Science.gov

Sample records for adsorbed surface layers

  1. Excitation energy migration in yellow fluorescent protein (citrine) layers adsorbed on modified gold surfaces

    NASA Astrophysics Data System (ADS)

    Yusoff, Hanis Mohd; Rzeźnicka, Izabela I.; Hoshi, Hirotaka; Kajimoto, Shinji; Horimoto, Noriko Nishizawa; Sogawa, Kazuhiro; Fukumura, Hiroshi

    2013-09-01

    The nature of functional proteins adsorbed on solid surfaces is interesting from the perspective of developing of bioelectronics and biomaterials. Here we present evidence that citrine (one of yellow fluorescent protein variants) adsorbed on modified gold surfaces would not undergo denaturation and energy transfer among the adsorbed citrine molecules would occur. Gold substrates were chemically modified with 3-mercaptopropionic acid and tert-butyl mercaptan for the preparation of hydrophilic and hydrophobic surfaces, respectively. A pure solution of citrine was dropped and dried on the modified gold substrates and their surface morphology was studied with scanning tunnelling microscopy (STM). The obtained STM images showed multilayers of citrine adsorbed on the modified surfaces. On hydrophobic surfaces, citrine was adsorbed more randomly, formed various non-uniform aggregates, while on hydrophilic surfaces, citrine appeared more aligned and isolated uniform protein clusters were observed. Fluorescence lifetime and anisotropy decay of these dried citrine layers were also measured using the time correlated single photon counting method. Fluorescence anisotropy of citrine on the hydrophobic surface decayed faster than citrine on the hydrophilic surface. From these results we concluded that fluorescence energy migration occurred faster among citrine molecules which were randomly adsorbed on the hydrophobic surface to compare with the hydrophilic surface.

  2. Study of the adsorbed layer on a solid electrode surface by specular reflection measurement

    NASA Astrophysics Data System (ADS)

    Kusu, Fumiyo; Takamura, Kiyoko

    1985-07-01

    Specular reflection measurements were carried out to study the adsorbed layers of certain heterocyclic compounds such as adenine, barbital, 2'-deoxyadenosine, phenobarbital, pyridine and thymine. When pyridine was present in 0.1M NaClO 4, a marked decrease in the reflectivity of a gold electrode was observed. In the potential range near the point of zero charge on the reflectivity-potential curve, the decrease was due to the adsorption of pyridine. Assuming the reflectivity change to be proportional to the surface coverage, the potential and concentration dependence of pyridine adsorption was determined and analysed on the basis of a Langmuir-type adsorption isotherm. The refractive indices and extinction coefficients for the adsorbed layers of the compounds investigated were evaluated using the observed reflectivity change, according to relations proposed by McIntyre and Aspnes.

  3. Effect of the interplay between protein and surface on the properties of adsorbed protein layers.

    PubMed

    Ouberai, Myriam M; Xu, Kairuo; Welland, Mark E

    2014-08-01

    Although protein adsorption to surface is a common phenomenon, investigation of the process is challenging due to the complexity of the interplay between external factors, protein and surface properties. Therefore experimental approaches have to measure the properties of adsorbed protein layers with high accuracy in order to achieve a comprehensive description of the process. To this end, we used a combination of two biosensing techniques, dual polarization interferometry and quartz crystal microbalance with dissipation. From this, we are able to extract surface coverage values, layer structural parameters, water content and viscoelastic properties to examine the properties of protein layers formed at the liquid/solid interface. Layer parameters were examined upon adsorption of proteins of varying size and structural properties, on surfaces with opposite polarity. We show that "soft" proteins such as unfolded α-synuclein and high molecular weight albumin are highly influenced by the surface polarity, as they form a highly diffuse and hydrated layer on the hydrophilic silica surface as opposed to the denser, less hydrated layer formed on a hydrophobic methylated surface. These layer properties are a result of different orientations and packing of the proteins. By contrast, lysozyme is barely influenced by the surface polarity due to its intrinsic structural stability. Interestingly, we show that for a similar molecular weight, the unfolded α-synuclein forms a layer with the highest percentage of solvation not related to surface coverage but resulting from the highest water content trapped within the protein. Together, these data reveal a trend in layer properties highlighting the importance of the interplay between protein and surface for the design of biomaterials. PMID:24780165

  4. Adsorption isotherms and structure of cationic surfactants adsorbed on mineral oxide surfaces prepared by atomic layer deposition.

    PubMed

    Wangchareansak, Thipvaree; Craig, Vincent S J; Notley, Shannon M

    2013-12-01

    The adsorption isotherms and aggregate structures of adsorbed surfactants on smooth thin-film surfaces of mineral oxides have been studied by optical reflectometry and atomic force microscopy (AFM). Films of the mineral oxides of titania, alumina, hafnia, and zirconia were produced by atomic layer deposition (ALD) with low roughness. We find that the surface strongly influences the admicelle organization on the surface. At high concentrations (2 × cmc) of cetyltrimethylammonium bromide (CTAB), the surfactant aggregates on a titania surface exhibit a flattened admicelle structure with an average repeat distance of 8.0 ± 1.0 nm whereas aggregates on alumina substrates exhibit a larger admicelle with an average separation distance of 10.5 ± 1.0 nm. A wormlike admicelle structure with an average separation distance of 7.0 ± 1.0 nm can be observed on zirconia substrates whereas a bilayered aggregate structure on hafnia substrates was observed. The change in the surface aggregate structure can be related to an increase in the critical packing parameter through a reduction in the effective headgroup area of the surfactant. The templating strength of the surfaces are found to be hafnia > alumina > zirconia > titania. Weakly templating surfaces are expected to have superior biocompatibility. PMID:24224944

  5. Raman spectra of adsorbed layers on space shuttle and AOTV thermal protection system surface

    NASA Technical Reports Server (NTRS)

    Willey, Ronald J.

    1987-01-01

    Surfaces of interest to space vehicle heat shield design were struck by a 2 W argon ion laser line while subjected to supersonic arc jet flow conditions. Emission spectra were taken at 90 deg to the angle of laser incidence on the test object. Results showed possible weak Raman shifts which could not be directly tied to any particular parameter such as surface temperature or gas composition. The investigation must be considered exploratory in terms of findings. Many undesirable effects were found and corrected as the project progressed. For instance, initial spectra settings led to ghosts which were eliminated by closing the intermediate of filter slit of the Spex from 8 to 3 mm. Further, under certain conditions, plasma lines from the laser were observed. Several materials were also investigated at room temperature for Raman shifts. Results showed Raman shifts for RCC and TEOS coated materials. The HRSI materials showed only weak Raman shifts, however, substantial efforts were made in studying these materials. Baseline materials showed the technique to be sound. The original goal was to find a Raman shift for the High-temperature Reusable Surface Insulation (HRSI) Reaction Cured borosilicate Glass (RCG) coated material and tie the amplitude of this peak to Arc jet conditions. Weak Raman shifts may be present, however, time limitations prevented confirmation.

  6. The density and refractive index of adsorbing protein layers.

    PubMed

    Vörös, Janos

    2004-07-01

    The structure of the adsorbing layers of native and denatured proteins (fibrinogen, gamma-immunoglobulin, albumin, and lysozyme) was studied on hydrophilic TiO(2) and hydrophobic Teflon-AF surfaces using the quartz crystal microbalance with dissipation and optical waveguide lightmode spectroscopy techniques. The density and the refractive index of the adsorbing protein layers could be determined from the complementary information provided by the two in situ instruments. The observed density and refractive index changes during the protein-adsorption process indicated the presence of conformational changes (e.g., partial unfolding) in general, especially upon contact with the hydrophobic surface. The structure of the formed layers was found to depend on the size of the proteins and on the experimental conditions. On the TiO(2) surface smaller proteins formed a denser layer than larger ones and the layer of unfolded proteins was less dense than that adsorbed from the native conformation. The hydrophobic surface induced denaturation and resulted in the formation of thin compact protein films of albumin and lysozyme. A linear correlation was found between the quartz crystal microbalance measured dissipation factor and the total water content of the layer, suggesting the existence of a dissipative process that is related to the solvent molecules present inside the adsorbed protein layer. Our measurements indicated that water and solvent molecules not only influence the 3D structure of proteins in solution but also play a crucial role in their adsorption onto surfaces. PMID:15240488

  7. Surface characterization of adsorbed asphaltene on a stainless steel surface

    NASA Astrophysics Data System (ADS)

    Abdallah, W. A.; Taylor, S. D.

    2007-05-01

    X-ray photoelectron spectroscopy was used to characterize a single layer of adsorbed asphaltene on a metallic surface. The deposits were created by immersing a stainless steel disc into a dilute asphaltene solution with either toluene or dichloromethane as the solvent, although the toluene solution allowed for better control of the adsorbed asphaltene layer and less atmospheric oxygen contamination. The analyses for C 1s, S 2p3/2, N 1s and O 1s photoemission peaks indicated that different functional groups are present in the asphaltene layer including carboxylic, pyrrolic, pyridininc, thiophenic and sulfite, with slight differences in their binding energies.

  8. Structure and properties of water film adsorbed on mica surfaces

    NASA Astrophysics Data System (ADS)

    Zhao, Gutian; Tan, Qiyan; Xiang, Li; Cai, Di; Zeng, Hongbo; Yi, Hong; Ni, Zhonghua; Chen, Yunfei

    2015-09-01

    The structure profiles and physical properties of the adsorbed water film on a mica surface under conditions with different degrees of relative humidity are investigated by a surface force apparatus. The first layer of the adsorbed water film shows ice-like properties, including a lattice constant similar with ice crystal, a high bearing capacity that can support normal pressure as high as 4 MPa, a creep behavior under the action of even a small normal load, and a character of hydrogen bond. Adjacent to the first layer of the adsorbed water film, the water molecules in the outer layer are liquid-like that can flow freely under the action of external loads. Experimental results demonstrate that the adsorbed water layer makes the mica surface change from hydrophilic to weak hydrophobic. The weak hydrophobic surface may induce the latter adsorbed water molecules to form water islands on a mica sheet.

  9. Volumetric Interpretation of Protein Adsorption: Capacity Scaling with Adsorbate Molecular Weight and Adsorbent Surface Energy

    PubMed Central

    Parhi, Purnendu; Golas, Avantika; Barnthip, Naris; Noh, Hyeran; Vogler, Erwin A.

    2009-01-01

    Silanized-glass-particle adsorbent capacities are extracted from adsorption isotherms of human serum albumin (HSA, 66 kDa), immunoglobulin G (IgG, 160 kDa), fibrinogen (Fib, 341 kDa), and immunoglobulin M (IgM, 1000 kDa) for adsorbent surface energies sampling the observable range of water wettability. Adsorbent capacity expressed as either mass-or-moles per-unit-adsorbent-area increases with protein molecular weight (MW) in a manner that is quantitatively inconsistent with the idea that proteins adsorb as a monolayer at the solution-material interface in any physically-realizable configuration or state of denaturation. Capacity decreases monotonically with increasing adsorbent hydrophilicity to the limit-of-detection (LOD) near τo = 30 dyne/cm (θ~65o) for all protein/surface combinations studied (where τo≡γlvocosθ is the water adhesion tension, γlvo is the interfacial tension of pure-buffer solution, and θ is the buffer advancing contact angle). Experimental evidence thus shows that adsorbent capacity depends on both adsorbent surface energy and adsorbate size. Comparison of theory to experiment implies that proteins do not adsorb onto a two-dimensional (2D) interfacial plane as frequently depicted in the literature but rather partition from solution into a three-dimensional (3D) interphase region that separates the physical surface from bulk solution. This interphase has a finite volume related to the dimensions of hydrated protein in the adsorbed state (defining “layer” thickness). The interphase can be comprised of a number of adsorbed-protein layers depending on the solution concentration in which adsorbent is immersed, molecular volume of the adsorbing protein (proportional to MW), and adsorbent hydrophilicity. Multilayer adsorption accounts for adsorbent capacity over-and-above monolayer and is inconsistent with the idea that protein adsorbs to surfaces primarily through protein/surface interactions because proteins within second (or higher

  10. Influence of surface chemistry on the structural organization of monomolecular protein layers adsorbed to functionalized aqueous interfaces.

    PubMed Central

    Lösche, M; Piepenstock, M; Diederich, A; Grünewald, T; Kjaer, K; Vaknin, D

    1993-01-01

    The molecular organization of streptavidin (SA) bound to aqueous surface monolayers of biotin-functionalized lipids and binary lipid mixtures has been investigated with neutron reflectivity and electron and fluorescence microscopy. The substitution of deuterons (2H) for protons (1H), both in subphase water molecules and in the alkyl chains of the lipid surface monolayer, was utilized to determine the interface structure on the molecular length scale. In all cases studied, the protein forms monomolecular layers underneath the interface with thickness values of approximately 40 A. A systematic dependence of the structural properties of such self-assembled SA monolayers on the surface chemistry was observed: the lateral protein density depends on the length of the spacer connecting the biotin moiety and its hydrophobic anchor. The hydration of the lipid head groups in the protein-bound state depends on the dipole moment density at the interface. Images FIGURE 1 FIGURE 2 FIGURE 3 FIGURE 5 FIGURE 11 FIGURE 12 FIGURE A1 PMID:8298041

  11. Block copolymer adsorbed layers on solids

    NASA Astrophysics Data System (ADS)

    Sen, Mani; Jiang, Naisheng; Gowd, Bhoje; Endoh, Maya; Koga, Tadanori

    Block copolymer thin films offer a simple and effective route to fabricate highly ordered periodic microdomain structures. The fundamental, yet unsolved question is whether these highly oriented microdomain structures persist even near an impenetrable solid wall. We here report the adsorbed structures of polystyrene-block-poly (4-vinylpyridine) (PS-block-P4VP, Mw = 41,000, PS (weight fraction =0.81) formed on planar silicon substrates. Perpendicularly aligned cylindrical microdomains were created by solvent vapor annealing (Gowd et al., Soft Matter, 2014, 10, 7753), and the adsorbed layer was derived by solvent leaching with chloroform, a good solvent for the polymers and thereafter characterized by using atomic force microscopy, scanning electron microscopy, grazing incidence small angle x-ray scattering, and x-ray reflectivity. The results showed that both PS and P4VP chains lie flat on the substrate, forming a microphase-separated structure (MSS) without long-range order. Moreover, a spin-coated PS-block-P4VP thin film annealed under vacuum at 190 °C showed similar MSS on the substrate, indicating the generality of the interfacial polymer structure. Details will be discussed in the presentation. NSF Grant No. CMMI-1332499.

  12. IR investigations of surfaces and adsorbates

    SciTech Connect

    Gwyn Williams

    2001-12-10

    Synchrotron infrared reflection-absorption measurements on single crystal metal surfaces with adsorbates have led to the determination of many key parameters related to the bonding vibrational modes and the dynamics of adsorbates. In particular, energy couplings between electrons and adsorbate motion have been shown to be a dominant mechanism on metal surfaces. Excellent agreement has been obtained with calculations for many of the observations, and the synergy between theory and experiment has led to a deeper understanding of the roles of electrons and phonons in determining the properties of interfaces and their roles in phenomena as diverse as friction, lubrication, catalysis and adhesion. Nonetheless, as the experiments are pushed harder, to describe such effects as co-adsorbed systems, disagreements continue to challenge the theory and our comprehension also is still evolving.

  13. Standoff Spectroscopy of Surface Adsorbed Chemicals

    SciTech Connect

    Van Neste, Charles W; Senesac, Larry R; Thundat, Thomas George

    2009-01-01

    Despite its immediate applications, selective detection of trace quantities of surface adsorbed chemicals, such as explosives, without physically collecting the sample molecules is a challenging task. Standoff spectroscopic techniques offer an ideal method of detecting chemicals without using a sample collection step. Though standoff spectroscopic techniques are capable of providing high selectivity, their demonstrated sensitivities are poor. Here we describe standoff detection of trace quantities of surface adsorbed chemicals using two quantum cascade lasers operated simultaneously, with tunable wavelength windows that match with absorption peaks of the analytes. This standoff method is a variation of photoacoustic spectroscopy, where scattered light from the sample surface is used for exciting acoustic resonance of the detector. We demonstrate a sensitivity of 100 ng/cm{sup 2} and a standoff detection distance of 20 m for surface adsorbed analytes such as explosives and tributyl phosphate.

  14. Structure of Non-Equilibrium Adsorbed Polymer Layers

    NASA Astrophysics Data System (ADS)

    O'Shaughnessy, Ben; Vavylonis, Dimitrios

    2004-03-01

    Equilibrium polymer adsorption has been widely studied theoretically. Many experiments however implicate strong non-equilibrium effects for monomer sticking energies somewhat larger than kT, the most common case. The structure and slow dynamics in these layers is not understood. We analyze theoretically non-equilibrium layers from dilute solutions in the limit of irreversible monomer adsorption. We find the density profile ˜ z-4/3 and loop distribution ˜ s-11/5 of the resulting layer are no different to equilibrium. However, single chain statistics are radically different: the layer consists of a flat inner portion of fully collapsed chains plus an outer part whose chains make only fN surface contacts where N is chain length. The contact fractions f follow a broad distribution, P(f) ˜ f-4/5, consistent with experiment [H. M. Schneider et al, Langmuir 12, 994 (1996)], and the lateral size R of adsorbed chains is of order the bulk coil size, R ˜ N^3/5. For equilibrium layers, by contrast, P has a unique peak at a value of f of order unity, while R ˜ N^1/2 is significantly less. The relaxation of a non-equilibrium layer towards equilibrium thus entails chain shrinkage and tighter binding. We speculate that the observed decrease of bulk-layer chain exchange rates with increasing aging reflects these internal layer dynamics.

  15. Do Methanethiol Adsorbates on the Au(111) Surface Dissociate?

    NASA Astrophysics Data System (ADS)

    Zhou, Jian-Ge; Hagelberg, Frank

    2006-07-01

    The interaction of methanethiol molecules CH3SH with the Au(111) surface is investigated, and it is found for the first time that the S-H bond remains intact when the methanethiol molecules are adsorbed on the regular Au(111) surface. However, it breaks if defects are present in the Au(111) surface. At low coverage, the fcc region is favored for S atom adsorption, but at saturated coverage the adsorption energies at various sites are almost isoenergetic. The presented calculations show that a methanethiol layer on the regular Au(111) surface does not dimerize.

  16. Photodecomposition of chloromethanes adsorbed on silica surfaces

    NASA Technical Reports Server (NTRS)

    Ausloos, P.; Rebbert, R. E.; Glasgow, L.

    1977-01-01

    Irradiation of CCl4, CFCl3, and CF2Cl2 in the presence of C2H6 in vessels containing silica sand or fused quartz tubing results in the formation of chlorine-containing products. The formation of these compounds occurs at wavelengths extending up to approximately 400 nm, that is, at wavelengths well beyond the absorption threshold of the chloromethanes in the gas phase. It is suggested that CCl4 adsorbed on silica surfaces photodissociates to yield CCl3 and CCl2 species. The poor material balance obtained in these experiments indicates that several of the chlorine-containing fragments are strongly adsorbed on the surface. At a CCl4 pressure of 13 Pa (0.1 torr), photolysis with 366 nm light in the presence of sand results in the decomposition of one molecule for every 10,000 photons striking the surface. Under otherwise identical conditions, the photon-induced breadkdown of CFCl3 and CF2Cl2 is respectively only 10% or 3% as efficient.

  17. Cellular Responses Modulated by FGF-2 Adsorbed on Albumin/Heparin Layer-by-Layer Assemblies

    PubMed Central

    Kumorek, Marta; Kubies, Dana; Filová, Elena; Houska, Milan; Kasoju, Naresh; Mázl Chánová, Eliška; Matějka, Roman; Krýslová, Markéta; Bačáková, Lucie; Rypáček, František

    2015-01-01

    In a typical cell culture system, growth factors immobilized on the cell culture surfaces can serve as a reservoir of bio-signaling molecules, without the need to supplement them additionally into the culture medium. In this paper, we report on the fabrication of albumin/heparin (Alb/Hep) assemblies for controlled binding of basic fibroblast growth factor (FGF-2). The surfaces were constructed by layer-by-layer adsorption of polyelectrolytes albumin and heparin and were subsequently stabilized by covalent crosslinking with glutaraldehyde. An analysis of the surface morphology by atomic force microscopy showed that two Alb/Hep bilayers are required to cover the surface of substrate. The formation of the Alb/Hep assemblies was monitored by the surface plasmon resonance (SPR), the infrared multiinternal reflection spectroscopy (FTIR MIRS) and UV/VIS spectroscopy. The adsorption of FGF-2 on the cross-linked Alb/Hep was followed by SPR. The results revealed that FGF-2 binds to the Alb/Hep assembly in a dose and time-dependent manner up to the surface concentration of 120 ng/cm2. The bioactivity of the adsorbed FGF-2 was assessed in experiments in vitro, using calf pulmonary arterial endothelial cells (CPAE). CPAE cells could attach and proliferate on Alb/Hep surfaces. The adsorbed FGF-2 was bioactive and stimulated both the proliferation and the differentiation of CPAE cells. The improvement was more pronounced at a lower FGF-2 surface concentration (30 ng/cm2) than on surfaces with a higher concentration of FGF-2 (120 ng/cm2). PMID:25945799

  18. Photostability enhancement of azoic dyes adsorbed and intercalated into Mg-Al-layered double hydroxide

    NASA Astrophysics Data System (ADS)

    Liu, Pengfei; Liu, Pei; Zhao, Kongcao; Li, Lei

    2015-11-01

    Two azoic dyes 4-aminoazobenzene-4-sulfonic (AS) and ethyl orange (EO) were adsorbed on or intercalated into Mg-Al-CO3 layered double hydroxide (LDH) for photostability enhancement. Fluorescence analysis results showed that the photostability of two dyes could be greatly improved after being adsorbed on the surface of Mg-Al-CO3-LDH matrix. Furthermore, photostability of adsorbed dyes was superior to that of intercalated dyes. It was suggested that AS or EO was adsorbed on LDHs surface through a strong chemisorption interaction, resulting in the enhancement of photostability. After the UV irradiation under N2 atmosphere, the absorbed dyes not only show great increase of fluorescence intensity but also exhibited high stability against UV irradiation. This work provides a feasible approach to enhance the photostability of azoic dye confined in an inorganic two-dimensional (2D) matrix via changing the microenvironment, which may be considered to be a promising method of improving photostability of solid fluorescent materials.

  19. Molecular Orientation of Hydroquinone Adsorbed at a Platinum(111) Thin-Layer Electrode.

    PubMed

    Ren; Hubbard

    1999-01-15

    Reported are new findings regarding the molecular orientation of hydroquinone (HQ) adsorbed on Pt surfaces. The packing density of hydroquinone adsorbed from 1 M HClO4 supporting electrolyte has been measured by use of a Pt(111) thin-layer electrode. The packing-density-vs-concentration profiles for hydroquinone, measured by a differential thin-layer electrode method at an ordered Pt(111) surface and at an electrochemically disordered Pt(111) surface, are identical within an experimental error of about 8%. The profiles from this study are similar to the ones obtained previously at an ordered Pt(111) surface by Auger spectroscopy, but they are significantly different from those reported previously for polycrystalline Pt thin-layer electrodes. A procedure based upon displacement of HQ by thiocyanate has been developed as an alternative method for determining the packing density of adsorbed HQ. Both methods afford information regarding the molecular state of HQ adsorbed at the Pt(111) surface. Copyright 1999 Academic Press. PMID:9885274

  20. Adsorbate modification of the structural, electronic, and magnetic properties of ferromagnetic fcc {110} surfaces

    NASA Astrophysics Data System (ADS)

    Gunn, D. S. D.; Jenkins, Stephen J.

    2011-03-01

    We identify trends in structural, electronic, and magnetic modifications that occur on ferromagnetic {110} surfaces upon varying either the substrate material or the adsorbate species. First, we have modeled the adsorption of several first-row p-block elements on the surface of fcc Co{110} at two coverages [0.5 and 1.0 monolayer (ML)]. All adsorbates were found to expand the distance between the first and second substrate layers and to contract the distance between the second and third layers. The energetic location of a characteristic trough in the density-of-d-states difference plot correlates with the direction of the adsorbate magnetic coupling to the surface, and a trend of antiferromagnetic to ferromagnetic coupling to the surface was observed across the elements from boron to fluorine. A high fluorine adatom coverage (1.0 ML) was found to enhance the surface spin magnetic moment by 11%. Second, we also calculate and contrast adsorption of 0.5 and 1.0 ML of carbon, nitrogen, and oxygen adatoms on fcc iron, cobalt, and nickel {110} surfaces and compare the structural, electronic, and magnetic properties of these systems. Carbon and nitrogen are found to couple antiferromagnetically, and oxygen ferromagnetically, to all surfaces. It was found that antiferromagnetically coupled adsorbates retained their largest spin moment values on iron, whereas ferromagnetically coupled adsorbates possessed their lowest moments on this surface. The strongly localized influence of these adsorbates is clearly illustrated in partial density-of-states plots for the surface atoms.

  1. Graphene-enhanced Raman spectroscopy of thymine adsorbed on single-layer graphene

    NASA Astrophysics Data System (ADS)

    Fesenko, Olena; Dovbeshko, Galyna; Dementjev, Andrej; Karpicz, Renata; Kaplas, Tommi; Svirko, Yuri

    2015-04-01

    Graphene-enhanced Raman scattering (GERS) spectra and coherent anti-Stokes Raman scattering (CARS) of thymine molecules adsorbed on a single-layer graphene were studied. The enhancement factor was shown to depend on the molecular groups of thymine. In the GERS spectra of thymine, the main bands are shifted with respect to those for molecules adsorbed on a glass surface, indicating charge transfer for thymine on graphene. The probable mechanism of the GERS enhancement is discussed. CARS spectra are in accord with the GERS results, which indicates similar benefit from the chemical enhancement.

  2. Adsorbate-metal bond effect on empirical determination of surface plasmon penetration depth.

    PubMed

    Kegel, Laurel L; Menegazzo, Nicola; Booksh, Karl S

    2013-05-21

    The penetration depth of surface plasmons is commonly determined empirically from the observed response for adsorbate loading on gold surface plasmon resonance (SPR) substrates. However, changes in the SPR spectrum may originate from both changes in the effective refractive index near the metal surface and changes in the metal permittivity following covalent binding of the adsorbate layer. Herein, the significance of incorporating an additional adsorbate-metal bonding effect in the calculation is demonstrated in theory and in practice. The bonding effect is determined from the nonzero intercept of a SPR shift versus adsorbate thickness calibration and incorporated into the calculation of penetration depth at various excitation wavelengths. Determinations of plasmon penetration depth with and without the bonding response for alkanethiolate-gold are compared and are shown to be significantly different for a thiol monolayer adsorbate system. Additionally, plasmon penetration depth evaluated with bonding effect compensation shows greater consistency over different adsorbate thicknesses and better agreement with theory derived from Maxwell's equation, particularly for adsorbate thicknesses that are much smaller (<5%) than the plasmon penetration depth. The method is also extended to a more practically applicable polyelectrolyte multilayer adsorbate system. PMID:23566015

  3. Optical anisotropy of flagellin layers: in situ and label-free measurement of adsorbed protein orientation using OWLS.

    PubMed

    Kovacs, Noemi; Patko, Daniel; Orgovan, Norbert; Kurunczi, Sandor; Ramsden, Jeremy J; Vonderviszt, Ferenc; Horvath, Robert

    2013-06-01

    The surface adsorption of the protein flagellin was followed in situ using optical waveguide lightmode spectroscopy (OWLS). Flagellin did not show significant adsorption on a hydrophilic waveguide, but very rapidly formed a dense monolayer on a hydrophobic (silanized) surface. The homogeneous and isotropic optical layer model, which has hitherto been generally applied in OWLS data interpretation for adsorbed protein films, failed to characterize the flagellin layer, but it could be successfully modeled as an uniaxial thin film. This anisotropic modeling revealed a significant positive birefringence in the layer, suggesting oriented protein adsorption. The adsorbed flagellin orientation was further evidenced by monitoring the surface adsorption of truncated flagellin variants, in which the terminal protein regions or the central (D3) domain were removed. Without the terminal regions the protein adsorption was much slower and the resulting films were significantly less birefringent, implying that intact flagellin adsorbs on the hydrophobic surface via its terminal regions. PMID:23631669

  4. Low-Friction Adsorbed Layers of a Triblock Copolymer Additive in Oil-Based Lubrication.

    PubMed

    Yamada, Shinji; Fujihara, Ami; Yusa, Shin-ichi; Tanabe, Tadao; Kurihara, Kazue

    2015-11-10

    The tribological properties of the dilute solution of an ABA triblock copolymer, poly(11-acrylamidoundecanoic acid)-block-poly(stearyl methacrylate)-block-poly(11-acrylamidoundecanoic acid (A5S992A5), in poly(α-olefin) (PAO) confined between mica surfaces were investigated using the surface forces apparatus (SFA). Friction force was measured as a function of applied load and sliding velocity, and the film thickness and contact geometry during sliding were analyzed using the fringes of equal chromatic order (FECO) in the SFA. The results were contrasted with those of confined PAO films; the effects of the addition of A5S992A5 on the tribological properties were discussed. The thickness of the A5S992A5/PAO system varied with time after surface preparation and with repetitive sliding motions. The thickness was within the range from 40 to 70 nm 1 day after preparation (the Day1 film), and was about 20 nm on the following day (the Day2 film). The thickness of the confined PAO film was thinner than 1.4 nm, indicating that the A5S992A5/PAO system formed thick adsorbed layers on mica surfaces. The friction coefficient was about 0.03 to 0.04 for the Day1 film and well below 0.01 for the Day2 film, which were 1 or 2 orders of magnitude lower than the values for the confined PAO films. The time dependent changes of the adsorbed layer thickness and friction properties should be caused by the relatively low solubility of A5S992A5 in PAO. The detailed analysis of the contact geometry and friction behaviors implies that the particularly low friction of the Day2 film originates from the following factors: (i) shrinkage of the A5S992A5 molecules (mainly the poly(stearyl methacrylate) blocks) that leads to a viscoelastic properties of the adsorbed layers; and (ii) the intervening PAO layer between the adsorbed polymer layers that constitutes a high-fluidity sliding interface. Our results suggest that the block copolymer having relatively low solubility in a lubricant base oil is

  5. Equilibrium molecular theory of two-dimensional adsorbate drops on surfaces of heterogeneous adsorbents

    NASA Astrophysics Data System (ADS)

    Tovbin, Yu. K.

