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Sample records for ionic surfaces implications

  1. Stability of Secondary and Tertiary Structures of Virus-Like Particles Representing Noroviruses: Effects of pH, Ionic Strength, and Temperature and Implications for Adhesion to Surfaces

    PubMed Central

    Samandoulgou, Idrissa; Hammami, Riadh; Morales Rayas, Rocio; Fliss, Ismail

    2015-01-01

    Loss of ordered molecular structure in proteins is known to increase their adhesion to surfaces. The aim of this work was to study the stability of norovirus secondary and tertiary structures and its implications for viral adhesion to fresh foods and agrifood surfaces. The pH, ionic strength, and temperature conditions studied correspond to those prevalent in the principal vehicles of viral transmission (vomit and feces) and in the food processing and handling environment (pasteurization and refrigeration). The structures of virus-like particles representing GI.1, GII.4, and feline calicivirus (FCV) were studied using circular dichroism and intrinsic UV fluorescence. The particles were remarkably stable under most of the conditions. However, heating to 65°C caused losses of β-strand structure, notably in GI.1 and FCV, while at 75°C the α-helix content of GII.4 and FCV decreased and tertiary structures unfolded in all three cases. Combining temperature with pH or ionic strength caused variable losses of structure depending on the particle type. Regardless of pH, heating to pasteurization temperatures or higher would be required to increase GII.4 and FCV adhesion, while either low or high temperatures would favor GI.1 adhesion. Regardless of temperature, increased ionic strength would increase GII.4 adhesion but would decrease GI.1 adhesion. FCV adsorption would be greater at refrigeration, pasteurization, or high temperature combined with a low salt concentration or at a higher NaCl concentration regardless of temperature. Norovirus adhesion mediated by hydrophobic interaction may depend on hydrophobic residues normally exposed on the capsid surface at pH 3, pH 8, physiological ionic strength, and low temperature, while at pasteurization temperatures it may rely more on buried hydrophobic residues exposed upon structural rearrangement. PMID:26296729

  2. Hybridization of ionic levels at metal surfaces

    NASA Astrophysics Data System (ADS)

    Kürpick, P.; Thumm, U.

    1998-09-01

    We investigated the hybridization of He+, Li2+, and Be3+ ionic levels and the creation of surface resonances for nuclear charges Z=2, 3, and 4 near an Al surface. Starting from a two-center basis set expansion with hydrogenic wave functions on the ion site and jellium wave functions in the metal half space, we calculate the self-energy for ion-surface system in the fixed-ion approximation. We obtain convergence by using a rather small set of bound ionic states. This ideally suits this method for the generation of adiabatic basis states that can be used in time-dependent close-coupling calculations for slow ion-surface collisions. We compare our resonance energies and widths with other theoretical approaches, discuss electronic density profiles, and analyze resonances in terms of Stark states.

  3. Ionic surface electrical conductivity in sandstone

    NASA Astrophysics Data System (ADS)

    Glover, Paul W. J.; Meredith, Philip G.; Sammonds, Peter R.; Murrell, Stanley A. F.

    1994-11-01

    Recent analyses of complex conductivity measurements have indicated that high-frequency dispersions encountered in rocks saturated with low-salinity fluids are due to ionic surface conduction and that the form of these dispersions may be dependent upon the nature of the pore and crack surfaces within the rock (Ruffet et al., 1991). Unfortunately, the mechanisms of surface conduction are not well understood, and no model based on rigorous physical principles exists. This paper is split into two parts: an experimental section followed by the development of a theoretical description of adsorption of ions onto mineral surfaces. We have made complex conductivity measurements upon samples of sandstone saturated with a range of different types and concentrations of aqueous solution with a frequency range of 20 Hz to 1 MHz. The frequency dependence of complex conductivity was analyzed using the empirical model of Cole and Cole (1941). The 'fractal' surface models of Le Mehaute and Crepy (1983), Po Zen Wong (1987), the Ruffet el at. (1991) were used to calculate apparent fractal pore surface dimensions for samples saturated with different solution types and concentrations. These showed a pronounced decrease of apparent fractal surface dimension with decreasing electrolyte concentration and a decrease of apparent fractal dimension with increasing relative ionic radius of the dominant cation in solution. A model for ionic surface concentration (ISCOM I) has been developed as the first step in producing a rigorous physicochemical model of surface conduction in quartz-dominated rocks. The results from ISCOM I show that quartz surfaces are overwhelmingly dominated by adsorbed Na(+) when saturated with NaCl solutions of salinities and pH found in actual geological situations. ISCOM I also shows that the concentration threshold for dominance of surface conduction over bulk conduction is aided by depletion of ions from the bulk fluid as a result of their adsorption onto the mineral

  4. Layering of ionic liquids on rough surfaces

    NASA Astrophysics Data System (ADS)

    Sheehan, Alexis; Jurado, L. Andres; Ramakrishna, Shivaprakash N.; Arcifa, Andrea; Rossi, Antonella; Spencer, Nicholas D.; Espinosa-Marzal, Rosa M.

    2016-02-01

    Understanding the behavior of ionic liquids (ILs) either confined between rough surfaces or in rough nanoscale pores is of great relevance to extend studies performed on ideally flat surfaces to real applications. In this work we have performed an extensive investigation of the structural forces between two surfaces with well-defined roughness (<9 nm RMS) in 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide by atomic force microscopy. Statistical studies of the measured layer thicknesses, layering force, and layering frequency reveal the ordered structure of the rough IL-solid interface. Our work shows that the equilibrium structure of the interfacial IL strongly depends on the topography of the contact.Understanding the behavior of ionic liquids (ILs) either confined between rough surfaces or in rough nanoscale pores is of great relevance to extend studies performed on ideally flat surfaces to real applications. In this work we have performed an extensive investigation of the structural forces between two surfaces with well-defined roughness (<9 nm RMS) in 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide by atomic force microscopy. Statistical studies of the measured layer thicknesses, layering force, and layering frequency reveal the ordered structure of the rough IL-solid interface. Our work shows that the equilibrium structure of the interfacial IL strongly depends on the topography of the contact. Electronic supplementary information (ESI) available: Optimized geometries and sizes for [HMIM] Ntf2, SEM images of the smooth and rough colloids, frequency of occurrence of layering in the resolved force-distance curves for all investigated systems with [HMIM] Ntf2, layer size and layering force measured with a sharp tip on mica for the same IL, and results of the kinetics experiments. See DOI: 10.1039/c5nr07805a

  5. Ionic Liquids Can Permanently Modify Porous Silicon Surface Chemistry.

    PubMed

    Trivedi, Shruti; Coombs, Sidney G; Wagle, Durgesh V; Bhawawet, Nakara; Baker, Gary A; Bright, Frank V

    2016-08-01

    To develop ionic liquid/porous silicon (IL/pSi) microarrays we have contact pin-printed 20 hydrophobic and hydrophilic ionic liquids onto as-prepared, hydrogen-passivated porous silicon (ap-pSi) and then determined the individual IL spot size, shape and associated pSi surface chemistry. The results reveal that the hydrophobic ionic liquids oxidize the ap-pSi slightly. In contrast, the hydrophilic ionic liquids lead to heavily oxidized pSi (i.e., ox-pSi). The strong oxidation arises from residual water within the hydrophilic ILs that is delivered from these ILs into the ap-pSi matrix causing oxidation. This phenomenon is less of an issue in the hydrophobic ILs because their water solubility is substantially lower. PMID:27405109

  6. Ionic-charge modification at the surface of polar crystals

    SciTech Connect

    Watson, R.E.; Davenport, J.W.

    1983-05-15

    A simple variational principle has been applied to obtain a bound on the change in ionic charge of a polar crystal between the surface and the interior. Central to the estimate is the assumption that the energy involves terms analytic in the ionic charge q and that these may be treated as a sum of Madelung, intra-atomic, and interatomic (overlap and hybridization) contributions. The Madelung terms are calculated explicitly, the intra-atomic contributions are obtained from the following paper (Phys. Rev. B 27, 6428 (1983)), and the change in interatomic terms on going from the bulk to the surface is estimated by scaling with coordination number. The results do not replace detailed quantum-mechanical calculations but they are simple computationally, and they suggest trends in the competition between the Madelung potential, which encourages ion charging, and hybridization, which discourages ionic charging, both at the surface and in the interior of a crystal. Nonpolar surfaces are of principal concern but one polar surface is considered indicating that the charge disturbance penetrates much further in from the surface than it does in nonpolar cases where the effect is largely limited to the first layer of atoms.

  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. Weighing the surface charge of an ionic liquid.

    PubMed

    Hjalmarsson, Nicklas; Wallinder, Daniel; Glavatskih, Sergei; Atkin, Rob; Aastrup, Teodor; Rutland, Mark W

    2015-10-14

    Electrochemical quartz crystal microbalance has been used to measure changes in the composition of the capacitive electrical double layer for 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)-trifluorophosphate, an ionic liquid, in contact with a gold electrode surface as a function of potential. The mass difference between the cation and anion means that the technique can effectively "weigh" the surface charge accurately with high temporal resolution. This reveals quantitatively how changing the potential alters the ratio of cations and anions associated with the electrode surface, and thus the charge per unit area, as well as the kinetics associated with these interfacial processes. The measurements reveal that it is diffusion of co-ions into the interfacial region rather than expulsion of counterions that controls the relaxation. The measured potential dependent double layer capacitance experimentally validates recent theoretical predictions for counterion overscreening (low potentials) and crowding (high potentials) at electrode surfaces. This new capacity to quantitatively measure ion composition is critical for ionic liquid applications ranging from batteries, capacitors and electrodeposition through to boundary layer structure in tribology, and more broadly provides new insight into interfacial processes in concentrated electrolyte solutions. PMID:26370450

  9. 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.

  10. 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

  11. Computer simulation of the structure of ionic surfaces and interfaces

    SciTech Connect

    Wolf, D.

    1994-09-01

    The classic Madelung problem, i.e., the divergence associated with the r{sup {minus}1} term in the Coulomb potential of condensed ionic systems, was recently cast into an absolutely convergent form that is readily evaluated by direct lattice summation, revealing a net r{sup {minus}5} range of this potential. This realization that Coulomb interactions in condensed systems can actually be rather short ranged (if the system is overall neutral) permits novel physical insights into their structure and energetics to be gained. As an example, the authors demonstrate that an understanding of the range and the nature of the convergence of the Coulomb potential leads naturally to the prediction, verified here by computer simulations for rocksalt-structured surfaces, that all surfaces in predominantly ionic materials should be fundamentally reconstructed. The work also provides a conceptual framework for the theoretical treatment of polar surfaces and interfaces, as demonstrated here for the case of the (111) stacking fault and of the (111) twin boundary in the rocksalt structure.

  12. Effect of Ionic Strength and Surface Charge on Convective Deposition.

    PubMed

    Joshi, Kedar; Muangnapoh, Tanyakorn; Stever, Michael D; Gilchrist, James F

    2015-11-17

    Particle-particle and particle-substrate interactions play a crucial role in capillary driven convective self-assembly for continuous deposition of particles. This systematic study demonstrates the nontrivial effects of varying surface charge and ionic strength of monosized silica microspheres in water on the quality of the deposited monolayer. Increase in particle surface charge results a broader range of parameters that result in monolayer deposition which can be explained considering the particle-substrate electrostatic repulsion in solution. Resulting changes in the coating morphology and microstructure at different solution conditions were observed using confocal microscopy enabling correlation of order to disorder transitions with relative particle stability. These results, in part, may explain similar results seen by Muangnapoh et al., 2013 in vibration-assisted convective deposition. PMID:26501996

  13. Photoresponsive Self-Assembly of Surface Active Ionic Liquid.

    PubMed

    Wu, Aoli; Lu, Fei; Sun, Panpan; Gao, Xinpei; Shi, Lijuan; Zheng, Liqiang

    2016-08-16

    A novel photoresponsive surface active ionic liquid (SAIL) 1-(4-methyl azobenzene)-3-tetradecylimidazolium bromide ([C14mimAzo]Br) with azobenzene located in the headgroup was designed. Reversible vesicle formation and rupture can be finely controlled by photostimuli without any additives in the aqueous solution of the single-tailed ionic liquid. The photoisomerization of the azobenzene derivative was investigated by (1)H NMR and UV-vis spectroscopy. Density functional theory (DFT) calculations further demonstrate that trans-[C14mimAzo]Br has less negative interaction energy, which is beneficial to aggregate formation in water. The incorporation of trans-azobenzene group increases the hydrophobicity of the headgroup and reduces the electrostatic repulsion by delocalization of charge, which are beneficial to the formation of vesicles. However, the bend of cis-azobenzene makes the cis-isomers have no ability to accumulate tightly, which induces the rupture of vesicles. Our work paves a convenient way to achieve controlled topologies and self-assembly of single SAIL. PMID:27445115

  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. 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.

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

    PubMed

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

    2011-09-01

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

  17. Influence of ionic strength on the surface charge and interaction of layered silicate particles.

    PubMed

    Liu, Jing; Miller, Jan D; Yin, Xihui; Gupta, Vishal; Wang, Xuming

    2014-10-15

    The surface charge densities and surface potentials of selected phyllosilicate surfaces were calculated from AFM surface force measurements and reported as a function of ionic strength at pH 5.6. The results show that the silica faces of clay minerals follow the constant surface charge model because of isomorphous substitution in the silica tetrahedral layer. A decreasing surface charge density sequence was observed as follows: muscovite silica face>kaolinite silica face>talc silica face, which is expected to be due to the extent of isomorphous substitution. In contrast, at pH 5.6, the alumina face and the edge surface of kaolinite follow the constant surface potential model with increasing ionic strength, and the surface charge density increased with increasing ionic strength. The cluster size of suspended kaolinite particles at pH 5.6 was found to increase with increasing ionic strength due to an increase in the surface charge density for the alumina face and the edge surface. However, the cluster size decreased at 100mM KCl as a result of an unexpected decrease in the surface charge of the alumina face. When the ionic strength continued to increase above 100mM KCl, the van der Waals attraction dominated and larger clusters of micron size were stabilized. PMID:25086721

  18. 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.

  19. Interfacial structure and orientation of confined ionic liquids on charged quartz surfaces.

    PubMed

    Wang, Yong-Lei; Laaksonen, Aatto

    2014-11-14

    Atomistic molecular dynamics simulations have been performed to study microscopic ionic structures and orientational preferences of absorbed [BMIM] cations and four paired anions ([BF4], [PF6], [TFO] and [TF2N]) on quartz surfaces. Two chemically different quartz surface models were adopted: one is saturated with silanol Si(OH)2 groups, and the other one is covered by silane SiH2 groups, respectively. Simulation results reveal that dense ionic layers, characterized by distinct mass, number, charge and electron densities, are formed in quartz interfacial region. The orientational preferences of confined ionic groups are characterized with different features depending on the size and shape of anionic groups, and the quartz surface charge. The [BMIM] cations attach exclusively onto the negatively charged Si(OH)2 surface. The imidazolium rings lie preferentially perpendicular to Si(OH)2 surface, to which the directly connected methyl and butyl chains are oriented and elongated along Si(OH)2 surface, respectively. The anions are mainly absorbed on positively charged SiH2 surface. The main axes of asymmetric [TFO] and [TF2N] anions are perpendicular and parallel to SiH2 surface, respectively. Such distinct structural and orientational preferences of confined ionic groups attribute to the strong electrostatic interactions and the formation of hydrogen bonds between confined ionic species and quartz interfacial groups. PMID:25260202

  20. Study of tribochemical decomposition of ionic liquids on a nascent steel surface

    NASA Astrophysics Data System (ADS)

    Lu, Renguo; Mori, Shigeyuki; Kobayashi, Kimihiro; Nanao, Hidetaka

    2009-08-01

    Tribological properties and the decomposition process of ionic liquids (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide) on a nascent surface of bearing steel 52100 were investigated by a ball-on-disk friction tester in a vacuum chamber equipped with a quadrupole mass spectrometer (Q-MS). Ionic liquids exhibited better tribological properties than synthetic hydrocarbon oil (multialkylated cyclopentane (MAC)) in high vacuum conditions. The induction period for decomposition of MAC was about 10 km, while no obvious gaseous products were observed for ionic liquids even after a sliding distance of 22 km under the same mechanical conditions. The mass spectra indicated that both the anionic and cationic moieties of ionic liquids decomposed on the nascent steel surface during friction processes. The cationic moiety with a longer alkyl chain was more difficult to decompose on the nascent steel surface than that with a shorter alkyl chain. XPS analysis revealed that the tribofilm formed by ionic liquid was mainly composed of FeF 2 and FeS, which deactivated the nascent surface. As a result, desorption rate of gaseous products decreased appreciably comparing with MAC. The critical load for the mechanical activation of the decomposition correspondingly increased from 1.1 N of MAC to 8 N of ionic liquids.

  1. Simulation of ionic surfaces from an absolutely convergent solution of the Madelung problem

    SciTech Connect

    Wolf, D.

    1995-04-01

    The classic Madelung problem is cast into an absolutely convergent form that is readily evaluated by direct lattice summation, revealing a net r{sup {minus}5} range of the net Coulomb potential in ionic crystals and liquids. The realization that Coulomb interactions in condensed systems can actually be rather short ranged (provided the system is overall neutral) leads to the prediction, verified by computer simulations for rocksalt-structure surfaces, that all surfaces in predominantly ionic crystals should be fundamentally reconstructed. The work also provides a conceptual framework for the theoretical treatment of polar surfaces, as demonstrated for the case of the (111) surfaces of NaCl and MgO.

  2. Surface Physicochemistry and Ionic Strength Affects eDNA’s Role in Bacterial Adhesion to Abiotic Surfaces

    PubMed Central

    Regina, Viduthalai R.; Lokanathan, Arcot R.; Modrzyński, Jakub J.; Sutherland, Duncan S.; Meyer, Rikke L.

    2014-01-01

    Extracellular DNA (eDNA) is an important structural component of biofilms formed by many bacteria, but few reports have focused on its role in initial cell adhesion. The aim of this study was to investigate the role of eDNA in bacterial adhesion to abiotic surfaces, and determine to which extent eDNA-mediated adhesion depends on the physicochemical properties of the surface and surrounding liquid. We investigated eDNA alteration of cell surface hydrophobicity and zeta potential, and subsequently quantified the effect of eDNA on the adhesion of Staphylococcus xylosus to glass surfaces functionalised with different chemistries resulting in variable hydrophobicity and charge. Cell adhesion experiments were carried out at three different ionic strengths. Removal of eDNA from S. xylosus cells by DNase treatment did not alter the zeta potential, but rendered the cells more hydrophilic. DNase treatment impaired adhesion of cells to glass surfaces, but the adhesive properties of S. xylosus were regained within 30 minutes if DNase was not continuously present, implying a continuous release of eDNA in the culture. Removal of eDNA lowered the adhesion of S. xylosus to all surfaces chemistries tested, but not at all ionic strengths. No effect was seen on glass surfaces and carboxyl-functionalised surfaces at high ionic strength, and a reverse effect occurred on amine-functionalised surfaces at low ionic strength. However, eDNA promoted adhesion of cells to hydrophobic surfaces irrespective of the ionic strength. The adhesive properties of eDNA in mediating initial adhesion of S. xylosus is thus highly versatile, but also dependent on the physicochemical properties of the surface and ionic strength of the surrounding medium. PMID:25122477

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

    DOE PAGESBeta

    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 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

  5. 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. PMID:27348604

  6. A study of the ionic conduction of mica surface by admittance spectroscopy

    NASA Astrophysics Data System (ADS)

    Dolci, D.; Aloisi, G.; Lanzi, L.; Carlà, M.

    2007-08-01

    The ionic conduction on the surface of humid mica has been analyzed by admittance spectroscopy as a function of relative humidity for different surface treatments. Measurements at low frequency indicate that water adsorption proceeds first in the form of a strongly adsorbed uniform thin layer, then with the formation of highly inhomogeneous thick aggregates.

