam films before reaching either equilibrium or rupture. The film elasticity and surface forces data were then compared with the foam stabilities measured in the present work in the presence of the various surfactants. It was found that foam stabilities are controlled both by film elasticity and by surface forces, the relative contributions of each changing with surfactant type and concentration. In general, surface forces play a more important role at relatively low surfactant concentrations, while elasticity plays a more important role at higher concentrations. At the surfactant additions usually employed in the mining industry, MIBC stabilizes foams by increasing disjoining pressures, while PPG-400 stabilizes foams by increasing film elasticity.

  16. Ionic Structure at Dielectric Interfaces

    NASA Astrophysics Data System (ADS)

    Jing, Yufei

    interfaces using molecular dynamics(MD) simulations and compared it with liquid state theory result. We explore the effects of high electrolyte concentrations, multivalent ions, and dielectric contrasts on the ionic distributions. We observe the presence of non-monotonous ionic density profiles leading to structure deformation in the fluid which is attributed to the competition between electrostatic and steric (entropic) interactions. We find that thermal forces that arise from symmetry breaking at the interfaces can have a profound effect on the ionic structure and can oftentimes overwhelm the influence of dielectric discontinuity. The combined effect of ionic correlations and inhomogeneous dielectric permittivity significantly changes the character of effective interaction between two interfaces. We show that, in concentrated electrolytes with confinement, it is imperative to take into account the finite-size of the ions as well as proper description of electrostatic interactions in heterogeneous media, which is not fully fulfilled by Poisson-Boltzmann based approaches. The effect of electric field at interface between two immiscible electrolyte solutions is studied as well. The classical Poisson-Boltzmann theory has been widely used to describe the corresponding ionic distribution, even though it neglects the polarization and ion correlations typical of these charged systems. Using Monte Carlo simulations, we provide an enhanced description of an oil-water interface in the presence of an electric field without needing any adjustable parameter, including realistic ionic sizes, ion correlations, and image charges. Our data agree with experimental measurements of excess surface tension for a wide range of electrolyte concentrations of LiCl and TBATPB (tetrabutylammonium-tetraphenylborate), contrasting with the result of the classical non-linear Poisson-Boltzmann theory. More importantly, we show that the size-asymmetry between small Li+ and large Cl- ions can significantly

  17. Insolation and Resulting Surface Temperatures of Study Regions on the Moon and Implications for Mercury

    NASA Astrophysics Data System (ADS)

    Bauch, Karin E.; Hiesinger, Harald

    2010-05-01

    The imaging spectrometer MERTIS (Mercury Radiometer and Thermal Infrared Spectrometer) is part of the payload of ESA's BepiColombo mission, which is scheduled for launch in 2014 (Hiesinger et al., 2010). The instrument consists of an IR-spectrometer and radiometer, which observe the surface in the wavelength range of 7-14 and 7-40µm, respectively. The four scientific objectives are to a) study Mercury's surface composition, b) identify rock-forming minerals, c) globally map the surface mineralogy and d) study surface temperature and thermal inertia (Hiesinger et al., 2010; Helbert et al., 2005). Previous studies of the lunar surface have shown that thermal emission contributes to the observed signal from the surface and can influence the spectral characteristics, e.g. the depth of absorption bands (e.g. Clark, 2009; Pieters et al., 2009; Sunshine et al., 2009). Therefore accurate knowledge of the solar insolation and resulting thermal variations is needed. In order to calculate insolation and surface temperatures, we use a numerical model which has been described by Bauch et al. (2009). Surface temperatures are depending on the surface and subsurface bulk thermophysical properties, such as bulk density, heat capacity, thermal conductivity, emissivity, and albedo. Topography also influences surface temperatures, as it changes the angle of solar incidence, but also leads to shadowed areas, e.g. the floors of polar craters. The model solves the one-dimensional heat transfer equation, based on a depth and temperature dependent thermal inertia. The surface boundary condition is based on the energy balance relation; the energy entering a surface equals the energy leaving the surface. In addition to the direct solar insolation, reflectance and scattering from adjacent surface regions also influence the surface temperatures. In preparation of the MERTIS experiment, we performed detailed thermal models of the lunar surface, which we extrapolated to Mercury. For our

  18. Water organization between oppositely charged surfaces: Implications for protein sliding along DNA a)

    NASA Astrophysics Data System (ADS)

    Marcovitz, Amir; Naftaly, Aviv; Levy, Yaakov

    2015-02-01

    Water molecules are abundant in protein-DNA interfaces, especially in their nonspecific complexes. In this study, we investigated the organization and energetics of the interfacial water by simplifying the geometries of the proteins and the DNA to represent them as two equally and oppositely charged planar surfaces immersed in water. We found that the potential of mean force for bringing the two parallel surfaces into close proximity comprises energetic barriers whose properties strongly depend on the charge density of the surfaces. We demonstrated how the organization of the water molecules into discretized layers and the corresponding energetic barriers to dehydration can be modulated by the charge density on the surfaces, salt, and the structure of the surfaces. The 1-2 layers of ordered water are tightly bound to the charged surfaces representing the nonspecific protein-DNA complex. This suggests that water might mediate one-dimensional diffusion of proteins along DNA (sliding) by screening attractive electrostatic interactions between the positively charged molecular surface on the protein and the negatively charged DNA backbone and, in doing so, reduce intermolecular friction in a manner that smoothens the energetic landscape for sliding, and facilitates the 1D diffusion of the protein.

  19. Intensity of nightside MARSIS AIS surface reflections and implications for low-altitude ionospheric densities

    NASA Astrophysics Data System (ADS)

    Němec, F.; Morgan, D. D.; Diéval, C.; Gurnett, D. A.

    2015-04-01

    Spacecraft radar sounding signals at frequencies higher than the ionospheric peak plasma frequency are not reflected by the ionosphere. Instead, they make it to the ground where they are reflected by the planetary surface. We analyze the intensity of the surface reflections measured by the Mars Advanced Radar for Subsurface and Ionosphere Sounding (MARSIS) ionospheric radar sounder on board the Mars Express spacecraft. Apart from the surface reflectivity and the spacecraft altitude, the detected intensity of surface reflections is controlled primarily by the signal attenuation during the ionospheric propagation. We focus on the nightside region, where the ionospheric densities in the main layer are too low to cause a significant attenuation and allow sampling of the surface reflections at frequencies down to 3 MHz. The attenuation occurs mainly at altitudes below 100 km, where the electron-neutral collision frequency is a maximum. The intensity of surface reflections can thus serve as a proxy for electron densities at low altitudes not accessible by the direct ionospheric radar sounding. We analyze the intensity of surface reflections as a function of relevant controlling parameters. The intensity of surface reflections is lower at higher solar zenith angles on the nightside and during the periods of larger solar activity. Moreover, it exhibits a seasonal variation that is related to the dust storm occurrence. The intensity of surface reflections is lower in areas of closed magnetic field lines, suggesting that nightside electron densities behave rather differently at low altitudes than at higher altitudes. This is confirmed by comparison with simultaneous observations of the main ionospheric layer.

  20. 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.

  1. 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.

  2. 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…

  3. The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

    NASA Technical Reports Server (NTRS)

    Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

    1993-01-01

    Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

  4. AATSR Land Surface Temperature Product Validation Using Ground Measurements in China and Implications for SLSTR

    NASA Astrophysics Data System (ADS)

    Zhou, Ji; Zmuda, Andy; Desnos, Yves-Louis; Ma, Jin

    2016-08-01

    Land surface temperature (LST) is one of the most important parameters at the interface between the earth's surface and the atmosphere. It acts as a sensitive indicator of climate change and is an essential input parameter for land surface models. Because of the intense variability at different spatial and temporal scales, satellite remote sensing provides the sole opportunity to acquire LSTs over large regions. Validation of the LST products is an necessary step before their applications conducted by scientific community and it is essential for the developers to improve the LST products.

  5. Stabilization of MgAl2O4 spinel surfaces via doping

    DOE PAGES

    Hasan, Md. M.; Dholabhai, Pratik P.; Castro, Ricardo H. R.; ...

    2016-02-06

    Here, the surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. We report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl2O4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y3+, Gd3+, La3+) and one tetravalentmore » dopant (Zr4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.« less

  6. Stabilization of MgAl2O4 spinel surfaces via doping

    NASA Astrophysics Data System (ADS)

    Hasan, Md. M.; Dholabhai, Pratik P.; Castro, Ricardo H. R.; Uberuaga, Blas P.

    2016-07-01

    Surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. Here, we report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl2O4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y3+, Gd3+, La3+) and one tetravalent dopant (Zr4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.

  7. Lidar-derived Correlations Between Lower-tropospheric Column and Surface Ozone: Implications for Satellite Observations

    NASA Astrophysics Data System (ADS)

    Senff, C. J.; Langford, A. O.; Alvarez, R. J. _II, II; Kirgis, G.; Choukulkar, A.; Brewer, A.; Banta, R. M.; Weickmann, A. M.; Sandberg, S.; Olson, E.

    2015-12-01

    One of the data products that will be provided by the TEMPO satellite mission is 0-2 km ozone column concentration. To make inferences about surface air quality from this data product, the relationship between lower-tropospheric column and surface ozone concentrations and their diurnal, seasonal, and spatial variations have to be well understood. To characterize these relationships, we have used ozone profile observations obtained with NOAA's truck-based, scanning TOPAZ ozone lidar from several recent field campaigns including Discover-AQ Houston and Colorado, the Uintah Basin Wintertime Ozone Study (UBWOS), and the Las Vegas Ozone Study (LVOS). The TOPAZ lidar is ideally suited for this kind of study because it provides ozone profiles from about 15 m above ground level (AGL) up to 3 km AGL at high spatial and temporal resolution. We have used the lidar observations closest to the ground as a proxy for surface ozone and compared them to the 0-2 km AGL average column ozone concentrations measured with the lidar. Results from the Discover-AQ Colorado campaign show that in the afternoon, when the boundary layer (BL) was deep and well mixed, ozone column and surface concentrations agreed quite well. However, during the morning hours, ozone column concentrations were significantly higher than those at the surface, because ozone was depleted in a shallow surface layer due to titration and deposition, whereas ozone levels in the residual layer aloft remained moderately high. The analysis of column and surface ozone correlations using ozone lidar observations from the Discover-AQ Houston, UBWOS and LVOS campaigns is currently underway. The results from these studies will provide additional insights into the relationship between column and surface ozone, in particular their variation as a function of measurement location and season, and their dependence on BL processes such as mixed layer height evolution, land-sea breeze circulation, and terrain-induced flows.

  8. Ionic Channels in Thunderclouds

    NASA Astrophysics Data System (ADS)

    Losseva, T. V.; Fomenko, A. S.; Nemtchinov, I. V.

    2007-12-01

    We proceed to study the formation and propagation of ionic channels in thunderclouds in the framework of the model of the corona discharge wave propagation (Fomenko A.S., Losseva T.V., Nemtchinov I.V. The corona discharge waves in thunderclouds and formation of ionic channels // 2004 Fall Meeting. EOS Trans. AGU. 2004. V. 85. ¹ 47. Suppl. Abstract AE23A-0835.). In this model we proposed a hypothesis that the structure of a thundercloud becomes nonuniform due to corona discharge on the drops and ice particles and formation of ionic channels with higher conductivity than the surrounding air. When the onset strength of corona discharge becomes smaller than the electric field strength the corona discharge increases concentrations of ions in a small part of the cloud (a hot spot). An additional charge at opposite ends of the hot spot forms due to polarization process. The increased electric field initiates corona discharge in other parts of the cloud on ice particles and water drops with smaller sizes. The corona discharge front moves as a wave with the velocity of the order of ion drift and formes a highly conductive channel. We model this non-stationary problem with Poisson equation which is solved simultaneously with a simplified set of kinetic equations for ions, small charged particles and electrons (at high electric fields), including ionization due to electronic impact, attachment and formation of positive ions. By applying 3D numerical simulations we obtain the parameters of formed ionic channels with respect to onset electric fields both from large particles (in hot spot) and from small particles (surrounding hot spot), microscopic currents from particles with different sizes and the external electric field in the cloud. The interaction of ionic channels is also investigated. This work was supported by Russian Foundation of Basic Research (Project No 07-05-00998-à).

  9. Digital surface models are not always representative of former glacier beds: Palaeoglaciological and geomorphological implications

    NASA Astrophysics Data System (ADS)

    Finlayson, Andrew

    2013-07-01

    Quantitative palaeoglaciological studies that use digital surface models (DSMs) may be subject to error because former glacier beds are not always accurately represented. This is because the Earth's surface may have changed significantly since deglaciation. This paper evaluates some of the potential errors caused by postglacial sedimentation, by comparing the results of physical palaeoglaciological reconstructions and bedform morphometric analyses in parts of Scotland, using both the modern land surface and interpolated former glacier beds derived from borehole data. For a former terrestrial outlet glacier, removal of postglacial sediments increases the modelled ice surface elevation and ice thickness by 0.7% and 5%, respectively, over a 27-km flow line. For a former tidewater glacier, the reconstructed steady state ice flux is increased by 250% when the modern land/seabed surface is replaced with an interpolated former glacier bed. In a classical drumlinised landscape, removal of postglacial sediments affects bedform morphometrics, with an increase in measured drumlin length, width, relief, and volume. The cases presented in this paper are from environments known to have experienced postglacial sedimentation. They provide situational examples of the degree of error that can be introduced when the modern land surface is used to represent former glacier beds in these environments. In some regions, sufficient subsurface data exists over large areas to create improved topographic representations of former glacier beds; these could form important inputs to the next generation of palaeo-ice-sheet and palaeo-glacier simulations.

  10. Adhesion energy between mica surfaces: Implications for the frictional coefficient under dry and wet conditions

    NASA Astrophysics Data System (ADS)

    Sakuma, Hiroshi

    2013-12-01

    frictional strength of faults is a critical factor that contributes to continuous fault slip and earthquake occurrence. Frictional strength can be reduced by the presence of sheet-structured clay minerals. In this study, two important factors influencing the frictional coefficient of minerals were quantitatively analyzed by a newly developed computational method based on a combination of first-principles study and thermodynamics. One factor that helps reduce the frictional coefficient is the low adhesion energy between the layers under dry conditions. Potassium ions on mica surfaces are easily exchanged with sodium ions when brought into contact with highly concentrated sodium-halide solutions. We found that the surface ion exchange with sodium ions reduces the adhesion energy, indicating that the frictional coefficient can be reduced under dry conditions. Another factor is the lubrication caused by adsorbed water films on mineral surfaces under wet conditions. Potassium and sodium ions on mica surfaces have a strong affinity for water molecules. In order to remove the adsorbed water molecules confined between mica surfaces, a differential compressive stress of the order of tens of gigapascals was necessary at room temperature. These water molecules inhibit direct contact between mineral surfaces and reduce the frictional coefficient. Our results imply that the frictional coefficient can be modified through contact with fluids depending on their salt composition. The low adhesion energy between fault-forming minerals and the presence of an adsorbed water film is a possible reason for the low frictional coefficient observed at continuous fault slip zones.

  11. Implications of Adhesion Studies for Dust Mitigation on Thermal Control Surfaces

    NASA Technical Reports Server (NTRS)

    Gaier, James R.; Berkebile, Stephen P.

    2012-01-01

    Experiments measuring the adhesion forces under ultrahigh vacuum conditions (10 (exp -10) torr) between a synthetic volcanic glass and commonly used space exploration materials have recently been described. The glass has a chemistry and surface structure typical of the lunar regolith. It was found that Van der Waals forces between the glass and common spacecraft materials was negligible. Charge transfer between the materials was induced by mechanically striking the spacecraft material pin against the glass plate. No measurable adhesion occurred when striking the highly conducting materials, however, on striking insulating dielectric materials the adhesion increased dramatically. This indicates that electrostatic forces dominate over Van der Waals forces under these conditions. The presence of small amounts of surface contaminants was found to lower adhesive forces by at least two orders of magnitude, and perhaps more. Both particle and space exploration material surfaces will be cleaned by the interaction with the solar wind and other energetic processes and stay clean because of the extremely high vacuum (10 (exp -12) torr) so the atomically clean adhesion values are probably the relevant ones for the lunar surface environment. These results are used to interpret the results of dust mitigation technology experiments utilizing textured surfaces, work function matching surfaces and brushing. They have also been used to reinterpret the results of the Apollo 14 Thermal Degradation Samples experiment.

  12. Surface Rupture of the 2005 Kashmir, Pakistan, Earthquake and its Active Tectonic Implications

    NASA Astrophysics Data System (ADS)

    Kaneda, H.; Nakata, T.; Tsutsumi, H.; Kondo, H.; Sugito, N.; Awata, Y.; Akhtar, S. S.; Majid, A.; Khattak, W.; Awan, A. A.; Yeats, R. S.

    2006-12-01

    The 8th October 2005 Kashmir earthquake of Mw 7.6 struck the westernmost area of the Indian-Eurasian collision zone, resulting in the worst earthquake disaster ever recorded along the frontal Himalaya. Although none of the historical Himalayan earthquakes is reported to have produced primary surface rupture, our field mapping reveals that the 2005 earthquake accompanied a NW-trending ~70-km-long distinctive surface rupture with maximum and mean vertical separations of ~7 m and ~3 m, respectively. Typical surface expression of faulting is a NE-side-up fault scarp or warp with surface shortening features at its base and tension cracks on its crest. Bulging and back-tilting are also observed on the upthrown side at many places. The surface rupture is subdivided into three geometrical segments separated by small steps. Location of the hypocenter suggests that the rupture was initiated at a deep portion of the northern-central segment boundary and bilaterally propagated to eventually break three segments. Mapped surface rupture trace clearly shows that neither the Himalayan Frontal Thrust (HFT) nor the Main Boundary Thrust (MBT) is responsible for the earthquake, but a geomorphologically-evident active fault within the Sub-Himalaya, the Balakot-Garhi fault, is a causative fault, although a part of the Balakot-Garhi fault appears to coincide with the surface trace of the MBT. Cumulative vertical separation of the most extensively recognized fluvial terrace surface is 7-8 times larger than the 2005 separation, implying occurrence of 7-8 similar earthquakes after the surface abandonment. If this deeply-incised fill surface is related to sediment yield increase due to the last major glaciation around 20 ka, the rupture interval and vertical slip rate of the Balakot-Garhi fault are estimated to be on the order of ~3000 years and ~1 mm/yr, respectively. By using the seismologically determined fault dip of ~30 degrees, horizontal shortening rate across the fault is then

  13. Variability of the temporal bone surface's topography: implications for otologic surgery

    NASA Astrophysics Data System (ADS)

    Lecoeur, Jérémy; Noble, Jack H.; Balachandran, Ramya; Labadie, Robert F.; Dawant, Benoit M.

    2012-02-01

    Otologic surgery is performed for a variety of reasons including treatment of recurrent ear infections, alleviation of dizziness, and restoration of hearing loss. A typical ear surgery consists of a tympanomastoidectomy in which both the middle ear is explored via a tympanic membrane flap and the bone behind the ear is removed via mastoidectomy to treat disease and/or provide additional access. The mastoid dissection is performed using a high-speed drill to excavate bone based on a pre-operative CT scan. Intraoperatively, the surface of the mastoid component of the temporal bone provides visual feedback allowing the surgeon to guide their dissection. Dissection begins in "safe areas" which, based on surface topography, are believed to be correlated with greatest distance from surface to vital anatomy thus decreasing the chance of injury to the brain, large blood vessels (e.g. the internal jugular vein and internal carotid artery), the inner ear, and the facial nerve. "Safe areas" have been identified based on surgical experience with no identifiable studies showing correlation of the surface with subsurface anatomy. The purpose of our study was to investigate whether such a correlation exists. Through a three-step registration process, we defined a correspondence between each of twenty five clinically-applicable temporal bone CT scans of patients and an atlas and explored displacement and angular differences of surface topography and depth of critical structures from the surface of the skull. The results of this study reflect current knowledge of osteogenesis and anatomy. Based on two features (distance and angular difference), two regions (suprahelical and posterior) of the temporal bone show the least variability between surface and subsurface anatomy.

  14. Atomic-scale surface roughness of rutile and implications for organic molecule adsorption.

    PubMed

    Livi, Kenneth J T; Schaffer, Bernhard; Azzolini, David; Seabourne, Che R; Hardcastle, Trevor P; Scott, Andrew J; Hazen, Robert M; Erlebacher, Jonah D; Brydson, Rik; Sverjensky, Dimitri A

    2013-06-11

    Crystal surfaces provide physical interfaces between the geosphere and biosphere. It follows that the arrangement of atoms at the surfaces of crystals profoundly influences biological components at many levels, from cells through biopolymers to single organic molecules. Many studies have focused on the crystal-molecule interface in water using large, flat single crystals. However, little is known about atomic-scale surface structures of the nanometer- to micrometer-sized crystals of simple metal oxides typically used in batch adsorption experiments under conditions relevant to biogeochemistry and the origins of life. Here, we present atomic-resolution microscopy data with unprecedented detail of the circumferences of nanosized rutile (α-TiO2) crystals previously used in studies of the adsorption of protons, cations, and amino acids. The data suggest that one-third of the {110} faces, the largest faces on individual crystals, consist of steps at the atomic scale. The steps have the orientation to provide undercoordinated Ti atoms of the type and abundance for adsorption of amino acids as inferred from previous surface complexation modeling of batch adsorption data. A remarkably uniform pattern of step proportions emerges: the step proportions are independent of surface roughness and reflect their relative surface energies. Consequently, the external morphology of rutile nanometer- to micrometer-sized crystals imaged at the coarse scale of scanning electron microscope images is not an accurate indicator of the atomic smoothness or of the proportions of the steps present. Overall, our data strongly suggest that amino acids attach at these steps on the {110} surfaces of rutile.

  15. Spatial and temporal distribution of cyanobacterial soil crusts in the Kalahari: Implications for soil surface properties

    NASA Astrophysics Data System (ADS)

    Thomas, A. D.; Dougill, A. J.

    2007-03-01

    Localised patterns of erosion and deposition in vegetated semi-arid rangelands have been shown to influence ecological change and biogeochemical cycles. In the flat, vegetated Kalahari rangelands of Southern Africa the factors regulating erodibility of the fine sand soils and the erosivity of wind regimes require further investigation. This paper reports on the spatial and temporal patterns of cyanobacterial soil crust cover from ten sites at five sampling locations in the semi-arid Kalahari and discusses the likely impact on factors regulating surface erodibility and erosivity. Cyanobacterial soil crust cover on Kalahari Sand varied between 11% and 95% of the ground surface and was higher than previously reported. Cover was inversely related to grazing with the lowest crust cover found close to boreholes and the highest in the Game Reserve and Wildlife Management Zone. In grazed areas, crusts form under the protective canopies of the thorny shrub Acacia mellifera. Fenced plot data showed that crusts recover quickly from disturbance, with a near complete surface crust cover forming within 15 months of disturbance. Crust development is restricted by burial by wind blown sediment and by raindrop impact. Crusts had significantly greater organic matter and total nitrogen compared to unconsolidated surfaces. Crusts also significantly increased the compressive strength of the surface (and thus decreased erodibility) and changed the surface roughness. Establishing exactly how these changes affect aeolian erosion requires further process-based studies. The proportion of shear velocity acting on the surface in this complex mixed bush-grass-crust environment will be the key to understanding how crusts affect erodibility.

  16. Virtual mission stage I: Implications of a spaceborne surface water mission

    NASA Astrophysics Data System (ADS)

    Clark, E. A.; Alsdorf, D. E.; Bates, P.; Wilson, M. D.; Lettenmaier, D. P.

    2004-12-01

    The interannual and interseasonal variability of the land surface water cycle depend on the distribution of surface water in lakes, wetlands, reservoirs, and river systems; however, measurements of hydrologic variables are sparsely distributed, even in industrialized nations. Moreover, the spatial extent and storage variations of lakes, reservoirs, and wetlands are poorly known. We are developing a virtual mission to demonstrate the feasibility of observing surface water extent and variations from a spaceborne platform. In the first stage of the virtual mission, on which we report here, surface water area and fluxes are emulated using simulation modeling over three continental scale river basins, including the Ohio River, the Amazon River and an Arctic river. The Variable Infiltration Capacity (VIC) macroscale hydrologic model is used to simulate evapotranspiration, soil moisture, snow accumulation and ablation, and runoff and streamflow over each basin at one-eighth degree resolution. The runoff from this model is routed using a linear transfer model to provide input to a much more detailed flow hydraulics model. The flow hydraulics model then routes runoff through various channel and floodplain morphologies at a 250 m spatial and 20 second temporal resolution over a 100 km by 500 km domain. This information is used to evaluate trade-offs between spatial and temporal resolutions of a hypothetical high resolution spaceborne altimeter by synthetically sampling the resultant model-predicted water surface elevations.

  17. Non-Debye relaxation in the dielectric response of nematic liquid crystals: surface and memory effects in the adsorption-desorption process of ionic impurities.

    PubMed

    de Paula, J L; Santoro, P A; Zola, R S; Lenzi, E K; Evangelista, L R; Ciuchi, F; Mazzulla, A; Scaramuzza, N

    2012-11-01

    We demonstrate theoretically that the presence of ions in insulating materials such as nematic liquid crystals may be responsible for the dielectric spectroscopy behavior observed experimentally. It is shown that, at low frequencies, an essentially non-Debye relaxation process takes place due to surface effects. This is accomplished by investigating the effects of the adsorption-desorption process on the electrical response of an electrolytic cell when the generation and recombination of ions is present. The adsorption-desorption is governed by a non-usual kinetic equation in order to incorporate memory effects related to a non-Debye relaxation and the roughness of the surface. The analysis is carried out by searching for solutions to the drift-diffusion equation that satisfy the Poisson equation relating the effective electric field to the net charge density. We also discuss the effect of the mobility of the ions, i.e., situations with equal and different diffusion coefficients for positive and negative ions, on the impedance and obtain an exact expression for the admittance. The model is compared with experimental results measured for the impedance of a nematic liquid crystal sample and a very good agreement is obtained.

  18. Non-Debye relaxation in the dielectric response of nematic liquid crystals: Surface and memory effects in the adsorption-desorption process of ionic impurities

    NASA Astrophysics Data System (ADS)

    de Paula, J. L.; Santoro, P. A.; Zola, R. S.; Lenzi, E. K.; Evangelista, L. R.; Ciuchi, F.; Mazzulla, A.; Scaramuzza, N.

    2012-11-01

    We demonstrate theoretically that the presence of ions in insulating materials such as nematic liquid crystals may be responsible for the dielectric spectroscopy behavior observed experimentally. It is shown that, at low frequencies, an essentially non-Debye relaxation process takes place due to surface effects. This is accomplished by investigating the effects of the adsorption-desorption process on the electrical response of an electrolytic cell when the generation and recombination of ions is present. The adsorption-desorption is governed by a non-usual kinetic equation in order to incorporate memory effects related to a non-Debye relaxation and the roughness of the surface. The analysis is carried out by searching for solutions to the drift-diffusion equation that satisfy the Poisson equation relating the effective electric field to the net charge density. We also discuss the effect of the mobility of the ions, i.e., situations with equal and different diffusion coefficients for positive and negative ions, on the impedance and obtain an exact expression for the admittance. The model is compared with experimental results measured for the impedance of a nematic liquid crystal sample and a very good agreement is obtained.

  19. Macroscopic frictional properties of poly(1-(2-methacryloyloxy)ethyl-3-butyl imidazolium bis(trifluoromethanesulfonyl)-imide) brush surfaces in an ionic liquid.

    PubMed

    Ishikawa, Tatsuya; Kobayashi, Motoyasu; Takahara, Atsushi

    2010-04-01

    Poly(1-(2-methacryloyloxy)ethyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide) (PMIS) and poly(n-hexyl methacrylate) (PHMA) brushes were prepared on initiator-immobilized silicon wafers by surface-initiated atom transfer radical polymerization. The macroscopic frictional properties of the brushes were determined using a ball-on-flat type tribotester under reciprocating motion in a dry nitrogen atmosphere, water, methanol, and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMImTFSI). When the PMIS and PHMA brushes were exposed to EMImTFSI, the friction coefficient of the former was lower than that of the latter. It is thought that the high affinity of the PMIS brush to EMImTFSI led to a reduction in the interaction between the brush and the friction probe, which resulted in a low friction coefficient. The friction force of the PMIS brush in EMImTFSI was proportional to a normal load in the range of 0.2-0.98 N. The friction coefficient gradually decreased to 0.01 with an increase in the sliding velocity from 1 x 10(-4) to 1 x 10(-1) m s(-1). The friction coefficient of the PMIS brush exhibited low magnitude until 800 friction cycles in the dry nitrogen atmosphere, whereas the PHMA brush was abraded away within 150 friction cycles. The XPS spectra of the worn surfaces on the PMIS brush suggested that the brush was gradually abraded by friction.

  20. Theoretical study of the acid-base properties of the montmorillonite/electrolyte interface: influence of the surface heterogeneity and ionic strength on the potentiometric titration curves.

    PubMed

    Zarzycki, Piotr; Thomas, Fabien

    2006-10-15

    The parallel shape of the potentiometric titration curves for montmorillonite suspension is explained using the surface complexation model and taking into account the surface heterogeneity. The homogeneous models give accurate predictions only if they assume unphysically large values of the equilibrium constants for the exchange process occurring on the basal plane. However, the assumption that the basal plane is energetically heterogeneous allows to fit the experimental data (reported by Avena and De Pauli [M. Avena, C.P. De Pauli, J. Colloid Interface Sci. 202 (1998) 195-204]) for reasonable values of exchange equilibrium constant equal to 1.26 (suggested by Fletcher and Sposito [P. Fletcher, G. Sposito, Clay Miner. 24 (1989) 375-391]). Moreover, we observed the typical behavior of point of zero net proton charge (pznpc) as a function of logarithm of the electrolyte concentration (log[C]). We showed that the slope of the linear dependence, pznpc=f(log[C]), is proportional to the number of isomorphic substitutions in the crystal phase, which was also observed in the experimental studies.

  1. Improvement of SOFC electrodes using mixed ionic-electronic conductors

    SciTech Connect

    Matsuzaki, Y.; Hishinuma, M.

    1996-12-31

    Since the electrode reaction of SOFC is limited to the proximity of a triple phase boundary (TPB), the local current density at the electrode and electrolyte interface is larger than mean current density, which causes large ohmic and electrode polarization. This paper describes an application of mixed ionic-electronic conductors to reduce such polarization by means of (1) enhancing ionic conductivity of the electrolyte surface layer by coating a high ionic conductors, and (2) reducing the local current density by increasing the electrochemically active sites.