    2016-08-01

    A molecular statistical theory for calculating the linear tension of small multicomponent droplets in two-dimensional adsorption systems is developed. The theory describes discrete distributions of molecules in space (on a scale comparable to molecular size) and continuous distributions of molecules (at short distances inside cells) in their translational and vibrational motions. Pair intermolecular interaction potentials (the Mie type potential) in several coordination spheres are considered. For simplicity, it is assumed that distinctions in the sizes of mixture components are slight and comparable to the sizes of adsorbent adsorption centers. Expressions for the pressure tensor components inside small droplets on the heterogeneous surface of an adsorbent are obtained, allowing calculations of the thermodynamic characteristics of a vapor-fluid interface, including linear tension. Problems in refining the molecular theory are discussed: describing the properties of small droplets using a coordination model of their structure, considering the effect an adsorbate has on the state of a near-surface adsorbent region, and the surface heterogeneity factor in the conditions for the formation of droplets.

  6. Electronic structure of benzene adsorbed on Ni and Cu surfaces

    SciTech Connect

    Weinelt, M.; Nilsson, A.; Wassdahl, N.

    1997-04-01

    Benzene has for a long time served as a prototype adsorption system of large molecules. It adsorbs with the molecular plane parallel to the surface. The bonding of benzene to a transition metal is typically viewed to involve the {pi} system. Benzene adsorbs weakly on Cu and strongly on Ni. It is interesting to study how the adsorption strength is reflected in the electronic structure of the adsorbate-substrate complex. The authors have used X-ray Emission (XE) and X-ray Absorption (XA) spectroscopies to selectively study the electronic states localized on the adsorbed benzene molecule. Using XES the occupied states can be studies and with XAS the unoccupied states. The authors have used beamline 8.0 and the Swedish endstation equipped with a grazing incidence x-ray spectrometer and a partial yield absorption detector. The resolution in the XES and XAS were 0.5 eV and 0.05 eV, respectively.

  7. Hydrodynamic thickness of petroleum oil adsorbed layers in the pores of reservoir rocks.

    PubMed

    Alkafeef, Saad F; Algharaib, Meshal K; Alajmi, Abdullah F

    2006-06-01

    The hydrodynamic thickness delta of adsorbed petroleum (crude) oil layers into the pores of sandstone rocks, through which the liquid flows, has been studied by Poiseuille's flow law and the evolution of (electrical) streaming current. The adsorption of petroleum oil is accompanied by a numerical reduction in the (negative) surface potential of the pore walls, eventually stabilizing at a small positive potential, attributed to the oil macromolecules themselves. After increasing to around 30% of the pore radius, the adsorbed layer thickness delta stopped growing either with time or with concentrations of asphaltene in the flowing liquid. The adsorption thickness is confirmed with the blockage value of the rock pores' area determined by the combination of streaming current and streaming potential measurements. This behavior is attributed to the effect on the disjoining pressure across the adsorbed layer, as described by Derjaguin and Churaev, of which the polymolecular adsorption films lose their stability long before their thickness has approached the radius of the rock pore. PMID:16414057

  8. DPPG Liposomes Adsorbed on Polymer Cushions: Effect of Roughness on Amount, Surface Composition and Topography.

    PubMed

    Duarte, Andreia A; Botelho do Rego, Ana M; Salerno, Marco; Ribeiro, Paulo A; El Bari, Nezha; Bouchikhi, Benachir; Raposo, Maria

    2015-07-01

    The adsorption of intact liposomes onto solid supports is a fundamental issue when preparing systems with encapsulated biological molecules. In this work, the adsorption kinetic of 1,2-dipalmitoyl-sn-glycero-3-[phospho-rac-(1-glycerol)] (sodium salt) liposomes onto cushions prepared from commom polyelectrolytes by the layer-by-layer technique was investigated with the main objective of finding the surface conditions leading to the adsorption of intact liposomes. For this purpose, different cushion surface roughnesses were obtained by changing the number of cushion bilayers. The adsorbed amount per unit area was measured through quartz crystal microbalance, surface morphology was characterized by atomic force microscopy, and the surface composition was assessed by X-ray photoelectron spectroscopy. The results show that (1) the amount of adsorbed lipids depends on the number of cushion bilayers, (2) the cushions are uniformly covered by the adsorbed lipids, and (3) the surface morphology of polymer cushions tunes liposome rupture and its adsorption kinetics. The fraction of ruptured liposomes, calculated from the measured amount of adsorbed lipids, is a function of surface roughness together with other surface morphology parameters, namely the dominating in-plane spatial feature size, the fractal dimension, and other textural features as well as amplitude and hybrid parameters. PMID:26076391

  9. Compliant layer chucking surface

    SciTech Connect

    Blaedel, Kenneth L.; Spence, Paul A.; Thompson, Samuel L.

    2004-12-28

    A method and apparatus are described wherein a thin layer of complaint material is deposited on the surface of a chuck to mitigate the deformation that an entrapped particle might cause in the part, such as a mask or a wafer, that is clamped to the chuck. The harder particle will embed into the softer layer as the clamping pressure is applied. The material composing the thin layer could be a metal or a polymer for vacuum or electrostatic chucks. It may be deposited in various patterns to affect an interrupted surface, such as that of a "pin" chuck, thereby reducing the probability of entrapping a particle.

  10. [DSC and FTIR study of adsorbed lysozyme on hydrophobic surface].

    PubMed

    Lei, Zu-meng; Geng, Xin-peng; Dai, Li; Geng, Xin-du

    2008-09-01

    During a process of hen egg white lysozyme adsorption and folding on a moderately hydrophobic surface (PEG-600), the effects of salt((NH4)2SO4) concentrations, surface coverage and denaturant (guanidine hydrochloride, GuHCl) concentrations on thermal stability and the changes in the molecular conformation of adsorbed native and denatured lysozyme without aqueous solution were studied with a combination of differential scanning calorimetry (DSC) with FTIR spectroscopy. The results showed that temperature due to endothermic peaks was reduced and the disturbance increased at higher temperature with the increase in salt concentration and surface coverage of adsorbed protein. beta-Sheet and beta-Turn stucture increased while alpha-Helix structure decreased after the adsorption. The peaks corresponding to both C-C stretching frequency in 1400-1425 cm(-1) and amide I band frequency in 1650-1670 cm(-1) of adsorbed denatured lysozyme can be detected in FTIR spectra while that due to amide I band frequency of adsorbed native lysozyme almost can't be observed. Adsorption resulted in structural loss of adsorbed native lysozyme, whose performance was less stable. PMID:19093560

  11. Vibrational Studies of Adsorbate-Induced Reconstruction on Molybdenum Surfaces.

    NASA Astrophysics Data System (ADS)

    Lopinski, Gregory Peter

    Adsorbate-induced rearrangement of the substrate structure strongly modifies the adsorbate-substrate and adsorbate-adsorbate interactions, leading to the complex behavior observed in many chemisorption systems. In this thesis the H/Mo(211), O/Mo(211) and Na/Mo(100) systems have been studied using high resolution electron energy loss spectroscopy (HREELS) to observe vibrations of the adsorbed atoms. The vibrational data is correlated with observations of the long-range order probed by LEED as well as the work function changes induced by adsorption. Adsorbate -induced substrate reconstruction plays an important role in all three of these systems. Studies of the coadsorption systems O+H/Mo(211) and Na+O/Mo(100) indicate how these effects can influence interactions between adsorbates. For H/Mo(211), above 1ML a (1 x 1) to (1 x 2) transition is observed and attributed to modification of the substrate periodicity. Below 1ML, H atoms are bridge bonded and induce local distortions of the substrate. The transition to the (1 x 2) phase involves the ordering of these displacements and occupation of three-fold sites partially populated by conversion of the bridge bonded species. This conversion accounts for the sawtooth-like coverage dependence of the work function. The structural model proposed for this system is also supported by the desorption parameters and partial molar entropy extracted from adsorption isobars. Oxygen adsorption on Mo(211) involves the occupation of multiple binding sites, with both the long-range order and the local geometry of the adsorbate phases strongly temperature dependent. Coadsorption of low coverages of oxygen and hydrogen leads to segregation of the two adsorbates which can be understood in terms of a substrate-mediated repulsive interaction between O and H. For Na/Mo(100), the frequency of the Na-Mo symmetric stretch mode does not shift with coverage although the mode intensity is strongly coverage dependent. The absence of a frequency shift

  12. Modeling colloid deposition on a protein layer adsorbed to iron-oxide-coated sand

    NASA Astrophysics Data System (ADS)

    Yang, X.; Flynn, R.; von der Kammer, F.; Hofmann, T.

    2012-11-01

    Our recent study reported that conformation change of granule-associated Bovine Serum Albumin (BSA) may influence the role of the protein controlling colloid deposition in porous media (Flynn et al., 2012). The present study conceptualized the observed phenomena with an ellipsoid morphology model, describing BSA as an ellipsoid taking a side-on or end-on conformation on granular surface, and identified the following processes: (1) at low adsorbed concentrations, BSA exhibited a side-on conformation blocking colloid deposition; (2) at high adsorbed concentrations, BSA adapted to an end-on conformation promoted colloid deposition; and (3) colloid deposition on the BSA layer may progressively generate end-on molecules (sites) by conformation change of side-on BSA, resulting in sustained increasing deposition rates. Generally, the protein layer lowered colloid attenuation by the porous medium, suggesting the overall effect of BSA was inhibitory at the experimental time scale. A mathematical model was developed to interpret the ripening curves. Modeling analysis identified the site generation efficiency of colloid as a control on the ripening rate (declining rate in colloid concentrations), and this efficiency was higher for BSA adsorbed from a more dilute BSA solution.

  13. Nanotribological properties of water films adsorbing atop, and absorbing below, graphene layers supported by metal substrates

    NASA Astrophysics Data System (ADS)

    Liu, Zijian; Curtis, C. K.; Stine, R.; Sheehan, P.; Krim, J.

    The tribological properties of graphite, a common lubricant with known sensitivity to the presence of water, have been studied extensively at the macroscopic and microscopic scales. Although far less attention has been devoted to the tribological properties of graphene, it has been established that the tribological response to the presence of water is dissimilar from that of graphite. We report here a quartz crystal microbalance study of the nanotribological properties of water films adsorbed/absorbed on graphene layers prepared by either chemical decomposition on nickel(111) substrates or transfer of freestanding graphene layers to aluminum substrates. Sliding friction levels of the water films were also measured for metal surfaces in the absence of a graphene layer. We observe very high friction levels for water adsorbed atop graphene on Ni(111) and very low levels for water on aluminum. For the case of graphene/aluminum, the data indicate that the water is absorbing between the graphene layer and the aluminum. Dissipation levels moreover indicate the presence of an interstitial water increases sliding friction between the graphene and the aluminum substrate Work supported by NSF and NRL.

  14. Coalescence behavior of oil droplets coated in irreversibly-adsorbed surfactant layers.

    PubMed

    Reichert, Matthew D; Walker, Lynn M

    2015-07-01

    Coalescence between oil caps with irreversibly adsorbed layers of nonionic surfactant is characterized in deionized water and electrolyte solution. The coalescence is characterized using a modified capillary tensiometer allowing for accurate measurement of the coalescence time. Results suggest two types of coalescence behavior, fast coalescence at low surface coverages that are independent of ionic strength and slow coalescence at high coverage. These slow coalescence events (orders of magnitude slower) are argued to be due to electric double layer forces or more complicated stabilization mechanisms arising from interfacial deformation and surface forces. A simple film drainage model is used in combination with measured values for interfacial properties to quantify the interaction potential between the two interfaces. Since this approach allows the two caps to have the same history, interfacial coverage and curvature, the results offer a tool to better understand a mechanism that is important to emulsion stability. PMID:25766654

  15. Silver diffusion over silicon surfaces with adsorbed tin atoms

    SciTech Connect

    Dolbak, A. E. Olshanetskii, B. Z.

    2015-02-15

    Silver diffusion over the (111), (100), and (110) surfaces of silicon with preliminarily adsorbed tin atoms is studied by Auger electron spectroscopy and low-energy electron diffraction. Diffusion is observed only on the surface of Si(111)-2√3 × 2√3-Sn. The diffusion mechanism is established. It is found that the diffusion coefficient depends on the concentration of diffusing atoms. The diffusion coefficient decreases with increasing silver concentration, while the activation energy and the preexponential factor increase.

  16. Pulling adsorbed self-avoiding walks from a surface

    NASA Astrophysics Data System (ADS)

    Guttmann, Anthony J.; Jensen, I.; Whittington, S. G.

    2014-01-01

    We consider a self-avoiding walk model of polymer adsorption where the adsorbed polymer can be desorbed by the application of a force, concentrating on the case of the square lattice. Using series analysis methods we investigate the behaviour of the free energy of the system when there is an attractive potential ɛ with the surface and a force f applied at the last vertex, normal to the surface, and extract the phase boundary between the ballistic and adsorbed phases. We believe this to be exact to graphical accuracy. We give precise estimates of the location of the transition from the free phase to the ballistic phase, which we find to be at yc = exp (f/kBTc) = 1, and from the free phase to the adsorbed phase, which we estimate to be at ac = exp ( - ɛ/kBTc) = 1.775 615 ± 0.000 005. In addition we prove that the phase transition from the ballistic to the adsorbed phase is first order.

  17. Photochemistry of adsorbed nitrate on aluminum oxide particle surfaces.

    PubMed

    Rubasinghege, Gayan; Grassian, Vicki H

    2009-07-01

    Nitrogen oxides, including nitrogen dioxide and nitric acid, react with mineral dust particles in the atmosphere to yield adsorbed nitrate. Although nitrate ion is a well-known chromophore in natural waters, little is known about the surface photochemistry of nitrate adsorbed on mineral particles. In this study, nitrate adsorbed on aluminum oxide, a model system for mineral dust aerosol, is irradiated with broadband light (lambda > 300 nm) as a function of relative humidity (RH) in the presence of molecular oxygen. Upon irradiation, the nitrate ion readily undergoes photolysis to yield nitrogen-containing gas-phase products including NO(2), NO, and N(2)O, with NO being the major product. The relative ratio and product yields of these gas-phase products change with RH, with N(2)O production being highest at the higher relative humidities. Furthermore, an efficient dark reaction readily converts the major NO product into NO(2) during post-irradiation. Photochemical processes on mineral dust aerosol surfaces have the potential to impact the chemical balance of the atmosphere, yet little is known about these processes. In this study, the impact that adsorbed nitrate photochemistry may have on the renoxification of the atmosphere is discussed. PMID:19534452

  18. Identification of vitronectin as a major plasma protein adsorbed on polymer surfaces of different copolymer composition.

    PubMed

    Bale, M D; Wohlfahrt, L A; Mosher, D F; Tomasini, B; Sutton, R C

    1989-12-01

    The arrays of proteins adsorbed from plasma onto a series of polystyrene copolymeric latexes were analyzed by enzyme-linked immunosorbent assay (ELISA) of washed beads and immunoblotting of proteins desorbed from the beads and separated by polyacrylamide gel electrophoresis (PAGE). Beads were prepared by continuous emulsion polymerization in the absence of surfactant. Coomassie brilliant blue staining of gel electropherograms of desorbed proteins indicated that the presence of small amounts of comonomers (1 to 10 mole %) significantly influenced the composition of the adsorbed protein layer. Immunoblotting revealed that fibrinogen, fibronectin, and vitronectin were adsorbed by all surfaces investigated. C3 and Clq adsorption varied significantly with copolymer composition. The ELISAs revealed that although the concentrations of vitronectin and fibronectin in plasma are similar, the extent of vitronectin adsorption from 70% to 85% plasma was greater by two orders of magnitude than fibronectin adsorption. Vitronectin adsorbed on carboxylic acid-containing copolymers reacted more strongly with a conformationally sensitive antivitronectin monoclonal antibody (MoAb) than vitronectin adsorbed to polystyrene and was more susceptible to cleavage by plasma proteases(s). The results show that vitronectin is a major protein adsorbed from concentrated plasma and that small changes in the chemical composition of a copolymer profoundly affects the extent and nature of protein adsorption from complex mixtures such as plasma. PMID:2479428

  19. Surface Adsorbate Fluctuations and Noise in Nanoelectromechanical Systems

    PubMed Central

    Yang, Y. T.; Callegari, C.; Feng, X. L.; Roukes, M. L.

    2013-01-01

    Physisorption on solid surfaces is important in both fundamental studies and technology. Adsorbates can also be critical for the performance of miniature electromechanical resonators and sensors. Advances in resonant nanoelectromechanical systems (NEMS), particularly mass sensitivity attaining the single-molecule level, make it possible to probe surface physics in a new regime, where a small number of adatoms cause a detectable frequency shift in a high quality factor (Q) NEMS resonator, and adsorbate fluctuations result in resonance frequency noise. Here we report measurements and analysis of the kinetics and fluctuations of physisorbed xenon (Xe) atoms on a high-Q NEMS resonator vibrating at 190.5 MHz. The measured adsorption spectrum and frequency noise, combined with analytic modeling of surface diffusion and adsorption–desorption processes, suggest that diffusion dominates the observed excess noise. This study also reveals new power laws of frequency noise induced by diffusion, which could be important in other low-dimensional nanoscale systems. PMID:21388120

  20. Theory of raman scattering from molecules adsorbed at semiconductor surfaces

    NASA Astrophysics Data System (ADS)

    Ueba, H.

    1983-09-01

    A theory is presented to calculate the Raman polarizability of an adsorbed molecule at a semiconductor surface, where the electronic excitation in the molecular site interacts with excitons (elementary excitations in the semiconductor) through non-radiative energy transfer between them, in an intermediate state in the Raman scattering process. The Raman polarizability thus calculated is found to exhibit a peak at the energy corresponding to a resonant excitation of excitons, thereby suggesting the possibility of surface enhanced Raman scattering on semiconductor surfaces. The mechanism studied here can also give an explanation of a recent observation of the Raman excitation profiles of p-NDMA and p-DMAAB adsorbed on ZnO or TiO 2, where those profiles were best described by assuming a resonant intermediate state of the exciton transition in the semiconductors. It is also demonstrated that in addition to vibrational Raman scattering, excitonic Raman scattering of adsorbed molecules will occur in the coupled molecule-semiconductor system, where the molecular returns to its ground electronic state by leaving an exciton in the semiconductor. A spectrum of the excitonic Raman scattering is expected to appear in the background of the vibrational Raman band and to be characterized by the electronic structure of excitons. A desirable experiment is suggested for an examination of the theory.

  1. Surface area of vermiculite with nitrogen and carbon dioxide as adsorbates

    USGS Publications Warehouse

    Thomas, J., Jr.; Bohor, B.F.

    1969-01-01

    Surface-area studies were made on several homoionic vermiculites with both nitrogen and carbon dioxide as adsorbates. These studies show that only very slight penetration occurs between individual vermiculite platelets. This is in contrast to an earlier investigation of montmorillonite where it was found that the degree of penetration between layers is quite high, particularly for carbon dioxide, and is governed by the size and charge of the interlayer cation. The inability of these adsorbates to penetrate substantially between vermiculite platelets is due primarily to this mineral's high surface-charge density. The extent of penetration of nitrogen and carbon dioxide at the edges of vermiculite platelets, though slight, is influenced by the coordinated water retained within the sample at a given degassing temperature. Forces between layers are weakened with increasing water content, which permits slightly greater penetration by adsorbate gases. Thus, the surface area of vermiculite, as determined by gas adsorption, is larger than the calculated external surface area based upon particle size and shape considerations. In addition, "extra" surface is provided by the lifting and scrolling of terminal platelets. These morphological features are shown in scanning electron micrographs of a naturally occuring vermiculite. ?? 1969.

  2. A simple model for electronic properties of surface adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Dhakal, Rajesh; Schwalm, William

    We adapt a minimal approximation to one electron quantum theory of molecules referred as Fast Accurate Kinetic Energy method. This in principle handles large complex molecular structures with less computational effort to compute electronic properties of adsorbed molecules. Kinetic energy integrals are calculated accurately but multi-electron potential energy integrals are approximated. The neighboring atom interactions are included also. For layers of isopthalic acids formed on pyrolytic graphite the configuration changes as a function of length of hydrocarbon tails. We study properties of this system as a function of tail length.

  3. Water adsorbate influence on the Cu(110) surface optical response

    NASA Astrophysics Data System (ADS)

    Baghbanpourasl, Amirreza; Schmidt, Wolf Gero; Denk, Mariella; Cobet, Christoph; Hohage, Michael; Zeppenfeld, Peter; Hingerl, Kurt

    2015-11-01

    Surface reflectance anisotropy may be utilized for characterizing surfaces, interfaces, and adsorption structures. Here, the reflectance anisotropy and surface dielectric functions of the thermodynamically most favored water adsorbate structures on the Cu(110) surface (i.e. hexagonal bilayers, pentagonal chains, and partially dissociated water structures) are calculated from density-functional theory and compared with recent experimental data. It is shown that the water overlayer structures modify in a geometry-specific way the optical anisotropy of the bare surface which can be exploited for in situ determination of the adsorption structures. For hexagonal bilayer overlayer geometries, strong features in the vacuum ultraviolet region are predicted. The theoretical analysis shows a noticeable influence of intraband transitions also for higher photon energies and rather slight influences of the van der Waals interaction on the spectral signatures. Water induced strain effects on the surface optical response are found to be negligible.

  4. Cooperation between adsorbates accounts for the activation of atomic layer deposition reactions.

    PubMed

    Shirazi, Mahdi; Elliott, Simon D

    2015-04-14

    Atomic layer deposition (ALD) is a technique for producing conformal layers of nanometre-scale thickness, used commercially in non-planar electronics and increasingly in other high-tech industries. ALD depends on self-limiting surface chemistry but the mechanistic reasons for this are not understood in detail. Here we demonstrate, by first-principle calculations of growth of HfO2 from Hf(N(CH3)2)4-H2O and HfCl4-H2O and growth of Al2O3 from Al(CH3)3-H2O, that, for all these precursors, co-adsorption plays an important role in ALD. By this we mean that previously-inert adsorbed fragments can become reactive once sufficient numbers of molecules adsorb in their neighbourhood during either precursor pulse. Through the calculated activation energies, this 'cooperative' mechanism is shown to have a profound influence on proton transfer and ligand desorption, which are crucial steps in the ALD cycle. Depletion of reactive species and increasing coordination cause these reactions to self-limit during one precursor pulse, but to be re-activated via the cooperative effect in the next pulse. This explains the self-limiting nature of ALD. PMID:25786200

  5. Photoinduced surface dynamics of CO adsorbed on a platinum electrode.

    PubMed

    Noguchi, Hidenori; Okada, Tsubasa; Uosaki, Kohei

    2006-08-10

    The surface dynamics of adsorbed CO molecules formed by dissociative adsorption of HCHO at a polycrystalline Pt electrode/electrolyte solution interface was studied by picosecond time-resolved sum-frequency generation (TR-SFG) spectroscopy. A SFG peak at 2050-2060 cm(-1) was observed at the Pt electrode in HClO(4) solution containing HCHO at 0-300 mV (vs Ag/AgCl), indicating the formation of adsorbed CO at an atop site of the Pt surface as a result of dissociative adsorption of HCHO. The peak position varied with potential by approximately 33 cm(-1)/V, as previously found in an infrared reflection absorption spectroscopy (IRAS) study. Irradiation of an intense picosecond visible pulse (25 ps, 532 nm) caused an instant intensity decrease and broadening of the CO peak accompanied by the emergence of a new broad peak at approximately 1980 cm(-1) within the time resolution of the system. These results suggest a decrease and increase in the populations of CO adsorbed on atop and bridge sites, respectively, upon visible pump pulse irradiation. PMID:16884215

  6. Molecular switches from benzene derivatives adsorbed on metal surfaces

    PubMed Central

    Liu, Wei; Filimonov, Sergey N.; Carrasco, Javier; Tkatchenko, Alexandre

    2013-01-01

    Transient precursor states are often experimentally observed for molecules adsorbing on surfaces. However, such precursor states are typically rather short-lived, quickly yielding to more stable adsorption configurations. Here we employ first-principles calculations to systematically explore the interaction mechanism for benzene derivatives on metal surfaces, enabling us to selectively tune the stability and the barrier between two metastable adsorption states. In particular, in the case of the tetrachloropyrazine molecule, two equally stable adsorption states are identified with a moderate and conceivably reversible barrier between them. We address the feasibility of experimentally detecting the predicted bistable behaviour and discuss its potential usefulness in a molecular switch. PMID:24157660

  7. Rod-like cyanophenyl probe molecules nanoconfined to oxide particles: Density of adsorbed surface species

    NASA Astrophysics Data System (ADS)

    Frunza, Stefan; Frunza, Ligia; Ganea, Constantin Paul; Zgura, Irina; Brás, Ana Rita; Schönhals, Andreas

    2016-02-01

    Surface layers have already been observed by broadband dielectric spectroscopy for composite systems formed by adsorption of rod-like cyanophenyl derivates as probe molecules on the surface of oxide particles. In this work, features of the surface layer are reported; samples with different amounts of the probe molecules adsorbed onto oxide (nano) particles were prepared in order to study their interactions with the surface. Thermogravimetric analysis (TGA) was applied to analyze the amount of loaded probe molecules. The density of the surface species ns was introduced and its values were estimated from quantitative Fourier transform infrared spectroscopy (FTIR) coupled with TGA. This parameter allows discriminating the composites into several groups assuming a similar interaction of the probe molecules with the hosts of a given group. An influence factor H is further proposed as the ratio of the number of molecules in the surface layer showing a glassy dynamics and the number of molecules adsorbed tightly on the surface of the support: It was found for aerosil composites and used for calculating the maximum filling degree of partially filled silica MCM-41 composites showing only one dielectric process characteristic for glass-forming liquids and a bulk behavior for higher filling degrees.

  8. NMR surface relaxivity of calcite with adsorbed Mn{sup 2+}

    SciTech Connect

    Kenyon, W.E.; Kolleeny, J.A.

    1995-03-15

    Calcite particles were exposed to Mn{sup 2+} in aqueous solution to allow adsorption. The calcite particles were then packed, and the NMR longitudinal relaxation time T{sub 1} of water saturating the interparticle pores was measured. NMR surface relaxivity was then computed as 1/(T{sub 1}{times}S{sub p}/V{sub p}), where S{sub p}/V{sub p} is the ratio of surface area to pore volume. Adsorbed manganese increases the NMR surface relaxivity to approximately 2.4 {times} 10{sup {minus}3} cm/s, roughly 50 times the surface relaxivity of very pure calcite. Flowing water with 4 {mu}M Mn{sup 2+} through a porous limestone plug decreased its T{sub 1} by a factor of 6. Iron as adsorbate produced relatively small increases in surface relaxivity. These results suggest that manganese dominates the surface relaxivity, of limestone rocks in situ, which is important in the interpretation of NMR borehole logs. Observations suggest that some adsorbed manganese eventually becomes buried by freshly precipitated calcite. In particular, the surface relaxivity increased with initial adsorption, but gradually decreased at long reaction times, even as the aqueous manganese concentration continued to decrease. NMR evidently senses only the manganese in the outermost atomic layer, and thus might prove useful in more detailed studies of adsorption.

  9. Measuring sub-nm adsorbed water layer thickness and desorption rate using a fused-silica whispering-gallery microresonator

    NASA Astrophysics Data System (ADS)

    Ganta, D.; Dale, E. B.; Rosenberger, A. T.

    2014-05-01

    We report an optical method for measuring the thickness of the water layer adsorbed onto the surface of a high-Q fused-silica microresonator. Light from a tunable diode laser operating near 1550 nm is coupled into the microresonator to excite whispering-gallery modes (WGMs). By observing thermal distortion or even bistability of the WGM resonances caused by absorption in the water layer, the contribution of that absorption to the total loss is determined. Thereby, the thickness of the water layer is found to be ˜0.1 nm (approximately one monolayer). This method is further extended to measure the desorption rate of the adsorbed water, which is roughly exponential with a decay time of ˜40 h when the fused-silica microresonator is held in a vacuum chamber at low pressure.

  10. Rupture force of adsorbed self-assembled surfactant layers. Effect of the dielectric exchange force

    NASA Astrophysics Data System (ADS)

    Teschke, O.; Ceotto, G.; de Souza, E. F.

    2001-08-01

    The tip applied force necessary to obtain tip/substrate contact, i.e., rupture force between adsorbed layers of self-assembled surfactant films and atomic force microscope (AFM) tips in water has been measured. A substantial contribution of this rupture force is due to the dielectric exchange force (DEF). The DEF model is in agreement with the observation that the surfactant layer rupture forces are smaller in the thickest layers, where the compactness of the adsorbed film results in the smallest values of the dielectric permittivity. Within experimental accuracy a dielectric permittivity value of ˜4 for bilayers and of ˜36 for monolayers is found.