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

    SciTech Connect

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

    1987-09-08

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

  8. Wire-to-Plate Surface Dielectric Barrier Discharge and Induced Ionic Wind

    NASA Astrophysics Data System (ADS)

    Zhang, Yu; Liu, Lijuan; Li, Ben; Ouyang, Jiting

    2016-06-01

    The electrical and mechanical characteristics of the wire-to-plate surface dielectric barrier discharge and the induced ionic wind are investigated experimentally. The different temporal behaviors in positive and negative half-cycles are studied by time-resolved images. It is shown that the discharge and the light emission are generally stronger in the positive half cycle. The discharge is inhomogeneous and propagates in streamer mode; however, in the negative half-cycle, the discharge appears visually uniformly and operates in the diffuse mode. The surface discharge can produce ionic wind about several m/s above the dielectric surface. There exists an optimal width of the grounded electrode to produce a larger plasma area or active wind region. Increasing of the applied voltage or normalized dielectric constant leads to a larger wind velocity. The performance of ionic wind on flow control is visualized by employing a smoke stream. supported by National Natural Science Foundation of China (Nos. 11175017 and 11475019)

  9. 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.

  10. 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

  11. 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. PMID:27137990

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

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

    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.

  13. 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. PMID:21341864

  14. Study of surface-bonded dicationic ionic liquids as stationary phases for hydrophilic interaction chromatography.

    PubMed

    Qiao, Lizhen; Li, Hua; Shan, Yuanhong; Wang, Shuangyuan; Shi, Xianzhe; Lu, Xin; Xu, Guowang

    2014-02-21

    In the present study, several geminal dicationic ionic liquids based on 1,4-bis(3-allylimidazolium)butane and 1,8-bis(3-allylimidazolium)octane in combination with different anions bromide and bis(trifluoromethanesulphonyl)imide were prepared and then bonded to the surface of 3-mercaptopropyl modified silica materials through the "thiol-ene" click chemistry as stationary phases for hydrophilic interaction chromatography (HILIC). Compared with their monocationic analogues, the dicationic ionic liquids stationary phases presented effective retention and good selectivity for typical hydrophilic compounds under HILIC mode with the column efficiency as high as 130,000 plates/m. Moreover, the influence of different alkyl chain spacer between dications and combined anions on the retention behavior and selectivity of the dicationic ionic liquids stationary phases under HILIC mode was displayed. The results indicated that the longer linkage chain would decrease the hydrophilicity and retention on the dicationic ionic liquid stationary phase, and while differently combined anions had no difference due to the exchangeability under the common HILIC mobile phase with buffer salt. Finally, the retention mechanism was investigated by evaluating the effect of chromatographic factors on retention, including the water content in the mobile phase, the mobile phase pH and buffer salt concentration. The results showed that the dicationic ionic liquids stationary phases presented a mixed-mode retention behavior with HILIC mechanism and anion exchange. PMID:24484692

  15. Surface morphology implications on Langmuir probe measurements

    NASA Astrophysics Data System (ADS)

    Suresh, Padmashri

    2011-12-01

    Langmuir probes are extensively employed to study the plasmas in space and laboratory environments. Successful measurements require a comprehensive modeling of both the plasma environment and the probe conditions in the form of current collection models. In this thesis, the surface morphology implications on the probe current collection are investigated. This problem is applied and solved in the context of a CubeSat regime. The first problem that is investigated is the consequence of surface structural variability on the current measurements. A new model for dealing with non-uniformity of the probe surface structure is developed in this paper. This model is applied to analyze the Langmuir probe data from a sounding rocket mission that was subjected to surface structural non-homogeneities. This model would be particularly useful for CubeSat platforms where elaborate probe design procedures are not feasible. The second problem that is investigated is the surface area implications on Langmuir probe measurements. It has been established that surface area ratio of the spacecraft to that of the probe needs to be sufficiently large to make successful plasma measurements. CubeSats would therefore pose a challenge for employing Langmuir-type instruments to study the space plasma. We inspect the feasibility of making plasma measurements using Langmuir probes subjected to CubeSat area constraints. This analysis is done for a forthcoming Utah State University (USU)/Space Dynamics Lab (SDL) CubeSat mission.

  16. Surface science and model catalysis with ionic liquid-modified materials.

    PubMed

    Steinrück, H-P; Libuda, J; Wasserscheid, P; Cremer, T; Kolbeck, C; Laurin, M; Maier, F; Sobota, M; Schulz, P S; Stark, M

    2011-06-17

    Materials making use of thin ionic liquid (IL) films as support-modifying functional layer open up a variety of new possibilities in heterogeneous catalysis, which range from the tailoring of gas-surface interactions to the immobilization of molecularly defined reactive sites. The present report reviews recent progress towards an understanding of "supported ionic liquid phase (SILP)" and "solid catalysts with ionic liquid layer (SCILL)" materials at the microscopic level, using a surface science and model catalysis type of approach. Thin film IL systems can be prepared not only ex-situ, but also in-situ under ultrahigh vacuum (UHV) conditions using atomically well-defined surfaces as substrates, for example by physical vapor deposition (PVD). Due to their low vapor pressure, these systems can be studied in UHV using the full spectrum of surface science techniques. We discuss general strategies and considerations of this approach and exemplify the information available from complementary methods, specifically photoelectron spectroscopy and surface vibrational spectroscopy. PMID:21520462

  17. Influence of Nanosegregation on the Surface Tension of Fluorinated Ionic Liquids.

    PubMed

    Luís, Andreia; Shimizu, Karina; Araújo, João M M; Carvalho, Pedro J; Lopes-da-Silva, José A; Canongia Lopes, José N; Rebelo, Luís Paulo N; Coutinho, João A P; Freire, Mara G; Pereiro, Ana B

    2016-06-21

    We have investigated, both theoretically and experimentally, the balance between the presence of alkyl and perfluoroalkyl side chains on the surface organization and surface tension of fluorinated ionic liquids (FILs). A series of ionic liquids (ILs) composed of 1-alkyl-3-methylimidazolium cations ([CnC1im] with n = 2, 4, 6, 8, 10, or 12) combined with the perfluorobutanesulfonate anion was used. The surface tensions of the investigated liquid salts are considerably lower than those reported for non-fluorinated ionic liquids. The most surprising and striking feature is the identification, for the first time, of a minimum at n = 8 in the surface tension versus the length of the IL cation alkyl side chain. Supported by molecular dynamics (MD) simulations, it was found that this trend is a result of the competition between the two nonpolar domains (perfluorinated and aliphatic) pointing toward the gas-liquid interface, a phenomenon which occurs in ILs with perfluorinated anions. Furthermore, these ILs present the lowest surface entropy reported to date. PMID:27218210

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

    SciTech Connect

    Roberts, J.G.

    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.

  19. 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.

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

    SciTech Connect

    Stephenson, G. B.; Highland, M. J.

    2011-01-01

    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 PbTiO{sub 3} (001) film coherently strained to SrTiO{sub 3} 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.

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

    PubMed Central

    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. PMID:25623295

  2. 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.

  3. 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.

  4. 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

  5. Potentiostatic control of ionic liquid surface film formation on ZE41 magnesium alloy.

    PubMed

    Efthimiadis, Jim; Neil, Wayne C; Bunter, Andrew; Howlett, Patrick C; Hinton, Bruce R W; MacFarlane, Douglas R; Forsyth, Maria

    2010-05-01

    The generation of potentially corrosion-resistant films on light metal alloys of magnesium have been investigated. Magnesium alloy, ZE41 [Mg-Zn-Rare Earth (RE)-Zr, nominal composition approximately 4 wt % Zn, approximately 1.7 wt % RE (Ce), approximately 0.6 wt % Zr, remaining balance, Mg], was exposed under potentiostatic control to the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate, denoted [P(6,6,6,14)][DPP]. During exposure to this IL, a bias potential, shifted from open circuit, was applied to the ZE41 surface. Electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) were used to monitor the evolution of film formation on the metal surface during exposure. The EIS data indicate that, of the four bias potentials examined, applying a potential of -200 mV versus OCP during the exposure period resulted in surface films of greatest resistance. Both EIS measurements and scanning electron microscopy (SEM) imaging indicate that these surfaces are substantially different to those formed without potential bias. Time of flight-secondary ion mass spectrometry (ToF-SIMS) elemental mapping of the films was utilized to ascertain the distribution of the ionic liquid cationic and anionic species relative to the microstructural surface features of ZE41 and indicated a more uniform distribution compared with the surface following exposure in the absence of a bias potential. Immersion of the treated ZE41 specimens in a chloride contaminated salt solution clearly indicated that the ionic liquid generated surface films offered significant protection against pitting corrosion, although the intermetallics were still insufficiently protected by the IL and hence favored intergranular corrosion processes. PMID:20433137

  6. Modification of Hydrophilic and Hydrophobic Surfaces Using an Ionic-Complementary Peptide

    PubMed Central

    Yang, Hong; Fung, Shan-Yu; Pritzker, Mark; Chen, P.

    2007-01-01

    Ionic-complementary peptides are novel nano-biomaterials with a variety of biomedical applications including potential biosurface engineering. This study presents evidence that a model ionic-complementary peptide EAK16-II is capable of assembling/coating on hydrophilic mica as well as hydrophobic highly ordered pyrolytic graphite (HOPG) surfaces with different nano-patterns. EAK16-II forms randomly oriented nanofibers or nanofiber networks on mica, while ordered nanofibers parallel or oriented 60° or 120° to each other on HOPG, reflecting the crystallographic symmetry of graphite (0001). The density of coated nanofibers on both surfaces can be controlled by adjusting the peptide concentration and the contact time of the peptide solution with the surface. The coated EAK16-II nanofibers alter the wettability of the two surfaces differently: the water contact angle of bare mica surface is measured to be <10°, while it increases to 20.3±2.9° upon 2 h modification of the surface using a 29 µM EAK16-II solution. In contrast, the water contact angle decreases significantly from 71.2±11.1° to 39.4±4.3° after the HOPG surface is coated with a 29 µM peptide solution for 2 h. The stability of the EAK16-II nanofibers on both surfaces is further evaluated by immersing the surface into acidic and basic solutions and analyzing the changes in the nanofiber surface coverage. The EAK16-II nanofibers on mica remain stable in acidic solution but not in alkaline solution, while they are stable on the HOPG surface regardless of the solution pH. This work demonstrates the possibility of using self-assembling peptides for surface modification applications. PMID:18091996

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

    PubMed

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

    2015-04-01

    Molecular simulations of the enzymes Candida rugosa lipase and Bos taurus α-chymotrypsin in aqueous ionic liquids 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium ethyl sulfate were used to study the change in enzyme-solvent interactions induced by modification of the enzyme surface charge. The enzymes were altered by randomly mutating lysine surface residues to glutamate, effectively decreasing the net surface charge by two for each mutation. These mutations resemble succinylation of the enzyme by chemical modification, which has been shown to enhance the stability of both enzymes in ILs. After establishing that the enzymes were stable on the simulated time scales, we focused the analysis on the organization of the ionic liquid substituents about the enzyme surface. Calculated solvent charge densities show that for both enzymes and in both solvents that changing positively charged residues to negative charge does indeed increase the charge density of the solvent near the enzyme surface. The radial distribution of IL constituents with respect to the enzyme reveals decreased interactions with the anion are prevalent in the modified systems when compared to the wild type, which is largely accompanied by an increase in cation contact. Additionally, the radial dependence of the charge density and ion distribution indicates that the effect of altering enzyme charge is confined to short range (≤1 nm) ordering of the IL. Ultimately, these results, which are consistent with that from prior experiments, provide molecular insight into the effect of enzyme surface charge on enzyme stability in ILs. PMID:25641162

  8. Concentration dependence of nanoparticle surface coverage for ionic self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Kim, Vincent; Simpson, Brian; Seredinski, Andrew; Schwen, Eric; Mazilu, Dan; Mazilu, Irina

    2014-03-01

    We investigate the concentration dependence of the surface coverage of thin films that consist of silica nanoparticles deposited on the substrates via the ISAM (ionically self-assembled monolayers) technique. Several experiments were conducted in order to investigate the factors that affected the quality of the coatings and one significant factor observed was the concentration of the colloidal silica solution. Using SEM micrographs, we analyzed the surface coverage and compared it to the analytical results obtained using a cooperative sequential adsorption model. The results we obtained matched the linear relation between particle density and the inverse of the concentration predicted by the theory.

  9. Surface-active ionic liquids in micellar catalysis: impact of anion selection on reaction rates in nucleophilic substitutions.

    PubMed

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

    2016-05-21

    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

  10. 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.

  11. 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.

  12. Surface interactions, corrosion processes and lubricating performance of protic and aprotic ionic liquids with OFHC copper

    NASA Astrophysics Data System (ADS)

    Espinosa, Tulia; Sanes, José; Jiménez, Ana-Eva; Bermúdez, María-Dolores

    2013-05-01

    In order to select possible candidates for use as lubricants or as precursors of surface coatings, the corrosion and surface interactions of oxygen-free high conductivity (OFHC) copper with two new protic (PIL) and four aprotic (APIL) room-temperature ionic liquids have been studied. The PILs, with no heteroatoms in their composition, are the triprotic di[(2-hydroxyethyl)ammonium] succinate (MSu) and the diprotic di[bis-(2-hydroxyethyl)ammonium] adipate (DAd). The four APILs contain imidazolium cations with short or long alkyl chain substituents and reactive anions: 1-ethyl-3-methylimidazolium phosphonate ([EMIM]EtPO3H); 1-ethyl-3-methylimidazolium octylsulfate ([EMIM]C8H17SO4); 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM]BF4) and 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIM]PF6). Contact angles between the ionic liquids and OFHC copper surface were measured. Mass and roughness changes of OFHC copper after 168 h in contact with the ionic liquids have been determined. Copper surfaces were studied by XRD, SEM-EDX and XPS surface analysis. FTIR spectra of the liquid phases recovered after being in contact with the copper surface were compared with that of the neat ionic liquids. The lowest corrosion rate is observed for the diprotic ammonium adipate PIL (DAd), which gives low mass and surface roughness changes and forms adsorbed layers on copper, while the triprotic ammonium succinate salt (MSu) produces a severe corrosive attack by reaction with copper to form a blue crystalline solid, which has been characterized by FTIR and thermal analysis (TGA). All imidazolium APILs react with copper, with different results as a function of the anion. As expected, [EMIM]C8H17SO4 reacts with copper to form the corresponding copper sulphate salt. [EMIM]EtPO3H produces severe corrosion to form a phosphonate-copper soluble phase. [HMIM]BF4 gives rise to the highest roughness increase of the copper surface. [HMIM]PF6 shows the lowest mass and roughness changes of

  13. Nearest Neighbor Hopping conduction observed with ionic liquid induced silicon surface states

    NASA Astrophysics Data System (ADS)

    Nelson, Jj; Reich, K. V.; Sammon, M.; Shklovskii, B. I.; Goldman, A. M.

    A two-dimensional hole gas can be created on the surface of a bulk Si wafer by using an ionic liquid in an electric double layer transistor configuration (EDLT). EDLTs are useful in observing metal to insulator and superconductor to insulator transitions due to record high carrier densities of 1015 cm-2 that can be achieved. In some cases the high carrier densities are due in part to oxidation of the sample surface. With an EDLT configuration we have observed a 2D insulator-to metal transition with low mobility Si at the highest reported critical carrier density. The experiment reported here is designed to promote electrostatic carrier induction over electrochemical reactions and is focused on carrier densities near 1011 cm-2. At such a low densities we observe nearest neighbor hopping conduction on the surface of Si. This observation suggests that the ionic liquid covering the surface should be treated as a series of discrete charges that can act as a platform to better understand EDLT physics at higher carrier densities. This work was supported in part by the National Science Foundation under Grant NSF-1263316.

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

    PubMed

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

    2016-08-23

    Bulk molecular ionic solids exhibit fascinating electronic properties, including electron correlations, phase transitions, and superconducting ground states. In contrast, few of these phenomena have been observed in low-dimensional molecular structures, including thin films, nanoparticles, and molecular blends, not in the least because most of such structures have been composed of nearly closed-shell molecules. It is therefore desirable to develop low-dimensional ionic molecular structures that can capture 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 a 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. PMID:27458890

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

    DOE PAGESBeta

    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 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

  16. Self-assembly of nanoparticles on the surface of ionic crystals: Structural properties

    NASA Astrophysics Data System (ADS)

    Nikolic, K.; Murugesan, M.; Forshaw, M.; Cunningham, D.; Martinez-Albertos, J.-L.; Moore, B. D.

    2007-07-01

    With a suitable combination of ligand-stabilised nanoparticle suspension and ionic salt solutions, it is possible to produce microcrystals that are coated with nanoparticles. The self-assembly process of coating microcrystals by gold nanoparticles (NP) is mediated by the crystal lattice. This is the so-called CLAMS process - a generic process for self-organisation of nanoparticles on the surface of crystals [M. Murugeshan, D. Cunningham, J.-L. Martnez-Albertos, R. Vrcelj, B.D. Moore, Chem. Commun. (2005) 2677]. We are exploring here the structural properties of these self-assembled structures by using different imaging techniques.

  17. Chemical and heating treatments of ionic monolayer-protected clusters (IMPCs) with different surface counter anions.

    PubMed

    Choo, Hosun; Isaacs, Steven R; Small, Adam; Parmley, Seth; Shon, Young-Seok

    2007-12-01

    This paper shows an in-depth study on the chemical and thermal responses of two ionic monolayer-protected gold clusters (Oct(4)N(+-)Br- and Oct(4)N(+-)O(3)SS-IMPCs). Two IMPCs displayed completely different phase-transfer behaviors when the solutions were in contact with the aqueous solution containing N-(2-mercaptopropionyl)glycine (tiopronin). Not Oct(4)N(+-)O(3)SS-IMPCs but Oct(4)N(+-)Br-IMPCs experienced a facile phase transfer from the organic layer to the aqueous layer, which was resulted from the displacement of ionic ligands by tiopronin monolayers on the gold nanoparticle surface. When the toluene solution containing Oct(4)N(+-)Br-IMPCs was treated with the aqueous solution containing NaCl salts, the UV-vis spectrum of the solution containing Oct(4)N(+-)Br-IMPCs undertook a fast spectral evolution caused by decomposition/agglomeration of IMPCs. In contrast, Oct(4)N(+-)O(3)SS-IMPCs exhibited much higher stability against the NaCl treatments. The Oct(4)N(+-)O(3)SS-IMPCs also displayed a superior thermal stability at relatively high temperature of approximately 110 degrees C. Core size evolutions of Oct(4)N(+-)O(3)SS-IMPCs without a fast decomposition or aggregation of clusters were also observed during solid-state heating treatments at approximately 150 and approximately 200 degrees C. These results support that the presence of different anions clearly affect the overall stability of ionic nanoparticles. The stronger binding property of thiosulfate anions compared to bromide anions with gold nanoparticle surfaces makes Oct(4)N(+-)O(3)SS-IMPCs chemically more inert and thermally more stable. PMID:17719060

  18. 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.

