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Sample records for air-water interface studied

  1. Smart nanogels at the air/water interface: structural studies by neutron reflectivity.

    PubMed

    Zielińska, Katarzyna; Sun, Huihui; Campbell, Richard A; Zarbakhsh, Ali; Resmini, Marina

    2016-03-01

    The development of effective transdermal drug delivery systems based on nanosized polymers requires a better understanding of the behaviour of such nanomaterials at interfaces. N-Isopropylacrylamide-based nanogels synthesized with different percentages of N,N'-methylenebisacrylamide as cross-linker, ranging from 10 to 30%, were characterized at physiological temperature at the air/water interface, using neutron reflectivity (NR), with isotopic contrast variation, and surface tension measurements; this allowed us to resolve the adsorbed amount and the volume fraction of nanogels at the interface. A large conformational change for the nanogels results in strong deformations at the interface. As the percentage of cross-linker incorporated in the nanogels becomes higher, more rigid matrices are obtained, although less deformed, and the amount of adsorbed nanogels is increased. The data provide the first experimental evidence of structural changes of nanogels as a function of the degree of cross-linking at the air/water interface. PMID:26697736

  2. Smart nanogels at the air/water interface: structural studies by neutron reflectivity

    NASA Astrophysics Data System (ADS)

    Zielińska, Katarzyna; Sun, Huihui; Campbell, Richard A.; Zarbakhsh, Ali; Resmini, Marina

    2016-02-01

    The development of effective transdermal drug delivery systems based on nanosized polymers requires a better understanding of the behaviour of such nanomaterials at interfaces. N-Isopropylacrylamide-based nanogels synthesized with different percentages of N,N'-methylenebisacrylamide as cross-linker, ranging from 10 to 30%, were characterized at physiological temperature at the air/water interface, using neutron reflectivity (NR), with isotopic contrast variation, and surface tension measurements; this allowed us to resolve the adsorbed amount and the volume fraction of nanogels at the interface. A large conformational change for the nanogels results in strong deformations at the interface. As the percentage of cross-linker incorporated in the nanogels becomes higher, more rigid matrices are obtained, although less deformed, and the amount of adsorbed nanogels is increased. The data provide the first experimental evidence of structural changes of nanogels as a function of the degree of cross-linking at the air/water interface.The development of effective transdermal drug delivery systems based on nanosized polymers requires a better understanding of the behaviour of such nanomaterials at interfaces. N-Isopropylacrylamide-based nanogels synthesized with different percentages of N,N'-methylenebisacrylamide as cross-linker, ranging from 10 to 30%, were characterized at physiological temperature at the air/water interface, using neutron reflectivity (NR), with isotopic contrast variation, and surface tension measurements; this allowed us to resolve the adsorbed amount and the volume fraction of nanogels at the interface. A large conformational change for the nanogels results in strong deformations at the interface. As the percentage of cross-linker incorporated in the nanogels becomes higher, more rigid matrices are obtained, although less deformed, and the amount of adsorbed nanogels is increased. The data provide the first experimental evidence of structural changes

  3. Brewster Angle Microscopy Study of Model Stratum Corneum Lipid Monolayers at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Adams, Ellen; Champagne, Alex; William, Joseph; Allen, Heather

    2012-04-01

    As the first and last barrier in the body, the stratum corneum (SC) is essential to life. Understanding the interactions and organization of lipids within the SC provides insight into essential physiological processes, including water loss prevention and the adsorption of substances from the environment. Langmuir monolayers have long been used to study complex systems, such as biological membranes and marine aerosols, due to their ability to shed light on intermolecular interactions. In this study, lipid mixtures with varying cholesterol and cerebroside ratios were investigated at the air/water interface. Surface tension measurements along with Brewster angle microscopy (BAM) images were used to examine the lipid phase transitions. Results indicate that cholesterol and cerebrosides form miscible monolayers, exhibiting ideal behavior. BAM images of a singular, uniform collapse phase also suggest formation of a miscible monolayer.

  4. The behavior of NaOH at the air-water interface, a computational study

    SciTech Connect

    Wick, Collin D.; Dang, Liem X.

    2010-07-14

    Molecular dynamics simulations with a polarizable multi-state empirical valence bond model were carried out to investigate NaOH dissociation and pairing in water bulk and at the air-water interface. It was found that NaOH readily dissociates in the bulk, and the effect of the air-water interface on NaOH dissociation is fairly minor. Also, NaOH complexes were found to be strongly repelled from the air-water interface, which is consistent with surface tension measurements. At the same time, a very strong preference for the hydroxide anion to be oriented towards the air was found that persisted a few angstroms towards the liquid from the Gibbs dividing surface of the air-water interface. This was due to a preference for the hydroxide anion to have its hydrogen pointing towards the air, and the fact that the sodium ion was more likely to be found near the hydroxide oxygen than hydrogen. As a consequence, the simulation results show that surfaces of NaOH solutions should be negatively charged, in agreement with experimental observations, but also that the hydroxide has little surface affinity. This provides the possibility that the surface of water can be devoid of hydroxide anions, but still have a strong negative charge. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  5. Physicochemical Study of Viral Nanoparticles at the Air/Water Interface.

    PubMed

    Torres-Salgado, Jose F; Comas-Garcia, Mauricio; Villagrana-Escareño, Maria V; Durán-Meza, Ana L; Ruiz-García, Jaime; Cadena-Nava, Ruben D

    2016-07-01

    The assembly of most single-stranded RNA (ssRNA) viruses into icosahedral nucleocapsids is a spontaneous process driven by protein-protein and RNA-protein interactions. The precise nature of these interactions results in the assembly of extremely monodisperse and structurally indistinguishable nucleocapsids. In this work, by using a ssRNA plant virus (cowpea chlorotic mottle virus [CCMV]) as a charged nanoparticle we show that the diffusion of these nanoparticles from the bulk solution to the air/water interface is an irreversible adsorption process. By using the Langmuir technique, we measured the diffusion and adsorption of viral nucleocapsids at the air/water interface at different pH conditions. The pH changes, and therefore in the net surface charge of the virions, have a great influence in the diffusion rate from the bulk solution to the air/water interface. Moreover, assembly of mesoscopic and microscopic viral aggregates at this interface depends on the net surface charge of the virions and the surface pressure. By using Brewster's angle microscopy we characterized these structures at the interface. Most common structures observed were clusters of virions and soap-frothlike micron-size structures. Furthermore, the CCMV films were compressed to form monolayers and multilayers from moderate to high surface pressures, respectively. After transferring the films from the air/water interface onto mica by using the Langmuir-Blodgett technique, their morphology was characterized by atomic force microscopy. These viral monolayers showed closed-packing nano- and microscopic arrangements. PMID:26999022

  6. A self-consistent field study of a hydrocarbon droplet at the air-water interface.

    PubMed

    Hilz, Emilia; Leermakers, Frans A M; Vermeer, Arnoldus W P

    2012-04-14

    A molecularly detailed self-consistent field (SCF) approach is applied to describe a sessile hydrocarbon droplet placed at the air-water interface. Predictions of the contact angle for macroscopic droplets follow from using Neumann's equation, wherein the macroscopic interfacial tensions are computed from one-gradient calculations for flat interfaces. A two-gradient cylindrical coordinate system with mirror-like boundary conditions is used to analyse the three dimensional shape of the nano-scale oil droplet at the air-water interface. These small droplets have a finite value of the Laplace pressure and concomitant line tension. It has been calculated that the oil-water and oil-vapour interfacial tensions are curvature dependent and increase slightly with increasing interfacial curvature. In contrast, the line tension tends to decrease with curvature. In all cases there is only a weak influence of the line tension on the droplet shape. We therefore argue that the nano-scale droplets, which are described in the SCF approach, are representative for macroscopic droplets and that the method can be used to efficiently generate accurate information on the spreading of oil droplets at the air-water interface in molecularly more complex situations. As an example, non-ionic surfactants have been included in the system to illustrate how a molecularly more complex situation will change the wetting properties of the sessile drop. This short forecast is aimed to outline and to stress the potential of the method. PMID:22395192

  7. Milk whey proteins and xanthan gum interactions in solution and at the air-water interface: a rheokinetic study.

    PubMed

    Perez, Adrián A; Sánchez, Cecilio Carrera; Patino, Juan M Rodríguez; Rubiolo, Amelia C; Santiago, Liliana G

    2010-11-01

    In this contribution, we present experimental information about the effect of xanthan gum (XG) on the adsorption behaviour of two milk whey protein samples (MWP), beta-lactoglobulin (beta-LG) and whey protein concentrate (WPC), at the air-water interface. The MWP concentration studied corresponded to the protein bulk concentration which is able to saturate the air-water interface (1.0 wt%). Temperature, pH and ionic strength of aqueous systems were kept constant at 20 degrees C, pH 7 and 0.05 M, respectively, while the XG bulk concentration varied in the range 0.00-0.25 wt%. Biopolymer interactions in solution were analyzed by extrinsic fluorescence spectroscopy using 1-anilino-8-naphtalene sulphonic acid (ANS) as a protein fluorescence probe. Interfacial biopolymer interactions were evaluated by dynamic tensiometry and surface dilatational rheology. Adsorption behaviour was discussed from a rheokinetic point of view in terms of molecular diffusion, penetration and conformational rearrangement of adsorbed protein residues at the air-water interface. Differences in the interaction magnitude, both in solution and at the interface vicinity, and in the adsorption rheokinetic parameters were observed in MWP/XG mixed systems depending on the protein type (beta-LG or WPC) and biopolymer relative concentration. beta-LG adsorption in XG presence could be promoted by mechanisms based on biopolymer segregative interactions and thermodynamic incompatibility in the interface vicinity, resulting in better surface and viscoelastic properties. The same mechanism could be responsible of WPC interfacial adsorption in the presence of XG. The interfacial functionality of WPC was improved by the synergistic interactions with XG, although WPC chemical complexity might complicate the elucidation of molecular events that govern adsorption dynamics of WPC/XG mixed systems at the air-water interface. PMID:20692133

  8. Methylglyoxal at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Wren, S. N.; Gordon, B. P.; McWilliams, L.; Valley, N. A.; Richmond, G.

    2014-12-01

    Recently, it has been suggested that aqueous-phase processing of atmospheric α-dicarbonyl compounds such as methylglyoxal (MG) could constitute an important source of secondary organic aerosol (SOA). The uptake of MG to aqueous particles is higher than expected due to the fact that its carbonyl moieties can hydrate to form diols, as well as the fact that MG can undergo aldol condensation reactions to form larger oligomers in solution. MG is known to be surface active but an improved description of its surface behaviour is crucial to understanding MG-SOA formation, in addition to understanding its gas-to-particle partitioning and cloud forming potential. Here, we employ a combined experimental and theoretical approach involving vibrational sum frequency generation spectroscopy (VSFS), surface tensiometry, molecular dynamics simulations, and density functional theory calculations to study MG's surface adsorption, in both the presence and absence of salts. We are particularly interested in determining MG's hydration state at the surface. Our experimental results indicate that MG slowly adsorbs to the air-water interface and strongly perturbs the water structure there. This perturbation is enhanced in the presence of NaCl. Together our experimental and theoretical results suggest that singly-hydrated MG is the dominant form of MG at the surface.

  9. Protein Folding at the Air-Water Interface Studied with X-Ray Reflectivity

    NASA Astrophysics Data System (ADS)

    Gidalevitz, David; Huang, Zhengqing; Rice, Stuart A.

    1999-03-01

    We report the results of x-ray reflectivity measurements of thin films formed by different water-soluble proteins at the air-aqueous solution interface. It is demonstrated that glucose oxidase, alcohol dehydrogenase, and urease molecules denaturate at the air-aqueous solution interface to form 8- to 14- angstrom -thick peptide sheets. X-ray reflectivity data indicate that the spreading of a lipid monolayer at the aqueous solution surface before protein injection does not prevent proteins from unfolding. On the other hand, crosslinking of proteins results in intact enzyme layers at the subphase surface. A model that involves interaction of glucose oxidase molecules with a phospholipid monolayer is proposed. In this model, an observed decrease of the lipid electron density in the protein presence is explained in terms of "holes" in the monolayer film caused by protein molecule adsorption.

  10. Organization of T-shaped facial amphiphiles at the air/water interface studied by infrared reflection absorption spectroscopy.

    PubMed

    Schwieger, Christian; Chen, Bin; Tschierske, Carsten; Kressler, Jörg; Blume, Alfred

    2012-10-11

    We studied the behavior of monolayers at the air/water interface of T-shaped facial amphiphiles which show liquid-crystalline mesophases in the bulk. The compounds are composed of a rigid p-terphenyl core (TP) with two terminal hydrophobic ether linked alkyl chains of equal length and one facial hydrophilic tri(ethylene oxide) chain with a carboxylic acid end group. Due to their amphiphilic nature they form stable Langmuir films at the air/water interface. Depending on the alkyl chain length they show markedly different compression isotherms. We used infrared reflection absorption spectroscopy (IRRAS) to study the changes in molecular organization of the TP films upon compression. We could retrieve information on layer thickness, alkyl chain crystallization, and the orientation of the TP cores within the films. Films of TPs with long (16 carbon atoms: TP 16/3) and short (10 carbon atoms: TP 10/3) alkyl chains were compared. Compression of TP 16/3 leads to crystallization of the terminal alkyl chains, whereas the alkyl chains of TP 10/3 stay fluid over the complete compression range. TP 10/3 shows an extended plateau in the compression isotherm which is due to a layering transition. The mechanism of this layering transition is discussed. Special attention was paid to the question of whether a so-called roll-over collapse occurs during compression. From the beginning to the end of the plateau, the layer thickness is increased from 15 to 38 Å and the orientation of the TP cores changes from parallel to the water surface to isotropic. We conclude that the plateau in the compression isotherm reflects the transition of a TP monolayer to a TP multilayer. The monolayer consists of a sublayer of well-organized TP cores underneath a sublayer of fluid alkyl chains whereas the multilayer consists of a well oriented bottom layer and a disordered top layer. Our findings do not support the model of a roll-over collapse. This study demonstrates how the IRRA band intensity of OH

  11. Surface Pressure Study of Lipid Aggregates at the Air Water Interface

    NASA Astrophysics Data System (ADS)

    Shew, Woody; Ploplis Andrews, Anna

    1996-11-01

    Qualitative and quantitative descriptions of the growth of fatty acid aggregates on a water/air interface were made by analyzing surface pressure measurements taken with a Langmuir Balance. High concentrations of palmitic acid, lauric acid, myristic acid, and also phosphatidylethanolamine in solution with chloroform were applied with a syringe to the surface of the Langmuir Balance and surface pressure was monitored as aggregates assembled spontaneously. The aggregation process for palmitic acid was determined to consist of three distinct parts. Exponential curves were fit to the individual regions of the data and growth and decay constants were determined. Surface pressure varied in very complex ways for lauric acid, myristic acid, and phosphatidylethanolamine yet kinetic measurements yield qualitative information about assembly of those aggregates. This research was supported by NSF Grant No. DMR-93-22301.

  12. Self-Assembly and Lipid Interactions of Diacylglycerol Lactone Derivatives Studied at the Air/Water Interface

    PubMed Central

    Philosof-Mazor, Liron; Volinsky, Roman; Comin, Maria J.; Lewin, Nancy E.; Kedei, Noemi; Blumberg, Peter M.; Marquez, Victor E.; Jelinek, Raz

    2009-01-01

    Synthetic diacylglycerol lactones (DAG-lactones) have been shown to be effective modulators of critical cellular signaling pathways. The biological activity of these amphiphilic molecules depends in part upon their lipid interactions within the cellular plasma membrane. This study explores the thermodynamic and structural features of DAG-lactone derivatives and their lipid interactions at the air/water interface. Surface-pressure/area isotherms and Brewster angle microscopy revealed the significance of specific side-groups attached to the terminus of a very rigid 4-(2-phenylethynyl) benzoyl chain of the DAG-lactones, which affected both the self-assembly of the molecules and their interactions with phospholipids. The experimental data highlight the formation of different phases within mixed DAG-lactone/phospholipid monolayers and underscore the relationship between the two components in binary mixtures of different mole ratios. Importantly, the results suggest that DAG-lactones are predominantly incorporated within fluid phospholipid phases rather than in the condensed phases that form, for example, by cholesterol. Moreover, the size and charge of the phospholipid headgroups do not seem to affect DAG-lactone interactions with lipids. PMID:18788772

  13. FTIR external reflectance studies of lipid monolayers at the air-water interface: Applications to pulmonary surfactant

    NASA Astrophysics Data System (ADS)

    Wilkin, Jennifer M.; Dluhy, Richard A.

    1998-06-01

    FTIR external reflectance spectra of monomolecular films of natural products and model mixtures relevant to pulmonary surfactant physiology were collected concurrently with surface measurements directly at the air-water interface. Films studied were calf lung surfactant extract (CLSE) and its phospholipid fraction (PPL) along with 2:1 DPPC-d62:DPPG and 2:1 DPPC-d62:DOPG containing 0, 1 or 2 wt % of the hydrophobic surfactant proteins SP-B and SP-C (SP-B+C). The CH2 antisymmetric and symmetric stretching bands (~2920 and 2852 cm-1) along with the analogous CD2 stretching bands (~2194 and 2089 cm-1) were analyzed, and band heights, integrated intensities and peak frequency positions were plotted as a function of measured surface pressure. Data suggest that 2:1 DPPC-d62:DPPG+2 wt % SP-B+C is the most ordered and stable of the films and can be compressed to the highest sustainable surface pressure. Data from the model mixtures indicate that the surfactant protein interacts differently with each of the lipid components. Plots of the CH/CD intensity ratios versus surface pressure show an increase in this ratio upon the addition of SP-B+C as the protein apparently orders the CH component (DPPG or DOPG) and slightly disorders the CD component (DPPC-d62).

  14. Studies on 2D hybrid films of half surfactant-covered Au nanoparticles at the air/water interface.

    PubMed

    Pang, Shufeng; Tetsuya, Oikawa; Tomoyuki, Watanabe; Kondo, Takeshi; Kawai, Takeshi

    2005-05-15

    A hybrid monolayer film of Au nanoparticles, half-covered with dioctadecyldimethylammonium chloride (DODAC), was prepared at the air/water interface and characterized using transmission electron microscopy (TEM), a quartz-crystal microbalance, and infrared spectra measurements. TEM images of the hybrid film showed that the distribution of Au nanoparticles depends on the surface density of DODAC and reaction time. IR spectral data provided evidence for a surface-enhanced effect of the Au nanoparticles. The wavenumber of CH(2)-stretch vibrations of DODAC in the infrared external reflection spectra revealed that the DODAC molecules were adsorbed onto the Au nanoparticles in a close-packed crystalline state for any surface density of DODAC, which is different from the usual behavior of Langmuir monolayers. PMID:15837481

  15. Tangential stress beneath wind-driven air water interfaces

    NASA Astrophysics Data System (ADS)

    Banner, Michael L.; Peirson, William L.

    1998-06-01

    The detailed structure of the aqueous surface sublayer flow immediately adjacent to the wind-driven air water interface is investigated in a laboratory wind-wave flume using particle image velocimetry (PIV) techniques. The goal is to investigate quantitatively the character of the flow in this crucial, very thin region which is often disrupted by microscale breaking events. In this study, we also examine critically the conclusions of Okuda, Kawai & Toba (1977), who argued that for very short, strongly forced wind-wave conditions, shear stress is the dominant mechanism for transmitting the atmospheric wind stress into the water motion waves and surface drift currents. In strong contrast, other authors have more recently observed very substantial normal stress contributions on the air side. The availability of PIV and associated image technology now permits a timely re-examination of the results of Okuda et al., which have been influential in shaping present perceptions of the physics of this dynamically important region. The PIV technique used in the present study overcomes many of the inherent shortcomings of the hydrogen bubble measurements, and allows reliable determination of the fluid velocity and shear within 200 [mu]m of the instantaneous wind-driven air water interface.

  16. Ellipsometric study of molecular orientations of Thermomyces lanuginosus lipase at the air-water interface by simultaneous determination of refractive index and thickness.

    PubMed

    Muth, Marco; Schmid, Reiner P; Schnitzlein, Klaus

    2016-04-01

    Ellipsometric studies of very thin organic films suffer from the low refractive index contrast between layer and bulk substrate. We demonstrate that null ellipsometry can not only provide detailed information about the adsorption kinetics and surface excess values, but in addition on layer thicknesses with submonolayer resolution of a lipase from Thermomyces lanuginosus at the air-water interface. While measuring very close to the Brewster angle, refractive indices and layer-thicknesses can both be determined with a precision that is sufficiently high to make conclusions on the density and orientation of the molecules at the interface. The orientation was found to be concentration- and pH value-dependent. At the isoelectric point, the lipase was almost vertically oriented with respect to the surface, while for pure distilled water and low lipase concentration a rather horizontal alignment was found. Further experiments, varying the size of the interfacial area in a Langmuir trough, confirm the different layer structures. PMID:26735895

  17. Microscopic dynamics of nanoparticle monolayers at air-water interface.

    PubMed

    Bhattacharya, R; Basu, J K

    2013-04-15

    We present results of surface mechanical and particle tracking measurements of nanoparticles trapped at the air-water interface as a function of their areal density. We monitor both the surface pressure (Π) and isothermal compression modulus (ϵ) as well as the dynamics of nanoparticle clusters, using fluorescence confocal microscopy while they are compressed to very high density near the two dimensional close packing density Φ∼0.82. We observe non-monotonic variation in both ϵ and the dynamic heterogeneity, characterized by the dynamical susceptibility χ4 with Φ, in such high density monolayers. We provide insight into the underlying nature of such transitions in close packed high density nanoparticle monolayers in terms of the morphology and flexibility of these soft colloidal particles. We discuss the significance our results in the context of related studies on two dimensional granular or colloidal systems. PMID:23411354

  18. Microrheology Using Optical Tweezers at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Boatwright, Thomas; Levine, Alex; Dennin, Michael

    2010-11-01

    Microrheological techniques have been used successfully to determine mechanical properties of materials important in cellular structure. Also critical to cellular mechanical functions are biological membranes. Many aspects of biological membranes can be modeled using Langmuir monolayers, which are single layers surfactants at the air-water interface. The macroscopic mechanical properties of Langmuir monolayers have been extensively characterized. In contrast to macroscopic measurements, we report on experimental methods for studying the rheological properties of Langmuir monolayers on the micron scale. A water immersion optical tweezers system is used to trap ˜1 micron diameter beads in a monolayer. The passive motion of the trapped beads is recorded at high frequency and the complex shear modulus is calculated. Preliminary microrheological data of a fatty acid monolayer showing dependence on surface pressure will be presented. Experimental obstacles will also be discussed.

  19. Self-assembly of diblock co-polymers at air-water interface: A microscopy and x-ray scattering study

    NASA Astrophysics Data System (ADS)

    Giri, R. P.; Mukhopadhyay, M. K.

    2016-05-01

    The spontaneous surface aggregation of diblock copolymer, containing polystyrene-polydimethylsiloxane or PS-PDMS, have been studied at air-water interface using Brewster's angle microscopy (BAM) and grazing incidence small angle x-ray scattering (GISAXS) technique. Pronounced differences in the molecular weight and solvent dependence of the size of aggregation on the water surface are observed. Structural characterization is done using atomic force microscopy (AFM) for a monolayer transferred to Si substrate. It shows that, individual polymer chains coalesce to form some disc like micelle aggregation on the Si surface which is also evident from the BAM image of the water floated monolayer. GISAXS study is also corroborating the same result.

  20. Interaction of Charged Colloidal Particles at the Air-Water Interface.

    PubMed

    Girotto, Matheus; Dos Santos, Alexandre P; Levin, Yan

    2016-07-01

    We study, using Monte Carlo simulations, the interaction between charged colloidal particles confined to the air-water interface. The dependence of force on ionic strength and counterion valence is explored. For 1:1 electrolyte, we find that the electrostatic interaction at the interface is very close to the one observed in the bulk. On the other hand, for salts with multivalent counterions, an interface produces an enhanced attraction between like charged colloids. Finally, we explore the effect of induced surface charge at the air-water interface on the interaction between colloidal particles. PMID:26551757

  1. Proton Transfers at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Mishra, Himanshu

    Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes. Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H3O +(g), can protonate most (non-alkane) organic species, whereas H 3O+(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the 'function' of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (< 1 nm thick) is an arduous task. While recent advances in surface-specific spectroscopies have provided

  2. Understanding the structure of hydrophobic surfactants at the air/water interface from molecular level.

    PubMed

    Zhang, Li; Liu, Zhipei; Ren, Tao; Wu, Pan; Shen, Jia-Wei; Zhang, Wei; Wang, Xinping

    2014-11-25

    Understanding the behavior of fluorocarbon surfactants at the air/water interface is crucial for many applications, such as lubricants, paints, cosmetics, and fire-fighting foams. In this study, molecular dynamics (MD) simulations were employed to investigate the microscopic properties of non-ionic fluorocarbon surfactants at the air/water interface. Several properties, including the distribution of head groups, the distribution probability of the tilt angle between hydrophobic tails with respect to the xy plane, and the order parameter of surfactants, were computed to probe the structure of hydrophobic surfactants at the air/water interface. The effects of the monomer structure on interfacial phenomena of non-ionic surfactants were investigated as well. It is observed that the structure of fluorocarbon surfactants at the air/water interface is more ordered than that of hydrocarbons, which is dominated by the van der Waals interaction between surfactants and water molecules. However, replacing one or two CF2 with one or two CH2 group does not significantly influence the interfacial structure, suggesting that hydrocarbons may be promising alternatives to perfluorinated surfactants. PMID:25358083

  3. [Virus adsorption from batch experiments as influenced by air-water interface].

    PubMed

    Zhang, Hui; Zhao, Bing-zi; Zhang, Jia-bao; Zhang, Cong-zhi; Wang, Qiu-ying; Chen, Ji

    2007-12-01

    The presence of air-water interface in batch sorption experiments may result in inaccurate estimation of virus adsorption onto various soils. A batch sorption experiment was conducted to compare the adsorption results of MS2 in different soils under presence/absence of air-water interface. Soils with sterilization/nonterilization treatment were used. Virus recovery efficiency in a blank experiment (no soil) was also evaluated as affected by different amount of air-water interface. The presence of air-water interface altered the results of virus adsorption in different soils with different extent, with Sandy fluvo-aquic soil being the most considerably affected, followed by Red loam soil, and the least being Red clay soil, probably because of different soil properties associated with virus adsorption/inactivation. Soil sterilization resulted in more significant difference of virus adsorption onto the Sandy fluvo-aquic soil between the presence and absence of air-water interface, while a reduced difference was observed in the Red loam soil. The presence of air-water interface significantly decreased virus recovery efficiency, with the values being decreased with increase in the amount of air-water interface. Soil particles likely prohibit viruses from reaching the air-water interface or alter the forces at the solid-water-air interface so that the results from the blank experiment did not truly represent results from control blank, which probably resulted in adsorption difference between presence and absence of the air-water interface. PMID:18290440

  4. Proton Transfers at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Mishra, Himanshu

    Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes. Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H3O +(g), can protonate most (non-alkane) organic species, whereas H 3O+(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the 'function' of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (< 1 nm thick) is an arduous task. While recent advances in surface-specific spectroscopies have provided

  5. Rheology and microrheology of materials at the air-water interface

    NASA Astrophysics Data System (ADS)

    Walder, Robert Benjamin

    2008-10-01

    The study of materials at the air-water interface is an important area of research in soft condensed matter physics. Films at the air-water interface have been a system of interest to physics, chemistry and biology for the last 20 years. The unique properties of these surface films provide ideal models for 2-d films, surface chemistry and provide a platform for creating 2 dimensional analogue materials to cellular membranes. Measurements of the surface rheology of cross-linked F-actin networks associated with a lipid monolayer at the air-water interface of a Langmuir monolayer have been performed. The rheological measurements are made using a Couette cell. These data demonstrate that the network has a finite elastic modulus that grows as a function of the cross-linking concentration. We also note that under steady-state flow the system behaves as a power law fluid in which the effective viscosity decreases with imposed shear. A Langmuir monolayer trough that is equipped for simultaneous microrheology and standard rheology measurements has been constructed. The central elements are the trough itself with a full range of optical tools accessing the air-water interface from below the trough and a portable knife-edge torsion pendulum that can access the interface from above. The ability to simultaneously measure the mechanical response of Langmuir monolayers on very different length scales is an important step for our understanding of the mechanical response of two-dimensional viscoelastic networks. The optical tweezer microrheometer is used to study the micromechanical properties of Langmuir monolayers. Microrheology measurements are made a variety of surface pressures that correspond to different ordered phases of the monolayer. The complex shear modulus shows an order of magnitude increase for the liquid condensed phase of DPPC compared to the liquid expanded phase.

  6. Thermodynamics of iodide adsorption at the instantaneous air-water interface

    NASA Astrophysics Data System (ADS)

    Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.

    2013-03-01

    We performed molecular dynamics simulations using both polarizable and non-polarizable force fields to study the adsorption of iodide to the air-water interface. A novel aspect of our analysis is that the progress of ion adsorption is measured as the distance from the instantaneous interface, which is defined by a coarse-graining scheme proposed recently by Willard and Chandler ["Instantaneous liquid interfaces," J. Phys. Chem. B 114, 1954-1958 (2010), 10.1021/jp909219k]. Referring structural and thermodynamic quantities to the instantaneous interface unmasks molecular-scale details that are obscured by thermal fluctuations when the same quantities are referred to an average measure of the position of the interface, such as the Gibbs dividing surface. Our results suggest that an ion adsorbed at the interface resides primarily in the topmost water layer, and the interfacial location of the ion is favored by enthalpy and opposed by entropy.

  7. New Mechanistic Pathways for Criegee-Water Chemistry at the Air/Water Interface.

    PubMed

    Zhu, Chongqin; Kumar, Manoj; Zhong, Jie; Li, Lei; Francisco, Joseph S; Zeng, Xiao Cheng

    2016-09-01

    Understanding Criegee chemistry has become one of central topics in atmospheric research recently. The reaction of Criegee intermediates with gas-phase water clusters has been widely viewed as a key Criegee reaction in the troposphere. However, the effect of aerosols or clouds on Criegee chemistry has received little attention. In this work, we have investigated the reaction between the smallest Criegee intermediate, CH2OO, and water clusters in the gas phase, as well as at the air/water surface using ab initio quantum chemical calculations and adaptive buffered force quantum mechanics/molecular mechanics (QM/MM) dynamics simulations. Our simulation results show that the typical time scale for the reaction of CH2OO with water at the air/water interface is on the order of a few picoseconds, 2-3 orders of magnitude shorter than that in the gas phase. Importantly, the adbf-QM/MM dynamics simulations suggest several reaction pathways for the CH2OO + water reaction at the air/water interface, including the loop-structure-mediated mechanism and the stepwise mechanism. Contrary to the conventional gas-phase CH2OO reaction, the loop-structure is not a prerequisite for the stepwise mechanism. For the latter, a water molecule and the CH2OO at the air/water interface, upon their interaction, can result in the formation of (H3O)(+) and (OH)CH2(OO)(-). Thereafter, a hydrogen bond can be formed between (H3O)(+) and the terminal oxygen atom of (OH)CH2(OO)(-), leading to direct proton transfer and the formation of α-hydroxy methylperoxide, HOCH2OOH. The mechanistic insights obtained from this simulation study should motivate future experimental studies of the effect of water clouds on Criegee chemistry. PMID:27509207

  8. Thermodynamics of Iodide Adsorption at the Instantaneous Air-Water Interface.

    SciTech Connect

    Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.

    2013-03-21

    We perform simulations using both polarizable and non-polarizable force fields to study the adsorption of iodide to the air-water interface. A novel aspect of our analysis is that the progress of the adsorption is measured as the distance from the instantaneous interface, which is defined by a coarse-graining scheme proposed recently by Willard and Chandler.\\cite{chandler1} Referring structural and thermodynamic quantities to the instantaneous interface unmasks molecular-scale details that are obscured by thermal fluctuations when the same quantities are referred to an average measure of the position of the interface, such as the Gibbs dividing surface. Our results suggest that an ion adsorbed at the interface resides primarily in the topmost layer water.

  9. Monolayers at air-water interfaces: from origins-of-life to nanotechnology.

    PubMed

    Ariga, Katsuhiko; Hill, Jonathan P

    2011-08-01

    The air-water interface presents several interesting features, namely a) a molecularly flat environment, b) a boundary region between two phases with different dielectric constants, c) permits or promotes dynamic interactions within the interface region, and d) a point of interaction between hydrophobic compounds and aqueous molecules. Accordingly, Langmuir monolayers at the air-water interface have several unique characteristics and properties, which require investigation. In this review-type personal account, typical examples of molecular recognition and molecular patterning at air-water interfaces are first introduced, followed by descriptions of specific and unusual properties of monolayers on water. In addition, two examples of our own results concerning Langmuir monolayers are explained. We have selected examples from two apparently unrelated research areas, these being the origin of life and future nanotechnology, in order to emphasize the diverse scientific contribution of research on monolayers at the air-water interface. PMID:21739568

  10. Interfacial properties of mixed films of long-chain organics at the air-water interface

    NASA Astrophysics Data System (ADS)

    Gilman, Jessica B.; Tervahattu, Heikki; Vaida, Veronica

    Organic molecules residing at the air-water interface of atmospheric aerosols will have a critical and direct effect on the aerosols' chemical, physical, and optical properties. It is important to study the interfacial properties of such compounds in order to accurately assess these effects. In this study, the compositions of two organic binary films at the air-water interface were monitored as a function of exposure time to the ambient atmosphere. One film was composed of tetracosanoic acid (lignoceric acid, CH 3(CH 2) 22COOH) and nonacosane (C 29H 60), and the second film was composed of octadecanoic acid (stearic acid, CH 3(CH 2) 16COOH) and octadecane (C 18H 38). These films were used as simplified proxies for the organic coating on atmospheric aerosols. The effect of lengthening the hydrocarbon chain on the interfacial longevity of the compounds in the mixed organic film at the air-aqueous interface was determined. The results show that octadecane in a mixed film desorbs from the interface after 72 h while octadecanoic acid remains. For nonacosane, further lengthening of the carbon chain greatly increased its interfacial longevity so that it was comparable with the fatty acids, which remained stable at the interface for at least 144 h. These results are used to explain the preponderance of long-chain fatty acids on the surfaces of collected aerosols and give insight into the degree to which the presence of other long-chain organics may affect the aerosol's chemical and physical properties.

  11. Propensity of Hydrated Excess Protons and Hydroxide Anions for the Air-Water Interface.

    PubMed

    Tse, Ying-Lung Steve; Chen, Chen; Lindberg, Gerrick E; Kumar, Revati; Voth, Gregory A

    2015-10-01

    Significant effort has been undertaken to better understand the molecular details governing the propensity of ions for the air-water interface. Facilitated by computationally efficient reactive molecular dynamics simulations, new and statistically conclusive molecular-scale results on the affinity of the hydrated excess proton and hydroxide anion for the air-water interface are presented. These simulations capture the dynamic bond breaking and formation processes (charge defect delocalization) that are important for correctly describing the solvation and transport of these complex species. The excess proton is found to be attracted to the interface, which is correlated with a favorable enthalpic contribution and consistent with reducing the disruption in the hydrogen bond network caused by the ion complex. However, a recent refinement of the underlying reactive potential energy function for the hydrated excess proton shows the interfacial attraction to be weaker, albeit nonzero, a result that is consistent with the experimental surface tension measurements. The influence of a weak hydrogen bond donated from water to the protonated oxygen, recently found to play an important role in excess hydrated proton transport in bulk water, is seen to also be important for this study. In contrast, the hydroxide ion is found to be repelled from the air-water interface. This repulsion is characterized by a reduction of the energetically favorable ion-water interactions, which creates an enthalpic penalty as the ion approaches the interface. Finally, we find that the fluctuation in the coordination number around water sheds new light on the observed entropic trends for both ions. PMID:26366480

  12. Linear and nonlinear microrheology of lysozyme layers forming at the air-water interface.

    PubMed

    Allan, Daniel B; Firester, Daniel M; Allard, Victor P; Reich, Daniel H; Stebe, Kathleen J; Leheny, Robert L

    2014-09-28

    We report experiments studying the mechanical evolution of layers of the protein lysozyme adsorbing at the air-water interface using passive and active microrheology techniques to investigate the linear and nonlinear rheological response, respectively. Following formation of a new interface, the linear shear rheology, which we interrogate through the Brownian motion of spherical colloids at the interface, becomes viscoelastic with a complex modulus that has approximately power-law frequency dependence. The power-law exponent characterizing this frequency dependence decreases steadily with increasing layer age. Meanwhile, the nonlinear microrheology, probed via the rotational motion of magnetic nanowires at the interface, reveals a layer response characteristic of a shear-thinning power-law fluid with a flow index that decreases with age. We discuss two possible frameworks for understanding this mechanical evolution: gelation and the formation of a soft glass phase. PMID:24969505

  13. Proteins at air-water interfaces: a coarse-grained model.

    PubMed

    Cieplak, Marek; Allan, Daniel B; Leheny, Robert L; Reich, Daniel H

    2014-11-01

    We present a coarse-grained model to describe the adsorption and deformation of proteins at an air-water interface. The interface is introduced empirically in the form of a localized field that couples to a hydropathy scale of amino acids. We consider three kinds of proteins: protein G, egg-white lysozyme, and hydrophobin. We characterize the nature of the deformation and the orientation of the proteins induced by their proximity to and association with the interface. We also study protein diffusion in the layer formed at the interface and show that the diffusion slows with increasing concentration in a manner similar to that for a colloidal suspension approaching the glass transition. PMID:25310625

  14. Specific ion adsorption at the air/water interface: The role of hydrophobic solvation

    NASA Astrophysics Data System (ADS)

    Horinek, Dominik; Herz, Alexander; Vrbka, Lubos; Sedlmeier, Felix; Mamatkulov, Shavkat I.; Netz, Roland R.

    2009-09-01

    Classical force fields for molecular simulations of aqueous electrolytes are still controversial. We study alkali and halide ions at the air/water interface using novel non-polarizable force fields that were optimized based on bulk thermodynamics. In qualitative agreement with polarizable force-field simulations, ion repulsion from the interface decreases with increasing ion size. Iodide is even enhanced at the interface, which is rationalized by hydrophobic solvation at the interface, but exhibits a smaller surface propensity than in previous polarizable simulations. Surprisingly, lithium is less repelled than other cations because of its tightly bound hydration shell. A generalized Poisson-Boltzmann approach that includes ionic potentials of mean force from simulation almost quantitatively matches experimental interfacial tension increments for 1 molar sodium halides and alkali chlorides. We conclude that properly optimized non-polarizable force fields are transferable to interfacial environments and hold the potential for unravelling ion-specific effects even in biological situations involving peptidic surfaces.

  15. Photosensitized Formation of Secondary Organic Aerosols above the Air/Water Interface.

    PubMed

    Bernard, F; Ciuraru, R; Boréave, A; George, C

    2016-08-16

    In this study, we evaluated photosensitized chemistry at the air-sea interface as a source of secondary organic aerosols (SOA). Our results show that, in addition to biogenic emissions, abiotic processes could also be important in the marine boundary layer. Photosensitized production of marine secondary organic aerosol was studied in a custom-built multiphase atmospheric simulation chamber. The experimental chamber contained water, humic acid (1-10 mg L(-1)) as a proxy for dissolved organic matter, and nonanoic acid (0.1-10 mM), a fatty acid proxy which formed an organic film at the air-water interface. Dark secondary reaction with ozone after illumination resulted in SOA particle concentrations in excess of 1000 cm(-3), illustrating the production of unsaturated compounds by chemical reactions at the air-water interface. SOA numbers via photosensitization alone and in the absence of ozone did not exceed background levels. From these results, we derived a dependence of SOA numbers on nonanoic acid surface coverage and dissolved organic matter concentration. We present a discussion on the potential role of the air-sea interface in the production of atmospheric organic aerosol from photosensitized origins. PMID:27434860

  16. Ligand interaction with the purified serotonin transporter in solution and at the air/water interface

    SciTech Connect

    Faivre, V.; Manivet, P.; Callaway, J.C.; Morimoto, H.; Airaksinen, M.M.; Baszkin, A.; Launay, J.M.; Rosilio, V.

    2000-06-01

    The purified serotonin transporter (SERT) was spread at the air/water interface and the effects both of its surface density and of the temperature on its interfacial behavior were studied. The recorded isotherms evidenced the existence of a stable monolayer undergoing a lengthy rearrangement. SERT/ligand interactions appeared to be dependent on the nature of the studied molecules. Whereas an unrelated drug (chlorcyclizine) did not bind to the spread SERT, it interacted with its specific ligands. Compared to heterocyclic drugs, for which binding appeared to be concentration-dependent, a 'two-site' mechanism was evidenced for pinoline and imipramine.

  17. Effect Of Air-Water Interface On Microorganism Transport Under Unsaturated Conditions

    NASA Astrophysics Data System (ADS)

    Torkzaban, S.; Hassanizadeh, S. M.; Schijven, J. F.

    2005-12-01

    Groundwater may become contaminated with pathogenic microorganisms from land application of treated wastewater, septic wells, and effluent from septic tanks, and leaking sewage pipes. The unsaturated zone is of special importance since it often represents the first line of natural defense against groundwater pollution. Moreover, many experimental studies have shown that contaminant removal is more significant under lower saturation levels. Interaction of microbial particles with the air-water interfaces (AWI) has been previously suggested to explain high removal of pathogenic microorganisms during transport through unsaturated soil. The objective of this research was to explore the effect of AWI on virus transport. The transport of bacteriophages MS2 and FiX174 in sand columns was studied under various conditions, such as different pH, and saturation levels. Fitting of a transport model to the breakthrough curves was performed to determine the adsorption parameters. FiX174 with isoelectric point of 6.7 exhibited high affinity to the air-water interface by decreasing pH from 7.5 to 6.2. MS2 with isoelectric point of 3.5 has lower affinity to air-water interfaces than FiX174, but has similar pH- dependence. These results show the importance of electrostatic interactions, instead of hydrophobic, between the AWI and viruses. Adsorption to AWI is strongly pH dependent, increasing as pH decreases. It was found that two-site kinetic model should be used for modeling of virus transport under unsaturated conditions Moreover, by draining the unsaturated column, we found out that the attached viruses to AWI are viable, which is in contrast with the literature where retained viruses to AWI are considered as inactivated.

  18. Effect of humidity on the adsorption kinetics of lung surfactant at air-water interfaces.

    PubMed

    Zuo, Yi Y; Gitiafroz, Roya; Acosta, Edgar; Policova, Zdenka; Cox, Peter N; Hair, Michael L; Neumann, A Wilhelm

    2005-11-01

    The in vitro adsorption kinetics of lung surfactant at air-water interfaces is affected by both the composition of the surfactant preparations and the conditions under which the assessment is conducted. Relevant experimental conditions are surfactant concentration, temperature, subphase pH, electrolyte concentration, humidity, and gas composition of the atmosphere exposed to the interface. The effect of humidity on the adsorption kinetics of a therapeutic lung surfactant preparation, bovine lipid extract surfactant (BLES), was studied by measuring the dynamic surface tension (DST). Axisymmetric drop shape analysis (ADSA) was used in conjunction with three different experimental methodologies, i.e., captive bubble (CB), pendant drop (PD), and constrained sessile drop (CSD), to measure the DST. The experimental results obtained from these three methodologies show that for 100% relative humidity (RH) at 37 degrees C the rate of adsorption of BLES at an air-water interface is substantially slower than for low humidity. It is also found that there is a difference in the rate of surface tension decrease measured from the PD and CB/CSD methods. These experimental results agree well with an adsorption model that considers the combined effects of entropic force, electrostatic interaction, and gravity. These findings have implications for the development and evaluation of new formulations for surfactant replacement therapy. PMID:16262325

  19. epi-Fluorescence imaging at the air-water interface of fibrillization of bovine serum albumin and human insulin.

    PubMed

    Sessions, Kristen; Sacks, Stuart; Li, Shanghao; Leblanc, Roger M

    2014-08-18

    Protein fibrillization is associated with many devastating neurodegenerative diseases. This process has been studied using spectroscopic and microscopic methods. In this study, epi-fluorescence at the air-water interface was developed as an innovative technique for observing fibrillization of bovine serum albumin and human insulin. PMID:24976597

  20. Characterization of predominantly hydrophobic poly(styrene)-poly(ethylene oxide) copolymers at air/water and cyclohexane/water interfaces

    SciTech Connect

    Gragson, D.E.; Jensen, J.M.; Baker, S.M.

    1999-09-14

    Interfacial tension measurements are employed to explore the spreading behavior of predominantly hydrophobic poly(styrene)--poly(ethylene oxide), PS-PEO, diblock copolymers at air/water and cyclohexane/water interfaces. Two copolymers with 7%- and 15.5%-PEO are examined in this study. The former is expected to have a PS block limiting area in air roughly equal to the limiting PEO pancake area, whereas the latter is expected to have a limiting PS block area in air approximately 3 times smaller than the limiting PEO pancake area. At the air/water interface, the 7%-PEO copolymer does not spread well, which is attributed to interference from the hydrophobic PS block. In contrast, the 7%-PEO copolymer spreads well at the cyclohexane/water interface, producing an isotherm with a terminating mean molecular area 3 times smaller than that obtained at the air/water interface. The 15.5%-PEO copolymer spreads well at both the air/water ad cyclohexane/water interfaces due to less interference from the smaller hydrophobic PS block. These observations are compared to compression isotherms, and the results are discussed in terms of the solvating nature of the adjacent cyclohexane phase for the PS block.

  1. Bromine and heavy halide chemistry at the air/water and air/ice interfaces: a computational approach

    NASA Astrophysics Data System (ADS)

    Gladich, I.; Shepson, P. B.; Szleifer, I.; Carignano, M.

    2010-12-01

    The air-water and air-ice interfaces are critically important surfaces, with respect to the physical and chemical properties of the Earth's atmosphere. In particular chloride, bromide and iodide ions are strongly involved in the reactions occurring at aerosol surfaces that are hydrated and at the air-ice interface in the polar boundary layer. Unfortunately, experimental access to these interfaces are quite problematic and the computational approach, based on molecular dynamic simulations and quantum mechanic calculations, is an interesting alternative approach. In this work, molecular dynamic (MD) simulations are used to study the halide enhancements at the air-water interface in the case of a dilute mixture of iodide, bromide and chloride ions. The MD results show how the air- water halide enhancement is different in the case of mixtures from the case of binary solutions (i.e. anions plus counter-positive ions) and how the presence of these halides at the interfaces depends from their relative concentrations in solution. In detail, heavy halides are strongly enhanced at the interfaces even if they are minor constituents in the bulk. Furthermore the enhancement of the larger halide ions, like bromide, at the surface is greater if lighter halides, like chloride, are in greater excess in the bulk. The applications of this last result on some real system, like sea-water, and the importance of bromide ions in the polar chemistry of ozone depletion events suggest a combined approach, MD and quantum mechanism (QM) calculation, to investigate the ozonation reaction of bromide (Br-+O3 → BrO-+O2 ) in the ice-QLL and in bulk water. The study of the reaction constants suggests how the different environments can affect the kinetics of such reaction. These results can help to understand the complex chemistry occurring at the air-water interface of hydrated aerosol and at the air-ice interface in the polar boundary layer.

  2. Amine Chemistry at Aqueous Interfaces: The Study of Organic Amines in Neutralizing Acidic Gases at an Air/Water Surface Using Vibrational Sum Frequency Spectroscopy

    NASA Astrophysics Data System (ADS)

    McWilliams, L.; Wren, S. N.; Valley, N. A.; Richmond, G.

    2014-12-01

    Small organic bases have been measured in atmospheric samples, with their sources ranging from industrial processing to animal husbandry. These small organic amines are often highly soluble, being found in atmospheric condensed phases such as fogwater and rainwater. Additionally, they display acid-neutralization ability often greater than ammonia, yet little is known regarding their kinetic and thermodynamic properties. This presentation will describe the molecular level details of a model amine system at the vapor/liquid interface in the presence of acidic gas. We find that this amine system shows very unique properties in terms of its bonding, structure, and orientation at aqueous surfaces. The results of our studies using a combination of computation, vibrational sum frequency spectroscopy, and surface tension will report the properties inherent to these atmospherically relevant species at aqueous surfaces.

  3. Dynamic mechanical properties of a polyelectrolyte adsorbed insoluble lipid monolayer at the air-water interface.

    PubMed

    Park, Chang Young; Kim, Mahn Won

    2015-04-23

    Polymers have been used to stabilize interfaces or to tune the mechanical properties of interfaces in various contexts, such as in oil emulsions or biological membranes. Although the structural properties of these systems are relatively well-studied, instrumental limitations continue to make it difficult to understand how the addition of polymer affects the dynamic mechanical properties of thin and soft films. We have solved this challenge by developing a new instrument, an optical-tweezer-based interface shear microrheometer (ISMR). With this technique, we observed that the interface shear modulus, G*, of a dioctadecyldimethylammonium chloride (DODAC) monolayer at the air-water interface significantly increased with adsorption of polystyrenesulfonate (PSS). In addition, the viscous film (DODAC monolayer) became a viscoelastic film with PSS adsorption. At a low salt concentration, 10 mM of NaCl in the subphase, the viscoelasticity of the DODAC/PSS composite was predominantly determined by a particular property of PSS, that is, it behaves as a Gaussian chain in a θ-solvent. At a high salt concentration, 316 mM of NaCl, the thin film behaved as a polymer melt excluding water molecules. PMID:25826703

  4. Structure of phospholipid monolayers containing poly(ethylene glycol) lipids at the air-water interface

    SciTech Connect

    Majewski, J.; Smith, G.S.; Kuhl, T.L.; Israelachvili, J.N.; Gerstenberg, M.C.

    1997-04-17

    The density distribution of a lipid monolayer at the air-water interface mixed with varying amounts of lipid with poly(ethylene glycol)polymer headgroups (polymer-lipid or PEG-lipid) was measured using neutron reflectometry. The structure of the monolayer at the interface was greatly perturbed by the presence of the bulky polymer-lipid headgroups resulting in a large increase in the thickness of the headgroup region normal to the interface and a systematic roughening of the interface with increasing polymer-lipid content. These results show how bulky hydrophilic moieties cause significant deformations and out-of-place protrusions of phospholipid monolayers and presumably bilayers, vesicles and biological membranes. In terms of polymer physics, very short polymer chains tethered to the air-water interface follow scaling behavior with a mushroom to brush transition with increasing polymer grafting density. 34 refs., 9 figs., 1 tab.

  5. Equation of state and adsorption dynamics of soft microgel particles at an air-water interface.

    PubMed

    Deshmukh, Omkar S; Maestro, Armando; Duits, Michel H G; van den Ende, Dirk; Stuart, Martien Cohen; Mugele, Frieder

    2014-09-28

    Understanding the adsorption dynamics of soft microgel particles is a key step in designing such particles for potential applications as stimuli-responsive Pickering stabilizers for foams or emulsions. In this study we experimentally determine an equation of state (EOS) for poly (N-isopropylacrylamide) (PNIPAM) microgel particles adsorbed onto an air-water interface using a Langmuir film balance. We detect a finite surface pressure at very low surface concentration of particles, for which standard theories based on hard disk models predict negligible pressures, implying that the particles must deform strongly upon adsorption to the interface. Furthermore, we study the evolution of the surface pressure due to the adsorption of PNIPAM particles as a function of time using pendant drop tensiometry. The equation of state determined in the equilibrium measurements allows us to extract the adsorbed amount as a function of time. We find a mixed-kinetic adsorption that is initially controlled by the diffusion of particles towards the interface. At later stages, a slow exponential relaxation indicates the presence of a coverage-dependent adsorption barrier related to crowding of particles at the interface. PMID:24954112

  6. It's Alive!: Students Observe Air-Water Interface Samples Rich with Organisms

    ERIC Educational Resources Information Center

    Avant, Thomas

    2002-01-01

    This article describes an experiment, designed by Cindy Henk, manager of the Socolofsky Microscopy Center at Louisiana State University (LSU), that involved collecting and viewing microorganisms in the air-water interface. The experiment was participated by Leesville High School microbiology students. The students found that the air-water…

  7. Hydrodynamics of a self-propelled camphor boat at the air-water interface

    NASA Astrophysics Data System (ADS)

    Akella, Sathish; Singh, Dhiraj; Singh, Ravi; Bandi, Mahesh

    2015-11-01

    A camphor tablet, when placed at the air-water interface undergoes sublimation and camphor vapour spreads radially outwards across the surface due to Marangoni forces. This steady camphor influx from tablet onto the air-water interface is balanced by the camphor outflux due to evaporation. When spontaneous fluctuations in evaporation break the axial symmetry of Marangoni force acting radially outwards, the camphor tablet is propelled like a boat along the water surface. We report experiments on the hydrodynamics of a self-propelled camphor boat at air-water interfaces. We observe three different modes of motion, namely continuous, harmonic and periodic, due to the volatile nature of camphor. We explain these modes in terms of ratio of two time-scales: the time-scale over which viscous forces are dominant over the Marangoni forces (τη) and the time-scale over which Marangoni forces are dominant over the viscous forces (τσ). The continuous, harmonic and periodic motions are observed when τη /τσ ~ 1 , τη /τσ >= 1 and τη /τσ >> 1 respectively. Experimentally, the ratio of the time scales is varied by changing the interfacial tension of the air-water interface using Sodium Dodecyl Sulfate. This work was supported by the Collective Interactions Unit, OIST Graduate University.

  8. Conformational changes of a calix[8]arene derivative at the air-water interface.

    PubMed

    de Miguel, Gustavo; Pedrosa, José M; Martín-Romero, María T; Muñoz, Eulogia; Richardson, Tim H; Camacho, Luis

    2005-03-10

    The particular behavior of a p-tert-butyl calix[8]arene derivative (C8A) has been studied at the air-water interface using surface pressure-area isotherms, surface potential-area isotherms, film relaxation measurements, Brewster angle microscopy (BAM), and infrared spectroscopy for Langmuir-Blodgett films. Thus, it is observed that the properties of the film, for example, isotherms, domain formation, and FTIR spectra, recorded during the first compression cycle differ appreciably from those during the second compression and following cycles. The results obtained are interpreted on the basis of the conformational changes of the C8A molecules by surface pressure, allowing us to inquire into the inter- and intramolecular interactions (hydrogen bonds) of those molecules. Thus, the compression induces changes in the kind of hydrogen bonds from intra- and intermolecular with other C8A molecules to hydrogen bonds with water molecules. PMID:16851456

  9. Transition States for Submerged Superhydrophobic Surfaces: Partially-Pinned Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Tafreshi, Hooman; Hemeda, Ahmed; VCU Team

    2015-11-01

    The pressure at which a superhydrophobic surface transitions from the Cassie state to the Wenzel state is often referred to as the critical pressure. Our mathematical simulations have shown that the Cassie-to-Wenzel transition is a gradual process that takes place over a range of pressures as oppose to an event that happens at a certain pressure. During the transition period, the air-water interface may go through a series pinned, partially-pinned, and de-pinned states that depend on the geometry of the surface asperities. This in turn indicates that the drag-reduction effect produced by a submerged superhydrophobic surface can vary with the hydrostatic pressure, and is highly dependent on sharpness of the surface asperities. The study reported here reviews our recent discoveries in simulating the wetted area and drag reduction effect of superhydrophobic surfaces with different microstructures. National Science Foundation CMM 1029924 and CBET 1402655 programs.

  10. Amyloid fibril formation at a uniformly sheared air/water interface

    NASA Astrophysics Data System (ADS)

    Posada, David; Hirsa, Amir

    2013-11-01

    Amyloid fibril formation is a process by which protein molecules in solution form nuclei and aggregate into fibrils. Amyloid fibrils have long been associated with several common diseases such as Parkinson's disease and Alzheimer's. More recently, fibril protein deposition has been implicated in uncommon disorders leading to the failure of various organs including the kidneys, heart, and liver. Fibrillization can also play a detrimental role in biotherapeutic production. Results from previous studies show that a hydrophobic interface, such air/water, can accelerate fibrillization. Studies also show that agitation accelerates fibrillization. When attempting to elucidate fundamental mechanisms of fibrillization and distinguish the effects of interfaces and flow, it can be helpful to experiment with uniformly sheared interfaces. A new Taylor-Couette device is introduced for in situ, real-time high resolution microscopy. With a sub-millimeter annular gap, surface tension acts as the channel floor, permitting a stable meniscus to be placed arbitrarily close to a microscope to study amyloid fibril formation over long periods.

  11. Real-time imaging of crystallization in polylactide enantiomeric monolayers at the air-water interface.

    PubMed

    Kim, Young Shin; Snively, Christopher M; Liu, Yujuan; Rabolt, John F; Chase, D Bruce

    2008-10-01

    A newly developed planar array infrared reflection-absorption spectrograph (PA-IRRAS) offers significant advantages over conventional approaches including fast acquisition speed, excellent compensation for water vapor, and an excellent capacity for large infrared accessories, e.g., a water trough. In this study, the origin of stereocomplexation in a polylactide enantiomeric monolayer at the air-water interface was investigated using PA-IRRAS. PA-IRRAS was used as a probe to follow the real-time conformational changes associated with intermolecular interactions of polymer chains during the compression of the monolayers. It was found that a mixture of poly(D-lactic acid) (PDLA) and poly(L-lactic acid) (PLLA) (D/L) formed a stereocomplex when the two-dimensional monolayer developed at the air-water interface before film compression, indicating that there is no direct correlation between film compression and stereocomplexation. PA-IRRAS spectra of the stereocomplex exhibited distinct band shifts in crystalline sensitive components, e.g., the vas(C-O-C, h) mode, as well as amorphous-dependent components, e.g., the vs(C-O-C) mode, when compared with the spectra of PLLA alone. On the other hand, time-resolved PA-IRRAS spectra, which were obtained as the films were being compressed, revealed that both monolayers of PLLA and mixed PLLA/PDLA stereocomplex were crystallized into a 10(3)-helix and a 3(1)-helix, respectively, with a distinct band shift in crystalline sensitive components only. Fourier self-deconvolution of the spectra demonstrated that the band shift in crystalline sensitive components is correlated with the intermolecular interaction of polymer chains. PMID:18781784

  12. Simulated Solvation of Organic Ions II: Study of Linear Alkylated Carboxylate Ions in Water Nanodrops and in Liquid Water. Propensity for Air/Water Interface and Convergence to Bulk Solvation Properties.

    PubMed

    Houriez, Céline; Meot-Ner Mautner, Michael; Masella, Michel

    2015-09-10

    We investigated the solvation of carboxylate ions from formate to hexanoate, in droplets of 50 to 1000 water molecules and neat water, by computations using standard molecular dynamics and sophisticated polarizable models. The carboxylate ions from methanoate to hexanoate show strong propensity for the air/water interface in small droplets. Only the ions larger than propanoate retain propensity for the interface in larger droplets, where their enthalpic stabilization by ion/water dispersion is reduced there by 3 kcal mol(-1) per CH2 group. This is compensated by entropy effects over +3.3 cal mol(-1) K(-1) per CH2 group. On the surface, the anionic headgroups are strongly oriented toward the aqueous core, while the hydrophobic alkyl chains are repelled into air and lose their structure-making effects. These results reproduce the structure-making effects of alkyl groups in solution, and suggest that the hydrocarbon chains of ionic headgroups and alkyl substituents solvate independently. Extrapolation to bulk solution using standard extrapolation schemes yields absolute carboxylate solvation energies. The results for formate and acetate yield a proton solvation enthalpy of about 270 kcal mol(-1), close to the experiment-based value. The largest carboxylate ions yield a value smaller by about 10 kcal mol(-1), which requires studies in much larger droplets. PMID:26287943

  13. Halide anion dependence of ionic surfactant adsorption in air/water interface

    NASA Astrophysics Data System (ADS)

    Kim, Doseok; Wang, Wenjie; Sung, Woongmo; Ao, Mingqi; Vaknin, David

    2014-03-01

    It was recently proposed that there is surface excess of halide anions at the air/water interface, and more surface excess of I- than Br- or Cl-, which cannot be explained by Debye-Huckel theory. In case of charged surfaces such as Gibbs monolayer consisting of cationic surfactant molecules, surface excess of anions can also be expected. In this study, by using surface-sensitive grazing angle X-ray fluorescence in conjunction with surface tension measurement, we investigated adsorption behavior of [C12mim]Cl, [C12mim]Br, [C12mim]I aqueous solutions, in which the surface is first covered by [C12mim]+ cations at low concentrations, and the adsorption of the halide anions to this charged interface would follow with the increase in the concentration of solutes. From the surface tension measurements, it was observed that critical micelle concentration of [C12mim]I solution was 4.6 mM, much smaller than that of [C12mim]Cl (16.7 mM) indicating surface activity of surfactant increases with size of halide anions. From X-ray fluorescence, surface excess of halide anion was measured quantitatively from the interface of these solutions. By putting NaCl and NaI in [C12mim]I and [C12mim]Cl solutions, respectively, competition between Cl- and I- adsorption was investigated, to find that I- has stronger adsorption on the charged surface than Cl-.

  14. Hydration, Orientation, and Conformation of Methylglyoxal at the Air-Water Interface.

    PubMed

    Wren, Sumi N; Gordon, Brittany P; Valley, Nicholas A; McWilliams, Laura E; Richmond, Geraldine L

    2015-06-18

    Aqueous-phase processing of methylglyoxal (MG) has been suggested to constitute an important source of secondary organic aerosol (SOA). The uptake of MG to aqueous particles is higher than expected because its carbonyl moieties can hydrate to form geminal diols, as well as because MG and its hydration products can undergo aldol condensation reactions to form larger oligomers in solution. MG is known to be surface active, but an improved description of its surface behavior is crucial to understanding MG-SOA formation. These studies investigate MG adsorption, focusing on its hydration state at the air-water interface, using a combined experimental and theoretical approach that involves vibrational sum frequency spectroscopy, molecular dynamics simulations, and density functional theory calculations. Together, the experimental and theoretical data show that MG exists predominantly in a singly hydrated state (diol) at the interface, with a diol-tetrol ratio at the surface higher than that for the bulk. In addition to exhibiting a strong surface activity, we find that MG significantly perturbs the water structure at the interface. The results have implications for understanding the atmospheric fate of methylglyoxal. PMID:25989368

  15. Demonstration of adaptive optics for mitigating laser propagation through a random air-water interface

    NASA Astrophysics Data System (ADS)

    Land, Phillip; Majumdar, Arun K.

    2016-05-01

    This paper describes a new concept of mitigating signal distortions caused by random air-water interface using an adaptive optics (AO) system. This is the first time the concept of using an AO for mitigating the effects of distortions caused mainly by a random air-water interface is presented. We have demonstrated the feasibility of correcting the distortions using AO in a laboratory water tank for investigating the propagation effects of a laser beam through an airwater interface. The AO system consisting of a fast steering mirror, deformable mirror, and a Shack-Hartmann Wavefront Sensor for mitigating surface water distortions has a unique way of stabilizing and aiming a laser onto an object underneath the water. Essentially the AO system mathematically takes the complex conjugate of the random phase caused by air-water interface allowing the laser beam to penetrate through the water by cancelling with the complex conjugates. The results show the improvement of a number of metrics including Strehl ratio, a measure of the quality of optical image formation for diffraction limited optical system. These are the first results demonstrating the feasibility of developing a new sensor system such as Laser Doppler Vibrometer (LDV) utilizing AO for mitigating surface water distortions.

  16. Thermodynamic and dynamic characteristics of hydroxypropylmethylcellulose adsorbed films at the air-water interface.

    PubMed

    Pérez, Oscar E; Sánchez, Cecilio Carrera; Rodríguez Patino, Juan M; Pilosof, Ana M R

    2006-01-01

    Surface pressure isotherms and structural and surface dilatational properties of three hydroxypropylmethycelluloses (HPMCs, called E4M, E50LV, and F4M) adsorbed films at the air-water interface were determined. In this work we present evidence that HPMC molecules are able to diffuse and saturate the air-water interface at very low concentrations in the bulk phase. As bulk concentration increased, structural changes at a molecular level occurred at the interface. These changes corresponded to transition from an expanded structure (structure I) to a condensed one (structure II). When the surface concentration of HPMC was high enough, the collapse of the monolayer was observed. The three HPMCs formed very elastic films at the air-water interface, even at low surface pressures. E4M showed features that make it unique. For instance it showed the highest surface activity, mainly at low bulk concentrations (<10(-4) wt %). The differences observed in surface activity may be attributed to differences in the hydroxypropyl molar substitution and molecular weight of HPMC. All three HPMCs formed films of similar viscoelasticity and elastic dilatational modulus, which can be accounted for by their similar degree of methyl substitution. PMID:16398540

  17. Microstructure of Hairy-Rod Polymers at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Chien, B. T.; Riou, S. A.; Su, Z.; Hsu, S. L.

    1997-03-01

    To better understand the role of long flexible side groups on the microstructure of "hairy-rod" polymer thin films, a series of poly(γ-methyl-L-glutamate-co-γ-n-octadecyl-L- glutamate) of varying degree copolymerization has been investigated at the air-water interface by external reflectance infrared spectroscopy. Coupled with a Langmuir trough, the microstructure of the monolayer films was charaterized directly at the air-water interface as a function of varying surface packing density. The conformational order of the n-octadecyl side groups was subsequently shown to vary strongly as a function of n-octadecyl side group content as well as surface packing density. When conformationally disordered, the n-octadecyl side groups could be likened to that of a Rsolvent-likeS matrix for the rigid- rod main chains in the plane of the interface. By controlling the conformational order and therefore the Rsolvent-likeS character of the n-octadecyl side groups, it was possible to control an in-plane orientation of the rigid-rod main chains relative to that of the compression axis of the Langmuir trough. The orientation of the n- octadecyl side groups out of the plane of the air-water interface was also determined.

  18. Effect of Particulate Contaminants on the Development of Biofilms at Air/Water Interfaces.

    PubMed

    Zhang, Zhenhuan; Christopher, Gordon

    2016-03-22

    The development of biofilms at air/water or oil/water interfaces has important ramifications on several applications, but it has received less attention than biofilm formation on solid surfaces. A key difference between the growth of biofilms on solid surfaces versus liquid interfaces is the range of complicated boundary conditions the liquid interface can create that may affect bacteria, as they adsorb onto and grow on the interface. This situation is exacerbated by the existence of complex interfaces in which interfacially adsorbed components can even more greatly affect interfacial boundary conditions. In this work, we present evidence as to how particle-laden interfaces impact biofilm growth at an air/water interface. We find that particles can enhance the rate of growth and final strength of biofilms at liquid interfaces by providing sites of increased adhesive strength for bacteria. The increased adhesion stems from creating localized areas of hydrophobicity that protrude in the water phase and provide sites where bacteria preferentially adhere. This mechanism is found to be primarily controlled by particle composition, with particle size providing a secondary effect. This increased adhesion through interfacial conditions creates biofilms with properties similar to those observed when adhesion is increased through biological means. Because of the generally understood ubiquity of increased bacteria attachment to hydrophobic surfaces, this result has general applicability to pellicle formation for many pellicle-forming bacteria. PMID:26943272

  19. Influence of the tyrosine environment on the second harmonic generation of iturinic antimicrobial lipopeptides at the air-water interface.

    PubMed

    Nasir, Mehmet Nail; Benichou, Emmanuel; Loison, Claire; Russier-Antoine, Isabelle; Besson, Françoise; Brevet, Pierre-François

    2013-12-01

    The second harmonic generation (SHG) response at the air-water interface from the tyrosine-containing natural iturinic cyclo-lipopeptides mycosubtilin, iturin A and bacillomycin D is reported. It is shown that this response is dominated by the single tyrosine residue present in these molecules owing to the large first hyperpolarizability arising from the non-centrosymmetric aromatic ring structure of this amino acid. The SHG response of these iturinic antibiotics is also compared to the response of surfactin, a cyclo-lipopeptide with a similar l,d-amino acid sequence but lacking a tyrosine residue, and PalmATA, a synthetic linear lipopeptide possessing a single tyrosine residue but lacking the amino acid sequence structuring the cycle of the iturinic antibiotics. From the light polarization analysis of the SHG response, it is shown that the tyrosine local environment is critical in defining the SHG response of these peptides at the air-water interface. Our results demonstrate that tyrosine, similar to tryptophan, can be used as an endogenous molecular probe of peptides and proteins for SHG at the air-water interface, paving the way for SHG studies of other tyrosine-containing bioactive molecules. PMID:24149982

  20. Anisotropic orientational motion of molecular adsorbates at the air-water interface

    SciTech Connect

    Zimdars, D.; Dadap, J.I.; Eisenthal, K.B.; Heinz, T.F.

    1999-04-29

    The ultrafast orientational motions of coumarin 314 (C314) adsorbed at the air/water interface were investigated by time-resolved surface second harmonic generation (TRSHG). The theory and method of using TRSHG to detect both out-of-plane and in-plane orientational motions are discussed. The interfacial solute motions were found to be anisotropic, with differing out-of-plane and in-plane reorientation time constants. This report presents the first direct observation of in-plane orientational motion of a molecule (C314) at the air/water interface using TRSHG. The in-plane reorientation time constant is 600 {+-} 40 ps. The out-of-plane reorientation time constant is 350 {+-} 20 ps. The out-of-plane orientational motion of C314 is similar to the previous results on rhodamine 6G at the air/water interface which indicated increased interfacial friction compared with bulk aqueous solution. The surface reorientation times are 2--3 times slower than the bulk isotropic orientational diffusion time.

  1. Hydrodynamics of a fixed camphor boat at the air-water interface

    NASA Astrophysics Data System (ADS)

    Singh, Dhiraj; Akella, Sathish; Singh, Ravi; Mandre, Shreyas; Bandi, Mahesh

    2015-11-01

    A camphor tablet, when introduced at the air-water interface undergoes sublimation and the camphor vapour spreads radially outwards across the surface. This radial spreading of camphor is due to Marangoni forces setup by the camphor concentration gradient. We report experiments on the hydrodynamics of this process for a camphor tablet held fixed at the air-water interface. During the initial transient, the time-dependent spread radius R (t) of camphor scales algebraically with time t (R (t) ~t 1 / 2) in agreement with empirical scalings reported for spreading of volatile oils on water surface. But unlike surfactants, the camphor stops spreading when the influx of camphor from the tablet onto the air-water interface is balanced by the outflux of camphor due to evaporation, and a steady-state condition is reached. The spreading camphor however, shears the underlying fluid and sets up bulk convective flow. We explain the coupled steady-state dynamics between the interfacial camphor spreading and bulk convective flow with a boundary layer approximation, supported by experimental evidence. This work was supported by the Collective Interactions Unit, OIST Graduate University.

  2. Formation of a Rigid Hydrophobin Film and Disruption by an Anionic Surfactant at an Air/Water Interface.

    PubMed

    Kirby, Stephanie M; Zhang, Xujun; Russo, Paul S; Anna, Shelley L; Walker, Lynn M

    2016-06-01

    Hydrophobins are amphiphilic proteins produced by fungi. Cerato-ulmin (CU) is a hydrophobin that has been associated with Dutch elm disease. Like other hydrophobins, CU stabilizes air bubbles and oil droplets through the formation of a persistent protein film at the interface. The behavior of hydrophobins at surfaces has raised interest in their potential applications, including use in surface coatings, food foams, and emulsions and as dispersants. The practical use of hydrophobins requires an improved understanding of the interfacial behavior of these proteins, alone and in the presence of added surfactants. In this study, the adsorption behavior of CU at air/water interfaces is characterized by measuring the surface tension and interfacial rheology as a function of adsorption time. CU is found to adsorb irreversibly at air/water interfaces. The magnitude of the dilatational modulus increases with adsorption time and surface pressure until CU eventually forms a rigid film. The persistence of this film is tested through the sequential addition of strong surfactant sodium dodecyl sulfate (SDS) to the bulk liquid adjacent to the interface. SDS is found to coadsorb to interfaces precoated with a CU film. At high concentrations, the addition of SDS significantly decreases the dilatational modulus, indicating disruption and displacement of CU by SDS. Sequential adsorption results in mixed layers with properties not observed in interfaces generated from complexes formed in the bulk. These results lend insight to the complex interfacial interactions between hydrophobins and surfactants. PMID:27164189

  3. Effect of grafted polymer species on particle monolayer structure at the air-water interface.

    PubMed

    Mouri, Emiko; Okazaki, Yoshitaka; Komune, Seishu; Yoshinaga, Kohji

    2011-03-01

    We have studied poly(methyl methacrylate)-grafted(PMMA) particle monolayer systems at the air-water interface. In previous papers, we reported that PMMA chains grafted from particles (silica particle and polystyrene latex) were extended on water surfaces. Through observing deposited particle monolayers on substrates using SEM, we have confirmed that PMMA of large molecular weights were either dispersed or arrayed in structure with long inter-particle distances approximately 500 nm. In contrast, low molecular weight PMMA were observed to aggregate upon deposition. We speculated that the difference in morphology in deposited particle monolayers would be attributed to the affinity between the grafted polymer and the substrate. To examine the effect of this affinity three new polymer-grafted silica particles were synthesized with a fairly high graft density of about 0.14 approximately 0.43 nm(-2). As well as PMMA-grafted silica particles (SiO2-PMMA), poly(2-hydroxyethyl methacrylate) and poly(t-butyl methacrylate)--grafted silica particles (SiO2-PHEMA and SiO2-PtBuMA) were also prepared and subjected to pi-A isotherm measurements and SEM observations. These pi-A isotherms indicated that polymer-grafted silica formed monolayer at the air-water interface, and the onset area of increasing surface pressure suggests that the polymer chains are extended on a water surface. However, the morphology of the deposited monolayer is highly dependent on polymer species: SiO2-PHEMA showed that the dispersed particle monolayer structure was independent of grafted molecular weight while SiO2-tBuMA showed an aggregated structure that was also independent of grafted moleculer weight. SiO2-PMMA showed intermediate tendencies: dispersed structure was observed with high grafted molecular weight and aggregated structure was observed with low grafted molecule weight. The morphology on glass substrate would be explaiened by hydrophilic interaction between grafted polymer and hydrophilic glass

  4. Fluorescence light microscopy of pulmonary surfactant at the air-water interface of an air bubble of adjustable size.

    PubMed

    Knebel, D; Sieber, M; Reichelt, R; Galla, H-J; Amrein, M

    2002-07-01

    The structural dynamics of pulmonary surfactant was studied by epifluorescence light microscopy at the air-water interface of a bubble as a model close to nature for an alveolus. Small unilamellar vesicles of dipalmitoylphosphatidylcholine, dipalmitoylphosphatidylglycerol, a small amount of a fluorescent dipalmitoylphosphatidylcholine-analog, and surfactant-associated protein C were injected into the buffer solution. They aggregated to large clusters in the presence of Ca(2+) and adsorbed from these units to the interface. This gave rise to an interfacial film that eventually became fully condensed with dark, polygonal domains in a fluorescent matrix. When now the bubble size was increased or decreased, respectively, the film expanded or contracted. Upon expansion of the bubble, the dark areas became larger to the debit of the bright matrix and reversed upon contraction. We were able to observe single domains during the whole process. The film remained condensed, even when the interface was increased to twice its original size. From comparison with scanning force microscopy directly at the air-water interface, the fluorescent areas proved to be lipid bilayers associated with the (dark) monolayer. In the lung, such multilayer phase acts as a reservoir that guarantees a full molecular coverage of the alveolar interface during the breathing cycle and provides mechanical stability to the film. PMID:12080141

  5. Multi-scale modeling of mycosubtilin lipopeptides at the air/water interface: structure and optical second harmonic generation.