  2. Mesoscale studies of ionic closed membranes with polyhedral geometries

    NASA Astrophysics Data System (ADS)

    Olvera de la Cruz, Monica

    2016-06-01

    Large crystalline molecular shells buckle spontaneously into icosahedra while multicomponent shells buckle into various polyhedra. Continuum elastic theory explains the buckling of closed shells with one elastic component into icosahedra. A generalized elastic model, on the other hand, describes the spontaneous buckling of inhomogeneous shells into regular and irregular polyhedra. By co-assembling water-insoluble anionic (-1) amphiphiles with cationic (3+) amphiphiles, we realized ionic vesicles. Results revealed that surface crystalline domains and the unusual shell shapes observed arise from the competition of ionic correlations with charge-regulation. We explain here the mechanism by which these ionic membranes generate a mechanically heterogeneous vesicle.

  3. Surface emission from neutron stars and implications for the physics of their interiors.

    PubMed

    Ozel, Feryal

    2013-01-01

    Neutron stars are associated with diverse physical phenomena that take place in conditions characterized by ultrahigh densities as well as intense gravitational, magnetic and radiation fields. Understanding the properties and interactions of matter in these regimes remains one of the challenges in compact object astrophysics. Photons emitted from the surfaces of neutron stars provide direct probes of their structure, composition and magnetic fields. In this review, I discuss in detail the physics that governs the properties of emission from the surfaces of neutron stars and their various observational manifestations. I present the constraints on neutron star radii, core and crust composition, and magnetic field strength and topology obtained from studies of their broadband spectra, evolution of thermal luminosity, and the profiles of pulsations that originate on their surfaces.

  4. Zeta potential of anoxygenic phototrophic bacteria and Ca adsorption at the cell surface: possible implications for cell protection from CaCO3 precipitation in alkaline solutions.

    PubMed

    Bundeleva, Irina A; Shirokova, Liudmila S; Bénézeth, Pascale; Pokrovsky, Oleg S; Kompantseva, Elena I; Balor, Stephanie

    2011-08-01

    Electrophoretic mobility measurements and surface adsorption of Ca on living, inactivated, and heat-killed haloalkaliphilic Rhodovulum steppense, A-20s, and halophilic Rhodovulum sp., S-17-65 anoxygenic phototrophic bacteria (APB) cell surfaces were performed to determine the degree to which these bacteria metabolically control their surface potential equilibria. Zeta potential of both species was measured as a function of pH and ionic strength, calcium and bicarbonate concentrations. For both live APB in 0.1M NaCl, the zeta potential is close to zero at pH from 2.5 to 3 and decreases to -30 to -40 mV at pH of 5-8. In alkaline solutions, there is an unusual increase of zeta potential with a maximum value of -10 to -20 mV at a pH of 9-10.5. This increase of zeta potential in alkaline solutions is reduced by the presence of NaHCO(3) (up to 10 mM) and only slightly affected by the addition of equivalent amount of Ca. At the same time, for inactivated (exposure to NaN(3), a metabolic inhibitor) and heat-killed bacteria cells, the zeta potential was found to be stable (-30 to -60 mV, depending upon the ionic strength) between pH 5 and 11 without any increase in alkaline solutions. Adsorption of Ca ions on A-20s cells surface was more significant than that on S-17-65 cells and started at more acidic pHs, consistent with zeta potential measurements in the presence of 0.001-0.01 mol/L CaCl(2). Overall, these results indicate that APB can metabolically control their surface potential to electrostatically attract nutrients at alkaline pH, while rejecting/avoiding Ca ions to prevent CaCO(3) precipitation in the vicinity of cell surface and thus, cell incrustation.

  5. Cell surface reactivity of Synechococcus sp. PCC 7002: Implications for metal sorption from seawater

    NASA Astrophysics Data System (ADS)

    Liu, Yuxia; Alessi, D. S.; Owttrim, G. W.; Petrash, D. A.; Mloszewska, A. M.; Lalonde, S. V.; Martinez, R. E.; Zhou, Qixing; Konhauser, K. O.

    2015-11-01

    The past two decades have seen a significant advancement in our understanding of bacterial surface chemistry and the ability of microbes to bind metals from aqueous solutions. Much of this work has been aimed at benthic, mat-forming species in an effort to model the mechanisms by which microbes may exert control over metal contaminant transport in soils and groundwater. However, there is a distinct paucity of information pertaining to the surface chemistry of marine planktonic species, and their ability to bind trace metals from the ocean's photic zone. To this end, the surface properties of the cyanobacterium Synechococcus sp. PCC 7002 were studied as this genus is one of the dominant marine phytoplankton, and as such, contributes significantly to metal cycling in the ocean's photic zone. Zeta potential measurement indicates that the cell surfaces display a net negative charge. This was supported by potentiometric titration and Fourier transform infrared spectroscopy analyses demonstrating that the cells are dominated by surface proton releasing ligands, including carboxyl, phosphoryl and amino functional groups, with a total ligand density of 34.18 ± 1.62 mmol/g (dry biomass). Cd adsorption experiments further reveal that carboxyl groups play a primary role in metal adsorption, with 1.0 g of dry biomass binding an equivalent of 7.05 × 10-5 M of Cd from solution at pH = 8. To put this value into context, in 1 L of seawater, and with an open-ocean population of Synechococcus of 105 cells/mL in the photic zone, approximately 10 nmol of Cd could potentially be adsorbed by the cyanobacteria; an amount equivalent to seawater Cd concentrations. Although we have only focused on one microbial species and one metal cation, and we have not considered trace element assimilation, our results highlight the potential role of surface sorption by phytoplankton in the cycling of metals in the ocean.

  6. Subsurface Emission Effects in AMSR-E Measurements: Implications for Land Surface Microwave Emissivity Retrieval

    NASA Technical Reports Server (NTRS)

    Galantowicz, John F.; Moncet, Jean-Luc; Liang, Pan; Lipton, Alan E.; Uymin, Gennady; Prigent, Catherine; Grassotti, Christopher

    2011-01-01

    An analysis of land surface microwave emission time series shows that the characteristic diurnal signature associated with subsurface emission in sandy deserts carry over to arid and semi-arid region worldwide. Prior work found that diurnal variation of Special Sensor Microwave/Imager (SSM/I) brightness temperatures in deserts was small relative to International Satellite Cloud Climatology Project land surface temperature (LST) variation and that the difference varied with surface type and was largest in sand sea regions. Here we find more widespread subsurface emission effects in Advanced Microwave Scanning Radiometer-EOS (AMSR-E) measurements. The AMSR-E orbit has equator crossing times near 01:30 and 13 :30 local time, resulting in sampling when near-surface temperature gradients are likely to be large and amplifying the influence of emission depth on effective emitting temperature relative to other factors. AMSR-E measurements are also temporally coincident with Moderate Resolution Imaging Spectroradiometer (MODIS) LST measurements, eliminating time lag as a source of LST uncertainty and reducing LST errors due to undetected clouds. This paper presents monthly global emissivity and emission depth index retrievals for 2003 at 11, 19, 37, and 89 GHz from AMSR-E, MODIS, and SSM/I time series data. Retrieval model fit error, stability, self-consistency, and land surface modeling results provide evidence for the validity of the subsurface emission hypothesis and the retrieval approach. An analysis of emission depth index, emissivity, precipitation, and vegetation index seasonal trends in northern and southern Africa suggests that changes in the emission depth index may be tied to changes in land surface moisture and vegetation conditions

  7. Beryllium in the Galactic halo - Surface abundances from standard, diffusive, and rotational stellar evolution, and implications

    NASA Technical Reports Server (NTRS)

    Deliyannis, Constantine P.; Pinsonneault, Marc H.

    1990-01-01

    The recently observed upper limits to the beryllium abundances in population II stars are much lower than population I detections. This difference reflects an intrinsic difference in the initial abundances and is not caused by different degrees of depletion driven by stellar evolution processes from similar initial abundances. Evolutionary sequences of models from the early premain sequence to beyond the turnoff that correspond to halo dwarfs with Fe/H abundances of -1.3, -2.3, and -3.3 are constructed, and standard, diffusive, and rotational mechanisms are used to estimate a maximal possible beryllium depletion. Halo star models in the T(eff) range 6000 to 5000 K might be rotationally depleted by a factor of 1.5-2, and the total depletion should be no more than (conservatively) a factor of 3. Implications for cosmology, cosmic-ray theory, and Galactic chemical evolution are discussed.

  8. VARIABILITY OF SURFACE FLOWS ON THE SUN AND THE IMPLICATIONS FOR EXOPLANET DETECTION

    SciTech Connect

    Makarov, Valeri V.

    2010-05-20

    The published Mount Wilson Doppler-shift measurements of the solar velocity field taken in 1967-1982 are revisited with a more accurate model, which includes two terms representing the meridional flow and three terms corresponding to the convective limb shift. Integration of the recomputed data over the visible hemisphere reveals significant variability of the net radial velocity at characteristic time scales of 0.1-10 years, with a standard deviation of 1.4 m s{sup -1}. This result is supported by independent published observations. The implications for exoplanet detection include reduced sensitivity of the Doppler method to Earth-like planets in the habitable zone, and an elevated probability of false detections at periods of a few to several years.

  9. Martian Buried Basins and Implications for Characteristics of the Burial Layer and Underlying Surface

    NASA Technical Reports Server (NTRS)

    Sarid, A. R.; Frey, H. V.; Roark, J. H.

    2003-01-01

    Deciphering the cratering record on Mars has been challenging because it may reflect the changes in both the population of impactors and in the resurfacing processes on Mars. However, it is possible to determine the breadth of impactors captured in the cratering record. Extensive areas of resurfacing are of particular interest because they likely contain material from various ages in Martian history. By deducing the impact populations in both surface and underlying layers of terrain, it is possible to determine the age of the layers and constrain theories on the development of the Martian surface. However, to do so requires a method of "seeing" impact features which are no longer visible.

  10. A much warmer Earth surface for most of geologic time: implications to biotic weathering

    NASA Technical Reports Server (NTRS)

    Schwartzman, D. W.; McMenamin, M.

    1993-01-01

    The authors present two scenarios for the temperature history of Earth. One scenario is conventional, the other relies on a warmer history. Both scenarios include surface cooling determined by the evolution of the biosphere and are similar until the Proterozoic period. The warmer scenario requires a higher plant/lichen terrestrial biota to increase weathering intensity. Justification for a warmer surface includes period temperatures from the oxygen isotope record of coexisting phosphates and cherts, an upper limit of 58 degrees C from primary gypsum precipitation, and the lack of fractionation of sulfur isotopes between sulfide and sulfates in Archean sediments.

  11. Tailoring biomaterial surface properties to modulate host-implant interactions: implication in cardiovascular and bone therapy

    PubMed Central

    Pacelli, Settimio; Manoharan, Vijayan; Desalvo, Anna; Lomis, Nikita; Jodha, Kartikeya Singh

    2016-01-01

    Host body response to a foreign medical device plays a critical role in defining its fate post implantation. It is thus important to control host-material interactions by designing innovative implant surfaces. In the recent years, biochemical and topographical features have been explored as main target to produce this new type of bioinert or bioresponsive implants. The review discusses specific biofunctional materials and strategies to achieve a precise control over implant surface properties and presents possible solutions to develop next generation of implants, particularly in the fields of bone and cardiovascular therapy. PMID:27630769

  12. Evidence for a basalt-free surface on Mercury and implications for internal heat.

    PubMed

    Jeanloz, R; Mitchell, D L; Sprague, A L; de Pater, I

    1995-06-09

    Microwave and mid-infrared observations reveal that Mercury's surface contains less FeO + TiO2 and at least as much feldspar as the lunar highlands. The results are compatible with the high albedo (brightness) of Mercury's surface at visible wavelengths in suggesting a rock and soil composition that is devoid of basalt, the primary differentiate of terrestrial mantles. The occurrence of a basalt-free, highly differentiated crust is in accord with recent models of the planet's thermal evolution and suggests that Mercury has retained a hot interior as a result of a combination of inefficient mantle convection and minimal volcanic heat loss.

  13. Successive ionic layer deposition. The use in nanotechnology

    NASA Astrophysics Data System (ADS)

    Tolstoy, Valeri P.

    2006-02-01

    The problems related to the synthesis of nanolayers of various classes of substances (inorganic, organic and hybrid, i.e., inorganic/organic) by successive ionic, ionic-molecular and ionic-colloidal layer deposition are discussed. The experimental data are systematised in terms of the type of reaction occurring on the surface during the synthesis. The use of successive ionic layer deposition in nanotechnology for the preparation of practically valuable nanolayers is considered. These nanolayers include the layers in SnO2-based conductometric gas sensors, passivating protective coatings on the metal surface, semiconductor cells for solar energy conversion, photo-, electrochromic and magnetic materials, pervaporation membranes, electrocatalysts, light diodes, and so on.

  14. Simulation of Galactic Cosmic Ray Interactions with Regolith: Implications for Cosmogenic Nuclide and Planetary Surface Studies

    NASA Astrophysics Data System (ADS)

    Bobias, S. G.; Dempsey, J. F.; Englert, P. A. J.; Drake, D. M.; Reedy, R. C.

    1992-07-01

    In planetary, asteroidal, and cometary surfaces the development of cosmic ray produced secondary particle cascades depends very much on the chemical composition. Most important is the abundance and distribution of neutron moderators, such as hydrogen and carbon. Their presence influences the distribution and flux of neutrons in extraterrestrial surfaces. Consequently, the distribution and activity of neutron produced cosmogenic nuclides, such as the neutron capture products ^36Cl (3.01x10^5y), ^41Ca (1.03x10^5y), ^59Ni (7.6x10^4 y) and ^60Co (5.271y), and the medium energy products such as ^22Na (2.605 y, from Al), ^26Al (7.4x10^5 y, from Si), ^53Mn (3.7x10^6, from Fe), etc., will be dependent on the development of the secondary neutron fluxes. Three thick target bombardments of artificial planetary surface soil (martian) [1,2,3] that measured the secondary particle cascade as well as surface neutron flux and leakage spectra were performed at the Los Alamos Meson Physics Facility's Weapons Neutron Research Laboratory. They provide data to study qualitatively and quantitatively the relation between bombarding galactic cosmic ray particles, the development of neutrons inside a surface and of neutrons emitted from a planetary surface. Past thick target bombardments were limited to only determining the secondary particle cascades or the emitted gamma radiation [4,5,6]. The experiments show that the second target, which was two times larger than the target for the first experiment, was holding more neutrons inside the target. The third irradiation utilized a polyethylene sheet in front of the second target to simulate the presence of water or ice on a planetary surface. Threshold monitors were placed both along the axis of symmetry and radially displaced axes. The monitors included foils of Ti, Mn, Fe, Co, Ni, and Au. The induced radioactivity was measured at Los Alamos by conventional gamma-ray spectrometry approximately 48 hours at the end of irradiation. Both the

  15. Ozone-surface interactions: Investigations of mechanisms, kinetics, mass transport, and implications for indoor air quality

    SciTech Connect

    Morrison, Glenn Charles

    1999-12-01

    In this dissertation, results are presented of laboratory investigations and mathematical modeling efforts designed to better understand the interactions of ozone with surfaces. In the laboratory, carpet and duct materials were exposed to ozone and measured ozone uptake kinetics and the ozone induced emissions of volatile organic compounds. To understand the results of the experiments, mathematical methods were developed to describe dynamic indoor aldehyde concentrations, mass transport of reactive species to smooth surfaces, the equivalent reaction probability of whole carpet due to the surface reactivity of fibers and carpet backing, and ozone aging of surfaces. Carpets, separated carpet fibers, and separated carpet backing all tended to release aldehydes when exposed to ozone. Secondary emissions were mostly n-nonanal and several other smaller aldehydes. The pattern of emissions suggested that vegetable oils may be precursors for these oxidized emissions. Several possible precursors and experiments in which linseed and tung oils were tested for their secondary emission potential were discussed. Dynamic emission rates of 2-nonenal from a residential carpet may indicate that intermediate species in the oxidation of conjugated olefins can significantly delay aldehyde emissions and act as reservoir for these compounds. The ozone induced emission rate of 2-nonenal, a very odorous compound, can result in odorous indoor concentrations for several years. Surface ozone reactivity is a key parameter in determining the flux of ozone to a surface, is parameterized by the reaction probability, which is simply the probability that an ozone molecule will be irreversibly consumed when it strikes a surface. In laboratory studies of two residential and two commercial carpets, the ozone reaction probability for carpet fibers, carpet backing and the equivalent reaction probability for whole carpet were determined. Typically reaction probability values for these materials were 10

  16. The impact of synoptic weather on UK surface ozone and implications for premature mortality

    NASA Astrophysics Data System (ADS)

    Pope, R. J.; Butt, E. W.; Chipperfield, M. P.; Doherty, R. M.; Fenech, S.; Schmidt, A.; Arnold, S. R.; Savage, N. H.

    2016-12-01

    Air pollutants, such as ozone, have adverse impacts on human health and cause, for example, respiratory and cardiovascular problems. In the United Kingdom (UK), peak surface ozone concentrations typically occur in the spring and summer and are controlled by emission of precursor gases, tropospheric chemistry and local meteorology which can be influenced by large-scale synoptic weather regimes. In this study we composite surface and satellite observations of summer-time (April to September) ozone under different UK atmospheric circulation patterns, as defined by the Lamb weather types. Anticyclonic conditions and easterly flows are shown to significantly enhance ozone concentrations over the UK relative to summer-time average values. Anticyclonic stability and light winds aid the trapping of ozone and its precursor gases near the surface. Easterly flows (NE, E, SE) transport ozone and precursor gases from polluted regions in continental Europe (e.g. the Benelux region) to the UK. Cyclonic conditions and westerly flows, associated with unstable weather, transport ozone from the UK mainland, replacing it with clean maritime (North Atlantic) air masses. Increased cloud cover also likely decrease ozone production rates. We show that the UK Met Office regional air quality model successfully reproduces UK summer-time ozone concentrations and ozone enhancements under anticyclonic and south-easterly conditions for the summer of 2006. By using established ozone exposure-health burden metrics, anticyclonic and easterly condition enhanced surface ozone concentrations pose the greatest public health risk.

  17. GROUNDWATER-SURFACE WATER EXCHANGE AND IMPLICATIONS FOR LARGE RIVER RESTORATION

    EPA Science Inventory

    Movement of river water into and out of high-porosity alluvial deposits can have an important influence on surface water quality and aquatic habitat. In our study of a 60-km reach of the Willamette River in Oregon, USA, we: 1) used tracers to estimate the rate of exchange betw...

  18. The role of the surface on microglia function: implications for central nervous system tissue engineering

    PubMed Central

    Pires, Liliana R.; Rocha, Daniela N.; Ambrosio, Luigi; Pêgo, Ana Paula

    2015-01-01

    In tissue engineering, it is well accepted that a scaffold surface has a decisive impact on cell behaviour. Here we focused on microglia—the resident immune cells of the central nervous system (CNS)—and on their response to poly(trimethylene carbonate-co-ε-caprolactone) (P(TMC-CL)) fibrous and flat surfaces obtained by electrospinning and solvent cast, respectively. This study aims to provide cues for the design of instructive surfaces that can contribute to the challenging process of CNS regeneration. Cell morphology was evidently affected by the substrate, mirroring the surface main features. Cells cultured on flat substrates presented a round shape, while cells with elongated processes were observed on the electrospun fibres. A higher concentration of the pro-inflammatory cytokine tumour necrosis factor-α was detected in culture media from microglia on fibres. Still, astrogliosis is not exacerbated when astrocytes are cultured in the presence of microglia-conditioned media obtained from cultures in contact with either substrate. Furthermore, a significant percentage of microglia was found to participate in the process of myelin phagocytosis, with the formation of multinucleated giant cells being observed only on films. Altogether, the results presented suggest that microglia in contact with the tested substrates may contribute to the regeneration process, putting forward P(TMC-CL) substrates as supporting matrices for nerve regeneration. PMID:25540243

  19. The role of the surface on microglia function: implications for central nervous system tissue engineering.

    PubMed

    Pires, Liliana R; Rocha, Daniela N; Ambrosio, Luigi; Pêgo, Ana Paula

    2015-02-06

    In tissue engineering, it is well accepted that a scaffold surface has a decisive impact on cell behaviour. Here we focused on microglia-the resident immune cells of the central nervous system (CNS)-and on their response to poly(trimethylene carbonate-co-ε-caprolactone) (P(TMC-CL)) fibrous and flat surfaces obtained by electrospinning and solvent cast, respectively. This study aims to provide cues for the design of instructive surfaces that can contribute to the challenging process of CNS regeneration. Cell morphology was evidently affected by the substrate, mirroring the surface main features. Cells cultured on flat substrates presented a round shape, while cells with elongated processes were observed on the electrospun fibres. A higher concentration of the pro-inflammatory cytokine tumour necrosis factor-α was detected in culture media from microglia on fibres. Still, astrogliosis is not exacerbated when astrocytes are cultured in the presence of microglia-conditioned media obtained from cultures in contact with either substrate. Furthermore, a significant percentage of microglia was found to participate in the process of myelin phagocytosis, with the formation of multinucleated giant cells being observed only on films. Altogether, the results presented suggest that microglia in contact with the tested substrates may contribute to the regeneration process, putting forward P(TMC-CL) substrates as supporting matrices for nerve regeneration.

  20. Temperature Dependence of Cryogenic Ammonia-Water Ice Mixtures and Implications for Icy Satellite Surfaces

    NASA Technical Reports Server (NTRS)

    Dalton, J. B., III; Curchin, J. M.; Clark, R. N.

    2001-01-01

    Infrared spectra of ammonia-water ice mixtures reveal temperature-dependent absorption bands due to ammonia. These features, at 1.04, 2.0, and 2.25 microns, may shed light on the surface compositions of the Galilean and Saturnian satellites. Additional information is contained in the original extended abstract.

  1. Multiscale controls on water surface roughness and implications for remote sensing of rivers

    NASA Astrophysics Data System (ADS)

    Overstreet, B. T.; Legleiter, C. J.; Harrison, L.; Pitcher, L. H.; Ryan, J.; Rennermalm, A. K.; Smith, L. C.

    2015-12-01

    Remote sensing has emerged as a viable and efficient tool for studying river systems and facilitating their rehabilitation. While many remote sensing applications utilize spectral information from the substrate and water column, light reflected from the water surface is often a significant component of the total at-sensor radiance. As water surface roughness (WSR) increases, a greater proportion of surface facets become oriented so as to reflect, rather than transmit, light. As a result, WSR exerts a primary control on the amount of surface reflected light measured by a remote sensor. WSR in rivers is a function of flow hydraulics, channel form, slope, bed roughness, and wind. While the relative influence of each of these components on WSR changes with scale, understanding these relationships could lead to methods for obtaining hydraulic information from image-derived metrics of WSR (i.e., surface reflectance). We collected field data on flow depth and velocity using an acoustic Doppler current profiler and simultaneously measured WSR using a custom built ultrasonic distance sensor on a diverse set of rivers ranging from a 15 m wide supraglacial river on the Greenland Ice Sheet to 100 m wide gravel-bed rivers in Wyoming and Oregon. Simultaneous multi- and hyperspectral image data sets indicate that image-derived surface reflectance is strongly correlated with WSR. Temporally distributed point measurements of flow depth, velocity, and WSR on the supraglacial river capture a threefold range in discharge (6 m3/s to 17 m3/s) and indicate that flow velocity is a primary control on WSR in smaller channels, even in the absence of sediment-induced bed roughness. Spatially distributed field measurements from large gravel-bed rivers suggests that spatial variability of WSR in the thalweg corresponds with geomorphic facies while WSR along the channel margins is more significantly influenced by grain size, relative submergence, and bank geometry. These findings suggest that

  2. An 800-kyr Record of Global Surface Ocean δ18Oand Implications for Ice Volume-Temperature Coupling

    NASA Astrophysics Data System (ADS)

    Shakun, J. D.; Lea, D. W.; Lisiecki, L. E.; Raymo, M. E.

    2015-12-01

    The sequence of feedbacks that characterized 100-kyr glacial cycles of the past million years remains uncertain, hampering an understanding of the interconnections between insolation, ice sheets, greenhouse gas forcing, and climate. Critical to addressing this issue is an accurate interpretation of the marine δ18O record, the main template for the Ice Ages. This study uses a global compilation of 49 paired sea surface temperature-planktonic δ18O records to extract the mean δ18O of surface ocean seawater over the past 800 kyr, which we interpret to dominantly reflect global ice volume. The results indicate that global surface temperature, inferred deep ocean temperature, and atmospheric CO2 decrease early during each glacial cycle in close association with one another, whereas major ice sheet growth occurs later in glacial cycles. These relationships suggest that ice volume may have exhibited a threshold response to global cooling, and that global deglaciations do not occur until after the growth of large ice sheets. This phase sequence also suggests that the ice sheets had relatively little feedback on global cooling. Simple modeling shows that the rate of ice volume change through time is largely determined by the combined influence of insolation, temperature, and ice sheet size, with possible implications for the evolution of glacial cycles over the past three million years.

  3. Saturn's Titan: Surface change, ammonia, and implications for atmospheric and tectonic activity

    USGS Publications Warehouse

    Nelson, R.M.; Kamp, L.W.; Matson, D.L.; Irwin, P.G.J.; Baines, K.H.; Boryta, M.D.; Leader, F.E.; Jaumann, R.; Smythe, W.D.; Sotin, C.; Clark, R.N.; Cruikshank, D.P.; Drossart, P.; Pearl, J.C.; Hapke, B.W.; Lunine, J.; Combes, M.; Bellucci, G.; Bibring, J.-P.; Capaccioni, F.; Cerroni, P.; Coradini, A.; Formisano, V.; Filacchione, G.; Langevin, R.Y.; McCord, T.B.; Mennella, V.; Nicholson, P.D.; Sicardy, B.

    2009-01-01

    Titan is known to have a young surface. Here we present evidence from the Cassini Visual and Infrared Mapping Spectrometer that it is currently geologically active. We report that changes in the near-infrared reflectance of a 73,000 km2 area on Titan (latitude 26° S, longitude 78° W) occurred between July 2004 and March of 2006. The reflectance of the area increased by a factor of two between July 2004 and March–April 2005; it then returned to the July 2004 level by November 2005. By late December 2005 the reflectance had surged upward again, establishing a new maximum. Thereafter, it trended downward for the next three months. Detailed spectrophotometric analyses suggest these changes happen at or very near the surface. The spectral differences between the region and its surroundings rule out changes in the distribution of the ices of reasonably expected materials such as H2O, CO2, and CH4 as possible causes. Remarkably, the change is spectrally consistent with the deposition and removal of NH3 frost over a water ice substrate. NH3 has been proposed as a constituent of Titan's interior and has never been reported on the surface. The detection of NH3 frost on the surface might possibly be explained by episodic effusive events occur which bring juvenile ammonia from the interior to the surface. If so, its decomposition would feed nitrogen to the atmosphere now and in the future. The lateral extent of the region exceeds that of active areas on the Earth (Hawaii) or Io (Loki).

  4. Nickel Alloy Primary Water Bulk Surface and SCC Corrosion Film Analytical Characterization and SCC Mechanistic Implications

    SciTech Connect

    Morton, D.; Lewis, N.; Hanson, M.; Rice, S.; Sanders, P.

    2007-04-18

    Alloy 600 corrosion coupon tests were performed: (1) to quantify the temperature dependency of general corrosion and (2) to characterize the composition and structure of bulk surface corrosion films for comparison with ongoing primary water SCC (PWSCC) crack tip corrosion film analyses. Results suggest that the thermal activation energy of Alloy 600 corrosion is consistent with the thermal activation energy of nickel alloy PWSCC. Analytical investigations of the structure and composition of Alloy 600 bulk surface corrosion oxides revealed a duplex (inner and outer) oxide layer structure. The outer layer is discontinuous and comprised of relatively large (1 to 3 {micro}m) nickel ferrite crystals and smaller ({approx}0.1 {micro}m) chromium containing nickel ferrite crystals. The inner layer consists of a relatively continuous chromite spinel (major phase) and chromia (Cr{sub 2}O{sub 3} minor phase) which formed through non-selective oxidation. Chromia and dealloyed Alloy 600 (highly Ni enriched metal) were only observed at 337 C (640 F) and only along the boundaries of deformation induced fine grains and subcells. Specimens having deformation free surfaces exhibited continuous uniform inner chromite spinel oxide layers. Specimens with machining induced surface deformation produced non-uniform inner layer oxides (chromite spinel, Cr{sub 2}O{sub 3} and unoxidized material). PWSCC crack tip oxides, in contrast, were fine grain (no duplex structure) and consisted of both chromium rich spinels and ''NiO'' structure oxides. Generally, nickel rich oxides were more abundant under more oxidized conditions (reduced coolant hydrogen) and spinel rich crack tip oxides were favored under more reducing conditions (increased coolant hydrogen). Bulk surface corrosion film thickness did not correlate with observed SCC growth rates. These results suggest that corrosion is not the rate controlling step of PWSCC but rather that PWSCC and corrosion have a common rate controlling sub

  5. Saturn's Titan: Surface change, ammonia, and implications for atmospheric and tectonic activity

    NASA Astrophysics Data System (ADS)

    Nelson, R. M.; Kamp, L. W.; Matson, D. L.; Irwin, P. G. J.; Baines, K. H.; Boryta, M. D.; Leader, F. E.; Jaumann, R.; Smythe, W. D.; Sotin, C.; Clark, R. N.; Cruikshank, D. P.; Drossart, P.; Pearl, J. C.; Hapke, B. W.; Lunine, J.; Combes, M.; Bellucci, G.; Bibring, J.-P.; Capaccioni, F.; Cerroni, P.; Coradini, A.; Formisano, V.; Filacchione, G.; Langevin, R. Y.; McCord, T. B.; Mennella, V.; Nicholson, P. D.; Sicardy, B.