  11. Vibrational spectroscopic studies of adsorbates on bimetallic surfaces. Doctoral thesis

    SciTech Connect

    Kuhn, W.K.

    1992-12-01

    In this work, well-defined bimetallic surfaces have been studied using carbon monoxide adsorption in conjunction with infrared reflection absorption spectroscopy (IRAS). These studies have indicated that for CO adsorbed on Cu overlayers, the bond between the CO and the Cu adatoms is comprised of both pi-back-donation and polarization interaction components. The sum of the contributions from these effects determines the observed bond strength with the observed CO stretching frequency being determined by the relative contributions of the components. In addition, it was determined that IR spectra of adsorbed CO show a remarkable sensitivity to surface structure. Three-dimensional Cu clusters, well-ordered two dimensional Cu islands and isolated Cu atoms are distinctively characterized by their CO IR peaks. In addition, both disorder-order and order-order transitions are observed for the metal overlayers on the single crystal metal substrates. It was also observed that localized segregation and ordering of mixed Co and S overlayers on a Mo(110) substrate occurs upon annealing.

  12. Graphene protected surface state on Ir(111) with adsorbed lithium

    NASA Astrophysics Data System (ADS)

    Lazic, Predrag; Pervan, Petar; Petrovic, Marin; Srut-Rakic, Iva; Pletikosic, Ivo; Kralj, Marko; Milun, Milorad; Valla, Tonica

    It is well known that electronic surface states (SS) get strongly perturbed upon the chemical adsorption of very small amount of adsorbates. Adsorption of lithium atoms on Ir(111) is no exception to that rule. Iridium SS gets strongly perturbed and is practically eradicated - it can not be seen as a sharp peak in the ARPES measurement. However, if the system is prepared with graphene on top of Ir/Li system, the iridium SS reappears. We present a combined experimental and theoretical study of the described system. Using the density functional theory calculations for large unit cells with disordered lithium atoms geometries on the (111) surface of iridium we were able to reproduce the results of the ARPES measurements - showing clearly that the SS signal is strongly suppressed when lithium is adsorbed, while it is almost unchanged when lithium is intercalated (i.e. with graphene on top of it). Looking at the projected density of states we constructed a rather simple model explaining this behavior which seems to be general.

  13. Surface geometry of tryptophan adsorbed on gold colloidal nanoparticles

    NASA Astrophysics Data System (ADS)

    Hussain, Shafqat; Pang, Yoonsoo

    2015-09-01

    Two distinct surface-enhanced Raman (SER) spectra of tryptophan depending on the surface adsorption geometry were obtained by using colloidal gold nanoparticles reduced by borohydride and citrate ions. According to the vibrational assignments based on DFT simulations, the SER spectra of tryptamine and 3-indolepropionic acid, and the pH dependence of tryptophan SER spectrum, we found that some indole ring vibrations are very sensitive to the surface adsorption geometry of the molecules. With citrate-reduced gold colloids, tryptophan and related molecules mainly adsorb via the protonated amine group while maintaining a perpendicular geometry of the indole ring to the surface. However, a flat geometry of the indole ring to the surface is preferred on the borohydride-reduced gold colloids where the surface adsorption occurs mainly through the indole ring π electrons. By comparing our results with previous reports on the SER spectra of tryptophan on various silver and gold surfaces, we propose a general adsorption model of tryptophan on metal nanosurfaces.

  14. Spin-polarized hydrogen adsorbed on the surface of superfluid {sup 4}He

    SciTech Connect

    Marín, J. M.; Boronat, J.; Markić, L. Vranješ

    2013-12-14

    The experimental realization of a thin layer of spin-polarized hydrogen H↓ adsorbed on top of the surface of superfluid {sup 4}He provides one of the best examples of a stable, nearly two-dimensional (2D) quantum Bose gas. We report a theoretical study of this system using quantum Monte Carlo methods in the limit of zero temperature. Using the full Hamiltonian of the system, composed of a superfluid {sup 4}He slab and the adsorbed H↓ layer, we calculate the main properties of its ground state using accurate models for the pair interatomic potentials. Comparing the results for the layer with the ones obtained for a strictly 2D setup, we analyze the departure from the 2D character when the density increases. Only when the coverage is rather small the use of a purely 2D model is justified. The condensate fraction of the layer is significantly larger than in 2D at the same surface density, being as large as 60% at the largest coverage studied.

  15. Use of layered double hydroxides and their derivatives as adsorbents for inorganic and organic pollutants

    NASA Astrophysics Data System (ADS)

    You, Youwen

    Contamination of surface and groundwaters by hazardous inorganic and organic pollutants has become an increasing threat to the safety of drinking waters. Cleanup of contaminated surface and groundwaters has, therefore, become a major focus of environmental research. Primary objectives of this dissertation study were to examine the adsorption properties of layered double hydroxides (LDHs) and their derivatives for inorganic and organic contaminants and to identify potential technologies that utilize LDHs and their derivatives for environment remediation. Studies examined the adsorption characteristics of anionic selenium, arsenic and dicamba (3,6 dichloro-2-methoxy benzoic acid) on original LDHs and calcined-LDHs. Adsorption of selenium and arsenic on LDHs was a function of pH. Competing anions in solution strongly affected adsorption of all three contaminants, with divalent anions decreasing adsorption more intensely than monovalent anions. Adsorbed selenium, arsenic and dicamba could be released from LDHs in anion solutions. Adsorption isotherms for selenium and arsenic retention could be fitted to a simple Langmuir equation. Calcination processes significantly increased adsorption capacities of LDHs. Because of adsorption-desorpion characteristics, LDHs could be recycled. X-ray diffraction patterns revealed an increase of d-spacing coupling with adsorption of contaminants, verifying the intercalation of contaminants into layer structure of LDHs. Long chain anionic surfactants intercalated into LDHs modified their surface properties, resulting in organo-LDHs with hydrophobic surface properties. Various organo-LDHs were developed by incorporating different surfactants into LDHs via different synthesis methods. Surfactant intercalation properties were examined and the geometrical arrangements of the intercalated surfactants were characterized. Results revealed that surfactant molecules could adopt various configurations within the LDH interlayer space. Intercalation

  16. Investigation of interparticle forces in natural waters: effects of adsorbed humic acids on iron oxide and alumina surface properties.

    PubMed

    Sander, Sylvia; Mosley, Luke M; Hunter, Keith A

    2004-09-15

    The nature of interparticle forces acting on colloid particle surfaces with adsorbed surface films of the internationally used humic acid standard material, Suwannee River Humic Acid (SHA), has been investigated using an atomic force microscope (AFM). Two particle surfaces were used, alumina and a hydrous iron oxide film coated onto silica particles. Adsorbed SHA dominated the interactive forces for both surface types when present. At low ionic strength and pH > 4, the force curves were dominated by electrostatic repulsion of the electrical double layers, with the extent of repulsion decreasing as electrolyte (NaCl) concentration increased, scaling with the Debye length (kappa(-1)) of the electrolyte according to classical theory. At pH approximately 4, electrostatic forces were largely absent, indicating almost complete protonation of carboxylic acid (-COOH) functional groups on the adsorbed SHA. Under these conditions and also at high electrolyte concentration ([NaCl] > 0.1 M), the absence of electrostatic forces allowed observation of repulsion forces arising from steric interaction of adsorbed SHA as the oxide surfaces approached closely to each other (separation < 10 nm). This steric barrier shrank as electrolyte concentration increased, implying tighter coiling of the adsorbed SHA molecules. In addition, adhesive bridging between surfaces was observed only in the presence of SHA films, implying a strong energy barrier to spontaneous detachment of the surfaces from each other once joined. This adhesion was especially strong in the presence of Ca2+ which appears to bridge SHA layers on each surface. Overall, our results show that SHA is a good model for the NOM adsorbed on colloids. PMID:15487789

  17. Stability, structural and electronic properties of benzene molecule adsorbed on free standing Au layer

    NASA Astrophysics Data System (ADS)

    Katoch, Neha; Kapoor, Pooja; Sharma, Munish; Kumar, Ashok; Ahluwalia, P. K.

    2016-05-01

    We report stability and electronic properties of benzene molecule adsorbed on the Au atomic layer within the framework of density function theory (DFT). Horizontal configuration of benzene on the top site of Au monolayer prefers energetically over other studied configurations. On the adsorption of benzene, the ballistic conductance of Au monolayer is found to decrease from 4G0 to 2G0 suggesting its applications for the fabrications of organic sensor devices based on the Au atomic layers.

  18. Structure of water adsorbed on a mica surface

    SciTech Connect

    Park, Sung-Ho; Sposito, Garrison

    2002-01-29

    Monte Carlo simulations of hydration water on the mica (001) surface under ambient conditions revealed water molecules bound closely to the ditrigonal cavities in the surface, with a lateral distribution of approximately one per cavity, and water molecules interposed between K{sup +} counter ions in a layer situated about 2.5 {angstrom} from a surface O along a direction normal to the (001) plane. The calculated water O density profile was in quantitative agreement with recent X-ray reflectivity measurements indicating strong lateral ordering of the hydration water but liquid-like disorder otherwise.

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

    PubMed

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

    2013-03-01

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

  20. Interrogating protonated/deuterated fibronectin fragment layers adsorbed to titania by neutron reflectivity and their concomitant control over cell adhesion

    PubMed Central

    McIntosh, Lisa; Whitelaw, Christine; Rekas, Agata; Holt, Stephen A.; van der Walle, Christopher F.

    2015-01-01

    The fibronectin fragment, 9th–10th-type III domains (FIII9–10), mediates cell attachment and spreading and is commonly investigated as a bioadhesive interface for implant materials such as titania (TiO2). How the extent of the cell attachment–spreading response is related to the nature of the adsorbed protein layer is largely unknown. Here, the layer thickness and surface fraction of two FIII9–10 mutants (both protonated and deuterated) adsorbed to TiO2 were determined over concentrations used in cell adhesion assays. Unexpectedly, the isotopic forms had different adsorption behaviours. At solution concentrations of 10 mg l−1, the surface fraction of the less conformationally stable mutant (FIII9′10) was 42% for the deuterated form and 19% for the protonated form (fitted to the same monolayer thickness). Similarly, the surface fraction of the more stable mutant (FIII9′10–H2P) was 34% and 18% for the deuterated and protonated forms, respectively. All proteins showed a transition from monolayer to bilayer between 30 and 100 mg l−1, with the protein longitudinal orientation moving away from the plane of the TiO2 surface at high concentrations. Baby hamster kidney cells adherent to TiO2 surfaces coated with the proteins (100 mg l−1) showed a strong spreading response, irrespective of protein conformational stability. After surface washing, FIII9′10 and FIII9′10–H2P bilayer surface fractions were 30/25% and 42/39% for the lower/upper layers, respectively, implying that the cell spreading response requires only a partial protein surface fraction. Thus, we can use neutron reflectivity to inform the coating process for generating bioadhesive TiO2 surfaces. PMID:25926699

  1. Surface layers of bacteria.

    PubMed Central

    Beveridge, T J; Graham, L L

    1991-01-01

    Since bacteria are so small, microscopy has traditionally been used to study them as individual cells. To this end, electron microscopy has been a most powerful tool for studying bacterial surfaces; the viewing of macromolecular arrangements of some surfaces is now possible. This review compares older conventional electron-microscopic methods with new cryotechniques currently available and the results each has produced. Emphasis is not placed on the methodology but, rather, on the importance of the results in terms of our perception of the makeup and function of bacterial surfaces and their interaction with the surrounding environment. Images PMID:1723487

  2. Influence of ionic strength changes on the structure of pre-adsorbed salivary films. A response of a natural multi-component layer.

    PubMed

    Macakova, Lubica; Yakubov, Gleb E; Plunkett, Mark A; Stokes, Jason R

    2010-05-01

    Salivary films coating oral surfaces are critically important for oral health. This study focuses on determining the underlying nature of this adsorbed film and how it responds to departures from physiological conditions due to changes in ionic strength. Under physiological conditions, it is found that pre-adsorbed in vitro salivary film on hydrophobic surfaces is present as a highly hydrated viscoelastic layer. We follow the evolution of this film in terms of its effective thickness, hydration and viscoelastic properties, as well as adsorbed mass of proteins, using complementary surface characterisation methods: a Surface Plasmon Resonance (SPR) and a Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D). Our results support a heterogeneous model for the structure of the salivary film with an inner dense anchoring layer and an outer highly extended hydrated layer. Further swelling of the film was observed upon decreasing the salt concentration down to 1mM NaCl. However, upon exposure to deionised water, a collapse of the film occurs that was associated with the loss of water contained within the adsorbed layer. We suggest that the collapse in deionised water is driven by an onset of electrostatic attraction between different parts of the multi-component salivary film. It is anticipated that such changes could also occur when the oral cavity is exposed to food, beverage, oral care and pharmaceutical formulations where drastic changes to the structural integrity of the film is likely to have implications on oral health, sensory perception and product performance. PMID:20133111

  3. Surface-enhanced Raman spectroscopy of Omethoate adsorbed on silver surface

    NASA Astrophysics Data System (ADS)

    Kim, Hee Jin; Lee, Chul Jae; Karim, Mohammad Rezaul; Kim, Mak Soon; Lee, Mu Sang

    2011-01-01

    We have investigated surface-enhanced Raman spectroscopy (SERS) spectrum of Omethoate (O,O-dimethyl-S-methylcarbamoylmethylthiophosphate). It is found significant signals in the ordinary Raman spectrum for solid-state Omethoate as well as strong vibrational signals absorbed on the silver sol surface which is prepared by γ-irradiation technique at a very low concentration. Effects of pH and anions (Cl -, Br -, I -) on the adsorption orientation are investigated as well. Two different adsorption mechanisms are deduced, depending on the experimental conditions. The sulfur atom or the sulfur and two oxygen atoms are adsorbed onto the silver sol surface. Among halide ions, Br - and I - are more strongly adsorbed onto the silver sol surface. As a result, the adsorption of Omethoate is less effective due to their steric hindrance.

  4. A study of surface enhanced Raman scattering for furfural adsorbed on silver surface

    NASA Astrophysics Data System (ADS)

    Jia, Ting-jian; Li, Peng-wei; Shang, Zhi-guo; Zhang, Ling; He, Ting-chao; Mo, Yu-jun

    2008-02-01

    The normal Raman spectrum (NRS) and the surface enhanced Raman scattering (SERS) spectrum of furfural in silver colloid were recorded and analyzed in this paper. The assignment of these bands to furfural molecules was performed by density functional theory (DFT) calculation. The data of the SERS by comparing with the one of NRS show that furfural molecules are adsorbed on the silver surface via the nonbonding electrons of the carbonyl oxygen.

  5. Adsorbate dynamics on a silica-coated gold surface measured by Rydberg Stark spectroscopy

    NASA Astrophysics Data System (ADS)

    Naber, J.; Machluf, S.; Torralbo-Campo, L.; Soudijn, M. L.; van Druten, N. J.; van Linden van den Heuvell, H. B.; Spreeuw, R. J. C.

    2016-05-01

    Trapping a Rydberg atom close to a surface is an important step towards the realisation of many proposals for quantum information processing or hybrid quantum systems. One of the challenges in these experiments is posed by the electric field emanating from contaminations on the surface. Here we report on measurements of an electric field created by 87Rb atoms adsorbed on a 25 nm thick layer of SiO2, covering a 90 nm layer of Au. The electric field is measured using a two-photon transition to the 23{D}5/2 and 25{S}1/2 states. The electric field value that we measure is higher than typical values measured above metal surfaces, but is consistent with a recent measurement above a SiO2 surface. In addition, we measure the temporal behaviour of the field and observe that we can reduce it in a single experimental cycle, using ultraviolet light or by mildly locally heating the surface with one of the excitation lasers, whereas the buildup of the field takes thousands of cycles. We explain these results by a change in the adatom distribution on the surface. These results indicate that, while the stray electric field can be reduced, achieving field-free conditions above a silica-coated gold chip remains challenging.

  6. The structure of PMDA-PDA polyimide monolayers adsorbed on gold surfaces

    NASA Astrophysics Data System (ADS)

    Keil, M.; Paggel, J. J.; Schedel-Niedrig, Th.; Yokoyama, S.; Sotobayashi, H.; Bradshaw, A. M.

    1995-11-01

    Monolayers of the rod-like PMDA-PDA polyimide adsorbed on flame-annealed polycrystalline gold films have been studied with scanning tunnelling microscopy (STM) and X-ray absorption spectroscopy. The polyimide layer was deposited using the Langmuir-Blodgett preparation technique of Imai and Kakimoto. STM measurements in air showed that the polyimide chains were aligned along the <211> directions of the {111}-oriented single crystal regions of the surface. Although {111}-oriented areas were barely identifiable in the corresponding UHV experiments, aligned polymer chains were also observed over large areas of the surface. X-ray absorption measurements on the latter samples at the nitrogen K-edge showed a preferential orientation of the aromatic ring planes.

  7. Using Microcontact Printing as a Novel Method for Patterned Dyeing of Surface-adsorbed DNA

    NASA Astrophysics Data System (ADS)

    Shea, Emily; Budassi, Julia; Zhu, Ke; Sokolov, Jonathan

    2012-02-01

    We use microcontact printing (MCP)^1 to stain individual DNA molecules adsorbed and combed onto a polymer-coated silicon surface. Polydimethylsiloxane (PDMS) stamps with micron-sized features have been used to selectively stain lambda DNA molecules with SyBr Gold dye. DNA was deposited out of dilute solution onto polymethylmethacrylate (PMMA) layers, 70nm thick, spun-coated on Si wafers, producing linearly stretched and aligned molecules. The stamps were soaked in dye solutions for one minute, followed by wiping of excess solution with a swap. The stamp was pressed onto the surface, varying the pressure and time of application (typically 5-10 minutes) to control the staining. The DNA molecules were imaged with a fluorescence microscope equipped with a cooled CCD camera. Single molecules of DNA were successfully dyed and imaged with stamps having a grating pattern either parallel to or perpendicular to the DNA orientation. Supported by NSF-DMR MRSEC program.

  8. [Surface layers of methanotrophic bacteria].

    PubMed

    Khmelenina, V N; Suzina, N E; Trotsenko, Iu A

    2013-01-01

    Structural and functional characteristics of the regular glycoprotein layers in prokaryotes are analyzed with a special emphasis on aerobic methanotrophic bacteria. S-layers are present at the surfaces of Methylococcus, Methylothermus, and Methylomicrobium cells. Different Methylomicrobium species either synthesize S-layers with planar (p2, p4) symmetry or form cup-shaped or conicalstructures with hexagonal (p6) symmetry. A unique, copper-binding polypeptide 'CorA'/MopE (27/45 kDa), which is coexpressed with the diheme periplasmic cytochrome c peroxidase 'CorB'/Mca (80 kDa) was found in Methylomicrobium album BG8, Methylomicrobium alcaliphilum 20Z, and Methylococcus capsulatus Bath. This tandem of the surface proteins is functionally analogous to a new siderophore, methanobactin. Importantly, no 'CorA'/MopE homologue was found in methanotrophs not forming S-layers. The role of surface proteins in copper metabolism and initial methane oxidation is discussed. PMID:25509389

  9. Dynamical Low-energy Electron Diffraction Analyses of Clean and H-adsorbed Ir(111) Surfaces

    NASA Astrophysics Data System (ADS)

    Matsumoto, Masuaki; Ogura, Syohei; Fukutani, Katsuyuki; Okano, Tatsuo; Okada, Michio

    Structures of Clean and H-adsorbed Ir(111) surfaces were studied by dynamical analyses of low-energy electron diffraction (LEED). LEED pattern for the Clean Ir(111) surface was 1×1. Dynamical analysis of LEED spot intensity vs incident electron enegy (I-V) curves for the clean Ir(111) surface revealed that the layer distance between the 1st and the 2nd layers (d12) equals to 0.2207±0.002 nm, which is almost equal to the bulk value (0.2217 nm). It appears that our result contradicts an previous report, which concluded that d12 equals to 0.216 nm which is 2.6% smaller than the bulk value. However their error bar was so large (±0.01 nm) that it is suggested that our result is the accurate atomic structure of the clean Ir(111) surface. LEED pattern was almost unchanged by H adsorption of 1 ML (1.56×1015 cm-2) at 80 K. The difference between LEED I-V curves before and after hydrogen adsorption was very small and it was impossible to determine the adsorption structure on Ir(111) but it can be conculded that no reconstruction occurs and only a very small relaxation occurs by the adsorption of hydrogen on Ir(111) surface.

  10. Adsorption Properties of Triethylene Glycol on a Hydrated {101̅4} Calcite Surface and Its Effect on Adsorbed Water.

    PubMed

    Olsen, Richard; Leirvik, Kim N; Kvamme, Bjørn; Kuznetsova, Tatiana

    2015-08-11

    Molecular dynamics (MD) and Born-Oppenheimer MD (BOMD) simulations were employed to investigate adsorption of aqueous triethylene glycol (TEG) on a hydrated {101̅4} calcite surface at 298 K. We analyzed the orientation of TEG adsorbed on calcite, as well as the impact of TEG on the water density and adsorption free energy. The adsorption energies of TEG, free energy profiles for TEG, details of hydrogen bonding between water and adsorbed TEG, and dihedral angle distribution of adsorbed TEG were estimated. We found that while the first layer of water was mostly unaffected by the presence of adsorbed TEG, the density of the second water layer was decreased by 71% at 75% surface coverage of TEG. TEG primarily attached to the calcite surface via two adjacent adsorption sites. Hydrogen bonds between water and adsorbed TEG in the second layer almost exclusively involved the hydroxyl oxygen of TEG. The adsorption energy of TEG on calcite in a vacuum environment calculated by classical MD amounted to 217 kJ/mol, which agreed very well with estimates found by using BOMD. Adsorption on hydrated calcite yielded a drastically lower value of 33 kJ/mol, with the corresponding adsorption free energy of 55.3 kJ/mol, giving an entropy increase of 22.3 kJ/mol due to adsorption. We found that the presence of TEG resulted in a decreased magnitude of the adsorption free energy of water, thus decreasing the calcite wettability. This effect can have a profound effect on oil and gas reservoir properties and must be carefully considered when evaluating the risk of hydrate nucleation. PMID:26161580

  11. Development and application of thin-layer spectroelectrochemical techniques for the study of organosulfur monolayers adsorbed at gold

    SciTech Connect

    Simmons, N.

    1997-10-08

    A main research interest is the characterization of monolayers formed by the spontaneous adsorption of organosulfur compounds at gold. This dissertation describes the development and application of long optical pathlength thin-layer spectroelectrochemistry in an attempt to address key issues regarding the reactivity of surface-immobilized molecules. The first section of this introductory chapter briefly describes the general approach to the preparation and characterization of these films. The last section provides an overview of the main principles and advantages of thin-layer spectroelectrochemistry for studying surface-adsorbed species. The body of this dissertation is divided into four chapters. Chapter 2 consists of a paper describing the design, construction, and characterization of a cuvette-based LOPTLC. Chapter 3 is a paper which examines the reductive desorption process using thin-layer spectroelectrochemistry to monitor and identify the desorption product. Chapter 4 is a paper describing the characterization of monolayers functionalized with a catechol terminal group which serves as a redox transformable coordination site for metal ion binding. Chapter 5 discusses the application of thin-layer spectroelectrochemistry to acid-base reactivity studies of surface-immobilized molecules. The final section provides some general conclusions and a prospectus for future studies. These chapters have been processed separately for inclusion on the data base. This report contains the introduction, references, and general conclusions. 78 refs.

  12. The role of adsorbed water on the friction of a layer of submicron particles

    USGS Publications Warehouse

    Sammis, Charles G.; Lockner, David A.; Reches, Ze’ev

    2011-01-01

    Anomalously low values of friction observed in layers of submicron particles deformed in simple shear at high slip velocities are explained as the consequence of a one nanometer thick layer of water adsorbed on the particles. The observed transition from normal friction with an apparent coefficient near μ = 0.6 at low slip speeds to a coefficient near μ = 0.3 at higher slip speeds is attributed to competition between the time required to extrude the water layer from between neighboring particles in a force chain and the average lifetime of the chain. At low slip speeds the time required for extrusion is less than the average lifetime of a chain so the particles make contact and lock. As slip speed increases, the average lifetime of a chain decreases until it is less than the extrusion time and the particles in a force chain never come into direct contact. If the adsorbed water layer enables the otherwise rough particles to rotate, the coefficient of friction will drop to μ = 0.3, appropriate for rotating spheres. At the highest slip speeds particle temperatures rise above 100°C, the water layer vaporizes, the particles contact and lock, and the coefficient of friction rises to μ = 0.6. The observed onset of weakening at slip speeds near 0.001 m/s is consistent with the measured viscosity of a 1 nm thick layer of adsorbed water, with a minimum particle radius of approximately 20 nm, and with reasonable assumptions about the distribution of force chains guided by experimental observation. The reduction of friction and the range of velocities over which it occurs decrease with increasing normal stress, as predicted by the model. Moreover, the analysis predicts that this high-speed weakening mechanism should operate only for particles with radii smaller than approximately 1 μm. For larger particles the slip speed required for weakening is so large that frictional heating will evaporate the adsorbed water and weakening will not occur.

  13. Relationship between surface viscosity and surface composition of adsorbed surfactant films

    SciTech Connect

    Djabbarah, N.F.; Wasan, D.T.

    1982-02-01

    The single-bubble foaming technique was used to determine the surface excess concentrations of aqueous solutions of sodium lauryl sulfate (SLS) and lauryl alcohol (LOH). The excess concentrations of sodium lauryl sulfate-lauryl alcohol showed that lauryl alcohol is preferentially adsorbed at the surface, but only partially displaces sodium lauryl sulfate. This causes a higher total surface concentration and, consequently, a closer packing of surfactant molecules. The total surface excess concentration increases with an increase in the bulk concentration of the 2 surfactants until the critical micelle concentration (CMC) is reached. At concentrations exceeding the CMC, the surface excess concentration of LOH remains virtually constant, while that of SLS declines. This is due to the formation of SLS micelles. The surface excess concentration data have been used to estimate the extent of molecular packing at the gas/liquid interface and to assess interactions among surfactant molecules in order to explain trends in surface viscosity of a mixed surfactant system adsorbed from an aqueous solution. 30 references.

  14. Glycobiology of surface layer proteins.

    PubMed

    Schäffer, C; Messner, P

    2001-07-01

    Over the last two decades, a significant change of perception has taken place regarding prokaryotic glycoproteins. For many years, protein glycosylation was assumed to be limited to eukaryotes; but now, a wealth of information on structure, function, biosynthesis and molecular biology of prokaryotic glycoproteins has accumulated, with surface layer (S-layer) glycoproteins being one of the best studied examples. With the designation of Archaea as a second prokaryotic domain of life, the occurrence of glycosylated S-layer proteins had been considered a taxonomic criterion for differentiation between Bacteria and Archaea. Extensive structural investigations, however, have demonstrated that S-layer glycoproteins are present in both domains. Among Gram-positive bacteria, S-layer glycoproteins have been identified only in bacilli. In Gram-negative organisms, their presence is still not fully investigated; presently, there is no indication for their existence in this class of bacteria. Extensive biochemical studies of the S-layer glycoprotein from Halobacterium halobium have, at least in part, unravelled the glycosylation pathway in Archaea; molecular biological analyses of these pathways have not been performed, so far. Significant observations concern the occurrence of unusual linkage regions both in archaeal and bacterial S-layer glycoproteins. Regarding S-layer glycoproteins of bacteria, first genetic data have shed some light into the molecular organization of the glycosylation machinery in this domain. In addition to basic S-layer glycoprotein research, the biotechnological application potential of these molecules has been explored. With the development of straightforward molecular biological methods, fascinating possibilities for the expression of prokaryotic glycoproteins will become available. S-layer glycoprotein research has opened up opportunities for the production of recombinant glycosylation enzymes and tailor-made S-layer glycoproteins in large quantities

  15. LEED structure analysis of Sb adsorbed Si(0 0 1) surface

    NASA Astrophysics Data System (ADS)

    Mitsui, T.; Hongo, S.; Urano, T.

    2001-06-01

    Sb adsorbed Si(0 0 1) surfaces have been investigated by LEED and AES. After a few monolayer (ML) deposition at room temperature, the LEED patterns of 1×1, 2×1 and c(4×4) have been observed successively as elevating the annealing temperature. Two structures (1×1 and 2×1) were examined by LEED I- V curve analysis. The genetic algorithm (GA) was operated to search a global optimum structure. For the 1×1 structure, a good R-factor value of 0.22 was obtained for the model in which topmost 1 ML Sb atoms sit on the Si atoms of fourth substrate layer. For the 2×1 structure, two cases of 1 ML and a half ML Sb coverage was examined, and an Sb dimer model with 1 ML coverage gave a better R-factor value.

  16. Steps or Terraces? Dynamics of Aromatic Hydrocarbons Adsorbed at Vicinal Metal Surfaces.

    PubMed

    Camarillo-Cisneros, Javier; Liu, Wei; Tkatchenko, Alexandre

    2015-08-21

    The study of how molecules adsorb, diffuse, interact, and desorb from imperfect surfaces is essential for a complete understanding of elementary surface processes under relevant pressure and temperature conditions. Here we use first-principles calculations to study the adsorption of benzene and naphthalene on a vicinal Cu(443) surface with the aim to gain insight into the behavior of aromatic hydrocarbons on realistic surfaces at a finite temperature. Upon strong adsorption at step edges at a low temperature, the molecules then migrate from the step to the (111) terraces, where they can freely diffuse parallel to the step edge. This migration happens at temperatures well below the onset of desorption, suggesting a more complex dynamical picture than previously proposed from temperature-programed desorption studies. The increase of the adsorption strength observed in experiments for Cu(443) when compared to Cu(111) is explained by a stronger long-range van der Waals attraction between the hydrocarbons and the step edges of the Cu(443) surface. Our calculations highlight the need for time-resolved experimental studies to fully understand the dynamics of molecular layers on surfaces. PMID:26340195

  17. Heterogeneous Ozonolysis of Surface Adsorbed Lignin Pyrolysis Products

    NASA Astrophysics Data System (ADS)

    Hinrichs, R. Z.