    PubMed

    Loison, Claire; Nasir, Mehmet Nail; Benichou, Emmanuel; Besson, Françoise; Brevet, Pierre-François

    2014-02-01

    Monolayers of the lipopeptide mycosubtilin are studied at the air/water interface. Their structure is investigated using molecular dynamics simulations. All-atom models suggest that the lipopeptide is flexible and aggregates at the interface. To achieve simulation times of several microseconds, a coarse-grained (CG) model based on the MARTINI force field was also used. These CG simulations describe the formation of half-micelles at the interface for surface densities up to 1 lipopeptide per nm(2). In these aggregates, the tyrosine side chain orientation is found to be constrained: on average, its main axis, as defined along the C-OH bond, aligns along the interface normal and points towards the air side. The origin of the optical second harmonic generation (SHG) from mycosubtilin monolayers at the air/water interface is also investigated. The molecular hyperpolarizability of the lipopeptide is obtained from quantum chemistry calculations. The tyrosine side chain contribution to the hyperpolarizability is found to be dominant. The orientation distribution of tyrosine, associated with a dominant hyperpolarizability component along the C-OH bond of the tyrosine, yields a ratio of the susceptibility elements χ((2))(ZZZ)/χ((2))(ZXX) consistent with the experimental measurements recently reported by M. N. Nasir et al. [Phys. Chem. Chem. Phys., 2013, 15, 19919]. PMID:24346061

  6. Self-Assembly of Peptides at the Air/Water Interface

    NASA Astrophysics Data System (ADS)

    Sayar, Mehmet

    2013-03-01

    Peptides are commonly used as building blocks for design and development of novel materials with a variety of application areas ranging from drug design to biotechnology. The precise control of molecular architecture and specific nature of the nonbonded interactions among peptides enable aggregates with well defined structural and functional properties. The interaction of peptides with interfaces leads to dramatic changes in their conformational and aggregation behavior. In this talk, I will discuss our research on the interplay of intermolecular forces and influence of interfaces. In the first part the amphiphilic nature of short peptide oligomers and their behavior at the air/water interface will be discussed. The surface driving force and its decomposition will be analyzed. In the second part aggregation of peptides in bulk water and at an interface will be discussed. Different design features which can be tuned to control aggregation behavior will be analyzed.

  7. Protein adsorption at the electrified air-water interface: implications on foam stability.

    PubMed

    Engelhardt, Kathrin; Rumpel, Armin; Walter, Johannes; Dombrowski, Jannika; Kulozik, Ulrich; Braunschweig, Björn; Peukert, Wolfgang

    2012-05-22

    The surface chemistry of ions, water molecules, and proteins as well as their ability to form stable networks in foams can influence and control macroscopic properties such as taste and texture of dairy products considerably. Despite the significant relevance of protein adsorption at liquid interfaces, a molecular level understanding on the arrangement of proteins at interfaces and their interactions has been elusive. Therefore, we have addressed the adsorption of the model protein bovine serum albumin (BSA) at the air-water interface with vibrational sum-frequency generation (SFG) and ellipsometry. SFG provides specific information on the composition and average orientation of molecules at interfaces, while complementary information on the thickness of the adsorbed layer can be obtained with ellipsometry. Adsorption of charged BSA proteins at the water surface leads to an electrified interface, pH dependent charging, and electric field-induced polar ordering of interfacial H(2)O and BSA. Varying the bulk pH of protein solutions changes the intensities of the protein related vibrational bands substantially, while dramatic changes in vibrational bands of interfacial H(2)O are simultaneously observed. These observations have allowed us to determine the isoelectric point of BSA directly at the electrolyte-air interface for the first time. BSA covered air-water interfaces with a pH near the isoelectric point form an amorphous network of possibly agglomerated BSA proteins. Finally, we provide a direct correlation of the molecular structure of BSA interfaces with foam stability and new information on the link between microscopic properties of BSA at water surfaces and macroscopic properties such as the stability of protein foams. PMID:22530646

  8. Free Energies of Cavity and Noncavity Hydrated Electrons Near the Instantaneous Air/Water Interface.

    PubMed

    Casey, Jennifer R; Schwartz, Benjamin J; Glover, William J

    2016-08-18

    The properties of the hydrated electron at the air/water interface are computed for both a cavity and a noncavity model using mixed quantum/classical molecular dynamics simulation. We take advantage of our recently developed formalism for umbrella sampling with a restrained quantum expectation value to calculate free-energy profiles of the hydrated electron's position relative to the water surface. We show that it is critical to use an instantaneous description of the air/water interface rather than the Gibbs' dividing surface to obtain accurate potentials of mean force. We find that noncavity electrons, which prefer to encompass several water molecules, avoid the interface where water molecules are scarce. In contrast, cavity models of the hydrated electron, which prefer to expel water, have a local free-energy minimum near the interface. When the cavity electron occupies this minimum, its absorption spectrum is quite red-shifted, its binding energy is significantly lowered, and its dynamics speed up quite a bit compared with the bulk, features that have not been found by experiment. The surface activity of the electron therefore serves as a useful test of cavity versus noncavity electron solvation. PMID:27479028

  9. Formation, disruption and mechanical properties of a rigid hydrophobin film at an air-water interface

    NASA Astrophysics Data System (ADS)

    Walker, Lynn; Kirby, Stephanie; Anna, Shelley; CMU Team

    Hydrophobins are small, globular proteins with distinct hydrophilic and hydrophobic regions that make them extremely surface active. The behavior of hydrophobins at surfaces has raised interest in their potential industrial applications, including use in surface coatings, food foams and emulsions, and as dispersants. Practical use of hydrophobins requires an improved understanding of the interfacial behavior of these proteins, both individually and in the presence of surfactants. Cerato-ulmin (CU) is a hydrophobin that has been shown to strongly stabilize air bubbles and oil droplets through the formation of a persistent protein film at the interface. In this work, we characterize the adsorption behavior of CU at air/water interfaces by measuring the surface tension and interfacial rheology as a function of adsorption time. CU is found to strongly, irreversibly adsorb at air/water interfaces; the magnitude of the dilatational modulus increases with adsorption time and surface pressure, until the CU eventually forms a rigid film. The persistence of this film is tested through the addition of SDS, a strong surfactant, to the bulk. SDS is found to co-adsorb to interfaces pre-coated with a CU film. At high concentrations, the addition of SDS significantly decreases the dilatational modulus, indicating disruption and displacement of CU. These results lend insight into the complex interfacial interactions between hydrophobins and surfactants. Funding from GoMRI.

  10. Semifluorinated Alkanes at the Air-Water Interface: Tailoring Structure and Rheology at the Molecular Scale.

    PubMed

    Theodoratou, Antigoni; Jonas, Ulrich; Loppinet, Benoit; Geue, Thomas; Stangenberg, Rene; Keller, Rabea; Li, Dan; Berger, Rüdiger; Vermant, Jan; Vlassopoulos, Dimitris

    2016-04-01

    Semifluorinated alkanes form monolayers with interesting properties at the air-water interface due to their pronounced amphi-solvophobic nature and the stiffness of the fluorocarbons. In the present work, using a combination of structural and dynamic probes, we investigated how small molecular changes can be used to control the properties of such an interface, in particular its organization, rheology, and reversibility during compression-expansion cycles. Starting from a reference system perfluor(dodecyl)dodecane, we first retained the linear structure but changed the linkage groups between the alkyl chains and the fluorocarbons, by introducing either a phenyl group or two oxygens. Next, the molecular structure was changed from linear to branched, with four side chains (two fluorocarbons and two hydrocarbons) connected to extended aromatic cores. Neutron reflectivity at the air-water interface and scanning force microscopy on deposited films show how the changes in the molecular structure affect molecular arrangement relative to the interface. Rheological and compression-expansion measurements demonstrate the significant consequences of these changes in molecular structure and interactions on the interfacial properties. Remarkably, even with these simple molecules, a wide range of surface rheological behaviors can be engineered, from viscous over viscoelastic to brittle solids, for very similar values of the surface pressure. PMID:26978461

  11. Dissecting the Molecular Structure of the Air/Water Interface from Quantum Simulations of the Sum-Frequency Generation Spectrum.

    PubMed

    Medders, Gregory R; Paesani, Francesco

    2016-03-23

    The molecular characterization of the air/water interface is a key step in understanding fundamental multiphase phenomena ranging from heterogeneous chemical processes in the atmosphere to the hydration of biomolecules. The apparent simplicity of the air/water interface, however, masks an underlying complexity associated with the dynamic nature of the water hydrogen-bond network that has so far hindered an unambiguous characterization of its microscopic properties. Here, we demonstrate that the application of quantum many-body molecular dynamics, which enables spectroscopically accurate simulations of water from the gas to the condensed phase, leads to a definitive molecular-level picture of the interface region. For the first time, excellent agreement is obtained between the simulated vibrational sum-frequency generation spectrum and the most recent state-of-the-art measurements, without requiring any empirical frequency shift or ad hoc scaling of the spectral intensity. A systematic dissection of the spectral features demonstrates that a rigorous representation of nuclear quantum effects as well as of many-body energy and electrostatic contributions is necessary for a quantitative reproduction of the experimental data. The unprecedented accuracy of the simulations presented here indicates that quantum many-body molecular dynamics can enable predictive studies of aqueous interfaces, which by complementing analogous experimental measurements will provide unique molecular insights into multiphase and heterogeneous processes of relevance in chemistry, biology, materials science, and environmental research. PMID:26943730

  12. Communication: Vibrational sum-frequency spectrum of the air-water interface, revisited.

    PubMed

    Ni, Yicun; Skinner, J L

    2016-07-21

    Before 2015, heterodyne-detected sum-frequency-generation experiments on the air-water interface showed the presence of a positive feature at low frequency in the imaginary part of the susceptibility. However, three very recent experiments indicate that this positive feature is in fact absent. Armed with a better understanding, developed by others, of how to calculate sum-frequency spectra, we recalculate the spectrum and find good agreement with these new experiments. In addition, we provide a revised interpretation of the spectrum. PMID:27448864

  13. Formation of H-type liquid crystal dimer at air-water interface

    SciTech Connect

    Karthik, C. Gupta, Adbhut Joshi, Aditya Manjuladevi, V. Gupta, Raj Kumar; Varia, Mahesh C.; Kumar, Sandeep

    2014-04-24

    We have formed the Langmuir monolayer of H-shaped Azo linked liquid crystal dimer molecule at the air-water interface. Isocycles of the molecule showed hysteresis suggesting the ir-reversible nature of the monolayer formed. The thin film deposited on the silicon wafer was characterized using Atomic Force Microscopy (AFM) and Field Emission Scanning Electron Microscopy (FESEM). The images showed uniform domains of the dimer molecule. We propose that these molecules tend to take book shelf configuration in the liquid phase.

  14. Communication: Vibrational sum-frequency spectrum of the air-water interface, revisited

    NASA Astrophysics Data System (ADS)

    Ni, Yicun; Skinner, J. L.

    2016-07-01

    Before 2015, heterodyne-detected sum-frequency-generation experiments on the air-water interface showed the presence of a positive feature at low frequency in the imaginary part of the susceptibility. However, three very recent experiments indicate that this positive feature is in fact absent. Armed with a better understanding, developed by others, of how to calculate sum-frequency spectra, we recalculate the spectrum and find good agreement with these new experiments. In addition, we provide a revised interpretation of the spectrum.

  15. Semiconductor Conjugated Polymer-Quantum Dot Nanocomposites at the Air/Water Interface and Their Performance in Thin Film Solar Cells

    NASA Astrophysics Data System (ADS)

    Lin, Zhiqun; Goodman, Matthew; Xu, Jun; Wang, Jun

    2009-03-01

    Organic-inorganic nanocomposites consisting of electroactive conjugated polymer, poly(3-hexylthiophene) (P3HT) intimately tethered on the surface of semiconductor CdSe quantum dot (i.e., P3HT-CdSe nanocomposites) at the air/water interface formed via Langmuir isotherms were explored for the first time. The P3HT-CdSe nanocomposites displayed a high pressure plateau in the Langmuir isotherm, illustrating their complex packing at the air/water interface. Furthermore, photovoltaic devices fabricated from the LB depositions of the P3HT-CdSe nanocomposites exhibited a relatively high short circuit current, ISC, while maintaining a thin film profile. These studies provide insights into the fundamental behaviors of semiconductor organic-inorganic nanocomposites confined at the air/water interface as well as in the active layer of an organic-based photovoltaic device.

  16. Towards Organized Hybrid Nanomaterials at the Air/Water Interface Based on Liquid-Crystal/ZnO Nanocrystals.

    PubMed

    Paczesny, Jan; Wolska-Pietkiewicz, Małgorzata; Binkiewicz, Ilona; Wróbel, Zbigniew; Wadowska, Monika; Matuła, Kinga; Dzięcielewski, Igor; Pociecha, Damian; Smalc-Koziorowska, Julita; Lewiński, Janusz; Hołyst, Robert

    2015-11-16

    The ability to self-assemble nanosized ligand-stabilized metal oxide or semiconductor materials offers an intriguing route to engineer nanomaterials with new tailored properties from the disparate components. We describe a novel one-pot two-step organometallic approach to prepare ZnO nanocrystals (NCs) coated with deprotonated 4-(dodecyloxy)benzoic acid (i.e., an X-type liquid-crystalline ligand) as a model LC system (termed ZnO-LC1 NCs). Langmuir and Langmuir-Blodgett films of the resulting hybrids are investigated. The observed behavior of the ZnO NCs at the air/water interface is rationalized by invoking a ZnO-interdigitation process mediated by the anchored liquid-crystalline shell. The ordered superstructures form according to mechanism based on a ZnO-interdigitation process mediated by liquid crystals (termed ZIP-LC). The external and directed force applied upon compression at the air/water interface and the packing of the ligands that stabilize the ZnO cores drives the formation of nanorods of ordered internal structure. To study the process in detail, we follow a nontraditional protocol of thin-film investigation. We collect the films from the air/water interface in powder form (ZnO-LC1 LB), resuspend the powder in organic solvents and utilize otherwise unavailable experimental techniques. The structural and physical properties of the resulting superlattices were studied by using electron microscopy, atomic force microscopy, X-ray studies, dynamic light scattering, thermogravimetric analysis, UV/Vis absorption, and photoluminescence spectroscopy. PMID:26427916

  17. OH-Radical Oxidation of Surface-Active cis-Pinonic Acid at the Air-Water Interface.

    PubMed

    Enami, Shinichi; Sakamoto, Yosuke

    2016-05-26

    Gaseous biogenic volatile organic compounds (BVOCs) are immediately oxidized by gaseous oxidants to form BVOC-acids that rapidly condense onto aqueous aerosol phase and thus contribute to the growth of atmospheric particles. Because BVOC-acids are highly hydrophobic and hence surface-active in nature, it seems critical to study the oxidation by gaseous hydroxyl radical (·OH(g)) at the air-water interface. Here we report on the fast (≤10 μs) oxidation of aqueous cis-pinonic acid (C10H16O3, CPA, cis-pinonate anion's m/z = 183), a representative BVOC-acid, by ·OH(g) at the air-water interface for the first time. We find that cis-pinonate anion is more enriched at the air-water interface by ∼4 and ∼14 times than n-octanoate anion at 10 and 100 μM, respectively, as revealed by an interface-specific mass spectrometry of the equimolar mixture of microjets. Exposure of aqueous CPA microjets to ·OH(g) pulses from the 266 nm laser photolysis of O3(g)/O2(g)/H2O(g)/N2(g) mixtures yields pinonic peroxyl radicals (m/z = 214) that lead to the functionalization products carbonyls (m/z = 197), alcohols (m/z = 199), and pinonic hydroperoxides (m/z = 215) in addition to smaller-mass products including carbonyls (m/z = 155 and 157). We confirmed the formation of the corresponding alcohols, aldehydes, and hydroperoxides in experiments performed in D2O solvent. The analysis of total mass balance implies a significant amount (>70%) of products would be emitted into the gas-phase during the heterogeneous ·OH-oxidations. Our results suggest ·OH-oxidations of amphiphilic BVOC-acids at the air-water interface may play a far more significant role in photochemical aging process of aqueous aerosols than previously assumed. PMID:27098046

  18. Mechanisms of Polyelectrolyte Enhanced Surfactant Adsorption at the Air-Water Interface

    PubMed Central

    Stenger, Patrick C.; Palazoglu, Omer A.; Zasadzinski, Joseph A.

    2009-01-01

    Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids. PMID:19366599

  19. Rapid Facial Fabrication of Silica Colloidal Crystal Film at the Air/Water Interface.

    PubMed

    Wang, Xia; Wang, Yun; Chen, Qiming

    2015-12-01

    A rapid and facial strategy has been developed to self-assemble 2D or 3D silica colloidal crystals at the air/water interface. The surface hydrophilicity of monodisperse silica microspheres were prepared by the Stöber method and modified by physical adsorption of a cationic surfactant (CTAB). The surface-modified silica microspheres were dispersed into an organic solvent and readily self-assemble at the air/water interface to form 2D monolayer film. The surface potential (ζ ) of silica microspheres could be changed with different concentration of CTAB aqueous solution. When the surface potential of silica particles was of -36.67 mV, a 2D monolayer film with close-packed and high-ordered structure could be easily obtained and may further be transferred onto a solid substrate layer by layer to develop a 3D multilayer film. UV-visible spectrophotometer was used to analyze the orderliness of colloidal crystal film, the Bragg diffraction positions and silica diameters were in good agreement with those were theoretically calculated. In addition, Atomic Force microscopy (AFM) was used to observe the arrangement of colloidal crystals. PMID:26682401

  20. Langmuir-Blodgett film of hydrophobin protein from Pleurotus ostreatus at the air-water interface.

    PubMed

    Houmadi, S; Ciuchi, F; De Santo, M P; De Stefano, L; Rea, I; Giardina, P; Armenante, A; Lacaze, E; Giocondo, M

    2008-11-18

    We present results concerning the formation of Langmuir-Blodgett (LB) films of a class I hydrophobin from Pleurotus ostreatus at the air-water interface, and their structure as Langmuir-Blodgett (LB) films when deposited on silicon substrates. LB films of the hydrophobin were investigated by atomic force microscopy (AFM). We observed that the compressed film at the air-water interface exhibits a molecular depletion even at low surface pressure. In order to estimate the surface molecular concentration, we fit the experimental isotherm with Volmer's equation describing the equation of state for molecular monolayers. We found that about (1)/ 10 of the molecules contribute to the surface film formation. When transferred on silicon substrates, compact and uniform monomolecular layers about 2.5 nm thick, comparable to a typical molecular size, were observed. The monolayers coexist with protein aggregates, under the typical rodlet form with a uniform thickness of about 5.0 nm. The observed rodlets appear to be a hydrophilic bilayer and can then be responsible for the surface molecular depletion. PMID:18925762

  1. Photoswitching the mechanical properties in Langmuir layers of semifluorinated alkyl-azobenzenes at the air-water interface.

    PubMed

    Theodoratou, Antigoni; Jonas, Ulrich; Loppinet, Benoit; Geue, Thomas; Stangenberg, René; Li, Dan; Berger, Rüdiger; Vlassopoulos, Dimitris

    2015-11-21

    Semifluorinated alkyl-azobenzene derivatives (SFAB) can form stable Langmuir layers at the air-water interface. These systems combine the amphiphobic character of semifluorinated alkyl units as structure-directing motifs with photochromic behavior based on the well-known reversible cis-trans isomerization upon irradiation with UV and visible light. Herein, we report our investigations of the structural and dynamic tunability of these SFAB layers at the air-water interface in response to an external light stimulus. The monolayer structures and properties of [4-(heptadecafluorooctyl)phenyl](4-octylphenyl)diazene (F8-azo-H8) and bis(4-octylphenyl)diazene (H8-azo-H8) were studied by neutron reflectivity, surface pressure-area isotherms with compression-expansion cycles, and interfacial rheology. We find that UV irradiation reversibly influences the packing behavior of the azobenzene molecules and interpret this as a transition from organized layer structures with the main axis of the molecule vertically oriented in the trans form to random packing of the cis isomer. Interestingly, this trans-cis isomerization leads to an increase in surface pressure, which is accompanied by a decrease in viscoelastic moduli. These results suggest ways of tailoring the properties of responsive fluid interfaces. PMID:26451399

  2. Trapping of Sodium Dodecyl Sulfate at the Air-Water Interface of Oscillating Bubbles.

    PubMed

    Corti, Mario; Pannuzzo, Martina; Raudino, Antonio

    2015-06-16

    We report that at very low initial bulk concentrations, a couple of hundred times below the critical micellar concentration (CMC), anionic surfactant sodium dodecyl sulfate (SDS) adsorbed at the air-water interface of a gas bubble cannot be removed, on the time scale of the experiment (hours), when the surrounding solution is gently replaced by pure water. Extremely sensitive interferometric measurements of the resonance frequency of the bubble-forced oscillations give precise access to the concentration of the surfactant monolayer. The bulk-interface dynamic exchange of SDS molecules is shown to be inhibited below a concentration which we believe refers to a kind of gas-liquid phase transition of the surface monolayer. Above this threshold we recover the expected concentration-dependent desorption. The experimental observations are interpreted within simple energetic considerations supported by molecular dynamics (MD) calculations. PMID:26039913

  3. Atmospheric photochemistry at a fatty acid-coated air-water interface.

    PubMed

    Rossignol, Stéphanie; Tinel, Liselotte; Bianco, Angelica; Passananti, Monica; Brigante, Marcello; Donaldson, D James; George, Christian

    2016-08-12

    Although fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over a monolayer of NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase, and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet-state NA molecules excited by direct absorption of actinic light at the water surface. Because fatty acids-covered interfaces are ubiquitous in the environment, such photochemical processing will have a substantial impact on local ozone and particle formation. PMID:27516601

  4. Atmospheric photochemistry at a fatty acid–coated air-water interface

    NASA Astrophysics Data System (ADS)

    Rossignol, Stéphanie; Tinel, Liselotte; Bianco, Angelica; Passananti, Monica; Brigante, Marcello; Donaldson, D. James; George, Christian

    2016-08-01

    Although fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over a monolayer of NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase, and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet-state NA molecules excited by direct absorption of actinic light at the water surface. Because fatty acids–covered interfaces are ubiquitous in the environment, such photochemical processing will have a substantial impact on local ozone and particle formation.

  5. Dynamic adsorption of weakly interacting polymer/surfactant mixtures at the air/water interface.

    PubMed

    Angus-Smyth, Anna; Campbell, Richard A; Bain, Colin D

    2012-08-28

    The dynamic adsorption of polymer/surfactant mixtures containing poly(ethylene oxide) (PEO) with either tetradecyltrimethylammonium bromide (C(14)TAB) or sodium dodecyl sulfate (SDS) has been studied at the expanding air/water interface created by an overflowing cylinder, which has a surface age of 0.1-1 s. The composition of the adsorption layer is obtained by a new approach that co-models data obtained from ellipsometry and only one isotopic contrast from neutron reflectometry (NR) without the need for any deuterated polymer. The precision and accuracy of the polymer surface excess obtained matches the levels achieved from NR measurements of different isotopic contrasts involving deuterated polymer, and requires much less neutron beamtime. The PEO concentration was fixed at 100 ppm and the electrolyte concentration at 0.1 M while the surfactant concentration was varied over three orders of magnitude. For both systems, at low bulk surfactant concentrations, adsorption of the polymer is diffusion-controlled while surfactant adsorption is under mixed kinetic/diffusion control. Adsorption of PEO is inhibited once the surfactant coverage exceeds 2 μmol m(-2). For PEO/C(14)TAB, polymer adsorption drops abruptly to zero over a narrow range of surfactant concentration. For PEO/SDS, inhibition of polymer adsorption is much more gradual, and a small amount remains adsorbed even at bulk surfactant concentrations above the cmc. The difference in behavior of the two mixtures is ascribed to favorable interactions between the PEO and SDS in the bulk solution and at the surface. PMID:22746543

  6. Reactivity of aldehydes at the air-water interface. Insights from molecular dynamics simulations and ab initio calculations.

    PubMed

    Martins-Costa, Marilia T C; García-Prieto, Francisco F; Ruiz-López, Manuel F

    2015-02-14

    Understanding the influence of solute-solvent interactions on chemical reactivity has been a subject of intense research in the last few decades. Theoretical studies have focused on bulk solvation phenomena and a variety of models and methods have been developed that are now widely used by both theoreticians and experimentalists. Much less attention has been paid, however, to processes that occur at liquid interfaces despite the important role such interfaces play in chemistry and biology. In this study, we have carried out sequential molecular dynamics simulations and quantum mechanical calculations to analyse the influence of the air-water interface on the reactivity of formaldehyde, acetaldehyde and benzaldehyde, three simple aldehydes of atmospheric interest. The calculated free-energy profiles exhibit a minimum at the interface, where the average reactivity indices may display large solvation effects. The study emphasizes the role of solvation dynamics, which are responsible for large fluctuations of some molecular properties. We also show that the photolysis rate constant of benzaldehyde in the range 290-308 nm increases by one order of magnitude at the surface of a water droplet, from 2.7 × 10(-5) s(-1) in the gas phase to 2.8 × 10(-4) s(-1) at the air-water interface, and we discuss the potential impact of this result on the chemistry of the troposphere. Experimental data in this domain are still scarce and computer simulations like those presented in this work may provide some insights that can be useful to design new experiments. PMID:25451554

  7. Catechol oxidation by ozone and hydroxyl radicals at the air-water interface.

    PubMed

    Pillar, Elizabeth A; Camm, Robert C; Guzman, Marcelo I

    2014-12-16

    Anthropogenic emissions of aromatic hydrocarbons promptly react with hydroxyl radicals undergoing oxidation to form phenols and polyphenols (e.g., catechol) typically identified in the complex mixture of humic-like substances (HULIS). Because further processing of polyphenols in secondary organic aerosols (SOA) can continue mediated by a mechanism of ozonolysis at interfaces, a better understanding about how these reactions proceed at the air-water interface is needed. This work shows how catechol, a molecular probe of the oxygenated aromatic hydrocarbons present in SOA, can contribute interfacial reactive species that enhance the production of HULIS under atmospheric conditions. Reactive semiquinone radicals are quickly produced upon the encounter of 40 ppbv-6.0 ppmv O3(g) with microdroplets containing [catechol] = 1-150 μM. While the previous pathway results in the instantaneous formation of mono- and polyhydroxylated aromatic rings (PHA) and chromophoric mono- and polyhydroxylated quinones (PHQ), a different channel produces oxo- and dicarboxylic acids of low molecular weight (LMW). The cleavage of catechol occurs at the 1,2 carbon-carbon bond at the air-water interface through the formation of (1) an ozonide intermediate, (2) a hydroperoxide, and (3) cis,cis-muconic acid. However, variable [catechol] and [O3(g)] can affect the ratio of the primary products (cis,cis-muconic acid and trihydroxybenzenes) and higher order products observed (PHA, PHQ, and LMW oxo- and dicarboxylic acids). Secondary processing is confirmed by mass spectrometry, showing the production of crotonic, maleinaldehydic, maleic, glyoxylic, and oxalic acids. The proposed pathway can contribute precursors to aqueous SOA (AqSOA) formation, converting aromatic hydrocarbons into polyfunctional species widely found in tropospheric aerosols with light-absorbing brown carbon. PMID:25423038

  8. Adsorption at the air-water interface and emulsification properties of grain legume protein derivatives from pea and broad bean.

    PubMed

    Tsoukala, A; Papalamprou, E; Makri, E; Doxastakis, G; Braudo, E E

    2006-12-01

    Functional properties of native and modified (through induced autolysis) pea (Pisum sativum L.) and broad bean (Vicia faba L.) protein derivatives are studied. In specific, protein solubility and behavior at the air-water interface through surface pressure measurements are investigated. Furthermore the ability of the protein products to act as emulsifying agents and to stabilize emulsions is studied through oil droplet size distribution measurements and by the protein adsorbed at the oil-water interface. The data reveal that the ability of the proteins to act as surfactants and build up a rigid film around the oil droplets, mainly depends on their suitable molecular configuration and structure. Hydrolysis did not promote the functionality of the legume proteins. Broad bean exhibited better functionality than pea, before and after hydrolysis. Some comparisons were also made with lupin (Lupinus albus L.) protein isolate. PMID:17049437

  9. Measuring interactions between polydimethylsiloxane and serum proteins at the air-water interface.

    PubMed

    Liao, Zhengzheng; Hsieh, Wan-Ting; Baumgart, Tobias; Dmochowski, Ivan J

    2013-07-30

    The interaction between synthetic polymers and proteins at interfaces is relevant to basic science as well as a wide range of applications in biotechnology and medicine. One particularly common and important interface is the air-water interface (AWI). Due to the special energetics and dynamics of molecules at the AWI, the interplay between synthetic polymer and protein can be very different from that in bulk solution. In this paper, we applied the Langmuir-Blodgett technique and fluorescence microscopy to investigate how the compression state of polydimethylsiloxane (PDMS) film at the AWI affects the subsequent adsorption of serum protein [e.g., human serum albumin (HSA) or immunoglobulin G (IgG)] and the interaction between PDMS and protein. Of particular note is our observation of circular PDMS domains with micrometer diameters that form at the AWI in the highly compressed state of the surface film: proteins were shown to adsorb preferentially to the surface of these circular PDMS domains, accompanied by a greater than 4-fold increase in protein found in the interfacial film. The PDMS-only film and the PDMS-IgG composite film were transferred to cover glass, and platinum-carbon replicas of the transferred films were further characterized by scanning electron microscopy and atomic force microscopy. We conclude that the structure of the PDMS film greatly affects the amount and distribution of protein at the interface. PMID:23819833

  10. Polystyrene-poly(ethylene oxide) diblock copolymer: the effect of polystyrene and spreading concentration at the air/water interface.

    PubMed

    Glagola, Cameron P; Miceli, Lia M; Milchak, Marissa A; Halle, Emily H; Logan, Jennifer L

    2012-03-20

    Polystyrene-block-poly(ethylene oxide) (PS-PEO) is an amphiphilic diblock copolymer that undergoes microphase separation when spread at the air/water interface, forming nanosized domains. In this study, we investigate the impact of PS by examining a series of PS-PEO samples containing constant PEO (~17,000 g·mol(-1)) and variable PS (from 3600 to 200,000 g·mol(-1)) through isothermal characterization and atomic force microscopy (AFM). The polymers separated into two categories: predominantly hydrophobic and predominantly hydrophilic with a weight percent of PEO of ~20% providing the boundary between the two. AFM results indicated that predominantly hydrophilic PS-PEO forms dots while more hydrophobic samples yield a mixture of dots and spaghetti with continent-like structures appearing at ~7% PEO or less. These structures reflect a blend of polymer spreading, entanglement, and vitrification as the solvent evaporates. Changing the spreading concentration provides insight into this process with higher concentrations representing earlier kinetic stages and lower concentrations demonstrating later ones. Comparison of isothermal results and AFM analysis shows how polymer behavior at the air/water interface correlates with the observed nanostructures. Understanding the impact of polymer composition and spreading concentration is significant in leading to greater control over the nanostructures obtained through PS-PEO self-assembly and their eventual application as polymer templates. PMID:22339480

  11. Reversible monolayer-to-crystalline phase transition in amphiphilic silsesquioxane at the air-water interface

    DOE PAGESBeta

    Banerjee, R.; Sanyal, M. K.; Bera, M. K.; Gibaud, A.; Lin, B.; Meron, M.

    2015-02-17

    We report on the counter intuitive reversible crystallisation of two-dimensional monolayer of Trisilanolisobutyl Polyhedral Oligomeric SilSesquioxane (TBPOSS) on water surface using synchrotron x-ray scattering measurements. Amphiphilic TBPOSS form rugged monolayers and Grazing Incidence X-ray Scattering (GIXS) measurements reveal that the in-plane inter-particle correlation peaks, characteristic of two-dimensional system, observed before transition is replaced by intense localized spots after transition. The measured x-ray scattering data of the non-equilibrium crystalline phase on the air-water interface could be explained with a model that assumes periodic stacking of the TBPOSS dimers. These crystalline stacking relaxes upon decompression and the TBPOSS layer retains its initialmore » monolayer state. The existence of these crystals in compressed phase is confirmed by atomic force microscopy measurements by lifting the materials on a solid substrate.« less

  12. Reversible monolayer-to-crystalline phase transition in amphiphilic silsesquioxane at the air-water interface

    SciTech Connect

    Banerjee, R.; Sanyal, M. K.; Bera, M. K.; Gibaud, A.; Lin, B.; Meron, M.

    2015-02-17

    We report on the counter intuitive reversible crystallisation of two-dimensional monolayer of Trisilanolisobutyl Polyhedral Oligomeric SilSesquioxane (TBPOSS) on water surface using synchrotron x-ray scattering measurements. Amphiphilic TBPOSS form rugged monolayers and Grazing Incidence X-ray Scattering (GIXS) measurements reveal that the in-plane inter-particle correlation peaks, characteristic of two-dimensional system, observed before transition is replaced by intense localized spots after transition. The measured x-ray scattering data of the non-equilibrium crystalline phase on the air-water interface could be explained with a model that assumes periodic stacking of the TBPOSS dimers. These crystalline stacking relaxes upon decompression and the TBPOSS layer retains its initial monolayer state. The existence of these crystals in compressed phase is confirmed by atomic force microscopy measurements by lifting the materials on a solid substrate.

  13. Entropy of adsorption of mixed surfactants from solutions onto the air/water interface

    USGS Publications Warehouse

    Chen, L.-W.; Chen, J.-H.; Zhou, N.-F.

    1995-01-01

    The partial molar entropy change for mixed surfactant molecules adsorbed from solution at the air/water interface has been investigated by surface thermodynamics based upon the experimental surface tension isotherms at various temperatures. Results for different surfactant mixtures of sodium dodecyl sulfate and sodium tetradecyl sulfate, decylpyridinium chloride and sodium alkylsulfonates have shown that the partial molar entropy changes for adsorption of the mixed surfactants were generally negative and decreased with increasing adsorption to a minimum near the maximum adsorption and then increased abruptly. The entropy decrease can be explained by the adsorption-orientation of surfactant molecules in the adsorbed monolayer and the abrupt entropy increase at the maximum adsorption is possible due to the strong repulsion between the adsorbed molecules.

  14. "Ene" Reactions of Singlet Oxygen at the Air-Water Interface.

    PubMed

    Malek, Belaid; Fang, William; Abramova, Inna; Walalawela, Niluksha; Ghogare, Ashwini A; Greer, Alexander

    2016-08-01

    Prenylsurfactants [(CH3)2C═CH(CH2)nSO3(-) Na(+) (n = 4, 6, or 8)] were designed to probe the "ene" reaction mechanism of singlet oxygen at the air-water interface. Increasing the number of carbon atoms in the hydrophobic chain caused an increase in the regioselectivity for a secondary rather than tertiary surfactant hydroperoxide, arguing for an orthogonal alkene on water. The use of water, deuterium oxide, and H2O/D2O mixtures helped to distinguish mechanistic alternatives to homogeneous solution conditions that include dewetting of the π bond and an unsymmetrical perepoxide transition state in the hydroperoxide-forming step. The prenylsurfactants and a photoreactor technique allowed a certain degree of interfacial control of the hydroperoxidation reaction on a liquid support, where the oxidant (airborne (1)O2) is delivered as a gas. PMID:27385423

  15. Reversible monolayer-to-crystalline phase transition in amphiphilic silsesquioxane at the air-water interface

    PubMed Central

    Banerjee, R.; Sanyal, M. K.; Bera, M. K.; Gibaud, A.; Lin, B.; Meron, M.

    2015-01-01

    We report on the counter intuitive reversible crystallisation of two-dimensional monolayer of Trisilanolisobutyl Polyhedral Oligomeric SilSesquioxane (TBPOSS) on water surface using synchrotron x-ray scattering measurements. Amphiphilic TBPOSS form rugged monolayers and Grazing Incidence X-ray Scattering (GIXS) measurements reveal that the in-plane inter-particle correlation peaks, characteristic of two-dimensional system, observed before transition is replaced by intense localized spots after transition. The measured x-ray scattering data of the non-equilibrium crystalline phase on the air-water interface could be explained with a model that assumes periodic stacking of the TBPOSS dimers. These crystalline stacking relaxes upon decompression and the TBPOSS layer retains its initial monolayer state. The existence of these crystals in compressed phase is confirmed by atomic force microscopy measurements by lifting the materials on a solid substrate. PMID:25687953

  16. Near-surface turbulence for evaporative convection at an air/water interface

    NASA Astrophysics Data System (ADS)

    Flack, K. A.; Saylor, J. R.; Smith, G. B.

    2001-11-01

    Turbulence measurements are reported for the flow beneath an air/water interface undergoing evaporative convection. Measurements were obtained using a two component laser Doppler velocimeter system. Two hydrodynamic boundary conditions were considered for the free surface: a shear free surface, which is the case when surfactants are absent, and a constant elasticity surface, created by depositing a monolayer of oleyl alcohol. The shear free boundary condition case results in significantly higher levels of near surface turbulence than the constant elasticity case. This difference between the two cases decreases with distance from the free surface. Profiles of the turbulent fluctuations were obtained for the horizontal and vertical velocity components and are compared with the somewhat analogous case of a heated solid wall.

  17. Coadsorption of human milk lactoferrin into the dipalmitoylglycerolphosphatidylcholine phospholipid monolayer spread at the air/water interface.

    PubMed

    Miano, Fausto; Zhao, Xiubo; Lu, Jian R; Penfold, Jeff

    2007-02-15

    The coadsorption of human milk lactoferrin into a spread monolayer of dipalmitoylglycerol phosphatidylcholine (DPPC) at the air/water interface has been studied by neutron reflection. The system is a good model of the preocular tear film outer interface, which was the motivation for the study. The association of the protein with the surface was indicated by an increase of the surface pressure exerted by the DPPC monolayer. The extent of lactoferrin coadsorption was found to decrease with increasing surface pressure in the lipid monolayer, a trend consistent with the observation reported for other proteins, such as lysozyme and beta-lactoglobulin. The neutron reflectivity measurements were subsequently carried out at the three surface pressures of 8, 15, and 35 mN/m to examine the structure and composition of lactoferrin coadsorbed at the interface. Whereas the DPPC monolayer effectively prevented lactoferrin insertion at the high surface pressure, a measurable amount of lactoferrin was found at the air/water interface at the two lower surface pressures. At 15 mN/m it was difficult to identify the distribution of lactoferrin with respect to the DPPC monolayer, due to its relatively low adsorbed amount and much broader distribution. At the lowest surface pressure of 8 mN/m, the lactoferrin coadsorption was found to increase with time over the first few hours. After 5 h the distribution of the lactoferrin layer became similar to, though quantitatively lower than, that adsorbed in the absence of the DPPC monolayer. It is characterized by a top dense sublayer of 15 A with a bottom diffuse sublayer of 60 A, indicating structural unfolding induced by surface adsorption under these conditions. PMID:17114223

  18. Coadsorption of Human Milk Lactoferrin into the Dipalmitoylglycerolphosphatidylcholine Phospholipid Monolayer Spread at the Air/Water Interface

    PubMed Central

    Miano, Fausto; Zhao, Xiubo; Lu, Jian R.; Penfold, Jeff

    2007-01-01

    The coadsorption of human milk lactoferrin into a spread monolayer of dipalmitoylglycerol phosphatidylcholine (DPPC) at the air/water interface has been studied by neutron reflection. The system is a good model of the preocular tear film outer interface, which was the motivation for the study. The association of the protein with the surface was indicated by an increase of the surface pressure exerted by the DPPC monolayer. The extent of lactoferrin coadsorption was found to decrease with increasing surface pressure in the lipid monolayer, a trend consistent with the observation reported for other proteins, such as lysozyme and β-lactoglobulin. The neutron reflectivity measurements were subsequently carried out at the three surface pressures of 8, 15, and 35 mN/m to examine the structure and composition of lactoferrin coadsorbed at the interface. Whereas the DPPC monolayer effectively prevented lactoferrin insertion at the high surface pressure, a measurable amount of lactoferrin was found at the air/water interface at the two lower surface pressures. At 15 mN/m it was difficult to identify the distribution of lactoferrin with respect to the DPPC monolayer, due to its relatively low adsorbed amount and much broader distribution. At the lowest surface pressure of 8 mN/m, the lactoferrin coadsorption was found to increase with time over the first few hours. After 5 h the distribution of the lactoferrin layer became similar to, though quantitatively lower than, that adsorbed in the absence of the DPPC monolayer. It is characterized by a top dense sublayer of 15 Å with a bottom diffuse sublayer of 60 Å, indicating structural unfolding induced by surface adsorption under these conditions. PMID:17114223

  19. pH effects on the molecular structure of β-lactoglobulin modified air-water interfaces and its impact on foam rheology.

    PubMed

    Engelhardt, Kathrin; Lexis, Meike; Gochev, Georgi; Konnerth, Christoph; Miller, Reinhard; Willenbacher, Norbert; Peukert, Wolfgang; Braunschweig, Björn

    2013-09-17

    Macroscopic properties of aqueous β-lactoglobulin (BLG) foams and the molecular properties of BLG modified air-water interfaces as their major structural element were investigated with a unique combination of foam rheology measurements and interfacial sensitive methods such as sum-frequency generation and interfacial dilatational rheology. The molecular structure and protein-protein interactions at the air-water interface can be changed substantially with the solution pH and result in major changes in interfacial dilational and foam rheology. At a pH near the interfacial isoelectric point BLG molecules carry zero net charge and disordered multilayers with the highest interfacial dilatational elasticity are formed at the air-water interface. Increasing or decreasing the pH with respect to the isoelectric point leads to the formation of a BLG monolayer with repulsive electrostatic interactions among the adsorbed molecules which decrease the interfacial dilational elasticity. The latter molecular information does explain the behavior of BLG foams in our rheological studies, where in fact the highest apparent yield stresses and storage moduli are established with foams from electrolyte solutions with a pH close to the isoelectric point of BLG. At this pH the gas bubbles of the foam are stabilized by BLG multilayers with attractive intermolecular interactions at the ubiquitous air-water interfaces, while BLG layers with repulsive interactions decrease the apparent yield stress and storage moduli as stabilization of gas bubbles with a monolayer of BLG is less effective. PMID:23961700

  20. Field observations of turbulent dissipation rate profiles immediately below the air-water interface

    NASA Astrophysics Data System (ADS)

    Wang, Binbin; Liao, Qian

    2016-06-01

    Near surface profiles of turbulence immediately below the air-water interface were measured with a free-floating Particle Image Velocimetry (PIV) system on Lake Michigan. The surface-following configuration allowed the system to measure the statistics of the aqueous-side turbulence in the topmost layer immediately below the water surface (z≈0˜15 cm, z points downward with 0 at the interface). Profiles of turbulent dissipation rate (ɛ) were investigated under a variety of wind and wave conditions. Various methods were applied to estimate the dissipation rate. Results suggest that these methods yield consistent dissipation rate profiles with reasonable scattering. In general, the dissipation rate decreases from the water surface following a power law relation in the top layer, ɛ˜z-0.7, i.e., the slope of the decrease was lower than that predicted by the wall turbulence theory, and the dissipation was considerably higher in the top layer for cases with higher wave ages. The measured dissipation rate profiles collapse when they were normalized with the wave speed, wave height, water-side friction velocity, and the wave age. This scaling suggests that the enhanced turbulence may be attributed to the additional source of turbulent kinetic energy (TKE) at the "skin layer" (likely due to micro-breaking), and its downward transport in the water column.

  1. Spread Films of Human Serum Albumin at the Air-Water Interface: Optimization, Morphology, and Durability.

    PubMed

    Campbell, Richard A; Ang, Joo Chuan; Sebastiani, Federica; Tummino, Andrea; White, John W

    2015-12-22

    It has been known for almost one hundred years that a lower surface tension can be achieved at the air-water interface by spreading protein from a concentrated solution than by adsorption from an equivalent total bulk concentration. Nevertheless, the factors that control this nonequilibrium process have not been fully understood. In the present work, we apply ellipsometry, neutron reflectometry, X-ray reflectometry, and Brewster angle microscopy to elaborate the surface loading of human serum albumin in terms of both the macroscopic film morphology and the spreading dynamics. We show that the dominant contribution to the surface loading mechanism is the Marangoni spreading of protein from the bulk of the droplets rather than the direct transfer of their surface films. The films can be spread on a dilute subphase if the concentration of the spreading solution is sufficient; if not, dissolution of the protein occurs, and only a textured adsorbed layer slowly forms. The morphology of the spread protein films comprises an extended network with regions of less textured material or gaps. Further, mechanical cycling of the surface area of the spread films anneals the network into a membrane that approach constant compressibility and has increased durability. Our work provides a new perspective on an old problem in colloid and interface science. The scope for optimization of the surface loading mechanism in a range of systems leading to its exploitation in deposition-based technologies in the future is discussed. PMID:26607026

  2. Thermometric measurements of the molecular sublayer at the air-water interface

    NASA Astrophysics Data System (ADS)

    Ward, B.; Donelan, M. A.

    2006-04-01

    A series of measurements was conducted in the Air-Sea Interaction Saltwater Tank (ASIST) to study the response of the air-water interfacial molecular sublayer under various heat flux and wind speed conditions. In-situ gradients were measured with a platinum-plated tungsten wire microthermometer, which resolved the temperature of the thermally conductive sublayer. Air-sea heat flux was controlled by changing the air-water temperature difference (ΔTAW) and the wind speed, and measurements were made for three ΔTAW regimes over a range of wind speeds. A function was fitted to the measured temperature profiles as a way of extracting the boundary layer thickness in a consistent fashion, from which the λ coefficient after Saunders (1967) was computed. This dataset returned a mean λ coefficient of 2.4 +/- 0.5, which was generally lower than previous studies, and was found to be independent of wind speed in the range of 1 to 9 ms-1.

  3. Synthesis of a Two-Dimensional Covalent Organic Monolayer through Dynamic Imine Chemistry at the Air/Water Interface.

    PubMed

    Dai, Wenyang; Shao, Feng; Szczerbiński, Jacek; McCaffrey, Ryan; Zenobi, Renato; Jin, Yinghua; Schlüter, A Dieter; Zhang, Wei

    2016-01-01

    A two-dimensional covalent organic monolayer was synthesized from simple aromatic triamine and dialdehyde building blocks by dynamic imine chemistry at the air/water interface (Langmuir-Blodgett method). The obtained monolayer was characterized by optical microscopy, scanning electron microscopy, and atomic force microscopy, which unambiguously confirmed the formation of a large (millimeter range), unimolecularly thin aromatic polyimine sheet. The imine-linked chemical structure of the obtained monolayer was characterized by tip-enhanced Raman spectroscopy, and the peak assignment was supported by spectra simulated by density functional theory. Given the modular nature and broad substrate scope of imine formation, the work reported herein opens up many new possibilities for the synthesis of customizable 2D polymers and systematic studies of their structure-property relationships. PMID:26768822

  4. The Equilibria of Diosgenin-Phosphatidylcholine and Diosgenin-Cholesterol in Monolayers at the Air/Water Interface.

    PubMed

    Janicka, Katarzyna; Jastrzebska, Izabella; Petelska, Aneta Dorota

    2016-08-01

    Diosgenin (Dio) has shown many treatment properties, but the most important property is cytotoxic activity in cancer cells. In this study, we investigated monolayers of Dio, cholesterol (Ch), and phosphatidylcholine (PC) at the air/water interface. The measurements were carried with a Langmuir Teflon trough and a Nima 9000 tensiometer program. The surface tension values of pure and mixed monolayers were used to calculate π-A isotherms and determine molecular surface areas. We were able to demonstrate the formation of complexes between Dio and PC and Dio and Ch molecules also. We considered the equilibrium between individual components and the formed complexes. In addition, we established that diosgenin and the lipids formed highly stable 1:1 complexes. PMID:27350149

  5. Supramolecular 1-D polymerization of DNA origami through a dynamic process at the 2-dimensionally confined air-water interface.

    PubMed

    Yonamine, Yusuke; Cervantes-Salguero, Keitel; Minami, Kosuke; Kawamata, Ibuki; Nakanishi, Waka; Hill, Jonathan P; Murata, Satoshi; Ariga, Katsuhiko

    2016-05-14

    In this study, a Langmuir-Blodgett (LB) system has been utilized for the regulation of polymerization of a DNA origami structure at the air-water interface as a two-dimensionally confined medium, which enables dynamic condensation of DNA origami units through variation of the film area at the macroscopic level (ca. 10-100 cm(2)). DNA origami sheets were conjugated with a cationic lipid (dioctadecyldimethylammonium bromide, 2C18N(+)) by electrostatic interaction and the corresponding LB-film was prepared. By applying dynamic pressure variation through compression-expansion processes, the lipid-modified DNA origami sheets underwent anisotropic polymerization forming a one-dimensionally assembled belt-shaped structure of a high aspect ratio although the thickness of the polymerized DNA origami was maintained at the unimolecular level. This approach opens up a new field of mechanical induction of the self-assembly of DNA origami structures. PMID:27091668

  6. Dipolar interactions between domains in lipid monolayers at the air-water interface.

    PubMed

    Rufeil-Fiori, Elena; Wilke, Natalia; Banchio, Adolfo J

    2016-05-25

    A great variety of biologically relevant monolayers present phase coexistence characterized by domains formed by lipids in an ordered phase state dispersed in a continuous, disordered phase. From the difference in surface densities between these phases, inter-domain dipolar interactions arise. These interactions are relevant for the determination of the spacial distribution of domains as well as their dynamics. In this work, we propose a novel way of estimating the dipolar repulsion using a passive method that involves the analysis of images of the monolayer with phase coexistence. This method is based on the comparison of the pair correlation function obtained from experiments with that obtained from Brownian dynamics simulations of a model system. As an example, we determined the difference in dipolar density of a binary monolayer of DSPC/DMPC at the air-water interface from the analysis of the radial distribution of domains, and the results are compared with those obtained by surface potential determinations. A systematic analysis for the experimentally relevant parameter range is given, which may be used as a working curve for obtaining the dipolar repulsion in different systems. PMID:27139819

  7. Duolayers at the Air/Water Interface: Improved Lifetime through Ionic Interactions.

    PubMed

    Prime, Emma L; Solomon, David H; Dagley, Ian J; Qiao, Greg G

    2016-08-01

    Ionic interactions to stabilize Langmuir films at the air/water interface have been used to develop improved duolayer films. Two-component mixtures of octadecanoic (stearic) acid and poly(diallyldimethylammonium chloride) (polyDADMAC) with different ratios were prepared and applied to the water surface. Surface pressure isotherm cycles demonstrated a significant improvement in film stability with the inclusion of the polymer. Viscoelastic properties were measured using canal viscometry and oscillating barriers, with both methods showing that the optimum ratio for improved properties was four octadecanoic acid molecules to one DADMAC unit (1:0.25). At this ratio it is expected multiple strong ionic interactions are formed along each polymer chain. Brewster angle microscopy showed decreased domain size with increased ratios of polyDADMAC, indicating that the polymer is interspersed across the surface. This new method to stabilize and increase the viscoelastic properties of charged monolayer films, using a premixed composition, will have application in areas such as water evaporation mitigation, optical devices, and foaming. PMID:27420341

  8. Compression-Induced Fusion of Glassy Core Polymer Micelles at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Kim, Hyun Chang; Won, You-Yeon

    The surface mechanical and morphological properties of glassy core polymer micelles at the air-water interface were investigated. Asymmetric PS-PEG and PtBMA-PEG block copolymers with PEG weight fractions larger than 0.5 were formulated in the form of aqueous micelles and spread onto water. Compressed films of PS-PEG and PtBMA-PEG micelles reach high dynamic surface pressures. On the detailed level, however, PS-PEG and PtBMA-PEG micelles exhibit different surface pressure-area profiles. The PtBMA-PEG isotherm shows a transition to a plateau around a surface pressure of 24 mN/m, which is attributed to the PtBMA block as it forms a continuous film; this interpretation is supported by the fact that the surface pressure at the plateau transition is identical to the value of the spreading coefficient for PtBMA. This presents evidence that the core domains of PtBMA-PEG micelles melt and merge into a film when the micellar monolayer is laterally compressed. Such behavior was not observed with PS-PEG micelles. We suspect that under lateral compression, PtBMA-PEG micelles undergo fusion into a continuous film because PtBMA has the natural tendency to spread on the water surface, whereas PS-PEG micelles does not because the dewetting tendency of PS preventing formation of a uniform layer.

  9. Substrateless Welding of Self-Assembled Silver Nanowires at Air/Water Interface.

    PubMed

    Hu, Hang; Wang, Zhongyong; Ye, Qinxian; He, Jiaqing; Nie, Xiao; He, Gufeng; Song, Chengyi; Shang, Wen; Wu, Jianbo; Tao, Peng; Deng, Tao

    2016-08-10

    Integrating connected silver nanowire networks with flexible polymers has appeared as a popular way to prepare flexible electronics. To reduce the contact resistance and enhance the connectivity between silver nanowires, various welding techniques have been developed. Herein, rather than welding on solid supporting substrates, which often requires complicated transferring operations and also may pose damage to heat-sensitive substrates, we report an alternative approach to prepare easily transferrable conductive networks through welding of self-assembled silver nanowires at the air/water interface using plasmonic heating. The intriguing welding behavior of partially aligned silver nanowires was analyzed with combined experimental observation and theoretical modeling. The underlying water not only physically supports the assembled silver nanowires but also buffers potential overheating during the welding process, thereby enabling effective welding within a broad range of illumination power density and illumination duration. The welded networks could be directly integrated with PDMS substrates to prepare high-performance stable flexible heaters that are stretchable, bendable, and can be easily patterned to explore selective heating applications. PMID:27437907

  10. Advances in simulating radiance signatures for dynamic air/water interfaces

    NASA Astrophysics Data System (ADS)

    Goodenough, Adam A.; Brown, Scott D.; Gerace, Aaron

    2015-05-01

    The air-water interface poses a number of problems for both collecting and simulating imagery. At the surface, the magnitude of observed radiance can change by multiple orders of magnitude at high spatiotemporal frequency due to glinting effects. In the volume, similarly high frequency focusing of photons by a dynamic wave surface significantly changes the reflected radiance of in-water objects and the scattered return of the volume itself. These phenomena are often manifest as saturated pixels and artifacts in collected imagery (often enhanced by time delays between neighboring pixels or interpolation between adjacent filters) and as noise and greater required computation times in simulated imagery. This paper describes recent advances made to the Digital Image and Remote Sensing Image Generation (DIRSIG) model to address the simulation issues to better facilitate an understanding of a multi/hyper-spectral collection. Glint effects are simulated using a dynamic height field that can be driven by wave frequency models and generates a sea state at arbitrary time scales. The volume scattering problem is handled by coupling the geometry representing the surface (facetization by the height field) with the single scattering contribution at any point in the water. The problem is constrained somewhat by assuming that contributions come from a Snell's window above the scattering point and by assuming a direct source (sun). Diffuse single scattered and multiple scattered energy contributions are handled by Monte Carlo techniques employed previously. The model is compared to existing radiative transfer codes where possible, with the objective of providing a robust movel of time-dependent absolute radiance at many wavelengths.

  11. Thermodynamic, morphological and structural properties of dissociated fatty acid monolayers at the air-water interface

    NASA Astrophysics Data System (ADS)

    Johann, Robert

    2001-10-01

    Research on monolayers of amphiphilic lipids on aqueous solution is of basic importance in surface science. Due to the applicability of a variety of surface sensitive techniques, floating insoluble monolayers are very suitable model systems for the study of order, structure formation and material transport in two dimensions or the interactions of molecules at the interface with ions or molecules in the bulk (headword 'molecular recognition'). From the behavior of monolayers conclusions can be drawn on the properties of lipid layers on solid substrates or in biological membranes. This work deals with specific and fundamental interactions in monolayers both on the molecular and on the microscopic scale and with their relation to the lattice structure, morphology and thermodynamic behavior of monolayers at the air-water interface. As model system especially monolayers of long chain fatty acids are used, since there the molecular interactions can be gradually adjusted by varying the degree of dissociation by means of the suphase pH value. For manipulating the molecular interactions besides the subphase composition also temperature and monolayer composition are systematically varied. The change in the monolayer properties as a function of an external parameter is analyzed by means of isotherm and surface potential measurements, Brewster-angle microscopy, X-ray diffraction at grazing incidence and polarization modulated infrared reflection absorption spectroscopy. For this a quantitative measure for the molecular interactions and for the chain conformational order is derived from the X-ray data. The most interesting results of this work are the elucidation of the origin of regular polygonal and dendritic domain shapes, the various effects of cholesterol on molecular packing and lattice order of long chain amphiphiles, as well as the detection of an abrupt change in the head group bonding interactions, the chain conformational order and the phase transition pressure

  12. Carbon dioxide partial pressure and carbon fluxes of air-water interface in Taihu Lake, China

    NASA Astrophysics Data System (ADS)

    Fan, Chengxin; Hu, Weiping; Ford, Phillip W.; Chen, Yuwei; Qu, Wenchuan; Zhang, Lu

    2005-03-01

    To obtain carbon dioxide (CO2) flux between water-air interface of Taihu lake, monthly water samplers at 14 sites and the local meteorological data of the lake were collected and analyzed in 1998. Carbon dioxide partial pressures (pCO2) at air-water interface in the lake were calculated using alkalinity, pH, ionic strength, active coefficient, and water temperature. The carbon fluxes at different sublakes and areas were estimated by concentration gradient between water and air in consideration of Schmidt numbers of 600 and daily mean windspeed at 10 m above water surface. The results indicated that the mean values of pCO2 in Wuli Lake, Meiliang Bay, hydrophyte area, west littoral zone, riverine mouths, and the open lake areas were 1 807.8±1 071.4 (mean±standard deviation) μatm (1atm=1.013 25×105Pa), 416.3±217.0 μatm, 576.5±758.8 μatm, 304.2±243.5 μatm, 1 933.6±1 144.7 μatm, and 448.5±202.6 μatm, respectively. Maximum and minimum pCO2 values were found in the hypertrophic (4 053.7 μatm) and the eutrophic (3.2 μatm) areas. The riverine mouth areas have the maximum fluxes (82.0±62.8 mmol/m2a). But there was no significant difference between eutrophic and mesotrophic areas in pCO2 and the flux of CO2. The hydrophyte area, however, has the minimum (-0.58±12.9 mmol/m2a). In respect to CO2 equilibrium, input of the rivers will obviously influence inorganic carbon distribution in the riverine estuary. For example, the annual mean CO2 flux in Zhihugang River estuary was 19 times of that in Meiliang Bay, although the former is only a part of the latter. The sites in the body of the lake show a clear seasonal cycle with pCO2 higher than atmospheric equilibrium in winter, and much lower than atmospheric in summer due to CO2 consumption by photosynthesis. The CO2 amount of the net annual evasion that enters the atmosphere is 28.42×104 t/a, of which those from the west littoral zone and the open lake account for 53.8% and 36.7%, respectively.

  13. Surface adsorption behaviour of milk whey protein and pectin mixtures under conditions of air-water interface saturation.

    PubMed

    Perez, Adrián A; Sánchez, Cecilio Carrera; Patino, Juan M Rodríguez; Rubiolo, Amelia C; Santiago, Liliana G

    2011-07-01

    Milk whey proteins (MWP) and pectins (Ps) are biopolymer ingredients commonly used in the manufacture of colloidal food products. Therefore, knowledge of the interfacial characteristics of these biopolymers and their mixtures is very important for the design of food dispersion formulations (foams and/or emulsions). In this paper, we examine the adsorption and surface dilatational behaviour of MWP/Ps systems under conditions in which biopolymers can saturate the air-water interface on their own. Experiments were performed at constant temperature (20 °C), pH 7 and ionic strength 0.05 M. Two MWP samples, β-lactoglobulin (β-LG) and whey protein concentrate (WPC), and two Ps samples, low-methoxyl pectin (LMP) and high-methoxyl pectin (HMP) were evaluated. The contribution of biopolymers (MWP and Ps) to the interfacial properties of mixed systems was evaluated on the basis of their individual surface molecular characteristics. Biopolymer bulk concentration capable of saturating the air-water interface was estimated from surface pressure isotherms. Under conditions of interfacial saturation, dynamic adsorption behaviour (surface pressure and dilatational rheological characteristics) of MWP/Ps systems was discussed from a kinetic point of view, in terms of molecular diffusion, penetration and configurational rearrangement at the air-water interface. The main adsorption mechanism in MWP/LMP mixtures might be the MWP interfacial segregation due to the thermodynamic incompatibility between MWP and LMP (synergistic mechanism); while the interfacial adsorption in MWP/HMP mixtures could be characterized by a competitive mechanism between MWP and HMP at the air-water interface (antagonistic mechanism). The magnitude of these phenomena could be closely related to differences in molecular composition and/or aggregation state of MWP (β-LG and WPC). PMID:21440425

  14. Capillarity-induced directed self-assembly of patchy hexagram particles at the air-water interface.

    PubMed

    Kang, Sung-Min; Choi, Chang-Hyung; Kim, Jongmin; Yeom, Su-Jin; Lee, Daeyeon; Park, Bum Jun; Lee, Chang-Soo

    2016-07-01

    Directed self-assembly can produce ordered or organized superstructures from pre-existing building blocks through pre-programmed interactions. Encoding desired information into building blocks with specific directionality and strength, however, poses a significant challenge for the development of self-assembled superstructures. Here, we demonstrate that controlling the shape and patchiness of particles trapped at the air-water interface can represent a powerful approach for forming ordered macroscopic complex structures through capillary interactions. We designed hexagram particles using a micromolding method that allowed for precise control over the shape and, more importantly, the chemical patchiness of the particles. The assembly behaviors of these hexagram particles at the air-water interface were strongly affected by chemical patchiness. In particular, two-dimensional millimeter-scale ordered structures could be formed by varying the patchiness of the hexagram particles, and we attribute this effect to the delicate balance between the attractive and repulsive interactions among the patchy hexagram particles. Our results provide important clues for encoding information into patchy particles to achieve macroscopic assemblies via a simple molding technique and potentially pave a new pathway for the programmable assembly of particles at the air-water interface. PMID:27328067

  15. Toward a unified picture of the water self-ions at the air-water interface: a density functional theory perspective.

    PubMed

    Baer, Marcel D; Kuo, I-Feng W; Tobias, Douglas J; Mundy, Christopher J

    2014-07-17

    The propensities of the water self-ions, H3O(+) and OH(-), for the air-water interface have implications for interfacial acid-base chemistry. Despite numerous experimental and computational studies, no consensus has been reached on the question of whether or not H3O(+) and/or OH(-) prefer to be at the water surface or in the bulk. Here we report a molecular dynamics simulation study of the bulk vs interfacial behavior of H3O(+) and OH(-) that employs forces derived from density functional theory with a generalized gradient approximation exchange-correlation functional (specifically, BLYP) and empirical dispersion corrections. We computed the potential of mean force (PMF) for H3O(+) as a function of the position of the ion in the vicinity of an air-water interface. The PMF suggests that H3O(+) has equal propensity for the interface and the bulk. We compare the PMF for H3O(+) to our previously computed PMF for OH(-) adsorption, which contains a shallow minimum at the interface, and we explore how differences in solvation of each ion at the interface vs in the bulk are connected with interfacial propensity. We find that the solvation shell of H3O(+) is only slightly dependent on its position in the water slab, while OH(-) partially desolvates as it approaches the interface, and we examine how this difference in solvation behavior is manifested in the electronic structure and chemistry of the two ions. PMID:24762096

  16. Bacterial Swimming at Air/Water and Oil/Water Interfaces

    NASA Astrophysics Data System (ADS)

    Morse, Michael; Huang, Athena; Li, Guanglai; Tang, Jay

    2012-02-01

    The microbes inhabiting the planet over billions of years have adapted to diverse physical environments of water, soil, and interfaces between water and either solid or air. Following recent studies on bacterial swimming and accumulation near solid surfaces, we turn our attention to the behavior of Caulobacter crescentus, a singly flagellated bacterium, at water/air and water/oil interfaces. The latter is motivated by relevance to microbial degradation of crude oil in light of the recent oil spill in the Gulf of Mexico. Our ongoing study suggests that Caulobacter swarmer cells tend to get physically trapped at both water/air and water/oil interfaces, accumulating at the surface to a greater degree than boundary confinement properties like that of solid surfaces would predict. At the water/air interface, swimmers move in tight circles at half the speed of swimmers in the bulk fluid. At the water/oil interface, swimming circles are even tighter with further reduced swimming speed. We report experimental data and present preliminary analysis of the findings based on low Reynolds number hydrodynamics, the known surface tension, and surface viscosity at the interface. The analysis will help determine properties of the bacterium such as their surface charge and hydrophobicity.

  17. Partially Hydrated Electrons at the Air/Water Interface Observed by UV-Excited Time-Resolved Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy.

    PubMed

    Matsuzaki, Korenobu; Kusaka, Ryoji; Nihonyanagi, Satoshi; Yamaguchi, Shoichi; Nagata, Takashi; Tahara, Tahei

    2016-06-22

    Hydrated electrons are the most fundamental anion species, consisting only of electrons and surrounding water molecules. Although hydrated electrons have been extensively studied in the bulk aqueous solutions, even their existence is still controversial at the water surface. Here, we report the observation and characterization of hydrated electrons at the air/water interface using new time-resolved interface-selective nonlinear vibrational spectroscopy. With the generation of electrons at the air/water interface by ultraviolet photoirradiation, we observed the appearance of a strong transient band in the OH stretch region by heterodyne-detected vibrational sum-frequency generation. Through the comparison with the time-resolved spectra at the air/indole solution interface, the transient band was assigned to the vibration of water molecules that solvate electrons at the interface. The analysis of the frequency and decay of the observed transient band indicated that the electrons are only partially hydrated at the water surface, and that they escape into the bulk within 100 ps. PMID:27281547

  18. Superposition-additive approach: thermodynamic parameters of clusterization of monosubstituted alkanes at the air/water interface.

    PubMed

    Vysotsky, Yu B; Belyaeva, E A; Fomina, E S; Fainerman, V B; Aksenenko, E V; Vollhardt, D; Miller, R

    2011-12-21

    The applicability of the superposition-additive approach for the calculation of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole electric polarisabilities, molecular diamagnetic susceptibilities, π-electron circular currents, as well as for the estimation of the thermodynamic parameters of substituted alkanes, was demonstrated earlier. Now the applicability of the superposition-additive approach for the description of clusterization of fatty alcohols, thioalcohols, amines, carboxylic acids at the air/water interface is studied. Two superposition-additive schemes are used that ensure the maximum superimposition of the graphs of the considered molecular structures including the intermolecular CH-HC interactions within the clusters. The thermodynamic parameters of clusterization are calculated for dimers, trimers and tetramers. The calculations are based on the values of enthalpy, entropy and Gibbs' energy of clusterization calculated earlier using the semiempirical quantum chemical PM3 method. It is shown that the proposed approach is capable of the reproduction with sufficiently enough accuracy of the values calculated previously. PMID:22042000

  19. Exchange of polycyclic aromatic hydrocarbons across the air-water interface in the Bohai and Yellow Seas

    NASA Astrophysics Data System (ADS)

    Chen, Yingjun; Lin, Tian; Tang, Jianhui; Xie, Zhiyong; Tian, Chongguo; Li, Jun; Zhang, Gan

    2016-09-01

    In this study, air and surface seawater samples collected from the Bohai (BS) and Yellow Seas (YS) in May 2012 were determined exchange of PAHs, especially of low-molecular-weight (LMW) PAHs (three- and four-ring PAHs) at the air-water interface. Net volatilization fluxes of LMW PAHs were 266-1454 ng/m2/d and decreased with distance from the coast, indicating that these PAHs transported from coastal runoff were potential contributors to the atmosphere in the BS and YS. Moreover, LMW PAHs were enriched in the dissolved phase compared with those in the particulate phase in the water column, possibly suggesting that the volatilized LMW PAHs were directly derived from wastewater discharge or petroleum pollution rather than released from contaminated sediments. The air-sea exchange fluxes of the three-ring PAHs were 2- to 20-fold higher than their atmospheric deposition fluxes in the BS and YS. The input to and output from the water reached equilibrium for four-ring PAHs. Differently, five- and six-ring PAHs were introduced into the marine environment primarily through dry and wet deposition, indicating that the water column was still a sink of these PAHs from the surrounding atmosphere.

  20. Investigating Langmuir films at the air-water interface using a planar array infrared reflection-absorption spectrograph

    NASA Astrophysics Data System (ADS)

    Kim, Young Shin

    In this work, a new planar array infrared reflection-absorption spectrograph (PA-IRRAS) was developed to investigate a broad range of Langmuir films at the air-water interface. This instrument is capable of recording sample and reference spectra simultaneously with an optical setup that is the same as that of a single-beam instrument but splits the incident infrared beam into two sections on a plane mirror (H) or a water trough. With this design, the instrument could accommodate large infrared accessories, such as a water trough. In addition, water bands were subtracted to obtain a high quality spectrum for a poly(lactic acid) (PLA) Langmuir film on the water subphase with a resolution of about 8 cm-1 in 10.8 sec. With this instrument, two types of monolayer systems were studied; polymeric and lipid Langmuir films at the air-water interface. For the polymeric monolayer system, PA-IRRAS was used as a probe to follow the real-time conformational changes associated with intermolecular interactions of the polymer chains during the compression of the monolayers. It was found that the mixture of poly(D-lactic acid) (PDLA) and poly(L-lactic acid) (PLLA) (D/L) formed a stereocomplex when the mixed solution developed the two-dimensional monolayer at the air-water interface. The stereocomplexation occurred before film compression, indicating that there is no direct correlation between film compression and stereocomplexation. For the lipid monolayer system, PA-IRRAS was also used as a probe to investigate the origin of the disruption of a lipid monolayer upon protein adsorption at the air-water interface. Analysis of the time-resolved PA-IRRAS spectra revealed that Cu(II) ion-chelated DSIDA lipid monolayer (Cu 2+-DSIDA) was readily disrupted by myoglobin adsorption as demonstrated by a blue shift of 1.7 cm-1 and a lower intensity in the vas(CH2) stretch mode of the lipid monolayer over a period of five hours. To find the origin of the disruption of the lipid monolayer, a

  1. Calcium phosphate growth beneath a polycationic monolayer at the air-water interface: effects of oscillating surface pressure on mineralization.

    PubMed

    Junginger, Mathias; Bleek, Katrin; Kita-Tokarczyk, Katarzyna; Reiche, Jürgen; Shkilnyy, Andriy; Schacher, Felix; Müller, Axel H E; Taubert, Andreas

    2010-11-01

    The self-assembly of the amphiphilic block copolymer poly(butadiene)-block-poly[2-(dimethylamino)ethyl methacrylate] at the air-water interface and the mineralization of the monolayers with calcium phosphate was investigated at different pH values. As expected for polyelectrolytes, the subphase pH strongly affects the monolayer properties. The focus of the current study, however, is on the effect of an oscillating (instead of a static) polymer monolayer on calcium phosphate mineralization. Monitoring of the surface pressure vs. mineralization time shows that the monolayer is quite stable if the mineralization is performed at pH 8. In contrast, the monolayer at pH 5 shows a measurable decrease of the surface pressure already after ca. 2 h of mineralization. Transmission electron microscopy reveals that mineralization at low pH under constant oscillation leads to small particles, which are arranged in circular features and larger entities with holes of ca. 200 nm. The larger features with the holes disappear as the mineralization is continued in favor of the smaller particles. These grow with time and form necklace-like architectures of spherical particles with a uniform diameter. In contrast, mineralization at pH 8 leads to very uniform particle morphologies already after 2 h. The mineralization products consist of a circular feature with a dark dot in the center. The increasing contrast of the precipitates in the electron micrographs with mineralization time indicates an increasing degree of mineralization vs. reaction time. The study therefore shows that mechanical effects on mineralization at interfaces are quite complex. PMID:20835481

  2. Calcium phosphate growth beneath a polycationic monolayer at the air-water interface: effects of oscillating surface pressure on mineralization

    NASA Astrophysics Data System (ADS)

    Junginger, Mathias; Bleek, Katrin; Kita-Tokarczyk, Katarzyna; Reiche, Jürgen; Shkilnyy, Andriy; Schacher, Felix; Müller, Axel H. E.; Taubert, Andreas

    2010-11-01

    The self-assembly of the amphiphilic block copolymer poly(butadiene)-block-poly[2-(dimethylamino)ethyl methacrylate] at the air-water interface and the mineralization of the monolayers with calcium phosphate was investigated at different pH values. As expected for polyelectrolytes, the subphase pH strongly affects the monolayer properties. The focus of the current study, however, is on the effect of an oscillating (instead of a static) polymer monolayer on calcium phosphate mineralization. Monitoring of the surface pressure vs. mineralization time shows that the monolayer is quite stable if the mineralization is performed at pH 8. In contrast, the monolayer at pH 5 shows a measurable decrease of the surface pressure already after ca. 2 h of mineralization. Transmission electron microscopy reveals that mineralization at low pH under constant oscillation leads to small particles, which are arranged in circular features and larger entities with holes of ca. 200 nm. The larger features with the holes disappear as the mineralization is continued in favor of the smaller particles. These grow with time and form necklace-like architectures of spherical particles with a uniform diameter. In contrast, mineralization at pH 8 leads to very uniform particle morphologies already after 2 h. The mineralization products consist of a circular feature with a dark dot in the center. The increasing contrast of the precipitates in the electron micrographs with mineralization time indicates an increasing degree of mineralization vs. reaction time. The study therefore shows that mechanical effects on mineralization at interfaces are quite complex.

  3. Adsorption, Ordering, and Local Environments of Surfactant-Encapsulated Polyoxometalate Ions Probed at the Air-Water Interface.