  19. New insights into the fundamental chemical nature of ionic liquid film formation on magnesium alloy surfaces.

    PubMed

    Forsyth, Maria; Neil, Wayne C; Howlett, Patrick C; Macfarlane, Douglas R; Hinton, Bruce R W; Rocher, Nathalie; Kemp, Thomas F; Smith, Mark E

    2009-05-01

    Ionic liquids (ILs) based on trihexyltetradecylphosphonium coupled with either diphenylphosphate or bis(trifluoromethanesulfonyl)amide have been shown to react with magnesium alloy surfaces, leading to the formation a surface film that can improve the corrosion resistance of the alloy. The morphology and microstructure of the magnesium surface seems critical in determining the nature of the interphase, with grain boundary phases and intermetallics within the grain, rich in zirconium and zinc, showing almost no interaction with the IL and thereby resulting in a heterogeneous surface film. This has been explained, on the basis of solid-state NMR evidence, as being due to the extremely low reactivity of the native oxide films on the intermetallics (ZrO2 and ZnO) with the IL as compared with the magnesium-rich matrix where a magnesium hydroxide and/or carbonate inorganic surface is likely. Solid-state NMR characterization of the ZE41 alloy surface treated with the IL based on (Tf)2N(-) indicates that this anion reacts to form a metal fluoride rich surface in addition to an organic component. The diphenylphosphate anion also seems to undergo an additional chemical process on the metal surface, indicating that film formation on the metal is not a simple chemical interaction between the components of the IL and the substrate but may involve electrochemical processes. PMID:20355890

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

    DOE PAGESBeta

    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 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

  1. Self-assembling array of magnetoelectrostatic jets from the surface of a superparamagnetic ionic liquid.

    PubMed

    King, Lyon B; Meyer, Edmond; Hopkins, Mark A; Hawkett, Brian S; Jain, Nirmesh

    2014-12-01

    Electrospray is a versatile technology used, for example, to ionize biomolecules for mass spectrometry, create nanofibers and nanowires, and propel spacecraft in orbit. Traditionally, electrospray is achieved via microfabricated capillary needle electrodes that are used to create the fluid jets. Here we report on multiple parallel jetting instabilities realized through the application of simultaneous electric and magnetic fields to the surface of a superparamagnetic electrically conducting ionic liquid with no needle electrodes. The ionic liquid ferrofluid is synthesized by suspending magnetic nanoparticles in a room-temperature molten salt carrier liquid. Two ILFFs are reported: one based on ethylammonium nitrate (EAN) and the other based on EMIM-NTf2. The ILFFs display an electrical conductivity of 0.63 S/m and a relative magnetic permeability as high as 10. When coincident electric and magnetic fields are applied to these liquids, the result is a self-assembling array of emitters that are composed entirely of the colloidal fluid. An analysis of the magnetic surface stress induced on the ILFF shows that the electric field required for transition to spray can be reduced by as much as 4.5 × 10(7) V/m compared to purely electrostatic spray. Ferrofluid mode studies in nonuniform magnetic fields show that it is feasible to realize arrays with up to 16 emitters/mm(2). PMID:25372842

  2. Effects of PCB Substrate Surface Finish, Flux, and Phosphorus Content on Ionic Contamination

    NASA Astrophysics Data System (ADS)

    Bacior, M.; Sobczak, N.; Siewiorek, A.; Kudyba, A.; Homa, M.; Nowak, R.; Dziula, M.; Masłoń, S.

    2015-02-01

    The ionic contamination on printed circuit boards (PCB) having different surface finishes was examined using ionograph. The study was performed at the RT on three types of PCBs covered with: (i) hot air solder leveling (HASL LF), (ii) electroless nickel immersion gold (ENIG), and (iii) organic surface protectant (OSP), all on Cu substrates, as well as two types of fluxes, namely EF2202 and RF800. In the group of boards without soldered components, the lowest average value of contamination was for the ENIG 18 µm surface (0.01 μg NaCl/cm2). Boards with soldered components were more contaminated (from 0.29 μg NaCl/cm2 for the HASL LF 18 µm surface). After spraying boards with fluxing agents, the values of contaminants were the highest. The influence of phosphorus content in Ni-P layer of ENIG finish on ionic contamination was examined. In the group of PCBs with Au coating, the smallest amount of surface contaminants (0.32 μg NaCl/cm2) was for Ni-2-5%P layer. PCBs with Ni-11%P layer were higher contaminated (0.47 μg NaCl/cm2), and another with Ni-8%P layer had 0.81 μg NaCl/cm2. PCBs without Au coating, had the lowest contamination (0.48 μg NaCl/cm2) at phosphorous content equal 11%P. Higher contamination (0.67 μg NaCl/cm2) was at 2-5%P, up to 1.98 μg NaCl/cm2 for 8% of P. Boards with Au finish have lower value of contamination than identical boards without Au layer thus contributing to better reliability of electronic assemblies, since its failures due to current leakage and corrosion can be caused by contaminants.

  3. 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.

  4. Controlled ionic condensation at the surface of a native extremophile membrane

    NASA Astrophysics Data System (ADS)

    Contera, Sonia Antoranz; Voïtchovsky, Kislon; Ryan, John F.

    2010-02-01

    At the nanoscale level biological membranes present a complex interface with the solvent. The functional dynamics and relative flexibility of membrane components together with the presence of specific ionic effects can combine to create exciting new phenomena that challenge traditional theories such as the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory or models interpreting the role of ions in terms of their ability to structure water (structure making/breaking). Here we investigate ionic effects at the surface of a highly charged extremophile membrane composed of a proton pump (bacteriorhodopsin) and archaeal lipids naturally assembled into a 2D crystal. Using amplitude-modulation atomic force microscopy (AM-AFM) in solution, we obtained sub-molecular resolution images of ion-induced surface restructuring of the membrane. We demonstrate the presence of a stiff cationic layer condensed at its extracellular surface. This layer cannot be explained by traditional continuum theories. Dynamic force spectroscopy experiments suggest that it is produced by electrostatic correlation mediated by a Manning-type condensation of ions. In contrast, the cytoplasmic surface is dominated by short-range repulsive hydration forces. These findings are relevant to archaeal bioenergetics and halophilic adaptation. Importantly, they present experimental evidence of a natural system that locally controls its interactions with the surrounding medium and challenges our current understanding of biological interfaces.At the nanoscale level biological membranes present a complex interface with the solvent. The functional dynamics and relative flexibility of membrane components together with the presence of specific ionic effects can combine to create exciting new phenomena that challenge traditional theories such as the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory or models interpreting the role of ions in terms of their ability to structure water (structure making/breaking). Here we

  5. Surface science of Cs, CsO and CsI ionic layers on Pt(111)

    NASA Astrophysics Data System (ADS)

    Drnec, Jakub

    surface structures observed by LEED during the coadsorption of Cs and I are in good agreement with atomic arrangements predicted for ionic layers. The validity of this conclusion and the general behavior of ionic layers was checked by an electrostatic energy calculation for various structures.

  6. Effective work functions for ionic and electronic emissions from mono- and polycrystalline surfaces

    NASA Astrophysics Data System (ADS)

    Kawano, Hiroyuki

    2008-02-01

    The effective work functions ( ϕ+, ϕe and ϕ-) for positive-ionic, electronic, and negative-ionic emissions from mono- and polycrystalline surfaces are surveyed comprehensively and also investigated critically for the main purposes of (1) evaluating the most probable values of ϕ+, ϕe and ϕ- for a variety of surface species, (2) explicating both thermionic contrasts (Δ ϕ∗ ≡ ϕ+ - ϕe and Δ ϕ∗∗ ≡ ϕ- - ϕe) and their dependence on experimental conditions, and (3) demonstrating the necessity of employing ϕ+ (not ϕe) for quantitative analysis of those data on positive ion emission from polycrystalline surfaces. Careful examination of both theoretical results and experimental data on the work functions yield several conclusions. By both theory and experiment, clean monocrystalline surfaces are verified to have Δ ϕ∗ = 0.0 eV within an error of ±0.05 eV. Next, as the density of local surface irregularities increases, the homogeneity in the work function over the whole surface area decreases and, hence, Δ ϕ∗ increases. Also, the most probable values of ϕ+ and ϕe are recommended for many mono- and polycrystalline surfaces, mostly (∼70%) with a standard deviation of ±0.02-0.08 eV. Compared with the probable or typical values of ϕe accepted in influential handbooks, the most probable values of ϕe recommended here are typically (∼70%) equal to each other within a narrow gap of less than ∼0.1 eV, but some (∼20%) are different by ∼0.2 eV or more (up to ∼1 eV). Furthermore, polycrystalline surfaces of Nb, Mo, Ta, W, Re, Ir, Pt, etc. hold Δ ϕ∗ ≈ 0.3-0.8 eV since each surface has a mean value that is different between ϕ+ and ϕe. Also, at the degree of monocrystallization ( δm) below ∼50%, the theoretical value of Δ ϕ∗ depends little on δm and agrees well with experimental data on each polycrystalline surface. As δm increases beyond ∼80%, Δ ϕ∗ decreases rapidly to 0, showing again a good agreement between theory

  7. 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.

  8. 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

  9. Temperature-dependent surface-enrichment effects of imidazolium-based ionic liquids.

    PubMed

    Kolbeck, Claudia; Deyko, Alexey; Matsuda, Takashi; Kohler, Florian T U; Wasserscheid, Peter; Maier, Florian; Steinrück, Hans-Peter

    2013-11-11

    We present the first systematic study of the influence of temperature on the degree of surface enrichment of 1-alkyl-3-methylimidazolium-based ionic liquids (ILs). Using angle-resolved X-ray photoelectron spectroscopy, we demonstrate that the degree of surface enrichment strongly decreases with increasing temperature for all the studied ILs. For ILs with the same cation, but different anions, [C8 C1 Im]Br, [C8 C1 Im][TfO] and [C8 C1 Im][Tf2 N], no significant differences of the temperature-induced partial loss of surface enrichment are found. Measurements for [C4 C1 Im][TfO], [C8 C1 Im][TfO] and [C18 C1 Im][TfO] indicate a small effect of the chain length. For [C18 C1 Im][TfO], a continuous decrease of alkyl surface enrichment is found with increasing temperature, with no abrupt changes at the phase-transition temperature from the smectic A to the isotropic phase, indicating that the surface enrichment is not affected by this phase transition. PMID:24123477

  10. Adsorbed and near surface structure of ionic liquids at a solid interface.

    PubMed

    Segura, Juan José; Elbourne, Aaron; Wanless, Erica J; Warr, Gregory G; Voïtchovsky, Kislon; Atkin, Rob

    2013-03-01

    The structure of solid-ionic liquid (IL) interfaces has been characterised with unprecedented clarity by employing a range of atomic force microscopy (AFM) imaging techniques and tip pressures appropriate for the system under study. Soft contact and amplitude-modulation (AM) AFM imaging have been used to elucidate the lateral structure of ILs adsorbed onto mica, and in the near surface ion layers. Data is presented for ethylammonium nitrate (EAN) and 1-ethyl-3-methylimidazolium bis(trifluoro-methylsulfonyl)imide (EMIm TFSI). Whereas EAN is a protic IL that forms a nanostructured sponge phase in the bulk, EMIm TFSI is aprotic and has weak (or absent) bulk association structure. Comparison of results obtained for the two liquids elucidates how the strength of bulk liquid morphology effects lateral organisation at the surface, and any effect of IL class, i.e. protic versus aprotic. Imaging reveals EAN self assembles at the solid surface in a worm-like morphology, whereas EMIm cations adsorb in a more isolated fashion, but still in rows templated by the mica surface. To the authors' knowledge, the wormlike structures present at the EAN-mica interface are the smallest self-assembled aggregates ever imaged on a solid surface. PMID:23361257

  11. 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).

  12. Emission spectrum of holmium atoms excited during ionic sputtering of a surface

    SciTech Connect

    Pop, S. S.; Braslavets, V. V.; Evdokimov, S. A.

    1988-08-01

    The article shows the fundamental possibility of using the bombardment of the surface of solids by kilo V ions for exciting the emission spectrum of particles of the target material and for obtaining spectroscopic data. The method is tested by studying the emission spectra of holmium as an example. It is shown that the sensitivity of the method can be substantially increased by using the so-called chemical effect, i.e., the effect of strengthening the spectral lines of sputtered excited metal atoms during bombardment of the target in the presence of oxygen. It is proposed that the chemical effect, which takes place only for atomic lines, in contrast to ionic ones, can also be used for simplifying the identification of atomic lines. It is noted that the proposed method is suitable for studying the atomic spectra of any solids, including refractory and chemically reactive substances.

  13. Fabrication of localized surface plasmon resonance fiber probes using ionic self-assembled gold nanoparticles.

    PubMed

    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

  14. Composition of the outermost layer and concentration depth profiles of ammonium nitrate ionic liquid surfaces.

    PubMed

    Ridings, Christiaan; Warr, Gregory G; Andersson, Gunther G

    2012-12-14

    Differences in the surface structure of protic ionic liquids (ILs) with three different cations and a common anion; ethyl-, propyl- and 2-hydroxyethyl- (or ethanol-) ammonium nitrate (EAN, PAN and EtAN, respectively) have been observed by neutral impact collision ion scattering spectroscopy (NICISS) and metastable induced electron spectroscopy/ultraviolet photoelectron spectroscopy (MIES/UPS). NICISS is used to determine the concentration depth profiles of the elements in each IL and it reveals an enrichment of cation alkyl chains of PAN and EtAN in the outermost layer compared to EAN, and a corresponding depletion of nitrate from the outermost layer of the EtAN surface. MIES probes the molecular orbitals of only the species in the outermost layer of a sample and confirms that, while both the anion and the cation are present to some degree at the surface of all three ILs, the cation is enriched to a greater extent at the surface of PAN and EtAN compared to EAN. PMID:23103987

  15. 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. PMID:25561415

  16. Surface study of metal-containing ionic liquids by means of photoemission and absorption spectroscopies

    NASA Astrophysics Data System (ADS)

    Caporali, Stefano; Pedio, Maddalena; Chiappe, Cinzia; Pomelli, Christian S.; Acres, Robert G.; Bardi, Ugo

    2016-06-01

    The vacuum/liquid interface of different ionic liquids obtained by dissolving bistriflimide salts of Ag, Al, Cu, Ni, and Zn in 1-butyl-3-methylimidazolium bistriflimide ([bmim][Tf2N]) was investigated under vacuum using AR-XPS and NEXAFS. The XPS spectra show chemical shifts of the nitrogen of the bistriflimide anion as a function of the metal type, indicating different strength of the coordination bonds. In silver bearing ILs, silver ions were found to be only weakly coordinated. On the contrary, Ni, Cu, Zn, and especially Al exhibit large chemical shifts attributable to strong interaction with the bistriflimide ions. The outermost surface was enriched with or depleted of metal ions as a function of the nature of the metals. Nickel and zinc tend to slightly concentrate at the surface while copper, silver, and especially aluminum are depleted at the surface. We also observed that the aliphatic alkyl chains of the cations tend to protrude outside the surface in all systems studied. However, the presence of metals generally increases the amount of bistriflimide at the vacuum/liquid interface.

  17. Contact angles and wettability of ionic liquids on polar and non-polar surfaces.

    PubMed

    Pereira, Matheus M; Kurnia, Kiki A; Sousa, Filipa L; Silva, Nuno J O; Lopes-da-Silva, José A; Coutinho, João A P; Freire, Mara G

    2015-12-21

    Many applications involving ionic liquids (ILs) require the knowledge of their interfacial behaviour, such as wettability and adhesion. In this context, herein, two approaches were combined aiming at understanding the impact of the IL chemical structures on their wettability on both polar and non-polar surfaces, namely: (i) the experimental determination of the contact angles of a broad range of ILs (covering a wide number of anions of variable polarity, cations, and cation alkyl side chain lengths) on polar and non-polar solid substrates (glass, Al-plate, and poly-(tetrafluoroethylene) (PTFE)); and (ii) the correlation of the experimental contact angles with the cation-anion pair interaction energies generated by the Conductor-like Screening Model for Real Solvents (COSMO-RS). The combined results reveal that the hydrogen-bond basicity of ILs, and thus the IL anion, plays a major role through their wettability on both polar and non-polar surfaces. The increase of the IL hydrogen-bond accepting ability leads to an improved wettability of more polar surfaces (lower contact angles) while the opposite trend is observed on non-polar surfaces. The cation nature and alkyl side chain lengths have however a smaller impact on the wetting ability of ILs. Linear correlations were found between the experimental contact angles and the cation-anion hydrogen-bonding and cation ring energies, estimated using COSMO-RS, suggesting that these features primarily control the wetting ability of ILs. Furthermore, two-descriptor correlations are proposed here to predict the contact angles of a wide variety of ILs on glass, Al-plate, and PTFE surfaces. A new extended list is provided for the contact angles of ILs on three surfaces, which can be used as a priori information to choose appropriate ILs before a given application. PMID:26554705

  18. Interaction of Ionic Liquids with Lipid Biomembrane: Implication from Supramolecular Assembly to Cytotoxicity

    NASA Astrophysics Data System (ADS)

    Jing, Benxin; Lan, Nan; Zhu, Y. Elaine

    2013-03-01

    An explosion in the research activities using ionic liquids (ILs) as new ``green'' chemicals in several chemical and biomedical processes has resulted in the urgent need to understand their impact in term of their transport and toxicity towards aquatic organisms. Though a few experimental toxicology studies have reported that some ionic liquids are toxic with increased hydrophobicity of ILs while others are not, our understanding of the molecular level mechanism of IL toxicity remains poorly understood. In this talk, we will discuss our recent study of the interaction of ionic liquids with model cell membranes. We have found that the ILs could induce morphological change of lipid bilayers when a critical concentration is exceeded, leading to the swelling and tube-like formation of lipid bilayers. The critical concentration shows a strong dependence on the length of hydrocarbon tails and hydrophobic counterions. By SAXS, Langmuir-Blodgett (LB) and fluorescence microscopic measurement, we have confirmed that tube-like lipid complexes result from the insertion of ILs with long hydrocarbon chains to minimize the hydrophobic interaction with aqueous media. This finding could give insight to the modification and adoption of ILs for the engineering of micro-organisms.

  19. 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

  20. Preparation and characterization of ultrathin dual-layer ionic liquid lubrication film assembled on silica surfaces.

    PubMed

    Pu, Jibin; Wang, Liping; Mo, Yufei; Xue, Qunji

    2011-02-15

    A novel ultrathin dual-layer film, which contained both bonded and mobile phases in ionic liquids (ILs) layer, was fabricated successfully on a silicon substrate modified by a self-assembled monolayer (SAM). The formation and surface properties of the films were analyzed using ellipsometer, water contact angle meter, attenuated total reflectance Fourier transform infrared spectroscopy, multi-functional X-ray photoelectron spectroscopy, and atomic force microscope. Meanwhile, the adhesive and nanotribological behaviors of the films were evaluated by a homemade colloidal probe. A ball-on-plate tribometer was used to evaluate the microtribological performances of the films. Compared with the single-layer ILs film deposited directly on the silicon surface, the as-prepared dual-layer film shows the improved tribological properties, which is attributed to the special chemical structure and outstanding physical properties of the dual-layer film, i.e., the strong adhesion between bonded phase of ILs and silicon substrate via the chemical bonding with SAM, the interlinked hydrogen bonds among the molecules, and two-phase structure composed of steady bonded phase with load-carrying capacity and flowable mobile phase with self-replenishment property. PMID:21111428

  1. Phenomenological Transition of an Aluminum Surface in an Ionic Liquid and Its Beneficial Implementation in Batteries.

    PubMed

    Shvartsev, B; Gelman, D; Amram, D; Ein-Eli, Y

    2015-12-29

    Aluminum (Al) electrochemical dissolution in organic nonaqueous media and room temperature ionic liquids (RTILs) is partially hampered by the presence of a native oxide. In this work, Al activation in EMIm(HF)2.3F RTIL is reported. It was confirmed that as a result of the interaction of Al with the RTIL, a new film is formed instead of the pristine oxide layer. Aluminum surface modifications result in a transformation from a passive state to the active behavior of the metal. This was confirmed via the employment of electrochemical methods and characterization by XPS, AFM, and TEM. It was shown that the pristine oxide surface film dissolves in EMIm(HF)2.3F, allowing an Al-O-F layer to be formed instead. This newly built up layer dramatically restricts Al corrosion while enabling high rates of Al anodic dissolution. These beneficial features allow the implementation of Al as an anode in advanced portable power sources, such as aluminum-air batteries. PMID:26636468

  2. Anisotropic surface roughness enhances the bending response of ionic polymer-metal composite (IPMC) artificial muscles

    NASA Astrophysics Data System (ADS)

    Stoimenov, Boyko L.; Rossiter, Jonathan M.; Mukai, Toshiharu

    2007-01-01

    Demands from the fields of bio-medical engineering and biologically-inspired robotics motivate a growing interest in actuators with properties similar to biological muscle, including ionic polymer-metal composites (IPMC), the focus of this study. IPMC actuators consist of an ion-conductive polymer membrane, coated with thin metal electrodes on both sides and bend when voltage is applied. Some of the advantages of IPMC actuators are their softness, lack of moving parts, easy miniaturization, light weight and low actuation voltage. When used in bio-mimetic robotic applications, such as a snake-like swimming robot, locomotion speed can be improved by increasing the bending amplitude. However, it cannot be improved much by increasing the driving voltage, because of water electrolysis. To enhance the bending response of IPMCs we created a "preferred" bending direction by anisotropic surface modification. Introduction of anisotropic roughness with grooves across the length of the actuator improved the bending response by a factor of 2.1. Artificially introduced cracks on the electrodes in direction, in which natural cracks form by bending, improved bending response by a factor of 1.6. Anisotropic surface modification is an effective method to enhance the bending response of IPMC actuators and does not compromise their rigidity under loads perpendicular to the bending plane.