    2009-02-01

    Titan is known to have a young surface. Here we present evidence from the Cassini Visual and Infrared Mapping Spectrometer that it is currently geologically active. We report that changes in the near-infrared reflectance of a 73,000 km 2 area on Titan (latitude 26° S, longitude 78° W) occurred between July 2004 and March of 2006. The reflectance of the area increased by a factor of two between July 2004 and March-April 2005; it then returned to the July 2004 level by November 2005. By late December 2005 the reflectance had surged upward again, establishing a new maximum. Thereafter, it trended downward for the next three months. Detailed spectrophotometric analyses suggest these changes happen at or very near the surface. The spectral differences between the region and its surroundings rule out changes in the distribution of the ices of reasonably expected materials such as H 2O, CO 2, and CH 4 as possible causes. Remarkably, the change is spectrally consistent with the deposition and removal of NH 3 frost over a water ice substrate. NH 3 has been proposed as a constituent of Titan's interior and has never been reported on the surface. The detection of NH 3 frost on the surface might possibly be explained by episodic effusive events occur which bring juvenile ammonia from the interior to the surface. If so, its decomposition would feed nitrogen to the atmosphere now and in the future. The lateral extent of the region exceeds that of active areas on the Earth (Hawaii) or Io (Loki).

  6. Can environmental conditions trigger cyanobacterial surfaces and following carbonate formation: implication for biomineralization and biotechnology

    NASA Astrophysics Data System (ADS)

    Paulo, C.; Dittrich, M.; Zhu, T.

    2015-12-01

    In this presentation we will give an overview what kind of the factors may trigger carbonate formations at the cell surfaces under a variety of environmental conditions. As examples, we will present the results from our recent studies on formation of calcium carbonates, dolomites and bio-cements. The extracellular polymeric substances (EPS) in the Synechococcuscell envelope are recognized key players in the nucleation of carbonates in marine and freshwater environments. Yet, little is known about a nutrient contents control over the molecular composition of Synechococcus cell envelope, and consequently, biomineralization. In the first study, we investigated how a variation of the phosphorus (P) in the growth media can lead to changes in the surface reactivity of the cells and impact their ability to form carbonates. The objective of the second study is to gain insights into the spatial distribution of cyanobacterial EPS and dolomite from different sediment layers of Khor Al-Adaid sabkha (Qatar). Here, we characterized microbial mats on molecular level in respect of organic and inorganic components using in-situ 2D Raman spectroscopy and Atomic Force Microscopy (AFM) were used. Additionally, 2D chemical maps of sediment layers documented spectral characterizations of minerals and organic matter of microbial origins at high spatial resolution. Finally, we will show the results from the experiments with auto-phototrophic cyanobacteria Gloeocapsa PCC73106, which habitat on the monument surfaces, towards its application for bio-concrete, a product of microbial carbonate precipitation. We studied the biomineralization in biofilm forming Gloeocapsa PCC73106 on the concrete surface as a pre-requirement for microbial carbonate precipitation. Biomineralization on the concrete surface by live cells and killed cells were compared with that under the abiotic condition. Our experiments allow us to conclude that environmental conditions play a significant role in the control of

  7. Ecological Filtering and Plant Traits Variation Across Quarry Geomorphological Surfaces: Implication for Restoration

    NASA Astrophysics Data System (ADS)

    Gilardelli, Federica; Sgorbati, Sergio; Armiraglio, Stefano; Citterio, Sandra; Gentili, Rodolfo

    2015-05-01

    Revegetation patterns after quarry abandonment have been widely studied from several ecological points of view, but a trait-based approach is still lacking. The aim of this study was to characterise the plant species assemblages and the associated functional traits filtered on different geomorphological surfaces in abandoned limestone quarry areas: artificial cliffs, embankments, and platforms. We then verified if species with certain traits were better able to overcome the dispersal and environmental filters necessary for establishment. To this aim, we analyzed 113 vegetation plots and collected data on 25 morphological, ecological, and dispersal traits to detect species adaptaions across these man-made environments. As a case study, we investigated the extraction basin of Botticino (Lombardy, Italy), the second largest in Italy. The results obtained by SIMPER and CCA analyses showed that rockiness, stoniness, slope, elevation, and time of surfaces are the main filters that varied across quarries and affected plant assemblages at the macro-scale level. Across the three geomorphological surfaces (meso-scale) of quarries, more specific abiotic filters selecting species were found. In turn, traits differentiation according to the three main geomorphological surfaces of quarry emphasized that further filters acting at the micro-scale imply differences in dispersal mechanisms and resource availability. This work highlighted the utility to study species assemblages and environmental filters to address quarry restoration according to the type of geomorphological surface. The investigation of some traits (chorological form, life forms, seed dispersal,s and plant height) can furnish some interesting indications for practice individuating further abiotic filters acting at the micro-scale.

  8. Switching the Structural Force in Ionic Liquid-Solvent Mixtures by Varying Composition.

    PubMed

    Smith, Alexander M; Lee, Alpha A; Perkin, Susan

    2017-03-03

    The structure and interactions in electrolytes at high concentration have implications from energy storage to biomolecular interactions. However, many experimental observations are yet to be explained in these mixtures, which are far beyond the regime of validity of mean-field models. Here, we study the structural forces in a mixture of ionic liquid and solvent that is miscible in all proportions at room temperature. Using the surface force balance to measure the force between macroscopic smooth surfaces across the liquid mixtures, we uncover an abrupt increase in the wavelength above a threshold ion concentration. Below the threshold concentration, the wavelength is determined by the size of the solvent molecule, whereas above the threshold, it is the diameter of a cation-anion pair that determines the wavelength.

  9. Switching the Structural Force in Ionic Liquid-Solvent Mixtures by Varying Composition

    NASA Astrophysics Data System (ADS)

    Smith, Alexander M.; Lee, Alpha A.; Perkin, Susan

    2017-03-01

    The structure and interactions in electrolytes at high concentration have implications from energy storage to biomolecular interactions. However, many experimental observations are yet to be explained in these mixtures, which are far beyond the regime of validity of mean-field models. Here, we study the structural forces in a mixture of ionic liquid and solvent that is miscible in all proportions at room temperature. Using the surface force balance to measure the force between macroscopic smooth surfaces across the liquid mixtures, we uncover an abrupt increase in the wavelength above a threshold ion concentration. Below the threshold concentration, the wavelength is determined by the size of the solvent molecule, whereas above the threshold, it is the diameter of a cation-anion pair that determines the wavelength.

  10. The footprint of Alaskan tundra fires during the past half-century: implications for surface properties and radiative forcing

    USGS Publications Warehouse

    Rocha, Adrian V.; Loranty, Michael M.; Higuera, Phil E.; Mack, Michelle C.; Hu, Feng Sheng; Jones, Benjamin M.; Breen, Amy L.; Rastetter, Edward B.; Goetz, Scott J.; Shaver, Gus R.

    2012-01-01

    Recent large and frequent fires above the Alaskan arctic circle have forced a reassessment of the ecological and climatological importance of fire in arctic tundra ecosystems. Here we provide a general overview of the occurrence, distribution, and ecological and climate implications of Alaskan tundra fires over the past half-century using spatially explicit climate, fire, vegetation and remote sensing datasets for Alaska. Our analyses highlight the importance of vegetation biomass and environmental conditions in regulating tundra burning, and demonstrate that most tundra ecosystems are susceptible to burn, providing the environmental conditions are right. Over the past two decades, fire perimeters above the arctic circle have increased in size and importance, especially on the North Slope, indicating that future wildfire projections should account for fire regime changes in these regions. Remote sensing data and a literature review of thaw depths indicate that tundra fires have both positive and negative implications for climatic feedbacks including a decadal increase in albedo radiative forcing immediately after a fire, a stimulation of surface greenness and a persistent long-term (>10 year) increase in thaw depth. In order to address the future impact of tundra fires on climate, a better understanding of the control of tundra fire occurrence as well as the long-term impacts on ecosystem carbon cycling will be required.

  11. 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.

  12. Polymer-supported ionic-liquid-like phases (SILLPs): transferring ionic liquid properties to polymeric matrices.

    PubMed

    Sans, Victor; Karbass, Naima; Burguete, M Isabel; Compañ, Vicente; García-Verdugo, Eduardo; Luis, Santiago V; Pawlak, Milena

    2011-02-07

    The physico-chemical properties of polymers with ionic-liquid-like moieties covalently bound to their surfaces (SILLPs) have been studied by thermal and spectroscopic techniques, as well as by direct impedance and dielectric measurements, and compared to those of the corresponding bulk ionic liquids. The effective transfer of properties from ionic liquids in solution to the supported species has thereby been demonstrated. The effects of the chemical nature of these tunable "solid solvents" on their macroscopic swelling and microwave heating, as well as the stabilities and activities of different catalytic moieties immobilized on the SILLPs, have been studied. Finally, the experimental effect observed in microwave heating can be directly correlated with the values of tan δ derived from dielectric measurements.

  13. VOC and HAP recovery using ionic liquids

    SciTech Connect

    Michael R. Milota : Kaichang Li

    2007-05-29

    During the manufacture of wood composites, paper, and to a lesser extent, lumber, large amounts of volatile organic compounds (VOCs) such as terpenes, formaldehyde, and methanol are emitted to air. Some of these compounds are hazardous air pollutants (HAPs). The air pollutants produced in the forest products industry are difficult to manage because the concentrations are very low. Presently, regenerative thermal oxidizers (RTOs and RCOs) are commonly used for the destruction of VOCs and HAPs. RTOs consume large amounts of natural gas to heat air and moisture. The combustion of natural gas generates increased CO2 and NOx, which have negative implications for global warming and air quality. The aforementioned problems are addressed by an absorption system containing a room-temperature ionic liquid (RTIL) as an absorbent. RTILs are salts, but are in liquid states at room temperature. RTILs, an emerging technology, are receiving much attention as replacements for organic solvents in industrial processes with significant cost and environmental benefits. Some of these processes include organic synthesis, extraction, and metal deposition. RTILs would be excellent absorbents for exhausts from wood products facilities because of their unique properties: no measurable vapor pressure, high solubility of wide range of organic compounds, thermal stability to 200°C (almost 400°F), and immisciblity with water. Room temperature ionic liquids were tested as possible absorbents. Four were imidizolium-based and were eight phosphonium-based. The imidizolium-based ionic liquids proved to be unstable at the conditions tested and in the presence of water. The phosphonium-based ionic liquids were stable. Most were good absorbents; however, cleaning the contaminates from the ionic liquids was problematic. This was overcome with a higher temperature (120°C) than originally proposed and a very low pressure (1 kPa. Absorption trials were conducted with tetradecy

  14. 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.

  15. 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.

  16. An ionic electro-active actuator made with graphene film electrode, chitosan and ionic liquid

    NASA Astrophysics Data System (ADS)

    He, Qingsong; Yu, Min; Yang, Xu; Kim, Kwang Jin; Dai, Zhendong

    2015-06-01

    A newly developed ionic electro-active actuator composed of an ionic electrolyte layer sandwiched between two graphene film layers was investigated. Scanning electronic microscopy observation and x-ray diffraction analysis showed that the graphene sheets in the film stacked in a nearly face-to-face fashion but did not restack back to graphite, and the resulting graphene film with low sheet resistance (10 Ω sq-1) adheres well to the electrolyte membrane. Contact angle measurement showed the surface energy (37.98 mJ m-2) of the ionic electrolyte polymer is 2.67 times higher than that (14.2 mJ m-2) of the Nafion membrane, contributing to the good adhesion between the graphene film electrode and the electrolyte membrane. An electric double-layer is formed at the interface between the graphene film electrode and the ionic electrolyte membrane under the input potential, resulting in a higher capacitance of 27.6 mF cm-2. We report that this ionic actuator exhibits adequate bending strain, ranging from 0.032 to 0.1% (305 to 945 μm) as functions of voltage.

  17. Hot electron dynamics at semiconductor surfaces: Implications for quantum dot photovoltaics

    NASA Astrophysics Data System (ADS)

    Tisdale, William A., III

    Finding a viable supply of clean, renewable energy is one of the most daunting challenges facing the world today. Solar cells have had limited impact in meeting this challenge because of their high cost and low power conversion efficiencies. Semiconductor nanocrystals, or quantum dots, are promising materials for use in novel solar cells because they can be processed with potentially inexpensive solution-based techniques and because they are predicted to have novel optoelectronic properties that could enable the realization of ultra-efficient solar power converters. However, there is a lack of fundamental understanding regarding the behavior of highly-excited, or "hot," charge carriers near quantum-dot and semiconductor interfaces, which is of paramount importance to the rational design of high-efficiency devices. The elucidation of these ultrafast hot electron dynamics is the central aim of this Dissertation. I present a theoretical framework for treating the electronic interactions between quantum dots and bulk semiconductor surfaces and propose a novel experimental technique, time-resolved surface second harmonic generation (TR-SHG), for probing these interactions. I then describe a series of experimental investigations into hot electron dynamics in specific quantum-dot/semiconductor systems. A two-photon photoelectron spectroscopy (2PPE) study of the technologically-relevant ZnO(1010) surface reveals ultrafast (sub-30fs) cooling of hot electrons in the bulk conduction band, which is due to strong electron-phonon coupling in this highly polar material. The presence of a continuum of defect states near the conduction band edge results in Fermi-level pinning and upward (n-type) band-bending at the (1010) surface and provides an alternate route for electronic relaxation. In monolayer films of colloidal PbSe quantum dots, chemical treatment with either hydrazine or 1,2-ethanedithiol results in strong and tunable electronic coupling between neighboring quantum dots

  18. Seasonal changes in Titan's weather patterns and the evolution and implications of accompanying surface changes

    NASA Astrophysics Data System (ADS)

    Turtle, Elizabeth; McEwen, Alfred

    2012-07-01

    Post-equinox changes in Titan's atmospheric circulation brought clouds and extensive methane rain to low latitudes [1,2]. Observations by Cassini ISS over the ensuing ~1.5 yr revealed surface changes to be short-lived; few rain-darkened areas persisted through 2011. In an unsaturated permeable medium, infiltration rates are >20 mm/week [3], so persistence of surface liquids over several months suggests that either an impermeable layer or the local methane table lies close to the surface. Evaporation rates >1 mm/week are predicted at low latitudes [4] and 20 mm/week has been documented at Titan's poles [5], thus areas where darkening persisted must be saturated ground at the level of a methane table or have had ponded liquid 2.5-50 cm deep. Several smaller areas of surface brightening were also observed, a phenomenon that is less well understood. Cassini VIMS spectra of these regions do not match clouds or other surface units [6]. Interpretations include cleaning by runoff [2] or deposition of a fine-grained volatile solid as the result of evaporative cooling of the surface [6]. In general, brightening has persisted longer than darkening, but these areas are also reverting to their original appearance, possibly due to evaporation/sublimation of the bright material or re-deposition of darker hydrocarbons by aeolian transport or precipitation from the atmosphere. Cassini and Earth-based observers monitor Titan frequently, but few clouds have been observed since Fall 2010, which may indicate that enough methane was removed from the atmosphere and the lapse rate stabilized sufficiently that activity will not resume until the onset of convection at mid-northern latitudes later in northern spring. A similar lapse followed a 2004 outburst of south-polar clouds [7], which also appeared to produce significant rainfall [8]. [1] Turtle et al., GRL 38, L03203, doi:10.1029/2010GL046266, 2011. [2] Turtle et al., Science 331, 10.1126/science.1201063. 2011. [3] Hayes et al., GRL 35

  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. Effects of peeling on the surface structure of the Avena coleoptile: Implications for hormone research.

    PubMed

    Rubinstein, B; Stein, O L

    1980-12-01

    Coleoptiles of oats (Avena sativa L.) are often peeled in order to observe hormone-enhanced acidification of the external medium. It is shown by means of the scanning electron microscope that peeling largely removes a single layer of cells, the epidermis with its cuticle. Strips of intact and damaged epidermal cells remain, but most of the newly exposed surface is composed of cortical cells. The cortical face is relatively intact, except that some cells appear punctured and some are broken when a vascular bundle is pulled out with the epidermis. The surface of the cortex is covered by a thin "film" which is partially digested by 2% pectinase. The pectinase pretreatment also inhibits indoleacetic-acid- and fusicoccin-enhanced acidification. Thus, although peeling could be involved in proton extrusion, physical damage to the coleoptile cells per se does not seem to be the major stimulus leading to hormone-enhanced acidification.

  1. Carbon clusters near the step of Rh surface: implication for the initial stage of graphene nucleation

    NASA Astrophysics Data System (ADS)

    Gao, Junfeng; Zhao, Jijun

    2013-03-01

    To understand the initial nucleation of graphene by chemical vapor deposition along metal step, carbon clusters ( N = 1 ˜ 24) near Rh (4 3 3) stepwise surface were systemically explored by first-principles calculations. Carbon chains are always more stable than carbon rings on stepped metal surface. Starting from C6, carbon chains prefer two-end passivation on the metal step. A structural transition of carbon clusters from one-dimensional sp chains to two-dimensional s p 2 networks are found at C10, which corresponds to the nucleation size at a wide range of chemical potentials. According to these theoretical results, we proposed that appropriately controlling the chemical potential may be helpful for observing the four stable carbon clusters along metal step and improving the quality of graphene.

  2. Modelling interstellar physics and chemistry: implications for surface and solid-state processes.

    PubMed

    Williams, David; Viti, Serena

    2013-07-13

    We discuss several types of regions in the interstellar medium of the Milky Way and other galaxies in which the chemistry appears to be influenced or dominated by surface and solid-state processes occurring on or in interstellar dust grains. For some of these processes, for example, the formation of H₂ molecules, detailed experimental and theoretical approaches have provided excellent fundamental data for incorporation into astrochemical models. In other cases, there is an astrochemical requirement for much more laboratory and computational study, and we highlight these needs in our description. Nevertheless, in spite of the limitations of the data, it is possible to infer from astrochemical modelling that surface and solid-state processes play a crucial role in astronomical chemistry from early epochs of the Universe up to the present day.

  3. Volatile organic compounds in the marine troposphere and surface oceans: methods, measurements and biogeochemical implications

    NASA Astrophysics Data System (ADS)

    Hudson, Edward

    2010-09-01

    Volatile organic compounds (VOCs), among them non-methane hydrocarbons (NMHCs) and low molecular weight carbonyl compounds (aldehydes and ketones), affect the oxidative capacity of the atmosphere and thus pollutant lifetimes and global climate. VOCs in the surface oceans may be transported into, or derived from, the atmosphere. This thesis describes the development and optimization of chromatographic and preconcentration methods to determine volatile organic compounds (VOCs) in surface seawater and marine air, and their use to explore VOC distribution and fluxes at the seaair interface. It includes the first measurements of many carbonyl compounds in temperate and subarctic marine waters and the first estimates of fluxes of several aldehydes from the ocean surface into the marine atmosphere. Sea surface air, size-fractionated marine aerosols, and surface ocean water dissolved organic matter were simultaneously sampled in the Nordic seas. Nineteen C2-C7 NMHCs were quantified in the air samples. Site-to-site variability in NMHC concentrations was high, suggesting variable, local sources. The aerosols consisted mainly of inorganic marine material, but a culturable bacterium identified as Micrococcus luteus was also isolated from the 9.9 -- 18 mum fraction, suggesting organic matter may be transferred from the surface oceans to the atmosphere by marine aerosols. Lastly, a number of VOCs, including acetone, were detected in the seawater samples using solid-phase microextraction (SPME), leading to the subsequent development of an SPME application for carbonyl compounds in seawater. A mobile, economical and solventless method for the detection and quantification of carbonyl compounds in seawater, a matrix of global importance, was developed. The compounds were derivatized using O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA)and then pre-concentrated by SPME for gas chromatography with mass spectrometric (GC/MS) or flame ionization (GC-FID) detection. The method was

  4. Spatial Arrangment of Organic Compounds on a Model Mineral Surface: Implications for Soil Organic Matter Stabilization

    SciTech Connect

    Petridis, Loukas; Ambaye, Haile Arena; Jagadamma, Sindhu; Kilbey, S. Michael; Lokitz, Bradley S; Lauter, Valeria; Mayes, Melanie

    2014-01-01

    The complexity of the mineral organic carbon interface may influence the extent of stabilization of organic carbon compounds in soils, which is important for global climate futures. The nanoscale structure of a model interface was examined here by depositing films of organic carbon compounds of contrasting chemical character, hydrophilic glucose and amphiphilic stearic acid, onto a soil mineral analogue (Al2O3). Neutron reflectometry, a technique which provides depth-sensitive insight into the organization of the thin films, indicates that glucose molecules reside in a layer between Al2O3 and stearic acid, a result that was verified by water contact angle measurements. Molecular dynamics simulations reveal the thermodynamic driving force behind glucose partitioning on the mineral interface: The entropic penalty of confining the less mobile glucose on the mineral surface is lower than for stearic acid. The fundamental information obtained here helps rationalize how complex arrangements of organic carbon on soil mineral surfaces may arise

  5. Crystal fractionation in the SNC meteorites: Implications for surface units on Mars

    NASA Technical Reports Server (NTRS)

    Treiman, Allan H.

    1987-01-01

    Almost all rock types in the SNC meteorites are cumulates, products of magma differentiation by crystal fractionation (addition or removal of crystals). If the SNC meteorites are from the surface of Mars or near sub-surface, then most of the igneous units on Mars are differentiated. Basaltic units probably experienced minor to moderate differentiation, but ultrabasic units probably experienced extreme differentiation. Products of this differentiation may include Fe-rich gabbro, pyroxenite, peridotite (and thus serpentine), and possibly massive sulfides. The SNC meteorites include ten lithologies (three in EETA79001), eight of which are crystal cumulates. The other lithologies, EETA79001 A and B are subophitic basalts. The cumulate lithologies ALHA77005 and EETA79001 C were not fully described or discussed.

  6. Vibrational Spectroscopy of Ionic Liquids.

    PubMed

    Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C

    2017-01-04

    Vibrational spectroscopy has continued use as a powerful tool to characterize ionic liquids since the literature on room temperature molten salts experienced the rapid increase in number of publications in the 1990's. In the past years, infrared (IR) and Raman spectroscopies have provided insights on ionic interactions and the resulting liquid structure in ionic liquids. A large body of information is now available concerning vibrational spectra of ionic liquids made of many different combinations of anions and cations, but reviews on this literature are scarce. This review is an attempt at filling this gap. Some basic care needed while recording IR or Raman spectra of ionic liquids is explained. We have reviewed the conceptual basis of theoretical frameworks which have been used to interpret vibrational spectra of ionic liquids, helping the reader to distinguish the scope of application of different methods of calculation. Vibrational frequencies observed in IR and Raman spectra of ionic liquids based on different anions and cations are discussed and eventual disagreements between different sources are critically reviewed. The aim is that the reader can use this information while assigning vibrational spectra of an ionic liquid containing another particular combination of anions and cations. Different applications of IR and Raman spectroscopies are given for both pure ionic liquids and solutions. Further issues addressed in this review are the intermolecular vibrations that are more directly probed by the low-frequency range of IR and Raman spectra and the applications of vibrational spectroscopy in studying phase transitions of ionic liquids.

  7. Martian Buried Basins and Implications for Characteristics of the Burial Layer and Underlying Surface

    NASA Technical Reports Server (NTRS)

    Sarid, A. R.; Frey, H. V.; Roark, J. H.

    2003-01-01

    Deciphering the cratering record on Mars has been challenging because it may reflect the changes in both the population of impactors and in the resurfacing processes on Mars. However, it is possible to determine the breadth of impactors captured in the cratering record. Extensive areas of resurfacing are of particular interest because they likely contain material from various ages in Martian history. By deducing the impact populations in both surface and underlying layers of terrain, it is possible to determine the age of the layers and constrain theories on the development of the Martian surface. However, to do so requires a method of seeing impact features which are no longer visible. Topographic data of Mars, taken by the Mars Orbiter Laser Altimeter (MOLA), has revealed impact features buried by resurfacing processes. These features are often indistinguishable on Viking images of the Martian surface. In this study, gridded MOLA data was analyzed in order to locate buried impact features, also called buried basins, in Syria, Solis, and Sinai Planum just south of Valles Marineris. The population statistics of buried features can be compared to those of visible features in order to determine the age of the underlying material and characteristics of the surface cover. Specifically, if the buried population in the Hesperian terrain is similar to the population of visible features in the Noachian, it would suggest that the underlying terrain is Noachian in age. The buried craters can then be compared to visible Noachian craters to reveal the amount of deterioration of the buried features. These comparisons allow us to explore the morphology of the terrain in the Hesperian region to determine if topographic variations are due to differences in the thickness of the overlying material or are a characteristic of the underlying terrain.

  8. Horizontal Transfer of Antibiotic Resistance Genes on Abiotic Touch Surfaces: Implications for Public Health

    PubMed Central

    Warnes, Sarah L.; Highmore, Callum J.; Keevil, C. William

    2012-01-01

    ABSTRACT Horizontal gene transfer (HGT) is largely responsible for increasing the incidence of antibiotic-resistant infections worldwide. While studies have focused on HGT in vivo, this work investigates whether the ability of pathogens to persist in the environment, particularly on touch surfaces, may also play an important role. Escherichia coli, virulent clone ST131, and Klebsiella pneumoniae harboring extended-spectrum-β-lactamase (ESBL) blaCTX-M-15 and metallo-β-lactamase blaNDM-1, respectively, exhibited prolonged survival on stainless steel, with approximately 104 viable cells remaining from an inoculum of 107 CFU per cm2 after 1 month at 21°C. HGT of bla to an antibiotic-sensitive but azide-resistant recipient E. coli strain occurred on stainless steel dry touch surfaces and in suspension but not on dry copper. The conjugation frequency was approximately 10 to 50 times greater and occurred immediately, and resulting transconjugants were more stable with ESBL E. coli as the donor cell than with K. pneumoniae, but blaNDM-1 transfer increased with time. Transconjugants also exhibited the same resistance profile as the donor, suggesting multiple gene transfer. Rapid death, inhibition of respiration, and destruction of genomic and plasmid DNA of both pathogens occurred on copper alloys accompanied by a reduction in bla copy number. Naked E. coli DNA degraded on copper at 21°C and 37°C but slowly at 4°C, suggesting a direct role for the metal. Persistence of viable pathogenic bacteria on touch surfaces may not only increase the risk of infection transmission but may also contribute to the spread of antibiotic resistance by HGT. The use of copper alloys as antimicrobial touch surfaces may help reduce infection and HGT. PMID:23188508

  9. Ascorbic acid modifies the surface of asbestos: possible implications in the molecular mechanisms of toxicity.

    PubMed

    Martra, Gianmario; Tomatis, Maura; Fenoglio, Ivana; Coluccia, Salvatore; Fubini, Bice

    2003-03-01

    Ascorbic acid is one of the major components of the antioxidants defenses of the lung lining layer where inhaled asbestos fibers are deposited. Crocidolite fibers were incubated at 37 degrees C in a 0.01 M aqueous solution of ascorbic acid for 25 days in order to investigate modifications in surface reactivity. Iron (820 nmol/mg) and monomeric silica (470 nmol/mg) were released in the supernatant, while ascorbic acid was consumed. The amount of iron and silicon released, respectively, 17 and 6% (in atoms) of the total fiber content, exceeded what was expected at the surface, suggesting a partial disgregation of crocidolite promoted by ascorbic acid. In the absence of ascorbic acid but at the same pH, the release of iron and monomeric silica was minimal. At time intervals, aliquots of fibers were withdrawn to evidence chemical modifications progressively taking place. Three families of Fe(II) centers, differing in coordinative unsaturation and progressively removed during incubation, have been evidenced from the FTIR spectra of NO adsorbed onto the fibers. The most uncoordinated ones are removed first. New highly uncoordinated iron sites are exposed at the fiber surface as a consequence of the erosion of the outmost layers while hydration of silica tetrahedra yields new silanol groups. The activity in the Fenton-like reaction (*OH from H(2)O(2)) decreases following surface iron depauperation. Conversely, the homolytic cleavage of the C-H bond (CO(2)*-) from the formate ion) appears related to the small fraction of iron ions always present but easily quenched by the adsorption of ascorbic acid or its oxidation products.

  10. Surface Electrical Potentials of Root Cell Plasma Membranes: Implications for Ion Interactions, Rhizotoxicity, and Uptake

    PubMed Central

    Wang, Yi-Min; Kinraide, Thomas B.; Wang, Peng; Hao, Xiu-Zhen; Zhou, Dong-Mei

    2014-01-01

    Many crop plants are exposed to heavy metals and other metals that may intoxicate the crop plants themselves or consumers of the plants. The rhizotoxicity of heavy metals is influenced strongly by the root cell plasma membrane (PM) surface’s electrical potential (ψ0). The usually negative ψ0 is created by negatively charged constituents of the PM. Cations in the rooting medium are attracted to the PM surface and anions are repelled. Addition of ameliorating cations (e.g., Ca2+ and Mg2+) to the rooting medium reduces the effectiveness of cationic toxicants (e.g., Cu2+ and Pb2+) and increases the effectiveness of anionic toxicants (e.g., SeO42− and H2AsO4−). Root growth responses to ions are better correlated with ion activities at PM surfaces ({IZ}0) than with activities in the bulk-phase medium ({IZ}b) (IZ denotes an ion with charge Z). Therefore, electrostatic effects play a role in heavy metal toxicity that may exceed the role of site-specific competition between toxicants and ameliorants. Furthermore, ψ0 controls the transport of ions across the PM by influencing both {IZ}0 and the electrical potential difference across the PM from the outer surface to the inner surface (Em,surf). Em,surf is a component of the driving force for ion fluxes across the PM and controls ion-channel voltage gating. Incorporation of {IZ}0 and Em,surf into quantitative models for root metal toxicity and uptake improves risk assessments of toxic metals in the environment. These risk assessments will improve further with future research on the application of electrostatic theory to heavy metal phytotoxicity in natural soils and aquatic environments. PMID:25493475

  11. Solar Wind Sputtering of Lunar Surface Materials: Role and Some Possible Implications of Potential Sputtering

    NASA Technical Reports Server (NTRS)

    Barghouty, A. F.; Adams, J. H., Jr.; Meyer, F.; Reinhold, c.

    2010-01-01

    Solar-wind induced sputtering of the lunar surface includes, in principle, both kinetic and potential sputtering. The role of the latter mechanism, however, in many focused studies has not been properly ascertained due partly to lack of data but can also be attributed to the assertion that the contribution of solar-wind heavy ions to the total sputtering is quite low due to their low number density compared to solar-wind protons. Limited laboratory measurements show marked enhancements in the sputter yields of slow-moving, highly-charged ions impacting oxides. Lunar surface sputtering yields are important as they affect, e.g., estimates of the compositional changes in the lunar surface, its erosion rate, as well as its contribution to the exosphere as well as estimates of hydrogen and water contents. Since the typical range of solar-wind ions at 1 keV/amu is comparable to the thickness of the amorphous rim found on lunar soil grains, i.e. few 10s nm, lunar simulant samples JSC-1A AGGL are specifically enhanced to have such rims in addition to the other known characteristics of the actual lunar soil particles. However, most, if not all laboratory studies of potential sputtering were carried out in single crystal targets, quite different from the rim s amorphous structure. The effect of this structural difference on the extent of potential sputtering has not, to our knowledge, been investigated to date.