    2012-12-01

    Biomass combustion releases semi-volatile organic compounds into the troposphere, including many phenols and methoxyphenols as the result of lignin pyrolysis. Given their relatively low vapor pressures, these compounds readily adsorb on inorganic and organic aerosol substrates where they may alter aerosol properties and undergo heterogeneous chemistry. We use infrared spectroscopy (DRIFTS and ATR-FTIR) to monitor the adsorption and subsequent heterogeneous ozonolysis of model lignin pyrolysis products, including catechol, eugenol, and 4-propylguaiacol. Ozonolysis reaction kinetics were compared on various inorganic substrates - such as Al2O3 and NaCl, which serve as mineral and sea salt aerosol substrates, respectively - and as a function of ozone concentration and relative humidity. Following in situ FTIR analysis, the adsorbed organics were extracted and analyzed using gas chromatography-mass spectroscopy to identify reaction products and quantify product branching ratios. Ozonolysis of catechol and 4-propylguaiacol readily resulted in ring cleavage forming dicarboxylic acids (e.g., muconic acid). Eugenol ozonolysis proceeded rapidly at the alkene side chain producing homovanillic acid and homovanillin in an approximate 2:1 branching ratio at 0% RH; ring cleavage was also observed. For all lignin pyrolysis products, heterogeneous ozonolysis was faster on NaCl versus Al2O3. Implications for the atmospheric chemistry of semi-volatile methoxylphenols adsorbed on aerosol substrates will be discussed.

  18. Fabrication of Micro-Lens Array using a Chemically Adsorbed Monomolecular Layer

    NASA Astrophysics Data System (ADS)

    Okada, Kazushi; Oohira, Fumikazu; Hosogi, Maho; Hashiguchi, Gen; Mihara, Yutaka; Ogawa, Kazufumi; Shiwaku, Kazuya

    We proposed a new method of patterning a chemically adsorbed monomolecular layer on the substrate and then dropping UV cure material to form a lens shape using oil repellent effect of this film. The curvature radius of the lens was controlled by the amount of the dropped UV cure material. Using this method, a micro-lens array of various radiuses was fabricated. The formed micro-lens array shapes are transferred by the electro-plating and then the micro dies are fabricated, which are used for molding the plastic lens array. The optical characteristic of the molded micro-lens was evaluated.

  19. Photoexcitation of adsorbates on metal surfaces: One-step or three-step

    SciTech Connect

    Petek, Hrvoje

    2012-09-07

    In this essay we discuss the light-matter interactions at molecule-covered metal surfaces that initiate surface photochemistry. The hot-electron mechanism for surface photochemistry, whereby the absorption of light by a metal surface creates an electron-hole pair, and the hot electron scatters through an unoccupied resonance of adsorbate to initiate nuclear dynamics leading to photochemistry, has become widely accepted. Yet, ultrafast spectroscopic measurements of molecule-surface electronic structure and photoexcitation dynamics provide scant support for the hot electron mechanism. Instead, in most cases the adsorbate resonances are excited through photoinduced substrate-to-adsorbate charge transfer. Based on recent studies of the role of coherence in adsorbate photoexcitation, as measured by the optical phase and momentum resolved two-photon photoemission measurements, we examine critically the hot electron mechanism, and propose an alternative description based on direct charge transfer of electrons from the substrate to adsorbate. The advantage of this more quantum mechanically rigorous description is that it informs how material properties of the substrate and adsorbate, as well as their interaction, influence the frequency dependent probability of photoexcitation and ultimately how light can be used to probe and control surface femtochemistry.

  20. Surface-enhanced Raman spectroscopic analysis of maleic hydrazide adsorbed on gold surface.

    PubMed

    Wang, Can; Gu, Huaimin; Lv, Meng; He, Ruoyu; Zhang, Juling

    2014-03-25

    In this paper, surface-enhanced Raman scattering (SERS) spectra of maleic hydrazide (MH, 6-hydroxy-3(2H)-pyridazinone) were studied by using citrate-reduced gold colloidal nanoparticles. Comparisons between the prominent SERS bands and the precise mode descriptions predicted through density functional theory (DFT) simulations at the B3LYP/6-311++g(d,p) level allowed an in-depth orientation analysis of the adsorbed species on gold surfaces. And main forms of hydrogen bonds in the solid state of MH were also determined to be O-H⋯O. Furthermore, the effects of concentration and pH on the SERS spectra of the molecule were discussed. It is found that with the different adsorbate concentration, the SERS spectra of MH show significant changes in their features, indicating different orientations and adsorption sites of the molecule on the gold colloidal surface. The SERS and absorption spectra under different pH conditions show that a basic environment leads to the deprotonation of N2 and the nearly parallel orientation of the MH molecule on the gold surface. Moreover, the enhanced characteristic bands were observed at MH concentrations down to about 1 ppm with the gold colloids, demonstrating a potential of the technique in the analysis of MH residues. PMID:24295778

  1. Contact Forces between TiO2 Nanoparticles Governed by an Interplay of Adsorbed Water Layers and Roughness.

    PubMed

    Laube, Jens; Salameh, Samir; Kappl, Michael; Mädler, Lutz; Colombi Ciacchi, Lucio

    2015-10-20

    Interparticle forces govern the mechanical behavior of granular matter and direct the hierarchical assembling of nanoparticles into supramolecular structures. Understanding how these forces change under different ambient conditions would directly benefit industrial-scale nanoparticle processing units such as filtering and fluidization. Here we rationalize and quantify the contributions of dispersion, capillary, and solvation forces between hydrophilic TiO2 nanoparticles with sub-10 nm diameter and show that the humidity dependence of the interparticle forces is governed by a delicate interplay between the structure of adsorbed water layers and the surface roughness. All-atom molecular dynamics modeling supported by force-spectroscopy experiments reveals an unexpected decrease in the contact forces at increasing humidity for nearly spherical particles, while the forces between rough particles are insensitive to strong humidity changes. Our results also frame the limits of applicability of discrete solvation and continuum capillary theories in a regime where interparticle forces are dominated by the molecular nature of surface adsorbates. PMID:26414448

  2. Robust Maleimide-Functionalized Gold Surfaces and Nanoparticles Generated Using Custom-Designed Bidentate Adsorbates.

    PubMed

    Park, Chul Soon; Lee, Han Ju; Jamison, Andrew C; Lee, T Randall

    2016-07-26

    A series of custom-designed alkanethioacetate ligands were synthesized to provide a facile method of attaching maleimide-terminated adsorbates to gold nanostructures via thiolate bonds. Monolayers on flat gold substrates derived from both mono- and dithioacetates, with and without oligo(ethylene glycol) (OEG) moieties in their alkyl spacers, were characterized using X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, ellipsometry, and contact angle goniometry. For all adsorbates, the resulting monolayers revealed that a higher packing density and more homogeneous surface were generated when the film was formed in EtOH, but a higher percentage of bound thiolate was obtained in THF. A series of gold nanoparticles (AuNPs) capped with each adsorbate were prepared to explore how adsorbate structure influences aqueous colloidal stability under extreme conditions, as examined visually and spectroscopically. The AuNPs coated with adsorbates that include OEG moieties exhibited enhanced stability under high salt concentration, and AuNPs capped with dithioacetate adsorbates exhibited improved stability against ligand exchange in competition with dithiothreitol (DTT). Overall, the best results were obtained with a chelating dithioacetate adsorbate that included OEG moieties in its alkyl spacer, imparting improved stability via enhanced solubility in water and superior adsorbate attachment owing to the chelate effect. PMID:27385466

  3. Influence of surface charge on the rate, extent, and structure of adsorbed Bovine Serum Albumin to gold electrodes.

    PubMed

    Beykal, Burcu; Herzberg, Moshe; Oren, Yoram; Mauter, Meagan S

    2015-12-15

    The objective of this work is to investigate the rate, extent, and structure of amphoteric proteins with charged solid surfaces over a range of applied potentials and surface charges. We use Electrochemical Quartz Crystal Microbalance with Dissipation Monitoring (E-QCM-D) to investigate the adsorption of amphoteric Bovine Serum Albumin (BSA) to a gold electrode while systematically varying the surface charge on the adsorbate and adsorbent by manipulating pH and applied potential, respectively. We also perform cyclic voltammetry-E-QCM-D on an adsorbed layer of BSA to elucidate conformational changes in response to varied applied potentials. We confirm previous results demonstrating that increasing magnitude of applied potential on the gold electrode is positively correlated with increasing mass adsorption when the protein and the surface are oppositely charged. On the other hand, we find that the rate of BSA adsorption is not governed by simple electrostatics, but instead depends on solution pH, an observation not well documented in the literature. Cyclic voltammetry with simultaneous E-QCM-D measurements suggest that BSA protein undergoes a conformational change as the surface potential varies. PMID:26348658

  4. Surface Adsorbed Species: IR Studies of SO2 and H2S Adsorbed on Oxides

    NASA Astrophysics Data System (ADS)

    Lavalley, J. C.; Lamotte, J.; Saur, O.; Mohammed Saad, A. B.; Tripp, C.; Morrow, B. A.

    1985-12-01

    The adsorption of SO, on alumina leads to the formation of several species such as SO3=, HSO3- and coordinated SO2. In addition sulfates are produced under oxidizing conditions. However, definitive vibra- tional assignments are hampered by the paucity of data below 1000 cm-1 where alumina is strongly absorbing. On the other hand, silica is partially transparent at low frequencies and subtractive IR spectroscopy has permitted us to observe bands which are tentatively assigned to the SO bending modes of bisulfite (HSO3-, 635 cm-I) and disulfite (S2O5-, 660 cm-I) surface species on sodium promoted silica catalysts when SO and H2O are coadsorbed. H2S addition to a surface pretreated with SO2 gives rise to a new band at 680 cm-1 which is pos- sibly due to S2O3 orS2O on the surface. The results are discussed in terms of intermediates in the Claus process (2 H2S + SO2 + 3/n Sn + 2 H2O).

  5. Method for Controlling Electrical Properties of Single-Layer Graphene Nanoribbons via Adsorbed Planar Molecular Nanoparticles

    NASA Astrophysics Data System (ADS)

    Tanaka, Hirofumi; Arima, Ryo; Fukumori, Minoru; Tanaka, Daisuke; Negishi, Ryota; Kobayashi, Yoshihiro; Kasai, Seiya; Yamada, Toyo Kazu; Ogawa, Takuji

    2015-07-01

    A simple method for fabricating single-layer graphene nanoribbons (sGNRs) from double-walled carbon nanotubes (DWNTs) was developed. A sonication treatment was employed to unzip the DWNTs by inducing defects in them through annealing at 500 °C. The unzipped DWNTs yielded double-layered GNRs (dGNRs). Further sonication allowed each dGNR to be unpeeled into two sGNRs. Purification performed using a high-speed centrifuge ensured that more than 99% of the formed GNRs were sGNRs. The changes induced in the electrical properties of the obtained sGNR by the absorption of nanoparticles of planar molecule, naphthalenediimide (NDI), were investigated. The shape of the I-V curve of the sGNRs varied with the number of NDI nanoparticles adsorbed. This was suggestive of the existence of a band gap at the narrow-necked part near the NDI-adsorbing area of the sGNRs.

  6. Method for Controlling Electrical Properties of Single-Layer Graphene Nanoribbons via Adsorbed Planar Molecular Nanoparticles

    PubMed Central

    Tanaka, Hirofumi; Arima, Ryo; Fukumori, Minoru; Tanaka, Daisuke; Negishi, Ryota; Kobayashi, Yoshihiro; Kasai, Seiya; Yamada, Toyo Kazu; Ogawa, Takuji

    2015-01-01

    A simple method for fabricating single-layer graphene nanoribbons (sGNRs) from double-walled carbon nanotubes (DWNTs) was developed. A sonication treatment was employed to unzip the DWNTs by inducing defects in them through annealing at 500 °C. The unzipped DWNTs yielded double-layered GNRs (dGNRs). Further sonication allowed each dGNR to be unpeeled into two sGNRs. Purification performed using a high-speed centrifuge ensured that more than 99% of the formed GNRs were sGNRs. The changes induced in the electrical properties of the obtained sGNR by the absorption of nanoparticles of planar molecule, naphthalenediimide (NDI), were investigated. The shape of the I-V curve of the sGNRs varied with the number of NDI nanoparticles adsorbed. This was suggestive of the existence of a band gap at the narrow-necked part near the NDI-adsorbing area of the sGNRs. PMID:26205209

  7. Method for Controlling Electrical Properties of Single-Layer Graphene Nanoribbons via Adsorbed Planar Molecular Nanoparticles.

    PubMed

    Tanaka, Hirofumi; Arima, Ryo; Fukumori, Minoru; Tanaka, Daisuke; Negishi, Ryota; Kobayashi, Yoshihiro; Kasai, Seiya; Yamada, Toyo Kazu; Ogawa, Takuji

    2015-01-01

    A simple method for fabricating single-layer graphene nanoribbons (sGNRs) from double-walled carbon nanotubes (DWNTs) was developed. A sonication treatment was employed to unzip the DWNTs by inducing defects in them through annealing at 500 °C. The unzipped DWNTs yielded double-layered GNRs (dGNRs). Further sonication allowed each dGNR to be unpeeled into two sGNRs. Purification performed using a high-speed centrifuge ensured that more than 99% of the formed GNRs were sGNRs. The changes induced in the electrical properties of the obtained sGNR by the absorption of nanoparticles of planar molecule, naphthalenediimide (NDI), were investigated. The shape of the I-V curve of the sGNRs varied with the number of NDI nanoparticles adsorbed. This was suggestive of the existence of a band gap at the narrow-necked part near the NDI-adsorbing area of the sGNRs. PMID:26205209

  8. Heterogeneous Reactions of Surface-Adsorbed Catechol: A Comparison of Tropospheric Aerosol Surrogates

    NASA Astrophysics Data System (ADS)

    Hinrichs, R. Z.; Woodill, L. A.

    2009-12-01

    Surface-adsorbed organics can alter the chemistry of tropospheric solid-air interfaces, such as aerosol and ground level surfaces, thereby impacting photochemical cycles and altering aerosol properties. The nature of the surface can also influence the chemistry of the surface-adsorbed organic. We employed diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to monitor the adsorption of gaseous catechol on several tropospheric aerosol surrogates and to investigate the subsequent reactivity of adsorbed-catechol with nitrogen dioxide and, in separate preliminary experiments, ozone. Graphite, kaolinite, and sodium halide (NaF, NaCl, NaBr) powders served as carbonaceous, mineral and sea salt aerosol surrogates, respectively. Broad OH stretching bands for adsorbed catechol shifted to lower wavenumber with peak frequencies following the trend NaBr > NaCl > NaF ≈ kaolinite, consistent with the increasing basicity of the halide anions and basic Brønsted sites on kaolinite. The dark heterogeneous reaction of NO2 with NaCl-adsorbed catechol at relative humidity (RH) <2% promoted nitration forming 4-nitrocatechol and oxidation forming 1,2-benzoquinone and the ring cleavage product muconic acid, with product yields of 88%, 8%, and 4%, respectively. 4-Nitrocatechol was the dominant product for catechol adsorbed on NaF and kaolinite, while NaBr-adsorbed catechol produced less 4-nitrocatechol and more 1,2-benzoquinone and muconic acid. For all three sodium halides, the reactions of NO2 with adsorbed catechol were orders of magnitude faster than between NO2 and each NaX substrate. 4-Nitrocatechol rates and product yields were consistent with the relative ability of each substrate to enhance the deprotonated nature of adsorbed-catechol. Increasing the relative humidity caused the rate of each product channel to decrease and also altered the product branching ratios. Most notably, 1,2-benzoquinone formation decreased significantly even at 13% RH. The dramatic

  9. Controlled Uniform Coating from the Interplay of Marangoni Flows and Surface-Adsorbed Macromolecules

    NASA Astrophysics Data System (ADS)

    Kim, Hyoungsoo; Boulogne, François; Um, Eujin; Jacobi, Ian; Button, Ernie; Stone, Howard A.

    2016-03-01

    Surface coatings and patterning technologies are essential for various physicochemical applications. In this Letter, we describe key parameters to achieve uniform particle coatings from binary solutions. First, multiple sequential Marangoni flows, set by solute and surfactant simultaneously, prevent nonuniform particle distributions and continuously mix suspended materials during droplet evaporation. Second, we show the importance of particle-surface interactions that can be established by surface-adsorbed macromolecules. To achieve a uniform deposit in a binary mixture, a small concentration of surfactant and surface-adsorbed polymer (0.05 wt% each) is sufficient, which offers a new physicochemical avenue for control of coatings.

  10. Characterization of molecular and atomic species adsorbed on ferroelectric and semiconductor surfaces

    NASA Astrophysics Data System (ADS)

    Bharath, Satyaveda Chavi

    In order to clarify the mechanisms behind the adsorption of atomic and molecular species adsorbed on ferroelectric surfaces, single crystalline lithium niobate (LiNbO3, LN), 'Z-cut' along the (0001) plane, has been prepared, characterized and subsequently exposed to molecular and atomic species. 4-n-octyl-4'-cyanobiphenyl (8CB) liquid crystal was chosen as a polar molecule for our model system for this study. Low-energy electron diffraction (LEED), atomic force microscopy (AFM), surface contact angles (CA), and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface of LN as well as the nature of the liquid crystal films grown on the surface. Atomically flat LN surfaces were prepared as a support for monolayer thick, 8CB molecular domains. Also, for the purpose of gaining a fundamental understanding of low coverage interactions of metal atoms on ferroelectric surfaces, we choose to deposit gold onto the LN surface. These gold atomic layers were grown under UHV conditions and characterized. Understanding anchoring mechanisms and thin film organization for LC molecules and metal atoms on uniformly poled surfaces allows for a fuller appreciation of how molecular deposition of other polarizable molecules on patterned poled LN surfaces would occur as well as yielding greater insight on the atomic characteristics of metal on ferroelectric interfaces. Also, to reveal the mechanisms involved in the adsorption of organic aromatic molecules on high-index Si surfaces, thiophene (C4H 4S) and pyrrole (C4H5N) molecules were dosed on prepared Si(5 5 12)-2x1 surfaces as our experimental system. The Si(5 5 12) surface was prepared to produce a 2x1 reconstruction after which molecules were dosed at low exposure to observe the preferred adsorption sites on the surface. All surface preparation and experiments were performed in UHV and measurements of the surface before and after deposition were performed using scanning tunneling microscopy (STM). Fundamental

  11. Competition between Displacement and Dissociation of a Strong Acid Compared to a Weak Acid Adsorbed on Silica Particle Surfaces: The Role of Adsorbed Water.

    PubMed

    Fang, Yuan; Tang, Mingjin; Grassian, Vicki H

    2016-06-16

    The adsorption of nitric (HNO3) and formic (HCOOH) acids on silica particle surfaces and the effect of adsorbed water have been investigated at 296 K using transmission FTIR spectroscopy. Under dry conditions, both nitric and formic acids adsorb reversibly on silica. Additionally, the FTIR spectra show that both of these molecules remain in the protonated form. At elevated relative humidities (RH), adsorbed water competes both for surface adsorption sites with these acids as well as promotes their dissociation to hydronium ions and the corresponding anions. Compared to HNO3, the extent of dissociation is much smaller for HCOOH, very likely because it is a weaker acid. This study provides valuable insights into the interaction of HNO3 and HCOOH with silica surface on the molecular level and further reveals the complex roles of surface-adsorbed water in atmospheric heterogeneous chemistry of mineral dust particles-many of these containing silica. PMID:27220375

  12. Surface photochemistry of adsorbed nitrate: the role of adsorbed water in the formation of reduced nitrogen species on α-Fe2O3 particle surfaces.

    PubMed

    Nanayakkara, Charith E; Jayaweera, Pradeep M; Rubasinghege, Gayan; Baltrusaitis, Jonas; Grassian, Vicki H

    2014-01-01

    The surface photochemistry of nitrate, formed from nitric acid adsorption, on hematite (α-Fe2O3) particle surfaces under different environmental conditions is investigated using X-ray photoelectron spectroscopy (XPS). Following exposure of α-Fe2O3 particle surfaces to gas-phase nitric acid, a peak in the N1s region is seen at 407.4 eV; this binding energy is indicative of adsorbed nitrate. Upon broadband irradiation with light (λ > 300 nm), the nitrate peak decreases in intensity as a result of a decrease in adsorbed nitrate on the surface. Concomitant with this decrease in the nitrate coverage, there is the appearance of two lower binding energy peaks in the N1s region at 401.7 and 400.3 eV, due to reduced nitrogen species. The formation as well as the stability of these reduced nitrogen species, identified as NO(-) and N(-), are further investigated as a function of water vapor pressure. Additionally, irradiation of adsorbed nitrate on α-Fe2O3 generates three nitrogen gas-phase products including NO2, NO, and N2O. As shown here, different environmental conditions of water vapor pressure and the presence of molecular oxygen greatly influence the relative photoproduct distribution from nitrate surface photochemistry. The atmospheric implications of these results are discussed. PMID:24299394

  13. A surface extended X-ray absorption fine structure study of tellurium adsorbed onto Si(100)

    NASA Astrophysics Data System (ADS)

    Burgess, S. R.; Cowie, B. C. C.; Wilks, S. P.; Dunstan, P. R.; Dunscombe, C. J.; Williams, R. H.

    1996-09-01

    The adsorption of tellurium on Si(100) has been studied using surface extended X-ray adsorption fine structure (SEXAFS) and X-ray standing wave spectroscopy (XSW). This particular system is of interest due to its potential applicability in the surfactant aided growth of CdHgTeCdTeSi(100) based infra-red detectors. The Te/Si(100) structure was generated by depositing a thick layer (˜ 100 Å) of CdTe onto a clean Si (2 × 1) double domain surface, and annealing the sample to 350°C. This resulted is a ˜ 1 ML Te terminated surface where the (2 × 1) reconstruction was lost in favour of a (1 × 1) symmetry. X-ray absorption of the Te L 3 edge ( E = 4341 eV), with a photon energy range of 4440-4700 eV, was probed using a total yield detection scheme. The SEXAFS results indicated that the Te atoms sat in 2-fold bridge sites directly above a fourth layer Si atom. The corresponding bond length was measured to be 2.52 ± 0.05 Å. The XSW measurements of the (400) reflection gave a coherent position of 1.63 ± 0.03 Å and a coherent fraction of 0.65. This is consistent with the breaking of the SiSi dimers and thus could be an example of the phenomena of adsorbate-induced dereconstruction of the surface. These results are compared with those of Bennet et al. who examined a similar system using soft X-ray photoemission (SXPS) and the STM study of Yoshikawa et al.

  14. Role(s) of adsorbed water in the surface chemistry of environmental interfaces.

    PubMed

    Rubasinghege, Gayan; Grassian, Vicki H

    2013-04-18

    The chemistry of environmental interfaces such as oxide and carbonate surfaces under ambient conditions of temperature and relative humidity is of great interest from many perspectives including heterogeneous atmospheric chemistry, heterogeneous catalysis, photocatalysis, sensor technology, corrosion science, and cultural heritage science. As discussed here, adsorbed water plays important roles in the reaction chemistry of oxide and carbonate surfaces with indoor and outdoor pollutant molecules including nitrogen oxides, sulfur dioxide, carbon dioxide, ozone and organic acids. Mechanisms of these reactions are just beginning to be unraveled and found to depend on the details of the reaction mechanism as well as the coverage of water on the surface. As discussed here, adsorbed water can: (i) alter reaction pathways and surface speciation relative to the dry surface; (ii) hydrolyze reactants, intermediates and products; (iii) enhance surface reactivity by providing a medium for ionic dissociation; (iv) inhibit surface reactivity by blocking sites; (v) solvate ions; (vi) enhance ion mobility on surfaces and (vii) alter the stability of surface adsorbed species. In this feature article, drawing on research that has been going on for over a decade on the reaction chemistry of oxide and carbonate surfaces under ambient conditions of temperature and relative humidity, a number of specific examples showing the multi-faceted roles of adsorbed water are presented. PMID:23417201

  15. Electronic structure and binding geometry of tetraphenylporphyrin-derived molecules adsorbed on metal and metal oxide surfaces

    NASA Astrophysics Data System (ADS)

    Coh, Senia

    Tetraphenylporphyrin (TPP)-derived molecules have been studied extensively as efficient photosensitizers when chemisorbed on the metal oxide substrates in dye-sensitized solar cells. Still, many fundamental electronic properties of the dye/oxide interface are not understood and need careful consideration. In this thesis we present a comprehensive study of the electronic structure, energy level alignment and the adsorption geometry of the TPP-derived dye molecules adsorbed on TiO2(110), ZnO(1120) and Ag(100) single crystal surfaces using ultra-high vacuum (UHV) based surface sensitive techniques. The alignment of the molecular energy levels with respect to the TiO 2 and ZnO band edges for all TPP-derived molecules we studied was found to be insensitive to either the nature of the functional groups located on the phenyl rings, presence of zinc as a central metal ion and different binding geometry of the molecules. Binding geometry, molecule-molecule interaction and the aggregation effects in the adsorbed layer, that were observed in the UV-visible spectra of the molecules adsorbed on ZnO substrate were not observed in the ultraviolet photoemission (UPS) and inverse photoemission (IPS) spectra of the occupied and unoccupied molecular states. Using near edge X-ray absorption fine structure (NEXAFS) and scanning tunneling microscopy (STM), binding geometry of the two representative TPP-derivatives was directly determined to be upright, with the porphyrin ring under large angle with respect to the surface for the p-ZnTCPP molecules and with the porphyrin ring parallel to the surface for the m-ZnTCPP molecules. We observe that the energies and the energy level alignment of the ZnTPP molecular levels measured in UPS and IPS depend on the substrate on which the molecules are adsorbed (Ag(100) or TiO2(110) single crystal surfaces). The differences are attributed to different charge screening properties of these two materials. Image charges created in the substrates during

  16. Path-integral Monte Carlo simulation of the second layer of 4He adsorbed on graphite

    NASA Astrophysics Data System (ADS)

    Pierce, Marlon; Manousakis, Efstratios

    1999-02-01

    We have developed a path-integral Monte Carlo method for simulating helium films and apply it to the second layer of helium adsorbed on graphite. We use helium-helium and helium-graphite interactions that are found from potentials which realistically describe the interatomic interactions. The Monte Carlo sampling is over both particle positions and permutations of particle labels. From the particle configurations and static structure factor calculations, we find that this layer possesses, in order of increasing density, a superfluid liquid phase, a 7×7 commensurate solid phase that is registered with respect to the first layer, and an incommensurate solid phase. By applying the Maxwell construction to the dependence of the low-temperature total energy on the coverage, we are able to identify coexistence regions between the phases. From these, we deduce an effectively zero-temperature phase diagram. Our phase boundaries are in agreement with heat capacity and torsional oscillator measurements, and demonstrate that the experimentally observed disruption of the superfluid phase is caused by the growth of the commensurate phase. We further observe that the superfluid phase has a transition temperature consistent with the two-dimensional value. Promotion to the third layer occurs for densities above 0.212 atom/Å 2, in good agreement with experiment. Finally, we calculate the specific heat for each phase and obtain peaks at temperatures in general agreement with experiment.

  17. Chemisorption on surfaces — an historical look at a representative adsorbate: carbon monoxide

    NASA Astrophysics Data System (ADS)

    Yates, John T.

    1994-01-01

    The study of the interaction of molecules with clean surfaces extends back to the work of Irving Langmuir. In this historical account, the development of selected experimental methods for the study of molecular adsorption will be discussed. This will be done by historically reviewing research on one of the most well-studied adsorbate molecules, carbon monoxide. Many of the modern surface science techniques have first been used to study chemisorbed carbon monoxide, and the CO molecule is employed even today as a test molecule for currently developing surface measurement instruments such as the low temperature STM. In addition to being a good test molecule for new surface measurement techniques, adsorbed carbon monoxide is one of the centrally important molecules in the field of heterogeneous catalysis where the production of synthetic fuels and useful organic molecules often depends on the catalytic behavior of the adsorbed CO molecule. Interestingly, the carbon monoxide molecule also serves as a bridge between surface chemistry on the transition metals and the field of organometallic chemistry. Concepts about the chemical bonding and the reactive behavior of CO chemisorbed on transition metal surfaces and CO bound in transition metal carbonyls link these two fields together in a significant manner. The carbon monoxide molecule has been the historical focal point of many endeavors in surface chemistry and surface physics, and research on adsorbed carbon monoxide well represents many of the key advances which characterize the first thirty years of the development of surface science.

  18. The Dependence of the Oxidation Enhancement of InP(100) Surface on the Coverage of the Adsorbed Cs

    SciTech Connect

    Sun, Yun

    2010-06-07

    We report the oxidation of the InP(100) surface promoted by adsorbed Cs by synchrotron radiation photoemission. Oxygen exposure causes reduction of the charge transferred to the InP substrate from Cs and the growth of indium oxide and phosphorous oxide. The oxide growth displays a clear dependence on the Cs coverage. The oxidation of phosphorous is negligible up to 1000 L of O{sub 2} exposure when the Cs coverage is less than half a monolayer (ML), but the formation of the second half monolayer of Cs greatly accelerates the oxidation. This different enhancement of the InP oxidation by the first and the second half monolayer of Cs is due to the double layer structure of the adsorbed Cs atoms, and consequently the higher 6s electron density in the Cs atoms when Cs coverage is larger than 0.5 ML.