    PubMed

    Doughty, Benjamin; Yin, Panchao; Ma, Ying-Zhong

    2016-08-16

    The continued development and application of surfactant-encapsulated polyoxometalates (SEPs) relies on understanding the ordering and organization of species at their interface and how these are impacted by the various local environments to which they are exposed. Here, we report on the equilibrium properties of two common SEPs adsorbed to the air-water interface and probed with surface-specific vibrational sum-frequency generation (SFG) spectroscopy. These results reveal clear shifts in vibrational band positions, the magnitude of which scales with the charge of the SEP core, which is indicative of a static field effect on the surfactant coating and the associated local chemical environment. This static field also induces ordering in surrounding water molecules that is mediated by charge screening via the surface-bound surfactants. From these SFG measurements, we are able to show that Mo132-based SEPs are more polar than Mo72V30 SEPs. Disorder in the surfactant chain packing at the highly curved SEP surfaces is attributed to large conic volumes that can be sampled without interactions with neighboring chains. Measurements of adsorption isotherms yield free energies of adsorption to the air-water interface of -46.8 ± 0.4 and -44.8 ± 1.2 kJ/mol for the Mo132 and Mo72V30 SEPs, respectively, indicating a strong propensity for the fluid surface. The influence of intermolecular interactions on the surface adsorption energies is discussed. PMID:27452922

  4. Reorientation of the ‘free OH’ group in the top-most layer of air/water interface of sodium fluoride aqueous solution probed with sum-frequency generation vibrational spectroscopy

    SciTech Connect

    Feng, Ran-Ran; Guo, Yuan; Wang, Hongfei

    2014-09-17

    Many experimental and theoretical studies have established the specific anion, as well as cation effects on the hydrogen-bond structures at the air/water interface of electrolyte solutions. However, the ion effects on the top-most layer of the air/water interface, which is signified by the non-hydrogen-bonded so-called ‘free O-H’ group, has not been discussed or studied. In this report, we present the measurement of changes of the orientational angle of the ‘free O-H’ group at the air/water interface of the sodium fluoride (NaF) solutions at different concentrations using the interface selective sum-frequency generation vibrational spectroscopy (SFG-VS) in the ssp and ppp polarizations. The polarization dependent SFG-VS results show that the average tilt angle of the ‘free O-H’ changes from about 35.3 degrees ± 0.5 degrees to 43.4 degrees ± 2.1degrees as the NaF concentration increase from 0 to 0.94M (nearly saturated). Such tilt angle change is around the axis of the other O-H group of the same water molecule at the top-most layer at the air/water interface that is hydrogen-bonded to the water molecules below the top-most layer. These results provide quantitative molecular details of the ion effects of the NaF salt on the structure of the water molecules at the top-most layer of the air/water interfacial, even though both the Na+ cation and the F- anion are believed to be among the most excluded ions from the air/water interface.

  5. Mixed layers of β-lactoglobulin and SDS at air-water interfaces with tunable intermolecular interactions.

    PubMed

    Engelhardt, Kathrin; Weichsel, Ulrike; Kraft, Elena; Segets, Doris; Peukert, Wolfgang; Braunschweig, Björn

    2014-04-17

    Mixtures of β-lactoglobulin (BLG) and sodium dodecyl sulfate (SDS) were studied at pH 3.8 and 6.7 under equilibrium conditions. At these pH conditions, BLG carries either a positive or a negative net charge, respectively, which enables tunable electrostatic interactions between anionic SDS surfactants and BLG proteins. For pH 3.8, vibrational sum-frequency generation (SFG) and ellipsometry indicate strong BLG-SDS complex formation at air-water interfaces that is caused by attractive electrostatic interactions. The latter complexes are already formed in the bulk solution which was confirmed by a thermodynamic study of BLG-SDS mixtures using isothermal titration calorimetry (ITC). For acidic conditions we determine from our ITC data an exothermal binding enthalpy of -40 kJ mol(-1). Increasing SDS/BLG molar ratios above 10 leads to a surface excess of SDS and thus to a charge reversal from a positive net charge with BLG as the dominating surface adsorbed species to a negatively charged layer with SDS as the dominating surface species. The latter is evidenced by a pronounced minimum in SFG intensities that is also accompanied by a phase change of O-H stretching bands due to a reorientation of H2O within the local electric field. This phase change which occurs at SDS/BLG molar ratio between 1 and 10 causes a polarity change in SFG intensities from BLG aromatic C-H stretching vibrations. Conclusions from SFG spectra are corroborated by ellipsometry which shows a dramatic increase in layer thicknesses at molar ratios where a charge reversal occurs. The formation of interfacial multilayers comprising SDS-BLG complexes is, thus, caused by cancellation of electrostatic interactions which leads to agglomeration at the interface. In contrast to pH 3.8, behavior of BLG-SDS mixtures at pH 6.7 is different due to repulsive electrostatic interactions between SDS and BLG which lead to a significantly reduced binding enthalpy of -17 kJ mol(-1). Finally, it has to be mentioned that

  6. Surface Partitioning and Stability of Mixed Films of Fluorinated Alcohols and Acids at the Air- Water Interface

    NASA Astrophysics Data System (ADS)

    Rontu, N. A.; Vaida, V.

    2007-05-01

    The production of fluorinated compounds over the past 50 years has had numerous industrial applications. For example, perfluorinated carboxylic acids are used in the synthesis of polymers and fire retardants, perfluoroalkyl sulfonates act as surface protectors, and fluorotelomer alcohols are incorporated into products such as paints, coatings, polymers, and adhesives. Fluorotelomer alcohols (FTOHs) are linear polyfluorinated alcohols with the formula CF3(CF2)nCH2CH2OH (n=1,3,5,...). They have been suggested as possible precursors for perfluorinated carboxylic acids and detected in the troposphere over several North American sites. Perfluorocarboxylic acids have even been detected in the arctic food chain, human blood, tissues of animals and environmental waters. We report the surface activity of fluorotelomer alcohols and perfluorinated carboxylic acids at the air-water interface by using a Langmuir trough. Isotherms of the pure compounds along with mixed films with other organic carboxylic acids were collected. The main objective of these experiments was to understand their heterogeneous chemistry by characterizing the pure and mixed films, which serves as a representative model for organic films on atmospheric surfaces such as those found on oceans and aqueous aerosols. Film properties and behavior, notably stabilization, evaporation from the subphase, and miscibility in the single-component mixtures as well as in the mixed films will be discussed. An important consequence of FTOHs and perfluorocarboxylic acids being found to partition to the air-water interface is the possibility of their transport and widespread distribution and deposition using atmospheric aerosols.

  7. Electrochemical Surface Potential due to Classical Point Charge Models Drives Anion Adsorption to the Air-Water Interface

    SciTech Connect

    Baer, Marcel D.; Stern, Abraham C.; Levin, Yan; Tobias, Douglas J.; Mundy, Christopher J.

    2012-06-07

    Herein, we present research that suggests that the underlying physics that drive simple empirical models of anions (e.g. point charge, no polarization) to the air-water interface, with water described by SPC/E, or related partial charge models is different than when both ions and water are modeled with quantum mechanical based interactions. Specifically, we will show that the driving force of ions to the air-water interface for point charge models results from both cavitation and the negative electrochemical surface potential. We will demonstrate that we can fully characterize the role of the free energy due to the electrochemical surface potential computed from simple empirical models and its role in ionic adsorption within the context of dielectric continuum theory (DCT). Our research suggests that a significant part of the electrochemical surface potential in empirical models appears to be an artifact of the failure of point charge models in the vicinity of a broken symmetry. This work was supported by the U.S. Department of Energy‘s (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated for the Department of Energy by Battelle.

  8. Charge and pressure-tuned surface patterning of surfactant-encapsulated polyoxometalate complexes at the air-water interface.

    PubMed

    Xu, Miao; Li, Haolong; Zhang, Liying; Wang, Yizhan; Yuan, Yuan; Zhang, Jianming; Wu, Lixin

    2012-10-16

    In this paper, four organic-inorganic hybrid complexes were prepared using a cationic surfactant dimethyldioctadecylammonium (DODA) to replace the counter cations of four Keggin-type polyoxometalate (POM) clusters with gradually increased negative charges, PW(12)O(40)(3-), SiW(12)O(40)(4-), BW(12)O(40)(5-), and CoW(12)O(40)(6-). The formed surfactant-encapsulated POM (SEP) complexes showed typical amphiphilic properties and can be spread onto the air-water interface to form Langmuir monolayers. The interfacial behavior of the SEP monolayer films was systemically studied by multiple in situ and ex situ characterization methods including Brewster angle microscopy (BAM), atomic force microscopy (AFM), reflection-absorption infrared (RAIR), and X-ray photoelectron spectroscopy (XPS). We found that the increasing alkyl chain density of SEPs leads to an enhanced stability and a higher collapse pressure of SEP Langmuir monolayers. Moreover, a second layer evolved as patterns from the initial monolayers of all the SEPs, when the surface pressures approached the collapse values. The rational combination of alkyl chain density and surface pressure can precisely control the size and the morphology of SEP patterns transforming from disk-like to leaf-like structures on a micrometer scale. The pattern formation was demonstrated to be driven by the self-optimized surface energy of SEP monolayers. This finding can direct a new strategy for the fabrication of POM-hybrid films with controllable patterns, which should be instructive for designing POM-based thin film devices. PMID:22991980

  9. DNS and measurements of scalar transfer across an air-water interface during inception and growth of Langmuir circulation

    NASA Astrophysics Data System (ADS)

    Hafsi, A.; Ma, Y.; Buckley, M.; Tejada-Martinez, A. E.; Veron, F.

    2016-05-01

    Direct numerical simulations (DNS) of an initially quiescent coupled air-water interface driven by an air flow with free stream speed of 5 m/s have been conducted and scalar transfer from the air side to the water side and subsequent vertical transport in the water column have been analysed. Two simulations are compared: one with a freely deforming interface, giving rise to gravity-capillary waves and aqueous Langmuir turbulence (LT) characterized by small-scale (centimeter-scale) Langmuir cells (LC), and the other with the interface intentionally held flat, i.e., without LC. It is concluded that LT serves to enhance vertical transport of the scalar in the water side and in the process increases scalar transfer efficiency from the air side to the water side relative to the shear-dominated turbulence in the flat interface case. Furthermore, transition to LT was observed to be accompanied by a spike in scalar flux characterized by an order of magnitude increase. These episodic flux increases, if linked to gusts and overall unsteadiness in the wind field, are expected to be an important contributor in determining the long-term average of the air-sea gas fluxes.

  10. A semi-analytical calculation of the electrostatic pair interaction between nonuniformly charged colloidal spheres at an air-water interface

    NASA Astrophysics Data System (ADS)

    Lian, Zengju

    2016-07-01

    We study the electrostatic pair interaction between two nonuniformly like-charged colloidal spheres trapped in an air-water interface. Under the linear Poisson-Boltzmann approximation, a general form of the electrostatic potential for the system is shown in terms of multipole expansions. After combining the translation-rotation transform of the coordinates with the numerical multipoint collection, we give a semi-analytical result of the electrostatic pair interaction between the colloids. The pair interaction changes quantitatively or even qualitatively with different distributions of the surface charges on the particles. Because of the anisotropic distribution of the surface charge and the asymmetric dielectric medium, the dipole moment of the ion cloud associating with the particle orients diagonally to the air-water interface with an angle α. When the angle is large, the colloids interact repulsively, while they attract each other when the angle is small. The attractive colloids may be "Janus-like" charged and be arranged with some specific configurations. Whatever the repulsions or the attractions, they all decay asymptotically ∝1/d3 (d is the center-center distance of the particles) which is consistent with our general acknowledge. The calculation results also provide an insight of the effect of the ion concentration, particle size, and the total charge of the particle on the pair interaction between the particles.

  11. A semi-analytical calculation of the electrostatic pair interaction between nonuniformly charged colloidal spheres at an air-water interface.

    PubMed

    Lian, Zengju

    2016-07-01

    We study the electrostatic pair interaction between two nonuniformly like-charged colloidal spheres trapped in an air-water interface. Under the linear Poisson-Boltzmann approximation, a general form of the electrostatic potential for the system is shown in terms of multipole expansions. After combining the translation-rotation transform of the coordinates with the numerical multipoint collection, we give a semi-analytical result of the electrostatic pair interaction between the colloids. The pair interaction changes quantitatively or even qualitatively with different distributions of the surface charges on the particles. Because of the anisotropic distribution of the surface charge and the asymmetric dielectric medium, the dipole moment of the ion cloud associating with the particle orients diagonally to the air-water interface with an angle α. When the angle is large, the colloids interact repulsively, while they attract each other when the angle is small. The attractive colloids may be "Janus-like" charged and be arranged with some specific configurations. Whatever the repulsions or the attractions, they all decay asymptotically ∝1/d(3) (d is the center-center distance of the particles) which is consistent with our general acknowledge. The calculation results also provide an insight of the effect of the ion concentration, particle size, and the total charge of the particle on the pair interaction between the particles. PMID:27394119

  12. Mechanism of Action of Thymol on Cell Membranes Investigated through Lipid Langmuir Monolayers at the Air-Water Interface and Molecular Simulation.

    PubMed

    Ferreira, João Victor N; Capello, Tabata M; Siqueira, Leonardo J A; Lago, João Henrique G; Caseli, Luciano

    2016-04-01

    A major challenge in the design of biocidal drugs is to identify compounds with potential action on microorganisms and to understand at the molecular level their mechanism of action. In this study, thymol, a monoterpenoid found in the oil of leaves of Lippia sidoides with possible action in biological surfaces, was incorporated in lipid monolayers at the air-water interface that represented cell membrane models. The interaction of thymol with dipalmitoylphosphatidylcholine (DPPC) at the air-water interface was investigated by means of surface pressure-area isotherms, Brewster angle microscopy (BAM), polarization-modulation reflection-absorption spectroscopy (PM-IRRAS), and molecular dynamics simulation. Thymol expands DPPC monolayers, decreases their surface elasticity, and changes the morphology of the lipid monolayer, which evidence the incorporation of this compound in the lipid Langmuir film. Such incorporation could be corroborated by PM-IRRAS since some specific bands for DPPC were changed upon thymol incorporation. Furthermore, potential of mean force obtained by molecular dynamics simulations indicates that the most stable position of the drug along the lipid film is near the hydrophobic regions of DPPC. These results may be useful to understand the interaction between thymol and cell membranes during biochemical phenomena, which may be associated with its pharmaceutical properties at the molecular level. PMID:26982820

  13. Introducing high-quality planar defects into colloidal crystals via self-assembly at the air/water interface

    NASA Astrophysics Data System (ADS)

    Zhong, Kuo; Demeyer, Pieter-Jan; Zhou, Xingping; Kruglova, Olga; Verellen, Niels; Moshchalkov, Victor V.; Song, Kai; Clays, Koen

    2015-02-01

    We demonstrate a facile method for fabrication of colloidal crystals containing a planar defect by using PS@SiO2 core-shell spheres as building blocks. A monolayer of solid spheres was embedded in core-shell colloidal crystals serving as the defect layer, which formed by means of self-assembly at the air/water interface. Compared with previous methods, this fabrication method results in pronounced passbands in the band gaps of the colloidal photonic crystal. The FWHM of the obtained passband is only ~16nm, which is narrower than the previously reported results. The influence of the defect layer thickness on the optical properties of these sandwiched structures was also investigated. No high-cost processes or specific equipment is needed in our approach. Inverse opals with planar defects can be obtained via calcination of the PS cores, without the need of infiltration. The experimental results are in good agreement with simulations performed using the FDTD method.

  14. Effect of monolayer lipid charges on the structure and orientation of protein VAMP1 at the air-water interface.

    PubMed

    Yassine, Wissam; Milochau, Alexandra; Buchoux, Sebastien; Lang, Jochen; Desbat, Bernard; Oda, Reiko

    2010-05-01

    SNARE proteins are implicated in membrane fusion during neurotransmission and peptide hormone secretion. Relatively little is known about the molecular interactions of their trans- and juxtamembrane domains with lipid membranes. Here, we report the structure and the assembling behavior of one of the SNARE proteins, VAMP1/synaptobrevin1 incorporated in a lipid monolayer at an air-water interface which mimics the membrane environment. Our results show that the protein is extremely sensitive to surface pressure as well as the lipid composition. Monolayers of proteins alone or in the presence of the neutral phospholipid DMPC underwent structural transition from alpha-helix to beta-sheet upon surface compression. In contrast, the anionic phospholipid DMPG inhibited this transition in a concentration-dependent manner. Moreover, the orientation of the proteins was highly sensitive to the charge density of the lipid layers. Thus, the structure of VAMP1 is clearly controlled by protein-lipid interactions. PMID:20085749

  15. Gas exchange rates across the sediment-water and air-water interfaces in south San Francisco Bay

    USGS Publications Warehouse

    Hartman, Blayne; Hammond, Douglas E.

    1984-01-01

    Radon 222 concentrations in the water and sedimentary columns and radon exchange rates across the sediment-water and air-water interfaces have been measured in a section of south San Francisco Bay. Two independent methods have been used to determine sediment-water exchange rates, and the annual averages of these methods agree within the uncertainty of the determinations, about 20%. The annual average of benthic fluxes from shoal areas is nearly a factor of 2 greater than fluxes from the channel areas. Fluxes from the shoal and channel areas exceed those expected from simple molecular diffusion by factors of 4 and 2, respectively, apparently due to macrofaunal irrigation. Values of the gas transfer coefficient for radon exchange across the air-water interface were determined by constructing a radon mass balance for the water column and by direct measurement using floating chambers. The chamber method appears to yield results which are too high. Transfer coefficients computed using the mass balance method range from 0.4 m/day to 1.8 m/day, with a 6-year average of 1.0 m/day. Gas exchange is linearly dependent upon wind speed over a wind speed range of 3.2–6.4 m/s, but shows no dependence upon current velocity. Gas transfer coefficients predicted from an empirical relationship between gas exchange rates and wind speed observed in lakes and the oceans are within 30% of the coefficients determined from the radon mass balance and are considerably more accurate than coefficients predicted from theoretical gas exchange models.

  16. Turbulence at the Air-Water Interface in Lakes of Different Sizes: Consequences for Gas Transfer Coefficients

    NASA Astrophysics Data System (ADS)

    MacIntyre, S.; Crowe, A. T.; Amaral, J. H.; Arneborg, L.; Bastviken, D.; Forsberg, B. R.; Melack, J. M.; Tota, J.; Tedford, E. W.; Karlsson, J.; Podgrajsek, E.; Andersson, A.; Rutgersson, A.

    2014-12-01

    Similarity scaling predicts that wind induced shear will be the dominant source of turbulence near the air-water interface in lakes with low to moderate wind forcing. Turbulence is expected to be enhanced with wave activity; results are conflicting on the effects of heating and cooling. We measured turbulence with an acoustic Doppler velocimeter (ADV) and / or a temperature-gradient microstructure profiler and obtained correlative time series measurements of meteorology and water column temperature in a 800 m2 arctic pond, a 1 ha boreal lake, and a large tropical reservoir. Turbulence measurements with both instruments corroborated those calculated from similarity scaling in the boreal lake. Within the arctic pond, dissipation rates obtained with the ADV were in agreement with those from similarity scaling when winds exceeded ~1.5 m/s with a greater frequency of measurable dissipation rates when surface waves were present. Dissipation rates in the tropical reservoir reached and often exceeded 10-6 m2 s-3 in the upper meter under light winds and decreased by an order of magnitude with cooling or rainfall. Under cooling, dissipation rates were at least an order of magnitude higher in the uppermost 25 cm bin than in the water column below. Gas transfer coefficients calculated from concurrent measurements of greenhouse gas fluxes with floating chambers and the surface renewal model using the estimates of turbulence were in agreement. These results support the predictions of Monin-Obuhov similarity scaling in that shear dominates turbulence production near the air-water interface under heating and cooling, illustrate spatial variability in turbulence production in small water bodies due to the intermittency of wind interacting with the water's surface, are in agreement with prior oceanic observations that shear and associated turbulence can be intensified in shallow mixing layers under heating with light winds, and illustrate the utility of similarity scaling for

  17. Surface Tension Drives the Orientation of Crystals at the Air-Water Interface.

    PubMed

    Chevalier, Nicolas R; Guenoun, Patrick

    2016-07-21

    The fabrication of oriented crystalline thin films is essential for a range of applications ranging from semiconductors to optical components, sensors, and catalysis. Here we show by depositing micrometric crystal particles on a liquid interface from an aerosol phase that the surface tension of the liquid alone can drive the crystallographic orientation of initially randomly oriented particles. The X-ray diffraction patterns of the particles at the interface are identical to those of a monocrystalline sample cleaved along the {104} (CaCO3) or {111} (CaF2) face. We show how this orientation effect can be used to produce thin coatings of oriented crystals on a solid substrate. These results also have important implications for our understanding of heterogeneous crystal growth beneath amphiphile monolayers and for 2D self-assembly processes at the air-liquid interface. PMID:27389283

  18. Anomalously large electro-optic Pockels effect at the air-water interface with an electric field applied parallel to the interface

    NASA Astrophysics Data System (ADS)

    Suzuki, Yuto; Osawa, Kengo; Yukita, Shunpei; Kobayashi, Takayoshi; Tokunaga, Eiji

    2016-05-01

    The optical Pockels effect was observed at the air-water interface by electromodulation spectroscopy. When an AC electric field of frequency f was applied parallel to a water surface between Pt electrodes, the field induced a change in the transmitted light intensity synchronized at 1f proportional to the field strength. The 1f signals dominated over 2f signals by one order of magnitude and the signal disappeared when the electrodes were completely immersed under the water surface, strongly suggesting that the observed phenomena were due to the Pockels effect at the air-water interface. The Pockels coefficient was estimated to be | r | = 1.4 × 105 pm/V, which is much larger than that at the solid-water interface. However, this is unusual because the parallel electric field does not induce the break in inversion symmetry required for the appearance of the Pockels effect. The electrowetting effect was experimentally ruled out as a mechanism for the Pockels effect, and this made the existence of a field perpendicular to the surface, although extremely weak, the most likely explanation.

  19. Intraday evaporation and heat fluxes variation at air-water interface of extremely shallow lakes in Chilean Andean Plateau

    NASA Astrophysics Data System (ADS)

    Vergara, Jaime; de la Fuente, Alberto

    2016-04-01

    Salars are landscapes formed by evapo-concentration of salts that usually have extremely shallow terminal lagoons (de la Fuente & Niño, 2010). They are located in the altiplanic region of the Andes Mountains of Chile, Argentina, Bolivia and Peru, and they sustain highly vulnerable and isolated ecosystems in the Andean Desert. These ecosystems are sustained by benthic primary production, which is directly linked to mass, heat and momentum transfer between the water column and the atmosphere (de la Fuente, 2014). Despite the importance of these transport processes across the air-water interface, there are few studies describing their intraday variation and how they are influenced by the stability of the atmospheric boundary layer in the altiplano. The main objective of this work is to analyze the intraday vertical transport variation of water vapor, temperature and momentum between the atmosphere and a shallow water body on Salar del Huasco located in northern Chile (20°19'40"S, 68°51'25"W). To achieve this goal, we measured atmospheric and water variables in a campaign realized on late October 2015, using high frequency meteorological instruments (a sonic anemometer with an incorporated infrared gas analyzer, and a standard meteorological station) and water sensors. From these data, we characterize the intraday variation of water vapor, temperature and momentum fluxes, we quantify the influence of the atmospheric boundary layer stability on them, and we estimate transfer coefficients associated to latent heat, sensible heat, hydrodynamic drag and vertical transport of water vapor. As first results, we found that latent and sensible heat fluxes are highly influenced by wind speed rather buoyancy, and we can identify four intraday intervals with different thermo-hydrodynamic features: (1) cooling under stable condition with wind speed near 0 from midnight until sunrise; (2) free convection with nearly no wind speed under unstable condition from sunrise until midday

  20. Effects of the conjugation of whey proteins with gellan polysaccharides on surfactant-induced competitive displacement from the air-water interface.

    PubMed

    Cai, B; Ikeda, S

    2016-08-01

    Whey proteins can be used to stabilize foams and emulsions against coalescence because of their ability to form viscoelastic films at the interface that resist film rupture on collision between colloidal particles. However, whey proteins are competitively displaced from the interface if small-molecule surfactants are added, leading to destabilization of the entire system. This is because surfactants are more effective in molecular packing at the interface, and they lower interfacial tension to a greater degree than whey proteins do, but their interfacial films are poor in viscoelasticity. We hypothesized that whey proteins would become more resistant to surfactant-induced competitive displacement if they were conjugated with network-forming polysaccharides. The protein moiety of the conjugate would be expected to enable its adsorption to the interface, and the polysaccharide moiety would be expected to form self-assembled networks, strengthening the interfacial film as a whole. In this study, whey proteins were conjugated with gellan polysaccharides using the Maillard reaction. Atomic force microscopy images of interfacial films formed by the whey protein-gellan conjugate at the air-water interface and transferred onto mica sheets using the Langmuir-Blodgett method revealed that gellan did form self-assembled networks at the interface and that interfacial films also contained a large number of unconjugated whey protein molecules. Following the addition of a small-molecule surfactant (Tween 20) to the sub-phase, surface pressure increased, indicating spontaneous adsorption of surfactants to the interface. Atomic force microscopy images showed decreases in interfacial area coverage by whey proteins as surface pressure increased. At a given surface pressure, the interfacial area coverage by whey protein-gellan conjugates was greater than coverage by unconjugated whey proteins, confirming that whey proteins became more resistant to surfactant-induced displacement after

  1. X-ray reflectivity and grazing incidence diffraction studies of interaction between human adhesion/growth-regulatory galectin-1 and DPPE-GM1 lipid monolayer at an air/water interface.

    PubMed

    Majewski, J; André, S; Jones, E; Chi, E; Gabius, H-J

    2015-07-01

    The specific interaction of ganglioside GM1 with the homodimeric (prototype) endogenous lectin galectin-1 triggers growth regulation in tumor and activated effector T cells. This proven biorelevance directed interest to studying association of the lectin to a model surface, i.e. a 1,2-dihexadecanoyl-sn-glycero-3-phosphoethanolamine/ganglioside GM1 (80 : 20 mol%) monolayer, at a bioeffective concentration. Surface expansion by the lectin insertion was detected at a surface pressure of 20 mN/m. On combining the methods of grazing incidence X-ray diffraction and X-ray reflectivity, a transient decrease in lipid-ordered phase of the monolayer was observed. The measured electron density distribution indicated that galectin-1 is oriented with its long axis in the surface plane, ideal for cis-crosslinking. The data reveal a conspicuous difference to the way the pentameric lectin part of the cholera toxin, another GM1-specific lectin, is bound to the monolayer. They also encourage further efforts to monitor effects of structurally different members of the galectin family such as the functionally antagonistic chimera-type galectin-3. PMID:26542007

  2. Structure of Human Annexin A6 at the Air-Water Interface and in a Membrane-Bound State

    PubMed Central

    Golczak, Marcin; Kirilenko, Aneta; Bandorowicz-Pikula, Joanna; Desbat, Bernard; Pikula, Slawomir

    2004-01-01

    We postulate the existence of a pH-sensitive domain in annexin A6 (AnxA6), on the basis of our observation of pH-dependent conformational and orientation changes of this protein and its N- (AnxA6a) and C-terminal (AnxA6b) halves in the presence of lipids. Brewster angle microscopy shows that AnxA6, AnxA6a, and AnxA6b in the absence of lipids accumulate at the air-water interface and form a stable, homogeneous layer at pH below 6.0. Under these conditions polarization modulation IR absorption spectroscopy reveals significant conformational changes of AnxA6a whereas AnxA6b preserves its α-helical structure. The orientation of protein α-helices is parallel with respect to the interface. In the presence of lipids, polarization modulation IR reflection absorption spectroscopy experiments suggest that AnxA6a incorporates into the lipid/air interface, whereas AnxA6b is adsorbed under the lipid monolayer. In this case AnxA6a regains its α-helical structures. At a higher pressure of the lipid monolayer the average orientation of the α-helices of AnxA6a changes from flat to tilted by 45° with respect to normal to the membrane interface. For AnxA6b no such changes are detected, even at a high pressure of the lipid monolayer—suggesting that the putative pH-sensitive domain of AnxA6 is localized in the N-terminal half of the protein. PMID:15298924

  3. Ozonolysis of methyl oleate monolayers at the air-water interface: oxidation kinetics, reaction products and atmospheric implications.

    PubMed

    Pfrang, Christian; Sebastiani, Federica; Lucas, Claire O M; King, Martin D; Hoare, Ioan D; Chang, Debby; Campbell, Richard A

    2014-07-14

    Ozonolysis of methyl oleate monolayers at the air-water interface results in surprisingly rapid loss of material through cleavage of the C=C bond and evaporation/dissolution of reaction products. We determine using neutron reflectometry a rate coefficient of (5.7 ± 0.9) × 10(-10) cm(2) molecule(-1) s(-1) and an uptake coefficient of ∼3 × 10(-5) for the oxidation of a methyl ester monolayer: the atmospheric lifetime is ∼10 min. We obtained direct experimental evidence that <2% of organic material remains at the surface on atmospheric timescales. Therefore known long atmospheric residence times of unsaturated fatty acids suggest that these molecules cannot be present at the interface throughout their ageing cycle, i.e. the reported atmospheric longevity is likely to be attributed to presence in the bulk and viscosity-limited reactive loss. Possible reaction products were characterized by ellipsometry and uncertainties in the atmospheric fate of organic surfactants such as oleic acid and its methyl ester are discussed. Our results suggest that a minor change to the structure of the molecule (fatty acid vs. its methyl ester) considerably impacts on reactivity and fate of the organic film. PMID:24870051

  4. Impact of biogenic amine molecular weight and structure on surfactant adsorption at the air-water interface.

    PubMed

    Penfold, Jeffrey; Thomas, Robert K; Li, Peixun

    2016-02-01

    The oligoamines, such as ethylenediamine to pentaethylenetetramine, and the aliphatic biogenic amines, such as putrescine, spermidine and spermine, strongly interact with anionic surfactants, such as sodium dodecylsulfate, SDS. It has been shown that this results in pronounced surfactant adsorption at the air-water interface and the transition from monolayer to multilayer adsorption which depends upon solution pH and oligoamine structure. In the neutron reflectivity, NR, and surface tension, ST, results presented here the role of the oligoamine structure on the adsorption of SDS is investigated more fully using a range of different biogenic amines. The effect of the extent of the intra-molecular spacing between amine groups on the adsorption has been extended by comparing results for cadavarine with putrescine and ethylenediamine. The impact of more complex biogenic amine structures on the adsorption has been investigated with the aromatic phenethylamine, and the heterocyclic amines histamine and melamine. The results provide an important insight into how surfactant adsorption at interfaces can be manipulated by the addition of biogenic amines, and into the role of solution pH and oligoamine structure in modifying the interaction between the surfactant and oligoamine. The results impact greatly upon potential applications and in understanding some of the important biological functions of biogenic amines. PMID:26524255

  5. Relative Order of Sulfuric Acid, Bisulfate, Hydronium, and Cations at the Air-Water Interface.

    PubMed

    Hua, Wei; Verreault, Dominique; Allen, Heather C

    2015-11-01

    Sulfuric acid (H2SO4), bisulfate (HSO4(-)), and sulfate (SO4(2-)) are among the most abundant species in tropospheric and stratospheric aerosols due to high levels of atmospheric SO2 emitted from biomass burning and volcanic eruptions. The air/aqueous interfaces of sulfuric acid and bisulfate solutions play key roles in heterogeneous reactions, acid rain, radiative balance, and polar stratospheric cloud nucleation. Molecular-level knowledge about the interfacial distribution of these inorganic species and their perturbation of water organization facilitates a better understanding of the reactivity and growth of atmospheric aerosols and of the aerosol surface charge, thus shedding light on topics of air pollution, climate change, and thundercloud electrification. Here, the air/aqueous interface of NaHSO4, NH4HSO4, and Mg(HSO4)2 salt solutions as well as H2SO4 and HCl acid solutions are investigated by means of vibrational sum frequency generation (VSFG) and heterodyne-detected (HD) VSFG spectroscopy. VSFG spectra of all acid solutions show higher SFG response in the OH-bonded region relative to neat water, with 1.1 M H2SO4 being more enhanced than 1.1 M HCl. In addition, VSFG spectra of bisulfate salt solutions highly resemble that of the dilute H2SO4 solution (0.26 M) at a comparable pH. HD-VSFG (Im χ((2))) spectra of acid and bisulfate salt solutions further reveal that hydrogen-bonded water molecules are oriented preferentially toward the bulk liquid phase. General agreement between Im χ((2)) spectra of 1.1 M H2SO4 and 1.1 M HCl acid solutions indicate that HSO4(-) ions have a similar surface preference as that of chloride (Cl(-)) ions. By comparing the direction and magnitude of the electric fields arising from the interfacial ion distributions and the concentration of each species, the most reasonable relative surface preference that can be deduced from a simplified model follows the order H3O(+) > HSO4(-) > Na(+), NH4(+), Mg(2+) > SO4(2-). Interestingly

  6. Methane flux across the air-water interface - Air velocity effects

    NASA Technical Reports Server (NTRS)

    Sebacher, D. I.; Harriss, R. C.; Bartlett, K. B.

    1983-01-01

    Methane loss to the atmosphere from flooded wetlands is influenced by the degree of supersaturation and wind stress at the water surface. Measurements in freshwater ponds in the St. Marks Wildlife Refuge, Florida, demonstrated that for the combined variability of CH4 concentrations in surface water and air velocity over the water surface, CH4 flux varied from 0.01 to 1.22 g/sq m/day. The liquid exchange coefficient for a two-layer model of the gas-liquid interface was calculated as 1.7 cm/h for CH4 at air velocity of zero and as 1.1 + 1.2 v to the 1.96th power cm/h for air velocities from 1.4 to 3.5 m/s and water temperatures of 20 C.

  7. Toward a simple molecular understanding of sum frequency generation at air-water interfaces

    SciTech Connect

    Noah-Vanhoucke, Joyce; Smith, Jared D.; Geissler, Phillip L.

    2009-01-13

    Second-order vibrational spectroscopies successfully isolate signals from interfaces, but they report on intermolecular structure in a complicated and indirect way. Here we adapt a perspective on vibrational response developed for bulk spectroscopies to explore the microscopic fluctuations to which sum frequency generation (SFG), a popular surface-specific measurement, is most sensitive. We focus exclusively on inhomogeneous broadening of spectral susceptibilities for OH stretching of HOD as a dilute solute in D{sub 2}O. Exploiting a simple connection between vibrational frequency shifts and an electric field variable, we identify several functions of molecular orientation whose averages govern SFG. The frequency-dependence of these quantities is well captured by a pair of averages, involving alignment of OH and OD bonds with the surface normal at corresponding values of the electric field. The approximate form we obtain for SFG susceptibility highlights a dramatic sensitivity to the way a simulated liquid slab is partitioned for calculating second-order response.

  8. Hydrogen bonding and orientation effects on the accommodation of methylamine at the air-water interface.

    PubMed

    Hoehn, Ross D; Carignano, Marcelo A; Kais, Sabre; Zhu, Chongjing; Zhong, Jie; Zeng, Xiao C; Francisco, Joseph S; Gladich, Ivan

    2016-06-01

    Methylamine is an abundant amine compound detected in the atmosphere which can affect the nature of atmospheric aerosol surfaces, changing their chemical and optical properties. Molecular dynamics simulation results show that methylamine accommodation on water is close to unity with the hydrophilic head group solvated in the interfacial environment and the methyl group pointing into the air phase. A detailed analysis of the hydrogen bond network indicates stronger hydrogen bonds between water and the primary amine group at the interface, suggesting that atmospheric trace gases will likely react with the methyl group instead of the solvated amine site. These findings suggest new chemical pathways for methylamine acting on atmospheric aerosols in which the methyl group is the site of orientation specific chemistry involving its conversion into a carbonyl site providing hydrophilic groups for uptake of additional water. This conversion may explain the tendency of aged organic aerosols to form cloud condensation nuclei. At the same time, formation of NH2 radical and formaldehyde is suggested to be a new source for NH2 radicals at aerosol surfaces, other than by reaction of absorbed NH3. The results have general implications for the chemistry of other amphiphilic organics, amines in particular, at the surface of atmospherically relevant aerosols. PMID:27276960

  9. Stabilization of alkylated azacrown ether by fatty acid at the air-water interface.

    PubMed

    Zarbakhsh, Ali; Campana, Mario; Webster, John R P; Wojciechowski, Kamil

    2010-12-01

    The adsorbed amount of partially deuterated dihexadecyl-diaza-18-crown-6 ether (d-ACE16) in the presence of different chain length fatty acids as a function of surface pressure was determined by neutron reflectometry technique. The highest adsorbed amount of the azacrown ether was observed for the mixture of ACE16 with hexadecanoic (palmitic) acid, pointing to the importance of chain length matching between the two species for optimum stabilization of the mixed monolayer. The contrast variation technique was used to estimate the contribution to the total adsorbed amount from stearic acid and ACE16. It was found that the mixed Langmuir monolayer is stable against dissolution up to a surface pressure of 20 mN m(-1). Above this pressure, however, the spread and adsorbed amounts start to deviate, indicative of partial dissolution into the aqueous subphase. The consequences of this behavior for the transport of metal ions through the interfaces of permeation liquid membranes (PLMs) are discussed. PMID:21049946

  10. Hydrogen bonding and orientation effects on the accommodation of methylamine at the air-water interface

    NASA Astrophysics Data System (ADS)

    Hoehn, Ross D.; Carignano, Marcelo A.; Kais, Sabre; Zhu, Chongjing; Zhong, Jie; Zeng, Xiao C.; Francisco, Joseph S.; Gladich, Ivan

    2016-06-01

    Methylamine is an abundant amine compound detected in the atmosphere which can affect the nature of atmospheric aerosol surfaces, changing their chemical and optical properties. Molecular dynamics simulation results show that methylamine accommodation on water is close to unity with the hydrophilic head group solvated in the interfacial environment and the methyl group pointing into the air phase. A detailed analysis of the hydrogen bond network indicates stronger hydrogen bonds between water and the primary amine group at the interface, suggesting that atmospheric trace gases will likely react with the methyl group instead of the solvated amine site. These findings suggest new chemical pathways for methylamine acting on atmospheric aerosols in which the methyl group is the site of orientation specific chemistry involving its conversion into a carbonyl site providing hydrophilic groups for uptake of additional water. This conversion may explain the tendency of aged organic aerosols to form cloud condensation nuclei. At the same time, formation of NH2 radical and formaldehyde is suggested to be a new source for NH2 radicals at aerosol surfaces, other than by reaction of absorbed NH3. The results have general implications for the chemistry of other amphiphilic organics, amines in particular, at the surface of atmospherically relevant aerosols.

  11. Savinase action on bovine serum albumin (BSA) monolayers demonstrated with measurements at the air-water interface and liquid Atomic Force Microscopy (AFM) imaging.

    PubMed

    Balashev, Konstantin; Callisen, Thomas H; Svendsen, Allan; Bjørnholm, Thomas

    2011-12-01

    We studied the enzymatic action of Savinase on bovine serum albumin (BSA) organized in a monolayer spread at the air/water interface or adsorbed at the mica surface. We carried out two types of experiments. In the first one we followed the degradation of the protein monolayer by measuring the surface pressure and surface area decrease versus time. In the second approach we applied AFM imaging of the supported BSA monolayers adsorbed on mica solid supports and extracted information for the enzyme action by analyzing the obtained images of the surface topography in the course of enzyme action. In both cases we obtained an estimate for the turnover number (TON) of the enzyme reaction. PMID:21868205

  12. Towards a unified picture of the water self-ions at the air-water interface: a density functional theory perspective

    SciTech Connect

    Baer, Marcel D.; Kuo, I-F W.; Tobias, Douglas J.; Mundy, Christopher J.

    2014-07-17

    The propensities of the water self ions, H3O+ and OH- , for the air-water interface has implications for interfacial acid-base chemistry. Despite numerous experimental and computational studies, no consensus has been reached on the question of whether or not H3O+ and/or OH- prefer to be at the water surface or in the bulk. Here we report a molecular dynamics simulation study of the bulk vs. interfacial behavior of H3O+ and OH- that employs forces derived from density functional theory with a generalized gradient approximation exchangecorrelation functional (specifically, BLYP) and empirical dispersion corrections. We computed the potential of mean force (PMF) for H3O+ as a function of the position of the ion in a 215-molecule water slab. The PMF is flat, suggesting that H3O+ has equal propensity for the air-water interface and the bulk. We compare the PMF for H3O+ to our previously computed PMF for OH- adsorption, which contains a shallow minimum at the interface, and we explore how differences in solvation of each ion at the interface vs. the bulk are connected with interfacial propensity. We find that the solvation shell of H3O+ is only slightly dependent on its position in the water slab, while OH- partially desolvates as it approaches the interface, and we examine how this difference in solvation behavior is manifested in the electronic structure and chemistry of the two ions. DJT was supported by National Science Foundation grant CHE-0909227. CJM was supported by the U.S. Department of Energy‘s (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated for the Department of Energy by Battelle. The potential of mean force required resources of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DEAC05-00OR22725. The remaining simulations

  13. Hierarchical assembly of an achiral pi-conjugated molecule into a chiral nanotube through the air/water interface.

    PubMed

    Yao, Pingping; Wang, Haifeng; Chen, Penglei; Zhan, Xiaowei; Kuang, Xun; Zhu, Daoben; Liu, Minghua

    2009-06-16

    An achiral pi-conjugated fluorinated fused pyrazine derivative has been spread at the air/water interface, and its assembling property is investigated. It has been found that the compound, although without any long alkyl chain, could be spread as a floating film on water surface, the surface pressure of which can be compressed up to ca. 70 mN/m. An inflection point has been observed in the isotherm of the floating film on water surface. The atomic force microscope (AFM), scanning electron microscope (SEM) as well as the transmission electron microscope (TEM) observations revealed that the floating film first formed a multilayer structure and then was compressed into nanotubes after the inflection region as a result of the rolling of the ultrathin film. Interestingly, the rolled nanotubes show circular dichroism although the molecule itself is an achiral species, suggesting the chiral nanotube is predominantly produced on the water surface. The investigation provides an effective way to fabricate supramolecular-based organic chiral nanotubes through an interfacial supramolecular assembly process. PMID:19459675

  14. Influence of temperature on microdomain organization of mixed cationic-zwitterionic lipidic monolayers at the air-water interface.

    PubMed

    Bordi, F; Cametti, C; Di Venanzio, C; Sennato, S; Zuzzi, S

    2008-02-15

    The thermodynamic behavior of mixed DOTAP-DPPC monolayers at the air-water interface has been investigated in the temperature range from 15 to 45 degrees C, covering the temperature interval where the thermotropic phase transition of DPPC, from solid-like to liquid-like, takes place. Based on the regular solution theory, the miscibility of the two lipids in the mixed monolayer was evaluated in terms of the excess Gibbs free energy of mixing DeltaG(ex), activity coefficients f(1) and f(2) and interaction parameter omega between the two lipids. The mixed DOTAP-DPPC film was found to have positive deviations from ideality at low DOTAP mole fractions, indicating a phase-separated binary mixture. This effect depends on the temperature and is largely conditioned by the structural chain conformation of the DPPC lipid monolayer. The thermodynamic parameters associated to the stability and the miscibility of these two lipids in a monolayer structure have been discussed in the light of the phase diagram of the DOTAP-DPPC aqueous mixtures obtained from differential scanning calorimetry measurements. The correlation between the temperature behavior of DOTAP-DPPC monolayers and their bulk aqueous mixtures has been briefly discussed. PMID:17936597

  15. Solution self-assembly and adsorption at the air-water interface of the monorhamnose and dirhamnose rhamnolipids and their mixtures.

    PubMed

    Chen, M L; Penfold, J; Thomas, R K; Smyth, T J P; Perfumo, A; Marchant, R; Banat, I M; Stevenson, P; Parry, A; Tucker, I; Grillo, I

    2010-12-01

    The self-assembly in solution and adsorption at the air-water interface, measured by small-angle neutron scattering, SANS, and neutron reflectivity, NR, of the monorhamnose and dirhamnose rhamnolipids (R1, R2) and their mixtures, are discussed. The production of the deuterium-labeled rhamnolipids (required for the NR studies) from a Pseudomonas aeruginosa culture and their separation into the pure R1 and R2 components is described. At the air-water interface, R1 and R2 exhibit Langmuir-like adsorption isotherms, with saturated area/molecule values of about 60 and 75 Å(2), respectively. In R1/R2 mixtures, there is a strong partitioning of R1 to the surface and R2 competes less favorably because of the steric or packing constraints of the larger R2 dirhamnose headgroup. In dilute solution (<20 mM), R1 and R2 form small globular micelles, L(1), with aggregation numbers of about 50 and 30, respectively. At higher solution concentrations, R1 has a predominantly planar structure, L(α) (unilamellar, ULV, or bilamellar, BLV, vesicles) whereas R2 remains globular, with an aggregation number that increases with increasing surfactant concentration. For R1/R2 mixtures, solutions rich in R2 are predominantly micellar whereas solutions rich in R1 have a more planar structure. At an intermediate composition (60 to 80 mol % R1), there are mixed L(α)/L(1) and L(1)/L(α) regions. However, the higher preferred curvature associated with R2 tends to dominate the mixed R1/R2 microstructure and its associated phase behavior. PMID:21028852

  16. Phases, line tension and pattern formation in molecularly thin films at the air-water interface

    NASA Astrophysics Data System (ADS)

    Mandal, Pritam

    A Langmuir film, which is a molecularly thin insoluble film on a liquid substrate, is one practical realization of a quasi-two dimensional matter. The major advantages of this system for the study of phase separation and phase co-existence are (a) it allows accurate control of the components and molecular area of the film and (b) it can be studied by various methods that require very flat films. Phase separation in molecularly thin films plays an important role in a range of systems from biomembranes to biosensors. For example, phase-separated lipid nano-domains in biomembranes are thought to play crucial roles in membrane function. I use Brewster Angel Microscopy (BAM) coupled with Fluorescence Microscopy (FM) and static Light Scattering Microscopy (LSM) to image phases and patterns within Langmuir films. The three microscopic techniques --- BAM, FM and LSM --- are complimentary to each other, providing distinct sets of information. They allow direct comparison with literature results in lipid systems. I have quantitatively validated the use of detailed hydrodynamic simulations to determine line tension in monolayers. Line tension decreases as temperature rises. This decrease gives us information on the entropy associated with the line, and thus about line structure. I carefully consider the thermodynamics of line energy and entropy to make this connection. In the longer run, LSM will be exploited to give us further information about line structure. I have also extended the technique by testing it on domains within the curved surface of a bilayer vesicle. I also note that in the same way that the presence of surface-active agents, known as surfactants, affects surface energy, the addiction of line active agents alters the inter-phase line energy. Thus my results set to stage to systematically study the influence of line active agents ---'linactants' --- on the inter-phase line energy. Hierarchal self-assembled chiral patterns were observed as a function of

  17. Long-timescale dynamics of thiol capped Au nanoparticle clusters at the air-water interface

    NASA Astrophysics Data System (ADS)

    Choudhuri, Madhumita; Datta, Alokmay

    2014-04-01

    A two-dimensional network of thiol-capped Au nanoparticle (AuNP) clusters is self-organized on a Stearic Acid (amphiphilic fatty acid) Langmuir monolayer on water surface. The AuNP clusters are found to form a pattern of connected and enclosed microspaces in the stearic acid template. The network features can be controlled by changing the surface pressure of the monolayer during compression. The two-dimensional dynamics of this network has been studied over a long timescale using Brewster Angle Microscopy (BAM). The dynamics is very slow, indicating the stability of the network system, and is essentially driven by the tendency to lower the number of nodes or joints in the network.

  18. Large-scale recrystallization of the S-layer of Bacillus coagulans E38-66 at the air/water interface and on lipid films.

    PubMed Central

    Pum, D; Weinhandl, M; Hödl, C; Sleytr, U B

    1993-01-01

    S-layer protein isolated from Bacillus coagulans E38-66 could be recrystallized into large-scale coherent monolayers at an air/water interface and on phospholipid films spread on a Langmuir-Blodgett trough. Because of the asymmetry in the physiochemical surface properties of the S-layer protein, the subunits were associated with their more hydrophobic outer face with the air/water interface and oriented with their negatively charged inner face to the zwitterionic head groups of the dipalmitoylphosphatidylcholine and dipalmitoylphosphatidylethanolamine (DPPE) monolayer films. The dynamic crystal growth at both types of interfaces was first initiated at several distant nucleation points. The individual monocrystalline areas grew isotropically in all directions until the front edge of neighboring crystals was met. The recrystallized S-layer protein and the S-layer-DPPE layer could be chemically cross-linked from the subphase with glutaraldehyde. Images PMID:8478338

  19. Equation of state for a coarse-grained DPPC monolayer at the air/water interface

    NASA Astrophysics Data System (ADS)

    Adhangale, Parag S.; Gaver, Donald P., III

    Pulmonary surfactant, a complex mixture of phospholipids and proteins, secreted by the type II epithelial cells in the lungs, is crucial to reducing the effort required for breathing. A lack of adequate amounts of pulmonary surfactant in underdeveloped lungs of premature infants results in infant respiratory distress syndrome (RDS). Surfactant replacement therapy (SRT) is the approved method of mitigating the effects of RDS. The development of new SRT regimens requires a fundamental understanding of the links between surfactant biochemistry and functionality. We use a coarse-grained (CG) model to predict the surface pressure-surface concentration relationship (equation of state) for pure DPPC, which is a major component of endogenous and synthetic pulmonary surfactant mixtures. We show that the model can be efficiently used to predict the equation of state in excellent agreement with experimental results. We also study the structure of the monolayer as a function of the surface tension of the system. We show that a decrease in the applied surface tension results in an increase in order in the head group region and a decrease in order in the tail region of DPPC. This technique may be useful in the prediction of equations of state for surfactant replacements.

  20. Adsorption of egg phosphatidylcholine to an air/water and triolein/water bubble interface: use of the 2-dimensional phase rule to estimate the surface composition of a phospholipid/triolein/water surface as a function of surface pressure.

    PubMed

    Mitsche, Matthew A; Wang, Libo; Small, Donald M

    2010-03-11

    Phospholipid monolayers play a critical role in the structure and stabilization of biological interfaces, including all membranes, the alveoli of the lungs, fat droplets in adipose tissue, and lipoproteins. The behavior of phospholipids in bilayers and at an air-water interface is well understood. However, the study of phospholipids at oil-water interfaces is limited due to technical challenges. In this study, egg phosphatidylcholine (EPC) was deposited from small unilamellar vesicles onto a bubble of either air or triolein (TO) formed in a low-salt buffer. The surface tension (gamma) was measured using a drop tensiometer. We observed that EPC binds irreversibly to both interfaces and at equilibrium exerts approximately 12 and 15 mN/m of pressure (Pi) at an air and TO interface, respectively. After EPC was bound to the interface, the unbound EPC was washed out of the cuvette, and the surface was compressed to study the Pi/area relationship. To determine the surface concentration (Gamma), which cannot be measured directly, compression isotherms from a Langmuir trough and drop tensiometer were compared. The air-water interfaces had identical characteristics using both techniques; thus, Gamma on the bubble can be determined by overlaying the two isotherms. Both TO and EPC are surface-active, so in a mixed TO/EPC monolayer, both molecules will be exposed to water. Since TO is less surface-active than EPC, as Pi increases, the TO is progressively ejected. To understand the Pi/area isotherm of EPC on a TO bubble, a variety of TO-EPC mixtures were spread at the air-water interface. The isotherms show an abrupt break in the curve caused by the ejection of TO from the monolayer into a new bulk phase. By overlaying the compression isotherm above the ejection point with a TO bubble compression isotherm, Gamma can be estimated. This allows determination of Gamma of EPC on a TO bubble as a function of Pi. PMID:20151713

  1. Enhanced stabilization of aerosol-OT surfactant monolayer upon interaction with small amounts of bovine serum albumin at the air-water interface.

    PubMed

    Caetano, Wilker; Ferreira, Marystela; Oliveira, Osvaldo N; Itri, Rosangela

    2004-10-10

    An investigation is made of the influence from small amounts of the protein bovine serum albumin (BSA) on the lateral organization of low molecular weight surfactant sodium bis-2-ethylhexyl sulfosuccinate (AOT) at the air-water interface. Surface pressure (pi - A), surface potential (deltaV - A) and Brewster angle microscopy (BAM) experiments were carried out, with particular emphasis on the monolayer stability under successive compression-expansion cycles. AOT monolayer is not stable at the air-water interface, which means that the majority of AOT molecules go into the aqueous subphase as monomers and/or normal micelles. When a waiting time elapses between spreading and compression, the surfactant monolayer tends to reorganize partially at the air-water interface, with a monolayer expansion being observed for waiting times as large as 12 h. The incorporation of very small amount of BSA (10(-9)M) at the interface, also inferred from BAM, increases the monolayer stability as revealed by pi - A and deltaV - A results. For a waiting time of circa 3 h, the mixed monolayer reaches its maximum stability. This must be related to protein (and/or protein-surfactant complexes) adsorbed onto the AOT monolayer, thus altering the BSA conformation to accommodate its hydrophobic/hydrophilic residues. Furthermore, the effects from such small amounts of BSA in the monolayer formation and stabilization mean that the AOT monolayer responds cooperatively to BSA. PMID:15465300

  2. Unusual Adsorption at the Air-Water Interface of a Zwitterionic Carboxybetaine with a Large Charge Separation.

    PubMed

    Ma, Kun; Li, Pei Xun; Dong, Chu Chuan; Thomas, Robert K; Penfold, Jeffrey

    2016-04-12

    The structures of layers of three different dodecylcarboxybetaine surfactants adsorbed at the air-water interface have been determined by neutron reflection. The zwitterionic compounds differed in the length of the spacer separating the quaternary ammonium and carboxylate groups, which was (CH2)1, (CH2)4, or (CH2)8. The limiting area per molecule was found to be 45, 52, or 84 Å(2), respectively, and compared reasonably with results from surface tension showing that the Gibbs prefactor is 1 in each case. Isotopic labeling was used to distinguish between the position of the alkyl and spacer groups in the layer. The spacer was found to be well-immersed in water for the (CH2)1 and (CH2)4 spacers but significantly above water for the (CH2)8 spacer. The distribution of the (CH2)8 spacer along the surface normal was found to be similar to that of the dodecyl group; i.e., it projects out of the water, contrary to an earlier hypothesis that it forms a loop. Comparison of the overlap of water with dodecyl and spacer groups also indicates that the (CH2)8 spacer is well out of the water. This in turn suggests that the anionic carboxylic acid group, which is dissociated in solution, is not ionized in the adsorbed layer. A further observation is that the dodecylcarboxybetaine with the (CH2)8 spacer reaches surface saturation at one-tenth of the critical micelle concentration. This is highly unusual and is attributed to the long spacer destabilizing the micelle relative to the surface layer. PMID:27010322

  3. Langmuir structure of poly (2-vinylpyridine-b-hexyl isocyanate) rod-coil diblock copolymers at the air/water Interface

    NASA Astrophysics Data System (ADS)

    Ahmad, Farhan

    2005-03-01

    We conducted a systematic interfacial study for the complete range (5%-90% of rod mole percentage) of an amphiphilic rod-coil system, poly (hexyl isocyanate)-b-(2-vinylpyridine) at the air/water and air/solid interface. We applied Langmuir balance technique, scanning probe microscopy (SPM), transmission electron microscopy (TEM) and X-ray reflectivity for the complete characterization of the monolayer at the interfaces. The phase isotherms showed the well amphiphilic balance for the diblock copolymers, and the formation of stable monolayers. With the increasing rod content, the consistent increase in the monolayer packing density was observed by the phase isotherms and supported by X-ray reflectivity. SPM and TEM characterization showed their interesting surface morphology according to the varying rod mole percentage in the rod-coil system. Rod mole percentage 5%-15% showed micellar morphology. Rod mole percentage 23%-32% showed distinct and dispersed rods, whereas rod mole percentage 70%-90% showed well packed structure similar to lamella phase. We found the tendency of the diblock system to adopt a packed monomolecular structure has increased by the increasing rod content. This lead us to conclude that it is the hexyl-isocyanate (rod part) that governs mostly the interfacial behavior of rod-coil block copolymers.

  4. Surface interactions, thermodynamics and topography of binary monolayers of Insulin with dipalmitoylphosphatidylcholine and 1-palmitoyl-2-oleoylphosphatidylcholine at the air/water interface.

    PubMed

    Grasso, E J; Oliveira, R G; Maggio, B

    2016-02-15

    The molecular packing, thermodynamics and surface topography of binary Langmuir monolayers of Insulin and DPPC (dipalmitoylphosphatidylcholine) or POCP (1-palmitoyl-2-oleoylphosphatidylcholine) at the air/water interface on Zn(2+) containing solutions were studied. Miscibility and interactions were ascertained by the variation of surface pressure-mean molecular area isotherms, surface compressional modulus and surface (dipole) potential with the film composition. Brewster Angle Microscopy was used to visualize the surface topography of the monolayers. Below 20mN/m Insulin forms stable homogenous films with DPPC and POPC at all mole fractions studied (except for films with XINS=0.05 at 10mN/m where domain coexistence was observed). Above 20mN/m, a segregation process between mixed phases occurred in all monolayers without squeezing out of individual components. Under compression the films exhibit formation of a viscoelastic or kinetically trapped organization leading to considerable composition-dependent hysteresis under expansion that occurs with entropic-enthalpic compensation. The spontaneously unfavorable interactions of Insulin with DPPC are driven by favorable enthalpy that is overcome by unfavorable entropic ordering; in films with POPC both the enthalpic and entropic effects are unfavorable. The surface topography reveals domain coexistence at relatively high pressure showing a striped appearance. The interactions of Insulin with two major membrane phospholipids induces composition-dependent and long-range changes of the surface organization that ought to be considered in the context of the information-transducing capabilities of the hormone for cell functioning. PMID:26624532

  5. Experimentally probing the libration of interfacial water: the rotational potential of water is stiffer at the air/water interface than in bulk liquid.

    PubMed

    Tong, Yujin; Kampfrath, Tobias; Campen, R Kramer

    2016-07-21

    Most properties of liquid water are determined by its hydrogen-bond network. Because forming an aqueous interface requires termination of this network, one might expect the molecular level properties of interfacial water to markedly differ from water in bulk. Intriguingly, much prior experimental and theoretical work has found that, from the perspective of their time-averaged structure and picosecond structural dynamics, hydrogen-bonded OH groups at an air/water interface behave the same as hydrogen-bonded OH groups in bulk liquid water. Here we report the first experimental observation of interfacial water's libration (i.e. frustrated rotation) using the laser-based technique vibrational sum frequency spectroscopy. We find this mode has a frequency of 834 cm(-1), ≈165 cm(-1) higher than in bulk liquid water at the same temperature and similar to bulk ice. Because libration frequency is proportional to the stiffness of water's rotational potential, this increase suggests that one effect of terminating bulk water's hydrogen bonding network at the air/water interface is retarding rotation of water around intact hydrogen bonds. Because in bulk liquid water the libration plays a key role in stabilizing reaction intermediates and dissipating excess vibrational energy, we expect the ability to probe this mode in interfacial water to open new perspectives on the kinetics of heterogeneous reactions at aqueous interfaces. PMID:27339861

  6. Combined effect of synthetic protein, Mini-B, and cholesterol on a model lung surfactant mixture at the air-water interface.

    PubMed

    Chakraborty, Aishik; Hui, Erica; Waring, Alan J; Dhar, Prajnaparamita

    2016-04-01

    The overall goal of this work is to study the combined effects of Mini-B, a 34 residue synthetic analog of the lung surfactant protein SP-B, and cholesterol, a neutral lipid, on a model binary lipid mixture containing dipalmitolphosphatidylcholine (DPPC) and palmitoyl-oleoyl-phosphatidylglycerol (POPG), that is often used to mimic the primary phospholipid composition of lung surfactants. Using surface pressure vs. mean molecular area isotherms, fluorescence imaging and analysis of lipid domain size distributions; we report on changes in the structure, function and stability of the model lipid-protein films in the presence and absence of varying composition of cholesterol. Our results indicate that at low cholesterol concentrations, Mini-B can prevent cholesterol's tendency to lower the line tension between lipid domain boundaries, while maintaining Mini-B's ability to cause reversible collapse resulting in the formation of surface associated reservoirs. Our results also show that lowering the line tension between domains can adversely impact monolayer folding mechanisms. We propose that small amounts of cholesterol and synthetic protein Mini-B can together achieve the seemingly opposing requirements of efficient LS: fluid enough to flow at the air-water interface, while being rigid enough to oppose irreversible collapse at ultra-low surface tensions. PMID:26775740

  7. Interaction of poly(ethylene-glycols) with air-water interfaces and lipid monolayers: investigations on surface pressure and surface potential.

    PubMed Central

    Winterhalter, M; Bürner, H; Marzinka, S; Benz, R; Kasianowicz, J J

    1995-01-01

    We have characterized the surface activity of different-sized poly(ethylene-glycols) (PEG; M(r) 200-100,000 Da) in the presence or absence of lipid monolayers and over a wide range of bulk PEG concentrations (10(-8)-10% w/v). Measurements of the surface potential and surface pressure demonstrate that PEGs interact with the air-water and lipid-water interfaces. Without lipid, PEG added either to the subphase or to the air-water interface forms relatively stable monolayers. Except for very low molecular weight polymers (PEGs < 1000 Da), low concentrations of PEG in the subphase (between 10(-5) and 10(-4)% w/v) increase the surface potential from zero (with respect to the potential of a pure air-water interface) to a plateau value of approximately 440 mV. At much higher polymer concentrations, > 10(-1)% (w/v), depending on the molecular weight of the PEG and corresponding to the concentration at which the polymers in solution are likely to overlap, the surface potential decreases. High concentrations of PEG in the subphase cause a similar decrease in the surface potential of densely packed lipid monolayers spread from either diphytanoyl phosphatidylcholine (DPhPC), dipalmitoyl phosphatidylcholine (DPPC), or dioleoyl phosphatidylserine (DOPS). Adding PEG as a monolayer at the air-water interface also affects the surface activity of DPhPC or DPPC monolayers. At low lipid concentration, the surface pressure and potential are determined by the polymer. For intermediate lipid concentrations, the surface pressure-area and surface potential-area isotherms show that the effects due to lipid and PEG are not always additive and that the polymer's effect is distinct for the two lipids. When PEG-lipid-mixed monolayers are compressed to surface pressures greater than the collapse pressure for a PEG monolayer, the surface pressure-area and surface potential-area isotherms approach that of the lipid alone, suggesting that for this experimental condition PEG is expelled from the

  8. Monolayers of the lipid derivatives of isoniazid at the air/water interface and the formation of self-assembled nanostructures in water.

    PubMed

    Jin, Yiguang; Chen, Shufeng; Xin, Rui; Zhou, Yisheng

    2008-07-15

    Isoniazid (INH, isonicotinic acid hydrazide) is one of the most commonly used anti-tubercular drugs. However, resistance of Mycobacterium tuberculosis strains to anti-mycobacterial agents including INH is an increasing problem worldwide. Development of new anti-mycobacterial agents thus has attracted attention. Five lipid derivatives of INH were prepared in this study. They formed monolayers at the air/water interface, and some nanostructures with different morphologies were obtained through molecular self-assembly in water. The derivatives included one fatty acyl derivative containing a 12-C hydrocarbon-long chain (1), three fatty alcohol derivatives with a succinyl as spacer and an 8, 12 or 16-C hydrocarbon-long chain (2, 3 and 4), and one tetrahydro-2H-1,3,5-thiadiazine-2-thione (THTT) derivative containing a 12-C hydrocarbon-long chain (5). The surface pressure-area isotherms depended on the volume and configuration of heads and the length of tails of derivatives. Compound 2 had a relatively large head and a short tail, easily standing uprightly at the interface. Under a certain surface pressure, the linear polar head groups of 3 could be partly squeezed out and insert into subphase because the length of heads were comparable to the one of tails. The very long tails of 4 always maintained above the interface and led to a high collapse pressure. Compound 5 possessed an extended and large head consisting of the THTT and INH groups so that the relatively short tails tilted at the interface and difficultly contact with each other. The THTT rings might be partly squeezed out and enter into air under a certain surface pressure. The self-assembly behaviours of derivatives in water depended on the molecular configuration and agreed with the corresponding monolayer behaviours. The flexible and medium-long tails (1 and 3) led to the derivatives to form nanoscale vesicles, though the short or very long tails did not (2 and 4). Interestingly, intermolecular hydrogen

  9. External reflection FTIR of peptide monolayer films in situ at the air/water interface: experimental design, spectra-structure correlations, and effects of hydrogen-deuterium exchange.

    PubMed Central

    Flach, C R; Brauner, J W; Taylor, J W; Baldwin, R C; Mendelsohn, R

    1994-01-01

    A Fourier transform infrared spectrometer has been interfaced with a surface balance and a new external reflection infrared sampling accessory, which permits the acquisition of spectra from protein monolayers in situ at the air/water interface. The accessory, a sample shuttle that permits the collection of spectra in alternating fashion from sample and background troughs, reduces interference from water vapor rotation-vibration bands in the amide I and amide II regions of protein spectra (1520-1690 cm-1) by nearly an order of magnitude. Residual interference from water vapor absorbance ranges from 50 to 200 microabsorbance units. The performance of the device is demonstrated through spectra of synthetic peptides designed to adopt alpha-helical, antiparallel beta-sheet, mixed beta-sheet/beta-turn, and unordered conformations at the air/water interface. The extent of exchange on the surface can be monitored from the relative intensities of the amide II and amide I modes. Hydrogen-deuterium exchange may lower the amide I frequency by as much as 11-12 cm-1 for helical secondary structures. This shifts the vibrational mode into a region normally associated with unordered structures and leads to uncertainties in the application of algorithms commonly used for determination of secondary structure from amide I contours of proteins in D2O solution. PMID:7919013

  10. Gas exchange in wetlands with emergent vegetation: The effects of wind and thermal convection at the air-water interface

    NASA Astrophysics Data System (ADS)

    Poindexter, Cristina M.; Variano, Evan A.

    2013-07-01

    Methane, carbon dioxide, and oxygen are exchanged between wetlands and the atmosphere through multiple pathways. One of these pathways, the hydrodynamic transport of dissolved gas through the surface water, is often underestimated in importance. We constructed a model wetland in the laboratory with artificial emergent plants to investigate the mechanisms and magnitude of this transport. We measured gas transfer velocities, which characterize the near-surface stirring driving air-water gas transfer, while varying two stirring processes important to gas exchange in other aquatic environments: wind and thermal convection. To isolate the effects of thermal convection, we identified a semiempirical model for the gas transfer velocity as a function of surface heat loss. The laboratory results indicate that thermal convection will be the dominant mechanism of air-water gas exchange in marshes with emergent vegetation. Thermal convection yielded peak gas transfer velocities of 1 cm h-1. Because of the sheltering of the water surface by emergent vegetation, gas transfer velocities for wind-driven stirring alone are likely to exceed this value only in extreme cases.

  11. Controlled deposition of functionalized silica coated zinc oxide nano-assemblies at the air/water interface for blood cancer detection.

    PubMed

    Pandey, Chandra Mouli; Dewan, Srishti; Chawla, Seema; Yadav, Birendra Kumar; Sumana, Gajjala; Malhotra, Bansi Dhar

    2016-09-21

    We report results of the studies relating to controlled deposition of the amino-functionalized silica-coated zinc oxide (Am-Si@ZnO) nano-assemblies onto an indium tin oxide (ITO) coated glass substrate using Langmuir-Blodgett (LB) technique. The monolayers have been deposited by transferring the spread solution of Am-Si@ZnO stearic acid prepared in chloroform at the air-water interface, at optimized pressure (16 mN/m), concentration (10 mg/ml) and temperature (23 °C). The high-resolution transmission electron microscopic studies of the Am-Si@ZnO nanocomposite reveal that the nanoparticles have a microscopic structure comprising of hexagonal assemblies of ZnO with typical dimensions of 30 nm. The surface morphology of the LB multilayer observed by scanning electron microscopy shows uniform surface of the Am-Si@ZnO film in the nanometer range (<80 nm). These electrodes have been utilized for chronic myelogenous leukemia (CML) detection by covalently immobilizing the amino-terminated oligonucleotide probe sequence via glutaraldehyde as a crosslinker. The response studies of these fabricated electrodes carried out using electrochemical impedance spectroscopy show that this Am-Si@ZnO LB film based nucleic acid sensor exhibits a linear response to complementary DNA (10(-6)-10(-16) M) with a detection limit of 1 × 10(-16) M. This fabricated platform is validated with clinical samples of CML positive patients and the results demonstrate its immense potential for clinical diagnosis. PMID:27590542

  12. Molecular assemblies of 4-(hexadecyloxy)-n-(pyridinylmethylene)anilines at the air-water interface and Cu(II)-promoted vesicle formation via metal coordination.

    PubMed

    Wang, Haibo; Miao, Wangen; Liu, Huijin; Zhang, Xianfeng; Du, Xuezhong

    2010-09-01

    The molecular assemblies of 4-(hexadecyloxy)-N-(pyridinylmethylene)anilines (HPA) at the air-water interface on pure water and aqueous Cu(II) subphases have been investigated using in situ infrared reflection absorption spectroscopy (IRRAS). The Schiff base units were oriented with their long axes almost perpendicular to the water surface, and both imine and pyridinyl nitrogen atoms of the Schiff base units were coordinated to Cu(II) ions together with their geometrical conversions. The alkyl chains in the monolayers were quantitatively determined on the assumption that the HPA monolayers at the air-water interface were composed of sublayers of alkyl chains and Schiff base units, and the chain orientation angle on pure water was 30 +/- 2 degrees and increased to 37 +/- 2 degrees on the aqueous Cu(II) subphase. The HPA amphiphiles could not be dispersed in pure water but could self-organize into vesicles with metal-coordinated headgroups and interdigitated-packed alkyl chains in the presence of Cu(II) ions in aqueous solution. Transmission electron microscopy (TEM), differential scanning calorimetry (DSC), UV-vis spectroscopy, and small-angle X-ray diffraction (XRD) were used to investigate the aggregate structures and specific properties of the coordinated vesicles. PMID:20698514

  13. How does spacer length of imidazolium gemini surfactants control the fabrication of 2D-Langmuir films of silver-nanoparticles at the air-water interface?

    PubMed

    Datta, Sougata; Biswas, Joydeep; Bhattacharya, Santanu

    2014-09-15

    A series of gemini surfactants based on cationic imidazolium ring as polar headgroup, abbreviated as [Im-n-Im], 2Br(-) (n=2, 5, 6 and 12), was synthesized. Their ability to stabilize silver nanoparticles in aqueous media was investigated. The resulting suspensions were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). They exhibit specific morphologies by adopting different supramolecular assemblies in aqueous media depending on the internal packing arrangements and on the number of spacer methylene units [-(CH2)n-]. Individual colloids were extracted from the aqueous to chloroform layer and spread at the air/water interface to allow the formation of well-defined Langmuir films. By analysis of the surface pressure-area isotherms, the details about the packing behavior and orientation of the imidazolium gemini surfactant capped silver nanoparticles were obtained. Morphological features of the dynamic process of monolayer compression at the air-water interface were elucidated using Brewster angle microscopy (BAM). These monolayers were further transferred on mica sheets by the Langmuir-Blodgett technique at their associated collapse pressure and the morphology of these monolayers was investigated by atomic force microscopy (AFM). The number of spacer methylene units [-(CH2)n-] of the gemini surfactants exerted critical influence in modulating the characteristics of the resulting Langmuir films. PMID:24998058

  14. Self-Assembled Large-Scale Monolayer of Au Nanoparticles at the Air/Water Interface Used as a SERS Substrate.

    PubMed

    Guo, Qinghua; Xu, Minmin; Yuan, Yaxian; Gu, Renao; Yao, Jianlin

    2016-05-10

    Self-assembly of metal nanoparticles has attracted considerable attention because of its unique applications in technologies such as plasmonics, surface-enhanced optics, sensors, and catalysts. However, fabrication of ordered nanoparticle structures remains a significant challenge. Thus, developing an efficient approach for the assembly of large-scale Au nanoparticles films for theoretical studies and for various applications is highly desired. In this paper, a facial approach for fabricating a monolayer film of Au nanoparticles was developed successfully. Using the surfactant polyvinylpyrrolidone (PVP), a large-scale monolayer film of well-ordered, uniform-sized Au nanoparticles was fabricated at the air/water interface. The film exhibited a two-dimensional (2D) hexagonal close-packed (HCP) structure having interparticle gaps smaller than 2 nm. These gaps generated numerous uniform "hot spots" for surface-enhanced Raman scattering (SERS) activity. The as-prepared monolayer film could be transferred to a solid substrate for use as a suitable SERS substrate with high activity, high uniformity, and high stability. The low spot-to-spot and substrate-to-substrate variations of intensity (<10%), the large surface enhancement factor (∼10(6)), and the high stability (∼45 days) make the substrate suitable for SERS measurements. Transfer of the monolayer film onto a glassy carbon electrode produced an Au electrode with clean, well-defined nanostructure suitable for electrochemical SERS measurements. The adsorption process of ionic liquids on the electrode with the monolayer film is similar to that on bulk metal electrodes. The present strategy provides an effective way for self-assembly of Au nanoparticles into well-defined nanostructures that may form optimal reproducible SERS substrates for quantitative analysis. It also provides an electrode with clean, well-defined nanostructure for electrochemical investigations. PMID:27101361

  15. Influence of dissolved humic substances on the mass transfer of organic compounds across the air-water interface.

    PubMed

    Ramus, Ksenia; Kopinke, Frank-Dieter; Georgi, Anett

    2012-01-01

    The effect of dissolved humic substances (DHS) on the rate of water-gas exchange of two volatile organic compounds was studied under various conditions of agitation intensity, solution pH and ionic strength. Mass-transfer coefficients were determined from the rate of depletion of model compounds from an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution (dynamic system). Under these conditions, the overall transfer rate is controlled by the mass-transfer resistance on the water side of the water-gas interface. The experimental results show that the presence of DHS hinders the transport of the organic molecules from the water into the gas phase under all investigated conditions. Mass-transfer coefficients were significantly reduced even by low, environmentally relevant concentrations of DHS. The retardation effect increased with increasing DHS concentration. The magnitude of the retardation effect on water-gas exchange was compared for Suwannee River fulvic and humic acids, a commercially available leonardite humic acid and two synthetic surfactants. The observed results are in accordance with the concept of hydrodynamic effects. Surface pressure forces due to surface film formation change the hydrodynamic characteristics of water motion at the water-air interface and thus impede surface renewal. PMID:22051345

  16. Adsorption at air-water and oil-water interfaces and self-assembly in aqueous solution of ethoxylated polysorbate nonionic surfactants.