  3. 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

  4. 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

    2015-10-01

    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. PMID:26307480

  5. 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

  6. A novel urea-functionalized surface-confined octadecylimidazolium ionic liquid silica stationary phase for reversed-phase liquid chromatography.

    PubMed

    Zhang, Mingliang; Tan, Ting; Li, Zhan; Gu, Tongnian; Chen, Jia; Qiu, Hongdeng

    2014-10-24

    One-pot synthesis of surface-confined ionic liquid functionalized silica spheres was proposed using N-(3-aminopropyl)imidazole, γ-isopropyltriethoxysilane and 1-bromooctadecane as starting materials. The surface modification of the silica spheres was successful with a high surface density of octadecylimidazolium, enabling the utilization of this new urea-functionalized ionic liquid-grafted silica material as stationary phase for high-performance liquid chromatography in reversed-phase mode. The long aliphatic chain combined with the multiple polar group embedded in the ligands imparted the new stationary phase fine selectivity towards PAH isomers and polar aromatics and higher affinity for phenolic compounds. The unique features of the new material, especially the effect of the urea group on the retention were elucidated by mathematic modeling. PMID:25249489

  7. Stimuli-responsive surface localized ionic cluster (SLICs) formation from nonspherical colloidal particles.

    PubMed

    Lestage, David J; Urban, Marek W

    2005-07-19

    Structural features of phospholipids provide a unique opportunity for utilizing these amphiphilic species to stabilize the synthesis of colloidal dispersion particles by controlling concentration levels relative to dispersion synthesis components. 1,2-Bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine (DCPC) phospholipid was utilized as cosurfactant in the synthesis of sodium dioctyl sulfosuccinate (SDOSS) stabilized methyl methacrylate/n-butyl acrylate (MMA/nBA) colloidal dispersions. Aqueous dispersions containing various concentration levels of DCPC result in the formation of cocklebur particle morphologies, and when prepared in the presence of Ca2+ and annealed at various temperatures, stimuli-responsive behaviors of coalesced films were elucidated. The formation of surface localized ionic clusters (SLICs) at the film-air (F-A) and film-substrate (F-S) interfaces is shown to be responsive to concentration levels of DCPC, Ca2+/DCPC ratios, and temperature. These studies show that it is possible to control stratification and mobility to the F-A and F-S interfaces during and after coalescence. Using attenuated total reflectance Fourier transform infrared (ATR-FTIR) and internal reflection infrared imaging (IRIRI) spectroscopies, molecular entities responsible for SLIC formation were determined. These studies also show that stimuli-responsive behaviors during film formation can be controlled by colloidal solution morphologies and synergistic interactions of individual components. PMID:16008384

  8. Ionic liquid activated Bacillus subtilis lipase A variants through cooperative surface substitutions.

    PubMed

    Zhao, Jing; Jia, Ning; Jaeger, Karl-Erich; Bocola, Marco; Schwaneberg, Ulrich

    2015-10-01

    The interest in performing enzyme-catalyzed reactions in amphiphilic systems, e.g., imidazolium-based ionic liquids (ILs) or surfactants, has been increased over the past decades. Directed protein evolution has been successful in tailoring enzymes for desired properties. Herein, nine IL-resistant Bacillus subtilis lipase A variants, particularly an IL-activated variant M1 (M134N/N138S/L140S), were identified by directed evolution. For instance, variant M2 (M134R/L140S) showed almost doubled specific activity (16.9 vs. 9.4 U/mg) and resistance (233% vs. 111%) at 9 vol% 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4 mim][TfO]) compared with wild-type. The specific activities and resistance of purified individual single and double variants have been studied in five different IL-aqueous mixtures. The re-activation of lipase variant M1 (not wild-type) at high IL concentration was attributed to the cooperative effect of three surface substitutions (M134N, N138S, L140S) near the substrate-binding cleft. The presence of IL/substrate clusters under assay conditions was likely related to the re-activation effect. This study provides first example of IL-activated lipase variant generated by protein engineering, and helps to better understand the protein-IL interaction. PMID:25899108

  9. Identification of helicity-dependent photocurrents from topological surface states in Bi2Se3 gated by ionic liquid.

    PubMed

    Duan, Junxi; Tang, Ning; He, Xin; Yan, Yuan; Zhang, Shan; Qin, Xudong; Wang, Xinqiang; Yang, Xuelin; Xu, Fujun; Chen, Yonghai; Ge, Weikun; Shen, Bo

    2014-01-01

    Dirac-like surface states on surfaces of topological insulators have a chiral spin structure with spin locked to momentum, which is interesting in physics and may also have important applications in spintronics. In this work, by measuring the tunable helicity-dependent photocurrent (HDP), we present an identification of the HDP from the Dirac-like surface states at room temperature. It turns out that the total HDP has two components, one from the Dirac-like surface states, and the other from the surface accumulation layer. These two components have opposite directions. The clear gate tuning of the electron density as well as the HDP signal indicates that the surface band bending and resulted surface accumulation are successfully modulated by the applied ionic liquid gate, which provides a promising way to the study of the Dirac-like surface states and also potential applications in spintronic devices. PMID:24809330

  10. Ionic liquid lubrication: influence of ion structure, surface potential and sliding velocity.

    PubMed

    Li, Hua; Rutland, Mark W; Atkin, Rob

    2013-09-21

    Colloid probe atomic force microscopy (AFM) has been employed to investigate the nanotribology of the ionic liquid (IL)-Au(111) interface. Data is presented for four ILs, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIM] FAP), 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([BMIM] FAP), 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM] FAP) and 1-butyl-3-methylimidazolium iodide ([BMIM] I), at different Au(111) surface potentials. Lateral forces vary as a function of applied surface potential and ion structure because the composition of the confined ion layer changes from cation-enriched (at negative potentials) to mixed (at 0 V), and to anion-enriched (at positive potentials). ILs with FAP(-) anions all exhibit similar nanotribology: low friction at negative potentials and higher friction at positive potentials. [BMIM] I displays the opposite behaviour, as an I(-) anion-enriched layer is more lubricating than either the [BMIM](+) or FAP(-) layers. The effect of cation charged group (charge-delocalised versus charged-localised) was investigated by comparing [BMIM] FAP with 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py(1,4)] FAP). [BMIM] FAP is less lubricating at negative potentials, but more lubricating at positive potentials. This indicated that even at positive potentials the cation concentration in the boundary layer is sufficiently high to influence lubricity. The influence of sliding velocity on lateral force was investigated for the [EMIM] FAP-Au(111) system. At neutral potentials the behaviour is consistent with a discontinuous sliding process. When a positive or negative potential bias is applied, this effect is less pronounced as the colloid probe slides along a better defined ion plane. PMID:23836254

  11. 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. PMID:25890438

  12. Electromechanical model for a self-sensing ionic polymer-metal composite actuating device with patterned surface electrodes

    NASA Astrophysics Data System (ADS)

    Kruusamäe, Karl; Brunetto, Paola; Punning, Andres; Kodu, Margus; Jaaniso, Raivo; Graziani, Salvatore; Fortuna, Luigi; Aabloo, Alvo

    2011-12-01

    This paper further discusses a concept of creating a self-sensing ionic polymer-metal composite (IPMC) actuating device with patterned surface electrodes where the actuator and sensor elements are separated by a grounded shielding electrode. Different patterning methods are discussed and compared in detail; the presented experimental data give an understanding of the qualitative properties of the patterns created. Finally, an electromechanical model of the device is proposed and validated.

  13. Surface osteosarcoma: Clinical features and therapeutic implications

    PubMed Central

    Nouri, H.; Ben Maitigue, M.; Abid, L.; Nouri, N.; Abdelkader, A.; Bouaziz, M.; Mestiri, M.

    2015-01-01

    Introduction Surface osteosarcoma are rare variant of osteosarcoma that include parosteal osteosarcoma, periosteal osteosarcoma and high grade surface osteosarcoma. These lesions have different clinical presentation and biological behavior compared to conventional osteosarcoma, and hence need to be managed differently. Goal The aim of this study is to analyze the clinico-pathological features and outcome of a series of surface osteosarcoma in an attempt to define the adequate treatment of this rare entity. Patient and method It is a retrospective and bicentric study of 18 surface osteosarcoma that were seen at the KASSAB’s Institute and SAHLOUL Hospital from 2006 to 2013. The authors reviewed the clinical and radiologic features, histologic sections, treatments, and outcomes in this group of patients. Results Seven patients were male (38.9%) and 11 were female (61.1%) with mean age of 25 years (range from 16 to 55 years). Eleven lesions were in the femur and 7 in the tibia. We identified 11 parosteal osteosarcoma (six of them were dedifferentiated), 3 periosteal osteosarcoma and 4 high grade surface osteosarcoma. Six patients had neoadjuvant chemotherapy and all lesions had surgical resection. Margins were wide in 15 cases and intra lesional in 3 cases. Histological response to chemotherapy was poor in all cases. The mean follow up was 34.5 months. Six patients (33.3%) presented local recurrence and 8 patients (44.4%) presented lung metastases. Six patients (33.3%) died from the disease after a mean follow up of 12 months (6–30 months); all of them had high grade lesions. Conclusion Histological grade of malignancy is the main point to assess in surface osteosarcoma since it determines treatment and prognosis. Low grade lesions should be treated by wide resection, while high grade lesions need more aggressive surgical approach associated to post operative chemotherapy. PMID:26730360

  14. Effect of Ions and Ionic Strength on Surface Plasmon Absorption of Single Gold Nanowires.

    PubMed

    Baral, Susil; Green, Andrew J; Richardson, Hugh H

    2016-06-28

    The local temperature change from a single optically excited gold nanowire, lithographically prepared on Al0.94Ga0.06N embedded with Er(3+) ions, is measured in air, pure water, and various concentrations of aqueous solutions of ionic solutes of NaCl, Na2SO4, and MgSO4. The absorption cross section of the nanowire under pure water (2.25 × 10(-14) m(2)) and different solution ionic strength is measured from the slopes of temperature change versus laser intensity plots. Addition of charges into the solution decreases the amount of heat generated during optical excitation of the gold nanostructures because the absorption cross section of the gold nanowire is attenuated. A Langmuir-type behavior of the absorption cross section with ionic strength is observed that is identified with an increase in the occupancy of screened interfacial charges. The absorption cross section of the nanowire decreases with ionic strength until a saturation value of 9 × 10(-15) m(2), where saturation in the occupancy of screened interfacial charge occurs. Dynamic measurements of temperature for a single gold nanowire immersed in a microchannel flow cell show a sharp and fast temperature drop for the flow of ionic solution compared to the pure (deionized) water, suggesting that the technique can be developed as a sensor probe to detect the presence of ions in solution. PMID:27215955

  15. 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.

  16. 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.

  17. 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

  18. 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. PMID:21643581

  19. Release and formation of surface-localized ionic clusters (SLICs) into phospholipid rafts from colloidal solutions during coalescence.

    PubMed

    Lestage, David J; Urban, Marek W

    2005-03-15

    Stimuli-responsive behavior of phospholipids in the presence of ionic surfactants utilized in synthesis of MMA/nBA colloidal particles was investigated. Utilizing 1-myristoyl-2-hydroxy-sn-glycero-phosphocholine (MHPC) phospholipid, and sodium dioctyl sulfosuccinate (SDOSS) surfactant as dispersing media in H(2)O, narrow unimodal particle size distributions of methyl methacrylate (MMA)/n-butyl acrylate (nBA) copolymers were synthesized. The particle diameters were 154 nm when a SDOSS/MHPC mixture was used and 161 nm using MHPC as the only surface-stabilizing species. When such colloidal dispersions are exposed to 1.7, 3.3, and 6.7 mM aqueous CaCl(2) and KCl electrolyte solutions, surface-localized ionic clusters are generated at the film-air interface that may serve as lipid rafts composed of crystalline phases of MHPC deposited on poly(MMA)/nBA films. These studies illustrate that it is possible to control release and morphology developments of surface phospholipid rafts on artificial surfaces. PMID:15752001

  20. Adhesion of CO2 on hydrated mineral surfaces and its implications to geologic carbon sequestration

    NASA Astrophysics Data System (ADS)

    Wang, S.; Clarens, A. F.; Tao, Z.; Persily, S. M.

    2013-12-01

    Most mineral surfaces are water wetting, which has important implications for the transport of non-aqueous phase liquids, such as CO2, through porous media. In this work, contact angle experiments were carried out wherein unusual wetting behavior was observed between mineral surfaces and liquid or supercritical CO2 under certain geochemical conditions. This behavior can be understood in the context of adhesion between the CO2 and the mineral surface. When adhesion occurs, the wettability characteristics of the surfaces are significantly altered. More importantly, the CO2 exhibits a strong affinity for the surface and is highly resistant to shear forces in the aqueous phase. A static pendant drop method was used on a variety of polished mineral surfaces to measure contact angles. The composition of the aqueous phase (e.g., pH, ionic strength) and the characteristics of the mineral surface (e.g., composition, roughness), were evaluated to understand their impact on the prevalence of adhesion. Pressure and temperature conditions were selected to represent those that would be prevalent in geologic carbon sequestration (GCS) or during leakage from target repositories. Adhesion was widely observed on phlogopite mica, silica, and calcite surfaces with roughness on the order of ~10 nanometers. CO2 exhibited no adhesion on mineral surfaces with higher roughness (e.g., quartz). On smoother surfaces, the CO2 is thought to have more effective contact area with the mineral, enabling the weak van der Waals forces that drive most adhesion processes. Brine chemistry also had an important role in controlling CO2 adhesion. Increases in CO2 partial pressure and ionic strength both increased the incidence of adhesion. The addition of strong acid or strong base permanently inhibited the development of adhesion. These results suggest that the development of adhesion between the CO2 and the mineral surface is dependent on the integrity and thickness of the hydration layer between the CO2

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

    PubMed

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

    2015-03-16

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

  2. 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.

  3. Surface modification of compressor steels using thermally assisted ionic diffusion in the titanium plasma of a vacuum arc discharge

    NASA Astrophysics Data System (ADS)

    Muboyadzhyan, S. A.; Azarovskii, E. N.

    2015-11-01

    The thermally stimulated ionic diffusion (ionic modification) of titanium ions at the surfaces of EP866 and EI961 compressor steels is considered in the plasma of the high-current vacuum-arc discharge (VAD) in an ion-plasma MAP-3 plant. The dependences of the sample temperature in the sputtering chamber of the ion-plasma MAP-3 plant and the rate of specific change of the sample mass on the bias voltage at a VAD current of 300 A are obtained. The elemental composition of the surface layers of the samples subjected to ion treatment is studied. It is shown that, at a VAD current of 300 A and a bias voltage up to 400 V, the compressor steel sample temperature does not exceed 440°C and the inversion voltage, which determines the transition from coating condensation to ion etching of a substrate, is ~360 V for EP866 steel and ~390 V for EI961 steel. The corrosion resistance of the compressor steels modified at a VAD current of 300 A is investigated.

  4. Decay behavior of screened electrostatic surface forces in ionic liquids: the vital role of non-local electrostatics.

    PubMed

    Kjellander, Roland

    2016-07-28

    Screened electrostatic surface forces, also called double layer forces, between surfaces in ionic liquids can, depending on the circumstances, decay in an exponentially damped, oscillatory manner or in a plain exponential way (the latter as in dilute electrolyte solutions where ion-ion correlations are very weak). The occurrence of both of these behaviors in dense ionic liquids, where ion-ion correlations are very strong, is analyzed in the current work using exact statistical mechanics formulated in a manner that is physically transparent. A vital ingredient in understanding the decay behaviors is the fact that electrostatics in dense electrolytes have a non-local nature caused by the strong correlations. It is shown that the effects of non-locality can be elucidated by a remarkably simple, general expression for the decay parameter κ that replaces the classical expression for the inverse Debye length κDH of the Debye-Hückel (DH) and non-linear Poisson-Boltzmann approximations. This exact expression is valid for both the plain exponential and the oscillatory cases. It shows how strong correlations can give rise to plain exponential decay with a long decay length. Such a decay can arise from anion-cation associations of various kinds, for instance transient ion pairing or association caused by many-body correlations; ion pairing is a possibility but not a necessity for this to occur. Theoretical analysis is done for systems consisting of ions with an arbitrary shape and internal charge density and immersed planar walls with arbitrary internal charge distribution and any short-range ion-surface interaction. The screened electrostatic surface force between two walls is at large separations proportional to the product of effective surface charge densities of each wall. For the oscillatory case, each wall contributes with a phase shift to the oscillations of the interaction. PMID:27356099

  5. Surface modification of PCC with guar gum using organic titanium ionic crosslinking agent and its application as papermaking filler.

    PubMed

    Xie, Wei; Song, Zhanqian; Liu, Zhenhua; Qian, Xueren

    2016-10-01

    Utilized the principles of guar gum (GG) gelation and crosslinking, a novel modified precipitated calcium carbonate (MPCC) papermaking filler was prepared by using organic titanium (OT) ionic crosslinking agent. The MPCC was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). FTIR results confirmed that GG had been coated on the surface of PCC particles, XPS analysis indicated the presence of titanium atoms on MPCC particles, and SEM and XRD results showed that the modification treatment did change the surface morphology and crystal structure of PCC particles. The handsheet testing results showed that the strength properties of handsheets were obviously improved when using MPCC as papermaking filler, and the optimum preparation conditions of MPCC were obtained. This research suggests that the GG modified PCC by using OT as crosslinking agent can be used to manufacture high filler content paper products. PMID:27312620

  6. Influence of Water on the Interfacial Nanostructure and Wetting of [Rmim][NTf2] Ionic Liquids at Mica Surfaces.

    PubMed

    Wang, Zhantao; Li, Hua; Atkin, Rob; Priest, Craig

    2016-09-01

    The effect of water concentration on the interfacial nanostructure and wetting behavior of a family of ionic liquids (ILs), 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, [Rmim][NTf2], at the surface of mica was investigated by contact angle measurement and atomic force microscopy (AFM). AFM reveals that interfacial layers of ILs observed at the surface of mica for "dry" ILs are not present for water-saturated ILs. The interaction of the IL ions of [Rmim][NTf2] with water molecules through hydrogen bonding is suspected to disrupt IL ion layering and precursor film growth on mica. Without the IL precursor film, contact angle relaxation of "wet" ILs on mica is less significant and ambient vapor adsorption becomes more important in determining the macroscopic wetting behavior. PMID:27486675

  7. Structural and metal-insulator transitions in ionic liquid-gated Ca3Ru2O7 surface

    NASA Astrophysics Data System (ADS)

    Puls, Conor P.; Cai, Xinxin; Zhang, Yuhe; Peng, Jin; Mao, Zhiqiang; Liu, Ying

    2014-06-01

    We report the fabrication and measurements of ionic liquid gated Hall bar devices prepared on the ab face of a thin Ca3Ru2O7 flake exfoliated from bulk single crystals that were grown by a floating zone method. The devices were categorized into two types: those with their electrical transport properties dominated by c-axis transport in type A or that of the in-plane in type B devices. Bulk physical phenomena, including a magnetic transition near 56 K, a structural and metal-insulator transition at a slightly lower temperature, as well as the emergence of a highly unusual metallic state as the temperature is further lowered, were found in both types of devices. However, the Shubnikov-de Haas oscillations were found in type A but not type B devices, most likely due to enhanced disorder on the flake surface. Finally, the ionic liquid gating of a type B device revealed a shift in critical temperature of the structural and metal-insulator transition, suggesting that this transition is tunable by the electric field effect.

  8. 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. PMID:24835511

  9. Spatially resolved electrochemistry in ionic liquids: surface structure effects on triiodide reduction at platinum electrodes.