  19. Individual Detection and Electrochemically Assisted Identification of Adsorbed Nanoparticles by Using Surface Plasmon Microscopy.

    PubMed

    Nizamov, Shavkat; Kasian, Olga; Mirsky, Vladimir M

    2016-06-13

    The increasing production and application of nanoparticles necessitates a highly sensitive analytical method for the quantification and identification of these potentially hazardous materials. We describe here an application of surface plasmon microscopy for the individual detection of each adsorbed nanoparticle and for visualization of its electrochemical conversion. Whereas the adsorption rate characterizes the number concentration of nanoparticles, the potential at which the adsorbed nanoparticles disappear during an anodic potential sweep characterizes the type of material. All the adsorbed nanoparticles are subjected to the potential sweep simultaneously; nevertheless, each of the up to a million adsorbed nanoparticles is identified individually by its electrochemical dissolution potential. The technique has been tested with silver and copper nanoparticles, but can be extended to many other electrochemically active nanomaterials. PMID:27139913

  20. Interband interaction between bulk and surface resonance bands of a Pb-adsorbed Ge(001) surface

    NASA Astrophysics Data System (ADS)

    Sakata, Tomohiro; Takeda, Sakura N.; Kitagawa, Kosuke; Daimon, Hiroshi

    2016-08-01

    We investigated the valence band structure of a Pb-adsorbed Ge(001) surface by angle-resolved photoelectron spectroscopy. Three Ge bands, G1, G2, and G3, were observed in a Ge(001) 2 × 1 clean surface. In addition to these three bands, a fourth band (R band) is found on the surface with 2 ML of Pb. The R band continuously appeared even when the surface superstructure was changed. The position of the R band does not depend on Pb coverage. These results indicate that the R band derives from Ge subsurface states, known as surface resonance states. Furthermore, the effective mass of G3 is significantly reduced when the R band exists. We found that this reduction of G3 effective mass was explained by the interaction of the G3 and R bands. Consequently, the surface resonance band is considered to penetrate into the Ge subsurface region affecting the Ge bulk states. We determine the hybridization energy to be 0.068 eV by fitting the observed bands.

  1. Nonequilibrium Molecular Dynamics Simulations of Organic Friction Modifiers Adsorbed on Iron Oxide Surfaces.

    PubMed

    Ewen, James P; Gattinoni, Chiara; Morgan, Neal; Spikes, Hugh A; Dini, Daniele

    2016-05-10

    For the successful development and application of lubricants, a full understanding of the nanoscale behavior of complex tribological systems is required, but this is difficult to obtain experimentally. In this study, we use nonequilibrium molecular dynamics (NEMD) simulations to examine the atomistic structure and friction properties of commercially relevant organic friction modifier (OFM) monolayers adsorbed on iron oxide surfaces and lubricated by a thin, separating layer of hexadecane. Specifically, acid, amide, and glyceride OFMs, with saturated and Z-unsaturated hydrocarbon tail groups, are simulated at various surface coverages and sliding velocities. At low and medium coverage, the OFMs form liquidlike and amorphous monolayers, respectively, which are significantly interdigitated with the hexadecane lubricant, resulting in relatively high friction coefficients. At high coverage, solidlike monolayers are formed for all of the OFMs, which, during sliding, results in slip planes between well-defined OFM and hexadecane layers, yielding a marked reduction in the friction coefficient. When present at equal surface coverage, OFMs with saturated and Z-unsaturated tail groups are found to yield similar structure and friction behavior. OFMs with glyceride head groups yield significantly lower friction coefficients than amide and particularly carboxylic acid head groups. For all of the OFMs and coverages simulated, the friction coefficient is found to increase linearly with the logarithm of sliding velocity; however, the gradient of this increase depends on the coverage. The structure and friction details obtained from these simulations agree well with experimental results and also shed light on the relative tribological performance of these OFMs through nanoscale structural variations. This has important implications in terms of the applicability of NEMD to aid the development of new formulations to control friction. PMID:27064962

  2. Many-body dispersion effects in the binding of adsorbates on metal surfaces

    NASA Astrophysics Data System (ADS)

    Maurer, Reinhard J.; Ruiz, Victor G.; Tkatchenko, Alexandre

    2015-09-01

    A correct description of electronic exchange and correlation effects for molecules in contact with extended (metal) surfaces is a challenging task for first-principles modeling. In this work, we demonstrate the importance of collective van der Waals dispersion effects beyond the pairwise approximation for organic-inorganic systems on the example of atoms, molecules, and nanostructures adsorbed on metals. We use the recently developed many-body dispersion (MBD) approach in the context of density-functional theory [Tkatchenko et al., Phys. Rev. Lett. 108, 236402 (2012) and Ambrosetti et al., J. Chem. Phys. 140, 18A508 (2014)] and assess its ability to correctly describe the binding of adsorbates on metal surfaces. We briefly review the MBD method and highlight its similarities to quantum-chemical approaches to electron correlation in a quasiparticle picture. In particular, we study the binding properties of xenon, 3,4,9,10-perylene-tetracarboxylic acid, and a graphene sheet adsorbed on the Ag(111) surface. Accounting for MBD effects, we are able to describe changes in the anisotropic polarizability tensor, improve the description of adsorbate vibrations, and correctly capture the adsorbate-surface interaction screening. Comparison to other methods and experiment reveals that inclusion of MBD effects improves adsorption energies and geometries, by reducing the overbinding typically found in pairwise additive dispersion-correction approaches.

  3. Many-body dispersion effects in the binding of adsorbates on metal surfaces.

    PubMed

    Maurer, Reinhard J; Ruiz, Victor G; Tkatchenko, Alexandre

    2015-09-14

    A correct description of electronic exchange and correlation effects for molecules in contact with extended (metal) surfaces is a challenging task for first-principles modeling. In this work, we demonstrate the importance of collective van der Waals dispersion effects beyond the pairwise approximation for organic-inorganic systems on the example of atoms, molecules, and nanostructures adsorbed on metals. We use the recently developed many-body dispersion (MBD) approach in the context of density-functional theory [Tkatchenko et al., Phys. Rev. Lett. 108, 236402 (2012) and Ambrosetti et al., J. Chem. Phys. 140, 18A508 (2014)] and assess its ability to correctly describe the binding of adsorbates on metal surfaces. We briefly review the MBD method and highlight its similarities to quantum-chemical approaches to electron correlation in a quasiparticle picture. In particular, we study the binding properties of xenon, 3,4,9,10-perylene-tetracarboxylic acid, and a graphene sheet adsorbed on the Ag(111) surface. Accounting for MBD effects, we are able to describe changes in the anisotropic polarizability tensor, improve the description of adsorbate vibrations, and correctly capture the adsorbate-surface interaction screening. Comparison to other methods and experiment reveals that inclusion of MBD effects improves adsorption energies and geometries, by reducing the overbinding typically found in pairwise additive dispersion-correction approaches. PMID:26374001

  4. Free energy of electrical double layers: Entropy of adsorbed ions and the binding polynomial

    SciTech Connect

    Stigter, D.; Dill, K.A. )

    1989-09-07

    The authors adapt the method of binding polynomials to general problems of binding equilibria of ions to polybases, polyacids, and mixed polyelectrolytes, such as proteins and other colloids. For spherical particles with a smeared charge the interaction effects are taken into account using the Poisson-Boltzmann equation, which is shown to differ little from the Debye-Hueckel approximation under conditions met in most protein solutions. Examples are given of the salt dependence of pH titration equilibria. Binding polynomials produce an extra term in the free energy of the electrical double layer, which arises from the entropy of the adsorbed ions. The maximum term method applied to the binding polynominal yields an expression which is similar to that derived by the charging process of Chan and Mitchell. Applications to monolayers and to polyelectrolyte gels are also discussed.

  5. Ultra-Thin Optically Transparent Carbon Electrodes Produced from Layers of Adsorbed Proteins

    PubMed Central

    Alharthi, Sarah A.; Benavidez, Tomas E.; Garcia, Carlos D.

    2013-01-01

    This work describes a simple, versatile, and inexpensive procedure to prepare optically transparent carbon electrodes, using proteins as precursors. Upon adsorption, the protein-coated substrates were pyrolyzed under reductive conditions (5% H2) to form ultra-thin, conductive electrodes. Because proteins spontaneously adsorb to interfaces forming uniform layers, the proposed method does not require a precise control of the preparation conditions, specialized instrumentation, or expensive precursors. The resulting electrodes were characterized by a combination of electrochemical, optical, and spectroscopic means. As a proof-of-concept, the optically-transparent electrodes were also used as substrate for the development of an electrochemical glucose biosensor. The proposed films represent a convenient alternative to more sophisticated, and less available, carbon-based nanomaterials. Furthermore, these films could be formed on a variety of substrates, without classical limitations of size or shape. PMID:23421732

  6. Influences of Dilute Organic Adsorbates on the Hydration of Low-Surface-Area Silicates.

    PubMed

    Sangodkar, Rahul P; Smith, Benjamin J; Gajan, David; Rossini, Aaron J; Roberts, Lawrence R; Funkhouser, Gary P; Lesage, Anne; Emsley, Lyndon; Chmelka, Bradley F

    2015-07-01

    Competitive adsorption of dilute quantities of certain organic molecules and water at silicate surfaces strongly influence the rates of silicate dissolution, hydration, and crystallization. Here, we determine the molecular-level structures, compositions, and site-specific interactions of adsorbed organic molecules at low absolute bulk concentrations on heterogeneous silicate particle surfaces at early stages of hydration. Specifically, dilute quantities (∼0.1% by weight of solids) of the disaccharide sucrose or industrially important phosphonic acid species slow dramatically the hydration of low-surface-area (∼1 m(2)/g) silicate particles. Here, the physicochemically distinct adsorption interactions of these organic species are established by using dynamic nuclear polarization (DNP) surface-enhanced solid-state NMR techniques. These measurements provide significantly improved signal sensitivity for near-surface species that is crucial for the detection and analysis of dilute adsorbed organic molecules and silicate species on low-surface-area particles, which until now have been infeasible to characterize. DNP-enhanced 2D (29)Si{(1)H}, (13)C{(1)H}, and (31)P{(1)H} heteronuclear correlation and 1D (29)Si{(13)C} rotational-echo double-resonance NMR measurements establish hydrogen-bond-mediated adsorption of sucrose at distinct nonhydrated and hydrated silicate surface sites and electrostatic interactions with surface Ca(2+) cations. By comparison, phosphonic acid molecules are found to adsorb electrostatically at or near cationic calcium surface sites to form Ca(2+)-phosphonate complexes. Although dilute quantities of both types of organic molecules effectively inhibit hydration, they do so by adsorbing in distinct ways that depend on their specific architectures and physicochemical interactions. The results demonstrate the feasibility of using DNP-enhanced NMR techniques to measure and assess dilute adsorbed molecules and their molecular interactions on low-surface

  7. Surface free energy analysis of adsorbents used for radioiodine adsorption

    NASA Astrophysics Data System (ADS)

    González-García, C. M.; Román, S.; González, J. F.; Sabio, E.; Ledesma, B.

    2013-10-01

    In this work, the surface free energy of biomass-based activated carbons, both fresh and impregnated with triethylenediamine, has been evaluated. The contribution of Lifshitz van der Waals components was determined by the model proposed by van Oss et al. The results obtained allowed predicting the most probable configurations of the impregnant onto the carbon surface and its influence on the subsequent adsorption of radioactive methyl iodide.

  8. Enhanced removal of nitrate from water using surface modification of adsorbents--a review.

    PubMed

    Loganathan, Paripurnanda; Vigneswaran, Saravanamuthu; Kandasamy, Jaya

    2013-12-15

    Elevated concentration of nitrate results in eutrophication of natural water bodies affecting the aquatic environment and reduces the quality of drinking water. This in turn causes harm to people's health, especially that of infants and livestock. Adsorbents with the high capacity to selectively adsorb nitrate are required to effectively remove nitrate from water. Surface modifications of adsorbents have been reported to enhance their adsorption of nitrate. The major techniques of surface modification are: protonation, impregnation of metals and metal oxides, grafting of amine groups, organic compounds including surfactant coating of aluminosilicate minerals, and heat treatment. This paper reviews current information on these techniques, compares the enhanced nitrate adsorption capacities achieved by the modifications, and the mechanisms of adsorption, and presents advantages and drawbacks of the techniques. Most studies on this subject have been conducted in batch experiments. These studies need to include continuous mode column trials which have more relevance to real operating systems and pilot-plant trials. Reusability of adsorbents is important for economic reasons and practical treatment applications. However, only limited information is available on the regeneration of surface modified adsorbents. PMID:24211565

  9. Surface Chirality of Gly-Pro Dipeptide Adsorbed on a Cu(110) Surface.

    PubMed

    Cruguel, Hervé; Méthivier, Christophe; Pradier, Claire-Marie; Humblot, Vincent

    2015-07-01

    The adsorption of chiral Gly-Pro dipeptide on Cu(110) has been characterized by combining in situ polarization modulation infrared reflection absorption spectroscopy (PM-RAIRS) and X-ray photoelectron spectroscopy (XPS). The chemical state of the dipeptide, and its anchoring points and adsorption geometry, were determined at various coverage values. Gly-Pro molecules are present on Cu(110) in their anionic form (NH2 /COO(-)) and adsorb under a 3-point binding via both oxygen atoms of the carboxylate group and via the nitrogen atom of the amine group. Low-energy electron diffraction (LEED) and scanning tunneling microscopy (STM) have shown the presence of an extended 2D chiral array, sustained via intermolecular H-bonds interactions. Furthermore, due to the particular shape of the molecule, only one homochiral domain is formed, creating thus a truly chiral surface. PMID:25847844

  10. Unusual diffusing regimes caused by different adsorbing surfaces.

    PubMed

    Guimarães, Veridiana G; Ribeiro, Haroldo V; Li, Quan; Evangelista, Luiz R; Lenzi, Ervin K; Zola, Rafael S

    2015-03-01

    A confined liquid with dispersed neutral particles is theoretically studied when the limiting surfaces present different dynamics for the adsorption-desorption phenomena. The investigation considers different non-singular kernels in the kinetic equations at the walls, where the suitable choice of the kernel can account for the relative importance of physisorption or chemisorption. We find that even a small difference in the adsorption-desorption rate of one surface (relative to the other) can drastically affect the behavior of the whole system. The surface and bulk densities and the dispersion are calculated when several scenarios are considered and anomalous-like behaviors are found. The approach described here is closely related to experimental situations, and can be applied in several contexts such as dielectric relaxation, diffusion-controlled relaxation in liquids, liquid crystals, and amorphous polymers. PMID:25633342

  11. Relaxation dynamics of surface-adsorbed water molecules in nanoporous silica probed by terahertz spectroscopy

    NASA Astrophysics Data System (ADS)

    Huang, Yu-Ru; Liu, Kao-Hsiang; Mou, Chung-Yuan; Sun, Chi-Kuang

    2015-08-01

    Relaxation dynamics of an exclusively adsorbed water molecule in mesoporous silica MCM-41-S was studied by using terahertz spectroscopy. With the temperature controlled from 0 to 50 °C, we observed strongly frequency- and temperature-dependent dielectric relaxation responses, implying that, unlike ice, surface-adsorbed water molecules retained flourishing picosecond dynamics. Based on the Debye relaxation model, a relaxation time constant was found to increase from 1.77 to 4.83 ps when the water molecule was cooled from 50 to 0 °C. An activation energy of ˜15 kJ/mol, which was in close agreement with a hydrogen-bonding energy, was further extracted from the Arrhenius analysis. Combined with previous molecular dynamics simulations, our results indicate that the reorientation relaxation originated from the "flip-flop" rotation of a three hydrogen-bonded surface-adsorbed water molecule.

  12. Plasma-induced conversion of surface-adsorbed hydrocarbons

    SciTech Connect

    Sackinger, W.M.

    1992-07-01

    Experimental results are reported for an electrical device for direct conversion of methane into higher hydrocarbons. A microchannel plate is excited with electrons from a photoemissive source, and electron impact ionization of methane on the inner surfaces of the microchannels creates an ion feedback process. The resulting low-density plasma creates higher hydrocarbons when charged particles impact the surfaces at grazing incidence. The production Of C{sub 2} to C{sub 8}-containing gases was noted, with a selectivity for C{sub 2} of 39% in one case. The proportions of converted products and the conversion rates depend upon the electrical voltage, the microchannel geometry, and the operating pressure. Conversion rates increase with operating pressure.

  13. Plasma-induced conversion of surface-adsorbed hydrocarbons

    SciTech Connect

    Sackinger, W.M.

    1992-01-01

    Experimental results are reported for an electrical device for direct conversion of methane into higher hydrocarbons. A microchannel plate is excited with electrons from a photoemissive source, and electron impact ionization of methane on the inner surfaces of the microchannels creates an ion feedback process. The resulting low-density plasma creates higher hydrocarbons when charged particles impact the surfaces at grazing incidence. The production Of C{sub 2} to C{sub 8}-containing gases was noted, with a selectivity for C{sub 2} of 39% in one case. The proportions of converted products and the conversion rates depend upon the electrical voltage, the microchannel geometry, and the operating pressure. Conversion rates increase with operating pressure.

  14. Adsorbed serum albumin is permissive to macrophage attachment to perfluorocarbon polymer surfaces in culture

    PubMed Central

    Godek, M.L.; Michel, R.; Chamberlain, L. M.; Castner, D. G.; Grainger, D.W.

    2013-01-01

    Monocyte/macrophage adhesion to biomaterials, correlated with foreign body response, occurs through protein-mediated surface interactions. Albumin-selective perfluorocarbon (FC) biomaterials are generally poorly cell-conducive due to insufficient receptor-mediated surface interactions, but macrophages bind to albumin-coated substrates and also preferentially to highly hydrophobic fluorinated surfaces. Bone marrow macrophages (BMMO) and IC-21, RAW 264.7 and J774A.1 monocyte/macrophage cells were cultured on FC surfaces. Protein deposition onto two distinct FC surfaces from complex and single-component solutions was tracked using fluorescence and time-of-flight secondary ion mass spectrometry (ToF-SIMS) methods. Cell adhesion and growth on protein pre-treated substrates were compared by light microscopy. Flow cytometry and integrin-directed antibody receptor blocking assessed integrins critical for monocyte/macrophage adhesion in vitro. Albumin predominantly adsorbs onto both FC surfaces from 10% serum. In cultures pre-adsorbed with albumin or serum-dilutions, BMMO responded similar to IC-21 at early time points. Compared to Teflon® AF, plasma-polymerized FC was less permissive to extended cell proliferation. The β2 integrins play major roles in macrophage adhesion to FC surfaces: antibody blocking significantly disrupted cell adhesion. Albumin-mediated cell adhesion mechanisms to FC surfaces could not be clarified. Primary BMMO and secondary IC-21 macrophages behave similarly on FC surfaces, regardless of pre-adsorbed protein biasing, with respect to adhesion, cell morphology, motility and proliferation. PMID:18306309

  15. Immobilization of DNA at Glassy Ccarbon Electrodes: A Critical Study of Adsorbed Layer

    PubMed Central

    Pedano, M. L.; Rivas, G. A.

    2005-01-01

    In this work we present a critical study of the nucleic acid layer immobilized at glassy carbon electrodes. Different studies were performed in order to assess the nature of the interaction between DNA and the electrode surface. The adsorption and electrooxidation of DNA demonstrated to be highly dependent on the surface and nature of the glassy carbon electrode. The DNA layer immobilized at a freshly polished glassy carbon electrode was very stable even after applying highly negative potentials. The electron transfer of potassium ferricyanide, catechol and dopamine at glassy carbon surfaces modified with thin (obtained by adsorption under controlled potential conditions) and thick (obtained by casting the glassy carbon surface with highly concentrated DNA solutions) DNA layers was slower than that at the bare glassy carbon electrode, although this effect was dependent on the thickness of the layer and was not charge selective. Raman experiments showed an important decrease of the vibrational modes assigned to the nucleobases residues, suggesting a strong interaction of these residues with the electrode surface. The hybridization of oligo(dG)21 and oligo(dC)21 was evaluated from the guanine oxidation signal and the reduction of the redox indicator Co(phen)33+. In both cases the chronopotentiometric response indicated that the compromise of the bases in the interaction of DNA with the electrode surface is too strong, preventing further hybridization. In summary, glassy carbon is a useful electrode material to detect DNA in a direct and very sensitive way, but not to be used for the preparation of biorecognition layers by direct adsorption of the probe sequence on the electrode surface for detecting the hybridization event.

  16. Many-body dispersion effects in the binding of adsorbates on metal surfaces

    SciTech Connect

    Maurer, Reinhard J.; Ruiz, Victor G.; Tkatchenko, Alexandre

    2015-09-14

    A correct description of electronic exchange and correlation effects for molecules in contact with extended (metal) surfaces is a challenging task for first-principles modeling. In this work, we demonstrate the importance of collective van der Waals dispersion effects beyond the pairwise approximation for organic–inorganic systems on the example of atoms, molecules, and nanostructures adsorbed on metals. We use the recently developed many-body dispersion (MBD) approach in the context of density-functional theory [Tkatchenko et al., Phys. Rev. Lett. 108, 236402 (2012) and Ambrosetti et al., J. Chem. Phys. 140, 18A508 (2014)] and assess its ability to correctly describe the binding of adsorbates on metal surfaces. We briefly review the MBD method and highlight its similarities to quantum-chemical approaches to electron correlation in a quasiparticle picture. In particular, we study the binding properties of xenon, 3,4,9,10-perylene-tetracarboxylic acid, and a graphene sheet adsorbed on the Ag(111) surface. Accounting for MBD effects, we are able to describe changes in the anisotropic polarizability tensor, improve the description of adsorbate vibrations, and correctly capture the adsorbate–surface interaction screening. Comparison to other methods and experiment reveals that inclusion of MBD effects improves adsorption energies and geometries, by reducing the overbinding typically found in pairwise additive dispersion-correction approaches.

  17. Effect of the internal motions of an adsorbate on the characteristics of adsorption for structurally heterogenous surfaces of slit-like pores

    NASA Astrophysics Data System (ADS)

    Tovbin, Yu. K.; Zaitseva, E. S.; Rabinovich, A. B.

    2016-01-01

    The effect of internal motions of an adsorbate on the local characteristics of adsorption and layering phase diagrams are studied for structurally heterogeneous surfaces of slit-like pores. A molecular model describing adsorbate distributions inside slit-like pores, which is based on discrete distribution functions (lattice gas model), is used for the calculation. Molecular distributions are calculated by the Lennard-Jones potential (12-6) in a quasi-chemical approximation reflecting the effects of direct correlations of interacting particles and for the combined interaction of an adsorbate with walls in the average potential approximation (9-3) and the short-range Lennard-Jones potential for structurally heterogeneous surface areas. The conclusion is made that internal motions reflect the vibrational motion of molecules within a modified quasi-dimer model and a displacement of the adsorbate during its translational motion inside cells. It was found that the taking into account of internal motions decreases the critical temperature of adsorbate layering in slit-like pores.

  18. Static and dynamic properties of tethered chains at adsorbing surfaces: A Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Descas, Radu; Sommer, Jens-Uwe; Blumen, Alexander

    2004-05-01

    We present extensive Monte Carlo simulations of tethered chains of length N on adsorbing surfaces, considering the dilute case in good solvents, and analyze our results using scaling arguments. We focus on the mean number M of chain contacts with the adsorbing wall, on the chain's extension (the radius of gyration) perpendicular and parallel to the adsorbing surface, on the probability distribution of the free end and on the density profile for all monomers. At the critical adsorption strength ɛc one has Mc˜Nφ, and we find (using the above results) as best candidate φ to equal 0.59. However, slight changes in the estimation of ɛc lead to large deviations in the resulting φ; this might be a possible reason for the difference in the φ values reported in the literature. We also investigate the dynamical scaling behavior at ɛc, by focusing on the end-to-end correlation function and on the correlation function of monomers adsorbed at the wall. We find that at ɛc the dynamic scaling exponent a (which describes the relaxation time of the chain as a function of N) is the same as that of free chains. Furthermore, we find that for tethered chains the modes perpendicular to the surface relax quicker than those parallel to it, which may be seen as a splitting in the relaxation spectrum.

  19. Radiation-induced reactions of amino acids adsorbed on solid surfaces

    NASA Astrophysics Data System (ADS)

    López-Esquivel Kranksith, L.; Negrón-Mendoza, A.; Mosqueira, F. G.; Ramos-Bernal, Sergio

    2010-07-01

    The purpose of this work is to study the adsorption of compounds such as amino acids on clays and carbon nanotubes (CNTs) as a possible phase in the chemical evolution that may have occurred on the primitive Earth or in extraterrestrial environments. We further study the behavior of amino acids adsorbed on these solid surfaces at different conditions of pH and levels of irradiation, simulating a high-radiation field at early Earth conditions. The relevance of this work is to explain the possible contribution of solids (clays and CNTs) as promoters of polymerization and as shields for the adsorbed organic compounds against external sources of energy. To this end, tryptophan, aspartic acid, and glutamic acid were adsorbed on fixed amounts of solid surfaces and were irradiated by a 60Co source for different periods of time at fixed dose rates. After irradiation, the amino acids were extracted from the solid and analyzed with UV and IR spectroscopes and high-performance liquid chromatography. The most efficient surface for adsorption of amino acids was clay, followed by CNTs. Studies of the gamma irradiation of amino acids adsorbed on clay (in the solid phase) show a low yield of recovery of the amino acid.

  20. INTRODUCTION: Surface Dynamics, Phonons, Adsorbate Vibrations and Diffusion

    NASA Astrophysics Data System (ADS)

    Bruch, L. W.

    2004-07-01

    understanding of the underlying factors determining the optical quality of GaInNAs, such as composition, growth and annealing conditions. We are still far from establishing an understanding of the band structure and its dependence on composition. Fundamental electronic interactions such as electron-electron and electron-phonon scattering, dependence of effective mass on composition, strain and orientation, quantum confinement effects, effects of localized nitrogen states on high field transport and on galvanometric properties, and mechanisms for light emission in these materials, are yet to be fully understood. Nature and formation mechanisms of grown-in and processing-induced defects that are important for material quality and device performance are still unknown. Such knowledge is required in order to design strategies to efficiently control and eliminate harmful defects. For many potential applications (such as solar cells, HBTs) it is essential to get more information on the transport properties of dilute nitride materials. The mobility of minority carriers is known to be low in GaInNAs and related material. The experimental values are far from reaching the theoretical ones, due to defects and impurities introduced in the material during the growth. The role of the material inhomogeneities on the lateral carrier transport also needs further investigation. From the device's point of view most attention to date has been focused on the GaInNAs/GaAs system, mainly because of its potential for optoelectronic devices covering the 1.3-1.55 µm data and telecommunications wavelength bands. As is now widely appreciated, these GaAs-compatible structures allow monolithic integration of AlGaAs-based distributed Bragg reflector mirrors (DBRs) for vertical cavity surface-emitting lasers with low temperature sensitivity and compatibility with AlOx-based confinement techniques. In terms of conventional edge-emitting lasers (EELs), the next step is to extend the wavelength range for cw room

  1. Halide anion effect on surface enhanced Raman scattering of 2-amino,5-nitropyridine adsorbed on silver sols

    NASA Astrophysics Data System (ADS)

    Muniz-Miranda, Maurizio; Neto, Natale; Sbrana, Giuseppe

    1995-03-01

    2-Amino,5-nitropiridine (ANP) can be adsorbed on silver sols as neutral molecule or ANP- anion, as detected by SERS. The adsorption of the ANP- is related to the presence of hydroxide ions on the metal surface. Strongly adsorbed halide anions are able to remove hydroxide ions from the silver surface, inducing the adsorption of ANP as neutral molecule.

  2. NMR study of Li adsorbed on the Si (111) - (3×1) -Li surface

    NASA Astrophysics Data System (ADS)

    Bromberger, C.; Jänsch, H. J.; Kühlert, O.; Schillinger, R.; Fick, D.

    2004-06-01

    Li adsorption on the (3×1) -Li reconstructed Si(111) surface has been studied by β -nuclear magnetic resonance experiments (measurements of T1 times). A rich variety of temperature, coverage, and magnetic field dependencies were observed, which reflect a metal-semiconductor-metal transition while adsorbing Li with increasing coverage on a (7×7) -reconstructed Si(111) surface in such a way that the (3×1) reconstruction is driven. With the aid of a formulated concept of Li donors localized on a semiconducting surface the temperature dependence of relaxation rates for Li adsorbed at extremely low coverages (up to 0.01 ML ) could be understood consistently. The donor energy of adsorbed Li on the (3×1) surface has been determined to be ED ≈100 meV . This success proves additionally that the theoretical results of a completely ionized Li chain in the (3×1) reconstruction are correct. The observed semiconductor-metal transition for adsorption of 0.14 ML additional Li on the already (3×1) -reconstructed surface points to the existence of an empty state near the Fermi energy (probably the so-called S-1 state). The diffusion energy of Li on the Si (111) - (3×1) surface could be estimated to be Ediff ≈410 meV .

  3. INTRODUCTION: Surface Dynamics, Phonons, Adsorbate Vibrations and Diffusion

    NASA Astrophysics Data System (ADS)

    Bruch, L. W.