    PubMed

    Penfold, Jeffrey; Thomas, Robert K; Li, Peixun X; Petkov, Jordan T; Tucker, Ian; Webster, John R P; Terry, Ann E

    2015-03-17

    The Tween nonionic surfactants are ethoxylated sorbitan esters, which have 20 ethylene oxide groups attached to the sorbitan headgroup and a single alkyl chain, lauryl, palmityl, stearyl, or oleyl. They are an important class of surfactants that are extensively used in emulsion and foam stabilization and in applications associated with foods, cosmetics and pharmaceuticals. A range of ethoxylated polysorbate surfactants, with differing degrees of ethoxylation from 3 to 50 ethylene oxide groups, have been synthesized and characterized by neutron reflection, small-angle neutron scattering, and surface tension. In conjunction with different alkyl chain groups, this provides the opportunity to modify their surface properties, their self-assembly in solution, and their interaction with macromolecules, such as proteins. Adsorption at the air-water and oil-water interfaces and solution self-assembly of the range of ethoxylated polysorbate surfactants synthesized are presented and discussed. PMID:25697294

  17. Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface.

    NASA Astrophysics Data System (ADS)

    Tinel, Liselotte; Rossignol, Stéphanie; Ciuraru, Raluca; George, Christian

    2015-04-01

    Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface. Liselotte Tinel, Stéphanie Rossignol, Raluca Ciuraru and Christian George Université de Lyon, Université Lyon 1, CNRS, UMR5256, IRCELYON, Institut de recherches sur la catalyse et l'environnement de Lyon, Villeurbanne, F-69626, France Recently the surface microlayer (SML) has received growing attention for its role in the deposition and emission of trace gases. This SML is presumably a highly efficient environment for photochemical reactions thanks to its physical and chemical properties, showing enrichment in chromophores [1]. Still, little is known about the possible photochemical processes that could influence the emission and deposition of volatile organic compounds (VOCs) in the SML. A recent study underlines the particularity of the presence of an organic microlayer, showing enhanced formation of peptide bonds at the air-water interface, although this reaction is thermodynamically disfavoured in bulk water [2]. Also, emissions of small gas phase carbonyl compounds formed photochemically by dissolved organic matter have been measured above natural water and glyoxal, for example, measured above the open ocean is thought to be photochemically produced [3, 4]. This study presents the results of a set of laboratory studies set up in order to better understand the role of the SML in the photochemical production of VOCs. Recently, our group has shown the formation of VOCs by light driven reactions in a small quartz reactor (14mL) containing aqueous solutions of humic acids (HA) in the presence of an organic (artificial or natural) microlayer [5]. The main VOCs produced were oxidized species, such as aldehydes, ketones and alcohols, as classically can be expected by the oxidation of the organics present at the interface initiated by triplet excited chromophores present in the HA. But also alkenes, dienes, including isoprene and

  18. Visualization of an adsorption model for surfactant transport from micelle solutions to a clean air/water interface using fluorescence microscopy.

    PubMed

    Song, Qing; Yuan, Mingjun

    2011-05-01

    This work pertains to visualizing a transport model for adsorption of surfactants from micelle solutions onto a clean air/water interface. Under the condition of surfactant adsorption from very dilute solutions, the time scale for diffusion of a surfactant monomer is much slower than the time scale for kinetic breakdown of the aggregates. A theoretical model predicts two regimes for the adsorption dynamics. We visualize these two regimes under the mechanism of solubilization using fluorescence microscopy, in which an insoluble fluorescent probe, NBD-HAD (4-(hexadecylamino)-7-nitrobenz-2-oxa-1,3-diazole), is used to illuminate the micelles. The dye fluoresces in the microenvironment of micelles but is quenched in the aqueous solution on laser excitation. The region containing micelles is illuminated, but the region which does not contain micelles appears dark. For surfactant solution of C(14)E(6) at concentration just above the critical micelle concentration (C(CMC)), C(CMC)=4.4 mg/L, a dark region between the bright image of the air/water interface and the micelle-containing zone is observed. This dark region becomes smaller with time and finally disappears once equilibrium is reached. For a surfactant solution of C(14)E(6) at the concentration of 4.74C(CMC), which is higher than a critical total surfactant concentration (C(T)(c)) of 4.25C(CMC), we observe bright images through surfactant solutions during the adsorption process. Fluorescence images validate the theoretical model. PMID:21349535

  19. Quantum chemical approach in the description of the amphiphile clusterization at the air/liquid and liquid/liquid interfaces with phase nature accounting. I. Aliphatic normal alcohols at the air/water interface.

    PubMed

    Vysotsky, Yuri B; Belyaeva, Elena A; Kartashynska, Elena S; Fainerman, Valentine B; Smirnova, Natalia A

    2015-02-19

    A new model based on the quantum chemical approach is proposed to describe structural and thermodynamic parameters of clusterization for substituted alkanes at the air/liquid and liquid/liquid interfaces. The new model by the authors, unlike the previous one, proposes an explicit account of the liquid phase (phases) influence on the parameters of monomers, clusters and monolayers of substituted alkanes at the regarded interface. The calculations were carried out in the frameworks of the quantum chemical semiempirical PM3 method (Mopac 2012), using the COSMO procedure. The new model was tested in the calculations of the clusterization parameters of fatty alcohols under the standard conditions at the air/water interface. The enthalpy, Gibbs' energy and absolute entropy of formation for alcohol monomers alongside with clusterization parameters for the cluster series including the monolayer at air/water interface were calculated. In our calculations the sinkage of monomers, molecules in clusters and monolayers was varied from 1 up to 5 methylene groups. Thermodynamic parameters calculated using the proposed model for the alcohol monolayers are in a good agreement with the corresponding experimental data. However, the proposed model cannot define the most energetically preferable immersion of the monolayer molecules in the water phase. PMID:25640463

  20. Efficient Spectral Diffusion at the Air/Water Interface Revealed by Femtosecond Time-Resolved Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy.

    PubMed

    Inoue, Ken-Ichi; Ishiyama, Tatsuya; Nihonyanagi, Satoshi; Yamaguchi, Shoichi; Morita, Akihiro; Tahara, Tahei

    2016-05-19

    Femtosecond vibrational dynamics at the air/water interface is investigated by time-resolved heterodyne-detected vibrational sum frequency generation (TR-HD-VSFG) spectroscopy and molecular dynamics (MD) simulation. The low- and high-frequency sides of the hydrogen-bonded (HB) OH stretch band at the interface are selectively excited with special attention to the bandwidth and energy of the pump pulses. Narrow bleach is observed immediately after excitation of the high-frequency side of the HB OH band at ∼3500 cm(-1), compared to the broad bleach observed with excitation of the low-frequency side at ∼3300 cm(-1). However, the time-resolved spectra observed with the two different excitations become very similar at 0.5 ps and almost indistinguishable by 1.0 ps. This reveals that efficient spectral diffusion occurs regardless of the difference of the pump frequency. The experimental observations are well-reproduced by complementary MD simulation. There is no experimental and theoretical evidence that supports extraordinary slow dynamics in the high-frequency side of the HB OH band, which was reported before. PMID:27120559

  1. Spectroscopic [correction of eSpectroscopic] and structural properties of valine gramicidin A in monolayers at the air-water interface.

    PubMed Central

    Lavoie, Hugo; Blaudez, Daniel; Vaknin, David; Desbat, Bernard; Ocko, Benjamin M; Salesse, Christian

    2002-01-01

    Monomolecular films of valine gramicidin A (VGA) were investigated in situ at the air-water interface by x-ray reflectivity and x-ray grazing incidence diffraction as well as polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). These techniques were combined to obtain information on the secondary structure and the orientation of VGA and to characterize the shoulder observed in its pi-A isotherm. The thickness of the film was obtained by x-ray reflectivity, and the secondary structure of VGA was monitored using the frequency position of the amide I band. The PM-IRRAS spectra were compared with the simulated ones to identify the conformation adopted by VGA in monolayer. At large molecular area, VGA shows a disordered secondary structure, whereas at smaller molecular areas, VGA adopts an anti-parallel double-strand intertwined beta(5.6) helical conformation with 30 degrees orientation with respect to the normal with a thickness of 25 A. The interface between bulk water and the VGA monolayer was investigated by x-ray reflectivity as well as by comparing the experimental and the simulated PM-IRRAS spectra on D(2)O and H(2)O, which suggested the presence of oriented water molecules between the bulk and the monolayer. PMID:12496123

  2. Surface activity and molecular organization of metallacarboranes at the air-water interface revealed by nonlinear optics.

    PubMed

    Gassin, Pierre-Marie; Girard, Luc; Martin-Gassin, Gaelle; Brusselle, Damien; Jonchère, Alban; Diat, Olivier; Viñas, Clara; Teixidor, Francesc; Bauduin, Pierre

    2015-03-01

    Because of their amphiphilic structure, surfactants adsorb at the water-air interface with their hydrophobic tails pointing out of the water and their polar heads plunging into the liquid phase. Unlike classical surfactants, metallabisdicarbollides (MCs) do not have a well-defined amphiphilic structure. They are nanometer-sized inorganic anions with an ellipsoidal shape composed of two carborane semicages sandwiching a metal ion. However, MCs have been shown to share many properties with surfactants, such as self-assembly in water (formation of micelles and vesicles), formation of lamellar lyotropic phases, and surface activity. By combining second harmonic generation and surface tension measurement, we show here that cobaltabis(dicarbollide) anion {[(C2B9H11)2Co](-) also named [COSAN](-)} with H(+) as a counterion, the most representative metallacarborane, adsorbs vertically at the water surface with its long axis normal to the surface. This vertical molecular orientation facilitates the formation of intermolecular and nonconventional dihydrogen bonds such as the B-H(δ-)···(δ+)H-C bond that has recently been proven to be at the origin of the self-assembly of MCs in water. Therefore, it appears here that lateral dihydrogen bonds are also involved in the surface activity of MCs. PMID:25644035

  3. Conformational analyses of bacillomycin D, a natural antimicrobial lipopeptide, alone or in interaction with lipid monolayers at the air-water interface.

    PubMed

    Nasir, Mehmet Nail; Besson, Françoise

    2012-12-01

    Bacillomycin D is a natural antimicrobial lipopeptide belonging to the iturin family. It is produced by Bacillus subtilis strains. Bacillomycin D is characterized by its strong antifungal and hemolytic properties, due to its interaction with the plasma membrane of sensitive cells. Until now, only few limited analyses were conducted to understand the biological activities of bacillomycin D at the molecular level. Our purpose was to analyze the conformation of bacillomycin D using IR spectroscopy and to model its interactions with cytoplasmic membranes using Langmuir interfacial monolayers. Our findings indicate that bacillomycin D contains turns and allow to model its three-dimensional structure. Bacillomycin D formed a monolayer film at the air-water interface and kept its turn conformation, as shown by polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). To identify the membrane lipid target of bacillomycin D, its interactions with pure lipid monolayers were analyzed and an original behavior of the lipopeptide toward cholesterol-containing monolayers was shown. This original behavior was lost when bacillomycin D was interacting with pure cholesteryl acetate monolayers, suggesting the involvement of the alcohol group of cholesterol in the lipopeptide-cholesterol interaction. PMID:22967349

  4. Miscibility of dl-α-tocopherol β-glucoside in DPPC monolayer at air/water and air/solid interfaces.

    PubMed

    Neunert, G; Makowiecki, J; Piosik, E; Hertmanowski, R; Polewski, K; Martynski, T

    2016-10-01

    The role of newly synthesized tocopherol glycosidic derivative in modifying molecular organization and phase transitions of phospholipid monolayer at the air/water interface has been investigated. Two-component Langmuir films of dl-α-tocopheryl β-D-glucopyranoside (BG) mixed with dipalmitoyl phosphatidylcholine (DPPC) in the whole range of mole fractions were formed at the water surface. An analysis of surface pressure versus mean molecular area (π-A) isotherms and Brewster angle microscope images showed that the presence of BG molecules changes the structure and packing of the DPPC monolayer in a BG concentration dependent manner. BG molecules incorporated into DPPC monolayer inhibit its liquid expanded to liquid condensed phase transition proportionally to the BG concentration. The monolayers were also transferred onto solid substrates and visualized using an atomic force microscope. The results obtained indicate almost complete miscibility of BG and DPPC in the monolayers at surface pressures present in the biological cell membrane (30-35·10(-3) N·m(-1)) for a BG mole fraction as high as 0.3. This makes the monolayer less packed and more disordered, leading to an increased permeability. The results support our previous molecular dynamics simulation data. PMID:27287132

  5. Floatable, Self-Cleaning, and Carbon-Black-Based Superhydrophobic Gauze for the Solar Evaporation Enhancement at the Air-Water Interface.

    PubMed

    Liu, Yiming; Chen, Jingwei; Guo, Dawei; Cao, Moyuan; Jiang, Lei

    2015-06-24

    Efficient solar evaporation plays an indispensable role in nature as well as the industry process. However, the traditional evaporation process depends on the total temperature increase of bulk water. Recently, localized heating at the air-water interface has been demonstrated as a potential strategy for the improvement of solar evaporation. Here, we show that the carbon-black-based superhydrophobic gauze was able to float on the surface of water and selectively heat the surface water under irradiation, resulting in an enhanced evaporation rate. The fabrication process of the superhydrophobic black gauze was low-cost, scalable, and easy-to-prepare. Control experiments were conducted under different light intensities, and the results proved that the floating black gauze achieved an evaporation rate 2-3 times higher than that of the traditional process. A higher temperature of the surface water was observed in the floating gauze group, revealing a main reason for the evaporation enhancement. Furthermore, the self-cleaning ability of the superhydrophobic black gauze enabled a convenient recycling and reusing process toward practical application. The present material may open a new avenue for application of the superhydrophobic substrate and meet extensive requirements in the fields related to solar evaporation. PMID:26027770

  6. Interaction of the cationic peptide bactenecin with phospholipid monolayers at the air-water interface: i interaction with 1,2-dipalmitoyl-sn-glycero-3-phosphatidilcholine.

    PubMed

    López-Oyama, A B; Flores-Vázquez, A L; Burboa, M G; Gutiérrez-Millán, L E; Ruiz-García, J; Valdez, M A

    2009-07-23

    In this work we have investigated the influence of NaCl on the adsorption of the antimicrobial cationic peptide bactenecin in the monolayer of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) at the air-water interface, as a function of NaCl concentrations in the subphase. We show that the effect of the salt concentration on DPPC monolayers is a monotonic decrease of the liquid-condensed-liquid-expanded (LC-LE) coexistence region. By contrast, the effect of the bactenecin adsorption at the DPPC monolayer not only removed the LC-LE coexistence region plateau, but also shifted the DPPC isotherms to higher pressures and increased the compressibility of the DPPC/bactenecin monolayers with respect to the pure DPPC monolayer around the LC phase. Analysis of the domain structure, obtained by Brewster angle and atomic force microscopes, indicates that the salt concentration in the subphase builds an electrostatic barrier, increasing the rigidity of DPPC monolayers and limiting the bactenecin adsorption at the LC-LE phase coexistence. PMID:19569630

  7. Study of interfacial area transport and sensitivity analysis for air-water bubbly flow

    SciTech Connect

    Kim, S.; Sun, X.; Ishii, M.; Beus, S.G.

    2000-09-01

    The interfacial area transport equation applicable to the bubbly flow is presented. The model is evaluated against the data acquired by the state-of-the-art miniaturized double-sensor conductivity probe in an adiabatic air-water co-current vertical test loop under atmospheric pressure condition. In general, a good agreement, within the measurement error of plus/minus 10%, is observed for a wide range in the bubbly flow regime. The sensitivity analysis on the individual particle interaction mechanisms demonstrates the active interactions between the bubbles and highlights the mechanisms playing the dominant role in interfacial area transport. The analysis employing the drift flux model is also performed for the data acquired. Under the given flow conditions, the distribution parameter of 1.076 yields the best fit to the data.

  8. Morphology and thermochromic phase transition of merocyanine J-aggregate monolayers at the air-water and solid-water interfaces

    NASA Astrophysics Data System (ADS)

    Kato, Noritaka; Saito, Kentaro; Serata, Toshinori; Aida, Hiroaki; Uesu, Yoshiaki

    2001-07-01

    Thermal changes of the merocyanine dye (MD) monolayer at the air-water interface were investigated under various subphase conditions in order to elucidate the formation mechanism and to control morphological and chromatic properties of two-dimensional MD J-aggregate crystallites (JC) formed in the monolayer. The dissociation temperature (Td) of the JC to the monomer MD was measured for different counterions of MD molecules in the subphase. The JC size was found to be dependent on the subphase temperature; it becomes larger when the JC is formed at a temperature closer to Td. This phenomenon is qualitatively reproduced by the numerical simulation of the Cahn-Hilliard equation. In the case of the MD monolayer on the subphase which contains two kinds of counterions, it exhibits a reversible thermochromic transition between two different JC states. The chromatic change is discrete, and is attributed to the structural phase transition of the JC induced by the mutual recombination of two kinds of counterions to MD molecules. The structural difference between the high and low temperature JC states is examined by the point dipole model. The transition temperature and thermal hysteresis width can be varied by the fraction of 2 counterions. In situ observations using a multipurpose nonlinear optical microscope revealed that the transition is of first order and the nucleation and growth process of the low temperature phase in the high temperature matrix was observed. The JC size of the low temperature phase became much larger through the recrystallization process. For future application of this phenomenon, an airtight cell consisting of two monolayers at the solid-water interface and the subphase was developed. In the cell, the same reversible transition occurs, but with a slow relaxation.

  9. Measurement of the Surface Dilatational Viscosity of an Insoluble Surfactant Monolayer at the Air/Water Interface Using a Pendant Drop Apparatus

    NASA Technical Reports Server (NTRS)

    Lorenzo, Jose; Couzis, Alex; Maldarelli, Charles; Singh, Bhim S. (Technical Monitor)

    2000-01-01

    When a fluid interface with surfactants is at rest, the interfacial stress is isotropic (as given by the equilibrium interfacial tension), and is described by the equation of state which relates the surface tension to the surfactant surface concentration. When surfactants are subjected to shear and dilatational flows, flow induced interaction of the surfactants; can create interfacial stresses apart from the equilibrium surface tension. The simplest relationship between surface strain rate and surface stress is the Boussinesq-Scriven constitutive equation completely characterized by three coefficients: equilibrium interfacial tension, surface shear viscosity, and surface dilatational viscosity Equilibrium interfacial tension and surface shear viscosity measurements are very well established. On the other hand, surface dilatational viscosity measurements are difficult because a flow which change the surface area also changes the surfactant surface concentration creating changes in the equilibrium interfacial tension that must be also taken into account. Surface dilatational viscosity measurements of existing techniques differ by five orders of magnitude and use spatially damped surface waves and rapidly expanding bubbles. In this presentation we introduce a new technique for measuring the surface dilatational viscosity by contracting an aqueous pendant drop attached to a needle tip and having and insoluble surfactant monolayer at the air-water interface. The isotropic total tension on the surface consists of the equilibrium surface tension and the tension due to the dilation. Compression rates are undertaken slow enough so that bulk hydrodynamic stresses are small compared to the surface tension force. Under these conditions we show that the total tension is uniform along the surface and that the Young-Laplace equation governs the drop shape with the equilibrium surface tension replaced by the constant surface isotropic stress. We illustrate this technique using

  10. The Turbulent Boundary Layer Near the Air-Water Interface on a Surface-Piercing Flat Plate

    NASA Astrophysics Data System (ADS)

    Washuta, Nathan; Masnadi, Naeem; Duncan, James H.

    2015-11-01

    Turbulent fluctuations in the vicinity of the water free surface along a flat, vertically oriented surface-piercing plate are studied experimentally using a laboratory-scale experiment. In this experiment, a meter-wide stainless steel belt travels horizontally in a loop around two rollers with vertically oriented axes, which are separated by 7.5 meters. This belt device is mounted inside a large water tank with the water level set just below the top edge of the belt. The belt, rollers, and supporting frame are contained within a sheet metal box to keep the device dry except for one 6-meter-long straight test section between rollers. The belt is launched from rest with a 3- g acceleration in order to quickly reach steady state velocity. This creates a temporally evolving boundary layer analogous to the spatially evolving boundary layer created along a flat-sided ship moving at the same velocity, with a length equivalent to the length of belt that has passed the measurement region since the belt motion began. Cinematic Stereo PIV measurements are performed in planes parallel to the free surface by imaging the flow from underneath the tank in order to study the modification of the boundary layer flow field due to the effects of the water free surface. The support of the Office of Naval Research under grant N000141110029 is gratefully acknowledged.

  11. Interaction between a growth-hormone releasing hexapeptide and phospholipids spread as monolayers at the air/water interface.

    PubMed

    Issaurat, B; Teissié, J

    1988-10-20

    The interaction between a growth-hormone releasing hexapeptide and phospholipids was studied on mixed monolayers models by means of surface fluorescence. When in a monolayer this hexapeptide which contains two tryptophan molecules was observed to fluoresce. Isothermal compression experiments showed that the complex was destroyed upon compression in the case of phosphatidylethanolamine. With phosphatidylglycerol it was observed to be stable but a dramatic reversible decrease in emission was observed at high surface pressure. This is indicative of a reversible change in the organization of the peptide-phospholipid complex. These observations indicate that, in the complex, hydrophobic interactions were weak but electrostatic ones, when present, were strong enough to maintain the GHRP attached to the monolayer and not to destabilize it. The integrity of the lipid monolayer appeared not to be affected by the peptide. PMID:3179304

  12. Miscibility behavior of two-component monolayers at the air-water interface: perfluorocarboxylic acids and DMPE.

    PubMed

    Yokoyama, Hiroki; Nakahara, Hiromichi; Nakagawa, Takahiro; Shimono, Satoshi; Sueishi, Kunihiko; Shibata, Osamu

    2009-09-01

    Surface pressure (pi)-molecular area (A) and surface potential (DeltaV)-A isotherms have been measured for two-component monolayers of four different perfluorocarboxylic acids [FCn; perfluorododecanoic acid (FC12), perfluorotetradecanoic acid (FC14), perfluorohexadecanoic acid (FC16), and perfluorooctadecanoic acid (FC18)] and dimyristoylphosphatidylethanolamine (DMPE) on 0.15M NaCl (pH 2) at 298.2K. The present study is focused on the miscibility and the interfacial behavior for the binary DMPE/FCn monolayers upon compression. From the isotherms, the miscibility has been elucidated in terms of the additivity rule, the interaction parameter, and the interaction energy. The interaction parameter (or energy) is compared with that for the previous dipalmitoylphosphatidylcholine (DPPC)/FCn systems [Colloids Surf. B 41 (2005) 285-298] to understand the effect of phospholipids' polar headgroup on the binary miscibility. Furthermore, the phase behavior of the DMPE/FCn systems has been morphologically examined using fluorescence microscopy (FM) and atomic force microscopy (AFM). These images reveal the different interaction modes among the four systems; DMPE can be miscible with FC12 and FC14 and immiscible with FC16 and FC18 in the monolayer state. These systematic examinations indicate that the miscibility of perfluorocarboxylic acids and phospholipids depends on combination of hydrocarbon and fluorocarbon chain lengths and on phospholipids' polar headgroups within a monolayer. PMID:19481762

  13. Sea spray production by bag breakup mode of fragmentation of the air-water interface at strong and hurricane wind

    NASA Astrophysics Data System (ADS)

    Troitskaya, Yuliya; Kandaurov, Alexander; Ermakova, Olga; Kozlov, Dmitry; Sergeev, Daniil; Zilitinkevich, Sergej

    2016-04-01

    Sea sprays is a typical element of the marine atmospheric boundary layer (MABL) of large importance for marine meteorology, atmospheric chemistry and climate studies. They are considered as a crucial factor in the development of hurricanes and severe extratropical storms, since they can significantly enhance exchange of mass, heat and momentum between the ocean and the atmosphere. This exchange is directly provided by spume droplets with the sizes from 10 microns to a few millimeters mechanically torn off the crests of a breaking waves and fall down to the ocean due to gravity. The fluxes associated with the spray are determined by the rate of droplet production at the surface quantified by the sea spray generation function (SSGF), defined as the number of spray particles of radius r produced from the unit area of water surface in unit time. However, the mechanism of spume droplets' formation is unknown and empirical estimates of SSGF varied over six orders of magnitude; therefore, the production rate of large sea spray droplets is not adequately described and there are significant uncertainties in estimations of exchange processes in hurricanes. Experimental core of our work comprise laboratory experiments employing high-speed video-filming, which have made it possible to disclose how water surface looks like at extremely strong winds and how exactly droplets are torn off wave crests. We classified events responsible for spume droplet, including bursting of submerged bubbles, generation and breakup of "projections" or liquid filaments (Koa, 1981) and "bag breakup", namely, inflating and consequent blowing of short-lived, sail-like pieces of the water-surface film, "bags". The process is similar to "bag-breakup" mode of fragmentation of liquid droplets and jets in gaseous flows. Basing on statistical analysis of results of these experiments we show that the main mechanism of spray-generation is attributed to "bag-breakup mechanism On the base of general principles

  14. Effect of the fluorination degree of hydrophobic chains on the monolayer behavior of unsaturated diacylphosphatidylcholines bearing partially fluorinated 9-octadecynoyl (stearoloyl) groups at the air-water interface.

    PubMed

    Baba, Teruhiko; Takai, Katsuki; Takagi, Toshiyuki; Kanamori, Toshiyuki

    2014-11-01

    The effect of the fluorination degree of hydrophobic chains on the monolayer behavior of unsaturated diacylphosphatidylcholines (PCs) was examined by employing a series of PCs bearing partially fluorinated 9-octadecynoyl (stearoloyl) groups (DFnStPCs, n: the number of fluorinated carbon atoms in a stearoloyl group; n=1, 2, 4, 8), including their hydrophobic parts--partially fluorinated stearolic acids (FnStAs)--at the air-water interface. π-A isotherm measurements and Brewster angle microscope observations revealed: (i) all DFnStPCs including FnStAs form monolayers of liquid character at 25 °C; (ii) they form more expanded monolayers than their non-fluorinated counterparts, distearoloyl-PC (DStPC) and stearolic acid, while the monolayer stability increases with n; (iii) compared with DStPC and DF8StPC, DFnStPCs (n=1, 2, 4) in the low-π region tend to show a weakening in their self-aggregation property and an increase in the work required for monolayer compression; (iv) although DF8StPC forms the most expanded monolayer, the behavior of DF8StPC resembles that of DStPC rather than that of DFnStPCs (n=1, 2, 4). The monolayer behavior of DFnStPCs (n=1, 2, 4) is explained by postulating a flatly-lying conformation of hydrophobic chains, in which three polar parts (ester group, triple bond, CF2-CH2 linkage) in chains are immersed in the subphase at large areas. DStPC and DF8StPC lacking a CF2-CH2 linkage, however, do not likely adopt such a conformation. PMID:25264284

  15. Structure of Ceramide-1-Phosphate at the Air-Water Solution Interface in the Absence and Presence of Ca[superscript 2+

    SciTech Connect

    Kooijman, Edgar E.; Vaknin, David; Bu, Wei; Joshi, Leela; Kang, Shin-Woong; Gericke, Arne; Mann, Elizabeth K.; Kumar, Satyendra

    2009-03-24

    Ceramide-1-phosphate, the phosphorylated form of ceramide, gained attention recently due to its diverse intracellular roles, in particular in inflammation mediated by cPLA{sub 2}{alpha}. However, surprisingly little is known about the physical chemical properties of this lipid and its potential impact on physiological function. For example, the presence of Ca{sup 2+} is indispensable for the interaction of Cer-1-P with the C2 domain of cPLA{sub 2}{alpha}. We report on the structure and morphology of Cer-1-P in monomolecular layers at the air/water solution interface in the absence and presence of Ca{sup 2+} using diverse biophysical techniques, including synchrotron x-ray reflectivity and grazing angle diffraction, to gain insight into the role and function of Cer-1-P in biomembranes. We show that relatively small changes in pH and the presence of monovalent cations dramatically affect the behavior of Cer-1-P. On pure water Cer-1-P forms a solid monolayer despite the negative charge of the phosphomonoester headgroup. In contrast, pH 7.2 buffer yields a considerably less solid-like monolayer, indicating that charge-charge repulsion becomes important at higher pH. Calcium was found to bind strongly to the headgroup of Cer-1-P even in the presence of a 100-fold larger Na{sup +} concentration. Analysis of the x-ray reflectivity data allowed us to estimate how much Ca{sup 2+} is bound to the headgroup, 0.5 Ca{sup 2+} and 1.0 Ca{sup 2+} ions per Cer-1-P molecule for the water and buffer subphase respectively. These results can be qualitatively understood based on the molecular structure of Cer-1-P and the electrostatic/hydrogen-bond interactions of its phosphomonoester headgroup. Biological implications of our results are also discussed.

  16. DIFFUSIVE EXCHANGE OF GASEOUS POLYCYCLIC AROMATIC HYDROCARBONS AND POLYCHLORINATED BIPHENYLS ACROSS THE AIR-WATER INTERFACE OF THE CHESAPEAKE BAY. (R825245)

    EPA Science Inventory

    Dissolved and gas-phase concentrations of nine polycyclic aromatic hydrocarbons and 46 polychlorinated biphenyl congeners were measured at eight sites on the Chesapeake Bay at four different times of the year to estimate net diffusive air-water gas exchange rates. Gaseous PAHs ar...

  17. The formation of surface multilayers at the air-water interface from sodium polyethylene glycol monoalkyl ether sulfate/AlCl(3) solutions: the role of the size of the polyethylene oxide group.

    PubMed

    Xu, Hui; Penfold, Jeff; Thomas, Robert K; Petkov, Jordan T; Tucker, Ian; Webster, John P R

    2013-09-17

    Neutron reflectivity, NR, and surface tension, ST, have been used to study the surface adsorption properties at the air-water interface of the anionic surfactant sodium polyethylene glycol monododecyl ether sulfate (sodium lauryl ether sulfate, SLES) in the presence of Al(3+) multivalent counterions, by the addition of AlCl3. In the absence of AlCl3 and at low AlCl3 concentrations monolayer adsorption is observed. With increasing AlCl3 concentration, surface multilayer formation is observed, driven by SLES/Al(3+) complex formation. The onset of multilayer formation occurs initially as a single bilayer or a multilayer structure with a limited number of bilayers, N, ≤3, and ultimately at higher AlCl3 concentrations N is large, >20. The evolution in the surface structure is determined by the surfactant and AlCl3 concentrations, and the size of the polyethylene oxide group in the different SLES surfactants studied. From the NR data, approximate surface phase diagrams are constructed, and the evolution of the surface structure with surfactant and electrolyte concentration is shown to be dependent on the size of the polyethylene oxide group. As the polyethylene oxide group increases in size the multilayer formation requires increasingly higher surfactant and AlCl3 concentrations to promote the formation. This is attributed to the increased steric hindrance of the polyethylene oxide group disrupting SLES/Al(3+) complex formation. PMID:23968161

  18. Gas transfer velocities for quantifying methane, oxygen and other gas fluxes through the air-water interface of wetlands with emergent vegetation

    NASA Astrophysics Data System (ADS)

    Poindexter, C.; Variano, E. A.

    2012-12-01

    Empirical models for the gas transfer velocity, k, in the ocean, lakes and rivers are fairly well established, but there are few data to predict k for wetlands. We have conducted experiments in a simulated emergent marsh in the laboratory to explore the relationship between k, wind shear and thermal convection. Now we identify the implications of these results for gas transfer in actual wetlands by (1) quantifying the range of wind conditions in emergent vegetation canopies and the range of thermal convection intensities in wetland water columns, and (2) describing the non-linear interaction of these two stirring forces over their relevant ranges in wetlands. We measured mean wind speeds and wind speed variance within the shearless region of a Schoenoplectus-Typha marsh canopy in the Sacramento-San Joaquin Delta (Northern California, USA). The mean wind speed within this region, , is significantly smaller than wind above the canopy. Based on our laboratory experiments, for calm or even average wind conditions in this emergent marsh k600 is only on the order 0.1 cm hr-1 (for neutrally or stably stratified water columns). We parameterize unstable thermal stratification and the resulting thermal convection using the heat flux through the air-water interface, q. We analyzed a water temperature record for the Schoenoplectus-Typha marsh to obtain a long-term heat flux record. We used these heat flux data along with short-term heat flux data from other wetlands in the literature to identify the range of the gas transfer velocity associated with thermal convection in wetlands. The typical range of heat fluxes through water columns shaded by closed emergent canopies (-200 W m-2 to +200 W m-2) yields k600 values of 0.5 - 2.5 cm hr-1 according to the model we developed in the laboratory. Thus for calm or average wind conditions, the gas transfer velocity associated with thermal convection is significantly larger than the gas transfer velocity associated with wind

  19. Studies of air, water, and ethanol vapor atmospheric pressure plasmas for antimicrobial applications.

    PubMed

    Ferrell, James R; Bogovich, Erinn R; Lee, Nicholas R; Gray, Robert L; Pappas, Daphne D

    2015-01-01

    The generation of air-based plasmas under atmospheric plasma conditions was studied to assess their antimicrobial efficacy against commonly found pathogenic bacteria. The mixture of initial gases supplied to the plasma was found to be critical for the formation of bactericidal actives. The optimal gas ratio for bactericidal effect was determined to be 99% nitrogen and 1% oxygen, which led to a 99.999% reduction of a pathogenic strain of Escherichia coli on stainless steel surfaces. The experimental substrate, soil load on the substrate, flow rate of the gases, and addition of ethanol vapor all were found to affect antimicrobial efficacy of studied plasmas. Optical emission spectroscopy was used to identify the species that were present in the plasma bulk phase for multiple concentrations of nitrogen and oxygen ratios. The collected spectra indicate a unique series of bands present in the ultraviolet region of the electromagnetic spectrum that can be attributed to nitric oxide species known to be highly antimicrobial. This intense spectral profile dramatically changes as the concentration of nitrogen decreases. PMID:25810273

  20. SUPRAMOLECULAR SYSTEMS BEHAVIOR AT THE AIR-WATER INTERFACE. MOLECULAR DYNAMIC SIMULATION STUDY

    SciTech Connect

    Sandoval, C.; Saavedra, M.; Gargallo, L.; Radic, D.

    2008-08-28

    Atomistic molecular dynamics simulation (MDS) was development to investigate the structural and dynamic properties of a monolayer of supramolecular systems. The simulations were performed at room temperature, on inclusion complexes (ICs) of {alpha}-cyclodextrin (CD) with poly(ethylene-oxide)(PEO), poly({epsilon}-caprolactone)(PEC) and poly(tetrahydrofuran)(PTHF). The simulations were carried out for a surface area of 30A ring . The trajectories of the MDS show that the system more stable was IC-PEC, being the less stable IC-PEO. The disordered monolayer for the systems was proved by the orientation correlation function and the radial distribution function between the polar groups of ICs and the water molecules. We found that the system IC-PEC was more stable that the systems IC-PTHF and IC-PEO.

  1. Air/Water Purification

    NASA Technical Reports Server (NTRS)

    1992-01-01

    After 18 years of research into air/water pollution at Stennis Space Center, Dr. B. C. Wolverton formed his own company, Wolverton Environmental Services, Inc., to provide technology and consultation in air and water treatment. Common houseplants are used to absorb potentially harmful materials from bathrooms and kitchens. The plants are fertilized, air is purified, and wastewater is converted to clean water. More than 100 U.S. communities have adopted Wolverton's earlier water hyacinth and artificial marsh applications. Catfish farmers are currently evaluating the artificial marsh technology as a purification system.

  2. Formation of gas-phase carbonyls from heterogeneous oxidation of polyunsaturated fatty acids at the air-water interface and of the sea surface microlayer

    NASA Astrophysics Data System (ADS)

    Zhou, S.; Gonzalez, L.; Leithead, A.; Finewax, Z.; Thalman, R.; Vlasenko, A.; Vagle, S.; Miller, L. A.; Li, S.-M.; Bureekul, S.; Furutani, H.; Uematsu, M.; Volkamer, R.; Abbatt, J.

    2014-02-01

    Motivated by the potential for reactive heterogeneous chemistry occurring at the ocean surface, gas-phase products were observed when a reactive sea surface microlayer (SML) component, i.e. the polyunsaturated fatty acids (PUFA) linoleic acid (LA), was exposed to gas-phase ozone at the air-seawater interface. Similar oxidation experiments were conducted with SML samples collected from two different oceanic locations, in the eastern equatorial Pacific Ocean and from the west coast of Canada. Online proton-transfer-reaction mass spectrometry (PTR-MS) University of Colorado light-emitting diode cavity-enhanced differential optical absorption spectroscopy (LED-CE-DOAS) were used to detect oxygenated gas-phase products from the ozonolysis reactions. The LA studies indicate that oxidation of a PUFA monolayer on seawater gives rise to prompt and efficient formation of gas-phase aldehydes. The products are formed via the decomposition of primary ozonides which form upon the initial reaction of ozone with the carbon-carbon double bonds in the PUFA molecules. In addition, two highly reactive dicarbonyls, malondialdehyde (MDA) and glyoxal, were also generated, likely as secondary products. Specific yields relative to reactant loss were 78%, 29%, 4% and < 1% for n-hexanal, 3-nonenal, MDA and glyoxal, respectively, where the yields for MDA and glyoxal are likely lower limits. Heterogeneous oxidation of SML samples confirm for the first time that similar carbonyl products are formed via ozonolysis of environmental samples.

  3. Formation of gas-phase carbonyls from heterogeneous oxidation of polyunsaturated fatty acids at the air-water interface and of the sea surface microlayer

    NASA Astrophysics Data System (ADS)

    Zhou, S.; Gonzalez, L.; Leithead, A.; Finewax, Z.; Thalman, R.; Vlasenko, A.; Vagle, S.; Miller, L.; Li, S.-M.; Bureekul, S.; Furutani, H.; Uematsu, M.; Volkamer, R.; Abbatt, J.

    2013-07-01

    Motivated by the potential for reactive heterogeneous chemistry occurring at the ocean surface, gas-phase products were observed when a reactive sea surface microlayer (SML) component, i.e. the polyunsaturated fatty acid (PUFA) linoleic acid (LA), was exposed to gas-phase ozone at the air-seawater interface. Similar oxidation experiments were conducted with SML samples collected from two different oceanic locations, in the eastern equatorial Pacific Ocean and from the west coast of Canada. Online proton-transfer-reaction mass spectrometry (PTR-MS) and light-emitting diode cavity enhanced differential optical absorption spectroscopy (LED-CE-DOAS) were used to detect oxygenated gas-phase products from the ozonolysis reactions. The LA studies indicate that oxidation of a PUFA monolayer on seawater gives rise to prompt and efficient formation of gas phase aldehydes. The products are formed via the decomposition of primary ozonides which form upon the initial reaction of ozone with the carbon-carbon double bonds in the PUFA molecules. In addition, two highly reactive di-carbonyls, malondialdehyde (MDA) and glyoxal, were also generated, likely as secondary products. Specific yields relative to reactant loss were 78%, 29%, 4% and <1% for n-hexanal, 3-nonenal, MDA and glyoxal, respectively, where the yields for MDA and glyoxal are likely lower limits. Heterogeneous oxidation of SML samples confirm for the first time that similar carbonyl products are formed via ozonolysis of environmental samples. The potential impact of such chemistry on the atmosphere of the marine boundary layer is discussed.

  4. Superposition-additive approach in the description of thermodynamic parameters of formation and clusterization of substituted alkanes at the air/water interface.

    PubMed

    Vysotsky, Yu B; Belyaeva, E A; Fomina, E S; Vasylyev, A O; Vollhardt, D; Fainerman, V B; Aksenenko, E V; Miller, R

    2012-12-01

    The superposition-additive approach developed previously was shown to be applicable for the calculations of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole polarizability, molecular diamagnetic susceptibility, π-electronic ring currents, etc. In the present work, the applicability of this approach for the calculation of the thermodynamic parameters of formation and clusterization at the water/air interface of alkanes, fatty alcohols, thioalcohols, amines, nitriles, fatty acids (C(n)H(2n+1)X, X is the functional group) and cis-unsaturated carboxylic acids (C(n)H(2n-1)COOH) is studied. Using the proposed approach the thermodynamic quantities determined agree well with the available data, either calculated using the semiempirical (PM3) quantum chemical method, or obtained in experiments. In particular, for enthalpy and Gibbs' energy of the formation of substituted alkane monomers from the elementary substances, and their absolute entropy, the standard deviations of the values calculated according to the superposition-additive scheme with the mutual superimposition domain C(n-2)H(2n-4) (n is the number of carbon atoms in the alkyl chain) from the results of PM3 calculations for alkanes, alcohols, thioalcohols, amines, fatty acids, nitriles and cis-unsaturated carboxylic acids are respectively: 0.05, 0.004, 2.87, 0.02, 0.01, 0.77, and 0.01 kJ/mol for enthalpy; 2.32, 5.26, 4.49, 0.53, 1.22, 1.02, 5.30 J/(molK) for absolute entropy; 0.69, 1.56, 3.82, 0.15, 0.37, 0.69, 1.58 kJ/mol for Gibbs' energy, whereas the deviations from the experimental data are: 0.52, 5.75, 1.40, 1.00, 4.86 kJ/mol; 0.52, 0.63, 1.40, 6.11, 2.21 J/(molK); 2.52, 5.76, 1.58, 1.78, 4.86 kJ/mol, respectively (for nitriles and cis-unsaturated carboxylic acids experimental data are not available). The proposed approach provides also quite accurate estimates of enthalpy, entropy and Gibbs' energy of boiling and melting, critical temperatures and standard heat

  5. Nonlinear optical studies of aqueous interfaces, polymers, and nanowires

    NASA Astrophysics Data System (ADS)

    Onorato, Robert Michael

    Understanding the structure and composition of aqueous interfaces is one of the most important current problems in modern science. Aqueous interfaces are ubiquitous in Nature, ranging from aerosols to cellular structures. Aerosol chemistry is presently the most significant unknown factor in predicting climate change, and an understanding of the chemistry that occurs at aerosol interfaces would significantly improve climate models. Similarly, the nature of aqueous biological interfaces has a profound effect on the structure and function of proteins and other biological structures. Despite the importance of these problems, aqueous interfaces remain incompletely understood due to the challenges of experimentally probing them. Recent experimental and theoretical results have firmly established the existence of enhanced concentrations of selected ions at the air/water interface. In this dissertation, I use an interface-specific technique, UV second harmonic generation (SHG), to further investigate the adsorption of ions to the air/water interface and to extend the study of ion adsorption towards more biologically relevant systems, alcohol/water interfaces. In Chapter 2, I describe resonant UV-SHG studies of the strongly chaotropic thiocyanate ion adsorbed to the interface formed by water and a monolayer of dodecanol, wherein the Gibbs free energy of adsorption was determined to be -6.7 +/- 1.1 and -6.3 +/- 1.8 kJ/mol for sodium and potassium thiocyanate, respectively, coincident with the value determined for thiocyanate at the air/water interface. Interestingly, at concentrations near and above 4 M, the resonant SHG signal increases discontinuously, indicating a structural change in the interfacial region. Recent experimental and theoretical work has demonstrated that the adsorption of bromide is particularly important for chemical reactions on atmospheric aerosols, including the depletion of ozone. In Chapter 3, UV-SHG resonant with the bromide charge

  6. CdSe magic-sized quantum dots incorporated in biomembrane models at the air-water interface composed of components of tumorigenic and non-tumorigenic cells.

    PubMed

    Goto, Thiago E; Lopes, Carla C; Nader, Helena B; Silva, Anielle C A; Dantas, Noelio O; Siqueira, José R; Caseli, Luciano

    2016-07-01

    Cadmium selenide (CdSe) magic-sized quantum dots (MSQDs) are semiconductor nanocrystals with stable luminescence that are feasible for biomedical applications, especially for in vivo and in vitro imaging of tumor cells. In this work, we investigated the specific interaction of CdSe MSQDs with tumorigenic and non-tumorigenic cells using Langmuir monolayers and Langmuir-Blodgett (LB) films of lipids as membrane models for diagnosis of cancerous cells. Surface pressure-area isotherms and polarization modulation reflection-absorption spectroscopy (PM-IRRAS) showed an intrinsic interaction between the quantum dots, inserted in the aqueous subphase, and Langmuir monolayers constituted either of selected lipids or of tumorigenic and non-tumorigenic cell extracts. The films were transferred to solid supports to obtain microscopic images, providing information on their morphology. Similarity between films with different compositions representing cell membranes, with or without the quantum dots, was evaluated by atomic force microscopy (AFM) and confocal microscopy. This study demonstrates that the affinity of quantum dots for models representing cancer cells permits the use of these systems as devices for cancer diagnosis. PMID:27107554

  7. Effects of Temperature, Oxygen Level, Ionic Strength, and pH on the Reaction of Benzene with Hydroxyl Radicals at the Air-Water Interface in Comparison to the Bulk Aqueous Phase.

    PubMed

    Heath, Aubrey A; Valsaraj, Kalliat T

    2015-08-01

    Atmospheric aerosols (e.g., fog droplets) are complex, multiphase mediums. Depending on location, time of day, and/or air mass source, there can be considerable variability within these droplets, relating to temperature, pH, and ionic strength. Due to the droplets' inherently small size, the reactions that occur within these droplets are determined by bulk aqueous phase and air-water interfacial conditions. In this study, the reaction of benzene and hydroxyl radicals is examined kinetically in a thin-film flow-tube reactor. By varying the aqueous volume (e.g., film thickness) along the length of the reactor, both bulk and interfacial reaction rates are measured from a single system. Temperature, pH, and ionic strength are varied to model conditions typical of fog events. Oxygen-poor conditions are measured to study oxygen's overall effect on the reaction pathway. Initial rate activation energies and the bulk aqueous phase and interfacial contributions to the overall rate constant are also obtained. PMID:26158391

  8. Stereoselective synthesis of (2S,3S,4Z)-4-fluoro-1,3-dihydroxy-2-(octadecanoylamino)octadec-4-ene, [(Z)-4-fluoroceramide], and its phase behavior at the air/water interface

    PubMed Central

    Nikolova, Gergana S

    2008-01-01

    natural ceramide. Conclusions Asymmetric aldol reaction proved to be successful for the preparation of enantiopure 4-fluoroceramide. Surface/pressure isotherms and hysteresis curves of ceramide and its 4-fluoro derivative showed that the presence of fluorine leads to stronger intermolecular interactions between the hydrophobic chains of neighboring molecules, and therefore to increasing stability of the monolayer of 4-fluoroceramide at the air water interface. PMID:18941484

  9. 3-Dimensional numerical study of cooling performance of a heat sink with air-water flow through mini-channel

    NASA Astrophysics Data System (ADS)

    Majumder, Sambit; Majumder, Abhik; Bhaumik, Swapan

    2016-07-01

    The present microelectronics market demands devices with high power dissipation capabilities having enhanced cooling per unit area. The drive for miniaturizing the devices to even micro level dimensions is shooting up the applied heat flux on such devices, resulting in complexity in heat transfer and cooling management. In this paper, a method of CPU processor cooling is introduced where active and passive cooling techniques are incorporated simultaneously. A heat sink consisting of fins is designed, where water flows internally through the mini-channel fins and air flows externally. Three dimensional numerical simulations are performed for large set of Reynolds number in laminar region using finite volume method for both developing flows. The dimensions of mini-channel fins are varied for several aspect ratios such as 1, 1.33, 2 and 4. Constant temperature (T) boundary condition is applied at heat sink base. Channel fluid temperature, pressure drop are analyzed to obtain best cooling option in the present study. It has been observed that as the aspect ratio of the channel decreases Nusselt number decreases while pressure drop increases. However, Nusselt number increases with increase in Reynolds number.

  10. Experimental Study of the Morphology and Dynamics of Gas-Laden Layers Under the Anodes in an Air-Water Model of Aluminum Reduction Cells

    NASA Astrophysics Data System (ADS)

    Vékony, Klára; Kiss, László I.

    2012-10-01

    The bubble layer formed under an anode and the bubble-induced flow play a significant role in the aluminum electrolysis process. The bubbles covering the anode bottom reduce the efficient surface that can carry current. In our experiments, we filmed and studied the bubble layer under the anode in a real-size air-water electrolysis cell model. Three different flow regimes were found depending on the gas generation rate. The covering factor was found to be proportional to the gas generation rate and inversely proportional to the angle of inclination. A correlation between the average height of the entire bubble layer and the position under the anode was determined. From this correlation and the measured contact sizes, the volume of the accumulated gas was calculated. The sweeping effect of large bubbles was observed. Moreover, the small bubbles under the inner edge of the anode were observed to move backward as a result of the escape of huge gas pockets, which means large momentum transport occurs in the bath.

  11. Adsorption of Bovine Serum Albumin (BSA) at the Oil/Water Interface: A Neutron Reflection Study.

    PubMed

    Campana, M; Hosking, S L; Petkov, J T; Tucker, I M; Webster, J R P; Zarbakhsh, A; Lu, J R

    2015-05-26

    The structure of the adsorbed protein layer at the oil/water interface is essential to the understanding of the role of proteins in emulsion stabilization, and it is important to glean the mechanistic events of protein adsorption at such buried interfaces. This article reports on a novel experimental methodology for probing protein adsorption at the buried oil/water interface. Neutron reflectivity was used with a carefully selected set of isotopic contrasts to study the adsorption of bovine serum albumin (BSA) at the hexadecane/water interface, and the results were compared to those for the air/water interface. The adsorption isotherm was determined at the isoelectric point, and the results showed that a higher degree of adsorption could be achieved at the more hydrophobic interface. The adsorbed BSA molecules formed a monolayer on the aqueous side of the interface. The molecules in this layer were partially denatured by the presence of oil, and once released from the spatial constraint by the globular framework they were free to establish more favorable interactions with the hydrophobic medium. Thus, a loose layer extending toward the oil phase was clearly observed, resulting in an overall broader interface. By analogy to the air/water interface, as the concentration of BSA increased to 1.0 mg mL(-1) a secondary layer extending toward the aqueous phase was observed, possibly resulting from the steric repulsion upon the saturation of the primary monolayer. Results clearly indicate a more compact arrangement of molecules at the oil/water interface: this must be caused by the loss of the globular structure as a consequence of the denaturing action of the hexadecane. PMID:25875917

  12. Estuary Turbulence and Air-Water Carbon Dioxide Exchange

    NASA Astrophysics Data System (ADS)

    Orton, Philip Mark

    The mixing of constituents between estuarine bottom and surface waters or between estuarine surface waters and the atmosphere are two topics of growing interest, in part due to the potentially important role of estuaries in global carbon budgets. These two types of mixing are typically driven by turbulence, and a research project was developed to improve the scientific understanding of atmospheric and tidal controls on estuary turbulence and airwater exchange processes. Highlights of method development and field research on the Hudson River estuary include several deployments of bottom mounted current profilers to quantify the turbulent kinetic energy (TKE) budget, and construction and deployment of an instrumented catamaran that makes autonomous measurements of air-water CO2 exchange (FCO2), water TKE dissipation at 50 cm depth (epsilon50), and other physical properties just above and below the air-water interface. On the Hudson, wind correlates strongly with epsilon50, but surface water speed and airwater heat flux also have moderate correlations with epsilon50. In partially mixed estuaries such as the Hudson, as well as salt wedge estuaries, baroclinic pressure forcing typically causes spring ebb tides to have much stronger upper water column shear than flood tides. The Hudson data are used to show that this shear leads to local shear instability and stronger near-surface turbulence on spring ebbs. Also, buoyancy budget terms are compared to demonstrate how water-to-air heat fluxes can influence stratification and indirectly influence epsilon50. Looking more closely at the role of wind forcing, it is demonstrated that inland propagation of the sea breeze on warm sunny days leads to arrival in phase with peak solar forcing at seaward stations, but several hours later at up-estuary stations. Passage of the sea breeze front raises the air-water CO2 flux by 1-2 orders of magnitude, and drives epsilon50 comparable to spring tide levels in the upper meter of the water

  13. A study of dilational rheological properties of polymers at interfaces.

    PubMed

    Cao, Xulong; Li, Yang; Jiang, Shengxiang; Sun, Huanquan; Cagna, Alain; Dou, Lixia

    2004-02-15

    Viscoelastic properties of two polymers, partially hydrolyzed polyacrylamide and partially hydrolyzed modified polyacrylamide, widely used in chemical flooding in the petroleum industry, were investigated at three interfaces, water-air, water-dodecane, and water-crude oil, by means of a dilational method provided by I.T. Concept, France, at 85 degrees C. Polymer solutions were prepared in brine with 10,000 mg/l sodium chloride and 2000 mg/l calcium chloride. It has been shown that the viscoelastic modulus increases with the increment of polymer concentration in the range of 0-1500 mg/l at the water-air interface. Each polymer shows different viscoelatic behavior at different interfaces. Generally speaking, values of the viscoelastic modulus (E), the real part (E'), and the imaginary part (E") at the crude oil-water interface for each polymer are lower than at the air-water or water-dodecane interface. The two polymers display different interfacial properties at the same interface. Polymer No. 2 gives more viscous interfaces than polymer No. 1. All the information obtained from this paper will be helpful in understanding the interfacial rheology of ultra-high-molecular-weight polymer solutions. PMID:14697692

  14. Cleaning verification by air/water impingement

    NASA Technical Reports Server (NTRS)

    Jones, Lisa L.; Littlefield, Maria D.; Melton, Gregory S.; Caimi, Raoul E. B.; Thaxton, Eric A.

    1995-01-01

    This paper will discuss how the Kennedy Space Center intends to perform precision cleaning verification by Air/Water Impingement in lieu of chlorofluorocarbon-113 gravimetric nonvolatile residue analysis (NVR). Test results will be given that demonstrate the effectiveness of the Air/Water system. A brief discussion of the Total Carbon method via the use of a high temperature combustion analyzer will also be given. The necessary equipment for impingement will be shown along with other possible applications of this technology.

  15. The air-water CO2 exchange of a coastal sea—A sensitivity study on factors that influence the absorption and outgassing of CO2 in the Baltic Sea

    NASA Astrophysics Data System (ADS)

    Gustafsson, Erik; Omstedt, Anders; Gustafsson, Bo G.

    2015-08-01

    In this study, the BALTSEM model is used to estimate how air-water CO2 fluxes in the Baltic Sea respond to parameterizations of organic alkalinity (Aorg), gas transfer, and phytoplankton growth, and further to changes in river loads. The forcing data include the most complete compilation of Baltic river loads for dissolved inorganic and organic carbon (DIC and DOC) and total alkalinity (TA). In addition, we apply the most recent estimates of internal TA generation in the system. Our results clearly demonstrate how air-water CO2 fluxes of a coastal sea depend on river loads of carbon, TA, and nutrients as well the freshwater import itself. Long-term changes in DIC loads are shown to be compensated by corresponding changes in air-water CO2 exchange. By adding Aorg, a discrepancy in the carbonate system calculations was removed, and the simulated net CO2 absorption of the system decreased by 11%. A new parameterization for cyanobacteria growth significantly improved the seasonal development of pCO2 in the central Baltic Sea, although the net effect on CO2 fluxes was below 5%. By applying either a linear, quadratic, or cubic wind speed dependence for gas transfer, the long-term net CO2 exchange was adjusted by less than 5%. There is no clear indication that any one of these parameterizations provides a more accurate estimate of CO2 fluxes than the other two. Our findings are applicable in other coastal areas that are heavily influenced by river loads of TA, DIC, and DOC.

  16. Propagation of density disturbances in air-water flow

    NASA Technical Reports Server (NTRS)

    Nassos, G. P.

    1969-01-01

    Study investigated the behavior of density waves propagating vertically in an atmospheric pressure air-water system using a technique based on the correlation between density change and electric resistivity. This information is of interest to industries working with heat transfer systems and fluid power and control systems.

  17. Application of the ultrasonic technique and high-speed filming for the study of the structure of air-water bubbly flows

    SciTech Connect

    Carvalho, R.D.M.; Venturini, O.J.; Tanahashi, E.I.; Neves, F. Jr.; Franca, F.A.

    2009-10-15

    Multiphase flows are very common in industry, oftentimes involving very harsh environments and fluids. Accordingly, there is a need to determine the dispersed phase holdup using noninvasive fast responding techniques; besides, knowledge of the flow structure is essential for the assessment of the transport processes involved. The ultrasonic technique fulfills these requirements and could have the capability to provide the information required. In this paper, the potential of the ultrasonic technique for application to two-phase flows was investigated by checking acoustic attenuation data against experimental data on the void fraction and flow topology of vertical, upward, air-water bubbly flows in the zero to 15% void fraction range. The ultrasonic apparatus consisted of one emitter/receiver transducer and three other receivers at different positions along the pipe circumference; simultaneous high-speed motion pictures of the flow patterns were made at 250 and 1000 fps. The attenuation data for all sensors exhibited a systematic interrelated behavior with void fraction, thereby testifying to the capability of the ultrasonic technique to measure the dispersed phase holdup. From the motion pictures, basic gas phase structures and different flows patterns were identified that corroborated several features of the acoustic attenuation data. Finally, the acoustic wave transit time was also investigated as a function of void fraction. (author)

  18. Nonlinear optical studies of polymer interfaces

    SciTech Connect

    Shen, Y.R. |

    1993-11-01

    Second-order nonlinear optical processes can be used as effective surface probes. They can provide some unique opportunities for studies of polymer interfaces. Here the author describes two examples to illustrate the potential of the techniques. One is on the formation of metal/polymer interfaces. The other is on the alignment of liquid crystal films by mechanically rubbed polymer surfaces.

  19. High temperature ceramic interface study

    NASA Technical Reports Server (NTRS)

    Lindberg, L. J.

    1984-01-01

    Monolithic SiC and Si3N4 are susceptible to contact stress damage at static and sliding interfaces. Transformation-toughened zirconia (TTZ) was evaluated under sliding contact conditions to determine if the higher material fracture toughness would reduce the susceptibility to contact stress damage. Contact stress tests were conducted on four commercially available TTZ materials at normal loads ranging from 0.455 to 22.7 kg (1 to 50 pounds) at temperatures ranging from room temperature to 1204C (2200 F). Static and dynamic friction were measured as a function of temperature. Flexural strength measurements after these tests determined that the contact stress exposure did not reduce the strength of TTZ at contact loads of 0.455, 4.55, and 11.3 kg (1, 10, and 25 pounds). Prior testing with the lower toughness SiC and Si3N4 materials resulted in a substantial strength reduction at loads of only 4.55 and 11.3 kg (10 and 25 pounds). An increase in material toughness appears to improve ceramic material resistance to contact stress damage. Baseline material flexure strength was established and the stress rupture capability of TTZ was evaluated. Stress rupture tests determined that TTZ materials are susceptible to deformation due to creep and that aging of TTZ materials at elevated temperatures results in a reduction of material strength.

  20. Injury to deep benthos. Subtidal study number 2b (air/water study number 2). Exxon Valdez oil spill state/federal natural resource damage assessment final report

    SciTech Connect

    Feder, H.M.

    1995-06-01

    This study was designed to assess the possible injury by petroleum, derived from the Exxon Valdez oil spill to benthic infaunal resources within Prince William Sound in water deeper than 20 m. Analyses of benthic biological data collected from 14 bays in Prince William Sound in 1990 at 40, 100 and > 100 m, by univariate and multivariate techniques, demonstrated no obvious disturbance effects on the benthic biota 16 months after the oil spill. In all multivariate analyses, the major environmental variables related to the composition of benthic assemblages were sediment parameters such as percent silt, clay, mud, percent water and amount of nitrogen and carbon in sediment. Although limited amounts of petroleum hydrocarbons and presence of hydrocarbon degrading bacteria were detected at some sites at 40 and 100 m in 1989 and 1990, minor or no impact was sustained by benthic fauna of the deep benthos within the Sound.

  1. Solar thermochemical process interface study

    NASA Technical Reports Server (NTRS)

    1984-01-01

    The design and analyses of a subsystem of a hydrogen production process are described. The process is based on solar driven thermochemical reactions. The subject subsystem receives sulfuric acid of 60% concentration at 100 C, 1 atm pressure. The acid is further concentrated, vaporized, and decomposed (at a rate of 122 g moles/sec H2SO4) into SO2, O2, and water. The produce stream is cooled to 100 C. Three subsystem options, each being driven by direct solar energy, were designed and analyzed. The results are compared with a prior study case in which solar energy was provided indirectly through a helium loop.

  2. Gas transfer - A gas tension method for studying equilibration across a gas-water interface

    NASA Astrophysics Data System (ADS)

    Anderson, Meredith L.; Johnson, Bruce D.

    1992-11-01

    New strategies are required in the study of gas exchange under energetic and changeable conditions where current techniques are limited, especially in their ability to represent the contribution of injected bubbles. We have developed a gas tension device (GTD) that uses a solid-state differential pressure sensor to make continuous in situ measurements of the difference between pressure of dissolved gas (gas tension, for succinctness) and pressure of gas in the gas phase above a water parcel. This information allows the determination of the rate of approach to a dynamic equilibrium and of the degree of water phase saturation at steady state. The method is demonstrated in the lab by following the invasion of CO2 into seawater with bubble injection. The GTD introduces a new and versatile measurement method for the study of gas transfer across air-water interfaces, one which avoids many of the sampling and bias problems of traditional approaches.

  3. Surface Mechanical and Rheological Behaviors of Biocompatible Poly((D,L-lactic acid-ran-glycolic acid)-block-ethylene glycol) (PLGA-PEG) and Poly((D,L-lactic acid-ran-glycolic acid-ran-ε-caprolactone)-block-ethylene glycol) (PLGACL-PEG) Block Copolymers at the Air-Water Interface.

    PubMed

    Kim, Hyun Chang; Lee, Hoyoung; Khetan, Jawahar; Won, You-Yeon

    2015-12-29

    Air-water interfacial monolayers of poly((D,L-lactic acid-ran-glycolic acid)-block-ethylene glycol) (PLGA-PEG) exhibit an exponential increase in surface pressure under high monolayer compression. In order to understand the molecular origin of this behavior, a combined experimental and theoretical investigation (including surface pressure-area isotherm, X-ray reflectivity (XR) and interfacial rheological measurements, and a self-consistent field (SCF) theoretical analysis) was performed on air-water monolayers formed by a PLGA-PEG diblock copolymer and also by a nonglassy analogue of this diblock copolymer, poly((D,L-lactic acid-ran-glycolic acid-ran-caprolactone)-block-ethylene glycol) (PLGACL-PEG). The combined results of this study show that the two mechanisms, i.e., the glass transition of the collapsed PLGA film and the lateral repulsion of the PEG brush chains that occur simultaneously under lateral compression of the monolayer, are both responsible for the observed PLGA-PEG isotherm behavior. Upon cessation of compression, the high surface pressure of the PLGA-PEG monolayer typically relaxes over time with a stretched exponential decay, suggesting that in this diblock copolymer situation, the hydrophobic domain formed by the PLGA blocks undergoes glass transition in the high lateral compression state, analogously to the PLGA homopolymer monolayer. In the high PEG grafting density regime, the contribution of the PEG brush chains to the high monolayer surface pressure is significantly lower than what is predicted by the SCF model because of the many-body attraction among PEG segments (referred to in the literature as the "n-cluster" effects). The end-grafted PEG chains were found to be protein resistant even under the influence of the "n-cluster" effects. PMID:26633595

  4. Gas Gun Studies of Interface Wear Effects

    NASA Astrophysics Data System (ADS)

    Jackson, Tyler; Kennedy, Greg; Thadhani, Naresh

    2011-06-01

    The characteristics of interface wear were studied by performing gas gun experiments at velocities up to 1 km/s. The approach involved developing coefficients of constitutive strength models for Al 6061 and OFHC-Cu, then using those to design die geometry for interface wear gas gun experiments. Taylor rod-on-anvil impact experiments were performed to obtain coefficients of the Johnson-Cook constitutive strength model by correlating experimentally obtained deformed states of impacted samples with those predicted using ANSYS AUTODYN hydrocode. Simulations were used with validated strength models to design geometry involving acceleration of Al rods through a copper concentric cylindrical angular extrusion die. Experiments were conducted using 7.62 mm and 80 mm diameter gas guns. Differences in the microstructure of the interface layer and microhardness values illustrate that stress-strain conditions produced during acceleration of Al through the hollow concentric copper die, at velocities less than 800 m/s, result in formation of a layer via solid state alloying due to severe plastic deformation, while higher velocities produce an interface layer consisting of melted and re-solidified aluminum.

  5. Two-Fluid Interface Instability Being Studied

    NASA Technical Reports Server (NTRS)

    Niederhaus, Charles E.

    2003-01-01

    The interface between two fluids of different density can experience instability when gravity acts normal to the surface. The relatively well known Rayleigh-Taylor (RT) instability results when the gravity is constant with a heavy fluid over a light fluid. An impulsive acceleration applied to the fluids results in the Richtmyer-Meshkov (RM) instability. The RM instability occurs regardless of the relative orientation of the heavy and light fluids. In many systems, the passing of a shock wave through the interface provides the impulsive acceleration. Both the RT and RM instabilities result in mixing at the interface. These instabilities arise in a diverse array of circumstances, including supernovas, oceans, supersonic combustion, and inertial confinement fusion (ICF). The area with the greatest current interest in RT and RM instabilities is ICF, which is an attempt to produce fusion energy for nuclear reactors from BB-sized pellets of deuterium and tritium. In the ICF experiments conducted so far, RM and RT instabilities have prevented the generation of net-positive energy. The $4 billion National Ignition Facility at Lawrence Livermore National Laboratory is being constructed to study these instabilities and to attempt to achieve net-positive yield in an ICF experiment.

  6. Interfacial area measurement and transport modeling in air-water two-phase flow

    NASA Astrophysics Data System (ADS)

    Fu, Xinyu

    In two-fluid model, the interfacial area concentration (IAC) is an important parameter that characterizes the interaction of two-phases at the interface. The accuracy of IAC modeling and local measurements largely affects the efficiency of designing and assessing two-phase flow systems. The prediction of the dynamical evolution of IAC is one of the most challenging tasks in research and application. This thesis is focused on developing advanced local measurement techniques to obtain reliable two-phase parameters and implementing efficient theoretical models for IAC source and sink terms in a two-group interfacial area transport equation based on experiments. In this study, an advanced local measurement technique using a four-sensor conductivity probe has been presented for obtaining IAC in air-water flows. It extends the existing conductivity probe method to slug and churn-turbulent flows with a unified probe design and comprehensive signal processing system. Sophisticated algorithm and software have been implemented that is robust in handling most practical conditions with high reliability. Systematic analyses on the issues of probe applications and benchmarks have been performed. The improved four-sensor method has also been applied to flow conditions with significant local recirculation, which was considered the most challenging situation for local measurement in two-phase flow. Using the well-established instrumentation, solid databases for a two-inch air-water loop have been built with sufficient information on the axial development and the radial distribution of the local parameters. Mechanistic models of major fluid particle interaction phenomena involving two bubble groups have been proposed, including the shearing-off of small bubbles from slug/cap bubbles, the wake entrainment of group-1 bubble into group-2 bubble, the wake acceleration and coalescence between group-2 bubbles, and the breakup of group-2 bubbles due to surface instability. Prediction of

  7. [Charge generation and separation at liquid interfaces

    SciTech Connect

    Eisenthal, K.B.

    1992-01-01

    The research is divided into 3 parts: (1)Sum Frequency Generation (SFG) and Monolayer Structure. Picosecond lasers are combined by difference frequency mixing in a nonlinear crystal to generate picosecond, tunable IR pulses, which are used to study orientation of C[double bond]N and CD[sub 3] chromosphores (head group and tail) on lipid monolayers CD[sub 3](CH[sub 2])[sub 21]CN at air/water interface. (2)Femtosecond Dynamics. The femtosecond colliding pulse mode locked laser is being modified to carry out pump-second harmonic (SH) probe studies at liquid interfaces. Picosecond SH knowhow of intermolecular energy transfer, excited state isomerization, and rotational motions at interfaces is now being applied to femtosecond scale. Aromatics adsorbed at air/water interface, generated changes in SH probe signal and their decay back to original value. If the laser is tightly focussed at interface, multiphoton absorption processes occur which destroy the sample; this effect will be exploited. (3)Interface Potential and Acid-Base Equilibria. The interface potential is a key to charge transport; using SHG, we plan to measure the pKa of organic acids at interfaces. In these studies at silica/aqueous interface, the water molecules extending from the interface into the bulk (about 50[Angstrom]) were strongly polarized by SiO[sup [minus

  8. Molecular Design of Branched and Binary Molecules at Ordered Interfaces

    SciTech Connect

    Kirsten Larson Genson

    2005-12-27

    This study examined five different branched molecular architectures to discern the effect of design on the ability of molecules to form ordered structures at interfaces. Photochromic monodendrons formed kinked packing structures at the air-water interface due to the cross-sectional area mismatch created by varying number of alkyl tails and the hydrophilic polar head group. The lower generations formed orthorhombic unit cell with long range ordering despite the alkyl tails tilted to a large degree. Favorable interactions between liquid crystalline terminal groups and the underlying substrate were observed to compel a flexible carbosilane dendrimer core to form a compressed elliptical conformation which packed stagger within lamellae domains with limited short range ordering. A twelve arm binary star polymer was observed to form two dimensional micelles at the air-water interface attributed to the higher polystyrene block composition. Linear rod-coil molecules formed a multitude of packing structures at the air-water interface due to the varying composition. Tree-like rod-coil molecules demonstrated the ability to form one-dimensional structures at the air-water interface and at the air-solvent interface caused by the preferential ordering of the rigid rod cores. The role of molecular architecture and composition was examined and the influence chemically competing fragments was shown to exert on the packing structure. The amphiphilic balance of the different molecular series exhibited control on the ordering behavior at the air-water interface and within bulk structures. The shell nature and tail type was determined to dictate the preferential ordering structure and molecular reorganization at interfaces with the core nature effect secondary.

  9. Air/water oxydesulfurization of coal: laboratory investigation

    SciTech Connect

    Warzinski, R. P.; Friedman, S.; Ruether, J. A.; LaCount, R. B.

    1980-08-01

    Air/water oxidative desulfurization has been demonstrated in autoclave experiments at the Pittsburgh Energy Technology Center for various coals representative of the major US coal basins. This experimentation has shown that the reaction proceeds effectively for pulverized coals at temperatures of 150 to 200/sup 0/C with air at a total system pressure of 500 to 1500 psig. Above 200/sup 0/C, the loss of coal and product heating value increases due to oxidative consumption of carbon and hydrogen. The pyritic sulfur solubilization reactions are typically complete (95 percent removal) within 15 to 40 minutes at temperature; however, significant apparent organic sulfur removal requires residence times of up to 60 minutes at the higher temperatures. The principal products of the reaction are sulfuric acid, which can be neutralized with limestone, and iron oxide. Under certain conditions, especially for high pyritic sulfur coals, the precipitation of sulfur-containing compounds from the products of the pyrite reaction may cause anomalous variations in the sulfur form data. The influence of various parameters on the efficiency of sulfur removal from coal by air/water oxydesulfurization has been studied.

  10. Wind driven vertical transport in a vegetated, wetland water column with air-water gas exchange

    NASA Astrophysics Data System (ADS)

    Poindexter, C.; Variano, E. A.

    2010-12-01

    Flow around arrays of cylinders at low and intermediate Reynolds numbers has been studied numerically, analytically and experimentally. Early results demonstrated that at flow around randomly oriented cylinders exhibits reduced turbulent length scales and reduced diffusivity when compared to similarly forced, unimpeded flows (Nepf 1999). While horizontal dispersion in flows through cylinder arrays has received considerable research attention, the case of vertical dispersion of reactive constituents has not. This case is relevant to the vertical transfer of dissolved gases in wetlands with emergent vegetation. We present results showing that the presence of vegetation can significantly enhance vertical transport, including gas transfer across the air-water interface. Specifically, we study a wind-sheared air-water interface in which randomly arrayed cylinders represent emergent vegetation. Wind is one of several processes that may govern physical dispersion of dissolved gases in wetlands. Wind represents the dominant force for gas transfer across the air-water interface in the ocean. Empirical relationships between wind and the gas transfer coefficient, k, have been used to estimate spatial variability of CO2 exchange across the worlds’ oceans. Because wetlands with emergent vegetation are different from oceans, different model of wind effects is needed. We investigated the vertical transport of dissolved oxygen in a scaled wetland model built inside a laboratory tank equipped with an open-ended wind tunnel. Plastic tubing immersed in water to a depth of approximately 40 cm represented emergent vegetation of cylindrical form such as hard-stem bulrush (Schoenoplectus acutus). After partially removing the oxygen from the tank water via reaction with sodium sulfite, we used an optical probe to measure dissolved oxygen at mid-depth as the tank water re-equilibrated with the air above. We used dissolved oxygen time-series for a range of mean wind speeds to estimate the

  11. Air-Water Gas Exchange in Wetland Water Columns Due To Wind and Thermal Convection

    NASA Astrophysics Data System (ADS)

    Poindexter, C.; Variano, E. A.

    2011-12-01

    The goal of this work is to provide a parameterization of the air-water gas transfer rate in wetlands, and do so in terms of easily measured environmental variables. This parameterization is intended to support biogeochemical modeling in wetlands by providing an interfacial flux of key importance. Our approach uses laboratory experiments describe the oxygen transfer across an air-water interface in a model wetland. The oxygen transfer is sensitive to the externally imposed wind, vegetation characteristics, and vertical thermal convection. We vary these systematically, determining the gas transfer (or "piston") velocity that describes interfacial gas flux. We measure velocity vector fields near the air-water interface using particle image velocimetry, and use these measurements to help explain the mechanisms behind the measured trends in oxygen transfer. The explanatory power of these measurements includes the relationship between plant geometry and surface divergence. We explore the potential impact of our results on wetland modeling and management, for issues such as carbon sequestration and methane emission.

  12. Dynamics explorer: Interface definition study, volume 1

    NASA Technical Reports Server (NTRS)

    1978-01-01

    Work done in response to the work statement wherein a specific deliverable was not identified but where design and analysis tasks were identified is reported. The summary and baseline change list is included along with design notes for the spacecraft system, thermal subsystem, power subsystem, communications subsystem, plasma wave instrument interface definition, and the structure.

  13. Bifurcations of a creeping air-water flow in a conical container

    NASA Astrophysics Data System (ADS)

    Balci, Adnan; Brøns, Morten; Herrada, Miguel A.; Shtern, Vladimir N.

    2016-04-01

    This numerical study describes the eddy emergence and transformations in a slow steady axisymmetric air-water flow, driven by a rotating top disk in a vertical conical container. As water height Hw and cone half-angle β vary, numerous flow metamorphoses occur. They are investigated for β =30°, 45°, and 60°. For small Hw , the air flow is multi-cellular with clockwise meridional circulation near the disk. The air flow becomes one cellular as Hw exceeds a threshold depending on β . For all β , the water flow has an unbounded number of eddies whose size and strength diminish as the cone apex is approached. As the water level becomes close to the disk, the outmost water eddy with clockwise meridional circulation expands, reaches the interface, and induces a thin layer with anticlockwise circulation in the air. Then this layer expands and occupies the entire air domain. The physical reasons for the flow transformations are provided. The results are of fundamental interest and can be relevant for aerial bioreactors.