  12. Thermal convection in a rotating spherical body with free surface: Implications for Saturn's moon Iapetus

    NASA Astrophysics Data System (ADS)

    Kuchta, Milan; Čadek, O.; Tobie, G.

    2012-10-01

    We present a new numerical tool to simulate thermal cooling and spin evolution of a rotating body with freely deformable surface and complex rheology. While the long-term mechanical properties of the body are mimicked by visco-plastic rheology including different creep mechanisms, its despinning is controlled by Andrá de visco-elastic model. Variabledensity approximation (sticky air) and implicit description of the surface are combined in order to track the surface evolution. We use this tool to investigate the shape of Saturn's moon Iapetus, whose topography shows enigmatic remnant features from the moon's early history when the spin rate and temperature were significantly higher than at present. Our model is characterized by three parameters: the initial temperature (ranging from 230 to 270 K), the initial rotational period (8-15 hours), and the grain size of ice (0.01-100 mm) defining the relative role of diffusion creep in total deformation. For these three parameters, we systematically explore the model space and show for which combinations of parameters the body can be effectively despun while maintaining its strongly flattened shape. Our results indicate that the despinning of Iapetus could not occur without interaction with an external body.

  13. Vitrification darkening of rock powders - Implications for optical properties of the lunar surface

    NASA Technical Reports Server (NTRS)

    Nash, D. B.; Conel, J. E.

    1973-01-01

    Laboratory experiments show that albedoes as low as those on the moon can be produced by vacuum vitrification and associated chemical fractionation of ordinary terrestrial basaltic material. Vitrification is established as an unequivocal process that can account for the low albedo and apparent local darkening with age of the lunar surface. The spectral reflectance curves of glass powders are significantly different than those of the parent rock mineralogy; thus, the presence of ubiquitous glass in lunar surface material complicates compositional determinations by interpretation of spectral reflectance curves. Vitrification of rocks on the moon may highly modify the chemical composition of the resulting glass; thus, glass fragments found in lunar fines cannot be assumed to represent bulk parent rock material. Progressive impact vitrification of lunar surface material throughout the moon's history may have led to a fine-grain, opaque, refractory-rich material we call 'ultimate glass.' This unidentified and, at this point, hypothetical component may exist in dark regolith material; if found, it may be a useful indicator of regolith maturity.

  14. The Effect of Global Change on Surface Ozone and Reactive Nitrogen Concentrations: Implications for the Biosphere

    NASA Astrophysics Data System (ADS)

    Hess, P. G.; Murazaki, K.; Emmons, L.; Lamarque, J.

    2005-12-01

    We simulated two ten year periods using the global chemical transport model MOZART-2 (Model of Ozone and Related chemical Tracers version 2): 1990-2000 and 2090-2100. In each case MOZART-2 is driven by meteorology from the National Center for Atmospheric Research (NCAR) coupled Climate Systems Model (CSM) 1.0 forced with the (SRES) A1 scenario. Profound future changes in the summertime climate over the U.S. are found including changes in temperature, water vapor and clouds and the frequency of synoptic venting of the boundary layer. Even allowing for no changes in emissions in the future, the changes in climate alone drive a significant increase in the ozone concentration over the eastern U.S. (up to 5 ppbv on average) and an increase in the persistence of pollution events. Implications of these changes on the biosphere are assessed with and without allowing for the impact of climate on biogenic emissions. Furthermore the changes in climate alone cause large changes in the partitioning of NOy, decreasing PAN by over 20% over the U.S. Coupled with changes in precipitation; this induces significant changes in the deposition of nitrogen species to the biosphere in a future climate.

  15. Geomorphic adjustment to hydrologic modifications along a meandering river: Implications for surface flooding on a floodplain

    NASA Astrophysics Data System (ADS)

    Edwards, Brandon L.; Keim, Richard F.; Johnson, Erin L.; Hupp, Cliff R.; Marre, Saraline; King, Sammy L.

    2016-09-01

    Responses of large regulated rivers to contemporary changes in base level are not well understood. We used field measurements and historical analysis of air photos and topographic maps to identify geomorphic trends of the lower White River, Arkansas, USA, in the 70 years following base-level lowering at its confluence with the Mississippi River and concurrent with flood control by dams. Incision was identified below a knickpoint area upstream of St. Charles, AR, and increases over the lowermost ~90 km of the study site to ~2 m near the confluence with the Mississippi River. Mean bankfull width increased by 30 m (21%) from 1930 to 2010. Bank widening appears to be the result of flow regulation above the incision knickpoint and concomitant with incision below the knickpoint. Hydraulic modeling indicated that geomorphic adjustments likely reduced flooding by 58% during frequent floods in the incised, lowermost floodplain affected by backwater flooding from the Mississippi River and by 22% above the knickpoint area. Dominance of backwater flooding in the incised reach indicates that incision is more important than flood control on the lower White River in altering flooding and also suggests that the Mississippi River may be the dominant control in shaping the lower floodplain. Overall, results highlight the complex geomorphic adjustment in large river-floodplain systems in response to anthropogenic modifications and their implications, including reduced river-floodplain connectivity.

  16. Fast Conversion of Ionic Liquids and Poly(Ionic Liquid)s into Porous Nitrogen-Doped Carbons in Air.

    PubMed

    Men, Yongjun; Ambrogi, Martina; Han, Baohang; Yuan, Jiayin

    2016-04-08

    Ionic liquids and poly(ionic liquid)s have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m²/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection.

  17. Fast Conversion of Ionic Liquids and Poly(Ionic Liquid)s into Porous Nitrogen-Doped Carbons in Air

    PubMed Central

    Men, Yongjun; Ambrogi, Martina; Han, Baohang; Yuan, Jiayin

    2016-01-01

    Ionic liquids and poly(ionic liquid)s have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m2/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection. PMID:27070588

  18. Conjunctive Surface and Groundwater Management in Utah. Implications for Oil Shale and Oil Sands Development

    SciTech Connect

    Keiter, Robert; Ruple, John; Tanana, Heather; Holt, Rebecca

    2011-12-01

    Unconventional fuel development will require scarce water resources. In an environment characterized by scarcity, and where most water resources are fully allocated, prospective development will require minimizing water use and seeking to use water resources in the most efficient manner. Conjunctive use of surface and groundwater provides just such an opportunity. Conjunctive use includes two main practices: First, integrating surface water diversions and groundwater withdrawals to maximize efficiency and minimize impacts on other resource users and ecological processes. Second, conjunctive use includes capturing surplus or unused surface water and injecting or infiltrating that water into groundwater aquifers in order to increase recharge rates. Conjunctive management holds promise as a means of addressing some of the West's most intractable problems. Conjunctive management can firm up water supplies by more effectively capturing spring runoff and surplus water, and by integrating its use with groundwater withdrawals; surface and groundwater use can be further integrated with managed aquifer recharge projects. Such integration can maximize water storage and availability, while simultaneously minimizing evaporative loss, reservoir sedimentation, and surface use impacts. Any of these impacts, if left unresolved, could derail commercial-scale unconventional fuel development. Unconventional fuel developers could therefore benefit from incorporating conjunctive use into their development plans. Despite its advantages, conjunctive use is not a panacea. Conjunctive use means using resources in harmony to maximize and stabilize long-term supplies it does not mean maximizing the use of two separate but interrelated resources for unsustainable short-term gains and it cannot resolve all problems or provide water where no unappropriated water exists. Moreover, conjunctive use may pose risks to ecological values forgone when water that would otherwise remain in a stream is

  19. Groundwater and surface water discharge from an abandoned tailings impoundment: Implications for watershed water quality

    NASA Astrophysics Data System (ADS)

    Moncur, M. C.; Ptacek, C. J.; Blowes, D. W.; Birks, S. J.

    2006-12-01

    Release of acid drainage from mine-waste disposal areas is a problem of international scale. Drainage from sulfide-rich waste can result in contaminated surface waters, directly through surface runoff and indirectly, from discharge of contaminated groundwater flow. Camp Lake, located in Northern Manitoba, receives both direct and indirect drainage from an abandoned tailings impoundment, which has severely affected the quality of the downstream watershed. Nearly a century of sulfide oxidation at this mine site has resulted in extremely high concentrations of oxidation products in the surface water and groundwater discharging from the two tailings impoundments, both of which flow into an adjacent semi-isolated shallow bay in Camp Lake. The incorporation of these aqueous effluents has altered the composition of the lake water, which in turn has modified the physical limnology of the lake. The various sources of water and solutes to the lake (surface inflows, perched water table, primary water table) contribute varying concentrations of metals to the overall contaminant loadings to the lake, and can be characterized by distinct 3H, δ18O, and δ2H compositions. Geochemical profiles of the water column indicate that, despite its shallow depth (6 m), the bay is stratified throughout the year. The greatest accumulation of dissolved metals and SO4 is in the lower portion of the water column, with concentrations up to 8500 mg/L Fe, 20,000 mg/L SO4, 30 mg/L Zn, and 100 mg/L Al, including elevated concentrations of Cu, Cd, Pb, and Ni. This stratification is mirrored in the δ18O, δ2H and d-excess profiles within the lake water column, with an evaporatively enriched surface layer overlying the isotopically lighter, higher d-excess hypolimnion. Despite meromictic conditions and very high solute concentrations being limited to the semi-isolated bay, the annual loadings of acid, sulfate, and metals from Camp Lake to the adjacent lake are extremely large, and fluctuate seasonally

  20. Photoluminescence Imaging of Polyfluorene Surface Structures on Semiconducting Carbon Nanotubes: Implications for Thin Film Exciton Transport

    SciTech Connect

    Hartmann, Nicolai F.; Pramanik, Rajib; Dowgiallo, Anne-Marie; Ihly, Rachelle; Blackburn, Jeffrey L.; Doorn, Stephen K.

    2016-12-27

    Single-walled carbon nanotubes (SWCNTs) have potential to act as light-harvesting elements in thin film photovoltaic devices, but performance is in part limited by the efficiency of exciton diffusion processes within the films. Factors contributing to exciton transport can include film morphology encompassing nanotube orientation, connectivity, and interaction geometry. Such factors are often defined by nanotube surface structures that are not yet well understood. Here, we present the results of a combined pump-probe and photoluminescence imaging study of polyfluorene (PFO)-wrapped (6,5) and (7,5) SWCNTs that provide additional insight into the role played by polymer structures in defining exciton transport. Pump-probe measurements suggest exciton transport occurs over larger length scales in films composed of PFO-wrapped (7,5) SWCNTs, compared to those prepared from PFO-bpy-wrapped (6,5) SWCNTs. To explore the role the difference in polymer structure may play as a possible origin of differing transport behaviors, we performed a photoluminescence imaging study of individual polymer-wrapped (6,5) and (7,5) SWCNTs. The PFO-bpy-wrapped (6,5) SWCNTs showed more uniform intensity distributions along their lengths, in contrast to the PFO-wrapped (7,5) SWCNTs, which showed irregular, discontinuous intensity distributions. These differences likely originate from differences in surface coverage and suggest the PFO wrapping on (7,5) nanotubes produces a more open surface structure than is available with the PFO-bpy wrapping of (6,5) nanotubes. The open structure likely leads to improved intertube coupling that enhances exciton transport within the (7,5) films, consistent with the results of our pump-probe measurements.

  1. Variability in surface ozone background over the United States: Implications for air quality policy

    NASA Astrophysics Data System (ADS)

    Fiore, A.; Jacob, D. J.; Liu, H.; Yantosca, R. M.; Fairlie, T. D.; Li, Q.

    2003-12-01

    The U.S. Environmental Protection Agency (EPA) presently uses a 40 ppbv background O3 level as a baseline in its O3 risk assessments. This background is defined as those concentrations that would exist in the absence of North American emissions. [2001] have argued that frequent occurrences of O3 concentrations above 50-60 ppbv at remote northern U.S. sites in spring are of stratospheric origin, challenging the EPA background estimate and implying that the current O3 standard (84 ppbv, 8-hour average) may be unattainable. We show that a 3-D global model of tropospheric chemistry reproduces much of the observed variability in U.S. surface O3 concentrations, including the springtime high-O3 events, with only a minor stratospheric contribution (always <20 ppbv). We conclude that the previous interpretations of a stratospheric source for these events underestimated the role of regional and hemispheric pollution. While stratospheric intrusions might occasionally elevate surface O3 at high-altitude sites, our results indicate that these events are rare and would not compromise the O3 air quality standard. We find that the O3 background is generally 15-35 ppbv, with some incidences of 40-50 ppbv in the west in spring at high-elevation sites (>2 km). It declines from spring to summer and further decreases during O3 pollution episodes. The 40 ppbv background assumed by EPA thus actually underestimates the risk associated with O3 during polluted conditions. A better definition would represent background as a function of season, altitude, and total surface O3 concentration. Natural O3 levels are typically 10-25 ppbv and never exceed 40 ppbv. International controls to reduce the hemispheric pollution background would facilitate compliance with an AOT40-type standard (cumulative exposure to O3 above 40 ppbv) in the United States.

  2. Energy Crops and their Implications on Soil Carbon Sequestration, Surface Energy and Water Balance

    NASA Astrophysics Data System (ADS)

    Song, Y.; Barman, R.; Jain, A. K.

    2011-12-01

    The quest to meet growing energy demand with low greenhouse gas emissions has increased attention on the potential of existing and advanced biomass energy crops. Potential energy crops include row crops such as corn, and perennial grasses such as switchgrass. However, a massive expansion of bioenergy crops raises many questions such as: how and where to grow energy crops; and what will be the impacts of growing large scale biofuel crops on the terrestrial hydrological cycle, the surface energy budget, soil carbon sequestration and the concurrent effects on the climate system. An integrated modeling system is being developed with in the framework of a land surface model, the Integrated Science Assessment Model (ISAM), and being applied to address these questions.This framework accounts for the biophysical, physiological and biogeochemical systems governing important processes that regulate crop growth including water, energy and nutrient cycles within the soil-plant-atmosphere system. One row crop (Corn) and two energy crops (Switchgrass and Miscanthus) are studied in current framework. Dynamic phenology processes and parameters for simulating each crop have been developed using observed data from a north to south gradient of field trial sites. This study will specifically focus on the agricultural regions in the US and in Europe. The potential productivity of these three crops will be assessed in terms of carbon sequestration, surface energy and water balance and their spatial variability. This study will help to quantify the importance of various environmental aspects towards modeling bioenergy crops and to better understand the spatial and temporal dynamics of bioenergy crop yields.

  3. Photoluminescence Imaging of Polyfluorene Surface Structures on Semiconducting Carbon Nanotubes: Implications for Thin Film Exciton Transport.

    PubMed

    Hartmann, Nicolai F; Pramanik, Rajib; Dowgiallo, Anne-Marie; Ihly, Rachelle; Blackburn, Jeffrey L; Doorn, Stephen K

    2016-12-27

    Single-walled carbon nanotubes (SWCNTs) have potential to act as light-harvesting elements in thin film photovoltaic devices, but performance is in part limited by the efficiency of exciton diffusion processes within the films. Factors contributing to exciton transport can include film morphology encompassing nanotube orientation, connectivity, and interaction geometry. Such factors are often defined by nanotube surface structures that are not yet well understood. Here, we present the results of a combined pump-probe and photoluminescence imaging study of polyfluorene (PFO)-wrapped (6,5) and (7,5) SWCNTs that provide additional insight into the role played by polymer structures in defining exciton transport. Pump-probe measurements suggest exciton transport occurs over larger length scales in films composed of PFO-wrapped (7,5) SWCNTs, compared to those prepared from PFO-bpy-wrapped (6,5) SWCNTs. To explore the role the difference in polymer structure may play as a possible origin of differing transport behaviors, we performed a photoluminescence imaging study of individual polymer-wrapped (6,5) and (7,5) SWCNTs. The PFO-bpy-wrapped (6,5) SWCNTs showed more uniform intensity distributions along their lengths, in contrast to the PFO-wrapped (7,5) SWCNTs, which showed irregular, discontinuous intensity distributions. These differences likely originate from differences in surface coverage and suggest the PFO wrapping on (7,5) nanotubes produces a more open surface structure than is available with the PFO-bpy wrapping of (6,5) nanotubes. The open structure likely leads to improved intertube coupling that enhances exciton transport within the (7,5) films, consistent with the results of our pump-probe measurements.

  4. Health risk implications of potentially toxic metals in street dust and surface soil of Tehran, Iran.

    PubMed

    Dehghani, Sharareh; Moore, Farid; Keshavarzi, Behnam; Hale, Beverley A

    2017-02-01

    In this study a total of 30 street dusts and 10 surface soils were collected in the central district of Tehran and analyzed for major potentially toxic metals. Street dust was found to be greatly enriched in Sb, Pb, Cu and Zn and moderately enriched in Cr, Mn, Mo and Ni. Contamination of Cu, Sb, Pb and Zn was clearly related to anthropogenic sources such as brake wear, tire dust, road abrasion and fossil fuel combustion. Spatial distribution of pollution load index in street dust suggested that industries located south-west of the city intensify street dust pollution. Microscopic studies revealed six dominant group of morphological structures in calculation of the exposurethe street dusts and surface soils, with respect to different geogenic and anthropogenic sources. The BCR (the European Community Bureau of Reference) sequential extraction results showed that Sb, Ni, Mo, As and Cr bonded to silicates and sulfide minerals were highly resistant to dissolution. In contrast, Zn, Cd, and Mn were mostly associated with the exchangeable phase and thus would be easily mobilized in the environment. Cu was the most abundant metal in the reducible fraction, indicating its adsorption to iron and manganese oxy-hydroxides. Pb was equally extracted from exchangeable and reducible fractions. Anthropogenic sources related to traffic apparently play a small role in Cr, Ni and Mo contamination and dispersed them as bioavailable forms but with reduced mobility and bioavailablity due to high potential of complexation and adsorption to organic matter and iron and manganese oxy-hydroxides. Calculated Hazard Index (HI) suggests ingestion as the most important pathway for the majority of PTMs in children and dermal contact as the main exposure route for Cr, Cd and Sb for adults. The HIs and fractionation pattern of elements revealed Pb as the sole element that bears potential health risk in street dust and surface soil.

  5. Implications of atmospheric conditions for analysis of surface temperature variability derived from landscape-scale thermography

    NASA Astrophysics Data System (ADS)

    Hammerle, Albin; Meier, Fred; Heinl, Michael; Egger, Angelika; Leitinger, Georg

    2016-08-01

    Thermal infrared (TIR) cameras perfectly bridge the gap between (i) on-site measurements of land surface temperature (LST) providing high temporal resolution at the cost of low spatial coverage and (ii) remotely sensed data from satellites that provide high spatial coverage at relatively low spatio-temporal resolution. While LST data from satellite (LSTsat) and airborne platforms are routinely corrected for atmospheric effects, such corrections are barely applied for LST from ground-based TIR imagery (using TIR cameras; LSTcam). We show the consequences of neglecting atmospheric effects on LSTcam of different vegetated surfaces at landscape scale. We compare LST measured from different platforms, focusing on the comparison of LST data from on-site radiometry (LSTosr) and LSTcam using a commercially available TIR camera in the region of Bozen/Bolzano (Italy). Given a digital elevation model and measured vertical air temperature profiles, we developed a multiple linear regression model to correct LSTcam data for atmospheric influences. We could show the distinct effect of atmospheric conditions and related radiative processes along the measurement path on LSTcam, proving the necessity to correct LSTcam data on landscape scale, despite their relatively low measurement distances compared to remotely sensed data. Corrected LSTcam data revealed the dampening effect of the atmosphere, especially at high temperature differences between the atmosphere and the vegetated surface. Not correcting for these effects leads to erroneous LST estimates, in particular to an underestimation of the heterogeneity in LST, both in time and space. In the most pronounced case, we found a temperature range extension of almost 10 K.

  6. Implications of atmospheric conditions for analysis of surface temperature variability derived from landscape-scale thermography.

    PubMed

    Hammerle, Albin; Meier, Fred; Heinl, Michael; Egger, Angelika; Leitinger, Georg

    2017-04-01

    Thermal infrared (TIR) cameras perfectly bridge the gap between (i) on-site measurements of land surface temperature (LST) providing high temporal resolution at the cost of low spatial coverage and (ii) remotely sensed data from satellites that provide high spatial coverage at relatively low spatio-temporal resolution. While LST data from satellite (LSTsat) and airborne platforms are routinely corrected for atmospheric effects, such corrections are barely applied for LST from ground-based TIR imagery (using TIR cameras; LSTcam). We show the consequences of neglecting atmospheric effects on LSTcam of different vegetated surfaces at landscape scale. We compare LST measured from different platforms, focusing on the comparison of LST data from on-site radiometry (LSTosr) and LSTcam using a commercially available TIR camera in the region of Bozen/Bolzano (Italy). Given a digital elevation model and measured vertical air temperature profiles, we developed a multiple linear regression model to correct LSTcam data for atmospheric influences. We could show the distinct effect of atmospheric conditions and related radiative processes along the measurement path on LSTcam, proving the necessity to correct LSTcam data on landscape scale, despite their relatively low measurement distances compared to remotely sensed data. Corrected LSTcam data revealed the dampening effect of the atmosphere, especially at high temperature differences between the atmosphere and the vegetated surface. Not correcting for these effects leads to erroneous LST estimates, in particular to an underestimation of the heterogeneity in LST, both in time and space. In the most pronounced case, we found a temperature range extension of almost 10 K.

  7. Assessing metaldehyde concentrations in surface water catchments and implications for drinking water abstraction

    NASA Astrophysics Data System (ADS)

    Asfaw, Alemayehu; Shucksmith, James; Smith, Andrea; Cherry, Katherine

    2015-04-01

    Metaldehyde is an active ingredient in agricultural pesticides such as slug pellets, which are heavily applied to UK farmland during the autumn application season. There is current concern that existing drinking water treatment processes may be inadequate in reducing potentially high levels of metaldehyde in surface waters to below the UK drinking water quality regulation limit of 0.1 µg/l. In addition, current water quality monitoring methods can miss short term fluctuations in metaldehyde concentration caused by rainfall driven runoff, hampering prediction of the potential risk of exposure. Datasets describing levels, fate and transport of metaldehyde in river catchments are currently very scarce. This work presents results from an ongoing study to quantify the presence of metaldehyde in surface waters within a UK catchment used for drinking water abstraction. High resolution water quality data from auto-samplers installed in rivers are coupled with radar rainfall, catchment characteristics and land use data to i) understand which hydro-meteorological characteristics of the catchment trigger the peak migration of metaldehyde to surface waters; ii) assess the relationship between measured metaldehyde levels and catchment characteristics such as land use, topographic index, proximity to water bodies and runoff generation area; iii) describe the current risks to drinking water supply and discuss mitigation options based on modelling and real-time control of water abstraction. Identifying the correlation between catchment attributes and metaldehyde generation will help in the development of effective catchment management strategies, which can help to significantly reduce the amount of metaldehyde finding its way into river water. Furthermore, the effectiveness of current water quality monitoring strategy in accurately quantifying the generation of metaldehyde from the catchment and its ability to benefit the development of effective catchment management practices

  8. Spatiotemporal dynamics of surface water networks across a global biodiversity hotspot—implications for conservation

    NASA Astrophysics Data System (ADS)

    Tulbure, Mirela G.; Kininmonth, Stuart; Broich, Mark

    2014-11-01

    The concept of habitat networks represents an important tool for landscape conservation and management at regional scales. Previous studies simulated degradation of temporally fixed networks but few quantified the change in network connectivity from disintegration of key features that undergo naturally occurring spatiotemporal dynamics. This is particularly of concern for aquatic systems, which typically show high natural spatiotemporal variability. Here we focused on the Swan Coastal Plain, a bioregion that encompasses a global biodiversity hotspot in Australia with over 1500 water bodies of high biodiversity. Using graph theory, we conducted a temporal analysis of water body connectivity over 13 years of variable climate. We derived large networks of surface water bodies using Landsat data (1999-2011). We generated an ensemble of 278 potential networks at three dispersal distances approximating the maximum dispersal distance of different water dependent organisms. We assessed network connectivity through several network topology metrics and quantified the resilience of the network topology during wet and dry phases. We identified ‘stepping stone’ water bodies across time and compared our networks with theoretical network models with known properties. Results showed a highly dynamic seasonal pattern of variability in network topology metrics. A decline in connectivity over the 13 years was noted with potential negative consequences for species with limited dispersal capacity. The networks described here resemble theoretical scale-free models, also known as ‘rich get richer’ algorithm. The ‘stepping stone’ water bodies are located in the area around the Peel-Harvey Estuary, a Ramsar listed site, and some are located in a national park. Our results describe a powerful approach that can be implemented when assessing the connectivity for a particular organism with known dispersal distance. The approach of identifying the surface water bodies that act as

  9. Dissimilarity between temperature-humidity in the atmospheric surface layer and implications for estimates of evaporation

    NASA Astrophysics Data System (ADS)

    Cancelli, D. M.; Dias, N. L.; Chamecki, M.

    2012-12-01

    In several methods used in water resources to estimate evaporation from land and water surfaces, a fundamental assumption is that temperature (T) and specific humidity (q) fluctuations behave similarly in the atmospheric surface layer (ASL). In the Energy-Budget Bowen Ratio method it is assumed that both eddy diffusivities are equal, while in the variance method it is often assumed that all the Monin-Obukhov Similarity (MOS) functions for the two scalars are equal. However, it is well-known that the T-q similarity does not always hold and that the dissimilarity found in practice can significantly impact the estimates of evaporation. Given the frequent dissimilarity between temperature and humidity, two important problems arise. The first one is related to the choice of the function used to characterize scalar similarity, given that not all commonly used functions are equally capable of identifying scalar dissimilarity. The second problem is associated with the identification of the physical mechanisms behind scalar dissimilarity in each particular case: local advection, nonstationarity, surface heterogeneity, active/passive roles of the scalars, entrainment fluxes at the top of the atmospheric boundary layer are typically cited as possible causes, but seldom a convincing argument is presented. In this work we combine experimental data and numerical simulations to study similarity between T and q in the ASL. Data measured over a lake in Brazil suggests a strong relationship between scalar similarity and the balance between local production and dissipation of scalar variance, which is in practice related to the strength of the surface forcing. Scalar variance and covariance budgets are used to derive a set of dimensionless Scalar Flux numbers that are capable of diagnosing the balance between gradient production and molecular dissipation of scalar variance and covariance. Experimental data shows that these Scalar Flux numbers are good predictors of scalar (dis

  10. Plot-scale field experiment of surface hydrologic processes with EOS implications

    NASA Technical Reports Server (NTRS)

    Laymon, Charles A.; Macari, Emir J.; Costes, Nicholas C.

    1992-01-01

    Plot-scale hydrologic field studies were initiated at NASA Marshall Space Flight Center to a) investigate the spatial and temporal variability of surface and subsurface hydrologic processes, particularly as affected by vegetation, and b) develop experimental techniques and associated instrumentation methodology to study hydrologic processes at increasingly large spatial scales. About 150 instruments, most of which are remotely operated, have been installed at the field site to monitor ground atmospheric conditions, precipitation, interception, soil-water status, and energy flux. This paper describes the nature of the field experiment, instrumentation and sampling rationale, and presents preliminary findings.

  11. Seasonal changes in Titan's weather patterns and the evolution and implications of accompanying surface changes

    NASA Astrophysics Data System (ADS)

    Turtle, E. P.; Perry, J.; McEwen, A. S.; Barbara, J. M.; Del Genio, A. D.; West, R. A.; Barnes, J. W.; Hayes, A.; Lorenz, R. D.; Lunine, J. I.; Stofan, E. R.; Schaller, E. L.; Lopes, R. M.; Ray, T. L.

    2012-12-01

    Post-equinox changes in Titan's atmospheric circulation brought clouds and extensive methane rain to Titan's low latitudes [1,2]. Observations by Cassini ISS over the ~2 years since the storm revealed most of the changes to be short-lived; only a few darkened patches persisted through Fall 2011. In an unsaturated permeable medium, infiltration rates exceed 20 mm/week [3], so persistence of surface liquids over several months suggests either a shallow impermeable layer or that the local methane table lies close to the surface. Evaporation rates greater than 1 mm/week are predicted in equatorial regions [4] and rates of 20 mm/week have been documented at Titan's poles [5], thus areas where darkening persisted must be saturated ground at the level of a methane table or have had liquid ponded to depths of 2.5-50 cm. Several smaller areas of surface brightening were also observed, a phenomenon that is less well understood. Cassini VIMS spectra of these regions do not match those of clouds or other surface units [6, 7]. Interpretations include cleaning by runoff [2] or deposition of a fine-grained volatile solid as the result of evaporative cooling [6, 7]. In general, brightening has persisted longer than darkening, but these areas are also reverting to their original appearance, which could constrain rates of evaporation/sublimation of the bright material or re-deposition of darker hydrocarbons by aeolian transport or precipitation from the atmosphere. Cassini and Earth-based observers monitor Titan frequently (typically at least a few times per month), but few clouds have been observed since Fall 2010, which may indicate that enough methane was removed from the atmosphere and the lapse rate stabilized sufficiently that activity will not resume until the onset of convection at mid-northern latitudes later in northern spring. A similar lapse followed a 2004 outburst of south-polar clouds [8], which also appeared to produce significant rainfall [9]. [1] Turtle et al., GRL

  12. Surface temperatures of the Mid-Pliocene North Atlantic Ocean: Implications for future climate

    USGS Publications Warehouse

    Dowsett, Harry J.; Chandler, Mark A.; Robinson, Marci M.

    2009-01-01

    The Mid-Pliocene is the most recent interval in the Earth's history to have experienced warming of the magnitude predicted for the second half of the twenty-first century and is, therefore, a possible analogue for future climate conditions. With continents basically in their current positions and atmospheric CO2 similar to early twenty-first century values, the cause of Mid-Pliocene warmth remains elusive. Understanding the behaviour of the North Atlantic Ocean during the Mid-Pliocene is integral to evaluating future climate scenarios owing to its role in deep water formation and its sensitivity to climate change. Under the framework of the Pliocene Research, Interpretation and Synoptic Mapping (PRISM) sea surface reconstruction, we synthesize Mid-Pliocene North Atlantic studies by PRISM members and others, describing each region of the North Atlantic in terms of palaeoceanography. We then relate Mid-Pliocene sea surface conditions to expectations of future warming. The results of the data and climate model comparisons suggest that the North Atlantic is more sensitive to climate change than is suggested by climate model simulations, raising the concern that estimates of future climate change are conservative.