    2004-07-01

    understanding of the underlying factors determining the optical quality of GaInNAs, such as composition, growth and annealing conditions. We are still far from establishing an understanding of the band structure and its dependence on composition. Fundamental electronic interactions such as electron-electron and electron-phonon scattering, dependence of effective mass on composition, strain and orientation, quantum confinement effects, effects of localized nitrogen states on high field transport and on galvanometric properties, and mechanisms for light emission in these materials, are yet to be fully understood. Nature and formation mechanisms of grown-in and processing-induced defects that are important for material quality and device performance are still unknown. Such knowledge is required in order to design strategies to efficiently control and eliminate harmful defects. For many potential applications (such as solar cells, HBTs) it is essential to get more information on the transport properties of dilute nitride materials. The mobility of minority carriers is known to be low in GaInNAs and related material. The experimental values are far from reaching the theoretical ones, due to defects and impurities introduced in the material during the growth. The role of the material inhomogeneities on the lateral carrier transport also needs further investigation. From the device's point of view most attention to date has been focused on the GaInNAs/GaAs system, mainly because of its potential for optoelectronic devices covering the 1.3-1.55 µm data and telecommunications wavelength bands. As is now widely appreciated, these GaAs-compatible structures allow monolithic integration of AlGaAs-based distributed Bragg reflector mirrors (DBRs) for vertical cavity surface-emitting lasers with low temperature sensitivity and compatibility with AlOx-based confinement techniques. In terms of conventional edge-emitting lasers (EELs), the next step is to extend the wavelength range for cw room

  4. The Impact of Adsorbed Triethylene Glycol on Water Wettability of the {1014} Calcium Carbonate Surface

    NASA Astrophysics Data System (ADS)

    Olsen, R.

    2015-12-01

    Water flooding is increasingly being used as a method of enhanced oil recovery and frequently involves calcium carbonate reservoirs. Very often, thermodynamic conditions in the upper few hundred meters allow for hydrate formation. One possible method of preventing hydrates is to inject hydrate inhibitors such as triethylene glycol (TEG) into the reservoir. Thus, it is of importance to know how such glycols affect water wettability, which is an important factor defining the oil behavior in such reservoirs. Wettability of a surface is defined by the contact angle of a liquid drop on the surface. The stronger the liquid is attracted to the surface, the smaller the wetting angle becomes, implying an increased degree of wetting. Therefore, it is possible to gain qualitative knowledge of the change in wetting properties with respect to external influences by studying corresponding changes in free energy of adsorption of the liquid. In our work [1], we used molecular dynamics (MD) and Born-Oppenheimer molecular dynamics (BOMD) to study how adsorbed TEG on the {1014} calcium carbonate surface affected adsorbed water. We used the changes in density profiles of water to estimate changes in adsorption free energy of water. The adaptive biasing force (ABF) method was applied to TEG to calculate the adsorption free energy of TEG on the calcium carbonate surface. We found that water wetting of the calcium carbonate surface decreased in the presence of adsorbed TEG. [1] - Olsen, R.; Leirvik, K.; Kvamme, B.; Kuznetsova, T. Adsorption Properties of Triethylene Glycol on a Hydrated {1014} Calcite Surface and Its Effect on Adsorbed Water, Langmuir 2015, DOI: 10.1021/acs.langmuir.5b02228

  5. Layer by layer removal of Au atoms from passivated Au(111) surfaces using the scanning tunneling microscope: Nanoscale ``paint stripping''

    NASA Astrophysics Data System (ADS)

    Keel, J. M.; Yin, J.; Guo, Q.; Palmer, R. E.

    2002-04-01

    Layer by layer removal of gold atoms from the (111) surface of gold has been performed using the scanning tunneling microscope. The process is made possible by a chemisorbed self-assembled monolayer (SAM) of dodecanethiol molecules on the surface, which gives rise to a reduced bonding strength between the top two layers of gold atoms. The gold atoms and associated adsorbed molecules are peeled off and displaced laterally by the STM tip, and the size of the modified area (down to ˜10×10 nm) is more or less determined by the scan size.

  6. Structure analysis and photochemistry of adsorbates on platinum and palladium surfaces. [1,2-dichloroethene

    SciTech Connect

    Grassian, V.H.

    1987-05-01

    The vibrational spectra of benzene and toluene adsorbed on Pd(111) indicates at 180K these molecules weakly bond to the surface. The adsorption of benzene and toluene on Pt(111) is much stronger as indicated by large frequency shifts from gas phase values. Pyridine adsorption on both Pt(111) and Pd(111) was studied as a function of temperature. At room temperature pyridine decomposes on the surface to form an ..cap alpha..-pyridyl fragment (NC/sub 5/H/sub 4/) on Pt(111), whereas the molecule remains intact on Pd(111). The electron energy loss spectra of pyridine adsorbed on these surfaces is compared to the ir spectra of two osmium cluster compounds: Os/sub 3/(CO)/sub 11/(NC/sub 5/H/sub 5/), a pyridine complex, and HOs/sub 3/(CO)/sub 10/(NC/sub 5/H/sub 4/), a pyridyl complex. The stronger interaction of these molecules to the platinum surface is a consequence of the stronger bonding of the 5d orbitals as compared to the 4d orbitals. The uv photochemistry of 2-butene and 1,2-dichloroethene when adsorbed on Pt and Pd surfaces was also studied.

  7. Structure and friction of stearic acid and oleic acid films adsorbed on iron oxide surfaces in squalane.

    PubMed

    Doig, Michael; Warrens, Chris P; Camp, Philip J

    2014-01-14

    The structure and friction of fatty acid surfactant films adsorbed on iron oxide surfaces lubricated by squalane are examined using large-scale molecular dynamics simulations. The structures of stearic acid and oleic acid films under static and shear conditions, and at various surface coverages, are described in detail, and the effects of unsaturation in the tail group are highlighted. At high surface coverage, the measured properties of stearic acid and oleic acid films are seen to be very similar. At low and intermediate surface coverages, the presence of a double bond, as in oleic acid, is seen to give rise to less penetration of lubricant in to the surfactant film and less layering of the lubricant near to the film. The kinetic friction coefficient is measured as a function of shear rate within the hydrodynamic (high shear rate) lubrication regime. Lubricant penetration and layering are observed to be correlated with friction coefficient. The friction coefficient with oleic acid depends only weakly on surface coverage, while stearic acid admits more lubricant penetration, and its friction coefficient increases significantly with decreasing surface coverage. Connections between film structure and friction are discussed. PMID:24364665

  8. Efficient removal of dyes by a novel magnetic Fe3O4/ZnCr-layered double hydroxide adsorbent from heavy metal wastewater.

    PubMed

    Chen, Dan; Li, Yang; Zhang, Jia; Li, Wenhui; Zhou, Jizhi; Shao, Li; Qian, Guangren

    2012-12-01

    A novel magnetic Fe(3)O(4)/ZnCr-layered double hydroxide adsorbent was produced from electroplating wastewater and pickling waste liquor via a two-step microwave hydrothermal method. Adsorption of methyl orange (MO) from water was studied using this material. The effects of three variables have been investigated by a single-factor method. The response surface methodology (RSM) based on Box-Behnken design was successfully applied to the optimization of the preparation conditions. The maximum adsorption capacity of MO was found to be 240.16 mg/g, indicating that this material may be an effective adsorbent. It was shown that 99% of heavy metal ions (Fe(2+), Fe(3+), Cr(3+), and Zn(2+)) can be effectively removed into precipitates and released far less in the adsorption process. In addition, this material with adsorbed dye can be easily separated by a magnetic field and recycled after catalytic regeneration with advanced oxidation technology. Meanwhile, kinetic models, FTIR spectra and X-ray diffraction pattern were applied to the experimental data to examine uptake mechanism. The boundary layer and intra-particle diffusion played important roles in the adsorption mechanisms. PMID:23122732

  9. Product development studies on surface-adsorbed nanoemulsion of olmesartan medoxomil as a capsular dosage form.

    PubMed

    Singh, Sumita; Pathak, Kamla; Bali, Vikas

    2012-12-01

    The present study aimed at development of capsular dosage form of surface-adsorbed nanoemulsion (NE) of olmesartan medoxomil (OLM) so as to overcome the limitations associated with handling of liquid NEs without affecting their pharmaceutical efficacy. Selection of oil, surfactant, and cosurfactant for construction of pseudoternary phase diagrams was made on the basis of solubility of drug in these excipients. Rationally selected NE formulations were evaluated for percentage transmittance, viscosity, refractive index, globule size, zeta potential, and polydispersity index (PDI). Formulation (F3) comprising of Capmul MCM® (10% v/v), Tween 80® (11.25% v/v), polyethylene glycol 400 (3.75% v/v), and double-distilled water (75% v/v) displayed highest percentage cumulative drug release (%CDR; 96.69 ± 1.841), least globule size (17.51 ± 5.87 nm), low PDI (0.203 ± 0.032), high zeta potential (-58.93 ± 0.98 mV), and hence was selected as the optimized formulation. F3 was adsorbed over colloidal silicon dioxide (2 ml/400 mg) to produce free-flowing solid surface-adsorbed NE that presented a ready-to-fill capsule composition. Conversion of NE to surface-adsorbed NE and its reconstitution to NE did not affect the in vitro release profile of OLM as the similarity factor with respect to NE was found to be 66% and 73% respectively. The %CDR after 12 h for optimized NE, surface-adsorbed NE, and reconstituted NE was found to be 96.69 ± 0.54, 96.07 ± 1.76, and 94.78 ± 1.57, respectively (p > 0.05). The present study established capsulated surface-adsorbed NE as a viable delivery system with the potential to overcome the handling limitations of NE. PMID:22965661

  10. Surface enhanced Raman scattering of new acridine based fluorophore adsorbed on silver electrode

    NASA Astrophysics Data System (ADS)

    Solovyeva, Elena V.; Myund, Liubov A.; Denisova, Anna S.

    2015-10-01

    4,5-Bis(N,N-di(2-hydroxyethyl)iminomethyl)acridine (BHIA) is a new acridine based fluoroionophore and a highly-selective sensor for cadmium ion. The direct interaction of the aromatic nitrogen atom with a surface is impossible since there are bulky substituents in the 4,5-positions of the acridine fragment. Nevertheless BHIA molecule shows a reliable SERS spectrum while adsorbed on a silver electrode. The analysis of SERS spectra pH dependence reveals that BHIA species adsorbed on a surface can exist in both non-protonated and protonated forms. The adsorption of BHIA from alkaline solution is accompanied by carbonaceous species formation at the surface. The intensity of such "carbon bands" turned out to be related with the supporting electrolyte (KCl) concentration. Upon lowering the electrode potential the SERS spectra of BHIA do not undergo changes but the intensity of bands decreases. This indicates that the adsorption mechanism on the silver surface is realized via aromatic system of acridine fragment. In case of such an adsorption mechanism the chelate fragment of the BHIA molecule is capable of interaction with the solution components. Addition of Cd2+ ions to a system containing BHIA adsorbed on a silver electrode in equilibrium with the solution leads to the formation of BHIA/Cd2+ complex which desorption causes the loss of SERS signal.

  11. Electrohydrodynamic manipulation of particles adsorbed on the surface of a drop.

    PubMed

    Amah, Edison; Shah, Kinnari; Fischer, Ian; Singh, Pushpendra

    2016-02-14

    In our previous studies we have shown that particles adsorbed on the surface of a drop can be concentrated at its poles or equator by applying a uniform electric field. This happens because even when the applied electric field is uniform the electric field on the surface of the drop is nonuniform, and so particles adsorbed on the surface are subjected to dielectrophoretic (DEP) forces. In this paper, we study the behavior of adsorbed particles at low electric field frequencies when the drop and ambient liquids are weakly conducting dielectric liquids, and model it using a leaky dielectric model. The electrohydrodynamic (EHD) flow which arises because of the accumulation of charge on the surface of the drop can be from pole-to-equator or equator-to-pole depending on the properties of the drop and ambient liquids. The flow however diminishes with increasing frequency and there is a critical frequency at which the drag force on a particle due to the EHD flow becomes equal to the DEP force, and above this critical frequency the DEP force dominates. When the fluid and particles properties are such that the EHD and DEP forces are in the opposite directions, particles can be collected at the poles or the equator, and also can be moved from the poles to the equator, or vice versa, by varying the frequency. Also, it is possible to separate the particles of a binary mixture when the critical frequencies of the two types of particles are different. PMID:26679523

  12. Surface enhanced Raman scattering of new acridine based fluorophore adsorbed on silver electrode.

    PubMed

    Solovyeva, Elena V; Myund, Liubov A; Denisova, Anna S

    2015-10-01

    4,5-Bis(N,N-di(2-hydroxyethyl)iminomethyl)acridine (BHIA) is a new acridine based fluoroionophore and a highly-selective sensor for cadmium ion. The direct interaction of the aromatic nitrogen atom with a surface is impossible since there are bulky substituents in the 4,5-positions of the acridine fragment. Nevertheless BHIA molecule shows a reliable SERS spectrum while adsorbed on a silver electrode. The analysis of SERS spectra pH dependence reveals that BHIA species adsorbed on a surface can exist in both non-protonated and protonated forms. The adsorption of BHIA from alkaline solution is accompanied by carbonaceous species formation at the surface. The intensity of such "carbon bands" turned out to be related with the supporting electrolyte (KCl) concentration. Upon lowering the electrode potential the SERS spectra of BHIA do not undergo changes but the intensity of bands decreases. This indicates that the adsorption mechanism on the silver surface is realized via aromatic system of acridine fragment. In case of such an adsorption mechanism the chelate fragment of the BHIA molecule is capable of interaction with the solution components. Addition of Cd(2+) ions to a system containing BHIA adsorbed on a silver electrode in equilibrium with the solution leads to the formation of BHIA/Cd(2+) complex which desorption causes the loss of SERS signal. PMID:25956332

  13. Molecular orientation of rhodamine dyes on surfaces of layered silicates.

    PubMed

    Bujdák, Juraj; Iyi, Nobuo

    2005-03-17

    Films of the layered silicates fluorohectorite (FH) and saponite (Sap) with various rhodamine dyes were prepared. The dyes with acidic as well as large hydrophobic groups in their molecule were not adsorbed on the surface of FH, which was interpreted in terms of high charge density on the surface of this silicate. All adsorbed dyes formed similar forms, such as isolated cations and H-type molecular aggregates, which were characterized by different spectral properties. Polarized ultraviolet-visible (UV-vis) spectroscopy was used for the characterization of the molecular orientation of dye chromophores on the silicate surface. The isolated dye cations and species, which absorbed light at the low energy part of the spectra, were only slightly tilted with respect to the plane of the silicate surface. The cations forming H-aggregates and absorbing light at low wavelengths were oriented in a nearly perpendicular fashion. The nearly perpendicular orientation was observed as a strong increase of dichroic ratio with film tilting. The orientation of the cations in H-aggregates depends partially on the structure of the dye molecule, namely, on the type of amino group (primary, secondary, or tertiary) in the dye molecule. The type of amino groups probably plays a role in the suitable orientation of dye cations for effective electrostatic interaction between the cations and the negatively charged siloxane surface. X-ray powder diffraction could not distinguish dye phases of dye monomers and molecular aggregates. PMID:16851539

  14. TOF-SIMS measurements for toxic air pollutants adsorbed on the surface of airborne particles

    NASA Astrophysics Data System (ADS)

    Tomiyasu, Bunbunoshin; Hoshi, Takahiro; Owari, Masanori; Nihei, Yoshimasa

    2003-01-01

    Three kinds of particulate matter were collected: diesel and gasoline exhaust particles emitted directly from exhaust nozzle, and suspended particulate matter (SPM) near the traffic route. Soxhlet extraction was performed on each sample. By gas-chromatograph-mass spectrometer (GC-MS) analysis of these extracts, di-ethyl phthalate and di- n-butyl phthalate were detected from the extract of SPM and diesel exhaust particles (DEPs). Because these phthalates were sometimes suspected as contamination, time-of-flight secondary ion mass spectrometry (TOF-SIMS) measurements were also performed on the samples collected at the same environment. By comparing obtained spectra, it is clear that these environmental endocrine disrupters (EEDs) were adsorbed on DEP surface. Thus, we concluded that the combination of conventional method and TOF-SIMS measurement is one of the most powerful techniques for analyzing the toxic air pollutants adsorbed on SPM surface.

  15. Adsorbed Natural Gas Storage in Optimized High Surface Area Microporous Carbon

    NASA Astrophysics Data System (ADS)

    Romanos, Jimmy; Rash, Tyler; Nordwald, Erik; Shocklee, Joshua Shawn; Wexler, Carlos; Pfeifer, Peter

    2011-03-01

    Adsorbed natural gas (ANG) is an attractive alternative technology to compressed natural gas (CNG) or liquefied natural gas (LNG) for the efficient storage of natural gas, in particular for vehicular applications. In adsorbants engineered to have pores of a few molecular diameters, a strong van der Walls force allows reversible physisorption of methane at low pressures and room temperature. Activated carbons were optimized for storage by varying KOH:C ratio and activation temperature. We also consider the effect of mechanical compression of powders to further enhance the volumetric storage capacity. We will present standard porous material characterization (BET surface area and pore-size distribution from subcritical N2 adsorption) and methane isotherms up to 250 bar at 293K. At sufficiently high pressure, specific surface area, methane binding energy and film density can be extracted from supercritical methane adsorption isotherms. Research supported by the California Energy Commission (500-08-022).

  16. A Template-Free, Ultra-Adsorbing, High Surface Area Carbonate Nanostructure

    PubMed Central

    Grandfield, Kathryn; Mihranyan, Albert; Strømme, Maria

    2013-01-01

    We report the template-free, low-temperature synthesis of a stable, amorphous, and anhydrous magnesium carbonate nanostructure with pore sizes below 6 nm and a specific surface area of ∼ 800 m2 g−1, substantially surpassing the surface area of all previously described alkali earth metal carbonates. The moisture sorption of the novel nanostructure is featured by a unique set of properties including an adsorption capacity ∼50% larger than that of the hygroscopic zeolite-Y at low relative humidities and with the ability to retain more than 75% of the adsorbed water when the humidity is decreased from 95% to 5% at room temperature. These properties can be regenerated by heat treatment at temperatures below 100°C.The structure is foreseen to become useful in applications such as humidity control, as industrial adsorbents and filters, in drug delivery and catalysis. PMID:23874640

  17. Self-avoiding walks adsorbed at a surface and subject to a force

    NASA Astrophysics Data System (ADS)

    Janse van Rensburg, E. J.; Whittington, S. G.

    2016-06-01

    We consider self-avoiding walks terminally attached to an impenetrable surface at which they can adsorb. We call the vertices farthest away from this plane the top vertices and we consider applying a force at the plane containing the top vertices. This force can be directed away from the adsorbing surface or towards it. In both cases we prove that the free energy (in the thermodynamic limit) is identical to the free energy when the force is applied at the last vertex. This means that the criterion determining the critical force—temperature curve is identical for the two ways in which the force is applied and the response to pushing the walk is also the same in the two cases. Dedicated to Tony Guttmann on the occasion of his 70th birthday.

  18. NMR Study of Phase Transitions in Pure Water and Binary H(2)O/HNO(3) Films Adsorbed on Surface of Pyrogenic Silica.

    PubMed

    Bogdan; Kulmala; Gorbunov; Kruppa

    1996-01-15

    Pyrogenic silica (aerosil) was employed as host within which the phase transitions in the adsorbed pure water and binary H(2)O/HNO(3) films have been studied with NMR spectroscopy. The median freezing temperature and freezing temperature region were shown to be highly sensitive both to the average thickness of the adsorbed films and to the amount of adsorbed nitric acid. The molar concentration of nitric acid in the adsorbed films was found to be very small, on the order of 10(-3)-10(-2) (M/liter). The concentration was found to be greater in the layers adjacent to the surface of silica and sharply decreases with distance from the surface. The difference between the median freezing temperatures for adsorbed pure water and for the binary system was found to be about 9 K for films of equal thickness. This is about 150 times greater than the difference between the freezing temperatures of bulk pure water and a solution with the same concentration of nitric acid. PMID:10479419

  19. Uncertainties in Surface Layer Modeling

    NASA Astrophysics Data System (ADS)

    Pendergrass, W.

    2015-12-01

    A central problem for micrometeorologists has been the relationship of air-surface exchange rates of momentum and heat to quantities that can be predicted with confidence. The flux-gradient profile developed through Monin-Obukhov Similarity Theory (MOST) provides an integration of the dimensionless wind shear expression where is an empirically derived expression for stable and unstable atmospheric conditions. Empirically derived expressions are far from universally accepted (Garratt, 1992, Table A5). Regardless of what form of these relationships might be used, their significance over any short period of time is questionable since all of these relationships between fluxes and gradients apply to averages that might rarely occur. It is well accepted that the assumption of stationarity and homogeneity do not reflect the true chaotic nature of the processes that control the variables considered in these relationships, with the net consequence that the levels of predictability theoretically attainable might never be realized in practice. This matter is of direct relevance to modern prognostic models which construct forecasts by assuming the universal applicability of relationships among averages for the lower atmosphere, which rarely maintains an average state. Under a Cooperative research and Development Agreement between NOAA and Duke Energy Generation, NOAA/ATDD conducted atmospheric boundary layer (ABL) research using Duke renewable energy sites as research testbeds. One aspect of this research has been the evaluation of legacy flux-gradient formulations (the ϕ functions, see Monin and Obukhov, 1954) for the exchange of heat and momentum. At the Duke Energy Ocotillo site, NOAA/ATDD installed sonic anemometers reporting wind and temperature fluctuations at 10Hz at eight elevations. From these observations, ϕM and ϕH were derived from a two-year database of mean and turbulent wind and temperature observations. From this extensive measurement database, using a

  20. Optical second harmonic spectroscopy of silicon-adsorbate surfaces and silicon nanocrystals

    NASA Astrophysics Data System (ADS)

    Downer, Michael

    2002-03-01

    Second harmonic generation (SHG) provides a surface-specific, noninvasive probe of adsorbates. However, microscopic first-principles theory of adsorbate-specific spectroscopic SHG responses has proven elusive. Here we present experimental SHG spectra for six well-characterized, technologically important Si(001) surfaces in ultrahigh vacuum (UHV): clean Si(001)-2x1 and Si(001) terminated with hydrogen (H), [1] germanium (Ge), Ge and H, [2] boron (B) and B and H. [3] Each adsorbate (combination) alters SHG uniquely. Our microscopic theories based on ab initio pseudopotential or semi-empirical tight-binding (SETB) methods then explain observed trends, and predict new features in unexplored spectral regions. [3,4] Charge transfer among surface bonds is found to govern SHG spectroscopy of surface-adsorbate systems strongly. New results on SHG from Si nanocrystals embedded in SiO2 will also be presented. [5] SHG is sensitive to Si/SiO2 interface states, electrostatic charge on the nanocrystals, and macroscopic particle density gradients. Finally, a new frequency-domain interferometric second-harmonic (FDISH) spectroscopic technique to measure simultaneously the intensity and phase of SH radiation over a broad spectral range without laser tuning will be described. [6] 1. J. Dadap et al., Phys. Rev. B 56, 13367 (1997). 2. P. Parkinson et al., Appl. Phys. B 68, 641 (1999). 3. D. Lim et al., Phys. Rev. Lett. 84, 3406 (2000); Appl. Phys. Lett. 77, 181 (2000). 4. V. Gavrilenko et al., Phys. Rev. B 63, 1653 (2001); M. C. Downer et al., Surf. Interface Anal. 31, 966 (2001); M. C. Downer et al., phys. stat. sol. (a), in press (2001). 5. Y. Jiang et al., Appl. Phys. Lett. 78, 766 (2001). 6. P. T. Wilson et al., Opt. Lett. 24, 496 (1999).

  1. Removing adsorbed heavy metal ions from sand surfaces via applying interfacial properties of rhamnolipid.

    PubMed

    Haryanto, Bode; Chang, Chien-Hsiang

    2015-01-01

    In this study, the interfacial properties of biosurfactant rhamnolipid were investigated and were applied to remove adsorbed heavy metal ions from sand surfaces with flushing operations. The surface tension-lowering activity, micelle charge characteristic, and foaming ability of rhamnolipid were identified first. For rhamnolipid in water, the negatively charged characteristic of micelles or aggregates was confirmed and the foaming ability at concentrations higher than 40 mg/L was evaluated. By using the rhamnolipid solutions in a batch washing approach, the potential of applying the interfacial properties of rhamnolipid to remove adsorbed copper ions from sand surfaces was then demonstrated. In rhamnolipid solution flushing operations for sand-packed medium, higher efficiency was found for the removal of adsorbed copper ions with residual type than with inner-sphere interaction type, implying the important role of interaction type between the copper ion and the sand surface in the removal efficiency. In addition, the channeling effect of rhamnolipid solution flow in the sand-packed medium was clearly observed in the solution flushing operations and was responsible for the low removal efficiency with low contact areas between solution and sand. By using rhamnolipid solution with foam to flush the sand-packed medium, one could find that the channeling effect of the solution flow was reduced and became less pronounced with the increase in the rhamnolipid concentration, or with the enhanced foaming ability. With the reduced channeling effect in the flushing operations, the removal efficiency for adsorbed copper ions was significantly improved. The results suggested that the foam-enhanced rhamnolipid solution flushing operation was efficient in terms of surfactant usage and operation time. PMID:25748376

  2. Unsaturated hydrocarbons adsorbed on low coordinated Pd surface: A periodic DFT study

    NASA Astrophysics Data System (ADS)

    Belelli, Patricia G.; Ferullo, Ricardo M.; Castellani, Norberto J.

    2010-02-01

    In this work, the adsorption of several unsaturated hydrocarbon molecules on a stepped Pd(4 2 2) surface was studied. Using a periodic method based on the Density Functional Theory (DFT) formalism, different adsorption geometries for ethylene, three butene isomers ( cis/ trans-2-butene and 1-butene), acetylene and 2-butyne were investigated. The results were compared with those obtained for a free defect surface as Pd(1 1 1). The 1-butene is more stable on the free defect surface than on Pd(4 2 2). On the stepped surface, the olefins adsorb tilted towards the step and increases, in almost all the cases, the magnitude of the adsorption energy. Conversely, the 3-fold site is the most stable for the alkynes adsorption on the stepped surface, as it was found on Pd(1 1 1). The analysis of the dipole moment change indicate a charge transfer from the double bond of the olefin to the metallic surface, being higher for the Pd(1 1 1) surface. In case of the alkynes, an important back-donation is produced. Except the alkynes and the 1-butene molecule, the results show the preference of ethylene and cis/ trans-2-butene to be adsorbed on the stepped surface. These observations are related with experimental catalytic results.

  3. Electronic excited states as a probe of surface adsorbate structure and dynamics in liquid xenon

    SciTech Connect

    Peterson, E.S.

    1992-08-01

    A combination of second harmonic generation (SHG) and a simple dipole-dipole interaction model is presented as a new technique for determining adsorbate geometries on surfaces. The polarization dependence of SHG is used to define possible geometries of the adsorbate about the surface normal. Absorption band shifts using geometry constraints imposed by SHG data are derived for a dimer constructed from two arbitrarily placed monomers on the surface using the dipole-dipole interaction potential. These formulae can be used to determine the orientation of the two monomers relative to each other. A simplified version of this formalism is used to interpret absorption band shifts for rhodamine B adsorbed on fused silica. A brief history of the exciton is given with particular detail to Xe. Data are presented for transient absorption at RT in liquid xenon on the picosecond time scale. These are observations of both tunneling through the barrier that separates the free and trapped exciton states and the subsequent trapping of the exciton. In high densities both of these processes are found to occur within 2 to 6 picoseconds in agreement with theories of Kmiecik and Schreiber and of Martin. A threshold density is observed that separates relaxation via single binary collisions and relaxation that proceeds via Martin's resonant energy transfer hopping mechanism.

  4. Electronic excited states as a probe of surface adsorbate structure and dynamics in liquid xenon

    SciTech Connect

    Peterson, E.S.

    1992-08-01

    A combination of second harmonic generation (SHG) and a simple dipole-dipole interaction model is presented as a new technique for determining adsorbate geometries on surfaces. The polarization dependence of SHG is used to define possible geometries of the adsorbate about the surface normal. Absorption band shifts using geometry constraints imposed by SHG data are derived for a dimer constructed from two arbitrarily placed monomers on the surface using the dipole-dipole interaction potential. These formulae can be used to determine the orientation of the two monomers relative to each other. A simplified version of this formalism is used to interpret absorption band shifts for rhodamine B adsorbed on fused silica. A brief history of the exciton is given with particular detail to Xe. Data are presented for transient absorption at RT in liquid xenon on the picosecond time scale. These are observations of both tunneling through the barrier that separates the free and trapped exciton states and the subsequent trapping of the exciton. In high densities both of these processes are found to occur within 2 to 6 picoseconds in agreement with theories of Kmiecik and Schreiber and of Martin. A threshold density is observed that separates relaxation via single binary collisions and relaxation that proceeds via Martin`s resonant energy transfer hopping mechanism.

  5. Absorption cross sections of surface-adsorbed H2O in the 295-370 nm region and heterogeneous nucleation of H2O on fused silica surfaces.