    PubMed

    Aaronson, Barak D B; Lai, Stanley C S; Unwin, Patrick R

    2014-02-25

    Understanding the relationship between electrochemical activity and electrode structure is vital for improving the efficiency of dye-sensitized solar cells. Here, the reduction of triiodide to iodide in 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) room temperature ionic liquid (RTIL) is investigated on polycrystalline platinum using scanning electrochemical cell microscopy (SECCM) and correlated to the crystallographic orientation from electron backscatter diffraction (EBSD). Although the rate determining step in all grains was the first electron transfer, significant grain-dependent variations in activity were revealed, with grains with a dominant (110) crystallographic character exhibiting higher catalytic activity compared to those with a major (100) orientation. The SECCM technique is demonstrated to resolve heterogeneity in activity, highlighting that methods incorporating polycrystalline electrodes miss vital details for understanding and optimizing electrocatalysts. An additional advantage of the SECCM over single-crystal techniques is its ability to probe high index facets. PMID:24479903

  10. Coherent excitations at the neutral-ionic transition: Femtosecond dynamics on diabatic potential energy surfaces

    NASA Astrophysics Data System (ADS)

    Cavatorta, Lorenzo; Painelli, Anna; Soos, Zoltán G.

    2015-05-01

    Upon decreasing temperature (Tc˜81 K) tetrathiafulvalene-chloranil (TTF-CA) undergoes a discontinuous phase transition from a neutral regular stack to an ionic dimerized stack. The same system may undergo a phase transition upon photoexcitation. We discuss the early time (<3 ps) dynamics following ultrafast (<20 fs) excitation of TTF-CA crystals either near or far from the neutral-ionic transition (T ˜90 and 260 K, respectively). Adopting a modified Hubbard model with linear coupling of electrons to a zone-center lattice (dimerization) phonon and to a molecular vibration, both assumed to be harmonic, we are able to quantitatively reproduce coherent oscillations recently reported for this system [H. Uemura and H. Okamoto, Phys. Rev. Lett. 105, 258302 (2010), 10.1103/PhysRevLett.105.258302; T. Miyamoto, H. Uemura, and H. Okamoto, J. Phys. Soc. Jpn. 81, 073703 (2012), 10.1143/JPSJ.81.073703]. We demonstrate that the microscopic model with parameters optimized for ground state properties of TTF-CA also applies to the coherent dynamics following photoexcitation. The modulation of the frequency of coherent molecular oscillations at the frequency of the lattice phonon emerges naturally as due to strong anharmonic coupling between the two harmonic vibrational degrees of freedom through coupling to delocalized electrons. Detailed comparison with experiment validates the model and sheds light on other aspects of photoinduced dynamics, including the almost instantaneous transfer of several electrons upon absorption of a single photon, as due to a cooperative effect of electronic correlations and molecular vibrations.

  11. Effect of π-π+ stacking on the layering of ionic liquids confined to an amorphous carbon surface.

    PubMed

    Gong, Xiao; Kozbial, Andrew; Rose, Franck; Li, Lei

    2015-04-01

    In the current paper, AFM studies were conducted on nanometer-thick ionic liquids (ILs) confined to an amorphous carbon (AC) surface, which is critical to the design of the next-generation media lubricant for hard disk drives (HDDs). The results indicated that the existence of the delocalized ring in the cation is critical to layering of ILs. Extended layering was observed only when there is imidazolium ring in the cation. When the imidazolium ring is replaced by an aliphatic moiety, "drop-on-layer" (dewetting) structure was observed. On the basis of the experimental results, we proposed that π-π+ stacking between sp(2) carbon in the AC and the imidazolium cation in the ILs is the key to the extended layering of ILs at the ILs/AC interface. PMID:25808335

  12. 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.

  13. 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...

  14. 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…

  15. 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

  16. 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.

  17. X-ray reflectometry studies on the effect of water on the surface structure of [C4mpyr][NTf2] ionic liquid.

    PubMed

    Lauw, Y; Horne, M D; Rodopoulos, T; Webster, N A S; Minofar, B; Nelson, A

    2009-12-28

    The effect of water on the surface structure of 1-butyl-1-methylpyrrolidinium trifluoromethylsulfonylimide [C(4)mpyr][NTf(2)] ionic liquid was investigated using X-ray reflectometry. The measured reflectivity data suggests a significant amount of water is adsorbed at the surface, with the first layer from the gas (nitrogen)-liquid phase boundary mainly occupied by a mixture of cations and water. Beyond the cation + water layer, the scattering length density increases towards the bulk value, indicating a decreasing amount of water and cations, and/or an increasing amount of anions. The orientation of the butyl chain of cation at the phase boundary and the population of water at the surface were described based on results from an independent molecular dynamics (MD) simulation. We show that the presence of water in the ionic liquid has a non-monotonic effect on the overall thickness of the surface. At low water content, the addition of water does not change the surface thickness since water is mainly present in the bulk. As the water content increases, the surface swells before eventually shrinking down close to the solubility limit of water. The non-monotonic surface thickness is used to explain the anomalous trend of surface tension in ionic liquid-water mixtures reported in the literature. PMID:20024422

  18. 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

  19. Low-energy reactive ion scattering as a probe of surface femtochemical reaction: H+ and H- formation on ionic compound surfaces

    NASA Astrophysics Data System (ADS)

    Souda, R.; Suzuki, T.; Kawanowa, H.; Asari, E.

    1999-01-01

    Capture and loss of valence electrons during low-energy (50-500 eV) proton scattering from some alkali-halide surfaces such as LiCl, NaCl, and KF have been investigated in comparison with those from the TiO2(110) and Cs-adsorbed Si(100) surfaces. The primary H+ ion survives neutralization when scattered from the highly ionized target species existing on the surface. For H- ion formation, a close atomic encounter with individual target ions is found to be important; the H- ion is formed more efficiently on the cationic site than on the anionic site despite the fact that the valence electron is spacially localized on the latter. This is because the charge state of scattered hydrogen is determined during a transient chemisorption state and amphoteric hydrogen tends to be coordinated negatively (positively) on the cationic site (the anionic site). The final charge state of scattered hydrogen is fixed at a certain bond-breaking distance (˜5.0 a.u.) from the surface where the well-defined atomic orbital of hydrogen evolves. The competing nonlocal resonance tunneling is suppressed at the ionic-compound surfaces due to the existence of a large band gap, so that hydrogen is scattered without losing the memory of such a transient chemisorption state.

  20. Aggregation Behavior of Imidazolium-Based Surface-Active Ionic Liquids with Photoresponsive Cinnamate Counterions in the Aqueous Solution.

    PubMed

    Bi, Yanhui; Zhao, Liuchen; Hu, Qiongzheng; Gao, Yan'an; Yu, Li

    2015-11-24

    Two imidazolium-based surface active ionic liquids (SAILs) with photoresponsive cinnamate aromatic counterions, viz. 1-dodecyl-3-methylimidazolium cinnamate ([C12mim][CA]) and 1-dodecyl-3-methylimidazolium para-hydroxy-cinnamate ([C12mim][PCA]), were newly synthesized, and their self-assembly behaviors in aqueous solutions were systematically explored. Results of surface tension and conductivity measurements show that both [C12mim][CA] and [C12mim][PCA] display a superior surface activity in aqueous solutions compared to the common imidazolium-based SAIL, 1-dodecyl-3-methylimidazolium bromide (C12mimBr), which implies the incorporation of cinnamate aromatic counterions can promote the micellar formation. Furthermore, [C12mim][CA] shows higher surface activity due to the higher hydrophobicity of its counterion in comparison to [C12mim][PCA] that has a hydroxyl group. Both hexagonal liquid-crystalline phase (H1) and cubic liquid-crystalline phase (V2) were constructed in the [C12mim][CA] aqueous solutions. In contrast, the [C12mim][PCA]/H2O system only exhibits a single hexagonal liquid-crystalline phase (H1) in a broad concentration region. These lyotropic liquid crystal (LLC) phases were comprehensively characterized by polarized optical microscopy (POM), small-angle X-ray scattering (SAXS), and rheometer. Investigation on the temperature-dependent self-assembly nanostructures demonstrates that the higher temperature leads to a looser arrangement. Under UV irradiation, trans-cis photoisomerization of the phenylalkene group results in inferior surface activity of the prepared SAILs in aqueous solution with higher cmc values. Moreover, UV light irradiation induces obvious change of the structural parameters without altering the LLC phases. This work is expected to enrich the investigations of phase behaviors formed in SAILs systems and receive particular attention due to their unique properties and potential applications in drug delivery, biochemistry, materials

  1. 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.

  2. Ionic liquid-aqueous solution ultrasonic-assisted extraction of three kinds of alkaloids from Phellodendron amurense Rupr and optimize conditions use response surface.

    PubMed

    Wang, Wenchao; Li, Qingyong; Liu, Yuhui; Chen, Binbin

    2015-05-01

    In this paper, we chose diffident kinds of ionic liquids to optimal selection an optimal one to extract alkaloids from Phellodendron amurense Rupr. Four ionic liquids with diffident carbon chains or anions have been investigated and 1-butyl-3-methylimidazolium bromide with best productivity. Then, selections have been optimized in different conditions, including concentration of ionic liquid, time for ultrasonic treatment, ultrasonic power and solid-liquid ratio. Moreover, three conditions have been comprehensively assessment by response surface methodology, the optimal conditions were determined as follows ultrasonic power 100 W, extraction time 75 min and ratio of solvent to raw material 1:14. Under these conditions, the yield% (MIX) was 106.7% (extracted by heat reflux being defined 100%). Comparing with other methods, the advantages are saving conserving, time saving, high yield% and especially pollution-free. PMID:25443277

  3. 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

    2009-11-01

    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. PMID:19863141

  4. SURFACE COMPLEXATION OF ACTINIDES WITH IRON OXIDES: IMPLICATIONS FOR RADIONUCLIDE TRANSPORT IN NEAR-SURFACE AQUIFERS

    SciTech Connect

    J.L. Jerden Jr.; A.J. Kropf; Y. Tsai

    2005-08-25

    The surface complexation of actinides with iron oxides plays a key role in actinide transport and retardation in geosphere-biosphere systems. The development of accurate actinide transport models therefore requires a mechanistic understanding of surface complexation reactions (i.e. knowledge of chemical speciation at mineral/fluid interfaces). Iron oxides are particularly important actinide sorbents due to their pH dependent surface charges, relatively high surface areas and ubiquity in oxic and suboxic near-surface systems. In this paper we present results from field and laboratory investigations that elucidate the mechanisms involved in binding uranium and neptunium to iron oxide mineral substrates in near neutral groundwaters. The field study involved sampling and characterizing uranium-bearing groundwaters and solids from a saprolite aquifer overlying an unmined uranium deposit in the Virginia Piedmont. The groundwaters were analyzed by inductively coupled mass spectrometry and ion chromatography and the aquifer solids were analyzed by electron microprobe. The laboratory study involved a series of batch sorption tests in which U(VI) and Np(V) were reacted with goethite, hematite and magnetite in simulated groundwaters. The pH, ionic strength, aging time, and sorbent/sorbate ratios were varied in these experiments. The oxidation state and coordination environment of neptunium in solutions and sorbents from the batch tests were characterized by X-ray absorption spectroscopy (XAS) at the Advanced Photon Source, Argonne National Laboratory. Results from this work indicate that, in oxidizing near-surface aquifers, the dissolved concentration of uranium may be limited to less than 30 parts per billion due to uptake by iron oxide mineral coatings and the precipitation of sparingly soluble U(VI) phosphate minerals. Results from the batch adsorption tests showed that, in near neutral groundwaters, a significant fraction of the uranium and neptunium adsorbed as strongly

  5. Membrane interactions in nerve myelin. I. Determination of surface charge from effects of pH and ionic strength on period.

    PubMed Central

    Inouye, H.; Kirschner, D. A.

    1988-01-01

    We have used x-ray diffraction to study the interactions between myelin membranes in the sciatic nerve (PNS) and optic nerve (CNS) as a function of pH (2-10) and ionic strength (0-0.18). The period of myelin was found to change in a systematic manner with pH and ionic strength. PNS periods ranged from 165 to 250 A or more, while CNS periods ranged from 150 to 230 A. The native periods were observed only near physiological ionic strength at neutral or alkaline pH. The smallest periods were observed in the pH range 2.5-4 for PNS myelin and pH 2.5-5 for CNS myelin. The minimum period was also observed for PNS myelin after prolonged incubation in distilled water. At pH 4, within these acidic pH ranges, myelin period increased slightly with ionic strength; however, above these ranges, the period increased with pH and decreased with ionic strength. Electron density profiles calculated at different pH and ionic strength showed that the major structural alteration underlying the changes in period was in the width of the aqueous space at the extracellular apposition of membranes; the width of the cytoplasmic space was virtually constant. Assuming that the equilibrium myelin periods are determined by a balance of nonspecific forces/i.e., the electrostatic repulsion force and the van der Walls attractive force, as well as the short-range repulsion force (hydration force, or steric stabilization), then values in the period-dependency curve can be used to define the isoelectric pH and exclusion length of the membrane. The exclusion length, which is related to the minimum period at isoelectric pH, was used to calculate the electrostatic repulsion force given the other forces. The electrostatic repulsion was then used to calculate the surface potential, which in turn was used to calculate the surface charge density (at different pH and ionic strength). We found the negative surface charge increases with pH at constant ionic strength and with ionic strength at constant pH. We

  6. 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.

  7. 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. PMID:25900279

  8. Polypeptide nanogels with hydrophobic moieties in the cross-linked ionic cores: Synthesis, characterization and implications for anticancer drug delivery

    PubMed Central

    Kim, Jong Oh; Oberoi, Hardeep S.; Desale, Swapnil; Kabanov, Alexander V.; Bronich, Tatiana K.

    2014-01-01

    Polymer nanogels have gained considerable attention as a potential platform for drug delivery applications. Here we describe the design and synthesis of novel polypeptide-based nanogels with hydrophobic moieties in the cross-linked ionic cores. Diblock copolymer, poly(ethylene glycol)-b-poly(L-glutamic acid), hydrophobically modified with L-phenylalanine methyl ester moieties was used for controlled template synthesis of nanogels with small size (ca. 70 nm in diameter) and narrow particle size distribution. Steady-state and time-resolved fluorescence studies using coumarin C153 indicated the existence of hydrophobic domains in the ionic cores of the nanogels. Stable doxorubicin-loaded nanogels were prepared at high drug capacity (30 w/w%). We show that nanogels are enzymatically-degradable leading to accelerated drug release under simulated lysosomal acidic pH. Furthermore, we demonstrate that the nanogel-based formulation of doxorubicin is well tolerated and exhibit an improved antitumor activity compared to a free doxorubicin in an ovarian tumor xenograft mouse model. Our results signify the point to a potential of these biodegradable nanogels as attractive carriers for delivery of chemotherapeutics. PMID:23998716

  9. 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. PMID:20119601

  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 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.

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

    PubMed

    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. PMID:24320388

  12. 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.

  13. 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.

  14. 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. PMID:16971989

  15. 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. PMID:26549624

  16. The formation of carbonic and silicon dioxide structured films through the decomposition of molecules on the surface of ionic crystals under the action of IR femtosecond laser radiation

    NASA Astrophysics Data System (ADS)

    Kompanets, V. O.; Laptev, V. B.; Pigul’skii, S. V.; Ryabov, E. A.; Chekalin, S. V.; Blank, V. D.; Denisov, V. N.; Kravchuk, K. S.; Kulnitskiy, B. A.; Perezhogin, I. A.

    2016-06-01

    This study relates to the formation of carbon and silicon dioxide films that occurs as a result of the decomposition of organic and silicon-containing molecules on the surface of ionic crystals under IR femtosecond laser radiation of moderate intensity (~1011 W cm‑2) without molecular decomposition in the gas phase. We found that transparent graphite oxide films formed in the case of CO2 molecule decomposition.

  17. Changes in zeta potential of imidazolium ionic liquids modified minerals--Implications for determining mechanism of adsorption.

    PubMed

    Markiewicz, Marta; Mrozik, Wojciech; Rezwan, Kurosch; Thöming, Jorg; Hupka, Jan; Jungnickel, Christian

    2013-01-01

    As the amount of industrial processes involving ionic liquids (ILs) increase the question of their environmental fate awaits an answer. Should ILs become a source of pollution they will primarily be found in soils and water. Interaction of imidazolium IL with soils is a complex interplay of many parameters making predicting their fate and mobility a challenging task. In order to shed more light on the mechanism of adsorption in soils we examined the interactions of imidazolium ILs with the major component of soils, namely mineral fraction. Within this work adsorption on kaolinite and quartz was investigated in terms of adsorption isotherms, partition coefficients and changes of zeta potentials of clays modified by ILs aggregates. The zeta potential was found to be dependent on the alkyl chain length of the imidazolium homologues. It can therefore be concluded that although adsorption seems to rely on electrostatic attraction, at least in the initial stage, the hydrophobicity of molecules is just as significant. PMID:23079161

  18. 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. PMID:22608433

  19. Influence of Lithium Solutes on Double-Layer Structure of Ionic Liquids.

    PubMed

    Smith, Alexander M; Perkin, Susan

    2015-12-01

    The ionic liquid-electrode interface has attracted much recent interest owing to its importance for development of energy storage devices; however, the important step of adding electro-active ions is not yet well understood at the molecular level. Using direct force measurements across confined electrolyte films, we study the effect of added lithium-ion solute on the double-layer structure of an ionic liquid electrolyte with molecular resolution. We find anionic clusters involving lithium can persist adjacent to the surfaces, and in many cases, this inhibits direct adsorption of lithium ions to the negative surface. Two apparently similar ionic liquid solvents show diverging properties, with one facilitating and the other preventing direct Li-ion adsorption onto the negative surface. The results have implications for the selection of ionic liquids as electrolytes in lithium-ion batteries. PMID:26580815

  20. Wormlike micelles with photoresponsive viscoelastic behavior formed by surface active ionic liquid/azobenzene derivative mixed solution.

    PubMed

    Bi, Yanhui; Wei, Hongtu; Hu, Qiongzheng; Xu, Wenwen; Gong, Yanjun; Yu, Li

    2015-04-01

    The UV-light-stimulated self-assembly behavior of a surface active ionic liquid (SAIL), 1-hexadecyl-3-methylimidazolium bromide (C16mimBr), with an azobenzene derivative, sodium azobenzene 4-carboxylate (AzoCOONa), was investigated in aqueous solution. The properties and structures of the aggregates, formed at a concentration ratio equal to 2:1 ([C16mimBr]:[AzoCOONa]), were comprehensively characterized by rheometer and cryogenic transmission electron microscopy. Initially, viscoelastic wormlike micelles with a viscosity of 0.65 Pa·s were constructed in the C16mimBr/AzoCOONa system. Upon irradiation by UV light (365 nm), particularly fascinating is that the wormlike micelles become much longer and more entangled, exhibiting a high viscosity of 6.9 Pa·s. This can be attributed to photoisomerization of the AzoCOONa molecule from trans to cis form. It is the first time that, with exposure to UV or visible light, the aggregate type of the photoresponsive system has remained unchanged, with only a change of internal property parameters. The cation-π interaction prevailing over the hydrophobic interaction and electrostatic interaction between C16mimBr and AzoCOONa molecules is supposed to be responsible for this peculiar phase behavior. The wormlike micelles constructed with the SAIL and photosensitive additive exhibit controllable viscoelastic behavior in the photoresponsive process. In addition, the average contour length of wormlike micelles was found to slightly decrease with the increase of temperature. We expect this system will receive particular attention due to its unique properties and potential applications in drug delivery, biochemistry, and materials science, etc. PMID:25763685

  1. 5-Methyl Salicylic Acid-Induced Thermo Responsive Reversible Transition in Surface Active Ionic Liquid Assemblies: A Spectroscopic Approach.

    PubMed

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

    2016-07-19

    This article describes the formation of stable unilamellar vesicles involving surface active ionic liquid (SAIL), 1-hexadecyl-3-methylimidazolium chloride (C16mimCl), and 5-methyl salicylic acid (5mS). Turbidity, dynamic light scattering (DLS), transmission electron microscopy (TEM), and viscosity measurements suggest that C16mimCl containing micellar aggregates are transformed to elongated micelle and finally into vesicular aggregates with the addition of 5mS. Besides, we have also investigated the photophysical aspects of a hydrophobic (coumarin 153, C153) and a hydrophilic molecule (rhodamine 6G (R6G) perchlorate) during 5mS-induced micelle to vesicle transition. The rotational motion of C153 becomes slower, whereas faster motion is observed for R6G during micelle to vesicle transition. Moreover, the fluorescence correlation spectroscopy (FCS) measurements suggest that the translational diffusion of hydrophobic probe becomes slower in C16mimCl-5mS aggregates in comparison to C16mimCl micelle. However, a reverse trend in translational diffusion motion of hydrophilic molecule has been observed in C16mimCl-5mS aggregates. Moreover, we have also found that the C16mimCl-5mS containing vesicles are transformed into micelles upon enhanced temperature, and it is further confirmed by turbidity, DLS measurements that this transition is a reversible one. Finally, temperature-induced rotational motion of C153 and R6G has been monitored in C16mimCl-5mS aggregates to get a complete scenario regarding the temperature-induced vesicle to micelle transition. PMID:27345738

  2. 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

  3. 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…

  4. Effects of ionic strength on the surface tension and nonequilibrium interfacial characteristics of poly(sodium styrenesulfonate)/dodecyltrimethylammonium bromide mixtures.