  13. Surface Crystallization of Cloud Droplets: Implications for Climate Change and Ozone Depletion

    NASA Technical Reports Server (NTRS)

    Tabazadeh, A.; Djikaev, Y. S.; Reiss, H.; Gore, Warren J. (Technical Monitor)

    2002-01-01

    The process of supercooled liquid water crystallization into ice is still not well understood. Current experimental data on homogeneous freezing rates of ice nucleation in supercooled water droplets show considerable scatter. For example, at -33 C, the reported freezing nucleation rates vary by as much as 5 orders of magnitude, which is well outside the range of measurement uncertainties. Until now, experimental data on the freezing of supercooled water has been analyzed under the assumption that nucleation of ice took place in the interior volume of a water droplet. Here, the same data is reanalyzed assuming that the nucleation occurred "pseudoheterogeneously" at the air (or oil)-liquid water interface of the droplet. Our analysis suggest that the scatter in the nucleation data can be explained by two main factors. First, the current assumption that nucleation occurs solely inside the volume of a water droplet is incorrect. Second, because the nucleation process most likely occurs on the surface, the rates of nuclei formation could differ vastly when oil or air interfaces are involved. Our results suggest that ice freezing in clouds may initiate on droplet surfaces and such a process can allow for low amounts of liquid water (approx. 0.002 g per cubic meters) to remain supercooled down to -40 C as observed in the atmosphere.

  14. The general linear inverse problem - Implication of surface waves and free oscillations for earth structure.

    NASA Technical Reports Server (NTRS)

    Wiggins, R. A.

    1972-01-01

    The discrete general linear inverse problem reduces to a set of m equations in n unknowns. There is generally no unique solution, but we can find k linear combinations of parameters for which restraints are determined. The parameter combinations are given by the eigenvectors of the coefficient matrix. The number k is determined by the ratio of the standard deviations of the observations to the allowable standard deviations in the resulting solution. Various linear combinations of the eigenvectors can be used to determine parameter resolution and information distribution among the observations. Thus we can determine where information comes from among the observations and exactly how it constraints the set of possible models. The application of such analyses to surface-wave and free-oscillation observations indicates that (1) phase, group, and amplitude observations for any particular mode provide basically the same type of information about the model; (2) observations of overtones can enhance the resolution considerably; and (3) the degree of resolution has generally been overestimated for many model determinations made from surface waves.

  15. Chemical abundances in low surface brightness galaxies: Implications for their evolution

    NASA Technical Reports Server (NTRS)

    Mcgaugh, S. S.; Bothun, G. D.

    1993-01-01

    Low Surface Brightness (LSB) galaxies are an important but often neglected part of the galaxy content of the universe. Their importance stems both from the selection effects which cause them to be under-represented in galaxy catalogs, and from what they can tell us about the physical processes of galaxy evolution that has resulted in something other than the traditional Hubble sequence of spirals. An important constraint for any evolutionary model is the present day chemical abundances of LSB disks. Towards this end, spectra for a sample of 75 H 2 regions distributed in 20 LSB disks galaxies were obtained. Structurally, this sample is defined as having B(0) fainter than 23.0 mag arcsec(sup -2) and scale lengths that cluster either around 3 kpc or 10 kpc. In fact, structurally, these galaxies are very similar to the high surface brightness spirals which define the Hubble sequence. Thus, our sample galaxies are not dwarf galaxies but instead have masses comparable to or in excess of the Milky Way. The basic results from these observations are summarized.

  16. Causes and implications of the loss of small-scale surface texture in Viking Orbiter images

    SciTech Connect

    Kahn, R.; Guinness, E.; Arvidson, R.

    1985-01-01

    Previous studies of orbital images of Mars suggest that the equatorial regions have been stripped of sedimentary debris and that the polar regions are covered with a deposit that thins equatorward. These conclusions were based, in part, on the presence or absence of small-scale texture in images. The absence of small-scale features in Orbiter images must be interpreted with caution because of atmospheric haze that will also preferentially obscure high spatial frequency features. Two sets of overlapping images taken under different atmospheric conditions allow one to verify a single scattering atmospheric model that quantitatively accounts for the observations. Application of the model shows that twelve crater size-frequency distributions for areas in the northern hemisphere behave in the manner predicted for hazy conditions. Loss of surface resolution due to the nearly ubiquitous haze in the northern mid to high latitudes makes it impossible to assess, with existing images, the validity of suggestions that small-scale features have been preferentially degraded by surface processes. To the limited degree that the present data set samples the northern hemisphere, there is no evidence in these data for wide-spread young debris deposits hundreds of meters thick, other than the polar layered terrain. A debris deposit about 100 meters thick is a likely explanation for the observed crater size-frequency distribution at two mid northern latitude locations, one each in Arcadia and Acidalia Planitias.

  17. Surface energetics and protein-protein interactions: analysis and mechanistic implications

    NASA Astrophysics Data System (ADS)

    Peri, Claudio; Morra, Giulia; Colombo, Giorgio

    2016-04-01

    Understanding protein-protein interactions (PPI) at the molecular level is a fundamental task in the design of new drugs, the prediction of protein function and the clarification of the mechanisms of (dis)regulation of biochemical pathways. In this study, we use a novel computational approach to investigate the energetics of aminoacid networks located on the surface of proteins, isolated and in complex with their respective partners. Interestingly, the analysis of individual proteins identifies patches of surface residues that, when mapped on the structure of their respective complexes, reveal regions of residue-pair couplings that extend across the binding interfaces, forming continuous motifs. An enhanced effect is visible across the proteins of the dataset forming larger quaternary assemblies. The method indicates the presence of energetic signatures in the isolated proteins that are retained in the bound form, which we hypothesize to determine binding orientation upon complex formation. We propose our method, BLUEPRINT, as a complement to different approaches ranging from the ab-initio characterization of PPIs, to protein-protein docking algorithms, for the physico-chemical and functional investigation of protein-protein interactions.

  18. Martian planetwide crater distributions: Implications for geologic history and surface processes

    USGS Publications Warehouse

    Soderblom, L.A.; Condit, C.D.; West, R.A.; Herman, B.M.; Kreidler, T.J.

    1974-01-01

    Population-density maps of craters in three size ranges (0.6 to 1.2 km, 4 to 10 km, and >20 km in diameter) were compiled for most of Mars from Mariner 9 imagery. These data provide: historical records of the eolian processes (0.6 to 1.2 km craters); stratigraphic, relative, and absolute timescales (4 to 10 km craters); and a history of the early postaccretional evolution of the uplands (> 20 km craters). Based on the distribution of large craters (>20 km diameters), Mars is divisible into two general classes of terrain, densely cratered and very lightly cratered-a division remarkably like the uplands-maria dichotomy of the moon. It is probable that this bimodal character in the density distribution of large craters arose from an abrupt transition in the impact flux rate from an early intense period associated with the tailing off of accretion to an extended quiescent epoch, not from a void in geological activity during much of Mars' history. Radio-isotope studies of Apollo lunar samples show that this transition occurred on the moon in a short time. The intermediate-sized craters (4 to 10 km diameter) and the small-sized craters (0.6 to 1.2 km diameter) appear to be genetically related. The smaller ones are apparently secondary impact craters generated by the former. Most of the craters in the larger of these two size classes appear fresh and uneroded, although many are partly buried by dust mantles. Poleward of the 40?? parallels the small fresh craters are notably absent owing to these mantles. The density of small craters is highest in an irregular band centered at 20??S. This band coincides closely with (1) the zone of permanent low-albedo markings; (2) the "wind equator" (the latitude of zero net north or south transport at the surface); and (3) a band that includes a majority of the small dendritic channels. Situated in the southermost part of the equatorial unmantled terrain which extends from about 40??N to 40??S, this band is apparently devoid of even a

  19. Mantle dynamics and the atmospheres of Mars and Venus: implications for surface conditions and interactions.

    NASA Astrophysics Data System (ADS)

    Gillmann, C.; Tackley, P.

    2012-04-01

    We propose to investigate the interaction between the mantle and the atmosphere of terrestrial planets, in order to study whereas such coupling could be the cause of the divergent evolution of planets in our solar system. Therefore, we build a coupled model taking into account mantle dynamics, volatile exchanges and atmospheric processes. We focus on Mars and Venus and consider the evolution of CO2 and H2O in the atmosphere. The first main mechanism we consider is the volcanic source of volatiles. Therefore we need to model the mantle dynamics by adapting the highly advanced StagYY code (developed by P. Tackley, 2008) for Mars and Venus. When possible, we compare those results to published modeling (Breuer and Spohn, 2006; Grott et al., 2011) and observation. Atmospheric escape is considered as the main volatile loss flux. Early loss is thermal, caused by hydrodynamic escape. After the first few hundred million years, the main atmospheric escape flux is caused by non-thermal mechanisms. We model their evolution by comparing recent numerical study and ASPERA (Analyzer of Space Plasma and EneRgetic Atoms) measurements. We combine these models to calculate the state of the atmosphere of Venus and Mars. This lets us estimate the surface temperature of those planets either from a Mars Global Circulation Model (e.g. Forget at al., 1999), or with a gray radiative-convective atmosphere model, for Venus. In the case of Mars, we show that the present-day atmosphere of Mars is likely to be constituted by a large part (more than 50%) of volcanic gases emitted since 4 billion years ago, which corresponds to a mean age of 1.9 to 2.3 Gyr. The variations of CO2 pressure over this period seem relatively low (50 mbar at most). This seems in line with the assumption that the heavy loss of volatiles occurred before 500 Myr. Surface temperature variations are likely to be small (several Kelvin) and would not be responsible for periods of flowing liquid surface water by themselves

  20. Graphene-ionic liquid composites

    DOEpatents

    Aksay, Ilhan A.; Korkut, Sibel; Pope, Michael; Punckt, Christian

    2016-11-01

    Method of making a graphene-ionic liquid composite. The composite can be used to make elec-trodes for energy storage devices, such as batteries and supercapacitors. Dis-closed and claimed herein is method of making a graphene-ionic liquid com-posite, comprising combining a graphene source with at least one ionic liquid and heating the combination at a temperature of at least about 130 .degree. C.

  1. Design of Energetic Ionic Liquids

    DTIC Science & Technology

    2009-05-12

    effectiveness of the FMO method in both providing accurate results and reducing computational requirements, timings were performed for the ionic liquid ...Technical Paper 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Design of Energetic Ionic Liquids 5b. GRANT NUMBER 5c...Design of Energetic Ionic Liquids challenge project is to address several key technical issues and challenges associated with the characterization

  2. Particle self-assembly at ionic liquid-based interfaces.

    PubMed

    Frost, Denzil S; Nofen, Elizabeth M; Dai, Lenore L

    2014-04-01

    This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid-water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid-water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water-ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil

  3. Implications from Near-Shoemaker Imaging of Eros for Small-Scale Structure and Surface Sampling

    NASA Astrophysics Data System (ADS)

    Chapman, C. R.

    2000-01-01

    What we know about asteroids has always been bifurcated by the enormous gap between astronomical studies of small, distant bodies, and the close-up laboratory measurements of hand-sample sized meteorites. The gulf has been narrowed somewhat by improvements in Earth-based astronomical techniques (e.g. Hubble Space Telescope, radar, adaptive optics) and especially by spacecraft fly-bys of asteroids. But the Near Earth Asteroid Rendezvous (NEAR)-Shoemaker mission has gone considerably more in the direction of bridging the gap. Any consideration of intelligent sample-return from an asteroid must be based on the best possible knowledge of the asteroid at the spatial scales pertinent to operations at the asteroid and of the sample/s. Otherwise, we are in danger of succumbing to the 'Martian Horror Story' that Bruce Murray, in the 1960's, envisioned might impair our exploration of the surface of the red planet if we tried to land on it without first bolstering the information content of our database about Mars, especially at high resolutions. NEAR-Shoemaker is helping to bridge that gap in the case of Eros. The best resolution obtained by the Galileo spacecraft on Ida was 25 m/pixel. As of this writing, NEAR has already obtained images with resolutions at least five times better (information content 25 times better) and vastly better images may be available at the time of this Workshop from the late October low flyby. Already, we are seeing that the Martian horror story looks tame compared with Eros. Everywhere we have landed on Mars, the surface has been covered with rocks and boulders, with much higher spatial coverage than seen anywhere on the lunar surface. We have, in fact, been rather lucky that none of our Martian landers have tipped over so far, and there were justified fears in the early aftermath of last year's failure of Mars Polar Lander that it had suffered from inadequate high-resolution characterization of polar regions on Mars (the failure is now known to

  4. Surface exploration of a room-temperature ionic liquid-chitin composite film decorated with electrochemically deposited PdFeNi trimetallic alloy nanoparticles by pattern recognition: an elegant approach to developing a novel biotin biosensor.

    PubMed

    Gholivand, Mohammad-Bagher; Jalalvand, Ali R; Goicoechea, Hector C; Paimard, Giti; Skov, Thomas

    2015-01-01

    In this study, a novel biosensing system for the determination of biotin (BTN) based on electrodeposition of palladium-iron-nickel (PdFeNi) trimetallic alloy nanoparticles (NPs) onto a glassy carbon electrode (GCE) modified with a room-temperature ionic liquid (RTIL)-chitin (Ch) composite film (PdFeNi/ChRTIL/GCE) is established. NPs have a wide range of applications in science and technology and their sizes are often measured using transmission electron microscopy (TEM) or X-ray diffraction. Here, we used a pattern recognition method (digital image processing, DIP) for measuring particle size distributions (PSDs) from scanning electron microscopic (SEM) images in the presence of an uneven background. Different depositions were performed by varying the number of cyclic potential scans (N) during electroreduction step. It was observed that the physicochemical properties of the deposits were correlated to the performance of the PdFeNi/ChRTIL/GCE with respect to BTN assay. The best results were obtained for eight electrodeposition cyclic scans, where small-sized particles (19.54 ± 6.27 nm) with high density (682 particles µm(-2)) were obtained. Under optimized conditions, a linear range from 2.0 to 44.0 × 10(-9) mol L(-1) and a limit of detection (LOD) of 0.6 × 10(-9) mol L(-1) were obtained. The PdFeNi/ChRTIL nanocomposite showed excellent compatibility, enhanced electron transfer kinetics, large electroactive surface area, and was highly sensitive, selective, and stable toward BTN determination. Finally, the PdFeNi/ChRTIL/GCE was satisfactorily applied to the determination of BTN in infant milk powder, liver, and egg yolk samples.

  5. A review of the clinical implications of anti-infective biomaterials and infection-resistant surfaces.

    PubMed

    Campoccia, Davide; Montanaro, Lucio; Arciola, Carla Renata

    2013-11-01

    Infection is currently regarded as the most severe and devastating complication associated to the use of biomaterials. The important social, clinical and economic impacts of implant-related infections are promoting the efforts to obviate these severe diseases. In this context, the development of anti-infective biomaterials and of infection-resistant surfaces is being regarded as the main strategy to prevent the establishment of implant colonisation and biofilm formation by bacteria. In this review, the attention is focused on the biomaterial-associated infections, from which the need for anti-infective biomaterials originates. Biomaterial-associated infections differ markedly for epidemiology, aetiology and severity, depending mainly on the anatomic site, on the time of biomaterial application, and on the depth of the tissues harbouring the prosthesis. Here, the diversity and complexity of the different scenarios where medical devices are currently utilised are explored, providing an overview of the emblematic applicative fields and of the requirements for anti-infective biomaterials.

  6. Implication of femoral stem on performance of articular surface replacement (ASR) XL total hip arthroplasty.

    PubMed

    Cip, Johannes; von Strempel, Archibald; Bach, Christian; Luegmair, Matthias; Benesch, Thomas; Martin, Arno

    2014-11-01

    Taper junctions of large diameter metal-on-metal femoral heads and femoral stems were described as metal ion generator due to accelerated wear and corrosion. However, literature about the Articular Surface Replacement (ASR) total hip arthroplasty (THA) invariably deals with stems manufactured by DePuy Orthopedics (Warsaw, IN, USA). Nothing is known whether different stems with common 12/14 mm tapers affect failure rate or ion release. 99 ASR THA (88 patients) implanted with CoxaFit or ARGE Geradschaft stems (K-Implant, Hannover, Germany) were retrospectively analyzed. After a mean follow-up of 3.5 years revision rate was 24.5%, mostly due to adverse reaction to metal debris (ARMD). CT scan revealed component loosening in 10.3% and pseudotumoral lesions in 12.6%. Elevated ion concentrations (>7 μg/l) were found in 38.6%.

  7. Observations and implications of natural laminar flow on practical airplane surfaces

    NASA Technical Reports Server (NTRS)

    Holmes, B. J.; Obara, C. J.

    1982-01-01

    The results of natural laminar flow (NLF) experiments conducted by NASA to determine if modern aircraft structures can benefit from NLF as do sailplanes are presented. Seven aircraft, ranging from a Cessna 210 to a Learjet 28/29, with relatively stiff skins were flown in production configurations with no modifications. Measurements were made of the boundary-layer laminar to turbulent transition locations on various aerodynamic surfaces, the effect of a total loss of laminar flow, the effect of the propeller slipstream on the wing boundary-layer transition and the boundary-layer profiles, the wing section profile drag, the effect of flight through clouds, and insect debris contamination effects. Favorable pressure gradients for NLF were concluded to be feasible up to a transition Reynolds number of 11 million. Laminar flows were observed in propeller slipstreams, and insects were found to cause transition 1/4 of the time.

  8. Small-scale martian polygonal terrain: Implications for liquid surface water

    USGS Publications Warehouse

    Seibert, N.M.; Kargel, J.S.

    2001-01-01

    Images from the Mars Orbiter Camera (MOC) through August 1999 were analyzed for the global distribution of small-scale polygonal terrain not clearly resolved in Viking Orbiter imagery. With very few exceptions, small-scale polygonal terrain occurs at middle to high latitudes of the northern and southern hemisphere in Hesperian-age geologic units. The largest concentration of this terrain occurs in the Utopia basin in close association with scalloped depressions (interpreted as thermokarst) and appears to represent an Amazonia event. The morphology and occurence of small polygonal terrain suggest they are either mud desiccation cracks or ice-wedge polygons. Because the small-scale polygons in Utopia and Argyre Planitiae are associated with other cold-climate permafrost or glacial features, an ice-wedge model is preferred for these areas. Both cracking mechanisms work most effectively in water- or ice-rich finegrained material and may imply the seasonal or episodic existence of liquid water at the surface.

  9. Global climate impacts of bioenergy from forests: implications from biogenic CO2 fluxes and surface albedo

    NASA Astrophysics Data System (ADS)

    Cherubini, Francesco; Bright, Ryan; Strømman, Anders

    2013-04-01

    Production of biomass for bioenergy can alter biogeochemical and biogeophysical mechanisms, thus affecting local and global climate. Recent scientific developments mainly embraced impacts from land use changes resulting from area-expanded biomass production, with several extensive insights available. Comparably less attention, however, is given to the assessment of direct land surface-atmosphere climate impacts of bioenergy systems under rotation such as in plantations and forested ecosystems, whereby land use disturbances are only temporary. In this work, we assess bioenergy systems representative of various biomass species (spruce, pine, aspen, etc.) and climatic regions (US, Canada, Norway, etc.), for both stationary and vehicle applications. In addition to conventional greenhouse gas (GHG) emissions through life cycle activities (harvest, transport, processing, etc.), we evaluate the contributions to global warming of temporary effects resulting from the perturbation in atmospheric carbon dioxide (CO2) concentration caused by the timing of biogenic CO2 fluxes and in surface reflectivity (albedo). Biogenic CO2 fluxes on site after harvest are directly measured through Net Ecosystem Productivity (NEP) chronosequences from flux towers established at the interface between the forest canopy and the atmosphere and are inclusive of all CO2 exchanges occurring in the forest (e.g., sequestration of CO2 in growing trees, emissions from soil respiration and decomposition of dead organic materials). These primary data based on empirical measurements provide an accurate representation of the forest carbon sink behavior over time, and they are used in the elaboration of high-resolution IRFs for biogenic CO2 emissions. Chronosequence of albedo values from clear-cut to pre-harvest levels are gathered from satellite data (MODIS black-sky shortwave broadband, Collection 5, MCD43A). Following the cause-effect chain from emissions to damages, through radiative forcing and changes

  10. Adsorption of HO(x) on aerosol surfaces - Implications for the atmosphere of Mars

    NASA Technical Reports Server (NTRS)

    Anbar, A. D.; Leu, M.-T.; Nair, H. A.; Yung, Y. L.

    1993-01-01

    The potential impact of heterogeneous chemistry on the abundance and distribution of HO(x) in the Martian atmosphere is investigated using observational data on dust and ice aerosol distributions combined with an updated photochemical model. Critical parameters include the altitude distributions of aerosols and the surface loss coefficients of HO2 on dust and ice in the lower atmosphere and of H on ice above 40 km. Results of calculations indicate that adsorption of HO2 on dust, or ice near 30 km, can deplete OH abundances in the lower atmosphere by 10 percent or more and that the adsorption of H on ice at 50 km can result in even larger OH depletions (this effect is localized to altitudes greater than 40 km, where CO oxidation is relatively unimportant).

  11. The removal of pathogens in surface-flow constructed wetlands and its implications for water reuse.

    PubMed

    Ghermandi, A; Bixio, D; Traverso, P; Cersosimo, I; Thoeye, C

    2007-01-01

    Microbiological quality represents the biggest concern to the reuse of treated wastewater. This paper reports and discusses the results of an international survey on the removal of indicators of microbiological contamination in surface-flow constructed wetlands. Constructed wetlands consistently provide a reduction of 90-99% (1-2 log-removal) in the concentration of indicators such as coliform bacteria and faecal streptococci. This removal is found in wetlands treating water from different types of pretreatment (primary sedimentation, activated sludge, trickling filter, maturation ponds). On the other hand, when the influent is of high microbiological quality, wetlands act as sources of pathogenic contamination. The final water quality, however, is still compatible with medium to no-contact recreational activities and other final water uses. High variability in the effluent quality and seasonality might limit the opportunities for reuse. The role of constructed wetlands in different treatment schemes and the remaining open questions concerning removal mechanisms and reference pathogens are discussed.

  12. Earthing: health implications of reconnecting the human body to the Earth's surface electrons.

    PubMed

    Chevalier, Gaétan; Sinatra, Stephen T; Oschman, James L; Sokal, Karol; Sokal, Pawel

    2012-01-01

    Environmental medicine generally addresses environmental factors with a negative impact on human health. However, emerging scientific research has revealed a surprisingly positive and overlooked environmental factor on health: direct physical contact with the vast supply of electrons on the surface of the Earth. Modern lifestyle separates humans from such contact. The research suggests that this disconnect may be a major contributor to physiological dysfunction and unwellness. Reconnection with the Earth's electrons has been found to promote intriguing physiological changes and subjective reports of well-being. Earthing (or grounding) refers to the discovery of benefits-including better sleep and reduced pain-from walking barefoot outside or sitting, working, or sleeping indoors connected to conductive systems that transfer the Earth's electrons from the ground into the body. This paper reviews the earthing research and the potential of earthing as a simple and easily accessed global modality of significant clinical importance.

  13. Radioactive elements on Mercury's surface from MESSENGER: implications for the planet's formation and evolution.

    PubMed

    Peplowski, Patrick N; Evans, Larry G; Hauck, Steven A; McCoy, Timothy J; Boynton, William V; Gillis-Davis, Jeffery J; Ebel, Denton S; Goldsten, John O; Hamara, David K; Lawrence, David J; McNutt, Ralph L; Nittler, Larry R; Solomon, Sean C; Rhodes, Edgar A; Sprague, Ann L; Starr, Richard D; Stockstill-Cahill, Karen R

    2011-09-30

    The MESSENGER Gamma-Ray Spectrometer measured the average surface abundances of the radioactive elements potassium (K, 1150 ± 220 parts per million), thorium (Th, 220 ± 60 parts per billion), and uranium (U, 90 ± 20 parts per billion) in Mercury's northern hemisphere. The abundance of the moderately volatile element K, relative to Th and U, is inconsistent with physical models for the formation of Mercury requiring extreme heating of the planet or its precursor materials, and supports formation from volatile-containing material comparable to chondritic meteorites. Abundances of K, Th, and U indicate that internal heat production has declined substantially since Mercury's formation, consistent with widespread volcanism shortly after the end of late heavy bombardment 3.8 billion years ago and limited, isolated volcanic activity since.

  14. Soil Iodine Determination in Deccan Syneclise, India: Implications for Near Surface Geochemical Hydrocarbon Prospecting

    SciTech Connect

    Mani, Devleena; Kumar, T. Satish; Rasheed, M. A.; Patil, D. J.; Dayal, A. M.; Rao, T. Gnaneshwar; Balaram, V.

    2011-03-15

    The association of iodine with organic matter in sedimentary basins is well documented. High iodine concentration in soils overlying oil and gas fields and areas with hydrocarbon microseepage has been observed and used as a geochemical exploratory tool for hydrocarbons in a few studies. In this study, we measure iodine concentration in soil samples collected from parts of Deccan Syneclise in the west central India to investigate its potential application as a geochemical indicator for hydrocarbons. The Deccan Syneclise consists of rifted depositional sites with Gondwana-Mesozoic sediments up to 3.5 km concealed under the Deccan Traps and is considered prospective for hydrocarbons. The concentration of iodine in soil samples is determined using ICP-MS and the values range between 1.1 and 19.3 ppm. High iodine values are characteristic of the northern part of the sampled region. The total organic carbon (TOC) content of the soil samples range between 0.1 and 1.3%. The TOC correlates poorly with the soil iodine (r{sup 2} < 1), indicating a lack of association of iodine with the surficial organic matter and the possibility of interaction between the seeping hydrocarbons and soil iodine. Further, the distribution pattern of iodine compares well with two surface geochemical indicators: the adsorbed light gaseous hydrocarbons (methane through butane) and the propane-oxidizing bacterial populations in the soil. The integration of geochemical observations show the occurrence of elevated values in the northern part of the study area, which is also coincident with the presence of exposed dyke swarms that probably serve as conduits for hydrocarbon microseepage. The corroboration of iodine with existing geological, geophysical, and geochemical data suggests its efficacy as one of the potential tool in surface geochemical exploration of hydrocarbons. Our study supports Deccan Syneclise to be promising in terms of its hydrocarbon prospects.

  15. Retrodicting the Cenozoic evolution of the mantle: Implications for dynamic surface topography

    NASA Astrophysics Data System (ADS)

    Glišović, Petar; Forte, Alessandro; Rowley, David; Simmons, Nathan; Grand, Stephen

    2014-05-01

    Seismic tomography is the essential starting ingredient for constructing realistic models of the mantle convective flow and for successfully predicting a wide range of convection-related surface observables. However, the lack of knowledge of the initial thermal state of the mantle in the geological past is still an outstanding problem in mantle convection. The resolution of this problem requires models of 3-D mantle evolution that yield maximum consistency with a wide suite of geophysical constraints. Quantifying the robustness of the reconstructed thermal evolution is another major concern. We have carried out mantle dynamic simulations (Glišović & Forte, EPSL 2014) using a pseudo-spectral solution for compressible-flow thermal convection in 3-D spectral geometry that directly incorporate: 1) joint seismic-geodynamic inversions of mantle density structure with constraints provided by mineral physics data (Simmons et al., GJI 2009); and 2) constraints on mantle viscosity inferred by inversion of a suite of convection-related and glacial isostatic adjustment data sets (Mitrovica & Forte, EPSL 2004) characterised by Earth-like Rayleigh numbers. These time-reversed convection simulations reveal how the buoyancy associated with hot, active upwellings is a major driver of the mantle-wide convective circulation and the changes in dynamic topography at the Earth's surface. These simulations reveal, for example, a stable and long-lived superplume under the East Pacific Rise (centred under the Easter and Pitcairn hotspots) that was previously identified by Rowley et al. (AGU 2011, Nature in review) on the basis of plate kinematic data. We also present 65 Myr reconstructions of the Reunion plume that gave rise to the Deccan Traps.

  16. Climatic driven variability of surface water energy potential and implications for future hydroelectricity

    NASA Astrophysics Data System (ADS)

    Worman, A. L. E.; Lindstrom, G.

    2014-12-01

    An average year the production in Norway and Sweden is around 190 TWh and these two countries stand for about 70% of the hydropower energy stored in the available reservoirs of Europe. There are large challenges for the future use of this regulatory capacity with regard to balancing the electricity production in Europe under climate variability, compliance to water management plans under the Water Framework Directive and to the shifts to more renewable, but intermittent, energy sources required by the Renewable Energy Directive. A main aim of this project is to describe the variation over time of hydrological fluxes across Scandinavia in terms of their energy properties and to link that information to climatic factors and the regulation of hydroelectricty. Along these lines we explored daily data of digitalized hydro-climatological data from 1961, which were used to calibrate the HBV-model for 1001 watersheds in Sweden and the energy potential has been estimated as an average for that period (Figure below). These tentative results show that the surface water energy potential constitutes about one per mille of the latent heat flux due to evapotranspiration and it is, therefore, very sensitive to any fluctuation in the energy quantities of the hydrometeorological system. Tentative analysis suggests that the energy availability of surface water in Sweden exhibits significant decadal long fluctuations from 115 TWh/year up to 180 TWh/year, which follow several different time scales and periodicities, ranging from century-long trends to fluctuations occurring on time scales of a decade and shorter. In addition, recent investigations show that land-use changes and hydropower regulation has caused significant changes in the annual runoff periodicity in Swedish rivers during the 20th century. Those changes in the annual periodicities are caused by structural alterations in river basins affected by intense agriculture and hydropower regulation.