    PubMed

    Du, Juan; Huang, Li; Zhu, Lei

    2013-09-12

    We have determined absorption cross sections of a monolayer of H2O adsorbed on the fused silica surfaces in the 295-370 nm region at 293 ± 1 K by using Brewster angle cavity ring-down spectroscopy. Absorption cross sections of surface-adsorbed H2O vary between (4.66 ± 0.83) × 10(-20) and (1.73 ± 0.52) × 10(-21) cm(2)/molecule over this wavelength range, where errors quoted represent experimental scatter (1σ). Our experimental study provides direct evidence that surface-adsorbed H2O is an absorber of the near UV solar radiation. We also varied the H2O pressure in the surface study cell over the 0.01-17 Torr range and obtained probe laser absorptions at 295, 340, and 350 nm by multilayer of adsorbed H2O molecules until the heterogeneous nucleation of water occurred on fused silica surfaces. The average absorption cross sections of multilayer adsorbed H2O are (2.17 ± 0.53) × 10(-20), (2.48 ± 0.67) × 10(-21), and (2.34 ± 0.59) × 10(-21) cm(2)/molecule at 295, 340, and 350 nm. The average absorption cross sections of transitional H2O layer are (6.06 ± 2.73) × 10(-20), (6.48 ± 3.85) × 10(-21), and (8.04 ± 4.92) × 10(-21) cm(2)/molecule at 295, 340, and 350 nm. The average thin water film absorption cross sections are (2.39 ± 0.50) × 10(-19), (3.21 ± 0.81) × 10(-20), and (3.37 ± 0.94) × 10(-20) cm(2)/molecule at 295 nm, 340 nm, and 350 nm. Atmospheric implications of the results are discussed. PMID:23947798

  6. Water molecules orientation in surface layer

    NASA Astrophysics Data System (ADS)

    Klingo, V. V.

    2000-08-01

    The water molecules orientation has been investigated theoretically in the water surface layer. The surface molecule orientation is determined by the direction of a molecule dipole moment in relation to outward normal to the water surface. Entropy expressions of the superficial molecules in statistical meaning and from thermodynamical approach to a liquid surface tension have been found. The molecules share directed opposite to the outward normal that is hydrogen protons inside is equal 51.6%. 48.4% water molecules are directed along to surface outward normal that is by oxygen inside. A potential jump at the water surface layer amounts about 0.2 volts.

  7. Controlling Catalytic Selectivity via Adsorbate Orientation on the Surface: From Furfural Deoxygenation to Reactions of Epoxides.

    PubMed

    Pang, Simon H; Medlin, J Will

    2015-04-16

    Specificity to desired reaction products is the key challenge in designing solid catalysts for reactions involving addition or removal of oxygen to/from organic reactants. This challenge is especially acute for reactions involving multifunctional compounds such as biomass-derived aromatic molecules (e.g., furfural) and functional epoxides (e.g., 1-epoxy-3-butene). Recent surface-level studies have shown that there is a relationship between adsorbate surface orientation and reaction selectivity in the hydrogenation pathways of aromatic oxygenates and the ring-opening or ring-closing pathways of epoxides. Control of the orientation of reaction intermediates on catalytic surfaces by modifying the surface or near-surface environment has been shown to be a promising method of affecting catalytic selectivity for reactions of multifunctional molecules. In this Perspective, we review recent model studies aimed at understanding the surface chemistry for these reactions and studies that utilize this insight to rationally design supported catalysts. PMID:26263134

  8. Vibrational dynamics of fullerene molecules adsorbed on metal surfaces studied with synchrotron infrared radiation

    SciTech Connect

    P. Rudolf; R. Raval; P. Dumas; Gwyn P. Williams

    2002-04-01

    Infrared (IR) spectroscopy of chemisorbed C{sub 60} on Ag (111), Au (110) and Cu (100) reveals that a non-IR-active mode becomes active upon adsorption, and that its frequency shifts proportionally with the charge transferred from the metal to the molecule by about 5 cm{sup -1} per electron. The temperature dependence of the frequency and the width of this IR feature have also been followed for C{sub 60>}/Cu (100) and were found to agree well with a weak anharmonic coupling (dephasing) to a low-frequency mode, which we suggest to be the frustrated translational mode of the adsorbed molecules.

    Additionally, the adsorption is accompanied by a broadband reflectance change, which is interpreted as due to the scattering of conduction electrons of the metal surface by the adsorbate. The reflectance change allows determination of the friction coefficient of the C{sub 60} molecules, which results in rather small values ({approx}2 x 10{sup 9}s{sup -1} for Ag and Au, and {approx}1.6 x 10{sup 9}s{sup -1} for Cu), consistent with a marked metallic character of the adsorbed molecules.

    Pre-dosing of alkali atoms onto the metal substrates drastically changes the IR spectra recorded during subsequent C{sub 60} deposition: anti-absorption bands, as well as an increase of the broadband reflectance, occur and are interpreted as due to strong electron-phonon coupling with induced surface states.

  9. Polylactide-co-glycolide microparticles with surface adsorbed antigens as vaccine delivery systems.

    PubMed

    Singh, Manmohan; Kazzaz, Jina; Ugozzoli, Mildred; Malyala, Padma; Chesko, James; O'Hagan, Derek T

    2006-01-01

    Several groups have shown that vaccine antigens can be encapsulated within polymeric microparticles and can serve as potent antigen delivery systems. We have recently shown that an alternative approach involving charged polylactide co-glycolide (PLG) microparticles with surface adsorbed antigen(s) can also be used to deliver antigen into antigen presenting cell (APC). We have described the preparation of cationic and anionic PLG microparticles which have been used to adsorb a variety of agents, which include plasmid DNA, recombinant proteins and adjuvant active oligonucleotides. These PLG microparticles were prepared using a w/o/w solvent evaporation process in the presence of the anionic surfactants, including DSS (dioctyl sodium sulfosuccinate) or cationic surfactants, including CTAB (hexadecyl trimethyl ammonium bromide). Antigen binding to the charged PLG microparticles was influenced by several factors including electrostatic and hydrophobic interactions. These microparticle based formulations resulted in the induction of significantly enhanced immune responses in comparison to alum. The surface adsorbed microparticle formulation offers an alternative and novel way of delivering antigens in a vaccine formulation. PMID:16472100

  10. Changes in the quaternary structure of amelogenin when adsorbed onto surfaces

    SciTech Connect

    Tarasevich, Barbara J.; Lea, Alan S.; Bernt, William; Engelhard, Mark H.; Shaw, Wendy J.

    2009-02-02

    The amelogenin protein is involved in the formation of highly controlled and anisotropic hydroxyapatite crystals in tooth enamel. Amelogenin is unique in that it self assembles to form supramolecular quaternary structures called “nanospheres,” spherical aggregates of amelogenin monomers typically 20-60 nm in diameter. Although nanospheres have been observed in solution, the quaternary structure of amelogenin adsorbed onto surfaces is not well known. A better understanding of the surface structure is of great importance, however, because the function of amelogenin depends on it. We report studies of the adsorption of amelogenin onto self-assembled monolayers (SAMs) containing COOH and CH3 end group functionality as well as single crystal fluoroapatite (FAP), a biologically relevant surface. The supramolecular structures of the protein in solution as determined by dynamic light scattering (DLS) were compared with the supramolecular structures of the protein physisorbed onto surfaces as studied by atomic force microscopy (AFM). We found that although our solutions contained only nanospheres of narrow size distribution, smaller structures such as monomers and dimers were observed onto both hydrophilic and hydrophobic surfaces. This suggests that amelogenin can adsorb onto surfaces as small structures that peel away or “shed” from the nanospheres that are present in solution.

  11. Quantitative surface studies of protein adsorption by infrared spectroscopy. II. Quantification of adsorbed and bulk proteins

    SciTech Connect

    Fink, D.J.; Hutson, T.B.; Chittur, K.K.; Gendreau, R.M.

    1987-08-15

    Attenuated total reflectance Fourier transform infrared spectra of surface-adsorbed proteins are correlated with concentration measurements determined by /sup 125/I-labeled proteins. This paper demonstrates that linear correlations between the intensity of the major bands of proteins and the quantity of proteins can be obtained for human albumin and immunoglobulin G up to surface concentrations of approximately 0.25 microgram/cm2. A poorer correlation was observed for human fibrinogen. A linear correlation was also observed between the concentration in the bulk solution and the major bands of albumin up to a concentration of 60 mg/ml.

  12. Binding energy of adsorbates on a noble-metal surface: exchange and correlation effects.

    PubMed

    Rohlfing, Michael; Bredow, Thomas

    2008-12-31

    We discuss the adsorption of xenon and of PTCDA on the silver (111) surface within a first-principles approach, focusing on the adsorbate-substrate interaction energy as a function of distance. We combine exact exchange with correlation energy from the adiabatic-connection fluctuation-dissipation theorem. At a large distance Z from the surface, the correlation causes a van der Waals attraction [approximately -C3/(Z - Z0)3]. At a closer distance, the attraction deviates from its asymptotic form and, combined with the repulsive exact-exchange energy, yields an equilibrium in close agreement with experiment. PMID:19437654

  13. In situ ion gun cleaning of surface adsorbates and its effect on electrostatic forces

    NASA Astrophysics Data System (ADS)

    Schafer, Robert; Xu, Jun; Mohideen, Umar

    2016-01-01

    To obtain precise measurements of the Casimir force, it is crucial to take into account the electrostatic interactions that exist between the two boundaries. Two otherwise grounded conductors will continue to have residual electrostatic effects from patch potentials existing on the surfaces. In this paper, we look at the effect of in situ cleaning of adsorbate patches, and the resultant effect on the net electrostatic potential difference between two surfaces. We find a significant reduction in the residual potential due to in situ Ar+ cleaning for the samples used.

  14. Synthesis and characterization of macromolecular layers grafted to polymer surfaces

    NASA Astrophysics Data System (ADS)

    Burtovyy, Oleksandr

    membranes modified with a reactive anchoring layer can be successfully used to build membrane assemblies by incorporating silica, aluminum, or titanium oxide microparticles as spacers. It is expected that the proposed approaches for the surface modification of the membranes and for the generation of multilayered membrane assemblies can be employed straightforwardly to provide an efficient platform for fabrication of breathable protective materials. Characterization of modified membranes with a cantilever-based method, which can be used for prediction of properties and behavior of thin grafted films, is reported. This technique can be used as a method for fast screening of modified membranes. The method is very robust and capable of detecting very small quantities of substance adsorbed; kinetics of the process can be tracked, as well. This approach can be further developed as a handheld sensor for early warning of the presence of chemical vapors and nerve agents.

  15. Orientation and order of aqueous organic ions adsorbed to a solid surface

    SciTech Connect

    Sukhishvili, S.A.; Granick, S.

    1999-01-21

    The adsorption and orientation of an aqueous organic ion with anisotropic shape (1,4-dimethylpyridinium, P{sup +}) at the surface of oxidized silicon carrying opposite charge (produced by conditions of high pH) were studied using polarized infrared spectroscopy in attenuated total reflection (FTIR-ATR). Orientation relative to the surface was quantified from the dichroic ratio of in-plane skeletal vibrations of the pyridinium ring (1643 and 1523 cm{sup {minus}1}), and the adsorbed amount was inferred from the intensity of these bands. The sticking energy of the organic ion was slightly larger than that of small inorganic ions of the same charge (Li{sup +}, Na{sup +}, Cs{sup +}). From relative quantities adsorbed in competitive adsorption, the relative sticking energy was quantified ({approximately}7k{sub B}T relative to Na{sup +} at pH = 9.2 and varying in the order Cs{sup +} > Na{sup +} > Li{sup +} by the total amount of 0.6k{sub B}T). At low ionic strength (no inorganic ions present except those in the buffer solution), P{sup +} stood preferably parallel to the surface when the surface coverage was low but more nearly upright both as its surface coverage increased and as the concentration of coadsorbed small ions increased. This shows the influence of steric packing on the orientation of this ion of asymmetric shape. The larger the hydrated diameter of the coadsorbed ion, the more the P{sup +} ion tilted away from the surface (H{sup +} < Li{sup +}, Na{sup +}, Cs{sup +} < Mg{sup 2+}). Furthermore, if the mass adsorbed exceeded a critical level, both the tilt and the amount adsorbed jumped in response to increasing P{sup +} concentration in bulk solution, with hysteresis upon dilution. This jump, together with the measured ellipsometric thickness and contact angle, suggests that the discontinuity involved structural change within a single monolayer. The organic ion thus behaved at the surface as an embryonic amphiphile, although in the bulk, micelle formation has

  16. Equilibrium of wetting layers on rough surfaces

    NASA Astrophysics Data System (ADS)

    Liu, Kuang-Yu

    The objective of this dissertation is to study physical adsorption on solids with complex surface geometry--especially on self-similar and self-affine fractal surfaces--in the context of three phase equilibria. Such studies will facilitate the prediction of the adsorbed film from known surface properties, e.g., topography or interactions (direct problem), and the inference of unknown surface properties from experimental data (inverse problem). These results will then be compared against wetting phenomena on planar surfaces and with other methods of probing complex surface geometries of solids. Chapter One offers the basic context, including wetting phenomena on planar surfaces, the cornerstone prediction of wetting transition on planar surfaces by Cahn, the concepts of fractal geometry, and the formation of fractal objects, for later comparison. The rest of this dissertation will be devoted to the study of multilayer adsorption on fractal surfaces. When a liquid film completely wets the surface, the number of adsorbed molecules as a function of the vapor pressure will depend strongly on the underlying surface geometry. The fractal structure leads to the Frenkel-Halsey-Hill type isotherms with the exponents in the corresponding power laws depending on the fractal dimension and on whether the dominant influence is from the substrate potential (van der Waals wetting) or from the film-vapor surface tension (capillary wetting). The transition between the two is the analog of Cahn's transition: The thermal disorder is replaced by the quenched disorder. This analogy is studied in Chapter Two for self-similar surfaces, and in Chapter Four for self-affine surfaces. In Chapter Two the derivation framework also automatically identifies well-defined coexistence lines in the pressure-dimension diagram. The effect of the repulsive part is examined there too. A simple analysis of adsorption/desorption hysteresis on self-similar surfaces in Chapter Three concludes that the

  17. The leucine rich amelogenin protein (LRAP) adsorbs as monomers or dimers onto surfaces

    SciTech Connect

    Tarasevich, Barbara J.; Lea, Alan S.; Shaw, Wendy J.

    2010-03-15

    Amelogenin and amelogenin splice variants are believed to be involved in controlling the formation of the highly anisotropic and ordered hydroxyapatite crystallites that form enamel. The adsorption behavior of amelogenin proteins onto substrates is very important because protein-surface interactions are critical to it’s function. We have studied the adsorption of LRAP, a splice variant of amelogenin which may also contribute to enamel function, onto model self-assembled monolayers on gold containing of COOH, CH3, and NH2 end groups. Dynamic light scattering (DLS) experiments indicated that LRAP in phosphate buffered saline (PBS) and solutions at saturation with calcium phosphate contained aggregates of nanospheres. Null ellipsometry and atomic force microscopy (AFM) were used to study protein adsorption amounts and structures. Relatively high amounts of adsorption occurred onto the CH3 and NH2 surfaces from both calcium phosphate and PBS solutions. Adsorption was also promoted onto COOH surfaces when calcium was present in the solutions suggesting an interaction that involves calcium bridging with the negatively charged C-terminus. The ellipsometry and AFM studies suggested that the protein adsorbed onto all surfaces as LRAP monomers. We propose that the monomers adsorb onto the surfaces by disassembling or “shedding” from the nanospheres that are present in solution. This work reveals the importance of small subnanosphere-sized structures of LRAP at interfaces, structures that may be important in the biomineralization of tooth enamel.

  18. Self-Assembly of Thiol Adsorbates on the Au(111)surface

    NASA Astrophysics Data System (ADS)

    Hagelberg, Frank; Williams, Quinton; Zhou, Jian-Ge

    2007-03-01

    A long-standing controversy related to the dimer pattern formed by methanethiol (CH3SH) and methylthiolate (CH3S) on the Au(111) surface has been resolved using density functional theory within periodic boundary conditions. It is found that the S atoms of methanethiol adsorbates on the Au(111) surface form Van der Waals dimers. For methylthiolate, it is shown that no dimerization occurs at high coverage. At intermediate coverage, however, a Van der Waals dimer pattern emerges. The presence of defects in the Au(111) surface does not change this conclusion. Molecular dynamics simulation at high coverage demonstrates that the observed dialkyl disulfide species emerge during the desorption process, and thus are not attached to the surface. A meta-stable monomer pattern has been shown to be only marginally higher in adsorption energy than the dimer configuration which explains the observed fragility of the dimers. For the understanding of these results, it is of crucial importance that methanethiol molecules, contrary to a widely held assumption, remain stable when deposited on clean Au(111) surfaces /1, 2/. In the presence of defects, however, methanethiol adsorbates dissociate and form methylthiolate. /1/ I. Rzeznicka, J. Lee, P. Maksymovych, J. Yates, Jr., J. Phys. Chem. B109, 15992 (2005). /2/ J. Zhou, F. Hagelberg, Phys. Rev. Lett. 97, 45505 (2006).

  19. Survival of Purines and Pyrimidines Adsorbed on a Solid Surface in a High Radiation Field

    NASA Astrophysics Data System (ADS)

    Guzman-Marmolejo, A.; Ramos-Bernal, S.; Negrón-Mendoza, A.

    2009-12-01

    According to astronomical data, organic molecules are abundant in interstellar space. These molecules have arisen from non-equilibrium processes driven by the energy of photons and cosmic rays. The presence of dirty ices show that a rich low temperature solid phase chemistry takes place in such environments. These chemical evolution reactions have been assumed to proceed mainly within solid surfaces of interstellar dust particles, as well as on macrobodies. Among solid surfaces for chemical processes, alumino-silicates are widely distributed in terrestrial and extraterrestrial bodies, such as meteorites, and the Martian soil, which showed the presence of carbonates and clays. Therefore, alumino-silicates are considered a likely inorganic material to promote organic reactions that might have played a role in the survival of organic molecules adsorbed on their surfaces. It is also known that they have a high surface area and a high affinity for organic compounds. Purines and pyrimidines are important organic compounds due to their role in biological processes. Their synthesis and stability are of paramount importance in chemical evolution. In this work we propose a mechanism to account for the survival of purines and pyrimidines adsorbed in a solid surface in a high radiation field.

  20. Stable water layers on solid surfaces.

    PubMed

    Hong, Ying-Jhan; Tai, Lin-Ai; Chen, Hung-Jen; Chang, Pin; Yang, Chung-Shi; Yew, Tri-Rung

    2016-02-17

    Liquid layers adhered to solid surfaces and that are in equilibrium with the vapor phase are common in printing, coating, and washing processes as well as in alveoli in lungs and in stomata in leaves. For such a liquid layer in equilibrium with the vapor it faces, it has been generally believed that, aside from liquid lumps, only a very thin layer of the liquid, i.e., with a thickness of only a few nanometers, is held onto the surface of the solid, and that this adhesion is due to van der Waals forces. A similar layer of water can remain on the surface of a wall of a microchannel after evaporation of bulk water creates a void in the channel, but the thickness of such a water layer has not yet been well characterized. Herein we showed such a water layer adhered to a microchannel wall to be 100 to 170 nm thick and stable against surface tension. The water layer thickness was measured using electron energy loss spectroscopy (EELS), and the water layer structure was characterized by using a quantitative nanoparticle counting technique. This thickness was found for channel gap heights ranging from 1 to 5 μm. Once formed, the water layers in the microchannel, when sealed, were stable for at least one week without any special care. Our results indicate that the water layer forms naturally and is closely associated only with the surface to which it adheres. Our study of naturally formed, stable water layers may shed light on topics from gas exchange in alveoli in biology to the post-wet-process control in the semiconductor industry. We anticipate our report to be a starting point for more detailed research and understanding of the microfluidics, mechanisms and applications of gas-liquid-solid systems. PMID:26856872

  1. Layered protonated titanate nanosheets synthesized with a simple one-step, low-temperature, urea-modulated method as an effective pollutant adsorbent.

    PubMed

    Lin, Cheng-Hsien; Wong, David Shan-Hill; Lu, Shih-Yuan

    2014-10-01

    A simple one-step, low-temperature, urea-modulated method is developed for the synthesis of layered protonated titanate nanosheets (LPTNs). Urea serves as an indirect ammonium ion source, and the controlled supply of the ammonium ion slows the crystalline formation process and enables the production of the LPTNs from amorphous intermediate through aging-induced restructuring. The resulting LPTNs exhibit excellent adsorption capacities for methylene blue and Pb(2+) because of their high specific surface areas and excellent ion-exchange capability. Intercalation of Pb(2+) into the interlayer space of the LPTNs is evidenced by the relevant X-ray diffraction patterns on perturbation of the layered structure. The LPTNs prove to be a promising adsorbent in wastewater treatment for adsorption removal of metal ions or cationic organic dyes. PMID:25198517

  2. Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

    SciTech Connect

    López-Moreno, S.; Romero, A. H.

    2015-04-21

    Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O{sub 2} molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered.

  3. Solid particles adsorbed on capillary-bridge-shaped fluid polystyrene surfaces.

    PubMed

    McEnnis, Kathleen; Dinsmore, Anthony D; Russell, Thomas P

    2015-05-19

    Particles adsorbed on microscopic polystyrene (PS) capillary bridge surfaces were observed to investigate their motion under capillary forces arising from a nonuniform shape. Capillary bridges were created by placing thin PS films, heated above the glass transition temperature (Tg), between two electrodes with an air gap between the surface of the PS and the upper electrode. Silica particles, 100 nm in diameter, were placed on the surface of the PS capillary bridges, and the sample was heated above the Tg of PS to enable particle motion. Samples were cooled to below Tg, and the locations of the particles were observed using scanning electron microscopy. The particles did not preferentially locate around the center of the capillary bridge, as predicted by others, but instead segregated to the edges. These results indicate that the forces driving particles to the three-phase contact line (air/PS/electrode surface) are greater than those locating particles around the center. PMID:25938879

  4. Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni

    NASA Astrophysics Data System (ADS)

    López-Moreno, S.; Romero, A. H.

    2015-04-01

    Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O2 molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered.

  5. Atomic and molecular oxygen adsorbed on (111) transition metal surfaces: Cu and Ni.

    PubMed

    López-Moreno, S; Romero, A H

    2015-04-21

    Density functional theory is used to investigate the reaction of oxygen with clean copper and nickel [111]-surfaces. We study several alternative adsorption sites for atomic and molecular oxygen on both surfaces. The minimal energy geometries and adsorption energies are in good agreement with previous theoretical studies and experimental data. From all considered adsorption sites, we found a new O2 molecular precursor with two possible dissociation paths on the Cu(111) surface. Cross barrier energies for the molecular oxygen dissociation have been calculated by using the climbing image nudge elastic band method, and direct comparison with experimental results is performed. Finally, the structural changes and adsorption energies of oxygen adsorbed on surface when there is a vacancy nearby the adsorption site are also considered. PMID:25903900

  6. Two-dimensional electron gas formed on the indium-adsorbed Si(111)3×3-Au surface

    NASA Astrophysics Data System (ADS)

    Kim, J. K.; Kim, K. S.; McChesney, J. L.; Rotenberg, E.; Hwang, H. N.; Hwang, C. C.; Yeom, H. W.

    2009-08-01

    Electronic structure of the In-adsorbed Si(111)3×3-Au surface was investigated by core-level and angle-resolved photoelectron spectroscopy. On the Si(111)3×3-Au surface, In adsorbates were reported to remove the characteristic domain-wall network and produce a very well-ordered 3×3 surface phase. Detailed band dispersions and Fermi surfaces were mapped for the pristine and In-dosed Si(111)3×3-Au surfaces. After the In adsorption, the surface bands shift toward a higher binding energy, increasing substantially the electron filling of the metallic band along with a significant sharpening of the spectral features. The resulting Fermi surface indicates the formation of a perfect isotropic two-dimensional electron-gas system filled with 0.3 electrons. This band structure agrees well with that expected, in a recent density-functional theory calculation, for the conjugate-honeycomb trimer model of the pristine Si(111)3×3-Au surface. Core-level spectra indicate that In adsorbates interact mostly with Si surface atoms. The possible origins of the electronic structure modification by In adsorbates are discussed. The importance of the domain wall and the indirect role of In adsorbates are emphasized. This system provides an interesting playground for the study of two-dimensional electron gas on solid surfaces.

  7. Surface vibrational spectroscopy. A comparison of the EELS spectra of organic adsorbates at Pt(111) with IR and Raman spectra of the unadsorbed organics

    NASA Astrophysics Data System (ADS)

    Kahn, Bruce E.; Chaffins, Scott A.; Gui, John Y.; Lu, Frank; Stern, Donald A.; Hubbard, Arthur T.

    1990-02-01

    result in loss of double-bond character. Adsorption of propynol (PPYOH) lowers the frequency of the CC triple bond to approximately that of a double bond. EELS spectra of adsorbed pyridine (PY), 2-methylpyridine (2MPY) and 2,6-dimethylpyridine (26DMPY) were examined in order to contrast the vibrational behavior of adsorbates having the aromatic ring perpendicular to the Pt surface (PY and 2MPY), giving rise to strong perturbation of the vibrational spectra or parallel (26DMPY), leading to limited perturbation of the vibrational spectra. Compounds for which the surface interaction is limited primarily to bonding of a single sulfur atom were studied in order to observe the vibrational behavior of a comparatively unperturbed pendant ring or chain: thiophenol (TP); benzylmercaptan (BM); cysteine (CYS); and thiophene (TPE). The expected lack of perturbation was found, making TP, BM and CYS particularly suitable reference compounds for surface vibrational studies of aromatic rings and amino acids. In contrast, L-phenylalanine (PHE) interacts with the Pt(111) surface through the phenyl ring as well as the amino acid functionality. In general, chemisorption and intra-layer intermolecular interaction both lower the surface vibrational frequencies (EELS) and incidentally affect peak amplitudes. Orientation affects peak amplitudes and incidentally affects frequencies insofar as a change in orientation is accompanied by a change in mode of surface bonding. Surface roughness leads to a scrambling of adsorbed states which affects bandwidths, chemical/electrochemical reactivities, and in turn the frequencies and amplitudes of EELS peaks. Specific findings and conclusions are presented for each compound and correlated.

  8. Surface relaxation phenomena at electrified interfaces: Revealing adsorbate, potential, and solvent effects by combined x-ray diffraction, STM and DFT studies

    NASA Astrophysics Data System (ADS)

    Saracino, Martino; Broekmann, Peter; Gentz, Knud; Becker, Moritz; Keller, Hubert; Janetzko, Florian; Bredow, Thomas; Wandelt, Klaus; Dosch, Helmut

    2009-03-01

    Surface relaxation phenomena have been studied in an electrochemical environment using halide modified Cu(100) electrodes as model systems to unravel the impact of the chemical nature of the adsorbed halide, the applied potential, and the presence of solvent species on the surface interlayer spacings. Both, in situ STM and in situ x-ray scattering data point to lateral structures of the adsorbed halides on Cu(100) which are identical for both chloride and bromide. Under saturation conditions both halides form a p(1×1) adlayer on Cu(100) with reference to a conventional choice of the substrate fcc unit cell. The in situ x-ray scattering data clearly indicate that the copper-halide and the copper-copper interlayer spacings are much more affected by potential changes when bromide is adsorbed on the copper surface and are less affected when chloride is present. This difference in the potential dependence of both halides can be attributed to the larger polarizability of the bromide anion that is almost discharged on the copper surface at the highest applied potentials, while chloride remains largely ionic in the adsorbed state even at the highest applied potential. At the lowest applied potential of Ework=-150mV [vs reversible hydrogen electrode (RHE)] the Br-Cu and the topmost Cu-Cu layer distances are expanded by 0.150 and 0.058Å , respectively, with reference to their bulk analogs CuBr and Cu. These spacings continuously contract by up to 0.075 and 0.038Å when the electrode potential is increased to Ework=+50mV (RHE). Intriguingly, the second Cu layer experiences a potential-dependent buckling due to a different second-shell coordination of Cu by bromide while deeper Cu layers retain the bulk spacing at all potentials. Changes in the halide-copper and the copper-copper interlayer spacings are strongly correlated. An understanding of the in situ x-ray results is achieved by periodic quantum-chemical calculations at density-functional level that allow a modeling of

  9. Layering of ionic liquids on rough surfaces

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  10. Influence of ultrathin water layer on the van der Waals/Casimir force between gold surfaces

    SciTech Connect

    Palasantzas, G.; Zwol, P. J. van; Svetovoy, V. B.

    2009-06-15

    In this paper we investigate the influence of ultrathin water layer ({approx}1-1.5 nm) on the van der Waals/Casimir force between gold surfaces. Adsorbed water is inevitably present on gold surfaces at ambient conditions as jump-up-to contact during adhesion experiments demonstrate. Calculations based on the Lifshitz theory give very good agreement with the experiment in the absence of any water layer for surface separations d > or approx. 10 nm. However, a layer of thickness h < or approx. 1.5 nm is allowed by the error margin in force measurements. At shorter separations, d < or approx. 10 nm, the water layer can have a strong influence as calculations show for flat surfaces. Nonetheless, in reality the influence of surface roughness must also be considered, and it can overshadow any water layer influence at separations comparable to the total sphere-plate rms roughness w{sub shp}+w.

  11. Identification of polymer surface adsorbed proteins implicated in pluripotent human embryonic stem cell expansion.

    PubMed

    Hammad, Moamen; Rao, Wei; Smith, James G W; Anderson, Daniel G; Langer, Robert; Young, Lorraine E; Barrett, David A; Davies, Martyn C; Denning, Chris; Alexander, Morgan R

    2016-08-16

    Improved biomaterials are required for application in regenerative medicine, biosensing, and as medical devices. The response of cells to the chemistry of polymers cultured in media is generally regarded as being dominated by proteins adsorbed to the surface. Here we use mass spectrometry to identify proteins adsorbed from a complex mouse embryonic fibroblast (MEF) conditioned medium found to support pluripotent human embryonic stem cell (hESC) expansion on a plasma etched tissue culture polystyrene surface. A total of 71 proteins were identified, of which 14 uniquely correlated with the surface on which pluripotent stem cell expansion was achieved. We have developed a microarray combinatorial protein spotting approach to test the potential of these 14 proteins to support expansion of a hESC cell line (HUES-7) and a human induced pluripotent stem cell line (ReBl-PAT) on a novel polymer (N-(4-Hydroxyphenyl) methacrylamide). These proteins were spotted to form a primary array yielding several protein mixture 'hits' that enhanced cell attachment to the polymer. A second array was generated to test the function of a refined set of protein mixtures. We found that a combination of heat shock protein 90 and heat shock protein-1 encourage elevated adherence of pluripotent stem cells at a level comparable to fibronectin pre-treatment. PMID:27466628

  12. Effect of surface ionization on wetting layers

    NASA Technical Reports Server (NTRS)

    Kayser, R. F.