    PubMed

    Ábrahám, Ágnes; Kardos, Attila; Mezei, Amália; Campbell, Richard A; Varga, Imre

    2014-05-01

    We rationalize the surface tension behavior and nonequilibrium interfacial characteristics of high molecular weight poly(sodium styrenesulfonate)/dodecyltrimethylammonium bromide (NaPSS/DTAB) mixtures with respect to the ionic strength. Excellent agreement is achieved between experimental data and our recent empirical model [Langmuir 2013, 29, 11554], which is based on the lack of colloidal stability of bulk aggregates in the phase separation region and has no free fitting parameters. We show that the size of a surface tension peak positioned at the edge of the phase separation region can be suppressed by the addition of inert electrolyte, which lowers the critical micelle concentration in relation to the phase separation region. Such manipulation of the peak is possible for the 100 ppm NaPSS/DTAB system because there is a high free surfactant concentration in the phase separation region. The close agreement of our model with the experimental data of samples in the phase separation region with respect to the ionic strength indicates that the surface tension behavior can be rationalized in terms of comprehensive precipitation regardless of whether there is a peak or not. The time scale of precipitation for the investigated system is on the order of one month, which emphasizes the need to understand the dynamic changes in the state of bulk aggregation in order to rationalize the surface properties of strongly interacting mixtures; steady state surface properties measured in the interim period will represent samples far from equilibrium. We show also that the surface properties of samples of low ionic strength outside the equilibrium phase separation region can be extreme opposites depending on the sample history, which is attributed to the generation of trapped nonequilibrium states. This work highlights the need to validate the underlying nature of oppositely charged polyelectrolyte/surfactant systems prior to the interpretation of experimental data within an

  5. Taylor cones of ionic liquids from capillary tubes as sources of pure ions: The role of surface tension and electrical conductivity

    NASA Astrophysics Data System (ADS)

    Garoz, D.; Bueno, C.; Larriba, C.; Castro, S.; Romero-Sanz, I.; Fernandez de la Mora, J.; Yoshida, Y.; Saito, G.

    2007-09-01

    The emissions of Taylor cones from a wide range of ionic liquids (ILs) have been tested in vacuo in an attempt to identify what physical properties favor the purely ionic regime (PIR). This regime is well known in the case of Taylor cones of liquid metals. For nonmetallic liquids, it has been previously observed in conventional (capillary tube) electrospray sources at room temperature only for the room temperature molten salt (ionic liquid) EMI -BF4 (EMI =1-ethyl-3-methylimidazolium). A large number of other ILs and their mixtures have been studied here, most of which (but not all) are unable to reach the PIR at room temperature. Based on these results and additional theoretical considerations, strong support is assembled for the notion that the PIR is favored by ILs not only of high electrical conductivity but also of high surface tension. This hypothesis is confirmed by tests with three recently synthesized ILs, EMI -GaCl4, EMI -C(CN)3, and EMI -N(CN)2, all of which combine exceptional surface tension and electrical conductivity, and all of which reach the PIR at room temperature far more readily than EMI -BF4.

  6. Hydrophobic and Ionic-Interactions in Bulk and Confined Water with Implications for Collapse and Folding of Proteins

    NASA Astrophysics Data System (ADS)

    Vaitheeswaran, S.; Chen, Jie; Thirumalai, D.

    2011-10-01

    Water and water-mediated interactions determine the thermodynamics and kinetics of protein folding, protein aggregation and self-assembly in confined spaces. To obtain insights into the role of water in the context of folding problems, we describe computer simulations of a few related model systems. The dynamics of collapse of eicosane shows that upon expulsion of water the linear hydrocarbon chain adopts an ordered helical hairpin structure with 1.5 turns. The structure of dimer of eicosane molecules has two well ordered helical hairpins that are stacked perpendicular to each other. As a prelude to studying folding in confined spaces we used simulations to understand changes in hydrophobic and ionic interactions in nano-sized water droplets. Solvation of hydrophobic and charged species change drastically in nano-scale water droplets. Hydrophobic species are localized at the boundary. The tendency of ions to be at the boundary where water density is low increases as the charge density decreases. The interactions between hydrophobic, polar, and charged residue are also profoundly altered in confined spaces. Using the results of computer simulations and accounting for loss of chain entropy upon confinement we argue and then demonstrate, using simulations in explicit water, that ordered states of generic amphiphilic peptide sequences should be stabilized in cylindrical nanopores.

  7. 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.

  8. 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. PMID:26344308

  9. 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. PMID:26040001

  10. 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

  11. Electrochemical synthesis and surface characterization of poly(3,4-ethylenedioxythiophene) films grown in an ionic liquid.

    PubMed

    Ahmad, Shahzada; Deepa, M; Singh, S

    2007-11-01

    We report a facile method to synthesize poly(3,4-ethylenedioxythiophene) (PEDOT) films at room temperature in a waterproof ionic liquid, 1-ethyl-3-methylimidazolium bis(perfluoroethylsulfonyl)imide (EMIPFSI), by electropolymerization. The ionic liquid leads to the formation of randomly oriented nanofibers and particles confined to submicrometer-sized domains in the film microstructure. X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray (EDX) studies provide information about the intercalation of the cation apart from the reported anion in the polymer film, and on how the imidazolium ion controls the growth of PEDOT nanostructures. PMID:17915903

  12. 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}].

  13. Band effects on inelastic scattering of low-energy ions from metallic and ionic surfaces: A formalism beyond the adiabatic molecular-orbitals calculation

    NASA Astrophysics Data System (ADS)

    García, Evelina A.; Goldberg, E. C.

    1998-03-01

    Charge exchange and inelastic excitation processes have been analyzed in the scattering of low-energy He+ from metallic and ionic surfaces. An Anderson-like Hamiltonian is proposed, where the parameters are defined taking into account the electronic band structure of the surface as well as the atomic nature of the interaction between the projectile and the target atoms. The time-dependent collisional process is solved by using a Green-function formalism, which allows us to calculate not only the charge-state probabilities but also the one-electron interband excitations in the solid. Competitive effects of the hybridizations among the localized state at the projectile site and the localized and extended surface states are contemplated. In this way we can explain the observed energy dependences of the neutralization probability, as well as the occurrence of energy-loss processes due to the excitation of valence and core surface electrons induced by the collision.

  14. 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

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

    PubMed

    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

  16. 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.

  17. Leaching of metal(loid)s from a construction material: influence of the particle size, specific surface area and ionic strength.

    PubMed

    Schmukat, A; Duester, L; Ecker, D; Schmid, H; Heil, C; Heininger, P; Ternes, T A

    2012-08-15

    Construction materials are tested worldwide for a potential release of dangerous substances to prevent adverse effects on humans and biota. It is crucial to identify and understand the processes which are decisive for the release of hazardous substances. The current study compares the results of different test methods. Taking copper slag as model material, the influence of material particle size, eluant composition and ionic strength was tested. Ionic strength and salinity significantly influenced the release of metal(loid)s in the water phase. Furthermore, it was elucidated that colloids can cause methodological artefacts. The available specific surface area exhibited a positive correlation with the release of hazardous substances. The specific surface areas of materials were determined by the Brunauer, Emmett and Teller model (BET) and four other methods. The aluminium foil method showed the best results with regard to the statistical uncertainty, compared to a 3D laser scanning method. With help of the roughness factor λ it is possible to compare the results from surface area measurements with different material particle sizes (0-250 mm). This comparability offers the potential to match the release of metal(loid)s from laboratory studies with field applications and catchment area calculations/modelling, based on the release per m(2). PMID:22683212

  18. Surface melting of clusters and implications for bulk matter

    NASA Astrophysics Data System (ADS)

    Cheng, Hai-Ping; Berry, R. Stephen

    1992-06-01

    Surface melting on clusters is investigated by a combination of analytic modeling and computer simulation. Homogeneous argonlike clusters bound by Lennard-Jones forces and Cu-like clusters bound by ``embedded-atom'' potentials are the systems considered. Molecular-dynamics calculations have been carried out for clusters with 40-147 atoms. Well below the bulk melting temperature, the surfaces become very soft, exhibiting well-defined diffusion constants even while the cores remain nearly rigid and solidlike. The simulations, particularly animations, of atomic motion reveal that the surface melting is associated not with amorphous, random surface structures in constant, irregular motion, but rather with large-amplitude, organized, collective motion of most of the surface atoms accompanied by a few detached atoms (``floaters'') and holes. At any time, a few of the surface atoms are out of the surface layer, leaving vacancies; these promoted particles wander diffusively, the holes also but less so; the floaters occasionally exchange with atoms in the surface layer. This result is the basis for an analytic, statistical model. The caloric curves, particularly the latent heats, together with the results from an analytical model, show that surface melting of clusters is a ``phase change'' different from the homogeneous melting of clusters.

  19. Ionic compound mediated rearrangement of 3, 4, 9, 10-perylene tetracarboxylic dianhydride molecules on Ag(100) surface.

    PubMed

    Guo, Qinmin; Huang, Min; Lu, Shuangzan; Cao, Gengyu

    2015-07-10

    Tailoring of the assembly structure of organic molecular monolayer is of great importance to improve the performance of molecular devices. In this work, a typical ionic compound, namely KCl, was used to mediate the rearrangement of 3, 4, 9, 10-perylene tetracarboxylic dianhydride (PTCDA) monolayer on Ag(100). Combined scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) results indicate that both molecule and molecular superlattice would rotate after the dosing of KCl. The density functional theory calculation shows that KCl would exist in the form of molecules rather than ions on Ag(100) and demonstrates that experimentally observed structural transition induced by KCl molecules is energetically favored. PMID:26080855

  20. Ionic compound mediated rearrangement of 3, 4, 9, 10-perylene tetracarboxylic dianhydride molecules on Ag(100) surface

    NASA Astrophysics Data System (ADS)

    Guo, Qinmin; Huang, Min; Lu, Shuangzan; Cao, Gengyu

    2015-07-01

    Tailoring of the assembly structure of organic molecular monolayer is of great importance to improve the performance of molecular devices. In this work, a typical ionic compound, namely KCl, was used to mediate the rearrangement of 3, 4, 9, 10-perylene tetracarboxylic dianhydride (PTCDA) monolayer on Ag(100). Combined scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) results indicate that both molecule and molecular superlattice would rotate after the dosing of KCl. The density functional theory calculation shows that KCl would exist in the form of molecules rather than ions on Ag(100) and demonstrates that experimentally observed structural transition induced by KCl molecules is energetically favored.

  1. 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.

  2. Ionic self-assembly affords mesoporous ionic networks by crosslinking linear polyviologens with polyoxometalate clusters.

    PubMed

    Chen, Guojian; Hou, Wei; Li, Jing; Wang, Xiaochen; Zhou, Yu; Wang, Jun

    2016-03-21

    Ionic-bonded mesoporous ionic networks were prepared by the ionic self-assembly of polyoxometalate (POM) clusters with linear cationic polyviologens in water. The POM-enriched PMIN-2(V) possesses a high surface area up to 120 m(2) g(-1), exhibiting superior non-noble metal heterogeneous catalytic performance in the ambient aerobic selective oxidation of 5-hydroxymethylfurfural. PMID:26898883

  3. Multi-scale surface-groundwater interactions: Processes and Implications

    NASA Astrophysics Data System (ADS)

    Packman, A. I.; Harvey, J. W.; Worman, A.; Cardenas, M. B.; Schumer, R.; Jerolmack, D. J.; Tank, J. L.; Stonedahl, S. H.

    2009-05-01

    Site-based investigations of stream-subsurface interactions normally focus on a limited range of spatial scales - typically either very shallow subsurface flows in the hyporheic zone, or much larger scale surface- groundwater interactions - but subsurface flows are linked across this entire continuum. Broad, multi-scale surface-groundwater interactions produce complex patterns in porewater flows, and interfacial fluxes do not average in a simple fashion because of the competitive effects of flows induced at different scales. For example, reach-scale stream-groundwater interactions produce sequences of gaining and losing reaches that can either suppress or enhance local-scale hyporheic exchange. Many individual topographic features also produce long power-law tails in surface residence time distributions, and the duration of these tails is greatly extended by interactions over a wide range of spatial scales. Simultaneous sediment transport and landscape evolution further complicates the analysis of porewater flow dynamics in rivers. Finally, inhomogeneity in important biogeochemical processes, particularly microbial processes that are stimulated near the sediment- water interface, leads to a great degree of non-linearity in chemical transformation rates in stream channels. This high degree of complexity in fluvial systems requires that careful approaches be used to extend local observations of hyporheic exchange and associated nutrient, carbon, and contaminant transformations to larger spatial scales. It is important to recognize that conventional advection-dispersion models are not expected to apply, and instead anomalous transport models must be used. Unfortunately, no generally applicable model is available for stream-groundwater interactions at the present time. Alternative approaches for modeling conservative and reactive transport will be discussed, and a strategy articulated for coping with the complexity of coupled surface-subsurface dynamics in fluvial

  4. Interaction of ionic liquids with noble metal surfaces: structure formation and stability of [OMIM][TFSA] and [EMIM][TFSA] on Au(111) and Ag(111).

    PubMed

    Uhl, Benedikt; Huang, Hsinhui; Alwast, Dorothea; Buchner, Florian; Behm, R Jürgen

    2015-10-01

    Aiming at a comprehensive understanding of the interaction of ionic liquids (ILs) with metal surfaces we have investigated the adsorption of two closely related ILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM][TFSA] and 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide [OMIM][TFSA], with two noble metal surfaces, Au(111) and Ag(111), under ultrahigh vacuum (UHV) conditions using scanning tunneling microscopy (STM). At room temperature, the ILs form a 2D liquid on either of the two surfaces, while at lower temperatures they condense into two-dimensional (2D) islands which exhibit ordered structures or a short-range ordered 2D glass structure. Comparison of the adlayer structures formed in the different adsorption systems and also with those determined recently for n-butyl-n-methylpyrrolidinium [TFSA](-) adlayers on Ag(111) and Au(111) (B. Uhl et al., Beilstein J. Nanotechnol., 2013, 4, 903) gains detailed insight into the adsorption geometry of the IL ions on the surface. The close similarity of the adlayer structures indicates that (i) the structure formation is dominated by the tendency to optimize the anion adsorption geometry, and that (ii) also in the present systems the cation adsorbs with the alkyl chain pointing up from the surface. PMID:26305417

  5. Metallic 2D Surface State of Silicon by Ionic Liquid gating and observation of Reentrant Insulating behavior

    NASA Astrophysics Data System (ADS)

    Nelson, J. J.; Goldman, A. M.

    2015-03-01

    Metal insulator transitions are usually observed in high mobility and low carrier density 2D electron systems. There are several open questions regarding the metallic state including its existence in the limit of zero temperature. The current experimental focus is on the production of higher mobility samples to push the critical carrier density to even lower values, which will increase the effects of the Coulomb interaction. Here we report an unexpected result, the observation of the onset of a metallic state at high carrier densities in silicon gated with the ionic liquid DEME-TFSI. In addition we have observed a return to the insulating state as the carrier density was further increased. This reentrant insulting behavior is an effect that was recently predicted. Supported in part by NSF/DMR-1263316. Part of this work was carried out at the Minnesota Nanocenter.

  6. 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

  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

    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

  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. 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 PAGESBeta

    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 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

  10. 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.

  11. Catalytic peptide hydrolysis by mineral surface: Implications for prebiotic chemistry

    NASA Astrophysics Data System (ADS)

    Marshall-Bowman, Karina; Ohara, Shohei; Sverjensky, Dimitri A.; Hazen, Robert M.; Cleaves, H. James

    2010-10-01

    The abiotic polymerization of amino acids may have been important for the origin of life, as peptides may have been components of the first self-replicating systems. Though amino acid concentrations in the primitive oceans may have been too dilute for significant oligomerization to occur, mineral surface adsorption may have provided a concentration mechanism. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied mainly the reverse reaction of polymer degradation to measure the impact of mineral surface catalysis on peptide bonds. Aqueous glycine (G), diglycine (GG), diketopiperazine (DKP), and triglycine (GGG) were reacted with minerals (calcite, hematite, montmorillonite, pyrite, rutile, or amorphous silica) in the presence of 0.05 M, pH 8.1, KHCO 3 buffer and 0.1 M NaCl as background electrolyte in a thermostatted oven at 25, 50 or 70 °C. Below 70 °C, reaction kinetics were too sluggish to detect catalytic activity over amenable laboratory time-scales. Minerals were not found to have measurable effects on the degradation or elongation of G, GG or DKP at 70 °C in solution. At 70 °C pyrite was the most catalytic mineral with detectible effects on the degradation of GGG, although several others also displayed catalytic behavior. GGG degraded ˜1.5-4 times faster in the presence of pyrite than in control reactions, depending on the ratio of solution concentration to mineral surface area. The rate of pyrite catalysis of GGG hydrolysis was found to be saturable, suggesting the presence of discrete catalytic sites on the mineral surface. The mineral-catalyzed degradation of GGG appears to occur via a GGG → DKP + G mechanism, rather than via GGG → GG + G, as in solution-phase reactions. These results are compatible with many previous findings and suggest that minerals may have assisted in peptide synthesis in certain geological settings, specifically by speeding the approach to equilibrium

  12. 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. PMID:16237437

  13. Connexin-47 and connexin-32 in gap junctions of oligodendrocyte somata, myelin sheaths, paranodal loops and Schmidt-Lanterman incisures: implications for ionic homeostasis and potassium siphoning.

    PubMed

    Kamasawa, N; Sik, A; Morita, M; Yasumura, T; Davidson, K G V; Nagy, J I; Rash, J E

    2005-01-01

    The subcellular distributions and co-associations of the gap junction-forming proteins connexin 47 and connexin 32 were investigated in oligodendrocytes of adult mouse and rat CNS. By confocal immunofluorescence light microscopy, abundant connexin 47 was co-localized with astrocytic connexin 43 on oligodendrocyte somata, and along myelinated fibers, whereas connexin 32 without connexin 47 was co-localized with contactin-associated protein (caspr) in paranodes. By thin-section transmission electron microscopy, connexin 47 immunolabeling was on the oligodendrocyte side of gap junctions between oligodendrocyte somata and astrocytes. By freeze-fracture replica immunogold labeling, large gap junctions between oligodendrocyte somata and astrocyte processes contained much more connexin 47 than connexin 32. Along surfaces of internodal myelin, connexin 47 was several times as abundant as connexin 32, and in the smallest gap junctions, often occurred without connexin 32. In contrast, connexin 32 was localized without connexin 47 in newly-described autologous gap junctions in Schmidt-Lanterman incisures and between paranodal loops bordering nodes of Ranvier. Thus, connexin 47 in adult rodent CNS is the most abundant connexin in most heterologous oligodendrocyte-to-astrocyte gap junctions, whereas connexin 32 is the predominant if not sole connexin in autologous ("reflexive") oligodendrocyte gap junctions. These results clarify the locations and connexin compositions of heterologous and autologous oligodendrocyte gap junctions, identify autologous gap junctions at paranodes as potential sites for modulating paranodal electrical properties, and reveal connexin 47-containing and connexin 32-containing gap junctions as conduits for long-distance intracellular and intercellular movement of ions and associated osmotic water. The autologous gap junctions may regulate paranodal electrical properties during saltatory conduction. Acting in series and in parallel, autologous and

  14. 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

  15. A new strategy to prepare giant vesicles from surface active ionic liquids (SAILs): a study of protein dynamics in a crowded environment using a fluorescence correlation spectroscopic technique.