  17. Surface Elevation Changes in West Antarctica from Satellite Altimetry: Mass Balance Implications

    NASA Technical Reports Server (NTRS)

    Zwally, H. Jay; Brenner, Anita C.; Cornejo, Helen; Koblinsky, Chester J. (Technical Monitor)

    2001-01-01

    Time-series of surface elevation change, which are constructed from 7-years (1992-1999) of ERS-1 and 2 satellite radar altimeter data of Antarctica, show significant seasonal, inter-annual, and long-term changes. Elevation time-series are created from altimeter crossovers among 90-day data periods on a 50 km grid to 81.5 degrees S and fit with a multivariate linear/sinusoidal function to give the average rate of elevation change (dH/dt) and account for seasonal changes. On the major Ronne, Filchner, and Ronne ice shelves, the dH/dt are small or near zero. In contrast, the ice shelves of the Antarctic Peninsula and along the West Antarctic coast appear to be thinning significantly, with a 23 +/- 3 cm a(exp -1) surface elevation decrease on the Larsen ice shelf and a 65 +/- 4 cm a(exp -1) decrease on the Dotson ice shelf. Significant elevation decreases are obtained over most of the drainage basins of the Pine Island and Thwaites glaciers. Significant increases are obtained over most of the other grounded ice in Marie Byrd Land, the Antarctic Peninsula, and Coates Land. Over the sector from 85 degrees W to 115 degrees W, which includes the Pine Island and Thwaites basins, the average elevation is significantly decreasing by 8.1 cm a(exp -1). The corresponding ice thickness change is about -11 cm a(exp -1), with a corresponding mass loss of 82 Gt a(exp -1), and a 0.22 mm a(exp -1) contribution to global sea level rise. In terms of elevation change, the decrease in the Pine Island-Thwaites sector is largely balanced by the increase in the Marie Byrd Land, but only balanced by about 1/4 in terms of ice thickness change and contribution to sea level rise. The overall average elevation change for the grounded ice is + 1.2 cm a(exp -1). Using an average bedrock uplift of 2.5 cm a(exp -1), implies an average ice thickness decrease of 1.3 cm a(exp -1), a mass loss of 22 Gt a(exp -1), and a 0.06 mm a(exp -1) contribution to global sea level rise.

  18. Surface Velocities of Himalayan Glaciers: Implications for Glacial Erosion Potential During Climatic Change

    NASA Astrophysics Data System (ADS)

    Scherler, D.; Bookhagen, B.; Strecker, M. R.

    2007-12-01

    Mountain glaciers in the high elevations (> 3.5 km) of the Himalaya are very efficient erosion agents. Glacier size and thus the area affected by glacial erosion are controlled by climatic conditions. Understanding the impact of climate change and variability on glacial budgets and erosion requires knowledge of the erosive potential of glaciers, which is inferred to scale with ice flux. Here, we use ASTER satellite imagery in combination with the orthorectification and correlation tool COSI-Corr to derive horizontal surface velocities of glaciers from several regions across the Himalayan-Karakoram domain. Our results show that glaciers in the Eastern and Central Himalaya, where precipitation is mainly supplied by the Indian Summer Monsoon, are relatively slow, with velocities usually below 50-60 m/a. In contrast, glaciers in the Western Himalaya and Karakoram, receive a significant amount of precipitation during the winter months and are considerably faster with velocities often exceeding 80-100 m/a. This discrepancy is visible among glaciers of different size and orientation although local slope and catchment area effects may cause velocity excursions. A relatively sharp gradient appears to exist in the catchment area of the Sutlej River in the NW Himalaya of India at approximately 79°E. To the east, glaciers in the Garhwal Himalaya - among them Gangotri glacier, the largest in the Indian Himalaya - have mean velocities of around 20-40 m/a, whereas glaciers in the much drier Lahul region to the west attain mean velocities of around 30-60 m/a. Importantly, the Sutlej River valley marks a climatic transition zone from an annual summer-rainfall maximum (more than 75% of annual rainfall during the summer) to the east to a winter-rainfall maximum (more than 60% of annual rainfall during the winter) to the west. These observations corroborate the notion of a significant climatic boundary in this part of the Himalaya, which may have shifted west- and northward during

  19. Incompletely Mixed Surface Transient Storage Zones at River Restoration Structures: Modeling Implications

    NASA Astrophysics Data System (ADS)

    Endreny, T. A.; Robinson, J.

    2012-12-01

    River restoration structures, also known as river steering deflectors, are designed to reduce bank shear stress by generating wake zones between the bank and the constricted conveyance region. There is interest in characterizing the surface transient storage (STS) and associated biogeochemical processing in the STS zones around these structures to quantify the ecosystem benefits of river restoration. This research explored how the hydraulics around river restoration structures prohibits application of transient storage models designed for homogenous, completely mixed STS zones. We used slug and constant rate injections of a conservative tracer in a 3rd order river in Onondaga County, NY over the course of five experiments at varying flow regimes. Recovered breakthrough curves spanned a transect including the main channel and wake zone at a j-hook restoration structure. We noted divergent patterns of peak solute concentration and times within the wake zone regardless of transect location within the structure. Analysis reveals an inhomogeneous STS zone which is frequently still loading tracer after the main channel has peaked. The breakthrough curve loading patterns at the restoration structure violated the assumptions of simplified "random walk" 2 zone transient storage models which seek to identify representative STS zones and zone locations. Use of structure-scale Weiner filter based multi-rate mass transfer models to characterize STS zones residence times are similarly dependent on a representative zone location. Each 2 zone model assumes 1 zone is a completely mixed STS zone and the other a completely mixed main channel. Our research reveals limits to simple application of the recently developed 2 zone models, and raises important questions about the measurement scale necessary to identify critical STS properties at restoration sites. An explanation for the incompletely mixed STS zone may be the distinct hydraulics at restoration sites, including a constrained

  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. Survival of endospores of Bacillus subtilis on spacecraft surfaces under simulated martian environments: . implications for the forward contamination of Mars

    NASA Astrophysics Data System (ADS)

    Schuerger, Andrew C.; Mancinelli, Rocco L.; Kern, Roger G.; Rothschild, Lynn J.; McKay, Christopher P.

    2003-10-01

    Experiments were conducted in a Mars simulation chamber (MSC) to characterize the survival of endospores of Bacillus subtilis under high UV irradiation and simulated martian conditions. The MSC was used to create Mars surface environments in which pressure (8.5 mb), temperature (-80, -40, -10, or +23 °C), gas composition (Earth-normal N 2/O 2 mix, pure N 2, pure CO 2, or a Mars gas mix), and UV-VIS-NIR fluence rates (200-1200 nm) were maintained within tight limits. The Mars gas mix was composed of CO 2 (95.3%), N 2 (2.7%), Ar (1.7%), O 2 (0.2%), and water vapor (0.03%). Experiments were conducted to measure the effects of pressure, gas composition, and temperature alone or in combination with Mars-normal UV-VIS-NIR light environments. Endospores of B. subtilis, were deposited on aluminum coupons as monolayers in which the average density applied to coupons was 2.47×10 6 bacteria per sample. Populations of B. subtilis placed on aluminum coupons and subjected to an Earth-normal temperature (23 °C), pressure (1013 mb), and gas mix (normal N 2/O 2 ratio) but illuminated with a Mars-normal UV-VIS-NIR spectrum were reduced by over 99.9% after 30 sec exposure to Mars-normal UV fluence rates. However, it required at least 15 min of Mars-normal UV exposure to reduce bacterial populations on aluminum coupons to non-recoverable levels. These results were duplicated when bacteria were exposed to Mars-normal environments of temperature (-10 °C), pressure (8.5 mb), gas composition (pure CO 2), and UV fluence rates. In other experiments, results indicated that the gas composition of the atmosphere and the temperature of the bacterial monolayers at the time of Mars UV exposure had no effects on the survival of bacterial endospores. But Mars-normal pressures (8.5 mb) were found to reduce survival by approximately 20-35% compared to Earth-normal pressures (1013 mb). The primary implications of these results are (a) that greater than 99.9% of bacterial populations on sun

  2. Survival of endospores of Bacillus subtilis on spacecraft surfaces under simulated martian environments: implications for the forward contamination of Mars.

    PubMed

    Schuerger, Andrew C; Mancinelli, Rocco L; Kern, Roger G; Rothschild, Lynn J; McKay, Christopher P

    2003-10-01

    Experiments were conducted in a Mars simulation chamber (MSC) to characterize the survival of endospores of Bacillus subtilis under high UV irradiation and simulated martian conditions. The MSC was used to create Mars surface environments in which pressure (8.5 mb), temperature (-80, -40, -10, or +23 degrees C), gas composition (Earth-normal N2/O2 mix, pure N2, pure CO2, or a Mars gas mix), and UV-VIS-NIR fluence rates (200-1200 nm) were maintained within tight limits. The Mars gas mix was composed of CO2 (95.3%), N2 (2.7%), Ar (1.7%), O2 (0.2%), and water vapor (0.03%). Experiments were conducted to measure the effects of pressure, gas composition, and temperature alone or in combination with Mars-normal UV-VIS-NIR light environments. Endospores of B. subtilis, were deposited on aluminum coupons as monolayers in which the average density applied to coupons was 2.47 x 10(6) bacteria per sample. Populations of B. subtilis placed on aluminum coupons and subjected to an Earth-normal temperature (23 degrees C), pressure (1013 mb), and gas mix (normal N2/O2 ratio) but illuminated with a Mars-normal UV-VIS-NIR spectrum were reduced by over 99.9% after 30 sec exposure to Mars-normal UV fluence rates. However, it required at least 15 min of Mars-normal UV exposure to reduce bacterial populations on aluminum coupons to non-recoverable levels. These results were duplicated when bacteria were exposed to Mars-normal environments of temperature (-10 degrees C), pressure (8.5 mb), gas composition (pure CO2), and UV fluence rates. In other experiments, results indicated that the gas composition of the atmosphere and the temperature of the bacterial monolayers at the time of Mars UV exposure had no effects on the survival of bacterial endospores. But Mars-normal pressures (8.5 mb) were found to reduce survival by approximately 20-35% compared to Earth-normal pressures (1013 mb). The primary implications of these results are (a) that greater than 99.9% of bacterial populations on

  3. Plasmonic Purcell factor and coupling efficiency to surface plasmons. Implications for addressing and controlling optical nanosources

    NASA Astrophysics Data System (ADS)

    Colas des Francs, G.; Barthes, J.; Bouhelier, A.; Weeber, J. C.; Dereux, A.; Cuche, A.; Girard, C.

    2016-09-01

    The Purcell factor F p is a key quantity in cavity quantum electrodynamics (cQED) that quantifies the coupling rate between a dipolar emitter and a cavity mode. Its simple form {F}{{p}}\\propto Q/V unravels the possible strategies to enhance and control light-matter interaction. Practically, efficient light-matter interaction is achieved thanks to either (i) high quality factor Q at the basis of cQED or (ii) low modal volume V at the basis of nanophotonics and plasmonics. In the last decade, strong efforts have been done to derive a plasmonic Purcell factor in order to transpose cQED concepts to the nanocale, in a scale-law approach. In this work, we discuss the plasmonic Purcell factor for both delocalized (SPP) and localized (LSP) surface-plasmon-polaritons and briefly summarize the expected applications for nanophotonics. On the basis of the SPP resonance shape (Lorentzian or Fano profile), we derive closed form expression for the coupling rate to delocalized plasmons. The quality factor factor and modal confinement of both SPP and LSP are quantified, demonstrating their strongly subwavelength behavior.

  4. Implication of an Outer Surface Lipoprotein in Adhesion of Bifidobacterium bifidum to Caco-2 Cells▿

    PubMed Central

    Guglielmetti, Simone; Tamagnini, Isabella; Mora, Diego; Minuzzo, Mario; Scarafoni, Alessio; Arioli, Stefania; Hellman, Jukka; Karp, Matti; Parini, Carlo

    2008-01-01

    We found that the human intestinal isolate Bifidobacterium bifidum MIMBb75 strongly adhered to Caco-2 cells. Proteinase K and lithium chloride treatments showed that proteins play a key role in MIMBb75 adhesion to Caco-2 cells. By studying the cell wall-associated proteins, we identified a surface protein, which we labeled BopA. We purified the protein chromatographically and found that it functioned as an adhesion promoter on Caco-2 cells. In silico analysis of the gene coding for this protein and globomycin experiments showed that BopA is a cysteine-anchored lipoprotein expressed as a precursor polypeptide. A database search indicated that BopA appears to function biologically as an oligopeptide/tripeptide-solute-binding protein in the ABC transport system. We discovered a protein corresponding to BopA and its gene in eight other highly adherent B. bifidum strains. Finally, we found that B. bifidum MIMBb75 and BopA affected the production of interleukin-8 in Caco-2 epithelial cells. BopA is the first protein described to date to be directly involved in the adhesion of bifidobacteria to Caco-2 cells and to show immunomodulatory activity. PMID:18539800

  5. Implication of an outer surface lipoprotein in adhesion of Bifidobacterium bifidum to Caco-2 cells.

    PubMed

    Guglielmetti, Simone; Tamagnini, Isabella; Mora, Diego; Minuzzo, Mario; Scarafoni, Alessio; Arioli, Stefania; Hellman, Jukka; Karp, Matti; Parini, Carlo

    2008-08-01

    We found that the human intestinal isolate Bifidobacterium bifidum MIMBb75 strongly adhered to Caco-2 cells. Proteinase K and lithium chloride treatments showed that proteins play a key role in MIMBb75 adhesion to Caco-2 cells. By studying the cell wall-associated proteins, we identified a surface protein, which we labeled BopA. We purified the protein chromatographically and found that it functioned as an adhesion promoter on Caco-2 cells. In silico analysis of the gene coding for this protein and globomycin experiments showed that BopA is a cysteine-anchored lipoprotein expressed as a precursor polypeptide. A database search indicated that BopA appears to function biologically as an oligopeptide/tripeptide-solute-binding protein in the ABC transport system. We discovered a protein corresponding to BopA and its gene in eight other highly adherent B. bifidum strains. Finally, we found that B. bifidum MIMBb75 and BopA affected the production of interleukin-8 in Caco-2 epithelial cells. BopA is the first protein described to date to be directly involved in the adhesion of bifidobacteria to Caco-2 cells and to show immunomodulatory activity.

  6. Surface extra-vehicular activity emergency scenario management: Tools, procedures, and geologically related implications

    NASA Astrophysics Data System (ADS)

    Zea, Luis; Diaz, Alejandro R.; Shepherd, Charles K.; Kumar, Ranganathan

    2010-07-01

    Extra-vehicular activities (EVAs) are an essential part of human space exploration, but involve inherently dangerous procedures which can put crew safety at risk during a space mission. To help mitigate this risk, astronauts' training programs spend substantial attention on preparing for surface EVA emergency scenarios. With the help of two Mars Desert Research Station (MDRS) crews (61 and 65), wearing simulated spacesuits, the most important of these emergency scenarios were examined at three different types of locations that geologically and environmentally resemble lunar and Martian landscapes. These three platforms were analyzed geologically as well as topographically (utilizing a laser range finder with slope estimation capabilities and a slope determination software). Emergency scenarios were separated into four main groups: (1) suit issues, (2) general physiological, (3) attacks and (4) others. Specific tools and procedures were developed to address each scenario. The tools and processes were tested in the field under Mars-analog conditions with the suited subjects for feasibility and speed of execution.

  7. The characteristics and interpretability of land surface change and implications for project design

    USGS Publications Warehouse

    Sohl, Terry L.; Gallant, Alisa L.; Loveland, Thomas R.

    2004-01-01

    The need for comprehensive, accurate information on land-cover change has never been greater. While remotely sensed imagery affords the opportunity to provide information on land-cover change over large geographic expanses at a relatively low cost, the characteristics of land-surface change bring into question the suitability of many commonly used methodologies. Algorithm-based methodologies to detect change generally cannot provide the same level of accuracy as the analyses done by human interpreters. Results from the Land Cover Trends project, a cooperative venture that includes the U.S. Geological Survey, Environmental Protection Agency, and National Aeronautics and Space Administration, have shown that land-cover conversion is a relatively rare event, occurs locally in small patches, varies geographically and temporally, and is spectrally ambiguous. Based on these characteristics of change and the type of information required, manual interpretation was selected as the primary means of detecting change in the Land Cover Trends project. Mixtures of algorithm-based detection and manual interpretation may often prove to be the most feasible and appropriate design for change-detection applications. Serious examination of the expected characteristics and measurability of change must be considered during the design and implementation phase of any change analysis project.

  8. P Isotope Data of SNC Meteorites and Implications on the Age of the Martian Surface

    NASA Astrophysics Data System (ADS)

    Jagoutz, E.; Jotter, R.; Kubny, A.; Zartman, R.

    SNC meteorites might originate from the Martian surface. However, these meteorites have experienced a relative young metamorphosis which obscures their origin. Pb isotopes seem to be the best way to look through these young disturbances. A major fraction of the U and Th in the SNCs is not a primary constituent but was introduced at the time of disturbance and resides in the phosphates. By contrast, the Pb in the silicate minerals seems to have remained essentially in isotopic equilibration with the U and Th in the mineral since the time of original crystallization. The main cause of any scatter in the determined initial composition is probably due to the addition of terrestrial Pb, although some minor in situ isotopic disturbance cannot be ruled out. Our best values for the initial isotopic ratios of Shergotty, Zagami, and Los Angeles will be shown. The parent body formed and differentiated at 4.55 Ga, and the various meteorite source lithologies evolved isotopically undisturbed until 0.45 Ga (Los Angeles with a µ =238 U/204 Pb of ˜4, Zagami with a µ of ˜4.5, and Shergotty with a µ of ˜5). At ˜0.45 Ga the "young event" affected each of these meteorites and the initial Pb ratios, after being corrected for subsequent in situ growth of radiogenic Pb, are scattering on a fossilized 0.45 Ga geochron. Additional insight is gained from isotopic data for the Nakhlites, including several that have been newly found and analyzed. All Nakhlites appear to have been derived from an isotopic uniform reservoir, and share a well-defined "young event" age of 1.25 Ga. Of particular note is the fact that their initial Pb isotopic composition does not plot on the modern geochron, but instead to the right of it. If experiencing only a single stage evolution prior to 1.25 Ga, its initial Pb should actually plot on a fossilized 1.25 Ga geochron considerably to the left of the modern geochron. Only a relatively recent increase of the U/Pb ratio in the Nakhlite reservoir could

  9. Nanoporous membranes with electrochemically switchable, chemically stabilized ionic selectivity.

    PubMed

    Small, Leo J; Wheeler, David R; Spoerke, Erik D

    2015-10-28

    Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm(2) in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems.

  10. Contrasting strike-slip motions on thrust and normal faults: Implications for space-geodetic monitoring of surface deformation

    NASA Astrophysics Data System (ADS)

    Hampel, Andrea; Li, Tao; Maniatis, Georgios

    2013-04-01

    emphasizes that understanding fault-parallel slip components and associated surface displacements is essential for inferring regional deformation patterns from space-geodetic and fault-slip data. References: Cheloni, D., N. D'Agostino, E. D'Anastasio, A. Avallone, S. Mantenuto, R. Giuliani, M. Mattone, S. Calcaterra, P. Gambino, D. Dominici, F. Radicioni, G. Fastellini (2010) Coseismic and initial post-seismic slip of the 2009 Mw 6.3 L'Aquila earthquake, Italy, from GPS measurements: Geophysical Journal International, 181, 1539-1546. Hampel, A., T. Li, G. Maniatis (in press) Contrasting strike-slip motions on thrust and normal faults: Implications for space-geodetic monitoring of surface deformation: Geology. Hsu, Y.-J., S.-B Yu, H.-Y. Chen (2009) Coseismic and postseismic deformation associated with the 2003 Chengkung, Taiwan, earthquake: Geophysical Journal International, 176, 420-430. Jackson, J.A., J. Gagnepain, G. Houseman, G.C.P. King, P. Papadimitriou, C. Soufleris, J. Virieux (1982) Seismicity, normal faulting, and the geomorphological development of the Gulf of Corinth (Greece): The Corinth earthquakes of February and March 1981: Earth and Planetary Science Letters, 57, 377-397. Roberts, G.P., I. Koukouvelas (1996) Structural and seismological segmentation of the Gulf of Corinth fault system: Implications for models of fault growth: Annali di Geofisica, 39, 619-646. Serpelloni, E., L. Anderlini, M.E. Belardinelli (2012) Fault geometry, coseismic-slip distribution and Coulomb stress change associated with the 2009 April 6, Mw 6.3, L'Aquila earthquake from inversion of GPS displacements: Geophysical Journal International, 188, 473-489.

  11. VIS-IR study of brucite-clay-carbonate mixtures: Implications for Ceres surface composition

    NASA Astrophysics Data System (ADS)

    De Angelis, S.; Manzari, P.; De Sanctis, M. C.; Ammannito, E.; Di Iorio, T.

    2016-12-01

    Carbonates and clay minerals are present in Solar System bodies such as Mars and asteroid (1) Ceres. Brucite has been proposed in the recent past to fit absorption features in spectra of Ceres. In this study Visible-Near Infrared reflectance spectroscopic measurements have been performed on brucite-carbonate-clay minerals mixtures, in the 0.2-5.1 μm spectral range. Different sets of three- and two-components mixtures have been prepared using these three fine powdered endmembers, by varying the relative proportions of carbonate, clay and brucite. Spectra have been acquired on the endmembers components separately and on the mixtures. Absorption features diagnostic of the carbonate, clay and brucite phases have been analyzed and band parameters (position, depth, area, width) determined. Several trends and correlations with mineral phase content in each mixture have been investigated, with the aim to determining how endmember components influence the mixture spectra and their minimum detectability threshold. Our results indicate that brucite is detectable in mineral mixtures with carbonates and clays, based on its main absorption features at 0.95, 2.45-2.47 and 3.05 μm. While the 0.95 and 3.05 μm features are only discernible for very high brucite contents in the mixtures, the ∼2.45 μm band turns out to be highly diagnostic, also for very small amounts of brucite (of the order of 10 wt%). These experiments, together with DAWN observations of Ceres, substantially rule out the presence of great amounts of brucite globally distributed on the surface of Ceres.

  12. Ground state of Ho atoms on Pt(111) metal surfaces: Implications for magnetism

    NASA Astrophysics Data System (ADS)

    Karbowiak, M.; Rudowicz, C.

    2016-05-01

    We investigated the ground state of Ho atoms adsorbed on the Pt(111) surface, for which conflicting results exist. The density functional theory (DFT) calculations yielded the Ho ground state as | Jz=±8 > . Interpretation of x-ray absorption spectroscopy and x-ray magnetic circular dichroism spectra and the magnetization curves indicated the ground state as | Jz=±6 > . Superposition model is employed to predict the crystal-field (CF) parameters based on the structural data for the system Ho/Pt(111) obtained from the DFT modeling. Simultaneous diagonalization of the free-ion (HFI) and the trigonal CF Hamiltonian (HCF) within the whole configuration 4 f10 of H o3 + ion was performed. The role of the trigonal CF terms, neglected in the pure uniaxial CF model used previously for interpretation of experimental spectra, is found significant, whereas the sixth-rank CF terms may be neglected in agreement with the DFT predictions. The results provide substantial support for the experimental designation of the | Jz=±6 > ground state, albeit with subtle difference due to admixture of other | Jz> states, but run against the DFT-based designation of the | Jz=±8 > ground state. A subtle splitting of the ground energy level with the state (predominantly), | Jz=±6 > is predicted. This paper provides better insight into the single-ion magnetic behavior of the Ho/Pt(111) system by helping to resolve the controversy concerning the Ho ground state. Experimental techniques with greater resolution powers are suggested for direct confirmation of this splitting and C3 v symmetry experienced by the Ho atom.

  13. The Evolution and Development of the Lunar Regolith and Implications for Lunar Surface Operations and Construction

    NASA Technical Reports Server (NTRS)

    McKay, David

    2009-01-01

    The lunar regolith consists of about 90% submillimeter particles traditionally termed lunar soil. The remainder consists of larger particles ranging up to boulder size rocks. At the lower size end, soil particles in the 10s of nanometer sizes are present in all soil samples. Lunar regolith overlies bedrock which consists of either lava flows in mare regions or impact-produced megaregolith in highland regions. Lunar regolith has been produced over billions of years by a combination of breaking and communition of bedrock by meteorite bombardment coupled with a variety of complex space weathering processes including solar wind implantation, solar flare and cosmic ray bombardment with attendant radiation damage, melting, vaporization, and vapor condensation driven by impact, and gardening and turnover of the resultant soil. Lunar regolith is poorly sorted compared to most terrestrial soils, and has interesting engineering properties including strong grain adhesion, over-compacted soil density, an abundance of agglutinates with sharp corners, and a variety of properties related to soil maturity. The NASA program has supported a variety of engineering test research projects, the production of bricks by solar or microwave sintering, the production of concrete, the in situ sintering and glazing of regolith by microwave, and the extraction of useful resources such as oxygen, hydrogen, iron, aluminum, silicon and other products. Future requirements for a lunar surface base or outpost will include construction of protective berms, construction of paved roadways, construction of shelters, movement and emplacement of regolith for radiation shielding and thermal control, and extraction of useful products. One early need is for light weight but powerful digging, trenching, and regolith-moving equipment.

  14. Pyrrolidinium ionic liquid crystals.

    PubMed

    Goossens, Karel; Lava, Kathleen; Nockemann, Peter; Van Hecke, Kristof; Van Meervelt, Luc; Driesen, Kris; Görller-Walrand, Christiane; Binnemans, Koen; Cardinaels, Thomas

    2009-01-01

    N-alkyl-N-methylpyrrolidinium cations have been used for the design of ionic liquid crystals, including a new type of uranium-containing metallomesogen. Pyrrolidinium salts with bromide, bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate, thiocyanate, tetrakis(2- thenoyltrifluoroacetonato)europate(III) and tetrabromouranyl counteranions were prepared. For the bromide salts and tetrabromouranyl compounds, the chain length of the alkyl group C(n)H(2n+1) was varied from eight to twenty carbon atoms (n = 8, 10-20). The compounds show rich mesomorphic behaviour: highly ordered smectic phases (the crystal smectic E phase and the uncommon crystal smectic T phase), smectic A phases, and hexagonal columnar phases were observed, depending on chain length and anion. This work gives better insight into the nature and formation of the crystal smectic T phase, and the molecular requirements for the appearance of this highly ordered phase. This uncommon tetragonal mesophase is thoroughly discussed on the basis of detailed powder X-ray diffraction experiments and in relation to the existing literature. Structural models are proposed for self-assembly of the molecules within the smectic layers. In addition, the photophysical properties of the compounds containing a metal complex anion were investigated. For the uranium-containing mesogens, luminescence can be induced by dissolving them in an ionic liquid matrix. The europium-containing compound shows intense red photoluminescence with high colour purity.

  15. Present-Day Surface Changes on Mars: Implications for Recent Climate Variability and Habitability

    NASA Astrophysics Data System (ADS)

    McEwen, A. S.; Dundas, C. M.; Diniega, S.; Byrne, S.; Bridges, N. T.; Hansen, C. J.

    2012-12-01

    With the high-resolution and repeat-image capability of MRO/HiRISE, we have been documenting present-day surface activity. This activity includes seasonal defrosting (spots, fans, etc.), changes in polar deposits, new impacts, migrating sand dunes, enlargement of gullies, and a variety of slope flows. What does this tell us about possible environmental change and habitability? Perhaps the key result is that previous suggestions of recent climate change on Mars may have been somewhat exaggerated. One such suggestion is that the enlargement of pits in the south polar residual cap indicates present-day global warming. However, recent models of continuous sublimation and redeposition of the CO2 predict a suite of landforms that have been observed to exist today (Byrne, 2009, AREPS 37, 535). Another suggestion is that mid-latitude gullies formed by melting snow or shallow ice after a recent period of high obliquity, but HiRISE observations have shown rapid and widespread gully activity in the present climate (Diniega et al., 2010, Geology 38, 1047; Dundas et al., 2012, Icarus 220, 124; Dundas et al., this conference). Likewise, suggestions that Mars needed a significantly higher atmospheric density to explain the presence of well-preserved sand dunes have been countered by observations of widespread current activity (Bridges et al., 2012, Geology 40, 31; Bridges et al., 2012, Nature 485, 339). These observations do not rule out significantly different past climate conditions but do suggest that their effects were less pronounced, at least in recent times. There are features that do not appear active today; one example is the transverse aeolian ridges. Also, the mid-latitude icy lobate flows and ice-rich mantles have not shown current activity, appear to have partially sublimated, and are likely remnants of recent past climates. Ground ice excavated by new craters is observed closer to the equator than predicted for the present atmospheric water vapor content, but

  16. The UV Surface Environment on Young Planets: Implications for Prebiotic Chemistry & Life on Other Worlds

    NASA Astrophysics Data System (ADS)

    Ranjan, Sukrit; Simons Collaboration on the Origin of Life, Harvard Origins of Life Initiative

    2017-01-01

    Understanding the origin of life (abiogenesis) on Earth is key to understanding how it might start elsewhere. Recent laboratory studies suggest UV light may have played a critical role in the synthesis of molecules relevant to abiogenesis (prebiotic chemistry), such as RNA. I show that UV light interacts with prebiotic chemistry in ways that may be sensitive to the spectral shape and overall amplitude of irradiation. I use radiative transfer models to constrain the UV environment on early Earth (3.9 Ga). I find that the surface UV is insensitive to much of the considerable uncertainty in the atmospheric state, enabling me to constrain the UV environment for prebiotic chemistry on early Earth. Some authors have suggested Mars as a venue for prebiotic chemistry. Therefore, I explore plausible UV spectral fluences on Mars at 3.9 Ga. I find that the early Martian UV environment is comparable to Earth’s under conventional assumptions about the atmosphere. However, if the atmosphere was dusty or SO2 levels were high, UV fluence would have been strongly suppressed. Intriguingly, despite overall attenuation of UV fluence, SO2 preferentially attenuates destructive FUV radiation over prebiotically-useful NUV radiation, meaning high-SO2 epochs may have been more clement for the origin of life. Better measurements of the spectral dependence of prebiotic photoprocesses are required to constrain this hypothesis. Finally, I calculate the UV fluence on planets orbiting M-dwarfs. I find that UV irradiation on such planets is low compared to Earth. Laboratory studies are required to understand whether prebiotic photoprocesses that worked on Earth can function on low-UV M-dwarf planets. My work 1) provides initial conditions for laboratory studies of prebiotic chemistry, 2) constrains the inhabitability of Mars and planets orbiting M-dwarfs, and 3) demonstrates the need for laboratory studies to characterize the impact of variations in irradiating intensity and spectral shape on

  17. Affinity of functional groups for membrane surfaces: implications for physically irreversible fouling.

    PubMed

    Yamamura, Hiroshi; Kimura, Katsuki; Okajima, Takaharu; Tokumoto, Hiroshi; Watanabe, Yoshimasa

    2008-07-15

    Fouling in membranes used for water treatment has been attributed to the presence of natural organic matter (NOM) in water. There have been reports recently on the contribution of hydrophilic fractions of NOM (e.g., carbohydrate-like substances) to fouling, but there is still little information about the physicochemical interactions between membranes and carbohydrate-like substances. In this study, the affinity of carbohydrate-like substances to two different microfiltration (MF) membranes was investigated by using atomic force microscopy (AFM) and functionally modified microspheres. Microspheres were attached to the tip of the cantilever in an AFM apparatus and the adhesion forces working between the microspheres and the membranes were determined. The microspheres used in this study were coated with either hydroxyl groups or carboxyl groups to be used as surrogates of carbohydrate-like substances or humic acid, respectively. Measurements of adhesion force were carried out at pH of 6.8 and the experimental results demonstrated that the adhesion force to membranes was strong in the case of hydroxyl groups but weak in the case of carboxyl groups. The strong adhesion between the hydroxyl group and the membrane surface is explained by the strong hydrogen bond generated. It was also found that the affinity of the hydroxyl group to a polyvinylidenefluoride (PVDF) membrane was much higher than that to a polyethylene (PE) membrane, possibly due to the high electronegative nature of the PVDF polymer. The time course of changes in the affinity of hydroxyl group to a membrane used in a practical condition was investigated by repeatedly carrying out AFM force measurements with PE membrane specimens sampled from a pilot plant operated at an existing water treatment plant. Microspheres exhibited strong affinity to the membrane at the initial stage of operation (within 5 days), but subsequently exponential reduction of the affinity was seen until the end of operation, as a result

  18. Contrasting optical properties of surface waters across the Fram Strait and its potential biological implications

    NASA Astrophysics Data System (ADS)

    Pavlov, Alexey K.; Granskog, Mats A.; Stedmon, Colin A.; Ivanov, Boris V.; Hudson, Stephen R.; Falk-Petersen, Stig

    2015-03-01

    Underwater light regime is controlled by distribution and optical properties of colored dissolved organic matter (CDOM) and particulate matter. The Fram Strait is a region where two contrasting water masses are found. Polar water in the East Greenland Current (EGC) and Atlantic water in the West Spitsbergen Current (WSC) differ with regards to temperature, salinity and optical properties. We present data on absorption properties of CDOM and particles across the Fram Strait (along 79° N), comparing Polar and Atlantic surface waters in September 2009 and 2010. CDOM absorption of Polar water in the EGC was significantly higher (more than 3-fold) compared to Atlantic water in the WSC, with values of absorption coefficient, aCDOM(350), m- 1 of 0.565 ± 0.100 (in 2009) and 0.458 ± 0.117 (in 2010), and 0.138 ± 0.036 (in 2009) and 0.153 ± 0.039 (in 2010), respectively. An opposite pattern was observed for particle absorption with higher absorption found in the eastern part of the Fram Strait. Average values of particle absorption (aP(440), m- 1) were 0.016 ± 0.013 (in 2009) and 0.014 ± 0.011 (in 2010), and 0.047 ± 0.012 (in 2009) and 0.016 ± 0.014 (in 2010), respectively for Polar and Atlantic water. Thus absorption of light in eastern part of the Fram Strait is dominated by particles - predominantly phytoplankton, and the absorption of light in the western part of the strait is dominated by CDOM, with predominantly terrigenous origin. As a result the balance between the importance of CDOM and particulates to the total absorption budget in the upper 0-10 m shifts across Fram Strait. Under water spectral irradiance profiles were generated using ECOLIGHT 5.4.1 and the results indicate that the shift in composition between dissolved and particulate material does not influence substantially the penetration of photosynthetic active radiation (PAR, 400-700 nm), but does result in notable differences in ultraviolet (UV) light penetration, with higher attenuation in the

  19. Thermal evolution of Pluto and implications for despinning and sub-surface oceans

    NASA Astrophysics Data System (ADS)

    Robuchon, G.; Nimmo, F.