  14. A Narrow Amide I Vibrational Band Observed by Sum Frequency Generation Spectroscopy Reveals Highly Ordered Structures of a Biofilm Protein at the Air/Water Interface†

    PubMed Central

    Wang, Zhuguang; Morales-Acosta, M. Daniela; Li, Shanghao; Liu, Wei; Kanai, Tapan; Liu, Yuting; Chen, Ya-Na; Walker, Frederick J.; Ahn, Charles H.; Leblanc, Roger M.

    2016-01-01

    We characterized BslA, a bacterial biofilm protein, at the air/water interface using vibrational sum frequency generation spectroscopy and observed one of the sharpest amide I band ever reported. Combining methods of surface pressure measurements, thin film X-ray reflectivity, and atomic force microscopy, we showed extremely ordered BslA at the interface. PMID:26779572

  15. Influence of eutrophication on air-water exchange, vertical fluxes, and phytoplankton concentrations of persistent organic pollutants

    SciTech Connect

    Dachs, J.; Eisenreich, S.J.; Hoff, R.M.

    2000-03-15

    The influence of eutrophication on the biogeochemical cycles of persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) is largely unknown. In this paper, the application of a dynamic air-water-phytoplankton exchange model to Lake Ontario is used as a framework to study the influence of eutrophication on air-water exchange, vertical fluxes, and phytoplankton concentrations of POPs. The results of these simulations demonstrate that air-water exchange controls phytoplankton concentrations in remote aquatic environments with little influence from land-based sources of pollutants and supports levels in even historically contaminated systems. Furthermore, eutrophication or high biomass leads to a disequilibrium between the gas and dissolved phase, enhanced air-water exchange, and vertical sinking fluxes of PCBs. Increasing biomass also depletes the water concentrations leading to lower than equilibrium PCB concentrations in phytoplankton. Implications to future trends in PCB pollution in Lake Ontario are also discussed.

  16. Micro-engineered cathode interface studies

    SciTech Connect

    Doshi, R.; Kueper, T.; Nagy, Z.; Krumpelt, M.

    1997-08-01

    The aim of this work is to increase the performance of the cathode in solid oxide fuel cells (SOFCs) operating at 1,000 C by decreasing the polarization resistance from 0.2 {Omega}-cm{sup 2} at 300 mA/cm{sup 2}. Decreased polarization resistance will allow operation at higher current densities. This work is in support of the Westinghouse tubular SOFC technology using YSZ electrolyte and strontium doped lanthanum manganite (LSM) cathode. As a result of work performed last year at Argonne National Laboratory and information derived from the literature, the limitations at the cathode/electrolyte interface can be classified into two main areas. First, the ionic conductivity of the LSM cathode material is low which limits the reaction zone to an area very close to the interface, while the rest of the cathode thickness acts essentially as current collector with channels for gas access. Second, the electronic conductivity in YSZ is very low which limits the reaction zone to areas that are the boundaries between LSM and YSZ rather than the YSZ surface away from LSM at the interface. Possible solutions to this problem being pursued are: (1) introducing an ionic conducting YSZ phase in LSM to form a porous two-phase mixture of LSM and YSZ; (2) applying a thin interlayer between the electrolyte and the cathode where the interlayer has high ionic and electronic conductivity and high catalytic activity for reduction of O{sub 2}; (3) increasing the ionic conductivity in the LSM by suitable doping; and (4) increasing the electronic conductivity in the electrolyte by doping or by depositing an appropriate mixed conducting layer on the YSZ before applying the cathode.

  17. On the coefficients of small eddy and surface divergence models for the air-water gas transfer velocity

    NASA Astrophysics Data System (ADS)

    Wang, Binbin; Liao, Qian; Fillingham, Joseph H.; Bootsma, Harvey A.

    2015-03-01

    Recent studies suggested that under low to moderate wind conditions without bubble entraining wave breaking, the air-water gas transfer velocity k+ can be mechanistically parameterized by the near-surface turbulence, following the small eddy model (SEM). Field measurements have supported this model in a variety of environmental forcing systems. Alternatively, surface divergence model (SDM) has also been shown to predict the gas transfer velocity across the air-water interface in laboratory settings. However, the empirically determined model coefficients (α in SEM and c1 in SDM) scattered over a wide range. Here we present the first field measurement of the near-surface turbulence with a novel floating PIV system on Lake Michigan, which allows us to evaluate the SEM and SDM in situ in the natural environment. k+ was derived from the CO2 flux that was measured simultaneously with a floating gas chamber. Measured results indicate that α and c1 are not universal constants. Regression analysis showed that α˜log>(ɛ>) while the near-surface turbulence dissipation rate ɛ is approximately greater than 10-6 m2 s-3 according to data measured for this study as well as from other published results measured in similar environments or in laboratory settings. It also showed that α scales linearly with the turbulent Reynolds number. Similarly, coefficient c1 in the SDM was found to linearly scale with the Reynolds number. These findings suggest that larger eddies are also important parameters, and the dissipation rate in the SEM or the surface divergence β' in the SDM alone may not be adequate to determine k+ completely.

  18. Experimental study of interface properties between layer and substrate

    NASA Astrophysics Data System (ADS)

    Ko, Ray T.; Nagy, Peter B.; Adler, Laszlo

    A meshed intervening layer technique which makes it possible to study the interface properties between layer and substrate is presented. It is argued that the bonding condition of the interface can be monitored through the variation of the phase velocity of the modified Rayleigh mode. The experimental setup of the measurement of the reflection of ultrasonic waves from a layered substrate specimen is shown, and the frequency spectra from three typical bonding cases - perfectly bonded, partially bonded, and completely misbonded - are illustrated.

  19. Study of GaAs-oxide interface by transient capacitance spectroscopy - Discrete energy interface states

    NASA Technical Reports Server (NTRS)

    Kamieniecki, E.; Kazior, T. E.; Lagowski, J.; Gatos, H. C.

    1980-01-01

    Interface states and bulk GaAs energy levels were simultaneously investigated in GaAs MOS structures prepared by anodic oxidation. These two types of energy levels were successfully distinguished by carrying out a comparative analysis of deep level transient capacitance spectra of the MOS structures and MS structures prepared on the same samples of epitaxially grown GaAs. The identification and study of the interface states and bulk levels was also performed by investigating the transient capacitance spectra as a function of the filling pulse magnitude. It was found that in the GaAs-anodic oxide interface there are states present with a discrete energy rather than with a continuous energy distribution. The value of the capture cross section of the interface states was found to be 10 to the 14th to 10 to the 15th/sq cm, which is more accurate than the extremely large values of 10 to the -8th to 10 to the -9th/sq cm reported on the basis of conductance measurements.

  20. External exposure to radionuclides in air, water, and soil

    SciTech Connect

    Eckerman, K.F.; Ryman, J.C.

    1996-05-01

    Federal Guidance Report No. 12 tabulates dose coefficients for external exposure to photons and electrons emitted by radionuclides distributed in air, water, and soil. The dose coefficients are intended for use by Federal Agencies in calculating the dose equivalent to organs and tissues of the body.

  1. Hydrodynamical entrapment of ciliates at the air-liquid interface

    NASA Astrophysics Data System (ADS)

    Ferracci, Jonathan; Ueno, Hironori; Numayama-Tsuruta, Keiko; Imai, Yohsuke; Yamaguchi, Takami; Ishikawa, Takuji

    2012-11-01

    We found the new phenomenon of the entrapment of ciliates at the air-water interface, though they are not trapped by a solid interface. We first characterize the behaviours of cells at the interface by comparing it to those away from interfaces. The results showed that the cell's swimming velocity is considerably reduced at the air-water interface. In order to experimentally verify the possible physiological causes of the entrapment, we observed their behaviours in absence of positive chemotaxis for oxygen and the negative geotaxis. The results illustrated that the entrapment phenomenon was not dependent on these physiological conditions. The experiments using surfactant revealed that the entrapment phenomenon was strongly affected by the velocity-stress conditions at the interface. This fact was confirmed numerically by a boundary element method, i.e. the stress-free condition at the air-liquid interface is one of the main mechanisms of the entrapment phenomenon found in the experiments. Since the entrapment phenomenon found in this study affects the cell-cell interactions and the mass transport at the interface, the knowledge obtained in this study is useful for better understanding the complex behaviours of swimming microorganisms in nature. PhD student in the Physiological Flow Studies Laboratory.

  2. Interfaces in polymer nanocomposites - An NMR study

    NASA Astrophysics Data System (ADS)

    Böhme, Ute; Scheler, Ulrich

    2016-03-01

    Nuclear Magnetic Resonance (NMR) is applied for the investigation of polymer nanocomposites. Solid-state NMR is applied to study the modification steps to compatibilize layered double hydroxides with non-polar polymers. 1H relaxation NMR gives insight on the polymer dynamics over a wide range of correlation times. For the polymer chain dynamics the transverse relaxation time T2 is most suited. In this presentation we report on two applications of T2 measurements under external mechanical stress. In a low-field system relaxation NMR studies are performed in-situ under uniaxial stress. High-temperature experiments in a Couette cell permit the investigation of the polymer dynamics in the melt under shear flow.

  3. Computer modelling studies of the bilayer/water interface.

    PubMed

    Pasenkiewicz-Gierula, Marta; Baczynski, Krzysztof; Markiewicz, Michal; Murzyn, Krzysztof

    2016-10-01

    This review summarises high resolution studies on the interface of lamellar lipid bilayers composed of the most typical lipid molecules which constitute the lipid matrix of biomembranes. The presented results were obtained predominantly by computer modelling methods. Whenever possible, the results were compared with experimental results obtained for similar systems. The first and main section of the review is concerned with the bilayer-water interface and is divided into four subsections. The first describes the simplest case, where the interface consists only of lipid head groups and water molecules and focuses on interactions between the lipid heads and water molecules; the second describes the interface containing also mono- and divalent ions and concentrates on lipid-ion interactions; the third describes direct inter-lipid interactions. These three subsections are followed by a discussion on the network of direct and indirect inter-lipid interactions at the bilayer interface. The second section summarises recent computer simulation studies on the interactions of antibacterial membrane active compounds with various models of the bacterial outer membrane. This article is part of a Special Issue entitled: Biosimulations edited by Ilpo Vattulainen and Tomasz Róg. PMID:26825705

  4. [Charge generation and separation at liquid interfaces]. Technical progress report

    SciTech Connect

    Eisenthal, K.B.

    1992-12-01

    The research is divided into 3 parts: (1)Sum Frequency Generation (SFG) and Monolayer Structure. Picosecond lasers are combined by difference frequency mixing in a nonlinear crystal to generate picosecond, tunable IR pulses, which are used to study orientation of C{double_bond}N and CD{sub 3} chromosphores (head group and tail) on lipid monolayers CD{sub 3}(CH{sub 2}){sub 21}CN at air/water interface. (2)Femtosecond Dynamics. The femtosecond colliding pulse mode locked laser is being modified to carry out pump-second harmonic (SH) probe studies at liquid interfaces. Picosecond SH knowhow of intermolecular energy transfer, excited state isomerization, and rotational motions at interfaces is now being applied to femtosecond scale. Aromatics adsorbed at air/water interface, generated changes in SH probe signal and their decay back to original value. If the laser is tightly focussed at interface, multiphoton absorption processes occur which destroy the sample; this effect will be exploited. (3)Interface Potential and Acid-Base Equilibria. The interface potential is a key to charge transport; using SHG, we plan to measure the pKa of organic acids at interfaces. In these studies at silica/aqueous interface, the water molecules extending from the interface into the bulk (about 50{Angstrom}) were strongly polarized by SiO{sup {minus}} charges at the interface. In summary, a new spectroscopic technique is being applied to study of neutral and charged lipid monolayers, interface pKa values, interface potential and orientational structure and vibrational spectroscopy of lipids.

  5. Electron Microscopy Studies of Solid Surfaces and Interfaces.

    NASA Astrophysics Data System (ADS)

    Gajdardziska-Josifovska, Marija

    1991-02-01

    Electron microscopy techniques for study of surfaces and interfaces have been investigated and applied to (100) and (111) surfaces of MgO and to interfaces of Mo/Si multilayers and CoSi_2/Si epitaxial films. MgO surfaces subjected to different annealing and chemical treatments have been characterized by reflection electron microscopy imaging, reflection high-energy electron diffraction (RHEED), and reflection electron energy-loss spectroscopy (REELS). An oxygen rich (sqrt {3} times sqrt{3})R 30^circ reconstruction was found on the polar (111) surface upon annealing in oxygen at temperatures higher than 1500 ^circC. Transformation of the surface topography and segregation of calcium were observed on the cleaved (100) surface due to annealing. RHEED resonance conditions have been employed and studied with geometrical constructions, rocking curves and REELS. These conditions are associated with parabolas in the Kikuchi (K) patterns whose nature had been subject of much controversy. The parabolas have been explained as K lines of two-dimensional (2D) lattices in a general scheme which describes the K pattern geometry in terms of intersections of Brillouin zone boundaries with a sphere of reflections. Full treatment of the cases of 2D and 1D real lattices has revealed previously unknown boundaries in the form of parabolic surfaces (2D) and paraboloids of revolution (1D). These boundaries have been applied to lines which arise from electron channeling in 3D crystals and to RHEED parabolas from 2D surface reconstructions. Nanodiffraction, low angle dark-field imaging, electron holography, high spatial resolution EELS, and shadow imaging have been evaluated as means for measuring interface abruptness and change in mean-inner potential and compared to other microscopy techniques. Refraction effects at interfaces were observed as streaking of the nanodiffraction disks which was found to depend on the crystalline nature of the interface. For polycrystalline

  6. Forced convection heat transfer to air/water vapor mixtures

    NASA Technical Reports Server (NTRS)

    Richards, D. R.; Florschuetz, L. W.

    1986-01-01

    Heat transfer coefficients were measured using both dry air and air/water vapor mixtures in the same forced convection cooling test rig (jet array impingement configurations) with mass ratios of water vapor to air up to 0.23. The primary objective was to verify by direct experiment that selected existing methods for evaluation of viscosity and thermal conductivity of air/water vapor mixtures could be used with confidence to predict heat transfer coefficients for such mixtures using as a basis heat transfer data for dry air only. The property evaluation methods deemed most appropriate require as a basis a measured property value at one mixture composition in addition to the property values for the pure components.

  7. Thermodynamic and transport properties of air/water mixtures

    NASA Technical Reports Server (NTRS)

    Fessler, T. E.

    1981-01-01

    Subroutine WETAIR calculates properties at nearly 1,500 K and 4,500 atmospheres. Necessary inputs are assigned values of combinations of density, pressure, temperature, and entropy. Interpolation of property tables obtains dry air and water (steam) properties, and simple mixing laws calculate properties of air/water mixture. WETAIR is used to test gas turbine engines and components operating in relatively humid air. Program is written in SFTRAN and FORTRAN.

  8. Comprehensive Study of High-Tc Interface Superconductivity

    SciTech Connect

    Logvenov, G.; Gozar A.; Butko, V.Y.; Bollinger, A.T.; Bozovic, N.; Radovic, Z.; Bozovic, I.

    2010-08-01

    Using ALL-MBE technique, we have synthesized different heterostructures consisting of an insulator La{sub 2}CuO{sub 4} (I) and a metal La{sub 1.56}Sr{sub 0.44}CuO{sub 4} (M) layer neither of which is superconducting by itself. The M-I bilayers were superconducting with a critical temperature T{sub c} {approx} 30-36 K. This highly robust phenomenon is confined within 1-2 nm from the interface and is primarily caused by the redistribution of doped holes across the interface. In this paper, we present a comprehensive study of the interface superconductivity by a range of experimental techniques including transport measurements of superconducting properties.

  9. Sum-Frequency Generation Spectroscopy for Studying Organic Layers at Water-Air Interfaces: Microlayer Monitoring and Surface Reactivity

    NASA Astrophysics Data System (ADS)

    Laß, Kristian; Kleber, Joscha; Bange, Hermann; Friedrichs, Gernot

    2015-04-01

    The sea surface microlayer, according to commonly accepted terminology, comprises the topmost millimetre of the oceanic water column. It is often enriched with organic matter and is directly influenced by sunlight exposure and gas exchange with the atmosphere, hence making it a place for active biochemistry and photochemistry as well as for heterogeneous reactions. In addition, surface active material either is formed or accumulates directly at the air-water interface and gives rise to very thin layers, sometimes down to monomolecular thickness. This "sea surface nanolayer" determines the viscoelastic properties of the seawater surface and thus may impact the turbulent air-sea gas exchange rates. To this effect, this small scale layer presumably plays an important role for large scale changes of atmospheric trace gas concentrations (e.g., by modulating the ocean carbon sink characteristics) with possible implications for coupled climate models. To date, detailed knowledge about the composition, structure, and reactivity of the sea surface nanolayer is still scarce. Due to its small vertical dimension and the small amount of material, this surfactant layer is very difficult to separate and analyse. A way out is the application of second-order nonlinear optical methods, which make a direct surface-specific and background-free detection of this interfacial layer possible. In recent years, we have introduced the use of vibrational sum frequency generation (VSFG) spectroscopy to gain insight into natural and artificial organic monolayers at the air-water interface. In this contribution, the application of VSFG spectroscopy for the analysis of the sea surface nanolayer will be illustrated. Resulting spectra are interpreted in terms of layer composition and surfactant classes, in particular with respect to carbohydrate-containing molecules such as glycolipids. The partitioning of the detected surfactants into soluble and non-soluble ("wet" and "dry") surfactants will be

  10. Airborne Precision Spacing for Dependent Parallel Operations Interface Study

    NASA Technical Reports Server (NTRS)

    Volk, Paul M.; Takallu, M. A.; Hoffler, Keith D.; Weiser, Jarold; Turner, Dexter

    2012-01-01

    This paper describes a usability study of proposed cockpit interfaces to support Airborne Precision Spacing (APS) operations for aircraft performing dependent parallel approaches (DPA). NASA has proposed an airborne system called Pair Dependent Speed (PDS) which uses their Airborne Spacing for Terminal Arrival Routes (ASTAR) algorithm to manage spacing intervals. Interface elements were designed to facilitate the input of APS-DPA spacing parameters to ASTAR, and to convey PDS system information to the crew deemed necessary and/or helpful to conduct the operation, including: target speed, guidance mode, target aircraft depiction, and spacing trend indication. In the study, subject pilots observed recorded simulations using the proposed interface elements in which the ownship managed assigned spacing intervals from two other arriving aircraft. Simulations were recorded using the Aircraft Simulation for Traffic Operations Research (ASTOR) platform, a medium-fidelity simulator based on a modern Boeing commercial glass cockpit. Various combinations of the interface elements were presented to subject pilots, and feedback was collected via structured questionnaires. The results of subject pilot evaluations show that the proposed design elements were acceptable, and that preferable combinations exist within this set of elements. The results also point to potential improvements to be considered for implementation in future experiments.

  11. 14 CFR 1274.926 - Clean Air-Water Pollution Control Acts.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 5 2011-01-01 2010-01-01 true Clean Air-Water Pollution Control Acts. 1274... AGREEMENTS WITH COMMERCIAL FIRMS Other Provisions and Special Conditions § 1274.926 Clean Air-Water Pollution Control Acts. Clean Air-Water Pollution Control Acts July 2002 If this cooperative agreement or...

  12. A criterion for the onset of slugging in horizontal stratified air-water countercurrent flow

    SciTech Connect

    Chun, Moon-Hyun; Lee, Byung-Ryung; Kim, Yang-Seok

    1995-09-01

    This paper presents an experimental and theoretical investigation of wave height and transition criterion from wavy to slug flow in horizontal air-water countercurrent stratified flow conditions. A theoretical formula for the wave height in a stratified wavy flow regime has been developed using the concept of total energy balance over a wave crest to consider the shear stress acting on the interface of two fluids. From the limiting condition of the formula for the wave height, a necessary criterion for transition from a stratified wavy flow to a slug flow has been derived. A series of experiments have been conducted changing the non-dimensional water depth and the flow rates of air in a horizontal pipe and a duct. Comparisons between the measured data and the predictions of the present theory show that the agreement is within {plus_minus}8%.

  13. Insights from the study of high-temperature interface superconductivity.

    PubMed

    Pereiro, J; Bollinger, A T; Logvenov, G; Gozar, A; Panagopoulos, C; Bozović, I

    2012-10-28

    A brief overview is given of the studies of high-temperature interface superconductivity based on atomic-layer-by-layer molecular beam epitaxy (ALL-MBE). A number of difficult materials science and physics questions have been tackled, frequently at the expense of some technical tour de force, and sometimes even by introducing new techniques. ALL-MBE is especially suitable to address questions related to surface and interface physics. Using this technique, it has been demonstrated that high-temperature superconductivity can occur in a single copper oxide layer-the thinnest superconductor known. It has been shown that interface superconductivity in cuprates is a genuine electronic effect-it arises from charge transfer (electron depletion and accumulation) across the interface driven by the difference in chemical potentials rather than from cation diffusion and mixing. We have also understood the nature of the superconductor-insulator phase transition as a function of doping. However, a few important questions, such as the mechanism of interfacial enhancement of the critical temperature, are still outstanding. PMID:22987034

  14. Molecular Interactions in Monolayers οf Azo Dye/Liquid Crystal Mixtures at Interfaces

    NASA Astrophysics Data System (ADS)

    Bauman, D.; Płóciennik, A.; Inglot, K.

    2009-08-01

    Full Text PDF A study of azo dye/liquid crystal mixtures in monolayers formed at an air-water interface (the Langmuir films) and at a solid surface (the Langmuir-Blodgett films) has been performed. Five azo dyes with various molecular structure and the liquid crystal 4-octyl-4' cyanobiphenyl (8CB) have been used. The dyes have been added to the liquid crystal at various molar fractions. Surface pressure and surface potential versus mean molecular area isotherms for the Langmuir films have been recorded and information about intermolecular interactions at the air-water interface has been obtained. On the basis of electronic absorption measurements for the Langmuir and Langmuir-Blodgett films the conclusions about the ability of dyes molecules to form self aggregates at the interfaces have been drawn. The influence of the dye molecular structure and its concentration on aggregates' geometry has been found.

  15. Experimental study of the oscillating interface of a falling drop

    NASA Astrophysics Data System (ADS)

    Choi, Suhwan; Ward, Thomas

    2012-11-01

    The drop interface oscillation generated from detachment from a nozzle due to gravity are experimentally studied. The fluids used in the experiments are glycerol-water mixtures with viscosities ranging from 0.005 to 0.410 Pa s, mineral oil having a viscosity of 0.0270 Pa s, and DI water with viscosity of 0.0009 Pa s. The drop oscillating is taken by fast camera to make observations. For large drops, where the interface relative to a polar angle may be measured, the periodic deformation is plotted as a function of time. For smaller drops we measure the deformation as switching between an oblate and prolate drop as a function of time. The phenomenon is clearly a function of the fluid viscosity but we seek to propose a pinch-off mechanism for understanding the source of the observed oscillations.

  16. X-ray microtomography determination of air-water interfacial area-water saturation relationships in sandy porous media.

    PubMed

    Costanza-Robinson, Molly S; Harrold, Katherine H; Lieb-Lappen, Ross M

    2008-04-15

    In this work, total smooth air-water interfacial areas were measured for a series of nine natural and model sandy porous media as a function of water saturation using synchrotron X-ray microtomography. Interfacial areas decreased linearly with water satuation, while the estimated maximum interfacial area compared favorably to the media geometric surface areas. Importantly, relative interfacial area (i.e., normalized by geometric surface area) versus water saturation plots for all media collapsed into a single linear cluster (r2 = 0.93), suggesting that geometric surface area is an important, and perhaps sufficient, descriptor of sandy media that governs total smooth interfacial area-water saturation relationships. Measured relationships were used to develop an empirical model for estimating interfacial area-water saturation relationships for sandy porous media. Model-based interfacial area estimates for independent media were generally slightly higher than interfacial areas measured using aqueous-phase interfacial tracer methods, which may indicate that microtomography captures regions of the air-water interface that are not accessible to aqueous-phase interfacial tracers. The empirical model presented here requires only average particle diameter and porosity as input parameters and can be used to readily estimate air-water interfacial area-water saturation relationships for sandy porous media. PMID:18497149

  17. X-Ray Studies of Thin Films and Interfaces.

    NASA Astrophysics Data System (ADS)

    Woronick, Steven Charles

    1990-01-01

    Presented here are a series of x-ray studies utilizing synchrotron radiation to investigate a variety of properties of thin films and interfaces in technologically important materials. By far the largest part of this dissertation is devoted to studies of x-ray reflectivity as a function of angle (mainly soft x rays), although some extended x -ray absorption fine structure (EXAFS) results are included as reprinted published papers (briefly discussed). The reflectivity discussion covers theory, experimental techniques, data analysis (by curve-fitting), and specific applications. The material systems studied by the x-ray reflectivity technique include: bulk silicon, GaAs, InAs, ~250 -A InAs layers deposited by molecular-beam epitaxy (MBE) on GaAs(100) substrates, four thicknesses (~ 126-1100 A) of SiO_2 /Si(100) produced by dry thermal oxidation, and ~250-A layers of CoSi_2 /Si(111) (two samples, one produced by MBE and one by solid-phase epitaxy). Results determined from the reflectivity measurements include: interfacial roughness parameters, refractive index of materials (in the energy range ~400-1100 eV), and overlayer thicknesses. It has been found for example that the indium -stabilized growth mode of InAs on GaAs(100) results in a smoother buried interface than the arsenic-stabilized growth mode, while the indium-stabilized growth mode on 2^circ-off GaAs(100) produces the smoothest buried interface (with typical roughness parameters in the range 10-19 A). Preliminary results indicate that growth of CoSi_2/Si(111) by MBE produces smoother buried interfaces than growth by solid-phase epitaxy. The roughness parameters have been explained in terms of growth conditions, lattice mismatch, and material inhomogeneity in the vicinity of the buried interface. The oxygen atomic scattering factor for photons in the range 400-800 eV (oxygen K edge ~ 540 eV) has also been deduced from a determination the Si and SiO_2 refractive indices. The EXAFS studies were used to

  18. Atomistic study on the FCC/BCC interface structure with {112}KS orientation

    SciTech Connect

    Kang, Keonwook; Beyerlein, Irene; Han, Weizhong; Wang, Jian; Mara, Nathan

    2011-09-23

    In this study, atomistic simulation is used to explore the atomic interface structure, the intrinsic defect network, and mechanism of twin formation from the {112}KS Cu-Nb interface. The interface structure of different material systems AI-Fe and AI-Nb are also compared with Cu-Nb interface.

  19. Propagation of Stream Interfaces: An LFM-helio Study

    NASA Astrophysics Data System (ADS)

    Pahud, D. M.; Hughes, W.; Merkin, V. G.; McGregor, S. L.

    2012-12-01

    During the last solar minimum, the heliosphere was dominated by steady-state Stream Interaction Regions (SIRs). Carrington Rotation (CR) 2060, which occurred during this period, contained multiple SIRs and was free of transient phenomena which made it a good interval for the study of SIRs. We have used the Lyon-Fedder-Mobarry (LFM) heliospheric 3-D magnetohydrodynamic (MHD) model, the LFM-helio, to examine the radial evolution of SIRs, particularly the speed of the stream interface, from 0.1 AU to 2.0 AU. The LFM-helio is an adaptation of the magnetospheric LFM MHD code to heliospheric plasmas and fields. The ideal MHD equations are solved on a uniform spherical grid, excluding 10 degree cones centered at the poles. The inner boundary condition is obtained using the Wang-Sheeley-Arge (WSA) coronal model driven by photospheric magnetic field measurements for CR 2060. The global nature of the LFM-helio solution facilitates the study of the steepening of SIRs as well as their speed through the ambient plasma. For the SIR considered, the location of the stream interface is determined using multiple definitions, namely: the location of maximum total pressure, the location of maximum flow vorticity, the location of null azimuthal flow velocity and the location of steepest gradient of entropy. The speed of the plasma at these locations is compared to the mean speed of the interface to determine whether the interfaces are convected with the solar wind or propagate through it. In order to elucidate the physics of the evolution of the SIR, we also ran the LFM-helio using an idealized inner boundary condition. The idealized inner boundary specified the solar wind speed so as to ensure the presence of an SIR. Specifically, a source of fast wind was located at the same latitude as, and longitudinally near, a source of slow wind. The combined effect of radially outward plasma flow and rotation of the inner boundary align the fast wind behind the slow wind, creating an SIR. The

  20. 2008 ULTRASONIC BENCHMARK STUDIES OF INTERFACE CURVATURE--A SUMMARY

    SciTech Connect

    Schmerr, L. W.; Huang, R.; Raillon, R.; Mahaut, S.; Leymarie, N.; Lonne, S.; Spies, M.; Lupien, V.

    2009-03-03

    In the 2008 QNDE ultrasonic benchmark session researchers from five different institutions around the world examined the influence that the curvature of a cylindrical fluid-solid interface has on the measured NDE immersion pulse-echo response of a flat-bottom hole (FBH) reflector. This was a repeat of a study conducted in the 2007 benchmark to try to determine the sources of differences seen in 2007 between model-based predictions and experiments. Here, we will summarize the results obtained in 2008 and analyze the model-based results and the experiments.

  1. Video STM Studies of Adsorbate Diffusion at Electrochemical Interfaces

    NASA Astrophysics Data System (ADS)

    Tansel, T.; Magnussen, O. M.

    2006-01-01

    Direct in situ studies of the surface diffusion of isolated adsorbates at an electrochemical interface by high-speed scanning tunneling microscopy (video STM) are presented for sulfide adsorbates on Cu(100) in HCl solution. As revealed by a quantitative statistical analysis, the adsorbate motion can be described by thermally activated hopping between neighboring adsorption sites with an activation energy that increases linearly with electrode potential by 0.50 eV per V. This can be explained by changes in the adsorbate dipole moment during the hopping process and contributions from coadsorbates.

  2. Space station automation and robotics study. Operator-systems interface

    NASA Technical Reports Server (NTRS)

    1984-01-01

    This is the final report of a Space Station Automation and Robotics Planning Study, which was a joint project of the Boeing Aerospace Company, Boeing Commercial Airplane Company, and Boeing Computer Services Company. The study is in support of the Advanced Technology Advisory Committee established by NASA in accordance with a mandate by the U.S. Congress. Boeing support complements that provided to the NASA Contractor study team by four aerospace contractors, the Stanford Research Institute (SRI), and the California Space Institute. This study identifies automation and robotics (A&R) technologies that can be advanced by requirements levied by the Space Station Program. The methodology used in the study is to establish functional requirements for the operator system interface (OSI), establish the technologies needed to meet these requirements, and to forecast the availability of these technologies. The OSI would perform path planning, tracking and control, object recognition, fault detection and correction, and plan modifications in connection with extravehicular (EV) robot operations.

  3. Detailed simulations of air-water interaction phenomena in ocean waves

    NASA Astrophysics Data System (ADS)

    Iafrati, A.; Durante, D.

    2012-04-01

    In the present contribution the flow induced in air by ocean waves is investigated. The air-water interaction problem is of obvious interest in the context of wind generated waves. However, the flow induced in the lower atmosphere layer by ocean waves has also important effects on the exchange processes between atmosphere and ocean and in some circumstances it influences weather conditions on large scales. The problem is studied numerically by a two-dimensional Navier-Stokes solver which models the flow in air and water as that of a single incompressible fluid with density and viscosity expressed as a smooth function of the distance from the interface. The free surface is captured as the zero level set of the distance function. The distance from the interface is reinitialized every time step, so that the thickness of the transition region remains constant in time. The method is applied to two problems characterized by quite different length scales and steepnesses. In both cases the limits associated to the numerical approach and possible effects on the results are discussed. The first application is an attempt of investigating the role played by the flow in air on the dissipation rate of swells. The interest for such problem stems from some studies according to which the flow in air has an important effect on the dissipation of the steepest swells (Ardhuin et al, 2009). Motivated by the above findings, numerical simulations are performed in order to investigate the characteristics of the flow induced in air by swell with wavelengths in a range 50 to 300 m. Results are presented in terms of vorticity field in air with quantitative analyses of the vertical flux of horizontal momentum and of the viscous dissipation in the air phase. The thickness of the air layer which is influenced by the passage of the swell is also given. The second study analyzes the flow induced in air by the evolution of modulated wave trains. In this case the fundamental wavelength is 0.6 m

  4. Electrochemical impedance study of the hematite/water interface.

    PubMed

    Shimizu, Kenichi; Lasia, Andrzej; Boily, Jean-François

    2012-05-22

    Reactions taking place on hematite (α-Fe(2)O(3)) surfaces in contact with aqueous solutions are of paramount importance to environmental and technological processes. The electrochemical properties of the hematite/water interface are central to these processes and can be probed by open circuit potentials and cyclic voltammetric measurements of semiconducting electrodes. In this study, electrochemical impedance spectroscopy (EIS) was used to extract resistive and capacitive attributes of this interface on millimeter-sized single-body hematite electrodes. This was carried out by developing equivalent circuit models for impedance data collected on a semiconducting hematite specimen equilibrated in solutions of 0.1 M NaCl and NH(4)Cl at various pH values. These efforts produced distinct sets of capacitance values for the diffuse and compact layers of the interface. Diffuse layer capacitances shift in the pH 3-11 range from 2.32 to 2.50 μF·cm(-2) in NaCl and from 1.43 to 1.99 μF·cm(-2) in NH(4)Cl. Furthermore, these values reach a minimum capacitance at pH 9, near a probable point of zero charge for an undefined hematite surface exposing a variety of (hydr)oxo functional groups. Compact layer capacitances pertain to the transfer of ions (charge carriers) from the diffuse layer to surface hydroxyls and are independent of pH in NaCl, with values of 32.57 ± 0.49 μF·cm(-2)·s(-φ). However, they decrease with pH in NH(4)Cl from 33.77 at pH 3.5 to 21.02 μF·cm(-2)·s(-φ) at pH 10.6 because of the interactions of ammonium species with surface (hydr)oxo groups. Values of φ (0.71-0.73 in NaCl and 0.56-0.67 in NH(4)Cl) denote the nonideal behavior of this capacitor, which is treated here as a constant phase element. Because electrode-based techniques are generally not applicable to the commonly insulating metal (oxyhydr)oxides found in the environment, this study presents opportunities for exploring mineral/water interface chemistry by EIS studies of single

  5. Ultrafast studies of electron dynamics at metal-dielectric interfaces

    SciTech Connect

    Ge, Nien-Hui

    1998-10-01

    Femtosecond time- and angle-resolved two-photon photoemission spectroscopy has been used to study fundamental aspects of excited electron dynamics at metal-dielectric interfaces, including layer-by-layer evolution of electronic structure and two-dimensional electron localization. On bare Ag(111), the lifetimes of image states are dominated by their position with respect to the projected bulk band structure. The n = 2 state has a shorter lifetime than the n = 1 state due to degeneracy with the bulk conduction band. As the parallel momentum of the n = 1 image electron increases, the lifetime decreases. With decreasing temperatures, the n = 1 image electrons, with zero or nonzero parallel momentum, all become longer lived. Adsorption of one to three layers of n-heptane results in an approximately exponential increase in lifetime as a function of layer thickness. This results from the formation of a tunneling barrier through which the interfacial electrons must decay, consistent with the repulsive bulk electron affinity of n-alkanes. The lifetimes of the higher quantum states indicate that the presence of the monolayer significantly reduces coupling of the image states to the bulk band structure. These results are compared with predictions of a dielectric continuum model. The study of electron lateral motion shows that optical excitation creates interfacial electrons in quasifree states for motion parallel to the n-heptane/Ag(111) interface. These initially delocalized electrons decay into a localized state within a few hundred femtoseconds. The localized electrons then decay back to the metal by tunneling through the adlayer potential barrier. The localization time depends strongly on the electron's initial parallel momentum and exhibits a non-Arrhenius temperature dependence. The experimental findings are consistent with a 2-D self-trapping process in which electrons become localized by interacting with the topmost plane of the alkane layer. The energy dependence of

  6. Supported Lipid Bilayer Technology for the Study of Cellular Interfaces

    PubMed Central

    Crites, Travis J.; Maddox, Michael; Padhan, Kartika; Muller, James; Eigsti, Calvin; Varma, Rajat

    2015-01-01

    Glass-supported lipid bilayers presenting freely diffusing proteins have served as a powerful tool for studying cell-cell interfaces, in particular, T cell–antigen presenting cell (APC) interactions, using optical microscopy. Here we expand upon existing protocols and describe the preparation of liposomes by an extrusion method, and describe how this system can be used to study immune synapse formation by Jurkat cells. We also present a method for forming such lipid bilayers on silica beads for the study of signaling responses by population methods, such as western blotting, flow cytometry, and gene-expression analysis. Finally, we describe how to design and prepare transmembrane-anchored protein-laden liposomes, following expression in suspension CHO (CHOs) cells, a mammalian expression system alternative to insect and bacterial cell lines, which do not produce mammalian glycosylation patterns. Such transmembrane-anchored proteins may have many novel applications in cell biology and immunology. PMID:26331983

  7. Cathode interface studies of polymer light emitting devices

    NASA Astrophysics Data System (ADS)

    Swiontek, Stephen; Tzolov, Marian

    2010-03-01

    Efficient injection of charge carriers is a key factor for successful operation of any electronic device and especially of devices with non-crystalline or wide band gap active material. Our study concentrates on the cathode interface of light emitting devices with a conjugated polymer as light emitter. We apply two principally different methods for the cathode deposition, physical and chemical, in order to fundamentally understand if in addition to the commonly accepted notion for the matching of the work functions also material modification takes place. The completed devices are studies by steady-state electrical measurements, impedance spectroscopy, current and emission lifetime measurements, and electroluminescence spectroscopy. The morphology of the cathodes is studied by Scanning Electron Microscopy and the formation of additional phases by Energy Dispersive X-ray Spectroscopy. The results help to define ways for more cost efficient fabrication of light emitting devices with applications in displays, electronic newspapers, room illumination, etc.

  8. Air-water analogy and the study of hydraulic models

    NASA Technical Reports Server (NTRS)

    Supino, Giulio

    1953-01-01

    The author first sets forth some observations about the theory of models. Then he established certain general criteria for the construction of dynamically similar models in water and in air, through reference to the perfect fluid equations and to the ones pertaining to viscous flow. It is, in addition, pointed out that there are more cases in which the analogy is possible than is commonly supposed.

  9. Spatial Distribution and Air-Water Exchange of Organic Flame Retardants in the Lower Great Lakes.

    PubMed

    McDonough, Carrie A; Puggioni, Gavino; Helm, Paul A; Muir, Derek; Lohmann, Rainer

    2016-09-01

    Organic flame retardants (OFRs) such as polybrominated diphenyl ethers (PBDEs) and novel halogenated flame retardants (NHFRs) are ubiquitous, persistent, and bioaccumulative contaminants that have been used in consumer goods to slow combustion. In this study, polyethylene passive samplers (PEs) were deployed throughout the lower Great Lakes (Lake Erie and Lake Ontario) to measure OFRs in air and water, calculate air-water exchange fluxes, and investigate spatial trends. Dissolved Σ12BDE was greatest in Lake Ontario near Toronto (18 pg/L), whereas gaseous Σ12BDE was greatest on the southern shoreline of Lake Erie (11 pg/m(3)). NHFRs were generally below detection limits. Air-water exchange was dominated by absorption of BDEs 47 and 99, ranging from -964 pg/m(2)/day to -30 pg/m(2)/day. Σ12BDE in air and water was significantly correlated with surrounding population density, suggesting that phased-out PBDEs continued to be emitted from population centers along the Great Lakes shoreline in 2012. Correlation with dissolved Σ12BDE was strongest when considering population within 25 km while correlation with gaseous Σ12BDE was strongest when using population within 3 km to the south of each site. Bayesian kriging was used to predict dissolved Σ12BDE over the lakes, illustrating the utility of relatively highly spatially resolved measurements in identifying potential hot spots for future study. PMID:27458653

  10. Body Machine Interfaces for Neuromotor Rehabilitation: a Case Study

    PubMed Central

    Pierella, Camilla; Abdollahi, Farnaz; Farshchiansadegh, Ali; Pedersen, Jessica; Chen, David; Mussa-Ivaldi, Ferdinando A.; Casadio, Maura

    2015-01-01

    High-level spinal cord injury (SCI) survivors face every day two related problems: recovering motor skills and regaining functional independence. Body machine interfaces (BoMIs) empower people with sever motor disabilities with the ability to control an external device, but they also offer the opportunity to focus concurrently on achieving rehabilitative goals. In this study we developed a portable, and low-cost BoMI that addresses both problems. The BoMI remaps the user’s residual upper body mobility to the two coordinates of a cursor on a computer monitor. By controlling the cursor, the user can perform functional tasks, such as entering text and playing games. This framework also allows the mapping between the body and the cursor space to be modified, gradually challenging the user to exercise more impaired movements. With this approach, we were able to change the behavior of our SCI subject, who initially used almost exclusively his less impaired degrees of freedom - on the left side - for controlling the BoMI. At the end of the few practice sessions he had restored symmetry between left and right side of the body, with an increase of mobility and strength of all the degrees of freedom involved in the control of the interface. This is the first proof of concept that our BoMI can be used to control assistive devices and reach specific rehabilitative goals simultaneously. PMID:25569980

  11. Body machine interfaces for neuromotor rehabilitation: a case study.

    PubMed

    Pierella, Camilla; Abdollahi, Farnaz; Farshchiansadegh, Ali; Pedersen, Jessica; Chen, David; Mussa-Ivaldi, Ferdinando A; Casadio, Maura

    2014-01-01

    High-level spinal cord injury (SCI) survivors face every day two related problems: recovering motor skills and regaining functional independence. Body machine interfaces (BoMIs) empower people with sever motor disabilities with the ability to control an external device, but they also offer the opportunity to focus concurrently on achieving rehabilitative goals. In this study we developed a portable, and low-cost BoMI that addresses both problems. The BoMI remaps the user's residual upper body mobility to the two coordinates of a cursor on a computer monitor. By controlling the cursor, the user can perform functional tasks, such as entering text and playing games. This framework also allows the mapping between the body and the cursor space to be modified, gradually challenging the user to exercise more impaired movements. With this approach, we were able to change the behavior of our SCI subject, who initially used almost exclusively his less impaired degrees of freedom - on the left side - for controlling the BoMI. At the end of the few practice sessions he had restored symmetry between left and right side of the body, with an increase of mobility and strength of all the degrees of freedom involved in the control of the interface. This is the first proof of concept that our BoMI can be used to control assistive devices and reach specific rehabilitative goals simultaneously. PMID:25569980

  12. ISSUES IN SIMULATING ELEMENTAL MERCURY AIR/WATER EXCHANGE AND AQUEOUS MONOMETHYLMERCURY SPECIATION

    EPA Science Inventory

    This presentation focuses on two areas relevant to assessing the global fate and bioavailability of mercury: elemental mercury air/water exchange and aqueous environmental monomethylmercury speciation.

  13. Micrometeorological Measurement of Fetch- and Atmospheric Stability-Dependent Air- Water Exchange of Legacy Semivolatile Organic Contaminants in Lake Superior

    NASA Astrophysics Data System (ADS)

    Perlinger, J. A.; Tobias, D. E.; Rowe, M. D.

    2008-12-01

    Coastal waters including the Laurentian Great Lakes are particularly susceptible to local, regional, and long- range transport and deposition of semivolatile organic contaminants (SOCs) as gases and/or associated with particles. Recently-marketed SOCs can be expected to undergo net deposition in surface waters, whereas legacy SOCs such as polychlorinated biphenyls (PCBs) are likely to be at equilibrium with respect to air-water exchange, or, if atmospheric concentrations decrease through, e.g., policy implementation, to undergo net gas emission. SOC air-water exchange flux is usually estimated using the two-film model. This model describes molecular diffusion through the air and water films adjacent to the air-water interface. Air-water exchange flux is estimated as the product of SOC fugacity, typically based on on-shore gaseous concentration measurements, and a transfer coefficient, the latter which is estimated from SOC properties and environmental conditions. The transfer coefficient formulation commonly applied neglects resistance to exchange in the internal boundary layer under atmospherically stable conditions, and the use of on-shore gaseous concentration neglects fetch-dependent equilibration, both of which will tend to cause overestimation of flux magnitude. Thus, for legacy chemicals or in any highly contaminated surface water, the rate at which the water is cleansed through gas emission tends to be over-predicted using this approach. Micrometeorological measurement of air-water exchange rates of legacy SOCs was carried out on ships during four transect experiments during off-shore flow in Lake Superior using novel multicapillary collection devices and thermal extraction technology to measure parts-per-quadrillion SOC levels. Employing sensible heat in the modified Bowen ratio, fluxes at three over-water stations along the transects were measured, along with up-wind, onshore gaseous concentration and aqueous concentration. The atmosphere was unstable for

  14. Predicting Air-Water Geysers and Their Implications on Reducing Combined Sewer Overflows

    NASA Astrophysics Data System (ADS)

    Choi, Y.; Leon, A.; Apte, S.

    2014-12-01

    An air-water geyser in a closed conduit system is characterized by an explosive jetting of a mixture of air and water through drop-shafts. In this study, three scenarios of geysers are numerically simulated using a 3D computational fluid dynamics (CFD) model. The three tested scenarios are comprised of a drop shaft that is closed at its bottom and partially or fully open at the top. Initially, the lower section of the drop shaft is filled with pressurized air, the middle section with stagnant water and the upper section with air at atmospheric pressure. The pressure and volume of the pressurized air, and hence the stored energy, is different for all three test cases. The volume of the stagnant water and the air at atmospheric pressure are kept constant in the tests. The numerical simulations aim to identify the correlation between dimensionless energy stored in the pressurized air pocket and dimensionless maximum pressure reached at the outlet. This dimensionless correlation could be used to determine the energy threshold that does not produce air-water geyser, which in turn could be used in the design of combined sewer systems for minimizing geysers.

  15. An air-water interfacial area based variable tortuosity model for unsaturated sands

    SciTech Connect

    Khaleel, Raziuddin; Saripalli, Prasad

    2006-05-01

    Based on Kozeny-Carman equation for saturated media permeability, a new model is developed for the prediction of unsaturated hydraulic conductivity, K as a function of moisture content, ?. The K(???) estimates are obtained using laboratory measurements of moisture retention and saturated hydraulic conductivity, and a saturation-dependent tortuosity based on the immiscible fluid (air-water) interfacial area. Tortuosity (?a) for unsaturated media is defined as aaw/aaw,o (ratio of the specific air-water interfacial area of a real and the corresponding idealized porous medium). A correspondence between the real and idealized media is established by using the laboratory-measured soil moisture retention curve to calculate the interfacial area. The general trend in prediction of ?a as a function water saturation is in agreement with similar recent predictions based on diffusion theory. Unsaturated hydraulic conductivities measured for a number of coarse-textured, repacked Hanford sediments agree well with predictions based on the modified Kozeny-Carman relation. Because of the use of saturated hydraulic conductivity, a slight bias is apparent in measured and predicted K at low ?. While the modified Kozeny-Carman relation was found to be reasonably accurate in predicting K(??) for the repacked, sandy soils considered in this study, a further testing of the new model for undisturbed sediments and other soil textures would be useful.

  16. Adhesion at WC/diamond interfaces - A theoretical study

    SciTech Connect

    Padmanabhan, Haricharan; Rao, M. S. Ramachandra; Nanda, B. R. K.

    2015-06-24

    We investigate the adhesion at the interface of face-centered tungsten-carbide (001) and diamond (001) from density-functional calculations. Four high-symmetry model interfaces, representing different lattice orientations for either side of the interface, are constructed to incorporate different degrees of strain arising due to lattice mismatch. The adhesion, estimated from the ideal work of separation, is found to be in the range of 4 - 7 J m{sup −2} and is comparable to that of metal-carbide interfaces. Maximum adhesion occurs when WC and diamond slabs have the same orientation, even though such a growth induces large epitaxial strain at the interface. From electronic structure calculations, we attribute the adhesion to covalent interaction between carbon p-orbitals as well as partial ionic interaction between the tungsten d- and carbon p-orbitals across the interface.

  17. Determining Spatial Distribution And Air-Water Exchange Of Polycyclic Aromatic Hydrocarbons In Stormwater Runoff Catchment Basins

    NASA Astrophysics Data System (ADS)

    Kasaraneni, V. K.; Schifman, L. A.; Craver, V.; Boving, T. B.

    2014-12-01

    Stormwater runoff is a conduit for several pollutants such as polycyclic aromatic hydrocarbons (PAHs) in to surface and ground water bodies. The control of runoff and pollutants is typically addressed by best management practices (BMPs), such as retention/detention ponds or catchment basins in general. The effectiveness of catchment basins in reducing the volume of runoff and removal of some contaminants has been established. However, very little is known about the fate of the contaminants settled within these structures. In coastal regions and places with shallow groundwater tables accumulation of high concentrations of PAHs in the bottom sediments poses a potential threat for groundwater contamination. The concentrations of PAHs accumulated in the sediments of these catchment basins will primarily depend on the sources of runoff origin and the surrounding land use. Due to the physico-chemical characteristics of PAHs, their transport not only can occur in the liquid and solid phase, but it is also possible that gaseous emissions can be produced from BMP systems. For the purpose of this study, five stormwater catchment basins along the I-95 corridor in Rhode Island were selected based on the stormwater runoff origin and covering (industrial, urban, highway, and commercial) land uses. To study the stratification of PAHs sediment cores one foot were collected and analyzed for 31PAHs (16 EPA parent PAH and 15 methylated PAHs). In order to determine whether the catchment basins are a source of atmospheric pollution polyethylene passive samplers were deployed to determine the freely dissolved PAHs in the water column and gas phase PAHs at the air-water interface. This presentation will describe how PAH fluxes move between three environmental compartments (sediments, water column, atmosphere) within the five stormwater catchment basins. Further, it will be investigated whether these BMP structures can act as contaminant sources rather than sinks and whether BMP

  18. Translational viscous drags of an ellipsoid straddling an interface between two fluids

    NASA Astrophysics Data System (ADS)

    Boniello, Giuseppe; Stocco, Antonio; Gross, Michel; In, Martin; Blanc, Christophe; Nobili, Maurizio

    2016-07-01

    We study the dynamics of individual polystyrene ellipsoids of different aspect ratios trapped at the air-water interface. Using particle tracking and in situ vertical scanning interferometry techniques we are able to measure translational drags and the protrusion in air of the ellipsoids. We report that translational drags on the ellipsoid are unexpectedly enhanced: despite the fact that a noticeable part of the ellipsoid is in air, drags are found larger than the bulk one in water.

  19. Translational viscous drags of an ellipsoid straddling an interface between two fluids.

    PubMed

    Boniello, Giuseppe; Stocco, Antonio; Gross, Michel; In, Martin; Blanc, Christophe; Nobili, Maurizio

    2016-07-01

    We study the dynamics of individual polystyrene ellipsoids of different aspect ratios trapped at the air-water interface. Using particle tracking and in situ vertical scanning interferometry techniques we are able to measure translational drags and the protrusion in air of the ellipsoids. We report that translational drags on the ellipsoid are unexpectedly enhanced: despite the fact that a noticeable part of the ellipsoid is in air, drags are found larger than the bulk one in water. PMID:27575174

  20. Drainage flows: A mountain-plains interface numerical case study

    SciTech Connect

    Poulos, G.S.; Bossert, J.E.

    1992-01-01

    In January/February, 1991 an intensive set of measurements was taken around Rocky Flats near Denver, CO, USA under the auspices of the Atmospheric Studies in Complex Terrain (ASCOT) program. This region of the country is known as the Front Range, and is characterized by a transition from the relatively flat terrain of the Great Plains to the highly varied terrain of the Rocky Mountains. The mountains are oriented north-south and rise from 1800m above mean sea level (MSL) to 3600m MSL at the Continental Divide. Numerous east-west oriented valleys begin in the mountains and end at the plains interface. This terrain makes the Front Range a challenging region to model. One of the more important flows created by this severe terrain are the highly-varying drainage flows found during stagnant, wintertime conditions. These flows can interact with larger-scale mountain and synoptic winds. One goal of the ASCOT 1991 program was to gain insight into multi-scale meteorological interaction by observing wintertime drainage conditions at the mountain-valley-plains interface. ASCOT data included surface and upper air measurements on approximately a 50km{sup 2} scale. Simultaneously, an SF{sub 6} tracer release study was being conducted around Rocky Flats, a nuclear materials production facility. Detailed surface concentration measurements were completed for the SF{sub 6} plume. This combination of meteorological and tracer concentration data provided a unique data set for comparisons of mesoscale and dispersion modeling results with observations and for evaluating our capability to predict pollutant transport. Our approach is to use the Regional Atmospheric Modeling System (RAMS) mesoscale model to simulate atmospheric conditions and the Lagrangian Particle Dispersion Model (LPDM) to model the dispersion of the SF{sub 6}.

  1. Drainage flows: A mountain-plains interface numerical case study

    SciTech Connect

    Poulos, G.S.; Bossert, J.E.

    1992-09-01

    In January/February, 1991 an intensive set of measurements was taken around Rocky Flats near Denver, CO, USA under the auspices of the Atmospheric Studies in Complex Terrain (ASCOT) program. This region of the country is known as the Front Range, and is characterized by a transition from the relatively flat terrain of the Great Plains to the highly varied terrain of the Rocky Mountains. The mountains are oriented north-south and rise from 1800m above mean sea level (MSL) to 3600m MSL at the Continental Divide. Numerous east-west oriented valleys begin in the mountains and end at the plains interface. This terrain makes the Front Range a challenging region to model. One of the more important flows created by this severe terrain are the highly-varying drainage flows found during stagnant, wintertime conditions. These flows can interact with larger-scale mountain and synoptic winds. One goal of the ASCOT 1991 program was to gain insight into multi-scale meteorological interaction by observing wintertime drainage conditions at the mountain-valley-plains interface. ASCOT data included surface and upper air measurements on approximately a 50km{sup 2} scale. Simultaneously, an SF{sub 6} tracer release study was being conducted around Rocky Flats, a nuclear materials production facility. Detailed surface concentration measurements were completed for the SF{sub 6} plume. This combination of meteorological and tracer concentration data provided a unique data set for comparisons of mesoscale and dispersion modeling results with observations and for evaluating our capability to predict pollutant transport. Our approach is to use the Regional Atmospheric Modeling System (RAMS) mesoscale model to simulate atmospheric conditions and the Lagrangian Particle Dispersion Model (LPDM) to model the dispersion of the SF{sub 6}.

  2. The Effect of Rain on Air-Water Gas Exchange

    NASA Technical Reports Server (NTRS)

    Ho, David T.; Bliven, Larry F.; Wanninkhof, Rik; Schlosser, Peter

    1997-01-01

    The relationship between gas transfer velocity and rain rate was investigated at NASA's Rain-Sea Interaction Facility (RSIF) using several SF, evasion experiments. During each experiment, a water tank below the rain simulator was supersaturated with SF6, a synthetic gas, and the gas transfer velocities were calculated from the measured decrease in SF6 concentration with time. The results from experiments with IS different rain rates (7 to 10 mm/h) and 1 of 2 drop sizes (2.8 or 4.2 mm diameter) confirm a significant and systematic enhancement of air-water gas exchange by rainfall. The gas transfer velocities derived from our experiment were related to the kinetic energy flux calculated from the rain rate and drop size. The relationship obtained for mono-dropsize rain at the RSIF was extrapolated to natural rain using the kinetic energy flux of natural rain calculated from the Marshall-Palmer raindrop size distribution. Results of laboratory experiments at RSIF were compared to field observations made during a tropical rainstorm in Miami, Florida and show good agreement between laboratory and field data.

  3. Gas and liquid measurements in air-water bubbly flows

    SciTech Connect

    Zhou, X.; Doup, B.; Sun, X.

    2012-07-01

    Local measurements of gas- and liquid-phase flow parameters are conducted in an air-water two-phase flow loop. The test section is a vertical pipe with an inner diameter of 50 mm and a height of 3.2 m. The measurements are performed at z/D = 10. The gas-phase measurements are performed using a four-sensor conductivity probe. The data taken from this probe are processed using a signal processing program to yield radial profiles of the void fraction, bubble velocity, and interfacial area concentration. The velocity measurements of the liquid-phase are performed using a state-of-the-art Particle Image Velocimetry (PIV) system. The raw PIV images are acquired using fluorescent particles and an optical filtration device. Image processing is used to remove noise in the raw PIV images. The statistical cross correlation is introduced to determine the axial velocity field and turbulence intensity of the liquid-phase. Measurements are currently being performed at z/D = 32 to provide a more complete data set. These data can be used for computational fluid dynamic model development and validation. (authors)

  4. A Case Study on the Design of Learning Interfaces

    ERIC Educational Resources Information Center

    Perry, Gabriela Trindade; Schnaid, Fernando

    2012-01-01

    The design of educational software interfaces is a complex task, given its high domain dependency and multidisciplinary nature. It requires that teachers' knowledge and pedagogical beliefs be incorporated into the interface, posing a challenge to both teachers and designers, as they have to act as partners from the earliest phases of the process,…

  5. Effect of the β-propiolactone treatment on the adsorption and fusion of influenza A/Brisbane/59/2007 and A/New Caledonia/20/1999 virus H1N1 on a dimyristoylphosphatidylcholine/ganglioside GM3 mixed phospholipids monolayer at the air-water interface.

    PubMed

    Desbat, Bernard; Lancelot, Eloïse; Krell, Tino; Nicolaï, Marie-Claire; Vogel, Fred; Chevalier, Michel; Ronzon, Frédéric

    2011-11-15

    The production protocol of many whole cell/virion vaccines involves an inactivation step with β-propiolactone (BPL). Despite the widespread use of BPL, its mechanism of action is poorly understood. Earlier work demonstrated that BPL alkylates nucleotide bases, but its interaction with proteins has not been studied in depth. In the present study we use ellipsometry to analyze the influence of BPL treatment of two H1N1 influenza strains, A/Brisbane/59/2007 and A/New Caledonia/20/1999, which are used for vaccine production on an industrial scale. Analyses were conducted using a mixed lipid monolayer containing ganglioside GM3, which functions as the viral receptor. Our results show that BPL treatment of both strains reduces viral affinity for the mixed monolayer and also diminishes the capacity of viral domains to self-assemble. In another series of experiments, the pH of the subphase was reduced from 7.4 to 5 to provoke the pH-induced conformational change of hemagglutinin, which occurs following endocytosis into the endosome. In the presence of the native virus the pH decrease caused a reduction in domain size, whereas lipid layer thickness and surface pressure were increased. These observations are consistent with a fusion of the viral membrane with the lipid monolayer. Importantly, this fusion was not observed with adsorbed inactivated virus, which indicates that BPL treatment inhibits the first step of virus-membrane fusion. Our data also indicate that BPL chemically modifies hemagglutinin, which mediates the interaction with GM3. PMID:21981550

  6. Studies of interfaces and vapors with Optical Second Harmonic Generation

    SciTech Connect

    Mullin, C. S.

    1993-12-01

    Optical Second Harmonic Generation (SHG) has been applied to the study of soap-like molecules adsorbed to the water-air interface. By calibrating the signal from a soluble monolayer with that of an insoluble homolog, absolute measurements of the surface density could be obtained and related to the bulk concentration and surface tension. We could then demonstrate that the soluble surfactant forms a single monolayer at the interface. Furthermore, it deviates significantly from the ideal case in that its activity coefficients are far from 1, yet those coefficients remain constant over a broad range of surface pressures. We present evidence of a first-order phase transition taking place during the adsorption of this soluble monolayer. We consider the effects of the non-ideal behavior and the phase transition on the microscopic model of adsorption, and formulate an alternative to the Langmuir picture of adsorption which is just as simple, yet it can more easily allow for non-ideal behavior. The second half of this thesis considers the problem of SHG in bulk metal vapors. The symmetry of the vapor forbids SHG, yet it has been observed. We consider several models whereby the symmetry of the vapor is broken by the presence of the laser and compare their predictions to new observations we have made using a few-picosecond laser pulse. The two-lobed output beam profile shows that it is the vapor-plus-beam combination whose symmetry is important. The dependence on vapor pressure demonstrates the coherent nature of the radiation, while the dependence on buffer gas pressure hints at a change of the symmetry in time. The time-dependence is measured directly with a preliminary pump-probe measurement. The magnitude and intensity dependence of the signal are also measured. All but one of the models are eliminated by this comparison.

  7. 14 CFR 1274.926 - Clean Air-Water Pollution Control Acts.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 5 2012-01-01 2012-01-01 false Clean Air-Water Pollution Control Acts...-Water Pollution Control Acts. Clean Air-Water Pollution Control Acts July 2002 If this cooperative... Violating Facilities” published pursuant to 40 CFR 15.20. By acceptance of a cooperative agreement in...

  8. 14 CFR § 1274.926 - Clean Air-Water Pollution Control Acts.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 5 2014-01-01 2014-01-01 false Clean Air-Water Pollution Control Acts. Â...-Water Pollution Control Acts. Clean Air-Water Pollution Control Acts July 2002 If this cooperative... Violating Facilities” published pursuant to 40 CFR 15.20. By acceptance of a cooperative agreement in...

  9. 14 CFR 1274.926 - Clean Air-Water Pollution Control Acts.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 5 2013-01-01 2013-01-01 false Clean Air-Water Pollution Control Acts...-Water Pollution Control Acts. Clean Air-Water Pollution Control Acts July 2002 If this cooperative... Violating Facilities” published pursuant to 40 CFR 15.20. By acceptance of a cooperative agreement in...

  10. 14 CFR 1274.926 - Clean Air-Water Pollution Control Acts.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 5 2010-01-01 2010-01-01 false Clean Air-Water Pollution Control Acts. 1274.926 Section 1274.926 Aeronautics and Space NATIONAL AERONAUTICS AND SPACE ADMINISTRATION COOPERATIVE AGREEMENTS WITH COMMERCIAL FIRMS Other Provisions and Special Conditions § 1274.926 Clean Air-Water Pollution Control Acts. Clean...

  11. Surface potential of methyl isobutyl carbinol adsorption layer at the air/water interface.

    PubMed

    Phan, Chi M; Nakahara, Hiromichi; Shibata, Osamu; Moroi, Yoshikiyo; Le, Thu N; Ang, Ha M

    2012-01-26

    The surface potential (ΔV) and surface tension (γ) of MIBC (methyl isobutyl carbinol) were measured on the subphase of pure water and electrolyte solutions (NaCl at 0.02 and 2 M). In contrast to ionic surfactants, it was found that surface potential gradually increased with MIBC concentration. The ΔV curves were strongly influenced by the presence of NaCl. The available model in literature, in which surface potential is linearly proportional to surface excess, failed to describe the experimental data. Consequently, a new model, employing a partial charge of alcohol adsorption layer, was proposed. The new model predicted the experimental data consistently for MIBC in different NaCl solutions. However, the model required additional information for ionic impurity to predict adsorption in the absence of electrolyte. Such inclusion of impurities is, however, unnecessary for industrial applications. The modeling results successfully quantify the influence of electrolytes on surface potential of MIBC, which is critical for froth stability. PMID:22172075

  12. OXYGEN TRANSFER ACROSS THE AIR-WATER INTERFACE DUE TO NATURAL CONVECTION IN LAKES. (R825428)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  13. Photochemical Reactions at the Air-Water Interface in the Troposphere (Invited)

    NASA Astrophysics Data System (ADS)

    Hoffmann, M. R.; Kameel, F. R.; Colussi, A. J.

    2013-12-01

    Increasing awareness that isoprene, ISO, is only partially processed in the gas-phase has turned attention to its reactive uptake by fog, cloud and aerosol droplets. As a hydrophobic gas, ISO would preferentially partition to the surface rather than the bulk of aqueous media. Such media also contain dissolved O2 and water-soluble unsaturated organics, and support OH generation rates (from the solar photolysis of H2O2 dissolved therein) that are several orders of magnitude faster than in the gas-phase. Hence, ISO should be converted to heavier products rather than into the C4-C5 volatile compounds produced in the gas-phase. Here we substantiate such scenario by reporting that the λ > 305 nm photolysis of H2O2 in aqueous dilute ISO solutions yields C10H15OH species as primary products, whose formation both requires and is inhibited by O2. A minimum of seven C10H15OH isomers are resolved by reverse-phase high-performance liquid chromatography and detected as MH+ (m/z = 153) and MH+-18 (m/z = 135) signals by electrospray ionization mass spectrometry. Our findings are consistent with the addition of OH to ISO, followed by HO-ISO reactions with ISO (in competition with O2) leading to second generation HO(ISO)2 radicals that terminate as C10H15OH via β-H abstraction by O2. We show that a significant fraction of gas-phase olefins should be converted into less volatile species via this process on airborne wet particles.

  14. Crystal Perfection of Particle Monolayer at the Air-Water Interface.

    PubMed

    Shinotsuka, Kei; Kajita, Yasuhito; Hongo, Koki; Hatta, Yoshihisa

    2015-10-27

    Crystal growth in colloidal particle monolayers fabricated by Langmuir-Blodgett method on 4 in. sapphire wafers was investigated under the condition of two techniques, that is, ultrasonic annealing at 1.2 to 1.5 MHz and barrier-sway process at 0.2 to 0.5 Hz. Significant increases of the ordered area were obtained by the both techniques and more than 60 times growth was confirmed. The remaining crystal defects after the growth were categorized as grain boundary, vacancy, and line defect. Both techniques exhibited different features regarding the component ratio of the defects, and different mechanisms for the reorientation of particles are discussed. The driving force of these re-orientations is thought to be associated with the 2D Ostwald ripening of colloidal crystals. PMID:26434777

  15. Effect of cation enrichment on dipalmitoylphosphatidylcholine (DPPC) monolayers at the air-water interface.

    PubMed

    Adams, Ellen M; Casper, Clayton B; Allen, Heather C

    2016-09-15

    The effect of highly concentrated salt solutions of marine-relevant cations (Na(+), K(+), Mg(2+), and Ca(2+)) on Langmuir monolayers of dipalmitoylphosphatidylcholine (DPPC) was investigated by means of surface pressure-area isotherms, Brewster angle microscopy (BAM), and infrared reflection-absorption spectroscopy (IRRAS). It was found that monovalent cations and Mg(2+) have similar phase behavior, causing DPPC monolayers to expand, while Ca(2+) induces condensation. All cations disrupted the surface morphology at high cation concentration, resulting in decreased reflectivity from the monolayer. Monolayer refractive index was calculated from BAM image intensity in the liquid condensed phase and decreased with increasing cation concentration, which suggests that orientation of the alkyl chains change. Monovalent ions increase ordering of the alkyl chains, more than divalents, yet have little interaction with the DPPC headgroup. Mg(2+) induces gauche defects in the alkyl chain and increases headgroup hydration at low lipid coverage but increases chain ordering and dehydrates the headgroup at high lipid coverage. Ca(2+) orders alkyl chains and dehydrates the phosphate moiety, independent of lipid phase. At the highest salt concentration investigated, significant narrowing of the asymmetric PO2(-) vibrational mode occurs and is attributed to considerable dehydration of the DPPC headgroup. PMID:27322949

  16. Interaction of polyhedral oligomeric silsesquioxane containing epoxycyclohexyl groups with cholesterol at the air/water interface.

    PubMed

    Dopierała, Katarzyna; Maciejewski, Hieronim; Prochaska, Krystyna

    2016-04-01

    Binary mixtures of cholesterol and fully-condensed octakis[{2-(3,4-epoxycyclohexyl) etyl}dimethyl-silyloxy]octasilsesquioxane (OE-POSS) were characterized using Langmuir trough for obtaining surface pressure-area isotherms. The most characteristic feature of the mixed films is the presence of two collapse points on the isotherms. The first one is attributed to the collapse of less stable OE-POSS and it occurs at similar surface pressures for all compositions, while the second one corresponds to cholesterol collapse. Brewster angle microscopy observations confirmed the collapse behavior of the mixed film. Strong condensing effect was observed for the mean molecular areas dependence on cholesterol content in the film. Moreover, formation of microdomains of each component in the matrix of the other one was confirmed by BAM images. For the reasons of molecular structures and interactions a true mixed and homogenous film did not form in the systems considered. Phase separation was observed for all the compositions experimented. The lack of the interactions of OE-POSS with biomembrane components represented by cholesterol is beneficial for applications of OE-POSS in biomedical devices. PMID:26752210

  17. Thermal stability effects on the structure of the velocity field above an air-water interface

    NASA Technical Reports Server (NTRS)

    Papadimitrakis, Y. A.; Hsu, Y.-H. L.; Wu, J.

    1987-01-01

    Mean velocity and turbulence measurements are described for turbulent flows above laboratory water waves, under various wind and thermal stratification conditions. Experimental results, when presented in the framework of Monin-Obukhov (1954) similarity theory, support local scaling based on evaluation of stratification effects at the same nondimensional distance from the mean water surface. Such scaling allows an extension of application of the above theory to the outer region of the boundary layer. Throughout the fully turbulent region, ratios of mean velocity gradients, eddy viscosities, and turbulence intensities under nonneutral and neutral conditions correlate well with the parameter z/Lambda (Lambda being a local Obukhov length and z the vertical coordinate of the mean air flow) and show good agreement with established field correlations. The influence of stratification on the wind-stress coefficient can be estimated from an empirical relationship in terms of its value under neutral conditions and a bulk Richardson number.

  18. Forces Acting on Submillimeter Spheres at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Wang, Le-Feng; Liu, Lu; Xu, Hui-Chao; Rong, Wei-Bin; Sun, Li-Ning

    2015-11-01

    Not Available Supported by the National Natural Science Foundation of China under Grant No 61005072, and the Self-Planned Task of State Key Laboratory of Robotics and System under Grant Nos SKLRS201501A04 and SKLRS201301A01.

  19. Corrosion of copper-based materials in gamma-irradiated air/water vapor systems

    SciTech Connect

    Reed, D.T.

    1992-04-01

    Experiments were performed to investigate the atmospheric corrosion of copper-based materials in an irradiated air/water vapor system. The three materials investigated were oxygen-free copper (CDA-102), 7% aluminum-bronze (CDA-613), and 70-30 cupronickel (CDA-715). To support the corrosion studies, a number of irradiation studies were performed to characterize the gas phase radiation chemistry of the system. Both copper oxide and nitrate phases were identified as corrosion products depending on the dose rate, humidity and temperature. Uniform corrosion rates increased with temperature, humidity, and dose rate. A clear tie between the radiolytic products generated in the gas phase and the corrosion observed was established.

  20. Corrosion of copper-based materials in gamma-irradiated air/water vapor systems

    SciTech Connect

    Reed, D.T.

    1992-01-01

    Experiments were performed to investigate the atmospheric corrosion of copper-based materials in an irradiated air/water vapor system. The three materials investigated were oxygen-free copper (CDA-102), 7% aluminum-bronze (CDA-613), and 70-30 cupronickel (CDA-715). To support the corrosion studies, a number of irradiation studies were performed to characterize the gas phase radiation chemistry of the system. Both copper oxide and nitrate phases were identified as corrosion products depending on the dose rate, humidity and temperature. Uniform corrosion rates increased with temperature, humidity, and dose rate. A clear tie between the radiolytic products generated in the gas phase and the corrosion observed was established.

  1. Sea breeze forcing of estuary turbulence and air-water CO2 exchange

    NASA Astrophysics Data System (ADS)

    Orton, Philip M.; McGillis, Wade R.; Zappa, Christopher J.

    2010-07-01

    The sea breeze is often a dominant meteorological feature at the coastline, but little is known about its estuarine impacts. Measurements at an anchored catamaran and meteorological stations along the Hudson River and New York Bay estuarine system are used to illustrate some basic characteristics and impacts of the feature. The sea breeze propagates inland, arriving in phase with peak solar forcing at seaward stations, but several hours later at up-estuary stations. Passage of the sea breeze front raises the water-to-air CO2 flux by 1-2 orders of magnitude, and drives turbulence comparable to spring tide levels in the upper meter of the water column, where most primary productivity occurs in this highly turbid system. Modeling and observational studies often use remotely-measured winds to compute air-water fluxes (e.g., momentum, CO2), and this leads to a factor of two flux error on sea breeze days during the study.

  2. Interfacial structures of confined air-water two-phase bubbly flow

    SciTech Connect

    Kim, S.; Ishii, M.; Wu, Q.; McCreary, D.; Beus, S.G.

    2000-08-01

    The interfacial structure of the two-phase flows is of great importance in view of theoretical modeling and practical applications. In the present study, the focus is made on obtaining detailed local two-phase parameters in the air-water bubbly flow in a rectangular vertical duct using the double-sensor conductivity probe. The characteristic wall-peak is observed in the profiles of the interracial area concentration and the void fraction. The development of the interfacial area concentration along the axial direction of the flow is studied in view of the interfacial area transport and bubble interactions. The experimental data is compared with the drift flux model with C{sub 0} = 1.35.

  3. Ballistic Electron Emission Microscopy Studies of Ferromagnet - Semiconductor Interfaces

    NASA Astrophysics Data System (ADS)

    Mather, P. G.; Perrella, A. C.; Yurtsever, A.; Buhrman, R. A.

    2004-03-01

    Devices that employ spin as well as charge effects have been the subjects of extensive study recently. The magnetic tunneling transistor (1) is one important device that demonstrates an electrical means of injecting spin-polarized electrons into a semiconductor. A Schottky barrier lies at the heart of the device, and a high quality spatially homogenous and uniform barrier formed on GaAs is highly desirable. We have used ballistic electron emission microscopy (BEEM) to study CoFe, Fe and permalloy deposited on a GaAs substrate to give nanometer resolved evaluation of hot electron transport through the films and across the Schottky barrier. All films give a homogenous, uniform barrier as compared with evaporated Au/GaAs and Ag/GaAs interfaces. We will report on BEEM measurements of the hot electron transfer ratio across the Schottky barrier for the different ferromagnetic materials, and on the energy and spin-dependent hot electron attenuation lengths of the CoFe, Fe, and permalloy films. (1) Sebastiaan van Dijken, Xin Jiang, Stuart S. P. Parkin, APL, 80, 3364.

  4. Air-water oxygen exchange in a large whitewater river

    USGS Publications Warehouse

    Hall, Robert O.; Kennedy, Theodore A.; Rosi-Marshall, Emma J.