    PubMed

    Banerjee, Chiranjib; Roy, Arpita; Kundu, Niloy; Banik, Debasis; Sarkar, Nilmoni

    2016-06-01

    A simple procedure for the preparation of giant vesicles using surface active ionic liquids (SAILs) has been provided in this paper. SAILs, used to form vesicles, were synthesized by replacing the cationic part of Aerosol OT (AOT) with cations having alkyl chains of different lengths (ammonium and imidazolium cations). The number of carbons in the alkyl chains of the cations was varied from eight to sixteen. From the observed results, the formation of giant vesicles is found to be dependent on the alkyl chain length as well as the organic moieties of the respective cations. These giant vesicles were characterized using fluorescence lifetime imaging microscopy (FLIM). The conformational dynamics of bovine serum albumin (BSA) inside these giant vesicles was determined using fluorescence correlation spectroscopy (FCS) to get an idea about the protein dynamics in a constrained environment. The interaction of the giant vesicles with the protein was confirmed by the change in the diffusion coefficient and the conformational fluctuation time. PMID:27173474

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

    PubMed

    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

    1999-05-28

    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. PMID:10348732

  17. 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.

  18. 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.

  19. 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.

  20. Impact of ionic strength of growth on the physiochemical properties, structure, and adhesion of Listeria monocytogenes polyelectrolyte brushes to a silicon nitride surface in water.

    PubMed

    Gordesli, Fatma Pinar; Abu-Lail, Nehal I

    2012-12-15

    The adhesion energies between pathogenic Listeria monocytogenes EGDe to a model surface of silicon nitride were quantified using atomic force microscopy (AFM) in water for cells grown in pure media (as the control) and in media of four different ionic strengths of added NaCl (IS of 0.05 M, 0.1 M, 0.3 M and 0.5 M NaCl). The physiochemical properties of L. monocytogenes EGDe surface brushes were shown to have a strong influence on the adhesion of the microbe to the silicon nitride surface. The transitions in the adhesion energies, physiochemical properties, and the structure of bacterial surface polyelectrolyte brushes were observed for the cells grown in the media of 0.1M added NaCl. Our results suggested that the highest long-range electrostatic repulsion which was partially balanced by the Liftshitz-van der Waals attraction for the cells grown at 0.1M was responsible for the highest energy barrier to adhesion for these cells as predicted by the soft-particle analysis of DLVO theory and the lower adhesion measured by AFM. PMID:23010316

  1. 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. PMID:21831394

  2. 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. PMID:25984884

  3. Study of the effect of tribo-materials and surface finish on the lubricant performance of new halogen-free room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Saurín, N.; Minami, I.; Sanes, J.; Bermúdez, M. D.

    2016-03-01

    The present work evaluates different materials and surface finish in the presence of newly designed, hydrophobic halogen-free room temperature ionic liquids (RTILs) as lubricants. A reciprocating tribo-tester was employed with steel-ceramic and steel-thermosetting epoxy resin contacts under boundary lubrication conditions. Four different tetraalkylphosphonium organosilanesulfonate RTILs provided excellent lubricating performance, with friction coefficients as low as 0.057, and non-measurable wear for the higher roughness machine-finish stainless steel flat against sapphire balls, in the case of the lubricants containing the 2-trimethylsilylethanesulfonate anion. Higher friction coefficients of the order of 0.1 and wear volumes of the order of 10-4 mm3 were observed for the lower roughness fine-finished flat stainless steel surface. All RTILs prevent wear of epoxy resin against stainless steel balls, with friction coefficients in the range of 0.03-0.06. EDX analysis shows the presence of RTILs on the stainless steel surfaces after the tribological tests. Under the experimental conditions, no corrosive processes were observed.

  4. An ultrasensitive lysozyme chemiluminescence biosensor based on surface molecular imprinting using ionic liquid modified magnetic graphene oxide/β-cyclodextrin as supporting material.

    PubMed

    Duan, Huimin; Wang, Xiaojiao; Wang, Yanhui; Sun, Yuanling; Li, Jianbo; Luo, Chuannan

    2016-04-28

    In this work, ionic liquid modified Fe3O4@dopamine/graphene oxide/β-cyclodextrin (ILs-Fe3O4@DA/GO/β-CD) was used as supporting material to synthesize surface molecularly imprinted polymer (SMIP) which then was introduced into chemiluminescence (CL) to achieve an ultrasensitive and selective biosensor for determination of lysozyme (Lys). ILs and β-CD was applied to provide multiple binding sites to prepare Lys SMIP and Fe3O4@DA was designed to make the product separate easily and prevent the aggregation of GO which could improve absorption capacity for its large specific surface area. The ILs-Fe3O4@DA/GO/β-CD-SMIP showed high adsorption capacity (Q = 101 mg/g) to Lys in the adsorption isotherm assays. The adsorption equilibrium was reached within 10 min for all the concentrations, attributing to the binding sites situated exclusively at the surface, and the adsorption model followed Langmuir isotherm. Under the suitable CL conditions, the proposed biosensor could response Lys linearly in the range of 1.0 × 10(-9)-8.0 × 10(-8) mg/mL with a detection limit of 3.0 × 10(-10) mg/mL. When used in practical samples in determination of Lys, the efficient biosensor exhibited excellent result with the recoveries ranging from 94% to 112%. PMID:27046214

  5. Tetracene Aggregation on Polar and Nonpolar Surfaces: Implications for Singlet Fission.

    PubMed

    Strong, Steven E; Eaves, Joel D

    2015-04-01

    In molecular crystals that exhibit singlet fission, quantum yields depend strongly on intermolecular configurations that control the relevant electronic couplings. Here, we explore how noncovalent interactions between molecules and surfaces stabilize intermolecular structures with strong singlet fission couplings. Using molecular dynamics simulations, we studied the aggregation patterns of tetracene molecules on a solid surface as a function of surface polarity. Even at low surface concentrations, tetracene self-assembled into nanocrystallites where about 10-20% of the clustered molecules were part of at least one herringbone structure. The herringbone structure is the native structure of crystalline tetracene, which exhibits a high singlet fission quantum yield. Increasing the polarity of the surface reduced both the amount of clustering and the relative number of herringbone configurations, but only when the dipoles on the surface were orientationally disordered. These results have implications for the application of singlet fission in dye-sensitized solar cells. PMID:26262973

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

    NASA Astrophysics Data System (ADS)

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

    2002-06-01

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

  7. 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...

  8. Nonlinear ionic pulses along microtubules.

    PubMed

    Sekulić, D L; Satarić, B M; Tuszynski, J A; Satarić, M V

    2011-05-01

    Microtubules are cylindrically shaped cytoskeletal biopolymers that are essential for cell motility, cell division and intracellular trafficking. Here, we investigate their polyelectrolyte character that plays a very important role in ionic transport throughout the intra-cellular environment. The model we propose demonstrates an essentially nonlinear behavior of ionic currents which are guided by microtubules. These features are primarily due to the dynamics of tubulin C-terminal tails which are extended out of the surface of the microtubule cylinder. We also demonstrate that the origin of nonlinearity stems from the nonlinear capacitance of each tubulin dimer. This brings about conditions required for the creation and propagation of solitonic ionic waves along the microtubule axis. We conclude that a microtubule plays the role of a biological nonlinear transmission line for ionic currents. These currents might be of particular significance in cell division and possibly also in cognitive processes taking place in nerve cells. PMID:21604102

  9. 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.

  10. Effects of Ionic Strength on Bacteriophage MS2 Behavior and Their Implications for the Assessment of Virus Retention by Ultrafiltration Membranes ▿

    PubMed Central

    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. PMID:21075898

  11. 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.

  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. 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. PMID:26619139

  14. Interactional behavior of the polyelectrolyte poly sodium 4-styrene sulphonate (NaPSS) with imidazolium based surface active ionic liquids in an aqueous medium.

    PubMed

    Sharma, Renu; Kamal, Ajar; Kang, Tejwant Singh; Mahajan, Rakesh Kumar

    2015-09-28

    The present study aims to develop an understanding of the interactions between an anionic polyelectrolyte, poly sodium 4-styrene sulphonate (NaPSS), and cationic surface active imidazolium based ionic liquids (SAILs), [Cnmim][Cl] (n = 10, 12, 14) using a multi-technique approach. Various physicochemical and electrochemical techniques such as surface tension, conductivity, fluorescence, isothermal titration calorimetry (ITC), dynamic light scattering (DLS), turbidity, potentiometry, cyclic voltammetry (CV), and differential pulse voltammetry (DPV) are employed to obtain comprehensive information about NaPSS-SAIL interactions. Different stages of interaction, corresponding to the critical aggregation concentration (cac), critical saturation concentration (Cs) and critical micelle concentration (cmc) have been observed owing to the strong electrostatic and hydrophobic interactions, and the results obtained from different techniques complement each other very well. The results extracted from DLS and turbidity measurements clearly indicated that the size of the micelle like aggregates first decreases and then increases in the presence of polyelectrolyte. The binding isotherms obtained using potentiometry show a concentration dependence and the highly co-operative nature of the interactions which is attributed to aggregation of the polyelectrolyte-SAIL complexes. The diffusion coefficients (Dm) of the electroactive probe in the pure and NaPSS-SAIL mixed systems were obtained, which were further used to obtain the values of the micellar self-diffusion coefficients (D) and inter-micellar interaction parameters (kd). PMID:26300416

  15. 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

  16. 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

  17. Evaporites, surface roughness, and inundation in a playa dust source; implications of surface composition for erodibility

    NASA Astrophysics Data System (ADS)

    Tollerud, H.; Fantle, M.

    2013-12-01

    An understanding of fundamental controls on dust emission is critical in order to predict and model geochemical fluxes in the Earth system. Crucial parameters for dust emission include surface properties such as roughness, strength, and composition, which affect the erodibility of surface sediments. Accordingly, knowledge of the processes that govern surface properties is vital for predicting geochemical dust fluxes. In this study, we examine the spatial distribution of mineralogy within a playa dust source (Black Rock Desert, NV, USA) and its association with the spatial distribution of annual inundation, and employ a numerical model to assess the importance of transport by inundation for producing the distribution of mineralogy that we observe. Additionally, we experimentally investigate the effect of evaporite mineralogy on the development of surface roughness in a playa analog surface. We hypothesize that evaporite minerals in playa surface crusts reduce erodibility by contributing to sediment aggregation, promoting smoothing of the surface and a decrease in the availability of particles for saltation. Heterogeneity in surface mineralogy will then affect erodibility. Thus, it is useful to identify controls on the distribution of mineralogy (specifically evaporites) across a playa dust source. In particular, a connection between inundation and surface heterogeneity suggests that inundation could influence erodibility. Semi-quantitative X-ray diffraction analysis of surface sediments from the Black Rock Desert shows that evaporite content is variable; halite content varies from 0-40 wt%, and calcite from 2-15 wt%, with average sediment compositions of 30% quartz, 45% clay, and 10% plagioclase. Average calcite content is lower (7.6%) for sites within the inundated area of the previous year's playa lake (detected using MODIS satellite imagery; band 6, 1640 nm) than for sites outside this area (average calcite content 9.5%). Sites inundated the previous year are

  18. Scratching the surface of ice: Interfacial phase transitions and their kinetic implications

    NASA Astrophysics Data System (ADS)

    Limmer, David

    The surface structure of ice maintains a high degree of disorder down to surprisingly low temperatures. This is due to a number of underlying interfacial phase transitions that are associated with incremental changes in broken symmetry relative to the bulk crystal. In this talk I summarize recent work attempting to establish the nature and locations of these different phase transitions as well as how they depend on external conditions and nonequilibrium driving. The implications of this surface disorder is discussed in the context of simple kinetic processes that occur at these interfaces. Recent experimental work on the roughening transition is highlighted.

  19. 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.

  20. 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.

  1. 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.

  2. Process optimization of deposition conditions of PbS thin films grown by a successive ionic layer adsorption and reaction (SILAR) method using response surface methodology

    NASA Astrophysics Data System (ADS)

    Yücel, Ersin; Yücel, Yasin; Beleli, Buse

    2015-07-01

    In this study, lead sulfide (PbS) thin films were synthesized by a successive ionic layer adsorption and reaction (SILAR) method with different pH, dipping time and dipping cycles. Response surface methodology (RSM) and central composite design (CCD) were successfully used to optimize the PbS films deposition parameters and understand the significance and interaction of the factors affecting the film quality. 5-level-3-factor central composite design was employed to evaluate the effects of the deposition parameters (pH, dipping time and dipping cycles) on the response (the optical band gap of the films). Data obtained from RSM were subjected to the analysis of variance (ANOVA) and analyzed using a second order polynomial equation. The optimal conditions for the PbS films deposition have been found to be: pH of 9.1, dipping time of 10 s and dipping cycles of 10 cycles. The predicted band gap of PbS film was 2.13 eV under the optimal conditions. Verification experiment (2.24 eV) confirmed the validity of the predicted model. The film structures were characterized by X-ray diffractometer (XRD). Morphological properties of the films were studied with a scanning electron microscopy (SEM). The optical properties of the films were investigated using a UV-visible spectrophotometer.

  3. 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. PMID:23845390

  4. Surface Adsorption and Micelle Formation of Polyoxyethylene-type Nonionic Surfactants in Mixtures of Water and Hydrophilic Imidazolium-type Ionic Liquid.

    PubMed

    Misono, Takeshi; Okada, Kohei; Sakai, Kenichi; Abe, Masahiko; Sakai, Hideki

    2016-06-01

    The interfacial properties of polyoxyethylene alkyl ether-type nonionic surfactants (CnEm) were studied in a hydrophilic room-temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4), in the presence of water. These properties were assessed using static surface tension, pyrene fluorescence, and dynamic light scattering measurements. The interfacial properties were strongly dependent on the solution composition. Increased water concentration lowered the critical micelle concentration (cmc). The cmc was also affected by the lengths of both the alkyl and polyoxyethylene chains, but a greater impact was observed for the alkyl chain length. These results indicate that micellization occurs as a result of solvophobic interaction between surfactant molecules in the water/bmimBF4 mixed solutions, similar to aqueous surfactant systems. The cloud point phenomenon was observed for CnEm with a relatively low hydrophilic-lipophilic balance (HLB) value, and the relationship between the cloud point and water/bmimBF4 composition exhibited a convex upward curve. Furthermore, the mixing of bmimBF4 with water increased the surfactant solubility for water-rich compositions, suggesting that bmimBF4 acts as a chaotropic salt. PMID:27181249

  5. 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.

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

    NASA Astrophysics Data System (ADS)

    Tosi, Federico; Orosei, Roberto; Seu, Roberto; Coradini, Angioletta; Lunine, Jonathan; Filacchione, Gianrico; Capaccioni, Fabrizio; Cerroni, Priscilla; Brown, Robert

    2010-05-01

    We present new results combining the VIMS and RADAR 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. The use of data sets from different instruments onboard the Cassini spacecraft has the potential to deepen our understanding of the nature of the surface. 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 evidence, evaluated for the first time through a multivariate

  7. 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.; Brown, R. H.; Cassini Vims; Radar Teams

    2010-04-01

    We present new results combining the VIMS and RADAR 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. The use of data sets from different instruments onboard the Cassini spacecraft has the potential to deepen our understanding of the nature of the surface. 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 evidence, evaluated for the first time through a multivariate

  8. 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. PMID:26649483

  9. Year-round observations of water-soluble ionic species and trace metals in Sapporo aerosols: implication for significant contributions from terrestrial biological sources in Northeast Asia

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Fu, P.

    2013-03-01

    High aerosol loadings are prevalent in the atmosphere of East Asia, where the aerosols impact the Earth's climate system and human health; however, their sources and seasonal variations are not clearly understood. To better understand the sources of water-soluble ionic species and trace metals in Northeast Asia, we studied atmospheric aerosol samples collected in Sapporo, northern Japan for one-year period. SO42- (average 3.47 ± 1.03 μg m-3) was found as the most abundant ionic species, which accounted for on average 43 ± 15% of the measured total ionic mass followed by Cl- (13 ± 12%) ≈ NO3- ≈ Na+ > NH4+ > Ca2+ > Mg2+ > K+ > MSA-. Among the metals determined, Ca was found as the most abundant (45 ± 5.2%) followed by Fe (27 ± 4.5%), Al (21± 3.1%), Zn (3.2 ± 1.7), Ti, Mn, Ni, Pb, Cu, V, As, Cr and Cd. Based on factor analysis, linear relations of selected species with biomarkers, and backward air mass trajectories, we found that long-range atmospheric transport of soil dust (∼ 33%) from arid regions of Mongolia and/or Northeast China is a major source for Sapporo aerosols as well as terrestrial biogenic emissions (≥ 24%) including microbial activities and biomass burning mostly from distant source region(s) (e.g. Siberia). We also found that the contributions of soil dust to the aerosols maximized in early spring whereas those of vegetational emissions maximized in spring/summer. Contributions of microbial activities to aerosols peaked in autumn whereas forest fires/biomass burning peaked in autumn/winter. On the contrary, fossil fuel combustion/industrial activities and oceanic emissions to Sapporo aerosols are suggested to be rather minor. This study also suggests that fungal spores contribute to some trace metals (i.e. Ni, Cu, As) while pollen contributes to Zn in aerosols.

  10. 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

  11. How does the surface charge of ionic surfactant and cholesterol forming vesicles control rotational and translational motion of rhodamine 6G perchlorate (R6G ClO₄)?

    PubMed

    Ghosh, Surajit; Roy, Arpita; Banik, Debasis; Kundu, Niloy; Kuchlyan, Jagannath; Dhir, Anjali; Sarkar, Nilmoni

    2015-03-01

    The rotational dynamics and translational diffusion of a hydrophilic organic molecule, rhodamine 6G perchlorate (R6G ClO4) in small unilamellar vesicles formed by two different ionic surfactants, cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS), with cholesterol have been investigated using fluorescence spectroscopic methods. Moreover, in this article the formation of vesicle using anionic surfactant, SDS at different cholesterol-to-surfactant molar ratio (expressed by Q value (Q = [cholesterol]/[surfactant])) has also been reported. Visual observation, dynamic light scattering (DLS) study, turbidity measurement, steady state fluorescence anisotropy (r0) measurement, and eventually microscopic images reveal the formation of small unilamellar vesicles in aqueous solution. Also, in this study, an attempt has been made to observe whether the cationic probe molecule, rhodamine 6G (R6G) experiences similar or different microenvironment in cholesterol-SDS and cholesterol-CTAB assemblies with increase in cholesterol concentration. The influence of cholesterol on rotational and translational diffusion of R6G molecules has been investigated by monitoring UV-vis absorption, fluorescence, time-resolved fluorescence anisotropy, and finally fluorescence correlation spectroscopy (FCS) measurements. In cholesterol-SDS assemblies, due to the strong electrostatic attractive interaction between the negatively charged surface of vesicle and cationic R6G molecules, the rotational and diffusion motion of R6G becomes slower. However, in cholesterol-CTAB aggregates, the enhanced hydrophobicity and electrostatic repulsion induces the migration of R6G from vesicle bilayer to aqueous phase. The experimental observations suggest that the surface charge of vesicles has a stronger influence than the hydrophobicity of the vesicle bilayer on the rotational and diffusion motion of R6G molecules. PMID:25643899

  12. Ionic Graphitization of Ultrathin Films of Ionic Compounds.

    PubMed

    Kvashnin, A G; Pashkin, E Y; Yakobson, B I; Sorokin, P B

    2016-07-21

    On the basis of ab initio density functional calculations, we performed a comprehensive investigation of the general graphitization tendency in rocksalt-type structures. In this paper, we determine the critical slab thickness for a range of ionic cubic crystal systems, below which a spontaneous conversion from a cubic to a layered graphitic-like structure occurs. This conversion is driven by surface energy reduction. Using only fundamental parameters of the compounds such as the Allen electronegativity and ionic radius of the metal atom, we also develop an analytical relation to estimate the critical number of layers. PMID:27333810

  13. 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

  14. 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.