    2010-12-01

    low core potassium content convection still occurs but cannot prevent ice shell melting. Higher viscosities or higher potassium contents result in the formation of a sub-surface ocean. Despinning occurs over periods of a few to a few hundred million years, depending on the exact parameters adopted. In most cases, present-day Pluto consists of an ice shell ~100 km thick with an ocean ~200 km thick beneath. These simulations suggest that Pluto likely possesses an ocean at the present day [cf. 6,7,8]. The New Horizons spacecraft will be able to look for evidence of such an ocean, for instance by measuring the shape and Love number of Pluto. [1] McKinnon et al. (1997) Pluto and Charon [2] Canup (2005) Science [3] Choblet et al. (2007) Geophys. J. Int. [4] Robuchon et al. (2010) Icarus [5] McKinnon (2006) Icarus [6] Collins & Barr (2008) AGU [7] Hussmann et al. (2006) Icarus [8] Desch et al. (2009) Icarus

  20. 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

  1. Streptococcus mutans and Streptococcus intermedius adhesion to fibronectin films are oppositely influenced by ionic strength.

    PubMed

    Busscher, Henk J; van de Belt-Gritter, Betsy; Dijkstra, Rene J B; Norde, Willem; van der Mei, Henny C

    2008-10-07

    Bacterial adhesion to protein-coated surfaces is mediated by an interplay of specific and nonspecific interactions. Although nonspecific interactions are ubiquitously present, little is known about the physicochemical mechanisms of specific interactions. The aim of this paper is to determine the influence of ionic strength on the adhesion of two streptococcal strains to fibronectin films. Streptococcus mutans LT11 and Streptococcus intermedius NCTC11324 both possess antigen I/II with the ability to bind fibronectin from solution, but S. intermedius binds approximately 20x less fibronectin than does the S. mutans strain under identical conditions. Both strains as well as fibronectin films are negatively charged in low ionic strength phosphate buffered saline (PBS, 10x diluted), but bacteria appear uncharged in high ionic strength PBS. Physicochemical modeling on the basis of overall cell surface properties (cell surface hydrophobicity and zeta potentials) demonstrates that both strains should favor adhesion to fibronectin films in a high ionic strength environment as compared to in a low ionic strength environment, where electrostatic repulsion between equally charged surfaces is dominant. Adhesion of S. intermedius to fibronectin films in a parallel plate flow chamber was completely in line with this modeling, while in addition atomic force microscopy (AFM) indicated stronger adhesion forces upon retraction between fibronectin-coated tips and the cell surfaces in high ionic strength PBS than in low ionic strength PBS. Thus, the dependence of the interaction on ionic strength is dominated by the overall negative charge on the interacting surfaces. Adhesion of S. mutans to fibronectin films, however, was completely at odds with theoretical modeling, and the strain adhered best in low ionic strength PBS. Moreover, AFM indicated weaker repulsive forces upon approach between fibronectin-coated tips and the cell surfaces in low ionic strength PBS than in high ionic

  2. Strong sea surface cooling in the eastern equatorial Pacific and implications for Galápagos Penguin conservation

    NASA Astrophysics Data System (ADS)

    Karnauskas, K. B.; Jenouvrier, S.; Brown, C. W.; Murtugudde, R.

    2015-08-01

    The Galápagos is a flourishing yet fragile ecosystem whose health is particularly sensitive to regional and global climate variations. The distribution of several species, including the Galápagos Penguin, is intimately tied to upwelling of cold, nutrient-rich water along the western shores of the archipelago. Here we show, using reliable, high-resolution sea surface temperature observations, that the Galápagos cold pool has been intensifying and expanding northward since 1982. The linear cooling trend of 0.8°C/33 yr is likely the result of long-term changes in equatorial ocean circulation previously identified. Moreover, the northward expansion of the cold pool is dynamically consistent with a slackening of the cross-equatorial component of the regional trade winds—leading to an equatorward shift of the mean position of the Equatorial Undercurrent. The implied change in strength and distribution of upwelling has important implications for ongoing and future conservation measures in the Galápagos.

  3. Ionic Strength Is a Barrier to the Habitability of Mars

    NASA Astrophysics Data System (ADS)

    Fox-Powell, Mark G.; Hallsworth, John E.; Cousins, Claire R.; Cockell, Charles S.

    2016-06-01

    The thermodynamic availability of water (water activity) strictly limits microbial propagation on Earth, particularly in hypersaline environments. A considerable body of evidence indicates the existence of hypersaline surface waters throughout the history of Mars; therefore it is assumed that, as on Earth, water activity is a major limiting factor for martian habitability. However, the differing geological histories of Earth and Mars have driven variations in their respective aqueous geochemistry, with as-yet-unknown implications for habitability. Using a microbial community enrichment approach, we investigated microbial habitability for a suite of simulated martian brines. While the habitability of some martian brines was consistent with predictions made from water activity, others were uninhabitable even when the water activity was biologically permissive. We demonstrate experimentally that high ionic strength, driven to extremes on Mars by the ubiquitous occurrence of multivalent ions, renders these environments uninhabitable despite the presence of biologically available water. These findings show how the respective geological histories of Earth and Mars, which have produced differences in the planets' dominant water chemistries, have resulted in different physicochemical extremes which define the boundary space for microbial habitability.

  4. CADDIS Volume 2. Sources, Stressors and Responses: Ionic Strength

    EPA Pesticide Factsheets

    Introduction to the ionic strength module, when to list ionic strength as a candidate cause, ways to measure ionic strength, simple and detailed conceptual diagrams for ionic strength, ionic strength module references and literature reviews.

  5. Effect of the environmental humidity on the bulk, interfacial and nanoconfined properties of an ionic liquid.

    PubMed

    Jurado, L Andres; Kim, Hojun; Rossi, Antonella; Arcifa, Andrea; Schuh, Jonathon K; Spencer, Nicholas D; Leal, Cecilia; Ewoldt, Randy H; Espinosa-Marzal, Rosa M

    2016-08-10

    With reference to our previous surface-force study on 1-hexyl-3-methylimidazolium ethylsulfate ([HMIM] EtSO4) using an extended surface forces apparatus, which showed an ordered structure within the nanoconfined dry ionic liquid (IL) between mica surfaces that extended up to ∼60 nm from the surface, this work focuses on the influence of the environmental humidity on the bulk, interfacial and nanoconfined structure of [HMIM] EtSO4. Infrared spectroscopy and rheometry reflect the changes in chemical and physical properties of the bulk IL due to the uptake of water when exposed to ambient humidity, while wide-angle X-ray scattering shows a mild swelling of the bulk nanostructure, and the AFM sharp tip reveals an additional surface layer at the mica-IL interface. When the water-containing [HMIM] EtSO4 is nanoconfined between two mica surfaces, no long-range order is detected, in contrast to the results obtained for the dry IL, which demonstrates that the presence of water can prevent the liquid-to-solid transformation of this IL. A combination of techniques and the calculated Bjerrum length indicate that water molecules weaken interionic electrostatic and hydrogen-bonding interactions, which lessens ion-ion correlations. Our work shows that the solid-like behavior of the nanoconfined IL strongly depends on the presence of absorbed water and hence, it has implications with regard to the correct interpretation of laboratory studies and their extension to real applications in lubrication.

  6. Ionic liquids as surfactants

    NASA Astrophysics Data System (ADS)

    Smirnova, N. A.; Safonova, E. A.

    2010-10-01

    Problems of self-assembling in systems containing ionic liquids (ILs) are discussed. Main attention is paid to micellization in aqueous solutions of dialkylimidazolium ILs and their mixtures with classical surfactants. Literature data are reviewed, the results obtained by the authors and co-workers are presented. Thermodynamic aspects of the studies and problems of molecular-thermodynamic modeling receive special emphasis. It is shown that the aggregation behavior of dialkylimidazolium ILs is close to that of alkyltrimethylammonium salts (cationic surfactants) though ILs have a higher ability to self-organize, especially as it concerns long-range ordering. Some aspects of ILs applications are outlined where their common features with classical surfactants and definite specificity are of value.

  7. Thermal boundary conductance of hydrophilic and hydrophobic ionic liquids

    NASA Astrophysics Data System (ADS)

    Oyake, Takafumi; Sakata, Masanori; Yada, Susumu; Shiomi, Junichiro

    2015-03-01

    A solid/liquid interface plays a critical role for understanding mechanisms of biological and physical science. Moreover, carrier density of the surface is dramatically enhanced by electric double layer with ionic liquid, salt in the liquid state. Here, we have measured the thermal boundary conductance (TBC) across an interface of gold thin film and ionic liquid by using time-domain thermoreflectance technique. Following the prior researches, we have identified the TBC of two interfaces. One is gold and hydrophilic ionic liquid, N,N-Diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate (DEME-BF4), which is a hydrophilic ionic liquid, and the other is N,N-Diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide (DEME-TFSI), which is a hydrophobic ionic liquid. We found that the TBC between gold and DEME-TFIS (19 MWm-2K-1) is surprisingly lower than the interface between gold and DEME-BF4 (45 MWm-2K-1). With these data, the importance of the wetting angle and ion concentration for the thermal transport at the solid/ionic liquid interface is discussed. Part of this work is financially supported by Japan Society for the Promotion of Science (JSPS) and Japan Science and Technology Agency. The author is financially supported by JSPS Fellowship.

  8. Osmotic Pressure in Ionic Microgel Dispersions

    NASA Astrophysics Data System (ADS)

    Denton, Alan R.; Tang, Qiyun

    2015-03-01

    Microgels are microscopic gel particles, typically 10-1000 nm in size, that are swollen by a solvent. Hollow microgels (microcapsules) can encapsulate cargo, such as dye molecules or drugs, in their solvent-filled cavities. Their sensitive response to environmental conditions (e.g., temperature, pH) and influence on flow properties suit microgels to widespread applications in the chemical, pharmaceutical, food, and consumer care industries. When dispersed in water, polyelectrolyte gels become charged through dissociation of counterions. The electrostatic contribution to the osmotic pressure inside and outside of ionic microgels influences particle swelling and bulk materials properties, including thermodynamic, structural, optical, and rheological properties. Within the primitive and cell models of polyelectrolyte solutions, we derive an exact statistical mechanical formula for the contribution of mobile microions to the osmotic pressure within ionic microgels. Using Poisson-Boltzmann theory, we validate this result by explicitly calculating ion distributions across the surface of an ionic microgel and the electrostatic contribution to the osmotic pressure. Within a coarse-grained one-component model, we further chart the limits of the cell model for salty dispersions. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

  9. Lithium ion conductive behavior of TiO2 nanotube/ionic liquid matrices

    PubMed Central

    2014-01-01

    A series of TiO2 nanotube (TNT)/ionic liquid matrices were prepared, and their lithium ion conductive properties were studied. SEM images implied that ionic liquid was dispersed on the whole surface of TNT. Addition of TNT to ionic liquid (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (BMImTFSA)) resulted in significant increase of ionic conductivity. Furthermore, lithium transference number was also largely enhanced due to the interaction of anion with TNT. Vogel-Fulcher-Tammann parameter showed higher carrier ion number for TNT/BMImTFSA in comparison with BMImTFSA. PMID:25313300

  10. Mixed ionic-electronic conductor-based radiation detectors and methods of fabrication

    DOEpatents

    Conway, Adam; Beck, Patrick R; Graff, Robert T; Nelson, Art; Nikolic, Rebecca J; Payne, Stephen A; Voss, Lars; Kim, Hadong

    2015-04-07

    A method of fabricating a mixed ionic-electronic conductor (e.g. TlBr)-based radiation detector having halide-treated surfaces and associated methods of fabrication, which controls polarization of the mixed ionic-electronic MIEC material to improve stability and operational lifetime.

  11. Survival of endospores of Bacillus subtilis on spacecraft surfaces under simulated martian environments: implications for the forward contamination of Mars

    NASA Technical Reports Server (NTRS)

    Schuerger, Andrew C.; Mancinelli, Rocco L.; Kern, Roger G.; Rothschild, Lynn J.; McKay, Christopher P.

    2003-01-01

    Experiments were conducted in a Mars simulation chamber (MSC) to characterize the survival of endospores of Bacillus subtilis under high UV irradiation and simulated martian conditions. The MSC was used to create Mars surface environments in which pressure (8.5 mb), temperature (-80, -40, -10, or +23 degrees C), gas composition (Earth-normal N2/O2 mix, pure N2, pure CO2, or a Mars gas mix), and UV-VIS-NIR fluence rates (200-1200 nm) were maintained within tight limits. The Mars gas mix was composed of CO2 (95.3%), N2 (2.7%), Ar (1.7%), O2 (0.2%), and water vapor (0.03%). Experiments were conducted to measure the effects of pressure, gas composition, and temperature alone or in combination with Mars-normal UV-VIS-NIR light environments. Endospores of B. subtilis, were deposited on aluminum coupons as monolayers in which the average density applied to coupons was 2.47 x 10(6) bacteria per sample. Populations of B. subtilis placed on aluminum coupons and subjected to an Earth-normal temperature (23 degrees C), pressure (1013 mb), and gas mix (normal N2/O2 ratio) but illuminated with a Mars-normal UV-VIS-NIR spectrum were reduced by over 99.9% after 30 sec exposure to Mars-normal UV fluence rates. However, it required at least 15 min of Mars-normal UV exposure to reduce bacterial populations on aluminum coupons to non-recoverable levels. These results were duplicated when bacteria were exposed to Mars-normal environments of temperature (-10 degrees C), pressure (8.5 mb), gas composition (pure CO2), and UV fluence rates. In other experiments, results indicated that the gas composition of the atmosphere and the temperature of the bacterial monolayers at the time of Mars UV exposure had no effects on the survival of bacterial endospores. But Mars-normal pressures (8.5 mb) were found to reduce survival by approximately 20-35% compared to Earth-normal pressures (1013 mb). The primary implications of these results are (a) that greater than 99.9% of bacterial populations on

  12. Hydrogen bonding in ionic liquids.

    PubMed

    Hunt, Patricia A; Ashworth, Claire R; Matthews, Richard P

    2015-03-07

    Ionic liquids (IL) and hydrogen bonding (H-bonding) are two diverse fields for which there is a developing recognition of significant overlap. Doubly ionic H-bonds occur when a H-bond forms between a cation and anion, and are a key feature of ILs. Doubly ionic H-bonds represent a wide area of H-bonding which has yet to be fully recognised, characterised or explored. H-bonds in ILs (both protic and aprotic) are bifurcated and chelating, and unlike many molecular liquids a significant variety of distinct H-bonds are formed between different types and numbers of donor and acceptor sites within a given IL. Traditional more neutral H-bonds can also be formed in functionalised ILs, adding a further level of complexity. Ab initio computed parameters; association energies, partial charges, density descriptors as encompassed by the QTAIM methodology (ρBCP), qualitative molecular orbital theory and NBO analysis provide established and robust mechanisms for understanding and interpreting traditional neutral and ionic H-bonds. In this review the applicability and extension of these parameters to describe and quantify the doubly ionic H-bond has been explored. Estimating the H-bonding energy is difficult because at a fundamental level the H-bond and ionic interaction are coupled. The NBO and QTAIM methodologies, unlike the total energy, are local descriptors and therefore can be used to directly compare neutral, ionic and doubly ionic H-bonds. The charged nature of the ions influences the ionic characteristics of the H-bond and vice versa, in addition the close association of the ions leads to enhanced orbital overlap and covalent contributions. The charge on the ions raises the energy of the Ylp and lowers the energy of the X-H σ* NBOs resulting in greater charge transfer, strengthening the H-bond. Using this range of parameters and comparing doubly ionic H-bonds to more traditional neutral and ionic H-bonds it is clear that doubly ionic H-bonds cover the full range of weak

  13. The influence of plasma membrane electrostatic properties on the stability of cell ionic composition.

    PubMed Central

    Genet, S; Costalat, R; Burger, J

    2001-01-01

    An electro-osmotic model is developed to examine the influence of plasma membrane superficial charges on the regulation of cell ionic composition. Assuming membrane osmotic equilibrium, the ion distribution predicted by Gouy-Chapman-Grahame (GCG) theory is introduced into ion transport equations, which include a kinetic model of the Na/K-ATPase based on the stimulation of this ion pump by internal Na(+) ions. The algebro-differential equation system describing dynamics of the cell model has a unique resting state, stable with respect to finite-sized perturbations of various types. Negative charges on the membrane are found to greatly enhance relaxation toward steady state following these perturbations. We show that this heightened stability stems from electrostatic interactions at the inner membrane side that shift resting state coordinates along the sigmoidal activation curve of the sodium pump, thereby increasing the pump sensitivity to internal Na(+) fluctuations. The accuracy of electrostatic potential description with GCG theory is proved using an alternate formalism, based on irreversible thermodynamics, which shows that pressure contribution to ion potential energy is negligible in electrostatic double layers formed at the surfaces of biological membranes. We discuss implications of the results regarding a reliable operation of ionic process coupled to the transmembrane electrochemical gradient of Na(+) ions. PMID:11606261

  14. Ionic Conductivity of Nanostructured Block Copolymer and Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan L.; Virgili, Justin M.; Segalman, Rachel A.

    2010-03-01

    Block copolymer and ionic liquid mixtures are of interest for creating ionically conductive, thermally stable, and nanostructured membranes. For mixtures of poly(styrene-b-2-vinylpyridine) (S2VP) and the ionic liquid bis(trifluoromethanesulfonyl)imide ([Im][TFSI]), nanostructured ion-conducting domains are formed due to [Im][TFSI] selectively residing in the P2VP domains of the block copolymer. The dependence of ionic conductivity on temperature, ionic liquid loading, and volume fraction of PS in the neat block copolymer was investigated for membranes with the matrix phase being P2VP/[Im][TFSI]. It was determined that the temperature dependence of conductivity follows the Vogel-Tamman-Fulcher equation, with the activation energy determined by the ratio of [Im][TFSI] to 2VP monomers. The overall weight fraction of [Im][TFSI] in the mixtures, however, is the dominating factor determining conductivity, regardless of PS volume fraction. The insight gained from this work will be important for further investigation into the effect on the ion transport properties of ionic liquids when confined to minority nanostructured domains.

  15. Chiral discrimination by ionic liquids: impact of ionic solutes.

    PubMed

    Brown, Christopher J; Hopkins, Todd A

    2015-04-01

    Chiral ionic liquids hold promise in many asymmetric applications. This study explores the impact of ionic solutes on the chiral discrimination of five amino acid methyl ester-based ionic liquids, including L- and D-alanine methyl ester, L-proline methyl ester, L-leucine methyl ester, and L-valine methyl ester cations combined with bis(trifluoromethanesulfonimide) anion. Circularly polarized luminescence spectroscopy was used to study the chiral discrimination by measuring the racemization equilibrium of a dissymmetric europium complex, Eu(dpa)3(3-) (where dpa = 2,6-pyridinedicarboxylate). The chiral discrimination measured was dependent on the concentration of Eu(dpa)3(3-) and this concentration-dependence was different in each of the ionic liquids. Ionic liquids with L-leucine methyl ester and L-valine methyl ester even switched enantiomeric preference based on the solute concentration. Changing the cation of the Eu(dpa)3(3-) salt from tetrabutylammonium to tetramethylammonium ion also affected the chiral discrimination demonstrated by the ionic liquids.

  16. Stress-relaxation behavior in gels with ionic and covalent crosslinks.

    PubMed

    Zhao, Xuanhe; Huebsch, Nathaniel; Mooney, David J; Suo, Zhigang

    2010-03-15

    Long-chained polymers in alginate hydrogels can form networks by either ionic or covalent crosslinks. This paper shows that the type of crosslinks can markedly affect the stress-relaxation behavior of the gels. In gels with only ionic crosslinks, stress relaxes mainly through breaking and subsequent reforming of the ionic crosslinks, and the time scale of the relaxation is independent of the size of the sample. By contrast, in gels with only covalent crosslinks, stress relaxes mainly through migration of water, and the relaxation slows down as the size of the sample increases. Implications of these observations are discussed.

  17. Dynamic effects in thin liquid films containing ionic surfactants

    NASA Astrophysics Data System (ADS)

    Karakashev, S. I.; Tsekov, R.; Ivanova, D. S.

    2010-03-01

    This paper is dedicated to studying dynamic effects in thin liquid films (TLF) containing ionic surfactants. The standard theory of TLF drainage has been developed without considering the electrical double layer (EDL) in the hydrodynamic equations, although EDL always exists. In addition, it has been found that this theory very well describes the drainage of TLF containing non-ionic surfactants in the presence of electrolytes. The inclusion of EDL into the hydrodynamics of TLF complicates the theory, producing additional dynamic effects during film drainage. For example, a gradient of electrostatic disjoining pressure across the film arises, thus causing non-uniform electrostatic repulsion between the film surfaces. This paper analyzes the hydrodynamics of TLF with EDL. A new equation of drainage was derived. This equation accounts for the non-uniform distribution of surface charges during the films drainage, which is coupled with non-uniform electrostatic repulsion between the film surfaces and results in faster film drainage. The theory was tested with drainage experiments on TLF with ionic surfactants. Foam films containing sodium dodecyl sulfate (SDS) in the presence and in the absence of added electrolyte were studied and the experimental data compared to the theoretical predictions. The experimental results, however, disagree with the theory. For example, the kinetic equation predicted faster film drainage for foam films at low ionic strength; at high ionic strength the theory tends to wReynolds drainagew. Inversely, the experiment exhibited slower drainage than predicted by the Reynolds equation in both cases of low and high ionic strengths. Numerical simulations yielded V/VRe<1. In addition, cases of wpositivew and wnegativew velocity of film surfaces were shown. Despite the sign of the velocity the dependence V/VRe<1 remained. The analysis showed similarity between the experimental data and the prediction of the Manev-Tsekov-Radoev (MTR) drainage model at

  18. Detrital Thermochronology of the Indus-Yarlung suture zone and implications for the tectonic and surface evolution of southern Tibet

    NASA Astrophysics Data System (ADS)

    Carrapa, B.; Hassim, F.; Kapp, P. A.

    2015-12-01

    Detrital thermochronology has the unique potential to resolve the timing of source cooling associated with magmatic, tectonic and surface processes. Correct interpretation of the detrital signature requires a multi-dating approach involving chronometers sensitive to different temperatures and processes. A multi-dating study of modern river sands from southern Tibet reveals distinct cooling signals that provide significant information about tectonic and erosional evolution of the Indus-Yarlung suture (IYS) after the India-Asia collision with implications for the Cenozoic topographic evolution of the Tibetan Plateau. Modern sands from tributaries of the Yarlung River provide an opportunity to broadly sample source rocks exposed within the suture zone, including the Gangdese batholith, Xigaze forearc, Cenozoic basins, and Tethyan Himalayan rocks, and to investigate their regional geochemical signatures. Samples from rivers along the IYS in southern Tibet, between Xigaze and Mt. Kailas, were analyzed for detrital geochronology and low-temperature thermochronology. Comparison between ages recorded in the source and the detrital signature indicates that both the ages and their proportions directly reflect the ages and relative areas of source rocks in the catchment basins. Apatite fission track ages show two main cooling signals at 22-18 Ma and 12 Ma, which are consistent with accelerated exhumation of the Gangdese batholith and Oligo-Miocene Kailas basin and indicate significant regional exhumation of the IYS during the Miocene. Regional exhumation recorded throughout the IYS is likely the combined product of active Miocene tectonics and erosion of a paleo-Yarlung River. Efficient incision and evacuation of material from the IYS zone by a paleo-Yarlung River during the Miocene suggests a significantly different paleoenvironment than that which exists today. Miocene capture of the Yarlung River by the Brahmaputra River may have enhanced erosion in the IYS zone.

  19. Drip-Water Temperatures in Caves: Surface Signals or Cave Processes? - Implications for Speleothem Deposits and Paleoclimate Archives

    NASA Astrophysics Data System (ADS)

    Andersen, M. S.; Cuthbert, M. O.; Rau, G. C.; Baker, A.; Roshan, H.; Rutlidge, H.; Marjo, C.; Markowska, M.; Graham, P. W.; Mariethoz, G.

    2013-12-01

    Caves offer a unique opportunity to enter the subsurface to study vadose zone hydrological processes. Limestone caves, with their speleothem deposits, offer additional advantages as archives of past climate. As such they can serve as observatories for past and present hydrological observations. Correct interpretation of past climates using speleothem deposits requires a systematic understanding of karst physico-chemical processes. With the aim of studying near surface flow and heat transport processes, a series of controlled recharge experiments were carried out above Wellington Caves, located in the temperate semi-arid zone of NSW, Australia. Variable amounts of cooled water were irrigated onto the land surface on four consecutive days in January 2013. The applied recharge rates varied from 40 to 70 mm/d and are comparable to mid-sized recharge events. The temperature of the applied water was varied from 0.3 °C to 24.2 °C using ice. Miniature self-contained temperature loggers (DST micro-T, Star Oddi, Iceland) were deployed to measure the soil temperature and strapped directly on to stalactite features inside the cave located about 2 m below the surface. The stalactites have previously activated regularly by mid-sized precipitation events. Below on the cave floor, drip-loggers (Stalagmate, Driptych, UK) were aligned with the stalactites to capture onset of flow as well as drip rates. Three events of inflow were observed in the initially dry cave. The first irrigation did not produce any inflow since the amount of water applied was not large enough to overcome the soil moisture deficit. Subsequently, each inflow had a higher peak drip rate and duration than the previous event. Surprisingly the stalagmite temperature results showed no discernible effect of the cool water applied to the land surface, despite large changes in the soil temperature caused by the irrigation water. Considering the shallow location of the studied cave this highlights that the temperature

  20. 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.

  1. Ionic thermoelectric gating organic transistors

    PubMed Central

    Zhao, Dan; Fabiano, Simone; Berggren, Magnus; Crispin, Xavier

    2017-01-01

    Temperature is one of the most important environmental stimuli to record and amplify. While traditional thermoelectric materials are attractive for temperature/heat flow sensing applications, their sensitivity is limited by their low Seebeck coefficient (∼100 μV K−1). Here we take advantage of the large ionic thermoelectric Seebeck coefficient found in polymer electrolytes (∼10,000 μV K−1) to introduce the concept of ionic thermoelectric gating a low-voltage organic transistor. The temperature sensing amplification of such ionic thermoelectric-gated devices is thousands of times superior to that of a single thermoelectric leg in traditional thermopiles. This suggests that ionic thermoelectric sensors offer a way to go beyond the limitations of traditional thermopiles and pyroelectric detectors. These findings pave the way for new infrared-gated electronic circuits with potential applications in photonics, thermography and electronic-skins. PMID:28139738

  2. Ionic thermoelectric gating organic transistors

    NASA Astrophysics Data System (ADS)

    Zhao, Dan; Fabiano, Simone; Berggren, Magnus; Crispin, Xavier

    2017-01-01

    Temperature is one of the most important environmental stimuli to record and amplify. While traditional thermoelectric materials are attractive for temperature/heat flow sensing applications, their sensitivity is limited by their low Seebeck coefficient (~100 μV K-1). Here we take advantage of the large ionic thermoelectric Seebeck coefficient found in polymer electrolytes (~10,000 μV K-1) to introduce the concept of ionic thermoelectric gating a low-voltage organic transistor. The temperature sensing amplification of such ionic thermoelectric-gated devices is thousands of times superior to that of a single thermoelectric leg in traditional thermopiles. This suggests that ionic thermoelectric sensors offer a way to go beyond the limitations of traditional thermopiles and pyroelectric detectors. These findings pave the way for new infrared-gated electronic circuits with potential applications in photonics, thermography and electronic-skins.