    2012-01-01

    Air-water gas exchange governs fluxes of gas into and out of aquatic ecosystems. Knowing this flux is necessary to calculate gas budgets (i.e., O2) to estimate whole-ecosystem metabolism and basin-scale carbon budgets. Empirical data on rates of gas exchange for streams, estuaries, and oceans are readily available. However, there are few data from large rivers and no data from whitewater rapids. We measured gas transfer velocity in the Colorado River, Grand Canyon, as decline in O2 saturation deficit, 7 times in a 28-km segment spanning 7 rapids. The O2 saturation deficit exists because of hypolimnetic discharge from Glen Canyon Dam, located 25 km upriver from Lees Ferry. Gas transfer velocity (k600) increased with slope of the immediate reach. k600 was -1 in flat reaches, while k600 for the steepest rapid ranged 3600-7700 cm h-1, an extremely high value of k600. Using the rate of gas exchange per unit length of water surface elevation (Kdrop, m-1), segment-integrated k600 varied between 74 and 101 cm h-1. Using Kdrop we scaled k600 to the remainder of the Colorado River in Grand Canyon. At the scale corresponding to the segment length where 80% of the O2 exchanged with the atmosphere (mean length = 26.1 km), k600 varied 4.5-fold between 56 and 272 cm h-1 with a mean of 113 cm h-1. Gas transfer velocity for the Colorado River was higher than those from other aquatic ecosystems because of large rapids. Our approach of scaling k600 based on Kdrop allows comparing gas transfer velocity across rivers with spatially heterogeneous morphology.

  5. Statistical characterization of the optical interaction at a supercavitating interface

    NASA Astrophysics Data System (ADS)

    Walters, Gage; Kane, Tim; Jefferies, Rhett; Antonelli, Lynn

    2016-05-01

    The optical characteristics of an air/water interface have been widely studied for natural interface formations. However, the creation and management of artificial cavities creates a complicated interaction of gas and liquid that makes optical sensing and communication through the interface challenging. A ventilated cavity can reduce friction in underwater vehicles, but the resulting bubble drastically impedes optical and acoustic communication propagation. The complicated interaction at the air/water boundary yields surface waves and turbulence that make modeling and compensating of the optical properties difficult. Our experimental approach uses a narrow laser beam to probe the surface of the interface and measure the beam deflection and lensing effects. Using a vehicle model with a cavitator in a water tunnel, a laser beam is propagated outward from the model through the boundary and projected onto a target grid. The beam projection is captured using a high-speed camera, allowing us to measure and analyze beam shape and deflection. This approach has enabled us to quantify the temporal and spatial periodic variations in the beam propagation through the cavity boundary and fluid.

  6. Experimental study of an isochorically heated heterogeneous interface. A progress report

    SciTech Connect

    Fernandez, Juan Carlos

    2015-08-20

    Outline of the presentation: Studying possible mix / interface motion between heterogeneous low/high Z interfaces driven by 2-fluid or kinetic plasma effects (Heated to few eV, Sharp (sub µm) interface); Isochoric heating to initialize interface done with Al quasimonoenergetic ion beams on Trident; Have measured isochoric heating in individual materials intended for compound targets; Fielded experiments on Trident to measure interface motion (Gold-diamond, tin-aluminium); Measured heated-sample temperature with streaked optical pyrometry (SOP) (UT Austin led (research contract), SOP tests → heating uniformity Vs thickness on Al foils. Results are being analyzed.

  7. High-energy photoemission studies of oxide interfaces

    NASA Astrophysics Data System (ADS)

    Claessen, Ralph

    2015-03-01

    The interfaces of complex oxide heterostructures can host novel quantum phases not existing in the bulk of the constituents, with the high-mobility 2D electron system (2DES) in LaAlO3/SrTiO3 (LAO/STO) representing a prominent example. Despite extensive research the origin of the 2DES and its unusual properties - including the supposed coexistence of superconductivity and ferromagnetism - are still a matter of intense debate. Photoelectron spectroscopy, recently extended into the soft (SX-ARPES) and hard (HAXPES) X-ray regime, is a powerful method to provide detailed insight into the electronic structure of these heterostructures and, in particular, of the buried interface. This includes the identification of the orbital character of the 2DES as well as the determination of vital band structure information, such as band alignment, band bending, and even k-resolved band dispersions and Fermi surface topology. Moreover, resonant photoemission at the Ti L-edge reveals the existence of two different species of Ti 3d states, localized and itinerant, which can be distinguished and identified by their different resonance behavior. The role of oxygen vacancies is studied by controlled in-situ oxidation, which allows us to vary the composition from fully stoichiometric to strongly O-deficient. By comparison to free STO surfaces we can thus demonstrate that the metallicity of the heteointerfaces is intrinsic, i . e . it persists even in the absence of O defects. I will discuss our photoemission results on LAO/STO heterostructures in both (100) and (111) orientation as well as on the related system γ-Al2O3/STO(100), which also hosts a 2DES with an even higher mobility. Work in collaboration with J. Mannhart (MPI-FKF, Stuttgart), N. Pryds (TU Denmark), G. Rijnders (U Twente), S. Suga (U Osaka), M. Giorgoi (BESSY, HZB), W. Drube (DESY Photon Science), V.N. Strocov (Swiss Light Source), J. Denlinger (Advanced Light Source, LBNL), and T.-L. Lee (Diamond Light Source). Support by

  8. Experimental Studies of Nanobubbles at Solid-Water Interfaces

    NASA Astrophysics Data System (ADS)

    Zhang, Xuehua

    2013-11-01

    When a hydrophobic substrate is in contact with water, gas bubbles thinner than 100 nm can form at the interface and stay for long time under ambient conditions. These nanobubbles have significant influence on a range of interfacial processes. For example, they give rise to hydrodynamic slip on the boundary, initiate the rupture of thin liquid films, facilitate the long-ranged interactions between hydrophobic surfaces, and enhance the attachment of a macroscopic bubble to the substrate. Experimentally, it is nontrivial to characterize such small fragile bubbles and unravel their fundamental physical properties. Based on our established procedure for the nanobubble formation, we have systematically studied the formation, stability and response of nanobubbles to external fields (e.g. sonication, pressure drop and temperature rise). By following the bubble morphology by atomic force microscopy, we show that the loss or gain of the nanobubble volume is achieved mainly by the change in the bubble height. The pinning on the three-phase boundary has significant implication on the properties of nanobubbles under various conditions. This talk will cover the effects of the substrate structures on the nanobubble formation, and the response of nanobubbles to the gas dissolution, the temperature increase, the extended gentle ultrasound or the substantial pressure drop in the environment. We acknowledge the support from Australian Research Council (FFT120100473).

  9. Ultrafast optical studies of surface reaction processes at semiconductor interfaces

    SciTech Connect

    Miller, R.J.D.

    1993-03-01

    Rectifying properties of semiconductor liquid junctions make them a simple system for converting and storing optical energy. However, interfacial electron or hole carrier transfer and competing non-radiative (energy loss) channels are not well understood at surfaces. This research has explored the use of three optical techniques, Surface Space Charge Electrooptic Sampling, Surface Restricted Transient Grating Spectroscopy, and Femtosecond Optical Kerr Spectroscopy (OKE) to obtain time evolution of the surface spatial distribution of photogenerated charge carriers, photocarrier population dynamics at semiconductor interfaces, and solvent modes responsible for charge localization and separation. These studies have shown that carriers arrive at GaAs(100) surfaces on the hundred femtosecond time scale. Improvements in time resolution, using surface grating spectroscopy, have shown interfacial hole transfer is occurring on the picosecond time scale. The OKE approach to solvent dynamics has determined the response of water to a field is multiexpontential with a major relaxation component of 100 femtoseconds. The observed interfacial hole transfer to Se[sup [minus]2] acceptors is occurring on this same time scale. This observation illustrates charge transfer processes can occur in the strong electronic coupling limit and can be competitive with carrier thermalization.

  10. Air-water CO2 exchange in five hypereutrophic lakes in Bangalore, India

    NASA Astrophysics Data System (ADS)

    Singh, G.; Ghosh, P.; Bala, G.; Bastviken, D.

    2014-12-01

    Inland water bodies play a significant role in terrestrial carbon cycling, rather than being just conduits for the transport of terrestrial carbon to the oceans. Recent syntheses estimate that freshwaters emit substantial amounts of CO2 (1.4 Pg C yr-1) (Tranvik et al. 2009) and CH4 (0.65 Pg C yr-1) (Bastviken et al. 2011), which are similar in magnitude to the global terrestrial carbon sink (2.5 ± 1.7 Pg C yr-1) (IPCC 2013). However, eutrophic waters, which constitute the majority of the global freshwater supply (ILEC/UNEP 1994, Liu et al. 2012, Carpenter et al. 1998), are vastly underrepresented in these estimates. These waters, due to high primary productivity leading to CO2 undersaturation, can act as sinks rather than sources of CO2, thus reversing the role of lakes in the carbon cycle (Balmer and Downing 2011, Pacheco et al. 2013). We are investigating the air-water CO2 exchange of five hypereutrophic lakes in urban Bangalore using a novel Non-Dispersive Infrared (NDIR)-based CO2 sensor installed in flux chambers that can be used to measure CO2 exchange in lakes in situ. This work is a part of a larger study called Bangalore Carbon Mapping Study that aims to track the spatial flows of carbon in an urban area of a developing country. Preliminary observations reveal that these lakes absorb CO2 during the photosynthetic hours, at an average rate of 3.4 mg C m-2 h-1. The ongoing study will characterize the complete diurnal cycle of CO2 exchange, its variation over different seasons, and its relationships with various limnological and catchment characteristics. The flux estimates thus produced will also be compared with those predicted by the current models for air-water gas exchange based on wind speed.

  11. Reynolds and froude number effect on the flow past an interface-piercing circular cylinder

    NASA Astrophysics Data System (ADS)

    Koo, Bonguk; Yang, Jianming; Yeon, Seong Mo; Stern, Frederick

    2014-09-01

    The two-phase turbulent flow past an interface-piercing circular cylinder is studied using a high-fidelity orthogonal curvilinear grid solver with a Lagrangian dynamic subgrid-scale model for large-eddy simulation and a coupled level set and volume of fluid method for air-water interface tracking. The simulations cover the sub-critical and critical and post critical regimes of the Reynolds and sub and super-critical Froude numbers in order to investigate the effect of both dimensionless parameters on the flow. Significant changes in flow features near the air-water interface were observed as the Reynolds number was increased from the sub-critical to the critical regime. The interface makes the separation point near the interface much delayed for all Reynolds numbers. The separation region at intermediate depths is remarkably reduced for the critical Reynolds number regime. The deep flow resembles the single-phase turbulent flow past a circular cylinder, but includes the effect of the free-surface and the limited span length for sub-critical Reynolds numbers. At different Froude numbers, the air-water interface exhibits significantly changed structures, including breaking bow waves with splashes and bubbles at high Froude numbers. Instantaneous and mean flow features such as interface structures, vortex shedding, Reynolds stresses, and vorticity transport are also analyzed. The results are compared with reference experimental data available in the literature. The deep flow is also compared with the single-phase turbulent flow past a circular cylinder in the similar ranges of Reynolds numbers. Discussion is provided concerning the limitations of the current simulations and available experimental data along with future research

  12. Near-surface physics during convection affecting air-water gas transfer

    NASA Astrophysics Data System (ADS)

    Fredriksson, S. T.; Arneborg, L.; Nilsson, H.; Handler, R. A.

    2016-05-01

    The gas flux at the water surface is affected by physical processes including turbulence from wind shear, microscale wave breaking, large-scale breaking, and convection due to heat loss at the surface. The main route in the parameterizations of the gas flux has been to use the wind speed as a proxy for the gas flux velocity, indirectly taking into account the dependency of the wind shear and the wave processes. The interest in the contributions from convection processes has increased as the gas flux from inland waters (with typically lower wind and sheltered conditions) now is believed to play a substantial role in the air-water gas flux budget. The gas flux is enhanced by convection through the mixing of the mixed layer as well as by decreasing the diffusive boundary layer thickness. The direct numerical simulations performed in this study are shown to be a valuable tool to enhance the understanding of this flow configuration often present in nature.

  13. Measuring Air-Water Interfacial Area via the Interfacial Partitioning Tracer Test Method

    NASA Astrophysics Data System (ADS)

    El Ouni, A.; Zhong, H.; Mainhagu, J.; Araujo, J. B.; Brusseau, M. L.

    2012-12-01

    Interfacial partitioning tracer tests (IPTT) are one method available for measuring air-water interfacial area (Aa-w). Two variations of the aqueous IPTT method are compared. One involves the standard approach comprising tracer injection under steady unsaturated-flow conditions with a uniform water-saturation distribution within the column. The other involves tracer injection under steady saturated-flowconditions in the presence of trapped residual air. Sodium dodecylbezenesulfonate (SDBS) and pentafluorobenzoic acid (PFBA) were used as the partitioning andnonreactive tracers, respectively. A sandy soil with a median grain diameter of 0.234 mm was used as the porous medium. Initial water saturation, Sw,was approximately 80%. Water saturation was monitored gravimetrically during the experiments. The results of the experiments will be assessed and compared to those of prior studies.

  14. Performance of a combined three-hole conductivity probe for void fraction and velocity measurement in air-water flows

    NASA Astrophysics Data System (ADS)

    Borges, João Eduardo; Pereira, Nuno H. C.; Matos, Jorge; Frizell, Kathleen H.

    2010-01-01

    The development of a three-hole pressure probe with back-flushing combined with a conductivity probe, used for measuring simultaneously the magnitude and direction of the velocity vector in complex air-water flows, is described in this paper. The air-water flows envisaged in the current work are typically those occurring around the rotors of impulse hydraulic turbines (like the Pelton and Cross-Flow turbines), where the flow direction is not known prior to the data acquisition. The calibration of both the conductivity and three-hole pressure components of the combined probe in a rig built for the purpose, where the probe was placed in a position similar to that adopted for the flow measurements, will be reported. After concluding the calibration procedure, the probe was utilized in the outside region of a Cross-Flow turbine rotor. The experimental results obtained in the present study illustrate the satisfactory performance of the combined probe, and are encouraging toward its use for characterizing the velocity field of other complex air-water flows.

  15. Study of Composite Interface Fracture and Crack Growth Monitoring Using Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Bily, Mollie A.; Kwon, Young W.; Pollak, Randall D.

    2010-08-01

    Interface fracture of woven fabric composite layers was studied using Mode II fracture testing. Both carbon fiber and E-glass fiber composites were used with a vinyl ester resin. First, the single-step cured (i.e., co-cured) composite interface strength was compared to that of the two-step cured interface as used in the scarf joint technique. The results showed that the two-step cured interface was as strong as the co-cured interface. Carbon nanotubes were then applied to the composite interface using two-step curing, and then followed by Mode II fracture testing. The results indicated a significant improvement of the interface fracture toughness due to the dispersed carbon nanotube layer for both carbon fiber and E-glass fiber composites. The carbon nanotube layer was then evaluated as a means to monitor crack growth along the interface. Because carbon nanotubes have very high electrical conductivity, the electrical resistance was measured through the interface as a crack grew, thus disrupting the carbon nanotube network and increasing the resistance. The results showed a linear relationship between crack length and interface resistance for the carbon fiber composites, and allowed initial detection of failure in the E-glass fiber composites. This study demonstrated that the application of carbon nanotubes along a critical composite interface not only improves fracture properties but can also be used to detect and monitor interfacial damage.

  16. Discrete Element study of granular material - Bumpy wall interface behavior

    NASA Astrophysics Data System (ADS)

    El Cheikh, Khadija; Rémond, Sébastien; Pizette, Patrick; Vanhove, Yannick; Djelal, Chafika

    2016-09-01

    This paper presents a DEM study of a confined granular material sheared between two parallel bumpy walls. The granular material consists of packed dry spherical particles. The bumpiness is modeled by spheres of a given diameter glued on horizontal planes. Different bumpy surfaces are modeled by varying diameter or concentration of glued spheres. The material is sheared by moving the two bumpy walls at fixed velocity. During shear, the confining pressure applied on each bumpy wall is controlled. The effect of wall bumpiness on the effective friction coefficient and on the granular material behavior at the bumpy walls is reported for various shearing conditions. For given bumpiness and confining pressure that we have studied, it is found that the shear velocity does not affect the shear stress. However, the effective friction coefficient and the behavior of the granular material depend on the bumpiness. When the diameter of the glued spheres is larger than about the average grains diameter of the medium, the latter is uniformly sheared and the effective friction coefficient remains constant. For smaller diameters of the glued spheres, the effective friction coefficient increases with the diameter of glued spheres. The influence of glued spheres concentration is significant only for small glued spheres diameters, typically half of average particle diameter of the granular material. In this case, increasing the concentration of glued spheres leads to a decrease in effective friction coefficient and to shear localization at the interface. For different diameters and concentrations of glued spheres, we show that the effect of bumpiness on the effective friction coefficient can be characterized by the depth of interlocking.

  17. Positron annihilation lifetime study of interfaces in ternary polymer blends

    NASA Astrophysics Data System (ADS)

    Meghala, D.; Ramya, P.; Pasang, T.; Raj, J. M.; Ranganathaiah, C.; Williams, J. F.

    2013-06-01

    A new method based on positron lifetime spectroscopy is developed to characterize individual interfaces in ternary polymer blends and hence determine the composition dependent miscibility level. The method owes its origin to the Kirkwood-Risemann-Zimm (KRZ) model for the evaluation of the hydrodynamic interaction parameters (αij) which was used successfully for a binary blend with a single interface. The model was revised for the present work for ternary polymer blends to account for three interfaces. The efficacy of this method is shown for two ternary blends namely poly(styrene-co-acrylonitrile)/poly (ethylene-co-vinylacetate)/poly(vinyl chloride) (SAN/EVA/PVC) and polycaprolactone /poly(styrene-co-acrylonitrile)/poly(vinyl chloride) (PCL/SAN/PVC) at different compositions. An effective hydrodynamic interaction parameter, αeff, was introduced to predict the overall miscibility of ternary blends.

  18. Kinetic studies of the sucrose adsorption onto an alumina interface

    NASA Astrophysics Data System (ADS)

    Singh, Kaman; Mohan, Sudhanshu

    2004-01-01

    An account is given of an experimental kinetic study of adsorption of analar reagent sucrose (ARS) onto an alumina interface spectrometrically ( λmax=570 nm) at pH 8.0 and at room temperature. The adsorption isotherm is a typical Langmuirian isotherm (S-type) and adsorption parameters have been deduced according to the Langmuir's model. The adsorption coefficient evaluated from the Langmuir's equation was found to be 2.52×10 2 l mol -1. Adsorption mechanism has been interpreted on the basis of metal-saccharide interaction as found in organometallic compounds and interaction due to negatively charged ends on the disaccharide molecules and positively charge groups on the surface on alumina which depends on the pH value. The effects of variation in experimental conditions of the adsorption system have also been investigated. The adsorption exhibited a typical response to the pH effect and on going towards the PZC the net charge decreases and any reaction making dependence on charge and maximum adsorption (amount) was found near the isoelectric point of alumina (pH 9.0). The presence of ions like Cl -, SO 42- and PO 43- affect the adsorbed amount quantitatively and it seems that these anions compete with sucrose for the positively charged surface sites. The addition of similar concentration of cations was found to reduce the adsorbed amount. The temperature was found to have an inverse effect on adsorption. The additions of catonic and anionic detergents influence both the adsorbed amount and the adsorption rate. The thermodynamics of the titled adsorption model indicates the spontaneous and exothermic nature. The negative value of entropy is an indication of probability of favorable and complex nature of the adsorption.

  19. Study of lumineers' interfaces by means of optical coherence tomography

    NASA Astrophysics Data System (ADS)

    de Andrade Borges, Erica; Fernandes Cassimiro-Silva, Patrícia; Osório Fernandes, Luana; Leônidas Gomes, Anderson Stevens

    2015-06-01

    OCT has been used to evaluate dental materials, and is employed here to evaluate lumineers for the first time. Lumineers are used as esthetical indirect restoration, and after wearing and aging, several undesirable features such as gaps, bubbles and mismatch can appear in which would only be seen by invasive analysis. The OCT (spectral domain SD-OCT, 930nm central wavelength) was used to evaluate noninvasively the lumineer- cement-tooth interface. We analyzed 20 specimens of lumineers-teeth that were prepared in bovine teeth and randomly allocated in 4 experimental groups (n=5) with two different cementation techniques and two different types of cementing agent (RelyX U200 and RelyX Veneer, 3M ESPE, with the adhesive recommended by the manufacture). The lumineers were made of lithium disilicate and obtained using a vacuum injection technique. The analysis was performed by using 2D and 3D OCT images, obtained before and after cementing and the thermal cycling process to simulate thermal stress in a oral cavity. Initial measurements showed that the SD-OCT was able to see through the 500μm thick lumineer, as delivered by the fabricant, and internal stress was observed. Failures were found in the cementing process and also after ageing simulation by thermal cycling. The adhesive failures as bubbles, gaps and degradation of the cementation line are the natural precursors of other defects reported by several studies of clinical follow-up (detachments, fractures and cracks). Bubble dimensions ranging from 146 μm to 1427 μm were measured and the OCT was validated as an investigative and precise tool for evaluation of the lumineer-cement-tooth.

  20. A CRITICAL ASSESSMENT OF ELEMENTAL MERCURY AIR/WATER EXCHANGE PARTNERS

    EPA Science Inventory

    Although evasion of elemental mercury from aquatic systems can significantly deplete net mercury accumulation resulting from atmospheric deposition, the current ability to model elemental mercury air/water exchange is limited by uncertainties in our understanding of all gaseous a...

  1. XPS Study of Oxide/GaAs and SiO2/Si Interfaces

    NASA Technical Reports Server (NTRS)

    Grunthaner, F. J.; Grunthaner, P. J.; Vasquez, R. P.; Lewis, B. F.; Maserjian, J.; Madhukar, A.

    1982-01-01

    Concepts developed in study of SiO2/Si interface applied to analysis of native oxide/GaAs interface. High-resolution X-ray photoelectron spectroscopy (XPS) has been combined with precise chemical-profiling technique and resolution-enhancement methods to study stoichiometry of transitional layer. Results are presented in report now available.

  2. Feasibility study for future implantable neural-silicon interface devices.

    PubMed

    Al-Armaghany, Allann; Yu, Bo; Mak, Terrence; Tong, Kin-Fai; Sun, Yihe

    2011-01-01

    The emerging neural-silicon interface devices bridge nerve systems with artificial systems and play a key role in neuro-prostheses and neuro-rehabilitation applications. Integrating neural signal collection, processing and transmission on a single device will make clinical applications more practical and feasible. This paper focuses on the wireless antenna part and real-time neural signal analysis part of implantable brain-machine interface (BMI) devices. We propose to use millimeter-wave for wireless connections between different areas of a brain. Various antenna, including microstrip patch, monopole antenna and substrate integrated waveguide antenna are considered for the intra-cortical proximity communication. A Hebbian eigenfilter based method is proposed for multi-channel neuronal spike sorting. Folding and parallel design techniques are employed to explore various structures and make a trade-off between area and power consumption. Field programmable logic arrays (FPGAs) are used to evaluate various structures. PMID:22254974

  3. TEM and XPS studies on CdS/CIGS interfaces

    NASA Astrophysics Data System (ADS)

    Han, Jun-feng; Liao, Cheng; Cha, Li-mei; Jiang, Tao; Xie, Hua-mu; Zhao, Kui; Besland, M.-P.

    2014-12-01

    Copper indium gallium selenide (CIGS) was deposited by metallic precursors sputtering and subsequently submitted to a selenization process. The upper CdS layers were deposited by chemical bath deposition (CBD) technique. The CdS/CIGS interfaces were investigated by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). As checked by XPS analysis, the CIGS surface exhibited a hydroxide-terminated CdSe layer when treated with Cd Partial Electrolyte solution (Cd PE). Its thickness was roughly estimated to several nanometers. A 100 nm thick CdS layer was deposited onto CIGS surface. The TEM images revealed a clear and sharp interface between CdS and CIGS. XPS analysis showed a CIGS surface covered by a pinhole free and homogeneous CdS layer. XPS depth profile measurement of the CdS/CIGS interface did not evidence elemental inter-diffusion between the CIGS and CdS layers, in very good agreement with TEM observations.

  4. Interaction of monovalent ions with the water liquid-vapor interface - A molecular dynamics study

    NASA Technical Reports Server (NTRS)

    Wilson, Michael A.; Pohorille, Andrew

    1991-01-01

    Results of molecular dynamics calculations are presented for a series of ions at infinite dilution near the water liquid-vapor interface. The free energies of ion transfer from the bulk to the interface are discussed, as are the accompanying changes of water structure at the surface and ion mobilities as a function of their proximity to the interface. It is shown that simple dielectric models do not provide an accurate description of ions at the water surface. The results of the study should be useful in the development of better models incorporating the shape and molecular structure of the interface.

  5. First-principles study on oxidation of Ge and its interface electronic structures

    NASA Astrophysics Data System (ADS)

    Ono, Tomoya; Saito, Shoichiro; Iwase, Shigeru

    2016-08-01

    We review a series of first-principles studies on the defect generation mechanism and electronic structures of the Ge/GeO2 interface. Several experimental and theoretical studies proved that Si atoms at the Si/SiO2 interface are emitted to release interface stress. In contrast, total-energy calculation reveals that Ge atoms at the Ge/GeO2 interface are hardly emitted, resulting in the low trap density. Even if defects are generated, those at the Ge/GeO2 interface are found to behave differently from those at the Si/SiO2 interface. The states attributed to the dangling bonds at the Ge/GeO2 interface lie below the valence-band maximum of Ge, while those at the Si/SiO2 interface generate the defect state within the band gap of Si. First-principles electron-transport calculation elucidates that this characteristic behavior of the defect states is relevant to the difference in the leakage current through the Si/SiO2 and Ge/GeO2 interfaces.

  6. Application of a laser Doppler vibrometer for air-water to subsurface signature detection

    NASA Astrophysics Data System (ADS)

    Land, Phillip; Roeder, James; Robinson, Dennis; Majumdar, Arun

    2015-05-01

    There is much interest in detecting a target and optical communications from an airborne platform to a platform submerged under water. Accurate detection and communications between underwater and aerial platforms would increase the capabilities of surface, subsurface, and air, manned and unmanned vehicles engaged in oversea and undersea activities. The technique introduced in this paper involves a Laser Doppler Vibrometer (LDV) for acousto-optic sensing for detecting acoustic information propagated towards the water surface from a submerged platform inside a 12 gallon water tank. The LDV probes and penetrates the water surface from an aerial platform to detect air-water surface interface vibrations caused by an amplifier to a speaker generating a signal generated from underneath the water surface (varied water depth from 1" to 8"), ranging between 50Hz to 5kHz. As a comparison tool, a hydrophone was used simultaneously inside the water tank for recording the acoustic signature of the signal generated between 50Hz to 5kHz. For a signal generated by a submerged platform, the LDV can detect the signal. The LDV detects the signal via surface perturbations caused by the impinging acoustic pressure field; proving a technique of transmitting/sending information/messages from a submerged platform acoustically to the surface of the water and optically receiving the information/message using the LDV, via the Doppler Effect, allowing the LDV to become a high sensitivity optical-acoustic device. The technique developed has much potential usage in commercial oceanography applications. The present work is focused on the reception of acoustic information from an object located underwater.

  7. Water at an electrochemical interface - a simulation study

    SciTech Connect

    Willard, Adam; Reed, Stewart; Madden, Paul; Chandler, David

    2008-08-22

    The results of molecular dynamics simulations of the properties of water in an aqueous ionic solution close to an interface with a model metallic electrode are described. In the simulations the electrode behaves as an ideally polarizable hydrophilic metal, supporting image charge interactions with charged species, and it is maintained at a constant electrical potential with respect to the solution so that the model is a textbook representation of an electrochemical interface through which no current is passing. We show how water is strongly attracted to and ordered at the electrode surface. This ordering is different to the structure that might be imagined from continuum models of electrode interfaces. Further, this ordering significantly affects the probability of ions reaching the surface. We describe the concomitant motion and configurations of the water and ions as functions of the electrode potential, and we analyze the length scales over which ionic atmospheres fluctuate. The statistics of these fluctuations depend upon surface structure and ionic strength. The fluctuations are large, sufficiently so that the mean ionic atmosphere is a poor descriptor of the aqueous environment near a metal surface. The importance of this finding for a description of electrochemical reactions is examined by calculating, directly from the simulation, Marcus free energy profiles for transfer of charge between the electrode and a redox species in the solution and comparing the results with the predictions of continuum theories. Significant departures from the electrochemical textbook descriptions of the phenomenon are found and their physical origins are characterized from the atomistic perspective of the simulations.

  8. Atomic-Scale Studies of Defect Interactions with Homo- and Heterophase Interfaces

    NASA Astrophysics Data System (ADS)

    Martínez, Enrique; Uberuaga, Blas P.; Beyerlein, Irene J.

    2016-04-01

    Interfaces are planar metastable defects with singular features capable of controlling diverse material properties, including mechanical response and the microstructure evolution in materials under irradiation. This ability of interfaces to dictate the material response resides inherently in their atomic structure, which controls the interactions of dislocations as well as point and defect clusters with the interface. We recently showed how dislocations nucleated from defect clusters interact with a heterophase interface in Cu-Nb layered composites. We also showed how the ability of the interface to absorb vacancy clusters depends on the atomic structure at the interface. Herein, we elaborate on the effect of the atomic structure on the ability of the interface to absorb dislocations as well as vacancy and self-interstitial defect clusters. We study a physical-vapor-deposited Kurdjumov-Sachs orientation in a Cu-Nb interface and an asymmetric Σ 11 grain boundary in pure Cu. On the one hand, the manner in which dislocations react with the interface depends on the misfit dislocation arrangement, which substantially differs between these two cases. On the other hand, vacancy and self-interstitial clusters are absorbed similarly upon interaction with both structures.

  9. Atomic-Scale Studies of Defect Interactions with Homo- and Heterophase Interfaces

    NASA Astrophysics Data System (ADS)

    Martínez, Enrique; Uberuaga, Blas P.; Beyerlein, Irene J.

    2016-06-01

    Interfaces are planar metastable defects with singular features capable of controlling diverse material properties, including mechanical response and the microstructure evolution in materials under irradiation. This ability of interfaces to dictate the material response resides inherently in their atomic structure, which controls the interactions of dislocations as well as point and defect clusters with the interface. We recently showed how dislocations nucleated from defect clusters interact with a heterophase interface in Cu-Nb layered composites. We also showed how the ability of the interface to absorb vacancy clusters depends on the atomic structure at the interface. Herein, we elaborate on the effect of the atomic structure on the ability of the interface to absorb dislocations as well as vacancy and self-interstitial defect clusters. We study a physical-vapor-deposited Kurdjumov-Sachs orientation in a Cu-Nb interface and an asymmetric Σ 11 grain boundary in pure Cu. On the one hand, the manner in which dislocations react with the interface depends on the misfit dislocation arrangement, which substantially differs between these two cases. On the other hand, vacancy and self-interstitial clusters are absorbed similarly upon interaction with both structures.

  10. Air-water CO2 outgassing in the Lower Lakes (Alexandrina and Albert, Australia) following a millennium drought.

    PubMed

    Li, Siyue; Bush, Richard T; Ward, Nicholas J; Sullivan, Leigh A; Dong, Fangyong

    2016-01-15

    Lakes are an important source and sink of atmospheric CO2, and thus are a vital component of the global carbon cycle. However, with scarce data on potentially important subtropical and tropical areas for whole continents such as Australia, the magnitude of large-scale lake CO2 emissions is unclear. This study presents spatiotemporal changes of dissolved inorganic carbon and water - to - air interface CO2 flux in the two of Australia's largest connected, yet geomorphically different freshwater lakes (Lake Alexandrina and Lake Albert, South Australia), during drought (2007 to September-2010) and post-drought (October 2010 to 2013). Lake levels in the extreme drought were on average approximately 1m lower than long-term average (0.71 m AHD). Drought was associated with an increase in the concentrations of dissolved inorganic species, organic carbon, nitrogen, Chl-a and major ions, as well as water acidification as a consequence of acid sulfate soil (ASS) exposure, and hence, had profound effects on lake pCO2 concentrations. Lakes Alexandrina and Albert were a source of CO2 to the atmosphere during the drought period, with efflux ranging from 0.3 to 7.0 mmol/m(2)/d. The lake air-water CO2 flux was negative in the post-drought, ranging between -16.4 and 0.9 mmol/m(2)/d. The average annual CO2 emission was estimated at 615.5×10(6) mol CO2/y during the drought period. These calculated emission rates are in the lower range for lakes, despite the potential for drought conditions that shift the lakes from sink to net source for atmospheric CO2. These observations have significant implications in the context of predicted increasing frequency and intensity of drought as a result of climate change. Further information on the spatial and temporal variability in CO2 flux from Australian lakes is urgently warranted to revise the global carbon budget for lakes. PMID:26520269

  11. Maintenance support: case study for a multimodal mobile user interface

    NASA Astrophysics Data System (ADS)

    Fuchs, G.; Reichart, D.; Schumann, H.; Forbrig, P.

    2006-02-01

    Maintaining and repairing complex technical facilities such as generating plants requires comprehensive knowledge on subsystems, operational and safety procedures by the technician. Upgrades to the facility may mean that knowledge about these becomes outdated, raising the need for documentation at the working site. Today's commonplace availability of mobile devices motivates the use of digital, interactive manuals over printed ones. Such applications should provide high-quality illustrations and interaction techniques tailored for specific tasks, while at the same time allow flexible deployment of these components on a multitude of (mobile) hardware platforms. This includes the integration of multimodal interaction facilities like speech recognition into the user interface. To meet these demands, we propose a model-based approach that combines task, object and dialog models to specify platform-independent user interfaces. New concepts like relating tasks to domain objects and dialog views allow us to generate abstract canonical prototypes. Another focus is on the necessary adaptation of visual representations to the platform capabilities to remain effective and adequate, requiring tight coupling of the underlying model, the visualization, and alternative input/output modes. The above aspects have been addressed in a prototype for air-condition unit maintenance, presented on the CeBIT 2005 fair.

  12. A Theoretical Study of Remobilizing Surfactant Retarded Fluid Particle Interfaces

    NASA Technical Reports Server (NTRS)

    Wang, Yanping; Papageorgiou, Dimitri; Maldarelli, Charles

    1996-01-01

    Microgravity processes must rely on mechanisms other than bouyancy to move bubbles or droplets from one region to another in a continuous liquid phase. One suggested method is thermocapillary migration in which a temperature gradient is applied to the continuous phase. When a fluid particle contacts this gradient, one pole of the particle becomes warmer than the opposing pole. The interfacial tension between the drop or bubble phase and the continuous phase usually decreases with temperature. Thus the cooler pole is of higher interfacial tension than the warmer pole, and the interface is tugged in the direction of the cooler end. This thermocapillary or thermally induced Marangoni surface stress causes a fluid streaming in the continuous phase from which develops a viscous shear traction and pressure gradient which together propel the particle in the direction of the warmer fluid. In this paper, we provide a theoretical basis for remobilizing surfactant retarded fluid particle interfaces in an effort to make viable the use of thermocapillary migrations for the management of bubbles and drops in microgravity,

  13. Neutral buoyancy methodology for studying satellite servicing EVA crewmember interfaces

    NASA Technical Reports Server (NTRS)

    Barnby, Mary E.; Griffin, Thomas J.; Lewis, Ruthan

    1989-01-01

    Current economic constraints indicate the need for incorporating the satellite servicing philosophy of commonality within the design of spacecraft subsytems. This philosophy is essential for conserving resources including hardware/software development and implementation costs, on-orbit and ground-based manpower, crew training/testing time, and documentation. In addition, spacecraft subsystem commonality may be coupled with standardization of operation procedures, and test and verification techniques for spacecraft design. Several spacecraft have adopted this practice, including Hubble Space Telescope, Space Station Freedom, and the Explorer Platform. As these and other programs continue and if effective crew interfaces and procedures are clearly and consistently defined, crew retraining for similar spacecraft subsystems will lessen, and procurement efforts will diminish. A relatively high fidelity zero-gravity simulation using water immersion is available to establish crew interfaces economically. The flexibility and utility of this space simulation medium for planning and assisting on-orbit operations was exemplified by astronaut evaluations of potential EVA electrical connectors. The testing was conducted at a NASA underwater neutral buoyancy training facility.

  14. Vibrational spectroscopy of water interfaces

    SciTech Connect

    Du, Q.

    1994-12-01

    The second order nonlinear optical processes of second harmonic generation and sum frequency generation are powerful and versatile tools for studying all kinds of surfaces. They possess unusual surface sensitivity due to the symmetry properties of the second order nonlinear susceptibility. The technique of infrared-visible sum frequency generation (SFG) is particularly attractive because it offers a viable way to do vibrational spectroscopy on any surfaces accessible to light with submonolayer sensitivity. In this thesis, the author applies SFG to study a number of important water interfaces. At the air/water interface, hydrophobic solid/water and liquid/water interfaces, it was found that approximately 25% of surface water molecules have one of their hydrogen pointing away from the liquid water. The large number of unsatisfied hydrogen bonds contributes significantly to the large interfacial energy of the hydrophobic surfaces. At the hydrophilic fused quartz/water interface and a fatty acid monolayer covered water surface, the structure and orientation of surface water molecules are controlled by the hydrogen bonding of water molecules with the surface OH groups and the electrostatic interaction with the surface field from the ionization of surface groups. A change of pH value in the bulk water can significantly change the relative importance of the two interactions and cause a drastic change in orientation of the surface water molecules. SFG has also been applied to study the tribological response of some model lubricant films. Monolayers of Langmuir-Blodgett films were found to disorder orientationaly under mildly high pressure and recover promptly upon removal of the applied pressure.

  15. Spin labelled polymers for composite interface studies: Synthesis and characterization

    SciTech Connect

    Snow, A.W.; Pace, M.D.

    1993-12-31

    For the purpose of investigating the epoxy resin composite interface, a series of spin labelled epoxy polymers and model compounds were synthesized and characterized. Linear epoxy polymers were prepared by reacting systematically varying quantities of 4-amino-2,2,6,6-tetramethylpiperid-1-yloxy and cyclohexyl amine with an equivalence bisphenol A diglycidyl ether. The adducts of phenylgylcidyl ether and 4-cumylphenylgylcidyl ether with 4-amino-2,2,6,6-tetramethylpiperid-1-yloxy were synthesized as model compounds. Characterization determined that the 125{degrees}C polymerization temperature did not cause significant decomposition of the nitroxyl free radical, magnetic dilution of the spin label in the epoxy polymer to 3% of the amine repeat units is sufficient for observation of unobscured nitroxyl hyperfine structure in the ESR spectrum of the labelled epoxy polymer in the solid state, and a polymer glass transition temperature of 66{degrees}C as not affected by variation in the amine composition.

  16. Structural and phonon transmission study of Ge-Au-Ge eutectically bonded interfaces

    SciTech Connect

    Knowlton, W.B. |

    1995-07-01

    This thesis presents a structural analysis and phonon transparency investigation of the Ge-Au-Ge eutectic bond interface. Interface development was intended to maximize the interfacial ballistic phonon transparency to enhance the detection of the dark matter candidate WIMPs. The process which was developed provides an interface which produces minimal stress, low amounts of impurities, and insures Ge lattice continuity through the interface. For initial Au thicknesses of greater than 1,000 {angstrom} Au per substrate side, eutectic epitaxial growth resulted in a Au dendritic structure with 95% cross sectional and 90% planar Au interfacial area coverages. In sections in which Ge bridged the interface, lattice continuity across the interface was apparent. Epitaxial solidification of the eutectic interface with initial Au thicknesses < 500 A per substrate side produced Au agglomerations thereby reducing the Au planar interfacial area coverage to as little as 30%. The mechanism for Au coalescence was attributed to lateral diffusion of Ge and Au in the liquid phase during solidification. Phonon transmission studies were performed on eutectic interfaces with initial Au thicknesses of 1,000 {angstrom}, 500 {angstrom}, and 300 {angstrom} per substrate side. Phonon imaging of eutectically bonded samples with initial Au thicknesses of 300 {angstrom}/side revealed reproducible interfacial percent phonon transmissions from 60% to 70%. Line scan phonon imaging verified the results. Phonon propagation TOF spectra distinctly showed the predominant phonon propagation mode was ballistic. This was substantiated by phonon focusing effects apparent in the phonon imaging data. The degree of interface transparency to phonons and resulting phonon propagation modes correlate with the structure of the interface following eutectic solidification. Structural studies of samples with initial Au thickness of 1,000 {angstrom}/side appear to correspond with the phonon transmission study.

  17. Shuttle payload interface verification equipment study. Volume 2: Technical document, part 1

    NASA Technical Reports Server (NTRS)

    1976-01-01

    The technical analysis is reported that was performed during the shuttle payload interface verification equipment study. It describes: (1) the background and intent of the study; (2) study approach and philosophy covering all facets of shuttle payload/cargo integration; (3)shuttle payload integration requirements; (4) preliminary design of the horizontal IVE; (5) vertical IVE concept; and (6) IVE program development plans, schedule and cost. Also included is a payload integration analysis task to identify potential uses in addition to payload interface verification.

  18. Numerical and experimental study of the nonlinear interaction between a shear wave and a frictional interface.

    PubMed

    Blanloeuil, Philippe; Croxford, Anthony J; Meziane, Anissa

    2014-04-01

    The nonlinear interaction of shear waves with a frictional interface are presented and modeled using simple Coulomb friction. Analytical and finite difference implementations are proposed with both in agreement and showing a unique trend in terms of the generated nonlinearity. A dimensionless parameter ξ is proposed to uniquely quantify the nonlinearity produced. The trends produced in the numerical study are then validated with good agreement experimentally. This is carried out loading an interface between two steel blocks and exciting this interface with different amplitude normal incidence shear waves. The experimental results are in good agreement with the numerical results, suggesting the simple friction model does a reasonable job of capturing the fundamental physics. The resulting approach offers a potential way to characterize a contacting interface; however, the difficulty in activating that interface may ultimately limit its applicability. PMID:25234971

  19. Orientational dynamics of water at an extended hydrophobic interface

    NASA Astrophysics Data System (ADS)

    Figge, Florian; Xiao, Shunhao; McGuire, John A.; Stirnemann, Guillaume; Laage, Damien

    Aqueous interfaces are central to many physical processes, but the dynamics of interfacial water molecules have been little studied. We have measured the orientational dynamics of water at its interface with a self-assembled monolayer of octadecylsilane on fused silica. A surface-sensitive sum-frequency probe generated by mixing a visible and a vibrationally resonant infrared (IR) pulse is used to monitor the dangling (non-hydrogen-bonded) OH stretch vibration after excitation with a resonant IR pump pulse. By measuring pure and isotopically diluted water with orthogonal pump polarizations, we find that relaxation of the dangling OH stretch excitation is dominated by the out-of-plane jump from a dangling to a hydrogen-bonded configuration and the subsequent redistribution of energy from the surface hydrogen-bonded OH stretch excitation. The out-of-plane jump time is 1.5(1)ps, 30% slower than that reported for the air-water interface and twice as short as the jump time between hydrogen bonded configurations in the bulk. Molecular dynamics simulations indicate that the slower dynamics at the hydrophobic interface compared to the water-air interface are due to the hydrogen bonds at the hydrophobic interface being stronger than those at the water-air interface. The authors acknowledge support from the National Science Foundation (Grant No. CHE- 1151590).

  20. Sea Breeze Forcing of Estuary Turbulence and Air-Water Exchanges

    NASA Astrophysics Data System (ADS)

    Orton, P. M.; McGillis, W. R.; Zappa, C. J.

    2010-12-01

    The sea breeze is often a dominant meteorological feature at the coastline, but little is known about its estuarine impacts. It arises on sunny days with weak synoptic weather forcing, due to O(100 km) scale atmospheric pressure differences that develop as a result of the different solar absorption properties of sea and land. Here, measurements at an anchored catamaran and meteorological stations along the Hudson River and New York Bay estuarine system are used to illustrate some basic characteristics and impacts of the feature. The sea breeze propagates inland, arriving in phase with peak solar forcing at seaward stations, but several hours later at up-estuary stations. Passage of the sea breeze front raises the water-to-air CO2 flux by 1-2 orders of magnitude, and drives turbulence comparable to spring tide levels in the upper meter of the water column, where most primary productivity occurs in this highly turbid system. Modeling and observational studies often use remotely-measured winds with quadratic parameterizations to compute air-water fluxes (e.g. momentum, CO2), and this leads to a factor of two flux error on sea breeze days during the study. We conclude with a survey of how common these features are in the Hudson as well as other estuaries.

  1. Thermal boundary conductance enhancement using experimentally achievable nanostructured interfaces - analytical study combined with molecular dynamics simulation.

    PubMed

    Lee, Eungkyu; Zhang, Teng; Hu, Ming; Luo, Tengfei

    2016-06-22

    Interfacial thermal resistance presents great challenges to the thermal management of modern electronics. In this work, we perform an analytical study to enhance the thermal boundary conductance (TBC) of nanostructured interfaces with square-shape pillar arrays, extendable to the characteristic lengths that can be fabricated in practice. As a representative system, we investigate a SiC substrate with the square-shape pillar array combined with epitaxial GaN as the nanostructured interface. By applying a first-order ray tracing method and molecular dynamics simulations to analyze phonon incidence and transmission at the nanostructured interface, we systematically study the impact of the characteristic dimensions of the pillar array on the TBC. Based on the multi-scale analysis we provide a general guideline to optimize the nanostructured interfaces to achieve higher TBC, demonstrating that the optimized TBC value of the nanostructured SiC/GaN interfaces can be 42% higher than that of the planar SiC/GaN interfaces without nanostructures. The model used and results obtained in this study will guide the further experimental realization of nanostructured interfaces for better thermal management in microelectronics. PMID:27275647

  2. Shuttle payload interface verification equipment study. Volume 2: Technical document. Part 2: Appendices

    NASA Technical Reports Server (NTRS)

    1976-01-01

    Appendices to the shuttle payload integration study provide for: (1) The interface verification equipment hardware utilization list; (2) the horizontal IVE in-field assembly procedure; and (3) payload integration baseline functional flow block diagrams and options.

  3. Elemental and structural studies at the bone-cartilage interface

    NASA Astrophysics Data System (ADS)

    Kaabar, W.; Daar, E.; Bunk, O.; Farquharson, M. J.; Laklouk, A.; Bailey, M.; Jeynes, C.; Gundogdu, O.; Bradley, D. A.

    2011-10-01

    Micro-Proton Induced X-ray Emission (μ-PIXE) and Proton Induced Gamma-ray Emission (PIGE) techniques were employed in the investigation of trace and essential elements distribution in normal and diseased human femoral head sections affected by osteoarthritis (OA). PIGE was exploited in the determination of elements of low atomic number z<15 such as Na and F whereas elements with z>15 viz Ca, Z, P and S were determined by PIXE. Accumulations of key elements in the bone and cartilage sections were observed, significant S and Na concentrations being found in the cartilage region particularly in normal tissues. Zn showed enhanced concentrations at the bone-cartilage interface. At a synchrotron facility, small angle X-ray scattering (SAXS) was utilized on a decalcified human femoral head section affected by OA, direct measurements being made of spatial alterations of collagen fibres. The SAXS results showed a slight decrease in the axial periodicity between normal collagen type I and that in diseased tissue in various sites, in contrast with the findings of others.

  4. Critical air/water blow-down in safety valves at low qualities.

    PubMed

    Moncalvo, D; Friedel, L

    2011-02-28

    Critical air/water blow-downs in safety valves for qualities from 0.01 to 0.113 and mass flow rates from 1.5 up to 4.3 kg/s have been observed in our test facility. These critical blow-downs are characterized by a large void fraction and by an intense mixing of the phases both in the valve body and in the outlet pipe. A qualitative estimation of the flow pattern in the outlet pipe using the map of Taitel and Dukler suggests that these air/water flows are intermittent flows--presumably slug flows--evolving to annular flows for qualities above 0.1. Intermittent flows are also predicted for critical air/water and air/glycerine flows taken from the literature for the same safety valve at slightly larger relieving pressures. PMID:21227579

  5. Two-phase air-water stratified flow measurement using ultrasonic techniques

    SciTech Connect

    Fan, Shiwei; Yan, Tinghu; Yeung, Hoi

    2014-04-11

    In this paper, a time resolved ultrasound system was developed for investigating two-phase air-water stratified flow. The hardware of the system includes a pulsed wave transducer, a pulser/receiver, and a digital oscilloscope. The time domain cross correlation method is used to calculate the velocity profile along ultrasonic beam. The system is able to provide velocities with spatial resolution of around 1mm and the temporal resolution of 200μs. Experiments were carried out on single phase water flow and two-phase air-water stratified flow. For single phase water flow, the flow rates from ultrasound system were compared with those from electromagnetic flow (EM) meter, which showed good agreement. Then, the experiments were conducted on two-phase air-water stratified flow and the results were given. Compared with liquid height measurement from conductance probe, it indicated that the measured velocities were explainable.

  6. Hybrid density functional study of oligothiophene/ZnO interface for photovoltaics

    SciTech Connect

    Sai, Na; Leung, Kevin; Chelikowsky, James R.

    2011-03-21

    Organic-inorganic donor-acceptor interfaces are gaining growing attention in organic photovoltaic applications as each component of the interface offers unique attributes. Here we use hybrid density functional theory to examine the electronic structure of sexithiophene/ZnO interfaces. We find that interfacial molecular orientations strongly influence the adsorption energy, the energy level alignment, and the open-circuit voltage. We attribute the orientation dependence to the varied strength of electronic coupling between the molecule and the substrate. Our study suggests that photovoltaic performance can be optimized by controlling the interfacial design of molecular orientations.

  7. Computational Study of ions binding to the liquid interface of water

    SciTech Connect

    Dang, Liem X. )

    2002-08-12

    We have performed extensive classical molecular dynamics simulations to examine the molecular transport mechanisms of the I-, Br-, Cl- and Na+ ions across the liquid/vapor interface of water. The potentials of mean force were calculated using the constrained mean force approach and polarizable potential models were used to describe the interactions among the species. The simulated potentials of mean force were found to be different, depending on the type of anion. The larger I- and Br- anions bind more strongly to the liquid/vapor interface of water than did the smaller Cl-ion. It is important to note here that most of the gas phase and solution phase properties of the Br- anion are quite similar to that of the Cl- ion. At the interface, however, the interactions of the Br- and Cl- anions with the water interface appeared to be significantly different. We found that the anions approach the interface more closely do than cations. We have also studied the transport mechanism of an I- across the water/dichloromethane interface. The computed potential of mean force showed no well-defined minimum as in the liquid/vapor case, but a stabilization free energy of about?1 kcal/mol near the interface with respect to the bulk liquid was observed. The I- anion carried a water molecule with it as it crossed the interface. This result is in agreement with a recent experimental study on a similar system. Our work differs from earlier contributions in that our potential models have taken many-body effects into account, and in some cases, these effects cannot be neglected. To the best of our knowledge, this work significantly advances our understanding of molecular processes at the liquid interfaces.

  8. Verification and Validation of Numerical Models for Air/Water Flow on Coastal and Navigation Fluid-Structure Interaction Applications

    NASA Astrophysics Data System (ADS)

    Kees, C. E.; Farthing, M.; Dimakopoulos, A.; DeLataillade, T.

    2015-12-01

    Performance analysis and optimization of coastal and navigation structures is becoming feasible due to recent improvements in numerical methods for multiphase flows and the steady increase in capacity and availability of high performance computing resources. Now that the concept of fully three-dimensional air/water flow modelling for real world engineering analysis is achieving acceptance by the wider engineering community, it is critical to expand careful comparative studies on verification,validation, benchmarking, and uncertainty quantification for the variety of competing numerical methods that are continuing to evolve. Furthermore, uncertainty still remains about the relevance of secondary processes such as surface tension, air compressibility, air entrainment, and solid phase (structure) modelling so that questions about continuum mechanical theory and mathematical analysis of multiphase flow are still required. Two of the most popular and practical numerical approaches for large-scale engineering analysis are the Volume-Of-Fluid (VOF) and Level Set (LS) approaches. In this work we will present a publically available verification and validation test set for air-water-structure interaction problems as well as computational and physical model results including a hybrid VOF-LS method, traditional VOF methods, and Smoothed Particle Hydrodynamics (SPH) results. The test set repository and test problem formats will also be presented in order to facilitate future comparative studies and reproduction of scientific results.

  9. Computer Simulation study of polyhedral nanoparticle self-assembly at interfaces

    NASA Astrophysics Data System (ADS)

    Thapar, Vikram; Gupta, Unmukt; Escobedo, Fernando

    The self-assembly of polyhedral particles confined to a fluid-fluid interface is studied using Monte Carlo simulations. Several polyhedral shapes are studied, which are selected from a family of truncated cubes which include cubes, cuboctahedra, and octahedra. First we studied the case of hard particles pinned to the interface by restricting their movement in the direction perpendicular to it while allowing their free rotations. Our results suggest that the known solid phases and mesophases of these shapes in the 3D bulk are ``translated'' into variants in 2D space. These insights on 2D entropic self-assembly of polyhedral particles is a first step toward understanding the self-assembly of particles at fluid-fluid interfaces, which is driven by a complex interplay of entropic and enthalpic forces. As a second step we hence studied the particle-surface and particle-particle interactions associated with a fluid-fluid interface using both continuum and polybead models to assess the role of enthalpic interactions in determining the particle orientation behavior with respect to interface. We find that the thickness of the interface can introduce non-trivial effects on the preferential particle orientations.

  10. Image processing analysis on the air-water slug two-phase flow in a horizontal pipe

    NASA Astrophysics Data System (ADS)

    Dinaryanto, Okto; Widyatama, Arif; Majid, Akmal Irfan; Deendarlianto, Indarto

    2016-06-01

    Slug flow is a part of intermittent flow which is avoided in industrial application because of its irregularity and high pressure fluctuation. Those characteristics cause some problems such as internal corrosion and the damage of the pipeline construction. In order to understand the slug characteristics, some of the measurement techniques can be applied such as wire-mesh sensors, CECM, and high speed camera. The present study was aimed to determine slug characteristics by using image processing techniques. Experiment has been carried out in 26 mm i.d. acrylic horizontal pipe with 9 m long. Air-water flow was recorded 5 m from the air-water mixer using high speed video camera. Each of image sequence was processed using MATLAB. There are some steps including image complement, background subtraction, and image filtering that used in this algorithm to produce binary images. Special treatments also were applied to reduce the disturbance effect of dispersed bubble around the bubble. Furthermore, binary images were used to describe bubble contour and calculate slug parameter such as gas slug length, gas slug velocity, and slug frequency. As a result the effect of superficial gas velocity and superficial liquid velocity on the fundamental parameters can be understood. After comparing the results to the previous experimental results, the image processing techniques is a useful and potential technique to explain the slug characteristics.

  11. Polarization charge: Theory and applications to aqueous interfaces.

    PubMed

    Shi, Bobo; Agnihotri, Mithila V; Chen, Si-Han; Black, Richie; Singer, Sherwin J

    2016-04-28

    When an electric field is applied across an interface, a dielectric will acquire a polarization charge layer, assumed infinitely thin in the theory of macroscopic dielectrics and also in most treatments of electrokinetic phenomena in nanoscale structures. In this work we explore the polarization charge layer in molecular detail. Various formal relations and a linear response theory for the polarization charge are presented. Properties of the polarization charge layer are studied for three aqueous interfaces: air-water, a crystalline silica surface with water, and an amorphous silica surface with water. The polarization charge is calculated from equilibrium simulations via linear response theory and from non-equilibrium simulations, and the results are within statistical error. The polarization charge is found to be distributed within a region whose width is on the order of a nanometer. PMID:27131558

  12. Polarization charge: Theory and applications to aqueous interfaces

    NASA Astrophysics Data System (ADS)

    Shi, Bobo; Agnihotri, Mithila V.; Chen, Si-Han; Black, Richie; Singer, Sherwin J.

    2016-04-01

    When an electric field is applied across an interface, a dielectric will acquire a polarization charge layer, assumed infinitely thin in the theory of macroscopic dielectrics and also in most treatments of electrokinetic phenomena in nanoscale structures. In this work we explore the polarization charge layer in molecular detail. Various formal relations and a linear response theory for the polarization charge are presented. Properties of the polarization charge layer are studied for three aqueous interfaces: air-water, a crystalline silica surface with water, and an amorphous silica surface with water. The polarization charge is calculated from equilibrium simulations via linear response theory and from non-equilibrium simulations, and the results are within statistical error. The polarization charge is found to be distributed within a region whose width is on the order of a nanometer.

  13. Studies of the Si/SiO2 interface using synchrotron radiation

    NASA Technical Reports Server (NTRS)

    Hecht, M. H.; Grunthaner, F. J.

    1985-01-01

    Synchrotron radiation photoemission spectroscopy (SRPS) in the 1-4 KeV photon energy range is a useful tool for interface characterization. Results are presented of a series of studies of the near-interface region of Si/SiO2 which confirm that a bond strain gradient exists in the oxide as a result of lattice mismatch. These experiments include measurement of photoemission lineshape changes as a function of photon energy, corresponding changes in the electron escape depth near the interface, and surface extended X-ray absorption fine structure (SEXAFS) measurements directly indicating the shortening of the Si-Si second nearest neighbor distance in the near-interface region of the oxide.

  14. Advanced EVA system design requirements study: EVAS/space station system interface requirements

    NASA Technical Reports Server (NTRS)

    Woods, T. G.

    1985-01-01

    The definition of the Extravehicular Activity (EVA) systems interface requirements and accomodations for effective integration of a production EVA capability into the space station are contained. A description of the EVA systems for which the space station must provide the various interfaces and accomodations are provided. The discussion and analyses of the various space station areas in which the EVA interfaces are required and/or from which implications for EVA system design requirements are derived, are included. The rationale is provided for all EVAS mechanical, fluid, electrical, communications, and data system interfaces as well as exterior and interior requirements necessary to facilitate EVA operations. Results of the studies supporting these discussions are presented in the appendix.

  15. MONITORING CYCLICAL AIR-WATER ELEMENTAL MERCURY EXCHANGE

    EPA Science Inventory

    Previous experimental work has demonstrated that elemental mercury evasion from natural water displays a diel cycle; evasion rates during the day can be two to three times evasion rates observed at night. A study with polychlorinated biphenyls (PCBS) found that diurnal PCB air/wa...

  16. THE EFFECT OF SALINITY ON RATES OF ELEMENTAL MERCURY AIR/WATER EXCHANGE

    EPA Science Inventory

    The U.S. EPA laboratory in Athens, Georgia i spursuing the goal of developing a model for describing toxicant vapor phase air/water exchange under all relevant environmental conditions. To date, the two-layer exchange model (suitable for low wind speed conditions) has been modif...

  17. Tide and Wind Forcing of Estuarine Air-Water Gas Transfer

    NASA Astrophysics Data System (ADS)

    Orton, P. M.; Zappa, C. J.; McGillis, W. R.

    2008-12-01

    Recent studies have demonstrated that while gas transfer is primarily driven by wind, tidal currents can drive gas exchange in estuaries. Studies have also shown that the turbulent kinetic energy (TKE) dissipation just below the sea surface is a good proxy for the gas exchange velocity (k) for a wide range of forcing processes (e.g. wind, currents, rain). However, the connection between tidally-driven turbulence and gas exchange has not been investigated in detail. In this study, an autonomous instrumented surface platform deployment and one-dimensional numerical modeling are used to examine the influence of wind, tidal current shear, and water column bottom boundary layer (BBL) growth on gas transfer in an estuary. An autonomous instrumented surface platform was deployed for one month at a shallow site in the Hudson River estuary, measuring wind velocity, water velocity, TKE dissipation, air-water CO2 gradient and flux, and gas transfer velocity. Currents were 0-0.8 m s-1, winds 0-14 m s-1, depths 4.7-6.2 m, significant wave heights 0-0.8 m, and water pCO2 700-1600 μatm during the study. Surveys spanning the entire estuary from 2002 to the present broaden our understanding of tidal currents, stratification and turbulence to the entire estuary, with over a billion acoustic velocity measurements, millions of turbulence measurements, and 50 CTD surveys up the entire length of the estuary. The estuarine observations show a strong relationship between wind and k, but several recent parameterizations of k as a function of wind speed under-predict k for low-to-moderate winds (1-6 m s- 1). Upper water-column TKE dissipation and k are correlated, consistent with a recent parameterization. Both processes show enhancement when the turbulent BBL nears the sea surface. One-dimensional turbulence modeling is used to expand these results to a broad range of estuaries.

  18. A study of interface crack branching in dissimilar anisotropic bimaterial composites including thermal effects

    NASA Astrophysics Data System (ADS)

    Li, Renfu

    The interface crack branching phenomena, including thermal effects, has been investigated by using complex variable method and Stroh's dislocation theory, extended to thermo-elasticity in matrix notation. As one of the most catastrophic failure modes in structures like laminated and sandwich composites in aerospace and marine construction, thin film in electronic packaging, rotators in high speed engine of aircraft and reactor in nuclear power station, the study of interface crack branching has become a topic not only having theoretical importance, but also having practical significance. A unified approach is presented to address the thermoelastic interface crack problems in dissimilar anisotropic bimaterial composites, and a compact closed form solution is formulated by analytical continuation principle of complex analysis. Employing the contour integral method, an explicit solution to the interaction between the dislocations and the interface crack is obtained. By modeling the branched portion as a continuous distribution of the dislocations, the thermoelastic interface crack branching problem is then converted to a set of semi-coupled singular integral equations and solved by Gauss-Jacobi integration schemes. The influence of material property mismatches between the two constituents and the thermal loading effects on the interface crack branching are demonstrated by extensive numerical simulation. Some useful criteria for predicting the interface crack branching growth and guidance for optimal composites design are suggested. Further, a contact model to eliminate the overlapping between the two surfaces of an interface crack is also proposed and some new parameters which could influence the interpenetrating phenomena are also discovered. The technique to extend the current method to three dimensional problems is also outlined. Furthermore, the C++ source code has been implemented to manipulate the complicated complex operations for numerically solving the

  19. New research on bioregenerative air/water purification systems

    NASA Technical Reports Server (NTRS)

    Johnson, Anne H.; Ellender, R. D.; Watkins, Paul J.

    1991-01-01

    For the past several years, air and water purification systems have been developed and used. This technology is based on the combined activities of plants and microorganisms as they function in a natural environment. More recently, researchers have begun to address the problems associated with indoor air pollution. Various common houseplants are currently being evaluated for their abilities to reduce concentrations of volatile organic compounds (VOCS) such as formaldehyde and benzene. With development of the Space Exploration Initiative, missions will increase in duration, and problems with resupply necessitates implementation of regenerative technology. Aspects of bioregenerative technology have been included in a habitat known as the BioHome. The ultimate goal is to use this technology in conjunction with physicochemical systems for air and water purification within closed systems. This study continued the risk assessment of bioregenerative technology with emphasis on biological hazards. In an effort to evaluate the risk for human infection, analyses were directed at enumeration of fecal streptococci and enteric viruses with the BioHome waste water treatment system.

  20. Shuttle payload interface verification equipment study. Volume 3: Specification data

    NASA Technical Reports Server (NTRS)

    1976-01-01

    A complete description is given of the IVE physical and performance design requirements as evolved in this study. The data are presented in a format to facilitate the development of an item specification. Data were used to support the development of the project plan data (schedules, cost, etc.) contained in Volume 4 of this report.

  1. Atmosphere explorer missions C, D, and E. Spacecraft experiment interface definition study

    NASA Technical Reports Server (NTRS)

    1972-01-01

    The Atmosphere Explorer Missions C, D, & E Spacecraft/Experiment Interface Definition Study is discussed. The objectives of the study included an analysis of the accommodation requirements of the experiments for the three missions, an assessment of the overall effect of these requirements on the spacecraft system design and performance, and the detailed definition of all experiment/spacecraft electrical, mechanical, and environmental interfaces. In addition, the study included the identification and definition of system characteristics required to ensure compatibility with the consolidated STADAN and MSFN communications networks.

  2. Interstellar dust: interfacing laboratory, theoretical and observational studies

    NASA Astrophysics Data System (ADS)

    Jones, Anthony Peter

    2015-08-01

    In this talk I will consider how our understanding of interstellar dust can only be advanced through a combination of laboratory, theoretical and observational studies, which provide the critical framework for advancing our understanding. I will summarise what we currently know, or think we know, about the physical and compositional properties of dust and their evolution in interstellar media. Along the way I will question the utility of astronomical dust analogues and show, based on data from the laboratory, theoretical studies and from astronomical observations, that some of our prior interpretations need to be subjected to a critical re-evaluation. I will present interstellar dust modelling from a new vantage point and review ideas on the interpretation of observations within the framework of this model and its predictions for dust evolution within and between interstellar media. Finally, I will summarise some of the current outstanding issues and what we would like to learn in the future.

  3. On biomolecules and semiconductors: Analytical studies of interface dynamics

    NASA Astrophysics Data System (ADS)

    Slavin, John William Joseph

    The studies discussed here were undertaken to examine the use of III-V semiconducting materials as templates for biomolecules, to be applied in such technologies as Field-Effect Transistor (FET) and Light-emitting Diode (LED) biosensors. Materials application requires an informed analysis of interactions between chemical environments. Specific to surfaces, this means investigating the molecular interactions between the substrate and the bonding moieties. The analytical tools used to probe these interactions, and the changes that such communication causes on specific substrates are specifically discussed. Surface analysis tools included in this review are Atomic Force Microscopy (AFM), Nanoindentation, X-ray Photoelectron Spectroscopy (XPS), and Raman Microscopy. The interaction of biomolecules - deoxyribonucleic acid (DNA), proteins adhered to nanoparticles, and amino acids - on semiconductor surfaces is also examined. Proper investigation follows, as well, the methods of applying these biomolecular structures to the specified surfaces, through procedures such as solution phase transfer, as well as Dip-pen Nanolithography (DPN). The stretching and enzymatic cleavage of DNA, on silicon oxide surfaces, was studied to determine the recognition properties of dual-enzymatic systems on surfaces. Fundamental questions such as the interaction of functional groups with InAs(100) surfaces, the mechanical properties of protein modified systems, and the DPN application of biologically relevant linker molecules to InAs(100) surfaces were explored. These studies provide information applicable to the development of novel sensing platforms in the future.

  4. Interfacing anthropology and epidemiology: the Bedouin Arab Infant Feeding Study.

    PubMed

    Hundt, G A; Forman, M R

    1993-04-01

    This paper encapsulates a 10 year effort of multi-disciplinary research on the relationship between infant feeding, growth, and morbidity among the Negev Bedouin Arabs of Israel as they underwent a transition from semi-nomadism to urban settlement. The research team was multi-disciplinary including a nutritional epidemiologist and an anthropologist who both came to the study with previous experience in interdisciplinary work. The specific study objectives were (1) a description of infant feeding practices among Negev Bedouin Arab women at various stages of settlement, (2) an examination of the trend in these infant feeding practices, (3) a comparison of the extent to which different infant feeding practices are related to infant morbidity and growth after adjustment for exposure to social change and other covariates. The data collection took place in 1981-83 and the analysis from 1984-88. In this paper, two areas of the study are discussed in depth: the duration of exclusive breast feeding during the practice of the traditional postpartum 40 day rest period, and the development of a culture-specific scale of socioeconomic status. Through these examples, we highlight the use of ethnographic data and the merging of epidemiology and anthropology from hypothesis generation through data collection, data analysis and interpretation. PMID:8480241

  5. First principles study of band line up at defective metal-oxide interface: oxygen point defects at Al/SiO2 interface

    NASA Astrophysics Data System (ADS)

    Tea, Eric; Huang, Jianqiu; Hin, Celine

    2016-03-01

    The dielectric breakdown at metal-oxide interfaces is a critical electronic device failure mechanism. Electronic tunneling through dielectric layers is a well-accepted explanation for this phenomenon. Theoretical band alignment studies, providing information about tunneling, have already been conducted in the literature for metal-oxide interfaces. However, most of the time materials were assumed defect free. Oxygen vacancies being very common in oxides, their effect on band lineup is of prime importance in understanding electron tunneling in realistic materials and devices. This work explores the effect of oxygen vacancy and oxygen di-vacancy at the Al/SiO2 interface on the band line up within Density Functional Theory using PBE0 hybrid exchange and correlation functional. It is found that the presence of defects at the interface, and their charge state, strongly alters the band line up.

  6. First-principles study of interface doping in ferroelectric junctions

    PubMed Central

    Wang, Pin-Zhi; Cai, Tian-Yi; Ju, Sheng; Wu, Yin-Zhong

    2016-01-01

    Effect of atomic monolayer insertion on the performance of ferroelectric tunneling junction is investigated in SrRuO3/BaTiO3/SrRuO3 heterostrucutures. Based on first-principles calculations, the atomic displacement, orbital occupancy, and ferroelectric polarization are studied. It is found that the ferroelectricity is enhanced when a (AlO2)− monolayer is inserted between the electrode SRO and the barrier BTO, where the relatively high mobility of doped holes effectively screen ferroelectric polarization. On the other hand, for the case of (LaO)+ inserted layer, the doped electrons resides at the both sides of middle ferroelectric barrier, making the ferroelectricity unfavorable. Our findings provide an alternative avenue to improve the performance of ferroelectric tunneling junctions. PMID:27063704

  7. Theoretical study of reactions at the electrode-electrolyte interface

    SciTech Connect

    Halley, J.W.

    1993-01-01

    Electron transfer rates are predicted by numerical methods, in a collaboration with Argonne National Laboratory . Emphasis is on electron transfer involving ions known to be important in enhancing stress corrosion cracking in light water reactors and on electron transfer at oxide surfaces. We have produced a new theory for description of the Jahn Teller effect in the solvation shell of the cuprous ion in aqueous solution, have implemented it in a molecular dynamics simulation and compared the results with experimental neutron scattering measurements on solutions containing the cuprous ion. A large amount of numerical data has been collected on the transition state of the ferrous ferric electron transfer reaction at an electrode. Work was completed on a polarizable and dissociable model of water for use in the electron transfer studies. New calculations of the conductivity in models of oxides have shown the existence of impurity conduction bands in such models for the first time.

  8. An AFM study of the chlorite-fluid interface. [Atomic Force Microscopy

    SciTech Connect

    Vrdoljak, G.A.; Henderson, G.S.; Fawcett, J.J. . Dept. of Geology)

    1992-01-01

    Chlorite is a ubiquitous mineral in many geologic environments and plays an important role in elemental adsorption and retention in soils. Chlorite has a 2:1 layer structure consisting of two tetrahedral sheets with an octahedral sheet between them (talc-like layer). The 2:1 layer is charge balanced and hydrogen-bonded by an interlayer of MgOH[sub 6] octahedra (brucite-like layer). The nature of chlorite's structure, its ease of imaging, and perfect 001 cleavage, make this mineral an ideal substrate for use in elemental adsorption studies in solution, with the AFM. The 001 cleavage plane of a 2b polytype with composition (Mg[sub 4.4]Fe[sub 0.6]Al[sub 1.0])[(Si[sub 2.9]Al[sub 1.1])]O[sub 10](OH)[sub g] has been imaged in air, water, and oil by atomic force microscopy. Dissolution features are observed in water, showing sub-micron features dissolving in real-time. Atomic resolution of both the talc-like and brucite-like layers has been obtained in air. However, only the tetrahedral sheet of the talc-like layer has been imaged at atomic resolution in oil and water, which may indicate a structural instability of the brucite-like surface in solution. Measurements of the unit-cell dimensions (a and b) for the talc-like layer in the three different media indicate a structural expansion of the mineral surface in solution. The a unit cell dimension expands by 7.4 [+-] 0.1% when in water; conversely, the b dimension varies greatly when in oil ([minus]10% to +20%), relative to air. The effects of these solution media on the structure of chlorite are revealed by characterization with the AFM. This information should prove useful in future studies of adsorption onto layer silicates.

  9. An experimental study of recirculating flow through fluid sediment interfaces

    NASA Astrophysics Data System (ADS)

    Khalili, A.; Basu, A. J.; Pietrzyk, U.; Raffel, M.

    1999-03-01

    We report here visualizations and quantitative measurements of scalar transport, under the influence of rotation, through permeable sediments with an overlying fluid layer. The experimental set-up considered here is a stationary cylinder containing a fluid-saturated porous medium up to its midheight, with supernatant water on top. A rotating lid generates, in the upper fluid region, a flow that partially percolates into the porous layer below. The velocity field in the fluid layer is obtained using particle image velocimetry (PIV). Further, dye transport from the sediment is studied using two different techniques. The first one is positron emission tomography (PET), a non-invasive method which allowed us to ‘see’ through the opaque solid matrix, and to obtain full three-dimensional pictures of dye transport through the sediment. The second one is digital photographic visualization from outside, and subsequent image processing in order to obtain the near-wall dye-washout depth. The experimental data suggest that the temporal evolution of washout depth for different sediments follows near-logarithmic behaviour. This finding is of importance for the a priori estimation of the transport of fluid and other solute substances in sandy aquatic sediments.

  10. Iron oxide mineral-water interface reactions studied by AFM

    SciTech Connect

    Hawley, M.E.; Rogers, P.S.Z.

    1994-07-01

    Natural iron mineral surfaces have been examined in air by atomic force (AFM) and scanning tunneling (STM) microscopies. A number of different surface features were found to be characteristic of the native surface. Even surfaces freshly exposed by crushing larger crystals were found to have a pebbly surface texture caused by the presence of thin coatings of what might be surface precipitates. This finding is interpreted as evidence for previous exposure to water, probably through an extensive network of microfractures. Surface reactions on the goethite crystals were studied by AFM at size resolutions ranging from microns to atomic resolution before, during, and after reaction with distilled water and 0.lN HCl. Immediate and extensive surface reconfiguration occurred on contact with water. In one case, after equilibration with water for 3 days, surface reprecipitation, etching and pitting were observed. Atomic resolution images taken under water were found to be disordered. The result of surface reaction was generally to increase the surface area substantially through the extension of surface platelet arrays, present prior to reaction. This work is being done in support of the site characterization project at Yucca Mountain.

  11. Space shuttle/payload interface analysis (study 2.4). Volume 1: Executive summary

    NASA Technical Reports Server (NTRS)

    Pritchard, E. I.

    1973-01-01

    The space shuttle/payload interface analysis is presented. The analysis consists of the following sections: (1) payload capture and cost analysis, (2) business risk and value of operations in space analysis, and (3) payload community analysis. The primary objective of the study was to furnish a method for tracing capture/cost analyses conducted by other study groups.

  12. Dynamics of a bubble bouncing at a compound interface

    NASA Astrophysics Data System (ADS)

    Feng, Jie; Muradoglu, Metin; Stone, Howard A.