  15. Direct Mapping of Ionic Transport in a Si Anode on the Nanoscale: Time Domain Electrochemical Strain Spectroscopy Study

    SciTech Connect

    Jesse, Stephen; Balke, Nina; Eliseev, Eugene; Tselev, Alexander; Dudney, Nancy J; Morozovska, Anna N; Kalinin, Sergei V

    2011-01-01

    Local Li-ion transport in amorphous silicon is studied on the nanometer scale using time domain electrochemical strain microscopy (ESM). A strong variability of ionic transport controlled by the anode surface morphology is observed. The observed relaxing and nonrelaxing response components are discussed in terms of local and global ionic transport mechanisms, thus establishing the signal formation mechanisms in ESM. This behavior is further correlated with local conductivity measurements. The implications of these studies for Si-anode batteries are discussed. The universal presence of concentrationstrain coupling suggests that ESM and associated time and voltage spectroscopies can be applied to a broad range of electrochemical systems ranging from batteries to fuel cells.

  16. 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

  17. Experimental and DFT studies on the aggregation behavior of imidazolium-based surface-active ionic liquids with aromatic counterions in aqueous solution.

    PubMed

    Xu, Wenwen; Wang, Tao; Cheng, Ni; Hu, Qiongzheng; Bi, Yanhui; Gong, Yanjun; Yu, Li

    2015-02-01

    Two imidazolium-based surface-active ionic liquids with aromatic counterions, namely, 1-dodecyl-3-methylimidazolium salicylate (C12mimSal) and 1-dodecyl-3-methylimidazolium 3-hydroxy-2-naphthoate (C12mimHNC), were synthesized, and their aggregate behavior in aqueous solutions was systematically explored. Surface tension and conductivity measurements indicate that both C12mimSal and C12mimHNC show superior surface activity compared to the common imidazolium-based SAIL with the same hydrocarbon chain length, 1-dodecyl-3-methylimidazolium bromide (C12mimBr). This result demonstrates that the incorporation of aromatic counterions favors the formation of micelles. C12mimHNC displays a higher surface activity than C12mimSal, resulting from the different hydrophobicities of the counterions. In comparison with C12mimBr, C12mimSal not only can form hexagonal liquid-crystalline phase (H1) in aqueous solution, but also exhibits a broad region of cubic liquid-crystalline phase (V2) at higher concentration. As for the C12mimHNC/H2O system, a lamellar liquid-crystalline (L(α)) phase was observed. These lyotropic liquid crystals (LLCs) were characterized by polarized optical microscopy (POM) and small-angle X-ray scattering (SAXS). Structural parameters calculated from SAXS patterns suggest that a higher concentration of the SAIL leads to a denser arrangement whereas a higher temperature results in the opposite effect. The rheological results manifest that the formed H1 phase in the C12mimSal/H2O system exhibits an impressive viscoelastic behavior, indicated by a modulus (G' and G″) that is 1 order of magnitude higher than that of C12mimBr. Density functional theory (DFT) calculations reveal that C12mimSal has a more negative interaction energy with a water molecule and the Sal(-) counterion presents a stronger electronegativity than the HNC(-) counterion. The specific phase behavior of the C12mimSal/H2O and C12mimHNC/H2O systems can be attributed to the strong synergic

  18. Spectra of Fe-Ti silicate glasses - Implications to remote-sensing of planetary surfaces

    NASA Technical Reports Server (NTRS)

    Nolet, D. A.; Burns, R. G.; Flamm, S. L.; Besancon, J. R.

    1979-01-01

    Optical spectra of synthetic Fe-Ti silicate glasses and the temperature variations of the spectral features were investigated. The spectra are assigned to absorptions due to crystal field (CF) transitions in Ti(3+), Fe(2+) in octahedral coordination, and Fe(2+) in tetrahedral coordination, and to metal-metal and oxygen-metal charge transfer (CT) transitions which contribute to the near ultraviolet absorption edge. Temperature variations of the optical bands have been studied to explore implications for remote sensing. Caution is urged in the use of the absorption edge as a measure of TiO2 concentrations on planetary surfaces and in regolith samples.

  19. A new theory of bubble stability: Implications for nanobubbles at surfaces and in bulk solution

    NASA Astrophysics Data System (ADS)

    Craig, Vincent

    2013-11-01

    Nanobubbles on hydrophobic surfaces can be imaged using Atomic Force Microscopy and are implicated in the very long-range attraction measured between hydrophobic surfaces. However, the widely accepted theory of bubble dissolution predicts that small bubbles under the influence of Laplace pressure should rapidly dissolve resulting in bubble lifetimes of less than a second. Such short lifetimes should preclude nanobubbles from having an effect on surface force measurements or being observed by AFM, yet nanobubbles are readily observed by AFM and widely implicated in force measurements between hydrophobic surfaces. This has led to a number of attempts at describing their unexpected stability, though no explanation is currently widely accepted. Additionally, nanobubbles have contact angles substantially greater (measured through the more dense liquid phase) than the equivalent macroscopic contact angle. It is clear that nanobubbles at surfaces pose a number of problems that are yet to be resolved. Additionally, recent reports of long-lived nanobubbles in bulk solution add to the mystery. Here we present a new theory describing the stability of nanobubbles. We calculate their lifetimes as a function of gas supersaturation and explain the long lifetimes observed. The same theory predicts that bulk nanobubbles should be stable under certain circumstances. Further, in an extension of this work we explain the difference in contact angle between the nanoscopic and macroscopic measurements and describe in detail the process by which nanobubbles are formed during solvent exchange. Experimental evidence is presented supporting this new approach and showing that this theoretical framework has parallels in other nucleated systems. This work was supported by an ARC Future Fellowship.

  20. 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.

  1. Quantized friction across ionic liquid thin films.

    PubMed

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

    2013-10-01

    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. PMID:23942943

  2. 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.

  3. Acidic Ionic Liquids.

    PubMed

    Amarasekara, Ananda S

    2016-05-25

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

  4. Wettability by Ionic Liquids.

    PubMed

    Liu, Hongliang; Jiang, Lei

    2016-01-01

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

  5. 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.

  6. Facet personality and surface-level diversity as team mental model antecedents: implications for implicit coordination.

    PubMed

    Fisher, David M; Bell, Suzanne T; Dierdorff, Erich C; Belohlav, James A

    2012-07-01

    Team mental models (TMMs) have received much attention as important drivers of effective team processes and performance. Less is known about the factors that give rise to these shared cognitive structures. We examined potential antecedents of TMMs, with a specific focus on team composition variables, including various facets of personality and surface-level diversity. Further, we examined implicit coordination as an important outcome of TMMs. Results suggest that team composition in terms of the cooperation facet of agreeableness and racial diversity were significantly related to team-focused TMM similarity. TMM similarity was also positively predictive of implicit coordination, which mediated the relationship between TMM similarity and team performance. Post hoc analyses revealed a significant interaction between the trust facet of agreeableness and racial diversity in predicting TMM similarity. Results are discussed in terms of facilitating the emergence of TMMs and corresponding implications for team-related human resource practices. PMID:22468847

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

    PubMed

    Wang, Yuling; Irudayaraj, Joseph

    2013-02-01

    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. PMID:23267180

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

    PubMed Central

    Wang, Yuling; Irudayaraj, Joseph

    2013-01-01

    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. PMID:23267180

  9. 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.

  10. Ionic liquid lubrication at electrified interfaces

    NASA Astrophysics Data System (ADS)

    Kong, Lingling; Huang, Wei; Wang, Xiaolei

    2016-06-01

    The lubrication performances of ionic liquids at electrified interfaces have been investigated by using a reciprocating sliding tribometer. Experimental results indicated that the lubricity of the confined ionic liquids was markedly affected by the application of external electric field and strong interface electric field strength could result in high friction. The influence was more pronounced for the ionic liquid with a shorter alkyl side chain in particular. The main reason of the friction increment might be ascribed to the electrically influenced surface adsorption where the charged ions were structured to form robust and ordered layers.

  11. Asteroid Compositions and Surface Processes: Some Possible New Implications from Meteorite Studies

    NASA Astrophysics Data System (ADS)

    Sears, D. W. G.; Akridge, G. D.

    1997-07-01

    We have been exploring the idea that chondrules and chondrites formed in the regolith of asteroid-sized bodies made dynamic by the passage of gases from the interior. Such a process explains better than current ideas two of the chief properties of meteorites, their small deviations from solar Fe/Si and the abundance of chondrules. Variations in Fe/Si arise as a result of the separation of metal and silicates as gravity and aerodynamic drag sort the components by size and mass. Impact into a losely consolidated surface, new developments in chondrule chronology and regolith evolution, make the formation of chondrules by impact seem more viable than once thought. These ideas not only offer a new scenario for chondrite formation, but they have implications for asteroid studies. The proposed process is probably fairly rare, as it requires enough heat to dehydrate and mobilize the surface, but not enough to melt. Thus ordinary chondrites (i.e., unmelted dry surface) are probably rare and most asteroids are either igneous (i.e., once partially or fully melted) or CI/CM like (i.e., water-rich). Asteroid reflectance spectra, meteorite cosmic ray exposure ages, and induced thermoluminescence data for H chondrites, suggest that ordinary chondrites are coming from a very limited number of parent asteroids, such as 6 Hebe in the case of the H chondrites. Ordinary chondrites are overrepresented among terrestrial falls because only objects near resonances can send meteorites to Earth and because the earth's atmosphere screens all but the toughest meteorites. If these ideas have any merit, then there is no need to invoke space weathering or other devices to explain why asteroid surface compositions are so unlike the compositions of the major meteorite classes.

  12. Long tails in regional surface temperature probability distributions with implications for extremes under global warming

    NASA Astrophysics Data System (ADS)

    Ruff, Tyler W.; Neelin, J. David

    2012-02-01

    Prior work has shown that probability distributions of column water vapor and several passive tropospheric chemical tracers exhibit longer-than-Gaussian (approximately exponential) tails. The tracer-advection prototypes explaining the formation of these long-tailed distributions motivate exploration of observed surface temperature distributions for non-Gaussian tails. Stations with long records in various climate regimes in National Climatic Data Center Global Surface Summary of Day observations are used to examine tail characteristics for daily average, maximum and minimum surface temperature probability distributions. Each is examined for departures from a Gaussian fit to the core (here approximated as the portion of the distribution exceeding 30% of the maximum). While the core conforms to Gaussian for most distributions, roughly half the cases exhibit non-Gaussian tails in both winter and summer seasons. Most of these are asymmetric, with a long, roughly exponential, tail on only one side. The shape of the tail has substantial implications for potential changes in extreme event occurrences under global warming. Here the change in the probability of exceeding a given threshold temperature is quantified in the simplest case of a shift in the present-day observed distribution. Surface temperature distributions with long tails have a much smaller change in threshold exceedances (smaller increases for high-side and smaller decreases for low-side exceedances relative to exceedances in current climate) under a given warming than do near-Gaussian distributions. This implies that models used to estimate changes in extreme event occurrences due to global warming should be verified regionally for accuracy of simulations of probability distribution tails.

  13. Tidal Distortion of Titan: Implications for Surface Features and Tidal Measurements

    NASA Astrophysics Data System (ADS)

    Sohl, F.; Hussmann, H.; Coustenis, A.; Knapmeyer, M.; Lange, C.; Solomonidou, A.; Stephan, K.; Wagner, F. W.

    2012-04-01

    Titan is unique due to its similarity to the Earth and terrestrial planets in spite of the satellite's ice-rich bulk composition. Gravitational field data acquired by the Cassini spacecraft suggest that Titan's interior is composed of a mixture of rock and ice and is only partly differentiated. Titan is tidally locked with respect to Saturn and thereby subject to periodic tidal forcing of its interior and surface. Based on interior structure models and assumptions on rheological properties of planetary materials (i.e. ice, rock, water-ammonia ocean), we compute the elastic body tide Love numbers h2, k2, and l2 in order to describe Titan's tidal response. Key parameters, e.g., tidally-induced changes of local gravity, tilt relative to the direction of gravity, and areal strain are then given by linear combinations of h2, k2, and l2. We find peak-to-peak amplitudes of tidally-induced surface displacement and tilt variation on the order of up to a few tens of metres and a few arc seconds, respectively. Based on the obtained variations of tidal parameters, we will address possible implications for morphotectonic surface features and compositional heterogeneity on Titan. In addition, we will address possible measurements of global tidal distortion by using a network of several small landed stations. Each of those would have to carry an instrument suite to monitor tidally-induced changes of local gravity, tilt relative to the direction of gravity, and areal strain at the surface of Titan. Furthermore, tidal stresses are expected to induce significant seismic activity comparable to tidally-induced quakes on the Moon, and possibly along with seismicity induced by localized cryovolcanic activity.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Noble metal ionic catalysts.

    PubMed

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

    2009-06-16

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

  20. Ab initio study of EMIM-BF4 crystal interaction with a Li (100) surface as a model for ionic liquid/Li interfaces in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Valencia, Hubert; Kohyama, Masanori; Tanaka, Shingo; Matsumoto, Hajime

    2009-12-01

    We examined the atomic and electronic structures of an interface between a 1-ethyl-3-methyl imidazolium tetrafluoroborate (EMIM-BF4) ionic-liquid crystal and a Li(100) surface by periodic density-functional calculations, as a model for a room-temperature ionic-liquid (RTIL) electrolyte/Li interface at a Li-ion battery electrode. Results are compared with our previous theoretical study of the EMIM-BF4 molecular adsorption on Li surfaces [H. Valencia et al., Phys. Rev. B 78, 205402 (2008)]. For the EMIM-BF4 crystal structure, the present projector augmented wave scheme with the generalized gradient approximation can reproduce rather correct intramolecular structures as well as satisfactory short-ranged intermolecular distances, while long-range intermolecular distances are overestimated due to the lack of correct description of long-range dispersive interactions. We constructed a coherent crystal/crystal interface model where four EMIM-BF4 pairs are stacked on a p(4×3) Li (100) surface cell so as to simulate RTIL-layer deposition on a Li surface. We observed significant attraction of surface Li ions toward contacting BF4- anions, counterbalanced by electron transfer toward EMIM+ cations near the interface, revealing the tendency of easy ionization of Li and Lix-BF4 cluster formation, coupled with the reduction of EMIM+. These features are similar to those observed in the EMIM-BF4 molecular adsorption, while these have been proved to occur in the crystal-layer adsorption. We examined the adhesive energy, wetability, and detailed electronic structure at the crystal/crystal interface.

  1. Stability of Ionic Colloidal Crystals (ICCs)

    NASA Astrophysics Data System (ADS)

    Maskaly, Garry R.; Garcia, R. Edwin; Carter, W. Craig; Chiang, Yet-Ming

    2003-03-01

    Ionic colloidal crystals (ICCs) are here defined as ordered multicomponent colloids formed by attractive electrostatic interactions. Compared to previous approaches to colloidal crystallization, the ICC approach holds the potential for self-assembly of a wide range of structures not easily accessible by other methods. In this work, the colloid-chemical conditions under which ICCs are stable have been theoretically analyzed. A model is presented in which two dimensionless parameters are found to fully characterize an ICC system. We calculate the Madelung constant for ICCs of several classical ionic crystal structures as a function of these two parameters, and discuss the parallels between the ICC Madelung constants and the classical ionic case. Experimentally accessible regions of surface charge, particle sizes, salt concentration, and temperature where ionic colloidal crystallization should be possible are identified.

  2. 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.

  3. 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.

  4. 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

  5. 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 Central

    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 Ca2+ (8:1 [Ca2+]:[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 Ca2+ 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. PMID:25071599

  6. Ionic liquids behave as dilute electrolyte solutions

    PubMed Central

    Gebbie, Matthew A.; Valtiner, Markus; Banquy, Xavier; Fox, Eric T.; Henderson, Wesley A.; Israelachvili, Jacob N.

    2013-01-01

    We combine direct surface force measurements with thermodynamic arguments to demonstrate that pure ionic liquids are expected to behave as dilute weak electrolyte solutions, with typical effective dissociated ion concentrations of less than 0.1% at room temperature. We performed equilibrium force–distance measurements across the common ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]) using a surface forces apparatus with in situ electrochemical control and quantitatively modeled these measurements using the van der Waals and electrostatic double-layer forces of the Derjaguin–Landau–Verwey–Overbeek theory with an additive repulsive steric (entropic) ion–surface binding force. Our results indicate that ionic liquids screen charged surfaces through the formation of both bound (Stern) and diffuse electric double layers, where the diffuse double layer is comprised of effectively dissociated ionic liquid ions. Additionally, we used the energetics of thermally dissociating ions in a dielectric medium to quantitatively predict the equilibrium for the effective dissociation reaction of [C4mim][NTf2] ions, in excellent agreement with the measured Debye length. Our results clearly demonstrate that, outside of the bound double layer, most of the ions in [C4mim][NTf2] are not effectively dissociated and thus do not contribute to electrostatic screening. We also provide a general, molecular-scale framework for designing ionic liquids with significantly increased dissociated charge densities via judiciously balancing ion pair interactions with bulk dielectric properties. Our results clear up several inconsistencies that have hampered scientific progress in this important area and guide the rational design of unique, high–free-ion density ionic liquids and ionic liquid blends. PMID:23716690

  7. Surface wind variability and its implications for the Yucatan basin-Caribbean Sea dynamics

    NASA Astrophysics Data System (ADS)

    PéRez-Santos, IváN.; Schneider, Wolfgang; Sobarzo, Marcus; Montoya-SáNchez, Raúl; Valle-Levinson, Arnoldo; GarcéS-Vargas, José

    2010-10-01

    Sea surface wind data from the QuikSCAT satellite and two meteorological stations collected over 1 decade (1999-2008) were used to study the dominant time scales of the wind regime in the Yucatan basin. Wind data were used to quantify its implications on regional hydrodynamics by evaluating Ekman pumping and Ekman transport. The annual cycle of surface wind revealed different features than the Caribbean wind regime with a relative wind stress maximum observed in the Yucatan basin in June caused by the Caribbean low-level jet. The strongest wind stress occurred during November presumably due to the collapse of the Atlantic warm pool. This feature provides new evidence of the importance of local atmosphere-ocean coupling. Synoptic scale variability was detected during fall and winter, leaving spring and summer almost free from these activities. Empirical orthogonal functions revealed three dominant time scales of variability: an annual scale in mode 1 (46.3% of the total variance), a synoptic scale in mode 2 (27.7%), and a semiannual scale in mode 3 (6.4%). The third mode featured extreme pulses (six tropical storms and nine hurricanes). Ekman transport was found to contribute the most (93%) to total transport, whereas Ekman pumping contributed only 7%. However, upwelling induced by Ekman pumping persisted during some synoptic pulses, underscoring the importance of tropical storms and hurricanes. Offshore Ekman transport over the continental shelf north of the Yucatan Peninsula favored upwelling all year long. Onshore transport toward the coasts of southern Cuba and the eastern Yucatan Peninsula favored downwelling.

  8. 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.

  9. Growth kinetics of step edges on celestite (0 0 1) surfaces as a function of temperature, saturation state, ionic strength, and aqueous strontium:sulfate ratio: An in-situ atomic force microscopy study

    NASA Astrophysics Data System (ADS)

    Bracco, Jacquelyn N.; Gooijer, Yiscka; Higgins, Steven R.

    2016-02-01

    Step velocities on the celestite (0 0 1) surface have been measured as a function of temperature (23-45 °C), saturation state (S = 1.1-2.2), ionic strength (I = 0.01, 0.06, and 0.1 M), and aqueous strontium:sulfate ratio (r = 0.01-100) using atomic force microscopy (AFM). Celestite growth hillocks were flanked by [0 1 0]-aligned step edges, which are polar, and step edges vicinal to <1 2 0>, which are non-polar. [0 1 0] step velocities increased with temperature and saturation state, however step velocities did not vary significantly with ionic strength. Step velocities were non-linear with saturation state, suggesting a change in mechanism at high S as compared with low S. At constant S, the step velocities were maximized at r = 1 and decreased significantly at extreme r, demonstrating the governing role of solute stoichiometry. We successfully fit the step velocity data as a function of r using the Stack and Grantham (2010) nucleation and propagation model. Based on the results as a function of ionic strength and r, the mechanism at low S is likely ion-by-ion attachment to the step with an activation energy of 75 (±10) kJ mol-1. At high S the mechanism is a combination of the one at low S and possibly attachment of a neutral species such as an ion pair with an activation energy of 43 (±9) kJ mol-1.

  10. 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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    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 Fe2+ ion in ionic liquid (1-butyl-3-methylimidazoliumbromide) medium at different temperatures (298, 303, 308, 313, 318 and 323 K) 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.