  3. 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.

  4. Biopolymer Processing Using Ionic Liquids

    DTIC Science & Technology

    2014-08-07

    AFRL-OSR-VA-TR-2014-0181 (YIP-11) BIOPOLYMER PROCESSING USING IONIC LIQUIDS William Reichert UNIVERSITY OF SOUTH ALABAMA 08/07/2014 Final Report...3. DATES COVERED (From - To) May 2011-May 2014 4. TITLE AND SUBTITLE iopolymer Processing using Ionic Liquids for Feedstock Chemicals 5a...reaction and degradation products of the conversion of chitin and chitosan, and 3) investigate the effects of various reaction conditions, such as

  5. 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.

  6. Sonofragmentation of Ionic Crystals.

    PubMed

    Kim, Hyo Na; Suslick, Kenneth S

    2017-02-24

    Mechanochemistry deals with the interface between the chemical and the mechanical worlds and explores the physical and chemical changes in materials caused by an input of mechanical energy. As such, the chemical and physical effects of ultrasound, i.e., sonochemistry, are forms of mechanochemistry. In this paper, the fragmentation of ionic crystals during ultrasonic irradiation of slurries has been quantitatively investigated: the rate of fragmentation depends strongly on the strength of the materials (as measured by Vickers hardness or by Young's modulus). This is a mechanochemical extension of the Bell-Evans-Polanyi Principle or Hammond's Postulate: activation energies for solid fracture correlate with binding energies of solids. Sonofragmentation is unaffected by slurry loading or liquid vapor pressure, but is suppressed by increasing liquid viscosity. The mechanism of the particle breakage is consistent with a direct interaction between the shockwaves created by the ultrasound (through acoustic cavitation) and the solid particles in the slurry. Fragmentation is proposed to occur from defects in the solids induced by compression-expansion, bending, or torsional distortions of the crystals.

  7. Hydrophobic ionic liquids

    SciTech Connect

    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.

  8. 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.

  9. High performance ultracapacitors with carbon nanomaterials and ionic liquids

    DOEpatents

    Lu, Wen; Henry, Kent Douglas

    2012-10-09

    The present invention is directed to the use of carbon nanotubes and/or electrolyte structures in various electrochemical devices, such as ultracapacitors having an ionic liquid electrolyte. The carbon nanotubes are preferably aligned carbon nanotubes. Compared to randomly entangled carbon nanotubes, aligned carbon nanotubes can have better defined pore structures and higher specific surface areas.

  10. Recent applications of ionic liquids in separation technology.

    PubMed

    Han, Dandan; Row, Kyung Ho

    2010-04-05

    Ionic liquids (ILs) have been applied in different areas of separation, such as ionic liquid supported membranes, as mobile phase additives and surface-bonded stationary phases in chromatography separations and as the extraction solvent in sample preparations, because they can be composed from various cations and anions that change the properties and phase behavior of liquids. Although the applications of ILs in separations are still in their early stages, the academic interest in ILs is increasing. An overview of the principle applications of ILs in separation technology is present in this work. Furthermore, the prospects of the ILs in separation techniques are discussed.

  11. Direct synthesis of silver nanoparticles in ionic liquid

    NASA Astrophysics Data System (ADS)

    Corrêa, Cíntia M.; Bizeto, Marcos A.; Camilo, Fernanda F.

    2016-05-01

    Ionic liquids have structural organization at nanoscale that can trigger the spontaneous ordering of structures in nanoscopic range. Due to this characteristic, several metal nanoparticles have been prepared in this media. In this paper, we describe the direct preparation of silver nanoparticles in the following imidazolium ionic liquids: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dimethyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and in citrate tetrabutylammonium, that is an ionic liquid that acts as solvent and reducing agent at the same time. We also evaluated the morphology of the nanoparticles and the stability of the dispersions. Spherical silver nanoparticles with surface Plasmon bands in the range of 400-430 nm were produced in all the ionic liquids, with the only exception for the 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide that produced a black precipitate. The best results were obtained by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and citrate tetrabutylammonium ionic liquids. The former resulted in concentrated spherical silver nanoparticles dispersion (ca. 1.0 mM of Ag) with diameters ranging from 6 to 12 nm and by adding polyvinylpyrrolidone (PVP) to the dispersions they became stable for at least 1 month. The citrate tetrabutylammonium ionic liquid produced even more concentrated dispersion of spherical silver nanoparticles with diameters ranging from 2 to 6 nm. These dispersions were quite stable without the need of PVP, since the Plasmon band in the electronic absorption spectra remained unaltered for months after the preparation. The citrate tetrabutylammonium ionic liquid offers a slow kinetic for the silver nanoparticle formation as the citrate is a milder reducing agent than borohydride.

  12. Structure, morphology and ionic conductivity of solid polymer electrolyte

    SciTech Connect

    Dey, Arup; Karan, S.; Dey, Ashis; De, S.K.

    2011-11-15

    Graphical abstract: Two-dimensional atomic force image of pure polyethylene oxide presents a crystallized network of regular spherulites developing spirals and branches of well distributed surface contours. Highlights: {yields} The incorporation of ceria significantly modifies the morphology of polyethylene oxide (PEO)-KI complex. {yields} The ionic conductivity increases by about two orders of magnitude by the addition of ceria nanoparticles. {yields} Ionic conductivity as a function of ceria concentration reveals two maxima. {yields} Grain boundary effect of nanofiller, strong Lewis acid-base interaction between PEO and nanosized ceria, change of conformation of PEO molecule and epitaxial effect of ceria nanoparticles control the ionic conductivity of composite polymer electrolyte. -- Abstract: Polyethylene oxide (PEO) complexed with potassium iodide (KI) is synthesized to investigate the ionic conductivity of alkaline based polymer electrolytes. The structural and morphological characterizations of the nanocomposite polymer electrolytes are performed by X-ray diffractometry (XRD), atomic force microscopy (AFM), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) measurements. The ionic conductivity increases with the increase of KI concentration up to about 20 wt.%. The effect of nanosized ceria (CeO{sub 2} {approx} 10 nm) fillers on ionic conductivity in PEO-KI polymer electrolyte is also carried out, keeping PEO to KI wt.% ratio 80:20 and 85:15. The result reveals that the addition of ceria nanoparticles enhances the conductivity by two orders of magnitude. The presence of ceria at the highest concentration induces the same molecular environment within PEO chain as that of undoped PEO. Temperature dependence of ionic conductivity follows Arrhenius mechanism.

  13. Multilayer ionic polymer transducer

    NASA Astrophysics Data System (ADS)

    Akle, Barbar J.; Leo, Donald J.

    2003-07-01

    A transducer consisting of multiple layers of ionic polymer material is developed for applications in sensing, actuation, and control. The transducer consists of two to four individual layers each approximately 200 microns thick. The transducers are connected in parallel to minimize the electric field requirements for actuation. The tradeoff in deflection and force can be controlled by controlling the mechanical constraint at the interface. Packaging the transducer in an outer coating produces a hard constraint between layers and reduces the deflection with a force that increases linearly with the number of layers. This configuration also increases the bandwidth of the transducer. Removing the outer packaging produces an actuator that maintains the deflection of a single layer but has an increased force output. This is obtained by allowing the layers to slide relative to one another during bending. Experiments on transducers with one to three layers are performed and the results are compared to Newbury"s equivalent circuit model, which was modified to accommodate the multilayer polymers. The modification was performed on four different boundary conditions, two electrical the series and the parallel connection, and two mechanical the zero interfacial friction and the zero slip on the interface. Results demonstrate that the largest obstacle to obtaining good performance is water transport between the individual layers. Water crossover produces a near short circuit electrical condition and produces feedthrough between actuation layers and sensing layers. Electrical feedthrough due to water crossover eliminates the ability to produce a transducer that has combined sensing and actuation properties. Eliminating water crossover through good insulation enables the development of a small (5 mm x 30 mm) transducer that has sensing and actuation bandwidth on the order of 100 Hz.

  14. Electrotunable Lubricity with Ionic Liquid Nanoscale Films

    PubMed Central

    Fajardo, O. Y.; Bresme, F.; Kornyshev, A. A.; Urbakh, M.

    2015-01-01

    One of the main challenges in tribology is finding the way for an in situ control of friction without changing the lubricant. One of the ways for such control is via the application of electric fields. In this respect a promising new class of lubricants is ionic liquids, which are solvent-free electrolytes, and their properties should be most strongly affected by applied voltage. Based on a minimal physical model, our study elucidates the connection between the voltage effect on the structure of the ionic liquid layers and their lubricating properties. It reveals two mechanisms of variation of the friction force with the surface charge density, consistent with recent AFM measurements, namely via the (i) charge effect on normal and in-plane ordering in the film and (ii) swapping between anion and cation layers at the surfaces. We formulate conditions that would warrant low friction coefficients and prevent wear by resisting “squeezing-out” of the liquid under compression. These results give a background for controllable variation of friction. PMID:25572127

  15. Surface geochemistry of the clay minerals

    PubMed Central

    Sposito, Garrison; Skipper, Neal T.; Sutton, Rebecca; Park, Sung-ho; Soper, Alan K.; Greathouse, Jeffery A.

    1999-01-01

    Clay minerals are layer type aluminosilicates that figure in terrestrial biogeochemical cycles, in the buffering capacity of the oceans, and in the containment of toxic waste materials. They are also used as lubricants in petroleum extraction and as industrial catalysts for the synthesis of many organic compounds. These applications derive fundamentally from the colloidal size and permanent structural charge of clay mineral particles, which endow them with significant surface reactivity. Unraveling the surface geochemistry of hydrated clay minerals is an abiding, if difficult, topic in earth sciences research. Recent experimental and computational studies that take advantage of new methodologies and basic insights derived from the study of concentrated ionic solutions have begun to clarify the structure of electrical double layers formed on hydrated clay mineral surfaces, particularly those in the interlayer region of swelling 2:1 layer type clay minerals. One emerging trend is that the coordination of interlayer cations with water molecules and clay mineral surface oxygens is governed largely by cation size and charge, similarly to a concentrated ionic solution, but the location of structural charge within a clay layer and the existence of hydrophobic patches on its surface provide important modulations. The larger the interlayer cation, the greater the influence of clay mineral structure and hydrophobicity on the configurations of adsorbed water molecules. This picture extends readily to hydrophobic molecules adsorbed within an interlayer region, with important implications for clay–hydrocarbon interactions and the design of catalysts for organic synthesis. PMID:10097044

  16. 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

  17. Ionic imbalance induced self-propulsion of liquid metals

    PubMed Central

    Zavabeti, Ali; Daeneke, Torben; Chrimes, Adam F.; O'Mullane, Anthony P.; Zhen Ou, Jian; Mitchell, Arnan; Khoshmanesh, Khashayar; Kalantar-zadeh, Kourosh

    2016-01-01

    Components with self-propelling abilities are important building blocks of small autonomous systems and the characteristics of liquid metals are capable of fulfilling self-propulsion criteria. To date, there has been no exploration regarding the effect of electrolyte ionic content surrounding a liquid metal for symmetry breaking that generates motion. Here we show the controlled actuation of liquid metal droplets using only the ionic properties of the aqueous electrolyte. We demonstrate that pH or ionic concentration gradients across a liquid metal droplet induce both deformation and surface Marangoni flow. We show that the Lippmann dominated deformation results in maximum velocity for the self-propulsion of liquid metal droplets and illustrate several key applications, which take advantage of such electrolyte-induced motion. With this finding, it is possible to conceive the propulsion of small entities that are constructed and controlled entirely with fluids, progressing towards more advanced soft systems. PMID:27488954

  18. The use of supported acidic ionic liquids in organic synthesis.

    PubMed

    Skoda-Földes, Rita

    2014-06-26

    Catalysts obtained by the immobilisation of acidic ionic liquids (ILs) on solid supports offer several advantages compared to the use of catalytically active ILs themselves. Immobilisation may result in an increase in the number of accessible active sites of the catalyst and a reduction of the amount of the IL required. The ionic liquid films on the carrier surfaces provide a homogeneous environment for catalytic reactions but the catalyst appears macroscopically as a dry solid, so it can simply be separated from the reaction mixture. As another advantage, it can easily be applied in a continuous fixed bed reactor. In the present review the main synthetic strategies towards the preparation of supported Lewis acidic and Brønsted acidic ILs are summarised. The most important characterisation methods and structural features of the supported ionic liquids are presented. Their efficiency in catalytic reactions is discussed with special emphasis on their recyclability.

  19. Ionic imbalance induced self-propulsion of liquid metals.

    PubMed

    Zavabeti, Ali; Daeneke, Torben; Chrimes, Adam F; O'Mullane, Anthony P; Zhen Ou, Jian; Mitchell, Arnan; Khoshmanesh, Khashayar; Kalantar-Zadeh, Kourosh

    2016-08-04

    Components with self-propelling abilities are important building blocks of small autonomous systems and the characteristics of liquid metals are capable of fulfilling self-propulsion criteria. To date, there has been no exploration regarding the effect of electrolyte ionic content surrounding a liquid metal for symmetry breaking that generates motion. Here we show the controlled actuation of liquid metal droplets using only the ionic properties of the aqueous electrolyte. We demonstrate that pH or ionic concentration gradients across a liquid metal droplet induce both deformation and surface Marangoni flow. We show that the Lippmann dominated deformation results in maximum velocity for the self-propulsion of liquid metal droplets and illustrate several key applications, which take advantage of such electrolyte-induced motion. With this finding, it is possible to conceive the propulsion of small entities that are constructed and controlled entirely with fluids, progressing towards more advanced soft systems.

  20. Ionic imbalance induced self-propulsion of liquid metals

    NASA Astrophysics Data System (ADS)

    Zavabeti, Ali; Daeneke, Torben; Chrimes, Adam F.; O'Mullane, Anthony P.; Zhen Ou, Jian; Mitchell, Arnan; Khoshmanesh, Khashayar; Kalantar-Zadeh, Kourosh

    2016-08-01

    Components with self-propelling abilities are important building blocks of small autonomous systems and the characteristics of liquid metals are capable of fulfilling self-propulsion criteria. To date, there has been no exploration regarding the effect of electrolyte ionic content surrounding a liquid metal for symmetry breaking that generates motion. Here we show the controlled actuation of liquid metal droplets using only the ionic properties of the aqueous electrolyte. We demonstrate that pH or ionic concentration gradients across a liquid metal droplet induce both deformation and surface Marangoni flow. We show that the Lippmann dominated deformation results in maximum velocity for the self-propulsion of liquid metal droplets and illustrate several key applications, which take advantage of such electrolyte-induced motion. With this finding, it is possible to conceive the propulsion of small entities that are constructed and controlled entirely with fluids, progressing towards more advanced soft systems.

  1. Ionic conductivity enhancement of polymer electrolytes with ceramic nanowire fillers.

    PubMed

    Liu, Wei; Liu, Nian; Sun, Jie; Hsu, Po-Chun; Li, Yuzhang; Lee, Hyun-Wook; Cui, Yi

    2015-04-08

    Solid-state electrolytes provide substantial improvements to safety and electrochemical stability in lithium-ion batteries when compared with conventional liquid electrolytes, which makes them a promising alternative technology for next-generation high-energy batteries. Currently, the low mobility of lithium ions in solid electrolytes limits their practical application. The ongoing research over the past few decades on dispersing of ceramic nanoparticles into polymer matrix has been proved effective to enhance ionic conductivity although it is challenging to form the efficiency networks of ionic conduction with nanoparticles. In this work, we first report that ceramic nanowire fillers can facilitate formation of such ionic conduction networks in polymer-based solid electrolyte to enhance its ionic conductivity by three orders of magnitude. Polyacrylonitrile-LiClO4 incorporated with 15 wt % Li0.33La0.557TiO3 nanowire composite electrolyte exhibits an unprecedented ionic conductivity of 2.4 × 10(-4) S cm(-1) at room temperature, which is attributed to the fast ion transport on the surfaces of ceramic nanowires acting as conductive network in the polymer matrix. In addition, the ceramic-nanowire filled composite polymer electrolyte shows an enlarged electrochemical stability window in comparison to the one without fillers. The discovery in the present work paves the way for the design of solid ion electrolytes with superior performance.

  2. Ionic colloidal crystals: Ordered, multicomponent structures via controlled heterocoagulation.

    PubMed

    Maskaly, Garry R; García, R Edwin; Carter, W Craig; Chiang, Yet-Ming

    2006-01-01

    We propose a new type of ordered colloid, the "ionic colloidal crystal" (ICC), which is stabilized by attractive electrostatic interactions analogous to those in atomic ionic materials. The rapid self-organization of colloids via this method should result in a diversity of orderings that are analogous to ionic compounds. Most of these complex structures would be difficult to produce by other methods. We use a Madelung summation approach to evaluate the conditions where ICC's are thermodynamically stable. Using this model, we compare the relative electrostatic energies of various structures showing that the regions of ICC stability are determined by two dimensionless parameters representing charge balance and the spatial extent of the electrostatic interactions. Parallels and distinctions between ICC's and classical ionic crystals are discussed. Monte Carlo simulations are utilized to examine the glass transition and melting temperatures, between which crystallization can occur, of a model system having the rocksalt structure. These tools allow us to make a first-order prediction of the experimentally accessible regions of surface charge, particle size, ionic strength, and temperature where ICC formation is probable.

  3. Adsorption of xenon ions onto defects in organic surfaces: Implications for the origin and the nature of organics in primitive meteorites

    NASA Astrophysics Data System (ADS)

    Marrocchi, Yves; Marty, Bernard; Reinhardt, Peter; Robert, François

    2011-10-01

    Noble gases trapped in primitive meteorites are quantitatively hosted by a poorly defined organic phase, labeled phase Q. Xenon is enriched in heavy isotopes by +1.30 ± 0.06% per atomic mass unit (amu, 1 σ) in phase Q relative to solar. To understand the origin of this fractionation, we have performed adsorption experiments of xenon atoms and ions, ionized in a radiofrequency plasma. Within the reaction vessel, anthracite was heated and the resulting smoke deposited onto the walls of the vessel, resulting in carbon-rich films. Xenon was trapped in the carbon films either as ions in the ionization zone of the vessel, or as neutral atoms outside this zone. Xenon trapped as ionic Xe is tightly bound and is enriched by +1.36 ± 0.05%/amu (1 σ) in heavy isotopes, reproducing the isotopic fractionation of xenon trapped in phase Q relative to solar. Neutral xenon is more loosely trapped, is in much lower concentration, and is not isotopically fractionated. Ionized conditions allow the constant xenon isotopic composition observed in meteorite during stepwise heating release to be reproduced. Furthermore, the trapping efficiency of Xe + estimated from these experiments is consistent with the high xenon concentration measured in phase Q of primitives meteorites. Xenon was not trapped in the film by implantation because the energies of the incident Xe atoms and ions were far too low (<1 eV). From the difference of behavior between ionic and neutral forms, we propose that xenon ions were trapped via chemical bonding at the surface of the newly created C-rich film. The observed mass-dependent fractionation of xenon is unlikely to have occurred in the gas phase. It is more probably related to variations in chemical bonding strengths of Xe isotopes as chemical bonds involving heavy Xe isotopes are more stable than those involving light ones. For young stars, including the young Sun, photons emitted in the far UV energy range able to ionize noble gases (<100 nm) were orders of

  4. Recrystallized quinolinium ionic liquids for electrochemical analysis

    NASA Astrophysics Data System (ADS)

    Selvaraj, Gowri; Wilfred, Cecilia Devi; Eang, Neo Kian

    2016-11-01

    Ionic liquids have received a lot of attention due to their unique properties. In this work the prospect of quinolinium based ionic liquids as electrolyte for dye sensitised solar cell were tested using cyclic voltammetry. The results have shown electron transfer in the ionic liquid without undergoing any permanent chemical changes. Prior to testing, the ionic liquids were purified through recrystallization as electrochemical properties of ionic liquids are highly dependent on the purity of the ionic liquids. This results have shone new light for this work.

  5. Elucidating graphene - Ionic Liquid interfacial region: a combined experimental and computational study

    SciTech Connect

    Vijayakumar, M.; Schwenzer, Birgit; Shutthanandan, V.; Hu, Jian Z.; Liu, Jun; Aksay, Ilhan A.

    2014-01-10

    The interfacial region between graphene and an imidazolium based ionic liquid is studied using spectroscopic analysis and computational modelling. This combined approach reveals that the molecular level structure of the interfacial region is significantly influenced by functional group defects on the graphene surface.The combined experimental and computational study reveals that the molecular structure at interfacial region between graphene and imidazolium based ionic liquid is defined by the hydroxyl functional groups on the graphene surface

  6. Mathematical modeling of ionic interactions and deformation in ionic polymer-metal composite artificial muscles

    NASA Astrophysics Data System (ADS)

    Firoozbakhsh, K.; Shahinpoor, Mohsen; Shavandi, M.

    1998-07-01

    This paper presents a simple mathematical model for surface deformation due to ionic interaction in connection with ion- exchange polymer-noble metal composites (IPMC) as biomimetic sensors and actuators. These smart composites exhibit characteristics of both actuators and sensors. Strips of these composites can undergo large bending and flapping displacement if an electric field is imposed across their thickness. Thus, in this sense they are large motion actuators. Conversely by bending the composite strip, either quasi-statically or dynamically, a voltage is produced across the thickness of the strip between the two conducting electrodes attached. Thus they are also large motion sensors. In this paper a simple mathematical model is presented for the role of ionic interactions, and in particular the sulfonic group actions and the metallic electrode anions, in surface deformation observed under an electric field in ionic polymeric-metal composite artificial muscles. It is shown that the columbic attraction/repulsion force distribution has its maximum at the edges of the surface and sharply decreases towards the center of the surface. Furthermore, the maximum force is not macroscopically scale dependent. This means that is attains its maximum over a short finite length. This fact can be used to design large force arrays with collective action for a number of industrial and medical applications. According to our findings an optimal muscle in force/motion capability should consist of series of miniaturized IPMC muscle strips similar to the structure of actual biological muscles' myofibrils consisting of sarcomeres. This paper further identifies key parameters involving the contraction/expansion force characteristics of sensors and actuators made of IPMC's.

  7. A view of aqueous electrochemical carbon dioxide reduction to formate at indium electrodes, and the reversible electrodeposition of silver in ionic liquids through the lens of fundamental surface science

    NASA Astrophysics Data System (ADS)

    Detweiler, Zachary M.

    Two systems were studied using in situ measurement techniques, demonstrating the importance of creative experimental design. The electroreduction of CO2 at heterogeneous indium electrodes in aqueous solution was analyzed by cyclic voltammetry. Bulk electrolyses showed that increased indium oxide presence prior to electrolysis improved the Faradaic efficiency of CO 2 reduction to formate in 0.5 M K2SO2 aqueous solutions at a pH of 4.4. In order to more accurately assign speciation at the electrode surface ex situ O2 and H2O dosing of metallic indium under UHV was studied with XPS, HREELS and TPD. Ambient pressure XPS showed that the ratio of oxide to hydroxide at the indium interface is strongly dependent on the partial pressure of water; decreasing as P(H2O) increases. Using this information, a qualitative picture of the indium interface could be generated. In situ ATR-FTIR with an indium thin film as the working electrode showed that bulk oxide quickly reduces with applied potential, but an interfacial oxide is still present at high reductive overpotential. Additionally, an adsorbed carbonate at the thin film interface was observed upon introducing CO 2 to the cell. The implication of a surface bound carbonate as the CO 2 reduction intermediate draws on a mechanism that has not previously been discussed in the electrochemical reduction of CO2. The previous study of this mechanism from Ficscher-Tropsch literature helps to predict the further reduced products found at more electropositive metals, such as copper or magnesium, the latter of which is described here. Additionaly described here is a series of ILs that were employed as electrolyte for reversible silver deposition. BMIM N(TfO)2 was found to be the most promising of those studied, intrinsically giving a more uniform deposit that was bright and reversible. Deposit formation was studied using SEM and EDX as a function of deposition potential and deposition time. In situ reflectometry was employed to get a

  8. The role of water in the development of surface roughness and mineralogical variability on playa surface sediments: Implications for aeolian erodibility and dust emission

    NASA Astrophysics Data System (ADS)

    Tollerud, Heather J.

    Playas are significant sources for atmospheric mineral dust, but the evolution of their surface erodibility through time is not well established, leading to difficulties in modeling dust emission. Investigation of the spatial and temporal variability of surfaces within dust source regions has the potential to elucidate the processes that control erodibility and to improve model predictions of dust emission. In this dissertation the variability in time and space of surface mineralogical composition, particle size distribution, and surface roughness is measured in a playa (the Black Rock Desert, NV, USA). Water is found to be critical to the development of playa surfaces. Analysis of samples from the Black Rock playa demonstrates that the playa is mainly composed of quartz (˜30 wt%), clay (˜45 wt%), plagioclase (˜10 wt%), calcite (2-15 wt%), and halite (0-40 wt%). Composition varies between the center of the playa (more frequently inundated) and edge, with smaller particles, more clay, less plagioclase, and less calcite in the central areas. The surface roughness of the Black Rock playa is observed through time (2004-2010) using synthetic aperture radar (SAR) remote sensing data. Surface roughness is relatively constant during the dry summer months, but changes significantly from year to year, suggesting that water and inundation have more control on playa surfaces than anthropogenic activity or saltation abrasion. Roughness is low in years with heavy precipitation, but late drying areas of the playa are rough. Small scale lab experiments on a playa analog surface demonstrate that cycles of wetting/drying increase roughness, particularly for surfaces with added CaCO 3; a surface with added CaCO3 produced aggregates of a size appropriate for saltation (<100 microm) through wetting/drying cycles, while a surface with added NaCl remained relatively smooth. These observations suggest a conceptual framework for the development of surfaces in a playa: inundation smooths

  9. 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.

  10. 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.

  11. Programmable ionic conductance in a pH-regulated gated nanochannel.

    PubMed

    Ma, Yu; Xue, Song; Hsu, Shih-Chieh; Yeh, Li-Hsien; Qian, Shizhi; Tan, Heping

    2014-10-07

    An analytical model for the ionic conductance in a pH-regulated nanochannel gated by a field effect transistor is derived for the first time. In contrast to the existing studies, the developed model takes into account the practical effects of multiple ionic species, surface chemistry reactions, the Stern layer, and electroosmotic flow. The model is validated by the experimental data of ionic conductance available in the literature. Results show that the performance of the field effect control of the ionic conductance in the gated silica nanochannel is remarkable when the solution pH and salt concentration are low. In addition, the Stern layer effect on the ionic conductance is significant when the salt concentration is low.

  12. Monolayer to Bilayer Structural Transition in Confined Pyrrolidinium-Based Ionic Liquids.

    PubMed

    Smith, Alexander M; Lovelock, Kevin R J; Gosvami, Nitya Nand; Licence, Peter; Dolan, Andrew; Welton, Tom; Perkin, Susan

    2013-02-07

    Ionic liquids can be intricately nanostructured in the bulk and at interfaces resulting from a delicate interplay between interionic and surface forces. Here we report the structuring of a series of dialkylpyrrolidinium-based ionic liquids induced by confinement. The ionic liquids containing cations with shorter alkyl chain substituents form alternating cation-anion monolayer structures on confinement to a thin film, whereas a cation with a longer alkyl chain substituent leads to bilayer formation. The crossover from monolayer to bilayer structure occurs between chain lengths of n = 8 and 10 for these pyrrolidinium-based ionic liquids. The bilayer structure for n = 10 involves full interdigitation of the alkyl chains; this is in contrast with previous observations for imidazolium-based ionic liquids. The results are pertinent to these liquids' application as electrolytes, where the electrolyte is confined inside the pores of a nanoporous electrode, for example, in devices such as supercapacitors or batteries.

  13. Effects of ionic strength on membrane fouling in a membrane bioreactor.

    PubMed

    Wang, Fangyuan; Zhang, Meijia; Peng, Wei; He, Yiming; Lin, Hongjun; Chen, Jianrong; Hong, Huachang; Wang, Aijun; Yu, Haiying

    2014-03-01

    In this study, the effects of ionic strength on membrane fouling in a membrane bioreactor (MBR) were investigated. Ionic strength in range of 0.005-0.05mol/L exerted no apparent impacts on the resistance of virgin membrane, fouled membrane and pore clogging. Thermodynamic analysis showed existences of a secondary energy minimum and an energy barrier in the process of the sludge flocs approaching to membrane surface. Increase in ionic strength could significantly reduce the energy barrier. It was revealed that there existed a critical ionic strength above that the energy barrier would disappear, facilitating adhesion of the foulants. Cake resistance was not significantly affected by the ionic strength, but highly depended on SMP in supernatant. The high cake resistance caused by SMP could be explained by the osmotic pressure mechanism. The obtained results provided new insights into membrane fouling in MBRs.

  14. Investigation of Interface between Ge Electrodes and Ionic Liquid Electrolytes for Electric Double Layer Capacitors

    NASA Astrophysics Data System (ADS)

    Abeysinghe, R. M.; Oguchi, H.; Kuwano, H.

    2016-11-01

    This study discusses novel way of use of ionic liquids to develop Ge-based electrodes for electric double layer capacitors (EDLC). We found that ionic liquids change their electrochemical properties depending on the amount of the absorbed water. Wet ionic liquids work as solvents to dissolve Ge and make porous structures, whereas dry ones work as electrolytes of the EDLCs. The former property was used to increase surface area of the electrodes which is desired to increase the capacity of EDLCs. This method showed another advantage in contrast to the dry ionic liquids; wet ones could fill the complex Ge pores in parallel to porous structure formation. Finally, after porous formation, we dried the ionic liquid at 100 °C and prepared the EDLCs composed of Ge porous electrodes. Cyclic voltammetry and impedance measurements indicated that the obtaine