    2014-11-01

    Bubbly flow is extensively involved in a wide range of technological applications, which generate a great demand for understanding of bubble physics. The collision, bouncing and coalescence of moving bubbles with liquid/gas and liquid/solid interfaces, as the first stage for the formation of foams and flotation aggregates, have been the subject of many studies, but there are still unanswered questions related to how the properties of the interface influence the dynamics. For example, Zawala et al. 2013 have tried to investigate how the kinetic energy of the bubble affects the liquid film drainage during the collision with an air-water interface. Inspired by Feng et al. 2014, we study the dynamics of an air bubble bouncing at a liquid/liquid/gas interface, in which a thin layer of oil is put on top of the water. The presence of the oil layer changes the interfacial properties and thus the entire process. Combined with direct numerical simulations, extensive experiments were carried out to investigate the effects of the oil layer thickness, oil viscosity, bubble size and initial impact velocity on the bouncing of the bubble at the compound interface. In addition, a mass-spring model is proposed to describe the bubble dynamics and interactions with the oil layer.

  13. Development of a submersible shadowgraph for the study of interfaces in salt-gradient solar ponds

    SciTech Connect

    Huacuz, J.M.; Sierra, F.; Venegas, C.; Ramos, C. )

    1989-01-01

    In this paper the processes of development and testing of a submersible shadowgraph are described. This instrument was devised as a tool for the study of interfaces in salt-gradient solar ponds. Tests were carried out in the solar pond of the University of Texas at El Paso. Photographs of interfaces inside the pond were taken for the first time. The submersible shadowgraph can be stationed inside the pond for time dependent studies of a given region, or it can be used to scan the pond depth.

  14. First principles studies of the stability and Shottky barriers of metal/CdTe(111) interfaces

    NASA Astrophysics Data System (ADS)

    Liu, Zhen; Miao, Masoehng; Kioussis, Nicholas; Aqariden, Fikri; Chang, Y.; Grein, Christoph

    CdZnTe and CdTe based semiconductor X-Ray and Gamma-Ray detectors have been intensively studied recently due to their promising potentials for achieving high-resolution, high signal-to-noise ratios and low leakage current, all are desirable features in applications ranging from medical diagnostics to homeland security. Using density functional calculations, we systematically studied the stability, the atomic and electronic structures of the interfaces between CdTe (111) surfaces (Cd- and Te-terminated) and the selected metals (Cu, Al Ni, Pd and Pt). We also calculated the Schottky barrier height (SBH) by aligning the electrostatic potentials in semiconductor and metal regions. Our calculations revealed significant differences between the Cd- and Te- terminated interfaces. While metals tend to deposit directly on reconstructed Te-terminated surfaces, they form a Te-metal alloy layer at the Cd-Terminated metal/CdTe interface. For both Te- and Cd- terminated interfaces, the Schottky barrier heights do not depend much on the choice of metals despite the large variation of the work functions. On the other hand, the interface structure is found to have large effect on the SBH, which is attributed to the metal induced states in the gap.

  15. Experimental Study of the Richtmyer-Meshkov Instability for a He -- SF6 Interface

    NASA Astrophysics Data System (ADS)

    Motl, Bradley; Ranjan, Devesh; Oakley, Jason; Anderson, Mark; Bonazza, Riccardo

    2007-11-01

    Results are presented from a series of experiments studying the Richtmyer-Meshkov (RM) instability for the case of a perturbed gas interface at the Wisconsin Shock Tube Laboratory. A membraneless interface is formed by the head-on flow of helium and sulfur-hexafluoride (seeded with smoke) which creates a stagnation surface. A sinusoidal interface is created at the gas stagnation plane in the test section by oscillating pistons that are initially flush with the shock tube walls. Flow visualization for the initial condition and post-shock images is carried out using Mie scattering from a planar laser sheet. The RM instability is studied for varying incident shock wave strengths (1.1 <=M <= 2), and results are reported in the form of experimental images and perturbation growth rates which are compared to several analytic models.

  16. Usefulness of O-18 and deuterium to study transport processes at aquatic interfaces

    NASA Astrophysics Data System (ADS)

    Lewandowski, Jörg; Pöschke, Franziska; Rudnick, Sebastian; Meinikmann, Karin; Périllon, Cécile

    2014-05-01

    Several different tracers are used in ecohydrology to study the manifold transport processes across groundwater-surface water interfaces. The stable isotopes of oxygen (O-18) and hydrogen (deuterium) as parts of the water molecule might be perfect tracers since their behavior in the environment is quite conservative. Isotope signatures of water differ due to origin of the water and can help to identify processes such as in- or exfiltration at groundwater-surface water interfaces. The recent development of cavity ring-down spectroscopy facilitates reliable measurements by far compared to the previously common method of mass spectroscopy. Nowadays, stable isotope measurements are orders of magnitude cheaper, faster and easier than five years ago. Based on that analytical progress, an increasing number of studies employ the stable isotopes O-18 and deuterium. Ecohydrological applications and their limitations are critically discussed in this contribution focusing on aquifer-lake interfaces.

  17. Experimental study on interface region of two-dimensional Si layers by forming gas annealing

    NASA Astrophysics Data System (ADS)

    Mizuno, Tomohisa; Suzuki, Yuhya; Kikuchi, Reika; Suzuki, Ayaka; Inoue, Ryohsuke; Yamanaka, Masahiro; Yokoyama, Miki; Nagamine, Yoshiki; Aoki, Takashi; Maeda, Tatsuro

    2016-04-01

    We experimentally studied the SiO2/Si and Si/buried oxide (BOX) interface regions of a two-dimensional (2D) Si layer, by forming gas annealing (FGA). A photoluminescence (PL) result measured at various lattice temperature, T L, values shows that the PL intensity I PL of the 2D-Si layer rapidly increases and then saturates with increasing FGA temperature, T A, and time, t A. I PL also increases with decreasing T L. A one-dimensional (1D) Schroedinger equation simulator indicates that some of the electrons in the 2D-Si layer generated by a PL excitation laser are quantum-mechanically transmitted into Si interface regions. Actually, we experimentally confirmed that the PL spectra of the 2D-Si layer can be fitted by the PL emission from two regions with different PL peak photon energy values, E PH, which consist of a typical 2D-Si and the interface regions of both the surface SiO2/Si and Si/BOX. Thus, this forming gas dependence is probably attributable to the improved lifetime τ of electrons in the surface interface region, because the Si surface is terminated by H atoms. Moreover, the E PH of the interface region is higher than that of the 2D-Si layer, because of the graded increased bandgap in the interface regions. However, the E PH of 2D-Si is independent of both T A and T L, and this T L independence does not agree with that of a 3D-Si layer. Consequently, we experimentally verified the larger impact of the Si interface on the performance of 2D-Si layer.

  18. First-principles study of Mg(0001)/MgO(1-11) interfaces

    NASA Astrophysics Data System (ADS)

    Song, Hong-Quan; Zhao, Ming; Li, Jian-Guo

    2016-06-01

    By means of first-principles density-functional calculations, we studied the surface energy of a nonstoichiometric MgO(1-11) slab, the interfacial energy and interfacial bonding characteristics of Mg-terminated and O-terminated Mg/MgO(1-11) interfaces with three stacking-site (TOP, HCP and FCC sites) models, and the effect of the thickness of Mg films on the O-terminated MgO(1-11) surface. The results indicate that the surface energies of the nonstoichiometric MgO(1-11) slab and interfacial energies of Mg/Mg(1-11) interface depend on Mg chemical potential. We found that the Mg-terminated MgO(1-11) surface is more stable than the O-terminated MgO(1-11) surface at high Mg chemical potential, and Mg/MgO(1-11) with FCC stacking-site model is the most stable configuration in the Mg/MgO(1-11) interfaces. The results of the electronic structure reveals that the interfacial bonding of Mg-terminated interface with FCC site model mainly consists of metallic bond and of the O-terminated interface with FCC site model is mainly ionic with a small degree of σ-type covalent bond. Although the interfacial energy of Mg-terminated Mg/MgO interface with FCC stacking-site model is slightly higher than that of O-terminated Mg/MgO interface, the molten Mg would epitaxially grow on the FCC sites of the Mg-terminated MgO(1-11) surface because of the high evaporation pressure of Mg at high temperature.

  19. WETAIR: A computer code for calculating thermodynamic and transport properties of air-water mixtures

    NASA Technical Reports Server (NTRS)

    Fessler, T. E.

    1979-01-01

    A computer program subroutine, WETAIR, was developed to calculate the thermodynamic and transport properties of air water mixtures. It determines the thermodynamic state from assigned values of temperature and density, pressure and density, temperature and pressure, pressure and entropy, or pressure and enthalpy. The WETAIR calculates the properties of dry air and water (steam) by interpolating to obtain values from property tables. Then it uses simple mixing laws to calculate the properties of air water mixtures. Properties of mixtures with water contents below 40 percent (by mass) can be calculated at temperatures from 273.2 to 1497 K and pressures to 450 MN/sq m. Dry air properties can be calculated at temperatures as low as 150 K. Water properties can be calculated at temperatures to 1747 K and pressures to 100 MN/sq m. The WETAIR is available in both SFTRAN and FORTRAN.

  20. Thermodynamic Study of the Role of Interface Curvature on Multicomponent Vapor-Liquid Phase Equilibrium.

    PubMed

    Shardt, Nadia; Elliott, Janet A W

    2016-04-14

    The effect of interface curvature on phase equilibrium has been much more studied for single-component than multicomponent systems. We isolate the effect of curvature on multicomponent vapor-liquid equilibrium (VLE) phase envelopes and phase composition diagrams using the ideal system methanol/ethanol and the nonideal system ethanol/water as illustrative examples. An important finding is how nanoscale interface curvature shifts the azeotrope (equal volatility point) of nonideal systems. Understanding of the effect of curvature on VLE can be exploited in future nanoscale prediction and design. PMID:27028744

  1. Theoretical study of vibrational energy transfer of free OH groups at the water-air interface

    NASA Astrophysics Data System (ADS)

    Zheng, Renhui; Wei, Wenmei; Sun, Yuanyuan; Song, Kai; Shi, Qiang

    2016-04-01

    Recent experimental studies have shown that the vibrational dynamics of free OH groups at the water-air interface is significantly different from that in bulk water. In this work, by performing molecular dynamics simulations and mixed quantum/classical calculations, we investigate different vibrational energy transfer pathways of free OH groups at the water-air interface. The calculated intramolecular vibrational energy transfer rate constant and the free OH bond reorientation time scale agree well with the experiment. It is also found that, due to the small intermolecular vibrational couplings, the intermolecular vibrational energy transfer pathway that is very important in bulk water plays a much less significant role in the vibrational energy relaxation of the free OH groups at the water-air interface.

  2. A novel X-ray photoelectron spectroscopy study of the Al/SiO2 interface

    NASA Technical Reports Server (NTRS)

    Hecht, M. H.; Vasquez, R. P.; Grunthaner, F. J.; Zamani, N.; Maserjian, J.

    1985-01-01

    The nondestructive measurement of the chemical and physical characteristics of the interface between bulk SiO2 and thick aluminum films is reported. Both X-ray phototelectron spectroscopy (XPS) and electrical measurements of unannealed, resistively evaporated Al films on thermal SiO2 indicate an atomically abrupt interface. Post metallization annealing at 450 C induces reduction of the SiO2 by the aluminum, at a rate consistent with the bulk reaction rate. The XPS measurement is performed from the SiO2 side after the removal of the Si substrate with XeF2 gas and thinning of the SiO2 layer with HF:ETOH. This represents a powerful new approach to the study of metal-insulator and related interfaces.

  3. Theoretical study of vibrational energy transfer of free OH groups at the water-air interface.

    PubMed

    Zheng, Renhui; Wei, Wenmei; Sun, Yuanyuan; Song, Kai; Shi, Qiang

    2016-04-14

    Recent experimental studies have shown that the vibrational dynamics of free OH groups at the water-air interface is significantly different from that in bulk water. In this work, by performing molecular dynamics simulations and mixed quantum/classical calculations, we investigate different vibrational energy transfer pathways of free OH groups at the water-air interface. The calculated intramolecular vibrational energy transfer rate constant and the free OH bond reorientation time scale agree well with the experiment. It is also found that, due to the small intermolecular vibrational couplings, the intermolecular vibrational energy transfer pathway that is very important in bulk water plays a much less significant role in the vibrational energy relaxation of the free OH groups at the water-air interface. PMID:27083739

  4. Geochemical Insight from Nonlinear Optical Studies of Mineral-Water Interfaces

    NASA Astrophysics Data System (ADS)

    Covert, Paul A.; Hore, Dennis K.

    2016-05-01

    The physics and chemistry of mineral-water interfaces are complex, even in idealized systems. Our need to understand this complexity is driven by both pure and applied sciences, that is, by the need for basic understanding of earth systems and for the knowledge to mitigate our influences upon them. The second-order nonlinear optical techniques of second-harmonic generation and sum-frequency generation spectroscopy have proven adept at probing these types of interfaces. This review focuses on the contributions to geochemistry made by nonlinear optical methods. The types of questions probed have included a basic description of the structure adopted by water molecules at the mineral interface, how flow and porosity affect this structure, adsorption of trace metal and organic species, and dissolution mechanisms. We also discuss directions and challenges that lie ahead and the outlook for the continued use of nonlinear optical methods for studies of mineral-water boundaries.

  5. NiAl(110)/Cr(110) interface: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Liu, W.; Li, J. C.; Zheng, W. T.; Jiang, Q.

    2006-05-01

    The optimal geometries, thermodynamic properties, and electronic structures of NiAl(110)/Cr(110) interface are studied using a first-principle density functional plane-wave ultrasoft pseudopotential method. Surface energies of different NiAl surfaces are compared with those obtained based on the classical broken-bond rule. Simulation results indicate that the structure of Ni and Al placed in the hollow sites of Cr atoms at the interface is more thermodynamically stable, and the NiCr bonding is dominated by 3d electrons of Ni and Cr. It is found that NiAl(110)/Cr(110) alloying could lower brittleness of NiAl compounds. With simulated values of adhesion work and interface energy for NiAl(110)/Cr(110) system, its mechanical and thermodynamic properties are also discussed.

  6. A dual-surfactant approach for the interfacial partitioning tracer test measurement of air-water interfacial area

    NASA Astrophysics Data System (ADS)

    El Ouni, A.; Brusseau, M. L.

    2013-12-01

    Interfacial partitioning tracer tests (IPTT) are one method available for measuring air-water interfacial area (A_ia). The method has been shown to provide uncertain measurements that are influenced by surfactant-enhanced drainage. The purpose of this work is to test a revised method that minimizes formation of interfacial-tension gradients in order to prevent surfactant-induced drainage. The method employs a dual-surfactant injection under steady unsaturated-flow conditions. Sodium dodecylbezene sulfonate (SDBS) and pentafluorobenzoic acid (PFBA) were used as the partitioning and nonreactive tracers, respectively. Sodium dodecyl sulfate (SDS) was used as the surfactant in the background solution. Three types of porous media were used for the study: a sandy soil, a well-sorted sand, and glass beads. Water saturation was monitored gravimetrically during the experiments. The results obtained with the revised method are compared to those obtained with the standard IPTT method.

  7. Influence of current velocity and wind speed on air-water gas exchange in a mangrove estuary

    NASA Astrophysics Data System (ADS)

    Ho, David T.; Coffineau, Nathalie; Hickman, Benjamin; Chow, Nicholas; Koffman, Tobias; Schlosser, Peter

    2016-04-01

    Knowledge of air-water gas transfer velocities and water residence times is necessary to study the fate of mangrove derived carbon exported into surrounding estuaries and ultimately to determine carbon balances in mangrove ecosystems. For the first time, the 3He/SF6 dual tracer technique, which has been proven to be a powerful tool to determine gas transfer velocities in the ocean, is applied to Shark River, an estuary situated in the largest contiguous mangrove forest in North America. The mean gas transfer velocity was 3.3 ± 0.2 cm h-1 during the experiment, with a water residence time of 16.5 ± 2.0 days. We propose a gas exchange parameterization that takes into account the major sources of turbulence in the estuary (i.e., bottom generated shear and wind stress).

  8. Atomic Scale Study of Interfaces Involved in Epitaxial Fe/MgO/Fe Magnetic Tunnel Junctions

    SciTech Connect

    Andrieu, S.; Serra, R.; Bonell, F.; Tiusan, C.; Calmels, L.; Snoeck, E.; Varela del Arco, Maria; Pennycook, Stephen J; Walls, M.; Colliex, C.

    2009-01-01

    Epitaxial Fe/MgO/Fe(001) magnetic tunnel junctions grown by Molecular Beam Epitaxy have been studied by using spatially resolved Electron Energy Loss Spectroscopy (EELS). The structure, the chemical composition as well as the bonding variations across the interfaces were investigated up to the atomic scale.

  9. An experimental study of liquid drop - interface coalescence in the presence of surfactants

    NASA Astrophysics Data System (ADS)

    Angeli, Panagiota; Chinaud, Maxime; Li, Kai; Wang, Wei; University College London Team; Beijing Key Laboratory of Urban Oil; Gas Distribution Technology Team

    2014-11-01

    Drop-interface coalescence has been the subject of many studies both theoretical and experimental. It is of particular interest for the oil industries particularly during the transportation of multiphase mixtures where coalescence rates can affect the stability and separation of dispersions. It is well-known that the presence of surfactants can significantly affect the coalescence rates. In this work a silicon oil -water system has been studied in a rectangular coalescence cell. Both rising oil drops and falling water drops coalescing with the water-oil interface have been investigated. A water soluble surfactant, SPAN 80, was used. High speed imaging has been performed to study the coalescence phenomenon and obtain the coalescence time of the drops with the interface with and without the presence of the surfactant. The velocity fields in the bulk fluid and in the liquid film forming between the drop and the interface were studied with shadowgraphy (bright field Particle Image Velocimetry). To increase the spatial resolution particularly in the liquid film microscope lenses were implemented. Results have been compared against existing literature.

  10. Does Interface Matter? A Study of Web Authoring and Editing by Inexperienced Web Writers

    ERIC Educational Resources Information Center

    Dick, Rodney F.

    2006-01-01

    This study explores the complicated nature of the interface as a mediational tool for inexperienced writers as they composed hypertext documents. Because technology can become so quickly and inextricably connected to people's everyday lives, it is essential to explore the effects on these technologies before they become invisible. Because…

  11. Uranium(IV) Interaction with Aqueous/Solid Interfaces Studied by Nonlinear Optics

    SciTech Connect

    Geiger, Franz

    2015-03-27

    This is the Final Technical Report for "Uranium(IV) Interaction with Aqueous/Solid Interfaces Studied by Nonlinear Optics", by Franz M. Geiger, PI, from Northwestern University, IL, USA, Grant Number SC0004101 and/or DE-PS02-ER09-07.

  12. Coupling of phytoplankton uptake and air-water exchange of persistent organic pollutants

    SciTech Connect

    Dachs, J.; Eisenreich, S.J.; Baker, J.E.; Ko, F.C.; Jeremiason, J.D.

    1999-10-15

    A dynamic model that couples air-water exchange and phytoplankton uptake of persistent organic pollutants has been developed and then applied to PCB data from a small experimental lake. A sensitivity analysis of the model, taking into account the influence of physical environmental conditions such as temperature, wind speed, and mixing depth as well as plankton-related parameters such as biomass and growth rate was carried out for a number of PCBs with different physical-chemical properties. The results indicate that air-water exchange dynamics are influenced not only by physical parameters but also by phytoplankton biomass and growth rate. New phytoplankton production results in substantially longer times to reach equilibrium. Phytoplankton uptake-induced depletion of the dissolved phase concentration maintains air and water phases out of equilibrium. Furthermore, PCBs in phytoplankton also take longer times to reach equilibrium with the dissolved water phase when the latter is supported by diffusive air-water exchange. However, both model analysis and model application to the Experimental Lakes Area of northwestern Ontario (Canada) suggest that the gas phase supports the concentrations of persistent organic pollutants, such as PCBs, in atmospherically driven aquatic environments.

  13. Oxide surfaces and metal/oxide interfaces studied by grazing incidence X-ray scattering

    NASA Astrophysics Data System (ADS)

    Renaud, Gilles

    important physical properties such as superconductivity or magnetism is also briefly reviewed. The strengths and limitations of the technique, such as the need for single crystals and surfaces of high crystalline quality are discussed. Finally, an outlook of future prospects in the field is given, such as the study of more complex oxide surfaces, vicinal surfaces, reactive metal/oxide interfaces, metal oxidation processes, the use of surfactants to promote wetting of a metal deposited on an oxide surface or the study of oxide/liquid interfaces in a non-UHV environment.

  14. Design and usability study of an iconic user interface to ease information retrieval of medical guidelines

    PubMed Central

    Griffon, Nicolas; Kerdelhué, Gaétan; Hamek, Saliha; Hassler, Sylvain; Boog, César; Lamy, Jean-Baptiste; Duclos, Catherine; Venot, Alain; Darmoni, Stéfan J

    2014-01-01

    Background and objective Doc'CISMeF (DC) is a semantic search engine used to find resources in CISMeF-BP, a quality controlled health gateway, which gathers guidelines available on the internet in French. Visualization of Concepts in Medicine (VCM) is an iconic language that may ease information retrieval tasks. This study aimed to describe the creation and evaluation of an interface integrating VCM in DC in order to make this search engine much easier to use. Methods Focus groups were organized to suggest ways to enhance information retrieval tasks using VCM in DC. A VCM interface was created and improved using the ergonomic evaluation approach. 20 physicians were recruited to compare the VCM interface with the non-VCM one. Each evaluator answered two different clinical scenarios in each interface. The ability and time taken to select a relevant resource were recorded and compared. A usability analysis was performed using the System Usability Scale (SUS). Results The VCM interface contains a filter based on icons, and icons describing each resource according to focus group recommendations. Some ergonomic issues were resolved before evaluation. Use of VCM significantly increased the success of information retrieval tasks (OR=11; 95% CI 1.4 to 507). Nonetheless, it took significantly more time to find a relevant resource with VCM interface (101 vs 65 s; p=0.02). SUS revealed ‘good’ usability with an average score of 74/100. Conclusions VCM was successfully implemented in DC as an option. It increased the success rate of information retrieval tasks, despite requiring slightly more time, and was well accepted by end-users. PMID:24650636

  15. Dust Control with Use of Air-Water Spraying System / Redukcja Zapylenia Powietrza Z Wykorzystaniem Zraszania Powietrzno-Wodnego

    NASA Astrophysics Data System (ADS)

    Prostański, Dariusz

    2012-12-01

    Results from testing the dust control efficiency, when using air-water spraying system in comparison to the typical water spraying system are presented in the paper. The tests were carried out in conditions of longwall mining and at the places of run-of-mine transportation. Also the results of stand tests of different types of nozzles both for air-water and for water spaying systems carried out at KOMAG's laboratory and in real conditions are presented. The benefits resulting from air-water spraying system have been determined.

  16. First principles studies of the stability and Shottky barriers of metal/CdTe(111) interfaces

    NASA Astrophysics Data System (ADS)

    Dorj, Odkhuu; Miao, M. S.; Kioussis, N.; Tari, S.; Aqariden, F.; Chang, Y.; Grein, C.

    2015-03-01

    CdZnTe and CdTe based semiconductor X-Ray and Gamma-Ray detectors have been intensively studied recently due to their promising potentials for achieving high-resolution, high signal-to-noise ratios and low leakage current, all are desirable features in applications ranging from medical diagnostics to homeland security. Understanding the atomic and electronic structures of the metal/semiconductor interfaces is essential for the further improvements of performance. Using density functional calculations, we systematically studied the stability, the atomic and electronic structures of the interfaces between Cd-terminated CdTe (111) surface and the selected metals. We also calculated the Schottky barrier height (SBH) by aligning the electrostatic potentials in semiconductor and metal regions. Our calculations revealed the importance of intermixing between semiconductor and metal layers and the formation of Te-metal alloys at the interface. The obtained SBH does not depend much on the choice of metals despite the large variation of the work functions. On the other hand, the interface structure is found to have large effect to the SBH, which is attributed to the metal induced states in the gap. The position of such states is insensitive to the metal work functions, as revealed by the analysis of the electronic structures.

  17. Reactive ZnO/Ti/ZnO interfaces studied by hard x-ray photoelectron spectroscopy

    SciTech Connect

    Knut, Ronny Lindblad, Rebecka; Rensmo, Håkan; Karis, Olof; Grachev, Sergey; Faou, Jean-Yvon; Søndergård, Elin

    2014-01-28

    The chemistry and intermixing at buried interfaces in sputter deposited ZnO/Ti/ZnO thin layers were studied by hard x-ray photoelectron spectroscopy. The long mean free path of the photoelectrons allowed for detailed studies of the oxidation state, band bending effects, and intrinsic doping of the buried interfaces. Oxidation of the Ti layer was observed when ZnO was deposited on top. When Ti is deposited onto ZnO, Zn Auger peaks acquire a metallic character indicating a strong reduction of ZnO at the interface. Annealing of the stack at 200 °C results in further reduction of ZnO and oxidation of Ti. Above 300 °C, oxygen transport from the bulk of the ZnO layer takes place, leading to re-oxidation of ZnO at the interface and further oxidation of Ti layer. Heating above 500 °C leads to an intermixing of the layers and the formation of a Zn{sub x}TiO{sub y} compound.

  18. Density functional theory based study of chlorine doped WS2-metal interface

    NASA Astrophysics Data System (ADS)

    Chanana, Anuja; Mahapatra, Santanu

    2016-03-01

    Investigation of a transition metal dichalcogenide (TMD)-metal interface is essential for the effective functioning of monolayer TMD based field effect transistors. In this work, we employ the Density Functional Theory calculations to analyze the modulation of the electronic structure of monolayer WS2 with chlorine doping and the relative changes in the contact properties when interfaced with gold and palladium. We initially examine the atomic and electronic structures of pure and doped monolayer WS2 supercell and explore the formation of midgap states with band splitting near the conduction band edge. Further, we analyze the contact nature of the pure supercell with Au and Pd. We find that while Au is physiosorbed and forms n-type contact, Pd is chemisorped and forms p-type contact with a higher valence electron density. Next, we study the interface formed between the Cl-doped supercell and metals and observe a reduction in the Schottky barrier height (SBH) in comparison to the pure supercell. This reduction found is higher for Pd in comparison to Au, which is further validated by examining the charge transfer occurring at the interface. Our study confirms that Cl doping is an efficient mechanism to reduce the n-SBH for both Au and Pd, which form different types of contact with WS2.

  19. Molecular Modeling of Water Interfaces: From Molecular Spectroscopy to Thermodynamics.

    PubMed

    Nagata, Yuki; Ohto, Tatsuhiko; Backus, Ellen H G; Bonn, Mischa

    2016-04-28

    Understanding aqueous interfaces at the molecular level is not only fundamentally important, but also highly relevant for a variety of disciplines. For instance, electrode-water interfaces are relevant for electrochemistry, as are mineral-water interfaces for geochemistry and air-water interfaces for environmental chemistry; water-lipid interfaces constitute the boundaries of the cell membrane, and are thus relevant for biochemistry. One of the major challenges in these fields is to link macroscopic properties such as interfacial reactivity, solubility, and permeability as well as macroscopic thermodynamic and spectroscopic observables to the structure, structural changes, and dynamics of molecules at these interfaces. Simulations, by themselves, or in conjunction with appropriate experiments, can provide such molecular-level insights into aqueous interfaces. In this contribution, we review the current state-of-the-art of three levels of molecular dynamics (MD) simulation: ab initio, force field, and coarse-grained. We discuss the advantages, the potential, and the limitations of each approach for studying aqueous interfaces, by assessing computations of the sum-frequency generation spectra and surface tension. The comparison of experimental and simulation data provides information on the challenges of future MD simulations, such as improving the force field models and the van der Waals corrections in ab initio MD simulations. Once good agreement between experimental observables and simulation can be established, the simulation can be used to provide insights into the processes at a level of detail that is generally inaccessible to experiments. As an example we discuss the mechanism of the evaporation of water. We finish by presenting an outlook outlining four future challenges for molecular dynamics simulations of aqueous interfacial systems. PMID:27010817

  20. Interfacial area transport across vertical elbows in air-water two-phase flow

    NASA Astrophysics Data System (ADS)

    Yadav, Mohan Singh

    The accurate prediction of two-phase flow using the two-fluid model requires closure relations for the interfacial area concentration ( ai), which can be provided by the interfacial area transport equation (IATE). Models have been developed for the IATE in straight pipe geometries. However, to analyze practical systems, it is important that the IATE accounts for flows in pipes with varying orientation that are interconnected via different flow restrictions. In view of this, the current study performs experiments to investigate the geometric effects of 90- degree vertical elbows in air-water two-phase flows and develops a one-group IATE applicable to vertical-upward-to-horizontal two-phase flows. The experimental facility consists of both vertical and horizontal sections constructed from 50.8 mm inner diameter acrylic pipes that are interconnected via 90-degree glass elbows. The elbows have a radius of curvature of Rc/D = 3 and are installed at L/D = 63 and 244.7 from the inlet. Experiments are performed to characterize the elbow-effect on both global and local two-phase flow parameters. A four-sensor conductivity probe is used to acquire detailed measurements of local two-phase flow parameters at thirteen axial locations along the test section in eight flow conditions that are within the bubbly flow regime at inlet. The measurements show that in bubbly flow conditions, the vertical-upward elbow causes a characteristic bimodal-type bubble distribution and the change in this distribution farther downstream of the elbow corresponds to the dissipation of the elbow-effects. In view of developing the IATE for vertical-upward to horizontal two-phase flows, predictive models for the dissipation length of the elbow-effect and closure relations for advection of gas-phase, pressure loss, and covariance of bubble interactions are developed. The new models are evaluated against the current experimental database. Overall, the model predictions agree with the data within +/-7

  1. A theoretical study of wave dispersion and thermal conduction for HMX/additive interfaces

    NASA Astrophysics Data System (ADS)

    Long, Yao; Chen, Jun

    2014-04-01

    The wave dispersion rule for non-uniform material is useful for ultrasonic inspection and engine life prediction, and also is key in achieving an understanding of the energy dissipation and thermal conduction properties of solid material. On the basis of linear response theory and molecular dynamics, we derive a set of formulas for calculating the wave dispersion rate of interface systems, and study four kinds of interfaces inside plastic bonded explosives: HMX/{HMX, TATB, F2312, F2313}. (HMX: octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine; TATB: 1,3,5-triamino-2,4,6-trinitrobenzene; F2312, F2313: fluoropolymers). The wave dispersion rate is obtained over a wide frequency range from kHz to PHz. We find that at low frequency, the rate is proportional to the square of the frequency, and at high frequency, the rate couples with the molecular vibration modes at the interface. By using the results, the thermal conductivities of HMX/additive interfaces are derived, and a physical model is built for describing the total thermal conductivity of mixture explosives, including HMX multi-particle systems and {TATB, F2312, F2313}-coated HMX.

  2. A Study of Fluid Interface Configurations in Exploration Vehicle Propellant Tanks

    NASA Technical Reports Server (NTRS)

    Zimmerli, Gregory A.; Asipauskas, Marius; Chen, Yongkang; Weislogel, Mark M.

    2010-01-01

    The equilibrium shape and location of fluid interfaces in spacecraft propellant tanks while in low-gravity is of interest to system designers, but can be challenging to predict. The propellant position can affect many aspects of the spacecraft such as the spacecraft center of mass, response to thruster firing due to sloshing, liquid acquisition, propellant mass gauging, and thermal control systems. We use Surface Evolver, a fluid interface energy minimizing algorithm, to investigate theoretical equilibrium liquid-vapor interfaces for spacecraft propellant tanks similar to those that have been considered for NASA's new class of Exploration vehicles. The choice of tank design parameters we consider are derived from the NASA Exploration Systems Architecture Study report. The local acceleration vector employed in the computations is determined by estimating low-Earth orbit (LEO) atmospheric drag effects and centrifugal forces due to a fixed spacecraft orientation with respect to the Earth or Moon, and rotisserie-type spacecraft rotation. Propellant/vapor interface positions are computed for the Earth Departure Stage and Altair lunar lander descent and ascent stage tanks for propellant loads applicable to LEO and low-lunar orbit. In some of the cases investigated the vapor ullage bubble is located at the drain end of the tank, where propellant management device hardware is often located.

  3. Study of natural convection and interface shape in directional solidification of succinonitrile

    NASA Technical Reports Server (NTRS)

    Kawaji, M.; Ojah, M.; Stojanovic, M.; De Groh, H. C.

    1992-01-01

    Flow visualization experiments in a Bridgman furnace at zero growth velocity have been performed. The experiments were intended to investigate if the photochromic dye activation method could be used in a crystal growth study. The results from this work have confirmed that with a carefully designed experimental setup, the photochromic-dye method permits qualitative and quantitative evaluation of the flow field near the interface in crystal growth experiments. For the horizontal orientation of a 6 mm x 6 mm ampoule and an axial temperature gradient of 26.5 C/cm, velocity profiles have been obtained accurately at various positions near the interface. The maximum velocity of 1.29 mm/sec was measured in the central vertical plane and the flow was symmetrical about that plane. A flow inversion point was also noted, above which the flow was towards the interface and below it, away from the interface. The results obtained are useful for validating 3-dimensional numerical models and establishing a link between the macroscopic processing conditions and the formation of crystalline defects.

  4. First principles study of Al/SrTiO3 interface formation

    NASA Astrophysics Data System (ADS)

    Hamze, Ali; Posadas, Agham; Kormondy, Kristy; Demkov, Alexander

    Two-dimensional electron gasses (2DEGs) at the interfaces of oxides have been the subject of much interest in recent years due to their relatively high carrier mobilities and potential for use in all-oxide devices. In particular, the γ-Al2O3 (γ-alumina)-SrTiO3 (STO) system has been the focus of much research. It exhibits a 2DEG at the interface with a carrier mobility ranging from 103-105 cm2V-1 s-1, depending on the thickness of the STO and how the γ-alumina film was grown. It is believed that Al atoms steal oxygen from the STO substrate at growth temperature and thus create a conductive channel in STO near the interface. We investigate the initial studies of the interface formation using density functional theory. The results of first principles calculations are compared with those of x-ray photoemission spectroscopy (XPS) performed in situ on thin Al films deposited on STO by molecular beam epitaxy. Analysis of the Al 2p XPS spectrum shows one layer of aluminum is fully oxidized during growth at 40°C and 4 layers of aluminum are fully oxidized during growth at 600°C. Furthermore, the Ti 2p XPS spectrum shows the titanium atoms are reduced, which is consistent with the presence of oxygen vacancies in STO.

  5. Experimental Study of the Richtmyer-Meshkov Instability on a Coupled Multimode and Inclined Interface Perturbation

    NASA Astrophysics Data System (ADS)

    Reilly, David; Creel, Skylar; McFarland, Jacob; Mitruka, Jatin; McDonald, Christopher; Ranjan, Devesh

    2013-11-01

    The inclined shock tube in the Texas A&M Shock Tube and Advanced Mixing Laboratory was used to study the effect of small amplitude, long wavelength multimode perturbations imposed on the inclined interface initial condition of the Richtmyer-Meshkov instability. The inclined interface is essentially a long wavelength, extremely large amplitude perturbation. Images of the shocked flow-field were captured with the angle of the shock tube with respect to the horizontal at 60° (η/ λ = √{ 3}/6). The modal content of the initial conditions was determined by taking the Fourier decomposition of the interface. This work is a proof of concept for creating a coupled multimode and inclined interface. Work that is currently underway will investigate the effect of these initial conditions on intermediate and late-time mixing as well as the transition to turbulence before reshock by using qualitative comparisons of Mie scattering images, mixing width measurements, and circulation from Particle Image Velocimetry (PIV). This research was funded by the Air Force Office of Scientific Research Young Investigator Research Program (AFOSR-YIP) grant.

  6. Molecular dynamics study on condensation/evaporation coefficients of chain molecules at liquid–vapor interface

    SciTech Connect

    Nagayama, Gyoko Takematsu, Masaki; Mizuguchi, Hirotaka; Tsuruta, Takaharu

    2015-07-07

    The structure and thermodynamic properties of the liquid–vapor interface are of fundamental interest for numerous technological implications. For simple molecules, e.g., argon and water, the molecular condensation/evaporation behavior depends strongly on their translational motion and the system temperature. Existing molecular dynamics (MD) results are consistent with the theoretical predictions based on the assumption that the liquid and vapor states in the vicinity of the liquid–vapor interface are isotropic. Additionally, similar molecular condensation/evaporation characteristics have been found for long-chain molecules, e.g., dodecane. It is unclear, however, whether the isotropic assumption is valid and whether the molecular orientation or the chain length of the molecules affects the condensation/evaporation behavior at the liquid–vapor interface. In this study, MD simulations were performed to study the molecular condensation/evaporation behavior of the straight-chain alkanes, i.e., butane, octane, and dodecane, at the liquid–vapor interface, and the effects of the molecular orientation and chain length were investigated in equilibrium systems. The results showed that the condensation/evaporation behavior of chain molecules primarily depends on the molecular translational energy and the surface temperature and is independent of the molecular chain length. Furthermore, the orientation at the liquid–vapor interface was disordered when the surface temperature was sufficiently higher than the triple point and had no significant effect on the molecular condensation/evaporation behavior. The validity of the isotropic assumption was confirmed, and we conclude that the condensation/evaporation coefficients can be predicted by the liquid-to-vapor translational length ratio, even for chain molecules.

  7. Molecular dynamics study on condensation/evaporation coefficients of chain molecules at liquid-vapor interface

    NASA Astrophysics Data System (ADS)

    Nagayama, Gyoko; Takematsu, Masaki; Mizuguchi, Hirotaka; Tsuruta, Takaharu

    2015-07-01

    The structure and thermodynamic properties of the liquid-vapor interface are of fundamental interest for numerous technological implications. For simple molecules, e.g., argon and water, the molecular condensation/evaporation behavior depends strongly on their translational motion and the system temperature. Existing molecular dynamics (MD) results are consistent with the theoretical predictions based on the assumption that the liquid and vapor states in the vicinity of the liquid-vapor interface are isotropic. Additionally, similar molecular condensation/evaporation characteristics have been found for long-chain molecules, e.g., dodecane. It is unclear, however, whether the isotropic assumption is valid and whether the molecular orientation or the chain length of the molecules affects the condensation/evaporation behavior at the liquid-vapor interface. In this study, MD simulations were performed to study the molecular condensation/evaporation behavior of the straight-chain alkanes, i.e., butane, octane, and dodecane, at the liquid-vapor interface, and the effects of the molecular orientation and chain length were investigated in equilibrium systems. The results showed that the condensation/evaporation behavior of chain molecules primarily depends on the molecular translational energy and the surface temperature and is independent of the molecular chain length. Furthermore, the orientation at the liquid-vapor interface was disordered when the surface temperature was sufficiently higher than the triple point and had no significant effect on the molecular condensation/evaporation behavior. The validity of the isotropic assumption was confirmed, and we conclude that the condensation/evaporation coefficients can be predicted by the liquid-to-vapor translational length ratio, even for chain molecules.

  8. Co-Evolution of User and Organizational Interfaces: A Longitudinal Case Study of WWW Dissemination of National Statistics.

    ERIC Educational Resources Information Center

    Marchionini, Gary

    2002-01-01

    Describes how user interfaces for the Bureau of Labor Statistics (BLS) web site evolved over a 5-year period along with the larger organizational interface and how this co-evolution has influenced the institution. Interviews with BLS staff and transaction log analysis are the foci of this study, as well as user information-seeking studies and user…

  9. Studies in RF Power Communication, SAR, and Temperature Elevation in Wireless Implantable Neural Interfaces

    PubMed Central

    Zhao, Yujuan; Tang, Lin; Rennaker, Robert; Hutchens, Chris; Ibrahim, Tamer S.

    2013-01-01

    Implantable neural interfaces are designed to provide a high spatial and temporal precision control signal implementing high degree of freedom real-time prosthetic systems. The development of a Radio Frequency (RF) wireless neural interface has the potential to expand the number of applications as well as extend the robustness and longevity compared to wired neural interfaces. However, it is well known that RF signal is absorbed by the body and can result in tissue heating. In this work, numerical studies with analytical validations are performed to provide an assessment of power, heating and specific absorption rate (SAR) associated with the wireless RF transmitting within the human head. The receiving antenna on the neural interface is designed with different geometries and modeled at a range of implanted depths within the brain in order to estimate the maximum receiving power without violating SAR and tissue temperature elevation safety regulations. Based on the size of the designed antenna, sets of frequencies between 1 GHz to 4 GHz have been investigated. As expected the simulations demonstrate that longer receiving antennas (dipole) and lower working frequencies result in greater power availability prior to violating SAR regulations. For a 15 mm dipole antenna operating at 1.24 GHz on the surface of the brain, 730 uW of power could be harvested at the Federal Communications Commission (FCC) SAR violation limit. At approximately 5 cm inside the head, this same antenna would receive 190 uW of power prior to violating SAR regulations. Finally, the 3-D bio-heat simulation results show that for all evaluated antennas and frequency combinations we reach FCC SAR limits well before 1 °C. It is clear that powering neural interfaces via RF is possible, but ultra-low power circuit designs combined with advanced simulation will be required to develop a functional antenna that meets all system requirements. PMID:24223123

  10. Interactions of anesthetics with the water-hexane interface. A molecular dynamics study

    NASA Technical Reports Server (NTRS)

    Chipot, C.; Wilson, M. A.; Pohorille, A.

    1997-01-01

    The free energy profiles characterizing the transfer of nine solutes across the liquid-vapor interfaces of water and hexane and across the water-hexane interface were calculated from molecular dynamics simulations. Among the solutes were n-butane and three of its halogenated derivatives, as well as three halogenated cyclobutanes. The two remaining molecules, dichlorodifluoromethane and 1,2-dichloroperfluoroethane, belong to series of halo-substituted methanes and ethanes, described in previous studies (J. Chem. Phys. 1996, 104, 3760; Chem. Phys. 1996, 204, 337). Each series of molecules contains structurally similar compounds that differ greatly in anesthetic potency. The accuracy of the simulations was tested by comparing the calculated and the experimental free energies of solvation of all nine compounds in water and in hexane. In addition. the calculated and the measured surface excess concentrations of n-butane at the water liquid-vapor interface were compared. In all cases, good agreement with experimental results was found. At the water-hexane interface, the free energy profiles for polar molecules exhibited significant interfacial minima, whereas the profiles for nonpolar molecules did not. The existence of these minima was interpreted in terms of a balance between the free energy contribution arising from solute-solvent interactions and the work to form a cavity that accommodates the solute. These two contributions change monotonically, but oppositely, across the interface. The interfacial solubilities of the solutes, obtained from the free energy profiles, correlate very well with their anesthetic potencies. This is the case even when the Meyer-Overton hypothesis, which predicts a correlation between anesthetic potency and solubility in oil, fails.

  11. Mechanically Enhanced Liquid Interfaces at Human Body Temperature Using Thermosensitive Methylated Nanocrystalline Cellulose.

    PubMed

    Scheuble, N; Geue, T; Kuster, S; Adamcik, J; Mezzenga, R; Windhab, E J; Fischer, P

    2016-02-01

    The mechanical performance of materials at oil/water interfaces after consumption is a key factor affecting hydrophobic drug release. In this study, we methylated the surface of nanocrystalline cellulose (NCC) by mercerization and dimethyl sulfate exposure to produce thermosensitive biopolymers. These methylated NCC (metNCC) were used to investigate interfacial thermogelation at air/water and medium-chain triglyceride (MCT)/water interfaces at body temperature. In contrast to bulk fluid dynamics, elastic layers were formed at room temperature, and elasticity increased significantly at body temperature, which was measured by interfacial shear and dilatational rheology in situ. This unique phenomenon depends on solvent quality, temperature, and polymer concentration at interfaces. Thus, by adjusting the degree of hydrophobicity of metNCC, the interfacial elasticity and thermogelation of the interfaces could be varied. In general, these new materials (metNCC) formed more brittle interfacial layers compared to commercial methylcellulose (MC A15). Thermogelation of methylcellulose promotes attractive intermolecular forces, which were reflected in a change in self-assembly of metNCC at the interface. As a consequence, layer thickness and density increased as a function of temperature. These effects were measured by atomic force microscopy (AFM) images of the displaced interface and confirmed by neutron reflection. The substantial structural and mechanical change of methylcellulose interfaces at body temperature represents a controllable encapsulation parameter allowing optimization of lipid-based drug formulations. PMID:26779953

  12. Evaluation of a Novel Conjunctive Exploratory Navigation Interface for Consumer Health Information: A Crowdsourced Comparative Study

    PubMed Central

    Cui, Licong; Carter, Rebecca

    2014-01-01

    Background Numerous consumer health information websites have been developed to provide consumers access to health information. However, lookup search is insufficient for consumers to take full advantage of these rich public information resources. Exploratory search is considered a promising complementary mechanism, but its efficacy has never before been rigorously evaluated for consumer health information retrieval interfaces. Objective This study aims to (1) introduce a novel Conjunctive Exploratory Navigation Interface (CENI) for supporting effective consumer health information retrieval and navigation, and (2) evaluate the effectiveness of CENI through a search-interface comparative evaluation using crowdsourcing with Amazon Mechanical Turk (AMT). Methods We collected over 60,000 consumer health questions from NetWellness, one of the first consumer health websites to provide high-quality health information. We designed and developed a novel conjunctive exploratory navigation interface to explore NetWellness health questions with health topics as dynamic and searchable menus. To investigate the effectiveness of CENI, we developed a second interface with keyword-based search only. A crowdsourcing comparative study was carefully designed to compare three search modes of interest: (A) the topic-navigation-based CENI, (B) the keyword-based lookup interface, and (C) either the most commonly available lookup search interface with Google, or the resident advanced search offered by NetWellness. To compare the effectiveness of the three search modes, 9 search tasks were designed with relevant health questions from NetWellness. Each task included a rating of difficulty level and questions for validating the quality of answers. Ninety anonymous and unique AMT workers were recruited as participants. Results Repeated-measures ANOVA analysis of the data showed the search modes A, B, and C had statistically significant differences among their levels of difficulty (P<.001

  13. XPS Study of SiO2 and the Si/SiO2 Interface

    NASA Technical Reports Server (NTRS)

    Grunthaner, F. J.; Grunthaner, P. J.; Vasquez, R. P.; Lewis, B. F.; Maserjian, J.; Madhukar, A.

    1982-01-01

    X-ray photoelectron spectroscopy (XPS) is analytical technique for understanding electronic structure of atoms close to surface in solids, in preference to bulk structure of material. Study found evidence for core-level chemical shifts arising from changes in local structural environment in amorphous SiO2 and at Si/SiO2 interface. Observed XPS spectra may be understood as sequential convolution of several functions, each with well-defined physical interpretation.

  14. Studies of the analyte-carrier interface in flow injection analysis

    SciTech Connect

    Brown, S.D.

    1992-01-01

    Chemical analysis in flowing solution is popular for automation of classical methods. However, most of the classical methods are not specific enough for direct multicomponent analysis of simple mixtures. This research project has the goals of study of rapid multicomponent analysis of transient species in flowing media, and investigations of chemical reactions at interfaces and of effects of competition on distribution of products from interfacial reaction. This report summarizes work done over the past 4.5 years; support has been terminated.

  15. Air-Water Exchange of Legacy and Emerging Organic Pollutants across the Great Lakes

    NASA Astrophysics Data System (ADS)

    Lohmann, R.; Ruge, Z.; Khairy, M.; Muir, D.; Helm, P.

    2014-12-01

    Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) are transported to great water bodies via long-range atmospheric transport and released from the surface water as air concentrations continue to diminish. As the largest fresh water bodies in North America, the Great Lakes have both the potential to accumulate and serve as a secondary source of persistent bioaccumulative toxins. OCP and PCB concentrations were sampled at 30+ sites across Lake Superior, Ontario and Erie in the summer of 2011. Polyethylene passive samplers (PEs) were simultaneously deployed in surface water and near surface atmosphere to determine air-water gaseous exchange of OCPs and PCBs. In Lake Superior, surface water and atmospheric concentrations were dominated by α-HCH (average 250 pg/L and 4.2 pg/m3, respectively), followed by HCB (average 17 pg/L and 89 pg/m3, respectively). Air-water exchange varied greatly between sites and individual OCPs, however α-endosulfan was consistently deposited into the surface water (average 19 pg/m2/day). PCBs in the air and water were characterized by penta- and hexachlorobiphenyls with distribution along the coast correlated with proximity to developed areas. Air-water exchange gradients generally yielded net volatilization of PCBs out of Lake Superior. Gaseous concentrations of hexachlorobenzene, dieldrin and chlordanes were significantly higher (p < 0.05) at Lake Erie than Lake Ontario. A multiple linear regression that incorporated meteorological, landuse and population data was used to explain variability in the atmospheric concentrations. Results indicated that landuse (urban and/or cropland) greatly explained the variability in the data. Freely dissolved concentrations of OCPs (

  16. Storable droplet interface lipid bilayers for cell-free ion channel studies.

    PubMed

    Jung, Sung-Ho; Choi, Sangbaek; Kim, Young-Rok; Jeon, Tae-Joon

    2012-01-01

    An artificially created lipid bilayer is an important platform in studying ion channels and engineered biosensor applications. However, a lipid bilayer created using conventional techniques is fragile and short-lived, and the measurement of ion channels requires expertise and laborious procedures, precluding practical applications. Here, we demonstrate a storable droplet lipid bilayer precursor frozen with ion channels, resulting in a droplet interface bilayer upon thawing. A small vial with an aqueous droplet in organic solution was flash frozen in -80 °C methanol immediately after an aqueous droplet was introduced into the organic solution and gravity draws the droplet down to the interface upon thawing. A lipid bilayer created along the interface using this method had giga-ohm resistance and typical specific capacitance values. The noise level of this system is favorably comparable to the conventional system. The subsequent incorporation of ion channels, alpha-hemolysin and gramicidin A, showed typical conductance values consistent with those in previous literatures. This novel system to create a lipid bilayer as a whole can be automated from its manufacture to use and indefinitely stored when frozen. As a result, ion channel measurements can be carried out in any place, increasing the accessibility of ion channel studies as well as a number of applications, such as biosensors, ion channel drug screening, and biophysical studies. PMID:21909672

  17. Fermi-level pinning through defects at GaAs/oxide interfaces: A density functional study

    NASA Astrophysics Data System (ADS)

    Colleoni, Davide; Miceli, Giacomo; Pasquarello, Alfredo

    2015-09-01

    Using density functional calculations, we study a set of candidate defects for Fermi-level pinning at GaAs/oxide interfaces. The set of considered defects comprises both bulklike and interfacial defects, including As antisites, Ga and As dangling bonds, the As-As dimer/dangling bond defect, and several defect complexes. The defects are generated within atomistic model structures representing the GaAs /Al2O3 interface. Formation energies of bulklike defects are obtained and compared with those of corresponding bulk defects, while interfacial defects are studied through their relative defect energies. Finite-size corrections to the defect energies are applied through a scheme that accounts for the interfacial geometry of our models. Defect levels are defined as thermodynamic transition levels between different charge states and are calculated for all considered defects. Through an alignment procedure based on hybrid functional calculations, the defect levels are then positioned within the calculated band gap of GaAs that reproduces the experimental one, thereby enabling direct comparisons with the experimental density of defect states. Our study shows that several As-related defects show a similar amphoteric bistability between an As-As dimer state and a configuration with two doubly occupied As dangling bonds. The associated charge transition levels generally lie in the midgap region, in accord with experimental observations. This mechanism is proposed as the origin of the observed Fermi-level pinning at GaAs/oxide interfaces.

  18. Cholesterol Promotes Interaction of the Protein CLIC1 with Phospholipid Monolayers at the Air-Water Interface.

    PubMed

    Hossain, Khondker R; Al Khamici, Heba; Holt, Stephen A; Valenzuela, Stella M

    2016-01-01

    CLIC1 is a Chloride Intracellular Ion Channel protein that exists either in a soluble state in the cytoplasm or as a membrane bound protein. Members of the CLIC family are largely soluble proteins that possess the intriguing property of spontaneous insertion into phospholipid bilayers to form integral membrane ion channels. The regulatory role of cholesterol in the ion-channel activity of CLIC1 in tethered lipid bilayers was previously assessed using impedance spectroscopy. Here we extend this investigation by evaluating the influence of cholesterol on the spontaneous membrane insertion of CLIC1 into Langmuir film monolayers prepared using 1-palmitoyl-2-oleoylphosphatidylcholine, 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-ethanolamine and 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-L-serine alone or in combination with cholesterol. The spontaneous membrane insertion of CLIC1 was shown to be dependent on the presence of cholesterol in the membrane. Furthermore, pre-incubation of CLIC1 with cholesterol prior to its addition to the Langmuir film, showed no membrane insertion even in monolayers containing cholesterol, suggesting the formation of a CLIC1-cholesterol pre-complex. Our results therefore suggest that CLIC1 membrane interaction involves CLIC1 binding to cholesterol located in the membrane for its initial docking followed by insertion. Subsequent structural rearrangements of the protein would likely also be required along with oligomerisation to form functional ion channels. PMID:26875987

  19. Regionalized global budget of the CO2 exchange at the air-water interface in continental shelf seas

    NASA Astrophysics Data System (ADS)

    Laruelle, Goulven G.; Lauerwald, Ronny; Pfeil, Benjamin; Regnier, Pierre

    2014-11-01

    Over the past decade, estimates of the atmospheric CO2 uptake by continental shelf seas were constrained within the 0.18-0.45 Pg C yr-1 range. However, most of those estimates are based on extrapolations from limited data sets of local flux measurements (n < 100). Here we propose to derive the CO2 air-sea exchange of the shelf seas by extracting 3 · 106 direct surface ocean CO2 measurements from the global database SOCAT (Surface Ocean CO2 Atlas), atmospheric CO2 values from GlobalVIEW and calculating gas transfer rates using readily available global temperature, salinity, and wind speed fields. We then aggregate our results using a global segmentation of the shelf in 45 units and 152 subunits to establish a consistent regionalized CO2 exchange budget at the global scale. Within each unit, the data density determines the spatial and temporal resolutions at which the air-sea CO2 fluxes are calculated and range from a 0.5° resolution in the best surveyed regions to a whole unit resolution in areas where data coverage is limited. Our approach also accounts, for the first time, for the partial sea ice cover of polar shelves. Our new regionalized global CO2 sink estimate of 0.19 ± 0.05 Pg C yr-1 falls in the low end of previous estimates. Reported to an ice-free surface area of 22 · 106 km2, this value yields a flux density of 0.7 mol C m-2 yr-1, ~40% more intense than that of the open ocean. Our results also highlight the significant contribution of Arctic shelves to this global CO2 uptake (0.07 Pg C yr-1).

  20. Interaction between dimer interface residues of native and mutated SOD1 protein: a theoretical study.

    PubMed

    Keerthana, S P; Kolandaivel, P

    2015-04-01

    Cu-Zn superoxide dismutase 1 (SOD1) is a highly conserved bimetallic protein enzyme, used for the scavenging the superoxide radicals (O2 (-)) produced due to aerobic metabolism in the mitochondrial respiratory chain. Over 100 mutations have been identified and found to be in the homodimeric structure of SOD1. The enzyme has to be maintained in its dimeric state for the structural stability and enzymatic activity. From our investigation, we found that the mutations apart from the dimer interface residues are found to affect the dimer stability of protein and hence enhancing the aggregation and misfolding tendency of mutated protein. The homodimeric state of SOD1 is found to be held together by the non-covalent interactions. The molecular dynamics simulation has been used to study the hydrogen bond interactions between the dimer interface residues of the monomers in native and mutated forms of SOD1 in apo- and holo-states. The results obtained by this analysis reveal the fact that the loss of hydrogen bond interactions between the monomers of the dimer is responsible for the reduced stability of the apo- and holo-mutant forms of SOD1. The conformers with dimer interface residues in native and mutated protein obtained by the molecular dynamics simulation is subjected to quantum mechanical study using M052X/6-31G(d) level of theory. The charge transfer between N-H···O interactions in the dimer interface residues were studied. The weak interaction between the monomers of the dimer accounts for the reduced dimerization and enhanced deformation energy in the mutated SOD1 protein. PMID:25578810

  1. Cr/B4C multilayer mirrors: Study of interfaces and X-ray reflectance

    DOE PAGESBeta

    Burcklen, C.; Soufli, R.; Gullikson, E.; Meltchakov, E.; Dennetiere, D.; Polack, F.; Capitanio, B.; Thomasset, M.; Jerome, A.; de Rossi, S.; et al

    2016-03-24

    Here, we present an experimental study of the effect of layer interfaces on the x-ray reflectance in Cr/B4C multilayer interference coatings with layer thicknesses ranging from 0.7 nm to 5.4 nm. The multilayers were deposited by magnetron sputtering and by ion beam sputtering. Grazing incidence x-ray reflectometry, soft x-ray reflectometry, and transmission electron microscopy reveal asymmetric multilayer structures with a larger B4C-on-Cr interface, which we modeled with a 1–1.5 nm thick interfacial layer. Reflectance measurements in the vicinity of the Cr L2,3 absorption edge demonstrate fine structure that is not predicted by simulations using the currently tabulated refractive index (opticalmore » constants) values for Cr.« less

  2. The Pt(111)/electrolyte interface under oxygen reduction reaction conditions: an electrochemical impedance spectroscopy study.

    PubMed

    Bondarenko, Alexander S; Stephens, Ifan E L; Hansen, Heine A; Pérez-Alonso, Francisco J; Tripkovic, Vladimir; Johansson, Tobias P; Rossmeisl, Jan; Nørskov, Jens K; Chorkendorff, Ib

    2011-03-01

    The Pt(111)/electrolyte interface has been characterized during the oxygen reduction reaction (ORR) in 0.1 M HClO(4) using electrochemical impedance spectroscopy. The surface was studied within the potential region where adsorption of OH* and O* species occur without significant place exchange between the adsorbate and Pt surface atoms (0.45-1.15 V vs RHE). An equivalent electric circuit is proposed to model the Pt(111)/electrolyte interface under ORR conditions within the selected potential window. This equivalent circuit reflects three processes with different time constants, which occur simultaneously during the ORR at Pt(111). Density functional theory (DFT) calculations were used to correlate and interpret the results of the measurements. The calculations indicate that the coadsorption of ClO(4)* and Cl* with OH* is unlikely. Our analysis suggests that the two-dimensional (2D) structures formed in O(2)-free solution are also formed under ORR conditions. PMID:21244087

  3. A comparative study of the thermal interface materials with graphene and boron nitride fillers

    NASA Astrophysics Data System (ADS)

    Kargar, F.; Salgado, R.; Legedza, S.; Renteria, J.; Balandin, A. A.

    2014-09-01

    We report the results of an experimental study that compares the performance of graphene and boron nitride flakes as fillers in the thermal interface materials. The thickness of both fillers varied from a single atomic plane to about a hundred. The measurements have been conducted using a standard TIM tester. Our results show that the addition of a small fraction of graphene (f=4 wt%) to a commercial thermal interface material increases the resulting apparent thermal conductivity substantially stronger than the addition of boron nitride. The obtained data suggest that graphene and fewlayer graphene flakes couple better to the matrix materials than the boron nitride fillers. A combination of both fillers can be used to increase the thermal conductivity while controlling the electrical conduction.

  4. X-ray absorption studies of Ti/polymer and Cr/polymer interfaces

    SciTech Connect

    Opila, R.L.; Konstadinidis, K.; Ibidunni, A.O; Davenport, A.J.; Isaacs, H.S.

    1993-11-01

    The interface formed between metals, Ti and Cr, and polymers, epoxy, and triazine, have been studied, non-destructively, using x-ray absorption spectroscopy. The metals were sputtered onto the polymer surfaces. Titanium reacts extensively, up to Ti thickness of 100 {Angstrom} while Cr remains primarily metallic. In situ heating at 200{degree}C increases the extent of reaction for both metals. Heating has a greater effect on metal/epoxy interfaces than metal/triazine. Titanium and Cr were ion implanted into the polymer in order to determine the interactions of isolated metal atoms with the polymer. Titanium and Cr appear to form oxides as the final reaction product, and the Ti is tetrahedrally coordinated.

  5. First-principles study of the Fe | MgO(0 0 1) interface: magnetic anisotropy.

    PubMed

    Bose, Thomas; Cuadrado, Ramon; Evans, Richard F L; Chepulskii, Roman V; Apalkov, Dmytro; Chantrell, Roy W

    2016-04-20

    We present a systematic first-principles study of Fe | MgO bilayer systems emphasizing the influence of the iron layer thickness on the geometry, the electronic structure and the magnetic properties. Our calculations ensure the unconstrained structural relaxation at scalar relativistic level for various numbers of iron layers placed on the magnesium oxide substrate. Our results show that due to the formation of the interface the electronic structure of the interface iron atoms is significantly modified involving charge transfer within the iron subsystem. In addition, we find that the magnetic anisotropy energy increases from 1.9 mJ m(-2) for 3 Fe layers up to 3.0 mJ m(-2) for 11 Fe layers. PMID:26987845

  6. Cr/B4C multilayer mirrors: Study of interfaces and X-ray reflectance

    NASA Astrophysics Data System (ADS)

    Burcklen, C.; Soufli, R.; Dennetiere, D.; Polack, F.; Capitanio, B.; Gullikson, E.; Meltchakov, E.; Thomasset, M.; Jérome, A.; de Rossi, S.; Delmotte, F.

    2016-03-01

    We present an experimental study of the effect of layer interfaces on the x-ray reflectance in Cr/B4C multilayer interference coatings with layer thicknesses ranging from 0.7 nm to 5.4 nm. The multilayers were deposited by magnetron sputtering and by ion beam sputtering. Grazing incidence x-ray reflectometry, soft x-ray reflectometry, and transmission electron microscopy reveal asymmetric multilayer structures with a larger B4C-on-Cr interface, which we modeled with a 1-1.5 nm thick interfacial layer. Reflectance measurements in the vicinity of the Cr L2,3 absorption edge demonstrate fine structure that is not predicted by simulations using the currently tabulated refractive index (optical constants) values for Cr.

  7. Application of Neutron Reflectivity for Studies of Biomolecular Structures and Functions at Interfaces

    SciTech Connect

    Johs, Alexander; Liang, Liyuan; Gu, Baohua; Ankner, John Francis; Wang, Wei

    2009-01-01

    Structures and functions of cell membranes are of central importance in understanding processes such as cell signaling, chemotaxis, redox transformation, biofilm formation, and mineralization occurring at interfaces. This chapter provides an overview of the application of neutron reflectivity (NR) as a unique tool for probing biomolecular structures and mechanisms as a first step toward understanding protein protein, protein lipid, and protein mineral interactions at the membrane substrate interfaces. Emphasis is given to the review of existing literature on the assembly of biomimetic membrane systems, such as supported membranes for NR studies, and demonstration of model calculations showing the potential of NR to elucidate molecular fundamentals of microbial cell mineral interactions and structure functional relationships of electron transport pathways. The increased neutron flux afforded by current and upcoming neutron sources holds promise for elucidating detailed processes such as phase separation, formation of microdomains, and membrane interactions with proteins and peptides in biological systems.

  8. Theoretical Study of Excess Si Emitted from Si-oxide/Si Interfaces

    NASA Astrophysics Data System (ADS)

    Kageshima, Hiroyuki; Uematsu, Masahi; Akagi, Kazuto; Tsuneyuki, Shinji; Akiyama, Toru; Shiraishi, Kenji

    2004-12-01

    The excess Si emitted from the Si-oxide/Si interface is studied using the first-principles calculations. It is shown that the excess Si can have many (meta-) stable positions around the interface. In addition, some positions in the oxide do not have any dangling bonds or floating bonds in contrast to those in the bulk crystalline Si. The results indicate that the emitted Si can be located in the oxide layer but they do not necessarily cause charge traps in the oxide. The emitted Si atoms are thought to just be oxidized and absorbed into the oxide while a portion of them cause the E' centers, the Pb centers or charge traps.

  9. Molecular dynamics study of two-dimensional sum frequency generation spectra at vapor/water interface

    SciTech Connect

    Ishiyama, Tatsuya; Morita, Akihiro; Tahara, Tahei

    2015-06-07

    Two-dimensional heterodyne-detected vibrational sum frequency generation (2D HD-VSFG) spectra at vapor/water interface were studied by molecular dynamics (MD) simulation with a classical flexible and nonpolarizable model. The present model well describes the spectral diffusion of 2D infrared spectrum of bulk water as well as 2D HD-VSFG at the interface. The effect of isotopic dilution on the 2D HD-VSFG was elucidated by comparing the normal (H{sub 2}O) water and HOD water. We further performed decomposition analysis of 2D HD-VSFG into the hydrogen-bonding and the dangling (or free) OH vibrations, and thereby disentangled the different spectral responses and spectral diffusion in the 2D HD-VSFG. The present MD simulation demonstrated the role of anharmonic coupling between these modes on the cross peak in the 2D HD-VSFG spectrum.

  10. Ti/CeOx(111) interfaces studied by XPS and STM

    NASA Astrophysics Data System (ADS)

    Zhou, Yinghui; Zhou, Jing

    2012-04-01

    Low coverage of Ti was deposited on the well-ordered CeOx(111) (1.5 < x < 2) thin films grown on Ru(0001) by physical vapor deposition at room temperature. The structure and interaction of Ti/ceria interfaces were investigated with X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM) techniques under ultrahigh vacuum conditions. XPS data indicate that the deposition of Ti on both oxidized and reduced ceria surfaces causes the partial reduction of Ce from + 4 to + 3 state. Ti is formally in the + 4 state. STM data show the formation of small atomic-like titania features at 300 K, which coalesce to form chain structures upon heating. It is demonstrated in the study that the deposition of Ti can form mixed metal oxides at the interface and modify both electronic and structural properties of the ceria support. The structural study of Ti/ceria interfaces can be a key for understanding the higher catalytic activity of the Ti-CeOx mixed oxide catalysts as compared with the individual pure oxides.

  11. Studies of ferroelectric heterostructure thin films and interfaces via in situ analytical techniques.

    SciTech Connect

    Auciello, O.; Dhote, A.; Gao, Y.; Gruen, D. M.; Im, J.; Irene, E. A.; Krauss, A. R.; Mueller, A. H.; Ramesh, R.

    1999-08-30

    The science and technology of ferroelectric thin films has experienced an explosive development during the last ten years. Low-density non-volatile ferroelectric random access memories (NVFRAMs) are now incorporated in commercial products such as ''smart cards'', while high permittivity capacitors are incorporated in cellular phones. However, substantial work is still needed to develop materials integration strategies for high-density memories. We have demonstrated that the implementation of complementary in situ characterization techniques is critical to understand film growth and interface processes, which play critical roles in film microstructure and properties. We are using uniquely integrated time of flight ion scattering and recoil spectroscopy (TOF-ISARS) and spectroscopic ellipsometry (SE) techniques to perform in situ, real-time studies of film growth processes in the high background gas pressure required to growth ferroelectric thin films. TOF-ISARS provides information on surface processes, while SE permits the investigation of buried interfaces as they are being formed. Recent studies on SrBi{sub 2}Ta{sub 2}O{sub 9} (SBT) and Ba{sub x}Sr{sub 1{minus}x}TiO{sub 3} (BST) film growth and interface processes are discussed.

  12. Single-crystal-silicon-based microinstrument to study friction and wear at MEMS sidewall interfaces

    NASA Astrophysics Data System (ADS)

    Ansari, N.; Ashurst, W. R.

    2012-02-01

    Since the advent of microelectromechanical systems (MEMS) technology, friction and wear are considered as key factors that determine the lifetime and reliability of MEMS devices that contain contacting interfaces. However, to date, our knowledge of the mechanisms that govern friction and wear in MEMS is insufficient. Therefore, systematically investigating friction and wear at MEMS scale is critical for the commercial success of many potential MEMS devices. Specifically, since many emerging MEMS devices contain more sidewall interfaces, which are topographically and chemically different from in-plane interfaces, studying the friction and wear characteristics of MEMS sidewall surfaces is important. The microinstruments that have been used to date to investigate the friction and wear characteristics of MEMS sidewall surfaces possess several limitations induced either by their design or the structural film used to fabricate them. Therefore, in this paper, we report on a single-crystal-silicon-based microinstrument to study the frictional and wear behavior of MEMS sidewalls, which not only addresses some of the limitations of other microinstruments but is also easy to fabricate. The design, modeling and fabrication of the microinstrument are described in this paper. Additionally, the coefficients of static and dynamic friction of octadecyltrichlorosilane-coated sidewall surfaces as well as sidewall surfaces with only native oxide on them are also reported in this paper.

  13. Theoretical study of binding and permeation of ether-based polymers through interfaces.

    PubMed

    Samanta, Susruta; Hezaveh, Samira; Roccatano, Danilo

    2013-11-27

    We present a molecular dynamics simulation study on the interactions of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and their ABA-type block copolymer, poloxamers, at water/n-heptane and 1,2-dimyristoyl-sn-glycero-3-phospatidycholine (DMPC) lipid bilayer/water interfaces. The partition coefficients in water/1-octanol of the linear polyethers up to three monomers were calculated. The partition coefficients evidenced a higher hydrophobicity of the PPO in comparison to PEO. At the water/n-heptane interface, the polymers tend to adopt elongated conformations in agreement with similar experimental ellipsometry studies of different poloxamers. In the case of the poloxamers at the n-heptane/water interface, the stronger preference of the PPO block for the hydrophobic phase resulted in bottle-brush-type polymer conformations. At lipid bilayer/water interface, the PEO polymers, as expected from their hydrophilic nature, are weakly adsorbed on the surface of the lipid bilayer and locate in the water phase close to the headgroups. The free energy barriers of permeation calculated for short polymer chains suggest a thermodynamics propensity for the water phase that increase with the chain length. The lower affinity of PEO for the hydrophobic interior of the lipid bilayer resulted in the spontaneous expulsion within the simulation time. On the contrary, PPO chains and poloxamers have a longer residence time inside the bilayer, and they tend to concentrate in the tail region of the bilayer near the polar headgroups. In addition, polymers with PPO unit length comparable to the thickness of the hydrophobic region of the bilayer tend to span across the bilayer. PMID:24219592

  14. Air-water gas exchange and CO2 flux in a mangrove-dominated estuary

    USGS Publications Warehouse

    Ho, David T.; Ferrón, Sara; Engel, Victor C.; Larsen, Laurel G.; Barr, Jordan G.

    2014-01-01

    Mangrove forests are highly productive ecosystems, but the fate of mangrove-derived carbon remains uncertain. Part of that uncertainty stems from the fact that gas transfer velocities in mangrove-surrounded waters are not well determined, leading to uncertainty in air-water CO2 fluxes. Two SF6 tracer release experiments were conducted to determine gas transfer velocities (k(600) = 8.3 ± 0.4 and 8.1 ± 0.6 cm h−1), along with simultaneous measurements of pCO2 to determine the air-water CO2 fluxes from Shark River, Florida (232.11 ± 23.69 and 171.13 ± 20.28 mmol C m−2 d−1), an estuary within the largest contiguous mangrove forest in North America. The gas transfer velocity results are consistent with turbulent kinetic energy dissipation measurements, indicating a higher rate of turbulence and gas exchange than predicted by commonly used wind speed/gas exchange parameterizations. The results have important implications for carbon fluxes in mangrove ecosystems.

  15. Novel methods for measuring air-water interfacial area in unsaturated porous media.

    PubMed

    Brusseau, Mark L; El Ouni, Asma; Araujo, Juliana B; Zhong, Hua

    2015-05-01

    Interfacial partitioning tracer tests (IPTT) are used to measure air-water interfacial area for unsaturated porous media. The standard IPTT method involves conducting tests wherein an aqueous surfactant solution is introduced into a packed column under unsaturated flow conditions. Surfactant-induced drainage has been observed to occur for this method in some cases, which can complicate data analysis and impart uncertainty to the measured values. Two novel alternative approaches for conducting IPTTs are presented herein that are designed in part to prevent surfactant-induced drainage. The two methods are termed the dual-surfactant IPTT (IPTT-DS) and the residual-air IPTT (IPTT-RA). The two methods were used to measure air-water interfacial areas for two natural porous media. System monitoring during the tests revealed no measurable surfactant-induced drainage. The measured interfacial areas compared well to those obtained with the standard IPTT method conducted in such a manner that surfactant-induced drainage was prevented. PMID:25732632

  16. NOVEL METHODS FOR MEASURING AIR-WATER INTERFACIAL AREA IN UNSATURATED POROUS MEDIA

    PubMed Central

    Brusseau, Mark L.; Ouni, Asma El; Araujo, Juliana B.; Zhong, Hua

    2015-01-01

    Interfacial partitioning tracer tests (IPTT) are used to measure air-water interfacial area for unsaturated porous media. The standard IPTT method involves conducting tests wherein an aqueous surfactant solution is introduced into a packed column under unsaturated flow conditions. Surfactant-induced drainage has been observed to occur for this method in some cases, which can complicate data analysis and impart uncertainty to the measured values. Two novel alternative approaches for conducting IPTTs are presented herein that are designed in part to prevent surfactant-induced drainage. The two methods are termed the dual-surfactant IPTT (IPTT-DS) and the residual-air IPTT (IPTT-RA). The two methods were used to measure air-water interfacial areas for two natural porous media. System monitoring during the tests revealed no measurable surfactant-induced drainage. The measured interfacial areas compared well to those obtained with the standard IPTT method conducted in such a manner that surfactant-induced drainage was prevented. PMID:25732632

  17. Air-water ‘tornado’-type microwave plasmas applied for sugarcane biomass treatment

    NASA Astrophysics Data System (ADS)

    Bundaleska, N.; Tatarova, E.; Dias, F. M.; Lino da Silva, M.; Ferreira, C. M.; Amorim, J.

    2014-02-01

    The production of cellulosic ethanol from sugarcane biomass is an attractive alternative to the use of fossil fuels. Pretreatment is needed to separate the cellulosic material, which is packed with hemicellulose and lignin in cell wall of sugarcane biomass. A microwave ‘tornado’-type air-water plasma source operating at 2.45 GHz and atmospheric pressure has been applied for this purpose. Samples of dry and wet biomass (˜2 g) have been exposed to the late afterglow plasma stream. The experiments demonstrate that the air-water highly reactive plasma environment provides a number of long-lived active species able to destroy the cellulosic wrapping. Scanning electron microscopy has been applied to analyse the morphological changes occurring due to plasma treatment. The effluent gas streams have been analysed by Fourier-transform infrared spectroscopy (FT-IR). Optical emission spectroscopy and FT-IR have been applied to determine the gas temperature in the discharge and late afterglow plasma zones, respectively. The optimal range of the operational parameters is discussed along with the main active species involved in the treatment process. Synergistic effects can result from the action of singlet O2(a 1Δg) oxygen, NO2, nitrous acid HNO2 and OH hydroxyl radical.

  18. Air-water gas exchange and CO2 flux in a mangrove-dominated estuary

    NASA Astrophysics Data System (ADS)

    Ho, David T.; Ferrón, Sara; Engel, Victor C.; Larsen, Laurel G.; Barr, Jordan G.

    2014-01-01

    forests are highly productive ecosystems, but the fate of mangrove-derived carbon remains uncertain. Part of that uncertainty stems from the fact that gas transfer velocities in mangrove-surrounded waters are not well determined, leading to uncertainty in air-water CO2 fluxes. Two SF6 tracer release experiments were conducted to determine gas transfer velocities (k(600) = 8.3 ± 0.4 and 8.1 ± 0.6 cm h-1), along with simultaneous measurements of pCO2 to determine the air-water CO2 fluxes from Shark River, Florida (232.11 ± 23.69 and 171.13 ± 20.28 mmol C m-2 d-1), an estuary within the largest contiguous mangrove forest in North America. The gas transfer velocity results are consistent with turbulent kinetic energy dissipation measurements, indicating a higher rate of turbulence and gas exchange than predicted by commonly used wind speed/gas exchange parameterizations. The results have important implications for carbon fluxes in mangrove ecosystems.

  19. Synchrotron-radiation photoemission study of the ultrathin Ba/3C-SiC(111) interface

    NASA Astrophysics Data System (ADS)

    Kukushkin, S. A.; Benemanskaya, G. V.; Dementev, P. A.; Timoshnev, S. N.; Senkovskiy, B.

    2016-03-01

    Electronic structure of the Ba/3C-SiC(111) interface has been detailed studied in situ in an ultrahigh vacuum using synchrotron radiation photoemission spectroscopy with photon energies in the range of 100-450 eV. The 3C-SiC(111) samples were grown by a new method of epitaxy of low-defect unstressed nanoscaled silicon carbide films on silicon substrates. Valence band photoemission and both the Si 2p, C 1s core level spectra have been investigated as a function of Ba submonolayer coverage. Under Ba adsorption two induced surface bands are found at binding energies of 2 eV and 6 eV. It is obtained that Ba/3C-SiC(111) interface can be characterized as metallic-like. Modification of both the Si 2p and C 1s surface-related components were ascertained and shown to be provided by redistribution effect of electron density between Ba adatoms and both the Si surface and C interface atoms.

  20. First-Principles Study of Enhanced Magnetoelectric Effects at the Fe/MgO(001) Interface

    NASA Astrophysics Data System (ADS)

    Niranjan, M. K.; Jaswal, S. S.; Tsymbal, E. Y.; Duan, C.-G.

    2010-03-01

    The magnetoelectric effect allows affecting magnetic properties of materials by electric fields with potential for technological applications such as electrically controlled magnetic data storage. In this study we explore, using first-principles methods, the magnetoelectric effect at the Fe/MgO(001) interface^,1. By explicitly introducing an electric field in our density-functional calculations we demonstrate that the magnetic moment of Fe atoms at the interface changes linearly as a function of the applied electric field with the surface magnetoelectric coefficient being strongly enhanced as compared to that for the clean Fe(001) surface.^1 The effect originates from the increased screening charge associated with a large dielectric constant of MgO. The influence of electric field on relative occupancy of the Fe-3d orbitals leads to significant change in the surface magnetocrystalline anisotropy. These results are compared with the available experimental work.^2 Our results indicate that using high-k dielectrics at the interface with ferromagnetic metals may be very effective in controlling the magnetic properties by electric fields thereby leading to interesting device applications. ^1 C.-G. Duan et al., Phys. Rev. Lett. 101, 137201 (2008). ^2 T. Maruyama et al., Nat. Nanotech., 4, 158 (2009).

  1. A comparative study about electronic structures at rubrene/Ag and Ag/rubrene interfaces

    SciTech Connect

    Sinha, Sumona Mukherjee, M.

    2015-10-15

    The contact between the electrode and the organic semiconductor is one of the most crucial factors in determining the organic device performance. The development and production technology of different organic devices require the understanding of different types of metal/organic semiconducting thin film interfaces. Comparisons about the electronic structures at Rubrene/Ag and Ag/Rubrene interfaces have been studied using photoemission spectroscopy. The Ag on rubrene interfaces is found to show more interesting and complex natures than its counterpart. The vacuum level (VL) was shifted about 0.51 eV from push back effect for deposition of 5 Å rubrene onto Ag film whereas the electronic features of silver was only suppressed and no energy shift was resulted. While the deposition of 5 Å Ag onto rubrene film leads to the diffusion of the Ag atoms, as a cluster with quantum size effect, inside the film. Angle dependent XPS measurement indicates that diffused metal clusters were present at entire probed depth of the film. Moreover these clusters dope the uppermost surface of the rubrene film which consequences a shift of the electronic states of thick organic film towards higher binding energy. The VL was found to shift about 0.31 eV toward higher binding energy whereas the shift was around 0.21 eV for the electronic states of rubrene layer.

  2. XPS study of interface formation of CVD SiO2 on InSb

    NASA Astrophysics Data System (ADS)

    Vasquez, R. P.; Grunthaner, F. J.

    1981-10-01

    The interfacial chemistry of CVD SiO2 films deposited on thin native oxides grown on InSb substrates is examined using X-ray photoemission spectroscopy (XPS) and a relatively benign chemical etching technique for depth profiling. An intensity analysis of XPS spectra is used to derive the compositional structure of the interfaces obtained in the SiO2/native oxide/InSb system. Peak positions in these spectra are used to follow the change in substrate surface potential during the etch sequence, and to establish the chemical nature of the species formed during deposition and subsequent processing. Reaction of the substrate with oxygen resulted in an In-rich native oxide and 1-2 monolayers of excess elemental Sb at the native-oxide/substrate interface, incompletely oxidized silane reduced the native oxide, leaving less than 1 monolayer of elemental In at the SiO2/native oxide interface. Etch removal of this thin In-rich layer leads to a change in the substrate surface potential of 0.06 eV, corresponding to a net increase in positive charge. The results are consistent with simple thermodynamic considerations; they are also compared to previously reported studies of deposited dielectrics on III-V compound semiconductors.

  3. Spectroscopic studies of U(VI) sorption at the kaolinite-water interface. Final report

    SciTech Connect

    Thompson, H.A.; Parks, G.A.; Brown, G.E. Jr.

    1994-06-01

    Efficient use of U as a resource and safe handling, recycling and disposal of U-containing wastes require an understanding of the factors controlling the fate of U, where fate refers to the destination of U, typically expressed as an environmental medium or a process phase. The sorption process constitutes a change in elemental fate. Partitioning of an element from solution to a solid phase, or sorption, can be divided into three broad categories: adsorption, surface precipitation, and absorption. Extended X-ray absorption fine structure (EXAFS), a type of X-ray absorption spectroscopy (XAS), offers the possibility for distinguishing among different modes of sorption by characterizing the atomic environment of the sorbing element. In this study, the authors use EXAFS to determine the structure of U(VI) sorption complexes at the kaolinite-water interface. In Chapter One, they present an overview of selected aspects of U structural chemistry as a basis for considering the structural environment of U at the solid-water interface. To evaluate the utility of XAS for characterization of the structural environment of U(VI) at the solid-water interface, they have carried out an in-depth analysis of XAS data from U(VI)-containing solid and solution model compounds, which they describe in Chapter Two. In Chapter three, they consider sorption of U by kaolinite as a means of effecting the removal of U from surface collection pond waters on the Rocky Flats Plant site in northern Colorado.

  4. Interface dynamics under nonequilibrium conditions: from a self-propelled droplet to dynamic pattern evolution.

    PubMed

    Chen, Y-J; Yoshikawa, K

    2011-04-01

    In this article, we describe the instability of a contact line under nonequilibrium conditions mainly based on the results of our recent studies. Two experimental examples are presented: the self-propelled motion of a liquid droplet and spontaneous dynamic pattern formation. For the self-propelled motion of a droplet, we introduce an experiment in which a droplet of aniline sitting on an aqueous layer moves spontaneously at an air-water interface. The spontaneous symmetry breaking of Marangoni-driven spreading causes regular motion. In a circular Petri dish, the droplet exhibits either beeline motion or circular motion. On the other hand, we show the emergence of a dynamic labyrinthine pattern caused by dewetting of a metastable thin film from the air-water interface. The contact line between the organic phase and the aqueous phase forms a unique spatio-temporal pattern characterized as a dynamic labyrinth. Motion of the contact line is controlled by diffusion processes. We propose a theoretical model to interpret essential aspects of the observed dynamic behavior. PMID:21509663

  5. Nonlinear vibrational spectroscopic studies of molecular interaction and charging behavior at solid/liquid interfaces

    NASA Astrophysics Data System (ADS)

    Zhang, Luning

    Solid-liquid interfaces have been the focus of different communities of scientists due to its importance in industrial applications and chemical processes in nature. Molecular interactions and surface charges affect the physicochemical properties of these interfaces and a thorough understanding is still lacking now. This thesis describes our work in studying several model solid-liquid interfaces using sum-frequency vibrational spectroscopy. Through the studies of interfacial vibrational spectra, we hope to gain better understanding of molecular interactions in competitive adsorption process and also surface charging behavior at different pH and salt concentrations. We start by studying alcohol-water mixture and the adsorption behavior at both hydrophilic and hydrophobic surfaces. In both cases, alcohol adsorbs preferentially from water. The tendency for water to form strong hydrogen-bonding network is the driving force for preferential adsorption of alcohol. We proposed two different interfacial molecular structures on hydrophilic and hydrophobic surfaces. We move on to study the interaction of pure water with a solid surface. Single crystal alumina is used as a model system. At different pH, the surface can undergo protonation and deprotonation reactions and accumulates surface charge. Both the hydrogen-bonding with water and the surface field created by surface charge can affect interfacial water structure. Combining the information obtained with intensity and phase spectra, we find water molecules have two types of bonding within the interfacial layer: weakly hydrogen-bonded species near 3450 cm-1 that does not flip with switching surface charge, and strongly hydrogen-bonded species at 3200 cm-1 that readily flips with switching surface field. One other system we have studied is nanoporous silica-water interface. We found that signal from interfacial water is reduced due to the porous nature of the film. The water spectral features tell us about the interfacial

  6. Molecular interactions at the hexadecane/water interface in the presence of surfactants studied with second harmonic generation

    NASA Astrophysics Data System (ADS)

    Sang, Yajun; Yang, Fangyuan; Chen, Shunli; Xu, Hongbo; Zhang, Si; Yuan, Qunhui; Gan, Wei

    2015-06-01

    It is important to investigate the influence of surfactants on structures and physical/chemical properties of oil/water interfaces. This work reports a second harmonic generation study of the adsorption of malachite green (MG) on the surfaces of oil droplets in a hexadecane/water emulsion in the presence of surfactants including sodium dodecyl sulfate, polyoxyethylene-sorbitan monooleate (Tween80), and cetyltrimethyl ammonium bromide. It is revealed that surfactants with micromolar concentrations notably influence the adsorption of MG at the oil/water interface. Both competition adsorption and charge-charge interactions played very important roles in affecting the adsorption free energy and the surface density of MG at the oil/water interface. The sensitive detection of the changing oil/water interface with the adsorption of surfactants at such low concentrations provides more information for understanding the behavior of these surfactants at the oil/water interface.

  7. Molecular interactions at the hexadecane/water interface in the presence of surfactants studied with second harmonic generation.

    PubMed

    Sang, Yajun; Yang, Fangyuan; Chen, Shunli; Xu, Hongbo; Zhang, Si; Yuan, Qunhui; Gan, Wei

    2015-06-14

    It is important to investigate the influence of surfactants on structures and physical/chemical properties of oil/water interfaces. This work reports a second harmonic generation study of the adsorption of malachite green (MG) on the surfaces of oil droplets in a hexadecane/water emulsion in the presence of surfactants including sodium dodecyl sulfate, polyoxyethylene-sorbitan monooleate (Tween80), and cetyltrimethyl ammonium bromide. It is revealed that surfactants with micromolar concentrations notably influence the adsorption of MG at the oil/water interface. Both competition adsorption and charge-charge interactions played very important roles in affecting the adsorption free energy and the surface density of MG at the oil/water interface. The sensitive detection of the changing oil/water interface with the adsorption of surfactants at such low concentrations provides more information for understanding the behavior of these surfactants at the oil/water interface. PMID:26071724

  8. Atom-probe tomographic study of interfaces of Cu{sub 2}ZnSnS{sub 4} photovoltaic cells

    SciTech Connect

    Tajima, S. Asahi, R.; Itoh, T.; Hasegawa, M.; Ohishi, K.; Isheim, D.; Seidman, D. N.

    2014-09-01

    The heterophase interfaces between the CdS buffer layer and the Cu{sub 2}ZnSnS{sub 4} (CZTS) absorption layers are one of the main factors affecting photovoltaic performance of CZTS cells. We have studied the compositional distributions at heterophase interfaces in CZTS cells using three-dimensional atom-probe tomography. The results demonstrate: (a) diffusion of Cd into the CZTS layer; (b) segregation of Zn at the CdS/CZTS interface; and (c) a change of oxygen and hydrogen concentrations in the CdS layer depending on the heat treatment. Annealing at 573 K after deposition of CdS improves the photovoltaic properties of CZTS cells probably because of the formation of a heterophase epitaxial junction at the CdS/CZTS interface. Conversely, segregation of Zn at the CdS/CZTS interface after annealing at a higher temperature deteriorates the photovoltaic properties.

  9. Contact angle and detachment energy of shape anisotropic particles at fluid-fluid interfaces.

    PubMed

    Anjali, Thriveni G; Basavaraj, Madivala G

    2016-09-15

    The three phase contact angle of particles, a measure of its wettability, is an important factor that greatly influences their behaviour at interfaces. It is one of the principal design parameters for potential applications of particles as emulsion/foam stabilizers, functional coatings and other novel materials. In the present work, the effect of size, shape and surface chemistry of particles on their contact angle is investigated using the gel trapping technique, which facilitates the direct visualization of the equilibrium position of particles at interfaces. The contact angle of hematite particles of spherocylindrical, peanut and cuboidal shapes, hematite-silica core-shell and silica shells is reported at a single particle level. The spherocylindrical and peanut shaped particles are always positioned with their major axis parallel to the interface. However, for cuboidal particles at air-water as well as decane-water interfaces, different orientations namely - face-up, edge-up and the vertex-up - are observed. The influence of gravity on the equilibrium position of the colloidal particles at the interface is studied using the hematite-silica core-shell particles and the silica shells. The measured contact angle values are utilized in the calculations of the detachment and surface energies of the hematite particles adsorbed at the interface. PMID:27285780

  10. Study on Orbital Liquid Transport and Interface Behavior in Vane Tank

    NASA Astrophysics Data System (ADS)

    Kang, Qi; Rui, Wei

    2016-07-01

    Liquid propellant tank is used to supply gas free liquid for spacecraft as an important part of propulsion system. The liquid behavior dominated by surface tension in microgravity is obviously different with that on the ground, which put forward a new challenge to the liquid transport and relocation. The experiments which are investigated at drop tower in National Microgravity Lab have concentrated on liquid relocation following thruster firing. Considered that the liquid located at the bottom in the direction of the acceleration vector, a sphere scale vane tank is used to study the liquid-gas interface behaviors with different acceleration vector and different filling independently and we obtain a series of stable equilibrium interface and relocation time. We find that there is an obvious sedimentation in the direction of acceleration vector when fill rate greater than 2% fill. Suggestions have been put forward that outer vanes transferring liquid to the outlet should be fixed and small holes should be dogged at the vane close to the center post to improve the liquid flow between different vanes when B0 is greater than 2.5. The research about liquid transport alone ribbon vanes is simulated though software Flow3D. The simulation process is verified by comparing the liquid lip and vapor-liquid interface obtained from drop tower experiment and simulation result when fill rate is 15%. Then the influence of fill rate, numbers of vanes and the gap between vane and wall is studied through the same simulate process. Vanes' configurations are also changed to study the effect on the lip and liquid volume below some section. Some suggestions are put forward for the design of vanes.

  11. An Air-water Interfacial Area Based Variable Tortuosity Model for Unsaturated Sands

    NASA Astrophysics Data System (ADS)

    Khaleel, R.; Saripalli, P.

    2005-12-01

    A new variable tortuosity definition is introduced that is based on the immiscible fluid (air-water) interfacial area. Unsaturated media tortuosity (τa) is defined as the ratio of aaw to aaw,o where aaw is the estimated air-water interfacial area in a real unsaturated medium (i.e., a soil sample), and aaw,o is the same variable for the corresponding, idealized capillary bundle. We establish equivalence between the real and the idealized media by letting the laboratory-measured retention curve calculate the distribution of capillary tubes, thereby resulting in an identical pore-size distribution but a new retention curve for the idealized medium. The air-water interfacial area for both real and idealized media is directly proportional to the area under their respective retention curves. With τ being the saturated tortuosity, we relate the variable tortuosity ratio (ττa) to the Seɛ term in Mualem's (ɛ=0.5) and Burdine's (ɛ=2) pore-size distribution models. Thus, instead of using tortuosity and/or pore connectivity formulations that have empirical exponents of either 0.5 or 2, the new model depends on variable interfacial area for varying saturation and soil texture, as reflected in the measured retention data. We tested the new definition of tortuosity for 22 repacked Hanford sediments that are comprised of mostly coarse and fine sands but some also contain a sizeable fraction (as high as 27%) of fines (silt and clay). Replacing the Se2 term in van Genuchten-Mualem (VGM) model by the new interfacial area based variable tortuosity ratio, and still using saturated conductivity and retention parameters, as used in the conventional approach, we obtain interfacial area based K(θ) predictions that are nearly identical to the conventional VGM model predictions. We also compare the interfacial area based K(θ) predictions with the standard Brooks-Corey-Burdine (BCB) model predictions. Compared to the VGM model predictions, interfacial area based BCB K(θ) predictions

  12. A Lagrangian Model to Predict the Modification of Near-Surface Scalar Mixing Ratios and Air-Water Exchange Fluxes in Offshore Flow

    NASA Astrophysics Data System (ADS)

    Rowe, Mark D.; Perlinger, Judith A.; Fairall, Christopher W.

    2011-07-01

    A model was developed to predict the modification with fetch in offshore flow of mixing ratio, air-water exchange flux, and near-surface vertical gradients in mixing ratio of a scalar due to air-water exchange. The model was developed for planning and interpretation of air-water exchange flux measurements in the coastal zone. The Lagrangian model applies a mass balance over the internal boundary layer (IBL) using the integral depth scale approach, previously applied to development of the nocturnal boundary layer overland. Surface fluxes and vertical profiles in the surface layer were calculated using the NOAA COARE bulk algorithm and gas transfer model (e.g., Blomquist et al. 2006, Geophys Res Lett 33:1-4). IBL height was assumed proportional to the square root of fetch, and estimates of the IBL growth rate coefficient, α, were obtained by three methods: (1) calibration of the model to a large dataset of air temperature and humidity modification over Lake Ontario in 1973, (2) atmospheric soundings from the 2004 New England Air Quality Study and (3) solution of a simplified diffusion equation and an estimate of eddy diffusivity from Monin-Obukhov similarity theory (MOST). Reasonable agreement was obtained between the calibrated and MOST values of α for stable, neutral, and unstable conditions, and estimates of α agreed with previously published parametrizations that were valid for the stable IBL only. The parametrization of α provides estimates of IBL height, and the model estimates modification of scalar mixing ratio, fluxes, and near-surface gradients, under conditions of coastal offshore flow (0-50 km) over a wide range in stability.

  13. First-principles study of point defects at a semicoherent interface

    PubMed Central

    Metsanurk, E.; Tamm, A.; Caro, A.; Aabloo, A.; Klintenberg, M.

    2014-01-01

    Most of the atomistic modeling of semicoherent metal-metal interfaces has so far been based on the use of semiempirical interatomic potentials. We show that key conclusions drawn from previous studies are in contradiction with more precise ab-initio calculations. In particular we find that single point defects do not delocalize, but remain compact near the interfacial plane in Cu-Nb multilayers. We give a simple qualitative explanation for this difference on the basis of the well known limited transferability of empirical potentials. PMID:25524061

  14. Dual-probe scanning tunneling microscope for study of nanoscale metal-semiconductor interfaces

    NASA Astrophysics Data System (ADS)

    Yi, W.; Kaya, I. I.; Altfeder, I. B.; Appelbaum, I.; Chen, D. M.; Narayanamurti, V.

    2005-06-01

    Using a dual-probe scanning tunneling microscope, we have performed three-terminal ballistic electron emission spectroscopy on Au /GaAs(100) by contacting the patterned metallic thin film with one tip and injecting ballistic electrons with another tip. The collector current spectra agree with a Monte-Carlo simulation based on modified planar tunneling theory. Our results suggest that it is possible to study nanoscale metal-semiconductor interfaces without the requirement of an externally-contacted continuous metal thin film.

  15. Ion Scattering Studies of Silicon Surfaces and Interfaces: Structure and Neutralization.

    NASA Astrophysics Data System (ADS)

    Haight, Richard Alan

    This thesis chronicles three experiments which represent the major thrust of studies performed during my tenure as a graduate student at the State University of New York at Albany. Chapter 1 introduces the fundamental considerations of the physics of ion scattering and its applications to studies of surfaces, interfaces and ion neutralization. Basic formula are stated and the two atom model using the Coulomb interaction potential is developed as an approximate prediction of the surface peak intensity. The second chapter discusses a study of the neutralization of 75-180 KeV He ions scattered from clean and Cs covered Si (100); an experiment performed at Bell Laboratories. It is shown that ion neutralization occurs at the surface of the solid; the ion retains no memory of its journey within the bulk. It is also observed that the ion fraction exhibits no dependence upon takeoff angle, a result which differs markedly from the exponential angular dependence observed at lower velocities. Changes in the Si scattered ion fraction upon cesiation of the Si surface are correlated with the work function change observed by other workers. A model is proposed, and developed in mathematical detail, which includes resonant transitions to the motionally broadened He n=2 quantum level and is compared with the experimental data. The third chapter discusses an ion scattering study of the interfacial structure of the Si-SiO(,2) interface. It is shown that the oxide is stoichiometric to within (TURN)1 monolayer of the interface. Measurements to determine the magnitude and direction of the Si atomic displacements at the interface were compared with Monte Carlo computer simulations and show small lateral and larger vertical displacements in two layers. A model, consistent with the data, is proposed and the effects of these displacements are related qualitatively with theory. The fourth chapter describes a thin Si (111) crystal transmission channeling experiment. In this experiment, the use

  16. First-principles study of point defects at a semicoherent interface

    DOE PAGESBeta

    Metsanurk, E.; Tamm, A.; Caro, A.; Aabloo, A.; Klintenberg, M.

    2014-12-19

    Most of the atomistic modeling of semicoherent metal-metal interfaces has so far been based on the use of semiempirical interatomic potentials. Here, we show that key conclusions drawn from previous studies are in contradiction with more precise ab-initio calculations. In particular we find that single point defects do not delocalize, but remain compact near the interfacial plane in Cu-Nb multilayers. Lastly, we give a simple qualitative explanation for this difference on the basis of the well known limited transferability of empirical potentials.

  17. Resonant photoemission study of the 4f spectral function of cerium in Ce/Fe(100) interfaces

    SciTech Connect

    Witkowski, N.; Bertran, F.; Gourieux, T.; Kierren, B.; Malterre, D.; Panaccione, G. |

    1997-11-01

    In this paper, we present a resonant photoemission study of the cerium 4f spectral function in Ce/Fe(100) interfaces. By covering cerium ultrathin films with lanthanum, we completely suppress the surface contribution of the spectra. Then we show that the cerium atoms at the interface are in an intermediate valent state, whereas the f{sup 1} configuration is stabilized in the top layer. This method allows us to obtain the genuine 4f spectral function of the interface, and could be extended to a study of Ce-based compounds. {copyright} {ital 1997} {ital The American Physical Society}

  18. Study on crystal-melt interface shape of sapphire crystal growth by the KY method

    NASA Astrophysics Data System (ADS)

    Liu, Weina; Lu, Jijun; Chen, Hongjian; Yan, Wenbo; Min, Chunhua; Lian, Qingqing; Wang, Yunman; Cheng, Peng; Liu, Caichi; Xu, Yongliang

    2015-12-01

    In this article, the influence of the flow field structure and temperature gradient of forefront interface on the shape of crystal-melt interface which may reflect the interface stability were analyzed through the method of numerical simulation by using CGSim software. In order to get a suitable interface shape and grow high-quality sapphire crystal, the heater arrangement should be adjusted during the KY process. The results indicate that the effect of Marangoni convection cannot be neglected at the last stage, the crystal-melt interface is governed by the flow field structure and the temperature gradient in melt at the crystal-melt interface. The phenomenon of shoulder concave appears at the stage of shoulder turning and interface inversion appears at the last stage during the crystal growth is discussed. Adjusting heater arrangement may effectively optimize the shape of crystal-melt interface.

  19. Analysis of cementless implants using interface nonlinear friction--experimental and finite element studies.

    PubMed

    Dammak, M; Shirazi-Adl, A; Zukor, D J

    1997-02-01

    Measured interface nonlinear friction properties are used to develop models to study the short-term fixation response of smooth- and porous-surfaced posts, bone screws, and plates fixed with and without posts/screws. Experimental studies are carried out to validate the model predictions and identify the relative role of posts and screws in fixation of a plate on a polyurethane block under symmetric/eccentric axial compression loads. The idealized Coulomb's friction is also used for the sake of comparison. The incorporation of measured nonlinear, rather than the idealized Coulomb, friction is essential to compute realistic results. For plate fixation, the experimental and finite element results show that the screw fixation yields the stiffest response followed by the smooth- and then porous-coated post fixation. For example, under 1000 N eccentric axial compression, the edge of the plate opposite the loaded edge is measured to lift by 1147 +/- 72, 244 +/- 38, or 112 +/- 28 microns, respectively, for the cases with no fixation, with smooth-surfaced posts, or with screws. The corresponding models predict, respectively, values of 1538, 347, or 259 microns and also 556 microns for the plate fixed with porous coated posts. The satisfactory agreement between numerical and experimental results confirms the importance of proper interface modelling for the analysis of posts, screws, and complex fixation systems. This becomes further evident when considering cementless implants in which the bone-implant interface exhibits relatively large displacements as the maximum resistance force is reached. The developed models can be used to investigate the post-operative short-term stability of various cementless implant designs. PMID:9001932

  20. Mechanical properties of the interface structure of nanodiamond composite films: First-principles studies

    NASA Astrophysics Data System (ADS)

    Zhang, Suhui; Liu, Xuejie; Jiang, Yongjun; Ren, Yuan; Li, Suozhi

    2016-02-01

    The elastic properties of the interface structure of nanodiamond composite films are investigated using first-principles calculations. The nanodiamond grains in the films are surrounded by a monolayer heterogeneous interface. The interface phase comprises B, Si, P, and Ge. The elastic constants, bulk, shear and Young's modulus of the interface structures are all obtained with first principle calculations. Calculated elastic constants of the diamond (0 0 1) interface are larger than those of the (1 1 1) interface. For the B, Si, P, and Ge interface structures, as the average atomic distance increases, the average Young's modulus decrease, which follows the sequence EbarB>EbarSi >EbarP > EbarGe , with corresponding values of 927.05, 843.841, 840.152, and 819.805 GPa. The ductility and plasticity, as well as the anisotropy values (A and AU) of the interface structures were discussed based on the obtained mechanical parameters. The results show that P interface structures demonstrate ductile property when stressed longitudinally, whereas the other interface structures are all brittle. Then the visualization of the directional dependence of the Young's modulus are also presented. These reflected an interesting results. For the B, Si, and Ge interface structures, whether they show isotropy or anisotropy depends on the crystal structure, while it depends on the direction of the applied strain for the P interface structures.

  1. Laser studies of chemical dynamics at the gas-solid interface

    NASA Astrophysics Data System (ADS)

    Cavanagh, Richard R.; King, David S.

    The DOE funded research program Laser Studies of Chemical Dynamics at the Gas-Solid Interface has taken a detailed, microscopic view of molecules desorbed from surfaces in order to gain an understanding of energy flow and interaction potentials and how these control chemical reactivity at interfaces. Successful completion of these experiments required technical expertise both in surface science and laser-based molecular dynamics, a collaborative situation that exists in the NIST center for Atomic, Molecular and Optical Physics. During the three year period covered by this progress report, our goal was to use state-resolved techniques to examine a single chemisorption system in detail, and to observe how changes in the interaction potential or method of surface excitation are manifest in the desorption dynamics. The system chosen was NO/Pt(111). Studies were undertaken in which the effects on the NO-Pt interaction potential of coadsorbates--both weakly (CO) and strongly (NH(sub 3)) interacting-- could be examined. In addition, attempts were to be made to study non- equilibrium dynamics by using pulsed laser heating.

  2. Correlation of Oil-Water and Air-Water Contact Angles of Diverse Silanized Surfaces and Relationship to Fluid Interfacial Tensions

    SciTech Connect

    Grate, Jay W.; Dehoff, Karl J.; Warner, Marvin G.; Pittman, Jonathan W.; Wietsma, Thomas W.; Zhang, Changyong; Oostrom, Martinus

    2012-02-24

    The use of air-water, {Theta}{sub wa}, or air-liquid contact angles is customary in surface science, while oil-water contact angles {Theta}{sub ow}, are of paramount importance in subsurface multiphase flow phenomena including petroleum reocovery, nonaqueous phase liquid fate and transport, and geological carbon sequestration. In this paper we determine both the air-water and oil-water contact angles of silica surfaces modified with a diverse selection of silanes, using hexadecane as the oil. The silanes included alkylsilanes, alkylarylsilanes, and silanes with alkyl or aryl groups that are functionalized with heteroatoms such as N, O, and S. These silanes yielded surfaces with wettabilities from water-wet to oil wet, including specific silanized surfaces functionalized with heteroatoms that yield intermediate wet surfaces. The oil-water contact angles for clean and silanized surfaces, excluding one partially fluorinated surface, correlate linearly with air-water contact angles with a slope of 1.41 (R = 0.981, n = 13). These data were used to examine a previously untested theoretical treatment relating air-water and oil-water contact angles in terms of fluid interfacial energies. Plotting the cosines of these contact angles against one another, we obtain a linear relationship in excellent agreement with the theoretical treatment; the data fit cos {Theta}{sub ow} = 0.667 cos {Theta}{sub ow} + 0.384 (R = 0.981, n = 13), intercepting cos {Theta}{sub ow} = -1 at -0.284. The theoretical slope, based on the fluid interfacial tensions {Theta}{sub wa}, {Theta}{sub ow}, and {Theta}{sub oa}, is 0.67. We also demonstrate how silanes can be used to alter the wettability of the interior of a pore network micromodel device constructed in silicon/silica with a glass cover plate. Such micromodels are used to study multiphase flow phenomena. The contact angle of the resulting interior was determined in situ. An intermediate wet micromodel gave a contact angle in excellent agreement

  3. Precision cleaning verification of fluid components by air/water impingement and total carbon analysis

    NASA Technical Reports Server (NTRS)

    Barile, Ronald G.; Fogarty, Chris; Cantrell, Chris; Melton, Gregory S.

    1994-01-01

    NASA personnel at Kennedy Space Center's Material Science Laboratory have developed new environmentally sound precision cleaning and verification techniques for systems and components found at the center. This technology is required to replace existing methods traditionally employing CFC-113. The new patent-pending technique of precision cleaning verification is for large components of cryogenic fluid systems. These are stainless steel, sand cast valve bodies with internal surface areas ranging from 0.2 to 0.9 sq m. Extrapolation of this technique to components of even larger sizes (by orders of magnitude) is planned. Currently, the verification process is completely manual. In the new technique, a high velocity, low volume water stream impacts the part to be verified. This process is referred to as Breathing Air/Water Impingement and forms the basis for the Impingement Verification System (IVS). The system is unique in that a gas stream is used to accelerate the water droplets to high speeds. Water is injected into the gas stream in a small, continuous amount. The air/water mixture is then passed through a converging/diverging nozzle where the gas is accelerated to supersonic velocities. These droplets impart sufficient energy to the precision cleaned surface to place non-volatile residue (NVR) contaminants into suspension in the water. The sample water is collected and its NVR level is determined by total organic carbon (TOC) analysis at 880 C. The TOC, in ppm carbon, is used to establish the NVR level. A correlation between the present gravimetric CFC113 NVR and the IVS NVR is found from experimental sensitivity factors measured for various contaminants. The sensitivity has the units of ppm of carbon per mg/sq ft of contaminant. In this paper, the equipment is described and data are presented showing the development of the sensitivity factors from a test set including four NVRs impinged from witness plates of 0.05 to 0.75 sq m.

  4. Air-water exchange fluxes of polycyclic aromatic hydrocarbons in the tropical coast, Taiwan.

    PubMed

    Cheng, Jing-O; Ko, Fung-Chi; Lee, Chon-Lin; Fang, Meng-Der

    2013-03-01

    Air-water exchange fluxes of polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in air and water samples from two sites on the Kenting coast, located at the southern tip of Taiwan, from January to December 2010. There was no significant difference in the total PAH (t-PAH) concentrations in both gas and dissolved phases between these two sites due to the less local input which also coincided to the low levels of t-PAH concentration; the gas and dissolved phases averaged 1.29±0.59 ng m(-3) and 2.17±1.19 ng L(-1) respectively. The direction and magnitude of the daily flux of PAHs were significantly influenced by wind speed and dissolved PAH concentrations. Individual PAH flux ranged from 627 ng m(-2) d(-1) volatilization of phenanthrene during the rainy season with storm-water discharges raising dissolved phase concentration, to 67 ng m(-2) d(-1) absorption of fluoranthene during high wind speed periods. Due to PAH annual fluxes through air-water exchange, Kenting seawater is a source of low molecular weight PAHs and a reservoir of high molecular weight PAHs. Estimated annual volatilization fluxes ranged from 7.3 μg m(-2) yr(-1) for pyrene to 50 μg m(-2) yr(-1) for phenanthrene and the absorption fluxes ranged from -2.6 μg m(-2) yr(-1) for chrysene to -3.5 μg m(-2) yr(-1) for fluoranthene. PMID:23260251

  5. Air/water oxidative desulfurization of coal and sulfur-containing compounds

    NASA Astrophysics Data System (ADS)

    Warzinski, R. P.; Freidman, S.; LaCount, R. B.

    1981-02-01

    Air/water Oxydesulfurization has been demonstrated in autoclave experiments at the Pittsburgh Energy Technology Center for various coals representative of the major U. S. coal basins. The applicability at present of this treatment for producing an environmentally acceptable coal has been restricted by recently proposed SO2 emission standards for utility boilers. The product would, however, be attractive to the many smaller industrial coal users who cannot afford to operate and maintain flue gas desulfurization systems. It is also possible that the utility industry could realize a benefit by using chemically cleaned coal with partial flue gas scrubbing. The higher cost of the cleaned coal would be offset by the reduction in capital and operating costs resulting from decreased FGD requirements. The susceptibility of sulfur in coal to oxidative removal varies with the nature of the sulfur-containing species. The inorganic sulfur compounds, primarily pyrite, marcasite, and iron sulfate, are more amenable to treatment than the organically bound sulfur which exhibits varying degrees of resistance depending on its chemical environment. Air/water Oxydesulfurization consistently removes in excess of 90 percent of the pyritic sulfur; the extent and efficiency of organic sulfur removal however, depends on the type of coal and severity of treatment used. In general, the organic sulfur of the higher rank coals exhibits more resistance to treatment than that of the lower rank coals; however, the accompanying heating value is greater for the latter. Similar treatment of sulfur-containing model compounds further illustrates the relative susceptibilities of different chemical species to oxidation. Application of these data to the understanding of the complex chemistry involved in the treatment of coal is a preliminary step toward improving the efficiency of Oxydesulfurization.

  6. Precision Cleaning Verification of Fluid Components by Air/Water Impingement and Total Carbon Analysis

    NASA Technical Reports Server (NTRS)

    Barile, Ronald G.; Fogarty, Chris; Cantrell, Chris; Melton, Gregory S.

    1995-01-01

    NASA personnel at Kennedy Space Center's Material Science Laboratory have developed new environmentally sound precision cleaning and verification techniques for systems and components found at the center. This technology is required to replace existing methods traditionally employing CFC-113. The new patent-pending technique of precision cleaning verification is for large components of cryogenic fluid systems. These are stainless steel, sand cast valve bodies with internal surface areas ranging from 0.2 to 0.9 m(exp 2). Extrapolation of this technique to components of even larger sizes (by orders of magnitude) is planned. Currently, the verification process is completely manual. In the new technique, a high velocity, low volume water stream impacts the part to be verified. This process is referred to as Breathing Air/Water Impingement and forms the basis for the Impingement Verification System (IVS). The system is unique in that a gas stream is used to accelerate the water droplets to high speeds. Water is injected into the gas stream in a small, continuous amount. The air/water mixture is then passed through a converging-diverging nozzle where the gas is accelerated to supersonic velocities. These droplets impart sufficient energy to the precision cleaned surface to place non-volatile residue (NVR) contaminants into suspension in the water. The sample water is collected and its NVR level is determined by total organic carbon (TOC) analysis at 880 C. The TOC, in ppm carbon, is used to establish the NVR level. A correlation between the present gravimetric CFC-113 NVR and the IVS NVR is found from experimental sensitivity factors measured for various contaminants. The sensitivity has the units of ppm of carbon per mg-ft(exp 2) of contaminant. In this paper, the equipment is described and data are presented showing the development of the sensitivity factors from a test set including four NVR's impinged from witness plates of 0.05 to 0.75 m(exp 2).

  7. First principles studies of interface dielectric properties of polymer/metal-oxide nanocomposites

    NASA Astrophysics Data System (ADS)

    Yu, Liping

    This thesis is devoted to studying interface dielectric properties of polymer nanocomposites from first principles. We aim to understand at atomic scale the role of interface effects and the dielectric finite size effects of nanoparticles in determining the effective dielectric properties of polymer nanocomposites. To study surface effects from first principles, we first investigate the two common methods, namely dipole correction and Coulomb cutoff, used to eliminate the artificial effects introduced by using the supercell approximation. We implement Coulomb cutoff technique in a plane-wave-based density functional theory code and compare it with dipole correction for the same system under the same conditions. By comparison, both methods are shown to be equivalent and able to remove the artificial effects of periodic images very accurately. We also find that a combination of these two methods offers an easy way to distinguish the localized bound states of interest from highly delocalized unoccupied states while using a relatively small supercell, and to ascertain the convergence of the results with respect to supercell size. To understand the dielectric properties at the atomic scale, we develop a new nanoscale averaging model to connect the macroscopic quantities to the corresponding microscopic ones. This model allows us to compute the spatially resolved local dielectric permittivity, including the critically important ionic contributions, for interfaces and other complex structures. In this model, a simple way of evaluating real-space decay length of the nonlocal dielectric functions is also proposed. By using the dipole correction and our averaging model in supercells, we calculate the optical and static local dielectric permittivity profiles for polymer (polypropylene)/metal-oxide (PbTiO3 and alumina) nanocomposites. Our ab-initio results show that metal-oxide/polymer interface effects are very localized and are mostly confined to the metal-oxide surface side

  8. A first-principles study on interaction of Mg/Ni interface and its hydrogen absorption characteristics

    NASA Astrophysics Data System (ADS)

    Chen, Yuying; Dai, Jianhong; Xie, Ruiwen; Song, Yan

    2016-07-01

    We have investigated the interaction of Mg/Ni interface and its hydrogen adsorption characteristics using first-principles calculations to obtain a better understanding of the Mg/Ni interface as a hydrogen storage material. The smallest work of adhesion of Mg/Ni interface is 4.28 J/m2 with AB stacking sequence in the studied systems. Hydrogen adsorption energy and electronic structures were evaluated to study the interaction characteristics between hydrogen and Mg/Ni interface. The hydrogen adsorption is energetically favored on all considered sites. The hydrogen atom prefers to adsorb on the tetrahedral site of the Ni side of the interface owning the lowest adsorption energy. The plane-averaged charge density and the density of states analysis indicate that the absorption of hydrogen could stabilize the Mg/Ni interface owing to the strongly bonding interactions between hydrogen atom and the host Mg and Ni atoms. Therefore, Mg/Ni interface provides a promising medium for hydrogen storage.

  9. MHD modeling of atlas experiments to study transverse shear interface interactions

    SciTech Connect

    Cochran, F. L.; Hammerberg, J. E.; Keinigs, R. K.; Faehl, R. J.

    2001-01-01

    The transverse shear established at the interface of two solids moving at differential velocities on the order of the sound speed is being studied in experiments on the ATLAS capacitor bank at Los Alamos. The ATLAS bank has finished certification tests and has demonstrated peak currents of 27.5 MA into an inductive load with a risetime of 5 microseconds. One- and two-dimensional MHD calculations have been performed in support of these 'friction-like' ATLAS experiments. Current flowing along the outer surface of a thick aluminum liner, 10 mm thick at impact with the interaction target, accelerates the liner to velocities of {approx}1.0-1.5 km/s. This cylindrically imploding liner impacts a target assembly composed of alternating disks of high- and low-density materials. Different shock speeds in the two materials leads to a differential velocity along the interface. Shock heating, elastic-plastic flow, and stress transport are included in the calculations. Material strength properties are modeled with a Steinburg-Guinan treatment in these first studies. Various design configurations for the ATLAS experiments are now being considered and will be presented.

  10. Tunneling of electrons via rotor-stator molecular interfaces: Combined ab initio and model study

    NASA Astrophysics Data System (ADS)

    Petreska, Irina; Ohanesjan, Vladimir; Pejov, Ljupčo; Kocarev, Ljupčo

    2016-07-01

    Tunneling of electrons through rotor-stator anthracene aldehyde molecular interfaces is studied with a combined ab initio and model approach. Molecular electronic structure calculated from first principles is utilized to model different shapes of tunneling barriers. Together with a rectangular barrier, we also consider a sinusoidal shape that captures the effects of the molecular internal structure more realistically. Quasiclassical approach with the Simmons' formula for current density is implemented. Special attention is paid on conformational dependence of the tunneling current. Our results confirm that the presence of the side aldehyde group enhances the interesting electronic properties of the pure anthracene molecule, making it a bistable system with geometry dependent transport properties. We also investigate the transition voltage and we show that conformation-dependent field emission could be observed in these molecular interfaces at realistically low voltages. The present study accompanies our previous work where we investigated the coherent transport via strongly coupled delocalized orbital by application of Non-equilibrium Green's Function Formalism.

  11. Experimental study of the minority-carrier transport at the polysilicon-monosilicon interface

    NASA Astrophysics Data System (ADS)

    Neugroschel, A.; Arienzo, M.; Isaac, R. D.; Komem, Y.

    1985-04-01

    This paper presents the results of an experimental study designed to explore both qualitatively and quantitatively the mechanism of the improved current gain in bipolar transistors with polysilicon emitter contacts. Polysilicon contacts were deposited and heat treated at different conditions. The electrical properties were measured using p-n junction test structures that are much more sensitive to the contact properties than are bipolar transistors. A simple phenomenological model was used to correlate the structural properties with electrical measurements. Possible transport mechanisms are examined and estimates are made about upper bounds on transport parameters in the principal regions of the devices. The main conclusion of this study is that the minority-carrier transport in the polycrystalline silicon is dominated by a highly disordered layer at the polysilicon-monosilicon interface characterized by very low minority-carrier mobility. The effective recombination velocity at the n(+) polysilicon-n(+) monosilicon interface was found to be a strong function of fabrication conditions. The results indicate that the recombination velocity can be much smaller than 10,000 cm/s.

  12. The effect of copolymers on the interfaces in incompatible homopolymers blend: Molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Ryu, Jiho; Lee, Won Bo

    2015-03-01

    Using molecular dynamics simulations the effect of copolymers as compatibilizer for reducing interfacial tension and enhancement of interfacial adhesion at the interface of thermodynamic unfavorable homopolymers blend is studied with block- and graft-copolymers. We have calculated local pressure tensor of system along the axis perpendicular to interface, varying bending potential energy of one part, which consist of just one kind of beads, of copolymer chain to examine the effect of stiffness of surfactin molecules. Here we consider symmetric diblock copolymer (f =1/2) having 1/2 N make of beads of type A and the other part made of beads of type B, and graft copolymer having backbone linear chain consist of 1/2 N beads of type of A and branched with two side-chain consist of 1/4 N beads of type B. All simulations were performed under the constant NPT ensemble at T* =1, ρ* ~0.85. Also we studied changes of effect of copolymers with increasing pairwise repulsive interaction potential between two beads of types A and B while homopolymers chain length are fixed, N =30. Chemical and Biomolecular Engineering, Sogang University, Seoul, South Korea.

  13. Dispersion of pollutants over land-water-land interface: Study using CALPUFF model

    NASA Astrophysics Data System (ADS)

    Indumati, S.; Oza, R. B.; Mayya, Y. S.; Puranik, V. D.; Kushwaha, H. S.

    The CALMET/CALPUFF modeling system is used to study atmospheric dispersion of pollutant over land-water-land interface. It is shown that the default scheme used by CALMET/CALPUFF to handle inhomogeneous surfaces does not take care of the different turbulence characteristics over such surfaces. An alternative method is suggested to incorporate different turbulent characteristics over inhomogeneous surfaces by using the appropriate atmospheric stability category over different surfaces. The results show that the presence of water body can increase the ground level concentration by a factor of up to 50 for the width of water body varying from 1 km to 5 km. It is also shown that the effect of water body on the ground level concentration decreases as the distance from the water body increases. The present study showed that for land-water interface, the realistic specification of turbulence characteristics over inhomogeneous surfaces significantly changes the estimation of ground level concentration as compared to the default scheme available in the CALMET/CALPUFF modeling system and is expected to give realistic results.

  14. Ab initio study of the epitaxial ZrO2 /Si interface

    NASA Astrophysics Data System (ADS)

    Dogan, Mehmet; Kumah, Divine; Ahn, Charles; Walker, Frederick; Ismail-Beigi, Sohrab

    2015-03-01

    Growing thin films of crystalline metal oxides on semiconductors has been of much scientific interest because of the potential applications of such systems in electronic devices. One particular research goal is to achieve ferroelectricity in a crystalline and thin oxide film that is epitaxial on a semiconductor. This would enable one to realize non-volatile field-effect transistors where the state of the system is encoded in the polarization direction of the oxide. In this work, we study oxides that are not ferroelectric in the bulk but become ferroelectric as an ultrathin film on a semiconductor such as silicon. Recent developments in epitaxial growth methods also permit fabrication of such systems. Here, we use density functional theory to study the interface between ZrO2 and Si. When the oxide is only 1 monolayer thick, we find a set of stable structures with a variety of positive and negative out-of-plane ferroelectric polarizations. We present an analysis of these structures as a function of oxide thickness and the size of interface unit cell. Furthermore, the ZrO2 can be used as a buffer layer to induce ferroelectricity in ultrathin perovskite oxides such as SrTiO3 on Si which can couple the oxide polarization to the silicon carrier density. This work is supported by the National Science Foundation through Grant MRSEC NSF DMR-1119826.

  15. A study of System Interface Sets (SIS) for the host, target and integration environments of the Space Station Program (SSP)

    NASA Technical Reports Server (NTRS)

    Mckay, Charles; Auty, David; Rogers, Kathy

    1987-01-01

    System interface sets (SIS) for large, complex, non-stop, distributed systems are examined. The SIS of the Space Station Program (SSP) was selected as the focus of this study because an appropriate virtual interface specification of the SIS is believed to have the most potential to free the project from four life cycle tyrannies which are rooted in a dependance on either a proprietary or particular instance of: operating systems, data management systems, communications systems, and instruction set architectures. The static perspective of the common Ada programming support environment interface set (CAIS) and the portable common execution environment (PCEE) activities are discussed. Also, the dynamic perspective of the PCEE is addressed.

  16. Design of a monochromatic ellipsometer for studies at the solid-liquid interface

    NASA Astrophysics Data System (ADS)

    Pai-Panandiker, R. S.; Dorgan, J. R.

    1995-02-01

    A new design for a monochromatic ellipsometer used for studies at the solid-liquid interface is described. The design of the ellipsometer incorporates two novel features—a special optical glass cell and a thermally controlled sample oven. The ellipsometer design allows for in situ kinetic studies through use of the optical glass cell. Furthermore, the apparatus is modified to allow thermal equilibration over a range of temperatures. The temperature response of the cell assembly is presented and the response time is seen to be approximately 1 h. Data on the adsorption of a diblock copolymer [poly(ethylene oxide)-block-polystyrene] are presented; the analyzed data agree with previous studies on the same system.

  17. Sum-Frequency Generation from Chiral Media and Interfaces

    SciTech Connect

    Ji, Na

    2006-02-13

    Sum frequency generation (SFG), a second-order nonlinear optical process, is electric-dipole forbidden in systems with inversion symmetry. As a result, it has been used to study chiral media and interfaces, systems intrinsically lacking inversion symmetry. This thesis describes recent progresses in the applications of and new insights into SFG from chiral media and interfaces. SFG from solutions of chiral amino acids is investigated, and a theoretical model explaining the origin and the strength of the chiral signal in electronic-resonance SFG spectroscopy is discussed. An interference scheme that allows us to distinguish enantiomers by measuring both the magnitude and the phase of the chiral SFG response is described, as well as a chiral SFG microscope producing chirality-sensitive images with sub-micron resolution. Exploiting atomic and molecular parity nonconservation, the SFG process is also used to solve the Ozma problems. Sum frequency vibrational spectroscopy is used to obtain the adsorption behavior of leucine molecules at air-water interfaces. With poly(tetrafluoroethylene) as a model system, we extend the application of this surface-sensitive vibrational spectroscopy to fluorine-containing polymers.

  18. Orientational Dynamics of Water at an Extended Hydrophobic Interface.

    PubMed

    Xiao, Shunhao; Figge, Florian; Stirnemann, Guillaume; Laage, Damien; McGuire, John A

    2016-05-01

    We report on the orientational dynamics of water at an extended hydrophobic interface with an octadecylsilane self-assembled monolayer on fused silica. The interfacial dangling OH stretch mode is excited with a resonant pump, and its evolution followed in time by a surface-specific, vibrationally resonant, infrared-visible sum-frequency probe. High sensitivity pump-probe anisotropy measurements and isotopic dilution clearly reveal that the decay of the dangling OH stretch excitation is almost entirely due to a jump to a hydrogen-bonded configuration that occurs in 1.61 ± 0.10 ps. This is more than twice as fast as the jump time from one hydrogen-bonded configuration to another in bulk H2O but about 50% slower than the reported out-of-plane reorientation at the air/water interface. In contrast, the intrinsic population lifetime of the dangling OH stretch in the absence of such jumps is found to be >10 ps. Molecular dynamics simulations of air/water and hexane/water interfaces reproduce the fast jump dynamics of interfacial dangling OH with calculated jump times of 1.4 and 1.7 ps for the air and hydrophobic interfaces, respectively. The simulations highlight that while the air/water and hydrophobic/water surfaces exhibit great structural similarities, a small stabilization of the OH groups by the hydrophobic interface produces the pronounced difference in the dynamics of dangling bonds. PMID:27045950

  19. Liquid-Vapor Interfacial Properties of Aqueous Solutions of Guanidinium and Methyl Guanidinium Chloride: Influence of Molecular Orientation on Interface Fluctuations

    PubMed Central

    Ou, Shuching; Cui, Di; Patel, Sandeep

    2014-01-01

    The guanidinium cation (C(NH2)3+) is a highly stable cation in aqueous solution due to its efficient solvation by water molecules and resonance stabilization of the charge. Its salts increase the solubility of nonpolar molecules (”salting-in”) and decrease the ordering of water. It is one of the strongest denaturants used in biophysical studies of protein folding. We investigate the behavior of guanidinium and its derivative, methyl guanidinium (an amino acid analogue) at the air-water surface, using atomistic molecular dynamics (MD) simulations and calculation of potentials of mean force. Methyl guanidinium cation is less excluded from the air-water surface than guanidinium cation, but both cations show orientational dependence of surface affinity. Parallel orientations of the guanidinium ring (relative to the Gibbs dividing surface) show pronounced free energy minima in the interfacial region, while ring orientations perpendicular to the GDS exhibit no discernible surface stability. Calculations of surface fluctuations demonstrate that near the air-water surface, the parallel-oriented cations generate significantly greater interfacial fluctuations compared to other orientations, which induces more long-ranged perturbations and solvent density redistribution. Our results suggest a strong correlation with induced interfacial fluctuations and ion surface stability. These results have implications for interpreting molecular-level, mechanistic action of this osmolyte’s interaction with hydrophobic interfaces as they impact protein denaturation (solubilization). PMID:23937431

  20. Study of Au/TiO2 interface structure using Energy Density Method

    NASA Astrophysics Data System (ADS)

    Yu, Min; Trinkle, Dallas R.; Martin, Richard M.

    2010-03-01

    We propose a way to decompose the total energy in a material into the contribution associated with each of the atoms, using the first principles energy density formalism[1]. Although the energy density function is non-unique up to a gauge transformation, we show that unique defect energies can be found by defining volumes for each atoms using the Bader charge analysis[2]. The methods are applied to gold nanoclusters supported on rutile titanium dioxide, which are commonly used as catalysts for chemical reactions. The variation in structure and chemistry of the interface may affect catalytic acticity. In this work, we study four model interfaces; Au(111)//TiO2(110) and Au(100)//TiO2(110), with and without bridging oxygen. Calculations are performed using the projector augmented wave method implemented in the Vienna ab initio simulation package[3], and the energy density method computes the interfacial energies to determine the equlibrium interfacial structure. [1]Phys. Rev. B 45, 6074 (1992) [2]Comput. Mater. Sci. 36, 254 (2006) [3]Phys. Rev. B 59, 1758 (1999)

  1. A comparative experimental study on structural and interface damping approaches for vibration suppression purposes

    NASA Astrophysics Data System (ADS)

    Liu, Yi; Sanchez, Alberto; Zogg, Markus; Ermanni, Paolo

    2010-04-01

    Dynamic loadings in automotive structures may lead to reduction of driving comfort and even to failure of the components. Damping treatments are applied in order to attenuate the vibrations and improve the long term fatigue behavior of the structures. This experimental study is targeting applications in floor panels that are mounted to the loadcarrying primary structure of the vehicle. The objective is to reach outstanding damping performance considering the stringent weight and cost requirement in the automotive industry. An experimental setup has been developed and validated for the determination of the damping properties of structural specimens also considering interface damping effects. This contribution is structured in three main parts: test rig design, experimental results and discussion. Reliable and easy-to-use devices for the characterization of the damping properties of specimens between 200×40 mm2 and 400×400 mm2 are not available "on the shelf". In this context, we present a flexible experimental set-up which has been realized to (1) support the development of novel damping solutions for multi-functional composite structures; (2) characterize the loss-factor of the different damping concepts, including boundary effects. A variety of novel passive and active damping treatments have been investigated including viscoelastic, coulomb, magnetorheological (MR), particle, magnetic and eddy current damping. The particle, interface as well as active damping systems show promising performance in comparison to the classical viscoelastic treatments.

  2. A control volume study of the pressure tensor across a liquid-vapour interface

    NASA Astrophysics Data System (ADS)

    Braga, Carlos; Yatsyshin, Petr; Smith, Edward; Nold, Andreas; Goddard, Benjamin; Savva, Nikos; Schmuck, Markus; Duncan, Andrew; Sibley, David; Kalliadasis, Serafim

    2015-11-01

    The presence of an interface renders the properties of the system position dependent. The pressure tensor will no longer be uniform nor isotropic giving rise to the surface tension. The theory of Kirkwood-Buff gives a formal description of the surface tension based on the analysis of the local pressure tensor while capillary wave theory assumes the existence of an instantaneous intrinsic surface separating the liquid and vapour. Analysis of its Fourier components gives both structural and dynamical routes to compute the surface based on hydrodynamic theory. The defining equation of a capillary surface is given by the stress balance between the pressure tensors and the surface tension. Here, we employ the instantaneous interface as a representative surface across which we compute the local pressures following the seminal work of Irving and Kirkwood. The control volume approach to the Irving-Kirkwood expressions provides an exact balance between the stress and momentum transfer across the surface element allowing the study of the surface tension from a mechanical standpoint. We acknowledge financial support from European Research Council via Advanced Grant No. 247031.

  3. A novel tribological study on DLC-coated micro-dimpled orthopedics implant interface.

    PubMed

    Choudhury, Dipankar; Urban, Filip; Vrbka, Martin; Hartl, Martin; Krupka, Ivan

    2015-05-01

    This study investigates a tribological performance of diamond like carbon (DLC) coated micro dimpled prosthesis heads against ceramic cups in a novel pendulum hip joint simulator. The simulator enables determining friction coefficient and viscous effects of a concave shaped specimen interface (conformal contact). Two types of DLC such as hydrogenated amorphous carbon (a-C:H) and tetrahedral amorphous carbon (Ta-C) and one set of micro dimple (diameter of 300µm, depth of 70µm, and pitch of 900µm) were fabricated on metallic prosthesis heads. The experiment results reveal a significant friction coefficient reduction to the 'dimpled a-C:H/ceramic' prosthesis compared to a 'Metal (CoCr)/ceramic' prosthesis because of their improved material and surface properties and viscous effect. The post-experiment surface analysis displays that the dimpled a-C:H yielded a minor change in the surface roughness, and generated a larger sizes of wear debris (40-200nm sized, equivalent diameter), a size which could be certainly stored in the dimple, thus likely to reducing their possible third body abrasive wear rate. Thus, dimpled a:C-H can be used as a 'metal on ceramic hip joint interface', whereas the simulator can be utilized as an advanced bio-tribometer. PMID:25704181

  4. Study of Hydrophobic and Ionizable Hydrophilic Copolymers at Polymer/Solid and Polymer/Liquid Interfaces

    SciTech Connect

    Perahia, Dvora

    2011-11-01

    Joint experimental-computational efforts were set to characterize the interfacial effects on the structure and dynamics of polymers consisting of highly rigid hydrophilic-ionizable and hydrophobic sub-units within one polymeric chain casted into thin films of several molecular dimensions. Focusing on the ultra thin film region we separate out the interfacial effects from bulk characteristics. Specifically, the study sought to: identify the parameters that control the formation of a stable polymer-solid interface. The study consists of two components, experimental investigations and computational efforts. The experimental component was designed to derive empirical trends that can be used to correlate the set of coupled polymer molecular parameters with the interfacial characteristics of these polymers, and their response to presence of solvents. The computational study was designed to provide molecular insight into the ensemble averages provided by the experimental efforts on multiple length scales from molecular dimensions, to the nanometer lengths to a macroscopic understanding of solvent interactions with structured polymers. With the ultimate goal of correlating molecular parameters to structure, dynamics and properties of ionic polymers, the first stage of the research began with the study of two systems, one which allowed tailoring the flexibility of the backbone without the presence of ionic groups, but with a potential to sulfonate groups at a later stage, and a polymer whose backbone is rigid and the density of the ionic group can be varied. The combined experimental and computational studies significantly extended the understanding of polymers at interfaces from model systems to polydispersed copolymers with blocks of varying nature and complexity. This new insight directly affects the design of polymers for sustainable energy applications from batteries and fuel cells to solar energy.

  5. Space transfer vehicle concepts and requirements study. Volume 2, book 3: STV system interfaces

    NASA Technical Reports Server (NTRS)

    Weber, Gary A.

    1991-01-01

    This report presents the results of systems analyses and conceptual design of space transfer vehicles (STV). The missions examined included piloted and unpiloted lunar outpost support and spacecraft servicing, and unpiloted payload delivery to various earth and solar orbits. The study goal was to examine the mission requirements and provide a decision data base for future programmatic development plans. The final lunar transfer vehicles provided a wide range of capabilities and interface requirements while maintaining a constant payload mission model. Launch vehicle and space station sensitivity was examined, with the final vehicles as point design covering the range of possible options. Development programs were defined and technology readiness levels for different options were determined. Volume 1 presents the executive summary, volume 2 provides the study results, and volume 3 the cost and WBS data.

  6. Fluxes across double-diffusive interfaces: a one-dimensional-turbulence study

    NASA Astrophysics Data System (ADS)

    Gonzalez, E.; Kerstein, A.; Lignell, D.

    2010-12-01

    Double-diffusive convection in the diffusive regime is believed to occur, for example, in the Arctic and Southern Oceans, in geothermally-heated salty lakes, and in massive stars and giant planets. It is of interest in all these systems to know the parametrization of the fluxes of heat and salt across double-diffusive interfaces. The present work is a parametric study of these fluxes using one-dimensional-turbulence (ODT) simulations. Its main distinction is that it considers a parameter space larger than previous studies, which includes the effect of background shear. Specifically, this work considers the effect on the fluxes of the stability parameter, Rayleigh number, Prandtl number, Lewis number, and Richardson number. The ratio of the Rayleigh number and the stability parameter is found to be a dominant parameter. This parameter can be seen as a ratio of destabilizing and stabilizing effects. Trends predicted by the simulations are in good agreement with previous models and available measurements.

  7. Effect of Single-Electron Interface Trapping in Decanano MOSFETs: A 3D Atomistic Simulation Study

    NASA Technical Reports Server (NTRS)

    Asenov, Asen; Balasubramaniam, R.; Brown, A. R.; Davies, J. H.

    2000-01-01

    We study the effect of trapping/detrapping of a single-electron in interface states in the channel of n-type MOSFETs with decanano dimensions using 3D atomistic simulation techniques. In order to highlight the basic dependencies, the simulations are carried out initially assuming continuous doping charge, and discrete localized charge only for the trapped electron. The dependence of the random telegraph signal (RTS) amplitudes on the device dimensions and on the position of the trapped charge in the channel are studied in detail. Later, in full-scale, atomistic simulations assuming discrete charge for both randomly placed dopants and the trapped electron, we highlight the importance of current percolation and of traps with strategic position where the trapped electron blocks a dominant current path.

  8. Neuromechanism study of insect-machine interface: flight control by neural electrical stimulation.

    PubMed

    Zhao, Huixia; Zheng, Nenggan; Ribi, Willi A; Zheng, Huoqing; Xue, Lei; Gong, Fan; Zheng, Xiaoxiang; Hu, Fuliang

    2014-01-01

    The insect-machine interface (IMI) is a novel approach developed for man-made air vehicles, which directly controls insect flight by either neuromuscular or neural stimulation. In our previous study of IMI, we induced flight initiation and cessation reproducibly in restrained honeybees (Apis mellifera L.) via electrical stimulation of the bilateral optic lobes. To explore the neuromechanism underlying IMI, we applied electrical stimulation to seven subregions of the honeybee brain with the aid of a new method for localizing brain regions. Results showed that the success rate for initiating honeybee flight decreased in the order: α-lobe (or β-lobe), ellipsoid body, lobula, medulla and antennal lobe. Based on a comparison with other neurobiological studies in honeybees, we propose that there is a cluster of descending neurons in the honeybee brain that transmits neural excitation from stimulated brain areas to the thoracic ganglia, leading to flight behavior. This neural circuit may involve the higher-order integration center, the primary visual processing center and the suboesophageal ganglion, which is also associated with a possible learning and memory pathway. By pharmacologically manipulating the electrically stimulated honeybee brain, we have shown that octopamine, rather than dopamine, serotonin and acetylcholine, plays a part in the circuit underlying electrically elicited honeybee flight. Our study presents a new brain stimulation protocol for the honeybee-machine interface and has solved one of the questions with regard to understanding which functional divisions of the insect brain participate in flight control. It will support further studies to uncover the involved neurons inside specific brain areas and to test the hypothesized involvement of a visual learning and memory pathway in IMI flight control. PMID:25409523

  9. Neuromechanism Study of Insect–Machine Interface: Flight Control by Neural Electrical Stimulation

    PubMed Central

    Zhao, Huixia; Zheng, Nenggan; Ribi, Willi A.; Zheng, Huoqing; Xue, Lei; Gong, Fan; Zheng, Xiaoxiang; Hu, Fuliang

    2014-01-01

    The insect–machine interface (IMI) is a novel approach developed for man-made air vehicles, which directly controls insect flight by either neuromuscular or neural stimulation. In our previous study of IMI, we induced flight initiation and cessation reproducibly in restrained honeybees (Apis mellifera L.) via electrical stimulation of the bilateral optic lobes. To explore the neuromechanism underlying IMI, we applied electrical stimulation to seven subregions of the honeybee brain with the aid of a new method for localizing brain regions. Results showed that the success rate for initiating honeybee flight decreased in the order: α-lobe (or β-lobe), ellipsoid body, lobula, medulla and antennal lobe. Based on a comparison with other neurobiological studies in honeybees, we propose that there is a cluster of descending neurons in the honeybee brain that transmits neural excitation from stimulated brain areas to the thoracic ganglia, leading to flight behavior. This neural circuit may involve the higher-order integration center, the primary visual processing center and the suboesophageal ganglion, which is also associated with a possible learning and memory pathway. By pharmacologically manipulating the electrically stimulated honeybee brain, we have shown that octopamine, rather than dopamine, serotonin and acetylcholine, plays a part in the circuit underlying electrically elicited honeybee flight. Our study presents a new brain stimulation protocol for the honeybee–machine interface and has solved one of the questions with regard to understanding which functional divisions of the insect brain participate in flight control. It will support further studies to uncover the involved neurons inside specific brain areas and to test the hypothesized involvement of a visual learning and memory pathway in IMI flight control. PMID:25409523

  10. X-ray studies of III-V native oxide/gallium arsenide interface

    NASA Astrophysics Data System (ADS)

    Cheong, Seong-Kyun

    Three x-ray techniques have been employed to study wet-thermal native oxides of AlGaAs on GaAs. For these materials, a knowledge of the role of As at the interface is important for understanding Fermi-level pinning and is a central issue in efforts to develop high performance III-V MOSFET devices. This study is focused on how the As is incorporated at the interface, the interfacial strain, and related local structural parameters. X-ray absorption fine-structure spectroscopy (XAFS) was used to determine the site of residual As in wet-oxidized Al0.96Ga0.04As. In a ˜0.5 mum oxide film removed from its GaAs substrate, the remaining As atoms were found to be coordinated with oxygen in the form of amorphous As oxides, with a mixture of ˜80% As3+ and ˜20% As 5+ sites. These two sites are locally similar to As2O 3 and As2O5. Through this measurement, no evidence of interstitial or substitutional As, As precipitates, or GaAs was seen, implying that less than 10% of the As atoms are in these forms. To characterize the oxide structure in both the oxide film and the interfacial region, x-ray reflectivity and reflection-mode XAFS experiments were performed for a thin (300 A) oxidized AlxGa1-xAs (x = 0.96) film grown on GaAs. X-ray reflectivity studies showed that the composition of the surface oxidized film is not homogeneous as a function of depth. Reflection-mode XAFS, which uses the total external reflection of x-rays to confine an x-ray beam to the interfacial region, provided details of the local environment of As atoms at the interface of the oxide/GaAs. Analysis through this technique revealed that As atoms are in the form of mixed As oxides, with the local environment appearing to resemble As2O3 and As 2O5 in the interfacial region, which is consistent with the above observation from the isolated oxide film.

  11. Electronic and magnetic properties at rough alloyed interfaces of Fe/Co on Au substrates: An augmented space study

    NASA Astrophysics Data System (ADS)

    Priyadarshini, Parida; Biplab, Ganguli

    2016-05-01

    We studied the interface electronic and magnetic properties of Fe/Co deposited on Au substrate and researched the effects of roughness at the interfaces within augmented space formalism (ASF). The full calculation is carried out by recursion and tight-binding linear muffin tin orbital (TB-LMTO) methods. The amount of roughness is different at different atomic layers. The formalism is also applied to sharp interface, when interdiffusion of atoms is negligible. Our results of one monolayer transition metal agree with other reported results. A realistic rough interface is also modeled with three and four monolayers of transition metals, deposited on Au substrates. Project supported by the INSPIRE Program Division, Department of Science and Technology, India.

  12. Case study for the evaluation and selection of man-machine interface (MMI) software

    SciTech Connect

    Nekimken, H.; Pope, N.; Macdonald, J.; Bibeau, R.; Gomez, B.; Sellon, D.

    1996-06-01

    The authors evaluated three of the top man-machine interface (MMI) software systems. The main categories upon which they based their evaluation on were the following: operator interface; network and data distribution; input/output (I/O) interface; application development; alarms; real-time and historical trending; support, documentation, and training; processing tools (batch, recipe, logic); reports; custom interfacing; start-up/recovery; external database; and multimedia. They also present their MMI requirements and guidelines for the selection and evaluation of these MMI systems.

  13. Earth Observatory Satellite system definition study. Report 2: Instrument constraints and interfaces

    NASA Technical Reports Server (NTRS)

    1974-01-01

    The instrument constraints and interface specifications for the Earth Observatory Satellite (EOS) are discussed. The Land Use Classification Mission using a 7 band Thematic Mapper and a 4 band High Resolution Pointable Imager is stressed. The mission and performance of the instruments were reviewed and expanded to reflect the instrument as a part of the total remote sensing system. A preliminary EOS interface handbook is provided to describe the mission and system, to specify the spacecraft interfaces to potential instrument contractors, and to describe the instrument interface data required by the system integration contractor.

  14. Pollution: A Selected Bibliography of U.S. Government Publications on Air, Water, and Land Pollution 1965-1970.

    ERIC Educational Resources Information Center

    Kiraldi, Louis, Comp.; Burk, Janet L., Comp.

    Materials on environmental pollution published by the various offices of the federal government are presented in this select bibliography. Limited in scope to publications on air, water, and land pollution, the document is designed to serve teachers and researchers working in the field of environmental problems who wish reference to public…

  15. Poisson-Boltzmann study of the effective electrostatic interaction between colloids at an electrolyte interface

    NASA Astrophysics Data System (ADS)

    Majee, Arghya; Bier, Markus; Dietrich, S.

    2016-08-01

    The effective electrostatic interaction between a pair of colloids, both of them located close to each other at an electrolyte interface, is studied by employing the full, nonlinear Poisson-Boltzmann (PB) theory within classical density functional theory. Using a simplified yet appropriate model, all contributions to the effective interaction are obtained exactly, albeit numerically. The comparison between our results and those obtained within linearized PB theory reveals that the latter overestimates these contributions significantly at short inter-particle separations. Whereas the surface contributions to the linear and the nonlinear PB results differ only quantitatively, the line contributions show qualitative differences at short separations. Moreover, a dependence of the line contribution on the solvation properties of the two adjacent fluids is found, which is absent within the linear theory. Our results are expected to enrich the understanding of effective interfacial interactions between colloids.

  16. Impact of Participatory Design for Drug-Drug Interaction Alerts. A Comparison Study Between Two Interfaces.

    PubMed

    Luna, Daniel; Otero, Carlos; Risk, Marcelo; Stanziola, Enrique; González Bernaldo de Quirós, Fernán

    2016-01-01

    Decision support systems for alert drug-drug interactions have been shown as valid strategy to reduce medical error. Even so the use of these systems has not been as expected, probably due to the lack of a suitable design. This study compares two interfaces, one of them developed using participatory design techniques (based on user centered design processes). This work showed that the use of these techniques improves satisfaction, effectiveness and efficiency in an alert system for drug-drug interactions, a fact that was evident in specific situations such as the decrease of errors to meet the specified task, the time, the workload optimization and users overall satisfaction with the system. PMID:27577343

  17. Studies on electronic structure of interfaces between Ag and gelatin for stabilization of Ag nanoparticles

    NASA Astrophysics Data System (ADS)

    Tani, Tadaaki; Uchida, Takayuki

    2015-06-01

    Extremely high stability of Ag nanoparticles in photographic materials has forced us to study the electronic structures of the interfaces between thin layers of Ag, Au, and Pt and their surface membranes in ambient atmosphere by photoelectron yield spectroscopy in air and Kelvin probe method. Owing to the Fermi level equalization between a metal layer and a membrane coming from air, the electron transfer took place from the membrane to Pt and Au layers and from an Ag layer to the membrane, giving the reason for poor stability of Ag nanoparticles in air. The control of the Fermi level of an Ag layer with respect to that of a gelatin membrane in air could be widely made according to Nernst’s equation by changing the pH and pAg values of an aqueous gelatin solution used to form the membrane, and thus available to stabilize Ag nanoparticles in a gelatin matrix.

  18. Thermal study of interface between the Orbiter cold plate and typical Shuttle spacecraft payload flight electronics

    NASA Technical Reports Server (NTRS)

    Hwangbo, H.; Coyle, M. J.

    1979-01-01

    Spacelab provides a set of Freon line plumbing and cold plates for experiment equipments which are located in the Shuttle pallet and which need active thermal control. The reported study deals with the thermal problem of attaching a Command and Data Handling module with various electronic boxes whose combined footprints on the baseplate are much larger than the cold plate. A description of two modules and the cold plate assembly in the pallet is presented and a thermal model description is provided. The method employed in modeling heat pipes-honey-comb matrix is based upon an effective conductance between the heat pipe vapor and the walls of the heat pipe. The considered thermal models and a computer program are used to perform steady-state thermal analyses. The temperature gradients in the large module baseplate attached to the small cold plate are predicted as a function of the interface plate thickness.

  19. Density-functional study of the nematic-isotropic interface of hard spherocylinders.

    PubMed

    Velasco, E; Mederos, L; Sullivan, D E

    2002-08-01

    The Somoza-Tarazona density-functional theory is applied to the isotropic-nematic interface of hard spherocylinders with length (L)-to-diameter (D) ratios in the range L/D=5-20. Properties such as the density and orientational order-parameter profiles and the variation of interfacial tension with bulk nematic tilt angle agree qualitatively with results of previous studies at larger values of L/D using both computer simulation and the Onsager second-virial approximation. The minimum interfacial tension is obtained at a tilt angle of 90 degrees. For values of L/D approximately 5, it is found that the Onsager approximation predicts a spurious minimum in the interfacial tension at small tilt angles. PMID:12241197

  20. Photoemission spectroscopy study of the lanthanum lutetium oxide/silicon interface

    SciTech Connect

    Nichau, A.; Schnee, M.; Schubert, J.; Bernardy, P.; Hollaender, B.; Buca, D.; Mantl, S.; Besmehn, A.; Breuer, U.; Rubio-Zuazo, J.; Castro, G. R.; Muecklich, A.; Borany, J. von

    2013-04-21

    Rare earth oxides are promising candidates for future integration into nano-electronics. A key property of these oxides is their ability to form silicates in order to replace the interfacial layer in Si-based complementary metal-oxide field effect transistors. In this work a detailed study of lanthanum lutetium oxide based gate stacks is presented. Special attention is given to the silicate formation at temperatures typical for CMOS processing. The experimental analysis is based on hard x-ray photoemission spectroscopy complemented by standard laboratory experiments as Rutherford backscattering spectrometry and high-resolution transmission electron microscopy. Homogenously distributed La silicate and Lu silicate at the Si interface are proven to form already during gate oxide deposition. During the thermal treatment Si atoms diffuse through the oxide layer towards the TiN metal gate. This mechanism is identified to be promoted via Lu-O bonds, whereby the diffusion of La was found to be less important.