    1986-01-01

    A surface ionization model due to Langmuir is generalized to liquid mixtures of polar and nonpolar components in contact with ionizable substrates. When a predominantly nonpolar mixture is near a miscibility gap, thick wetting layers of the conjugate polar phase form on the substrate. Such charged layers can be much thicker than similar wetting layers stabilized by dispersion forces. This model may explain the 0.4- to 0.6-micron-thick wetting layers formed in stirred mixtures of nitromethane and carbon disulfide in contact with glass.

  13. Adsorbed serum albumin is permissive to macrophage attachment to perfluorocarbon polymer surfaces in culture.

    PubMed

    Godek, M L; Michel, R; Chamberlain, L M; Castner, D G; Grainger, D W

    2009-02-01

    Monocyte/macrophage adhesion to biomaterials, correlated with foreign body response, occurs through protein-mediated surface interactions. Albumin-selective perfluorocarbon (FC) biomaterials are generally poorly cell-conducive because of insufficient receptor-mediated surface interactions, but macrophages bind to albumin-coated substrates and also preferentially to highly hydrophobic fluorinated surfaces. Bone marrow macrophages (BMMO) and IC-21, RAW 264.7, and J774A.1 monocyte/macrophage cells were cultured on FC surfaces. Protein deposition onto two distinct FC surfaces from complex and single-component solutions was tracked using fluorescence and time-of-flight secondary ion mass spectrometry (ToF-SIMS) methods. Cell adhesion and growth on protein pretreated substrates were compared by light microscopy. Flow cytometry and integrin-directed antibody receptor blocking were used to assess integrins critical for monocyte/macrophage adhesion in vitro. Albumin predominantly adsorbs onto both FC surfaces from 10% serum. In cultures preadsorbed with albumin or serum-dilutions, BMMO responded similar to IC-21 at early time points. Compared with Teflon AF, plasma-polymerized FC was less permissive to extended cell proliferation. The beta(2) integrins play major roles in macrophage adhesion to FC surfaces: antibody blocking significantly disrupted cell adhesion. Albumin-mediated cell adhesion mechanisms to FC surfaces could not be clarified. Primary BMMO and secondary IC-21 macrophages behave similarly on FC surfaces, regardless of preadsorbed protein biasing, with respect to adhesion, cell morphology, motility, and proliferation. PMID:18306309

  14. Imparting Nonfouling Properties to Chemically Distinct Surfaces with a Single Adsorbing Polymer: A Multimodal Binding Approach.

    PubMed

    Serrano, Ângela; Zürcher, Stefan; Tosatti, Samuele; Spencer, Nicholas D

    2016-04-01

    Surface-active polymers that display nonfouling properties and carry binding groups that can adsorb onto different substrates are highly desirable. We present a postmodification protocol of an active-ester-containing polymer that allows the creation of such a versatile platform. Poly(pentafluorophenyl acrylate) has been postmodified with a fixed grafting ratio of a nonfouling function (mPEG) and various combinations of functional groups, such as amine, silane and catechol, which can provide strong affinity to two model substrates: SiO2 and TiO2 . Adsorption, stability and resistance to nonspecific protein adsorption of the polymer films were studied. A polymer was obtained that maintained its surface functionality under a variety of harsh conditions. EG surface-density calculations show that this strategy generates a denser packing when both negatively and positively charged groups are present within the backbone, and readily allows the fabrication of a broad combinatorial matrix. PMID:26858017

  15. Homeotropic orientation of a nematic liquid crystal by bent-core molecules adsorbed on its surface

    NASA Astrophysics Data System (ADS)

    Hwang, Jiyong; Yang, Seungbin; Lee, Hyojin; Kim, Jongyoon; Lee, Ji-Hoon; Kang, Shin-Woong; Choi, E.-Joon

    2015-06-01

    We reported the promotion of a homeotropic alignment of a nematic liquid crystal (NLC) by bent-core liquid-crystal (BLC) Molecules adsorbed its surface. The BLC was mixed at various concentrations with the NLC, and the mixtures were injected into an empty cell with a cell gap of 13 μm. Although the pure NLC showed a heterogeneous orientation, the BLC-NLC mixture was gradually transformed to a homeotropic alignment with increasing concentration of the BLC. We investigated the surface topography of the samples by using an atomic force microscopy (AFM) and found that the BLC molecules were segregated into a polyimide (PI) surface and formed protrusion domains with diameters of 50-100 nm. The BLC protrusions might promote the homeotropic orientation of the NLC molecules.

  16. Ultra-sensitive fluorescence spectroscopy of isolated surface-adsorbed molecules using an optical nanofiber.

    PubMed

    Stiebeiner, A; Rehband, O; Garcia-Fernandez, R; Rauschenbeutel, A

    2009-11-23

    The strong radial confinement and the pronounced evanescent field of the guided light in optical nanofibers yield favorable conditions for ultra-sensitive surface spectroscopy of molecules deposited on the fiber. Using the guided mode of the nanofiber for both excitation and fluorescence collection, we present spectroscopic measurements on 3,4,9,10-perylenetetracarboxylic dianhydride molecules (PTCDA) at ambient conditions. Surface coverages as small as 1 per thousand of a compact monolayer still give rise to fluorescence spectra with a good signal to noise ratio. Moreover, we analyze and quantify the self-absorption effects due to reabsorption of the emitted fluorescence light by circumjacent surface-adsorbed molecules distributed along the fiber waist. PMID:19997412

  17. Dry powder pulmonary delivery of cationic PGA-co-PDL nanoparticles with surface adsorbed model protein.

    PubMed

    Kunda, Nitesh K; Alfagih, Iman M; Dennison, Sarah R; Somavarapu, Satyanarayana; Merchant, Zahra; Hutcheon, Gillian A; Saleem, Imran Y

    2015-08-15

    Pulmonary delivery of macromolecules has been the focus of attention as an alternate route of delivery with benefits such as; large surface area, thin alveolar epithelium, rapid absorption and extensive vasculature. In this study, a model protein, bovine serum albumin (BSA) was adsorbed onto cationic PGA-co-PDL polymeric nanoparticles (NPs) prepared by a single emulsion solvent evaporation method using a cationic surfactant didodecyldimethylammonium bromide (DMAB) at 2% w/w (particle size: 128.64±06.01 nm and zeta-potential: +42.32±02.70 mV). The optimum cationic NPs were then surface adsorbed with BSA, NP:BSA (100:4) ratio yielded 10.01±1.19 μg of BSA per mg of NPs. The BSA adsorbed NPs (5 mg/ml) were then spray-dried in an aqueous suspension of L-leucine (7.5 mg/ml, corresponding to a ratio of 1:1.5/NP:L-leu) using a Büchi-290 mini-spray dryer to produce nanocomposite microparticles (NCMPs) containing cationic NPs. The aerosol properties showed a fine particle fraction (FPF, dae<4.46 μm) of 70.67±4.07% and mass median aerodynamic diameter (MMAD) of 2.80±0.21 μm suggesting a deposition in the respiratory bronchiolar region of the lungs.The cell viability was 75.76±03.55% (A549 cell line) at 156.25 μg/ml concentration after 24 h exposure. SDS-PAGE and circular dichroism (CD) confirmed that the primary and secondary structure of the released BSA was maintained. Moreover, the released BSA showed 78.76±1.54% relative esterolytic activity compared to standard BSA. PMID:26169146

  18. Large spin splitting of metallic surface-state bands at adsorbate-modified gold/silicon surfaces

    PubMed Central

    Bondarenko, L. V.; Gruznev, D. V.; Yakovlev, A. A.; Tupchaya, A. Y.; Usachov, D.; Vilkov, O.; Fedorov, A.; Vyalikh, D. V.; Eremeev, S. V.; Chulkov, E. V.; Zotov, A. V.; Saranin, A. A.

    2013-01-01

    Finding appropriate systems with a large spin splitting of metallic surface-state band which can be fabricated on silicon using routine technique is an essential step in combining Rashba-effect based spintronics with silicon technology. We have found that originally poor structural and electronic properties of the surface can be substantially improved by adsorbing small amounts of suitable species (e.g., Tl, In, Na, Cs). The resultant surfaces exhibit a highly-ordered atomic structure and spin-split metallic surface-state band with a momentum splitting of up to 0.052 Å−1 and an energy splitting of up to 190 meV at the Fermi level. The family of adsorbate-modified surfaces, on the one hand, is thought to be a fascinating playground for exploring spin-splitting effects in the metal monolayers on a semiconductor and, on the other hand, expands greatly the list of material systems prospective for spintronics applications. PMID:23661151

  19. X-ray standing wave investigation of the surface structure of selenite anions adsorbed on calcite.

    SciTech Connect

    Cheng, L.; Lyman, P. F.; Sturchio, N. C.; Bedzyk, M. J.; Northwestern Univ.

    1997-01-01

    The adsorption of selenite ions (SeO{sup 2-}{sub 3}) from a dilute aqueous solution onto a freshly-cleaved calcite (10 {ovr 1} 4) surface was studied with the X-ray standing wave (XSW) technique. The complex ion SeO{sup 2-}{sub 3} is found to selectively adsorb at the CO{sup 2-}{sub 3} site via ionic exchange, forming a two-dimensional solid-solution of the form Ca(SeO{sub 3}){sub x}(CO{sub 3}){sub 1-x} at the interface. The calcite (10 {ovr 1} 4), (0006) and (11 {ovr 2} 0) Bragg reflections were used to triangulate the Se position with respect to the calcite lattice. The local surface structure at the SeO{sup 2-}{sub 3} adsorbate site, derived from the XSW results, is consistent with a model in which the base of the SeO{sup 2-}{sub 3} trigonal pyramid aligns with (and replaces) the CO{sup 2-}{sub 3} equilateral triangular group. The SeO{sup 2-}{sub 3} adsorption saturated at a coverage of 0.02 monolayers. Under identical chemical conditions, selenate (SeO{sup 2-}{sub 4}) adsorption was inhibited.

  20. Surface layer effects on waste glass corrosion

    SciTech Connect

    Feng, X.

    1993-12-31

    Water contact subjects waste glass to chemical attack that results in the formation of surface alteration layers. Two principal hypotheses have been advanced concerning the effect of surface alteration layers on continued glass corrosion: (1) they act as a mass transport barrier and (2) they influence the chemical affinity of the glass reaction. In general, transport barrier effects have been found to be less important than affinity effects in the corrosion of most high-level nuclear waste glasses. However, they can be important under some circumstances, for example, in a very alkaline solution, in leachants containing Mg ions, or under conditions where the matrix dissolution rate is very low. The latter suggests that physical barrier effect may affect the long-term glass dissolution rate. Surface layers influence glass reaction affinity through the effects of the altered glass and secondary phases on the solution chemistry. The reaction affinity may be controlled by various precipitates and crystalline phases, amorphous silica phases, gel layer, or all the components of the glass. The surface alteration layers influence radionuclide release mainly through colloid formation, crystalline phase incorporation, and gel layer retention. This paper reviews current understanding and uncertainties.

  1. Towards 1D nanolines on a monolayered supramolecular network adsorbed on a silicon surface.

    PubMed

    Makoudi, Younes; Beyer, Matthieu; Lamare, Simon; Jeannoutot, Judicael; Palmino, Frank; Chérioux, Frédéric

    2016-06-16

    The growth of 3D extended periodic networks made up of π-conjugated molecules on semi-conductor surfaces is of interest for the integration of nano-components in the future generations of smart devices. In the work presented in this article, we successfully achieved the formation of bilayered networks on a silicon surface including 1D-isolated nanolines in the second layer. Firstly, we observed the formation of a 2D large-scale supramolecular network in the plane of a silicon surface through the deposition of tailored molecules. Then using the same molecules, a second-layer, based on 1D nanolines, grew above the first layer, thanks to a template effect. Mono- or bi-layered networks were found to be stable from 100 K up to room temperature. These networks were investigated by scanning tunnel microscopy imaging under an ultra-high vacuum (UHV-STM). PMID:27273449

  2. Surface-adsorbed reverse micelle-loaded solid self-nanoemulsifying drug delivery system of talinolol.

    PubMed

    Shakeel, Faiyaz; Haq, Nazrul; Alanazi, Fars K; Alsarra, Ibrahim A

    2016-03-01

    The aim of present investigation was to develop surface-adsorbed reverse-micelle-loaded solid self-nanoemulsifying drug delivery system (SNEDDS) of talinolol in order to enhance its in vitro dissolution rate, which in turn enhance the bioavailability. SNEDDS were prepared using aqueous phase titration method. Thermodynamically stable formulations were characterized in terms of droplet size, viscosity, % transmittance, drug content and surface morphology. Low cost acid-treated coffee husk was used as an effective biosorbent for preparation of solid SNEDDS. Developed SNEDDS were subjected to in vitro drug release/dissolution studies. In vitro drug release studies showed 99.6% release of talinolol from optimized solid SNEDDS TS3 after 120 min of study. The results of solubility studies showed 4849.5-folds enhancement in solubility of talinolol from optimized SNEDDS as compared to its aqueous solubility. PMID:25318634

  3. Evidence for photo-induced charge separation between dye molecules adsorbed to aluminium oxide surfaces

    PubMed Central

    Cappel, Ute B.; Moia, Davide; Bruno, Annalisa; Vaissier, Valerie; Haque, Saif A.; Barnes, Piers R. F.

    2016-01-01

    Excited state dynamics and photo-induced charge transfer of dye molecules have been widely studied due to their relevance for organic and dye-sensitised solar cells. Herein, we present a femtosecond transient absorption spectroscopy study of the indolene dye D131 when adsorbed to inert Al2O3 substrates for different surface concentration of the dye. Surprisingly, we find that at high surface concentrations, the first singlet excited state of the dye is converted into a new state with an efficiency of about 80%. We assign the absorption features of this state to the oxidised dye and discuss the possibility of photo-induced charge separation between neighboring dye molecules. Our study is the first to show that this process can be highly efficient without the use of donor and acceptor molecules of different chemical structures. PMID:26891851

  4. Molecular resonant dissociation of surface-adsorbed molecules by plasmonic nanoscissors

    NASA Astrophysics Data System (ADS)

    Zhang, Zhenglong; Sheng, Shaoxiang; Zheng, Hairong; Xu, Hongxing; Sun, Mengtao

    2014-04-01

    The ability to break individual bonds or specific modes in chemical reactions is an ardently sought goal by chemists and physicists. While photochemistry based methodologies are very successful in controlling e.g. photocatalysis, photosynthesis and the degradation of plastic, it is hard to break individual molecular bonds for those molecules adsorbed on the surface because of the weak light-absorption in molecules and the redistribution of the resulting vibrational energy both inside the molecule and to its surrounding environment. Here we show how to overcome these obstacles with a plasmonic hot-electron mediated process and demonstrate a new method that allows the sensitive control of resonant dissociation of surface-adsorbed molecules by `plasmonic' scissors. To that end, we used a high-vacuum tip-enhanced Raman spectroscopy (HV-TERS) setup to dissociate resonantly excited NC2H6 fragments from Malachite green. The surface plasmons (SPs) excited at the sharp metal tip not only enhance the local electric field to harvest the light incident from the laser, but crucially supply `hot electrons' whose energy can be transferred to individual bonds. These processes are resonant Raman, which result in some active chemical bonds and then weaken these bonds, followed by dumping in lots of indiscriminant energy and breaking the weakest bond. The method allows for sensitive control of both the rate and probability of dissociation through their dependence on the density of hot electrons, which can be manipulated by tuning the laser intensity or tunneling current/bias voltage in the HV-TERS setup, respectively. The concepts of plasmonic scissors open up new versatile avenues for the deep understanding of in situ surface-catalyzed chemistry.The ability to break individual bonds or specific modes in chemical reactions is an ardently sought goal by chemists and physicists. While photochemistry based methodologies are very successful in controlling e.g. photocatalysis

  5. Evidence for photo-induced charge separation between dye molecules adsorbed to aluminium oxide surfaces

    NASA Astrophysics Data System (ADS)

    Cappel, Ute B.; Moia, Davide; Bruno, Annalisa; Vaissier, Valerie; Haque, Saif A.; Barnes, Piers R. F.

    2016-02-01

    Excited state dynamics and photo-induced charge transfer of dye molecules have been widely studied due to their relevance for organic and dye-sensitised solar cells. Herein, we present a femtosecond transient absorption spectroscopy study of the indolene dye D131 when adsorbed to inert Al2O3 substrates for different surface concentration of the dye. Surprisingly, we find that at high surface concentrations, the first singlet excited state of the dye is converted into a new state with an efficiency of about 80%. We assign the absorption features of this state to the oxidised dye and discuss the possibility of photo-induced charge separation between neighboring dye molecules. Our study is the first to show that this process can be highly efficient without the use of donor and acceptor molecules of different chemical structures.

  6. Control of the morphology of lipid layers by substrate surface chemistry.

    PubMed

    Granqvist, Niko; Yliperttula, Marjo; Välimäki, Salla; Pulkkinen, Petri; Tenhu, Heikki; Viitala, Tapani

    2014-03-18

    In this study, surface coatings were used to control the morphology of the deposited lipid layers during vesicle spreading, i.e., to control if liposomes self-assemble on a surface into a supported lipid bilayer or a supported vesicular layer. The influence of the properties of the surface coating on formation of the deposited lipid layer was studied with quartz crystal microbalance and two-wavelength multiparametric surface plasmon resonance techniques. Control of lipid self-assembly on the surface was achieved by two different types of soft substrate materials, i.e., dextran and thiolated polyethylene glycol, functionalized with hydrophobic linkers for capturing the lipid layer. The low-molecular-weight dextran-based surface promoted formation of supported lipid bilayers, while the thiolated polyethylene glycol-based surface promoted supported vesicular layer formation. A silicon dioxide surface was used as a reference surface in both measurement techniques. In addition to promoting supported lipid bilayer formation of known lipid mixtures, the dextran surface also promoted supported lipid bilayer formation of vesicles containing the cell membrane extract of human hepatoblastoma cells. The new dextran-based surface was also capable of protecting the supported lipid bilayer against dehydration when exposed to a constant flow of air. The well-established quartz crystal microbalance technique was effective in determining the morphology of the formed lipid layer, while the two-wavelength surface plasmon resonance analysis enabled further complementary characterization of the adsorbed supported lipid bilayers and supported vesicular layers. PMID:24564782

  7. Ozonolysis of surface adsorbed methoxyphenols: kinetics of aromatic ring cleavage vs. alkene side-chain oxidation

    NASA Astrophysics Data System (ADS)

    O'Neill, E. M.; Kawam, A. Z.; Van Ry, D. A.; Hinrichs, R. Z.

    2013-07-01

    Lignin pyrolysis products, which include a variety of substituted methoxyphenols, constitute a major component of organics released by biomass combustion and may play a central role in the formation of atmospheric brown carbon. Understanding the atmospheric fate of these compounds upon exposure to trace gases is therefore critical to predicting the chemical and physical properties of biomass burning aerosol. We used diffuse reflectance infrared spectroscopy to monitor the heterogeneous ozonolysis of 4-propylguaiacol, eugenol, and isoeugenol adsorbed on NaCl and α-Al2O3 substrates. Adsorption of gaseous methoxyphenols onto these substrates produced near monolayer surface concentrations of 3 × 1018 molecules m-2. The subsequent dark heterogeneous ozonolysis of adsorbed 4-propylguaiacol cleaved the aromatic ring between the methoxy and phenol groups with the product conclusively identified by GC-MS and 1H-NMR. Kinetic analysis of eugenol and isoeugenol dark ozonolysis also suggested the formation of ring-cleaved products, although ozonolysis of the unsaturated substituent groups forming carboxylic acids and aldehydes was an order of magnitude faster. Average uptake coefficients for NaCl-adsorbed methoxyphenols were γ = 2.3 (±0.8) × 10-7 and 2 (±1) × 10-6 for ozonolysis of the aromatic ring and the unsaturated side chain, respectively, and reactions on α-Al2O3 were approximately two times slower. UV-visible radiation (λ>300 nm) enhanced eugenol ozonolysis of the aromatic ring by a factor of 4(±1) but had no effect on ozonolysis of the alkene side-chain.

  8. The surface layer for free-surface turbulent flows

    NASA Astrophysics Data System (ADS)

    Shen, Lian; Zhang, Xiang; Yue, Dick K. P.; Triantafyllou, George S.

    1999-05-01

    Direct numerical simulation (DNS) is used to examine low Froude number free-surface turbulence (FST) over a two-dimensional mean shear flow. The Navier Stokes equations are solved using a finite-difference scheme with a grid resolution of 1283. Twenty separate simulations are conducted to calculate the statistics of the flow. Based on the velocity deficit and the vertical extent of the shear of the mean flow, the Reynolds number is 1000 and the Froude number is 0.7. We identify conceptually and numerically the surface layer, which is a thin region adjacent to the free surface characterized by fast variations of the horizontal vorticity components. This surface layer is caused by the dynamic zero-stress boundary conditions at the free surface and lies inside a thicker blockage (or ‘source’) layer, which is due to the kinematic boundary condition at the free surface. The importance of the outer blockage layer is manifested mainly in the redistribution of the turbulence intensity, i.e. in the increase of the horizontal velocity fluctuations at the expense of the vertical velocity fluctuation. A prominent feature of FST is vortex connections to the free surface which occur inside the surface layer. It is found that as hairpin-shaped vortex structures approach the free surface, their ‘head’ part is dissipated quickly in the surface layer, while the two ‘legs’ connect almost perpendicularly to the free surface. Analysis of the evolution of surface-normal vorticity based on vortex surface-inclination angle shows that both dissipation and stretching decrease dramatically after connection. As a result, vortex structures connected to the free surface are persistent and decay slowly relative to non-connected vorticities. The effects of surface and blockage layers on the turbulence statistics of length scales, Reynolds-stress balance, and enstrophy dynamics are examined, which elucidate clearly the different turbulence mechanisms operating in the respective near-surface

  9. Hydrogen adsorbed at N-polar InN: Significant changes in the surface electronic properties

    NASA Astrophysics Data System (ADS)

    Eisenhardt, A.; Krischok, S.; Himmerlich, M.

    2015-06-01

    The interaction of atomic hydrogen and ammonia with as-grown N-polar InN surfaces is investigated using in situ photoelectron spectroscopy. Changes in the surface electronic properties, including the band alignment and work function, as well as the chemical bonding states of the substrate and adsorbates are characterized. Ammonia molecules are dissociating at the InN surface, resulting in adsorption of hydrogen species. Consequently, the considerable changes of the chemical and electronic properties of the InN surface during ammonia interaction are almost identical to those found for adsorption of atomic hydrogen. In both cases, hydrogen atoms preferentially bond to surface nitrogen atoms, resulting in the disappearance of the nitrogen dangling-bond-related occupied surface state close to the valence band edge at ˜1.6 eV binding energy and the formation of new occupied electron states at the conduction band edge. Furthermore, a decrease in work function during adsorption from 4.7 to 3.7-3.8 eV, as well as an increase in the surface downward band bending by 0.3 eV, confirm that hydrogen is acting as electron donor at InN surfaces and therefore has to be considered as one main reason for the surface electron accumulation observed at N-polar InN samples exposed to ambient conditions, for example as the dissociation product of molecules. The measured formation and occupation of electronic states above the conduction band minimum occur in conjunction with the observed increase in surface electron concentration and underline the relationship between the energy position of occupied electron states and surface band alignment for InN as a small-band-gap semiconductor.

  10. Photoinduced Reconfiguration Cycle in a Molecular Adsorbate Layer Studied by Femtosecond Inner-Shell Photoelectron Spectroscopy

    SciTech Connect

    Dachraoui, H.; Michelswirth, M.; Bartz, P.; Pfeiffer, W.; Heinzmann, U.; Siffalovic, P.; Schaefer, C.; Schnatwinkel, B.; Mattay, J.; Drescher, M.

    2011-03-11

    A time-resolved study of core-level chemical shifts in a monolayer of aromatic molecules reveals complex photoinduced reaction dynamics. The combination of electron spectroscopy for chemical analysis and ultrashort pulse excitation in the extreme ultraviolet allows performing time-correlated 4d-core-level spectroscopy of iodine atoms that probe the local chemical environment in the adsorbate molecule. The selectivity of the method unveils metastable molecular configurations that appear about 50 ps after the excitation and are efficiently quenched back to the ground state.

  11. Benzene derivatives adsorbed to the Ag(111) surface: Binding sites and electronic structure

    SciTech Connect

    Miller, Daniel P.; Tymińska, Nina; Zurek, Eva; Simpson, Scott

    2015-03-14

    Dispersion corrected Density Functional Theory calculations were employed to study the adsorption of benzenes derivatized with functional groups encompassing a large region of the activated/deactivated spectrum to the Ag(111) surface. Benzenes substituted with weak activating or deactivating groups, such as methyl and fluoro, do not have a strong preference for adsorbing to a particular site on the substrate, with the corrugations in the potential energy surface being similar to those of benzene. Strong activating (N(CH{sub 3}){sub 2}) and deactivating (NO{sub 2}) groups, on the other hand, possess a distinct site preference. The nitrogen in the former prefers to lie above a silver atom (top site), but in the latter a hollow hexagonal-closed-packed (H{sub hcp}) site of the Ag(111) surface is favored instead. Benzenes derivatized with classic activating groups donate electron density from their highest occupied molecular orbital to the surface, and those functionalized with deactivating groups withdraw electron density from the surface into orbitals that are unoccupied in the gas phase. For benzenes functionalized with two substituents, the groups that are strongly activating or deactivating control the site preference and the other groups assume sites that are, to a large degree, dictated by their positions on the benzene ring. The relative stabilities of the ortho, meta, and para positional isomers of disubstituted benzenes can, in some cases, be modified by adsorption to the surface.

  12. Phosphate adsorption on aluminum-impregnated mesoporous silicates: surface structure and behavior of adsorbents.

    PubMed

    Shin, Eun Woo; Han, James S; Jang, Min; Min, Soo-Hong; Park, Jae Kwang; Rowell, Roger M

    2004-02-01

    Phosphorus from excess fertilizers and detergents ends up washing into lakes, creeks, and rivers. This overabundance of phosphorus causes excessive aquatic plant and algae growth and depletes the dissolved oxygen supply in the water. In this study, aluminum-impregnated mesoporous adsorbents were tested for their ability to remove phosphate from water. The surface structure of the materials was investigated with X-ray diffraction (XRD), a N2 adsorption-desorption technique, Fourier transform-infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS) to understand the effect of surface properties on the adsorption behavior of phosphate. The mesoporous materials were loaded with Al components by reaction with surface silanol groups. In the adsorption test, the Al-impregnated mesoporous materials showed fast adsorption kinetics as well as high adsorption capacities, compared with activated alumina. The uniform mesopores of the Al-impregnated mesoporous materials caused the diffusion rate in the adsorption process to increase, which in turn caused the fast adsorption kinetics. High phosphate adsorption capacities of the Al-impregnated mesoporous materials were attributed to not only the increase of surface hydroxyl density on Al oxide due to well-dispersed impregnation of Al components but also the decrease in stoichiometry of surface hydroxyl ions to phosphate by the formation of monodentate surface complexes. PMID:14968882

  13. Revisiting the inelastic electron tunneling spectroscopy of single hydrogen atom adsorbed on the Cu(100) surface

    SciTech Connect

    Jiang, Zhuoling; Wang, Hao; Sanvito, Stefano; Hou, Shimin

    2015-12-21

    Inelastic electron tunneling spectroscopy (IETS) of a single hydrogen atom on the Cu(100) surface in a scanning tunneling microscopy (STM) configuration has been investigated by employing the non-equilibrium Green’s function formalism combined with density functional theory. The electron-vibration interaction is treated at the level of lowest order expansion. Our calculations show that the single peak observed in the previous STM-IETS experiments is dominated by the perpendicular mode of the adsorbed H atom, while the parallel one only makes a negligible contribution even when the STM tip is laterally displaced from the top position of the H atom. This propensity of the IETS is deeply rooted in the symmetry of the vibrational modes and the characteristics of the conduction channel of the Cu-H-Cu tunneling junction, which is mainly composed of the 4s and 4p{sub z} atomic orbitals of the Cu apex atom and the 1s orbital of the adsorbed H atom. These findings are helpful for deepening our understanding of the propensity rules for IETS and promoting IETS as a more popular spectroscopic tool for molecular devices.

  14. Revisiting the inelastic electron tunneling spectroscopy of single hydrogen atom adsorbed on the Cu(100) surface

    NASA Astrophysics Data System (ADS)

    Jiang, Zhuoling; Wang, Hao; Sanvito, Stefano; Hou, Shimin

    2015-12-01

    Inelastic electron tunneling spectroscopy (IETS) of a single hydrogen atom on the Cu(100) surface in a scanning tunneling microscopy (STM) configuration has been investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. The electron-vibration interaction is treated at the level of lowest order expansion. Our calculations show that the single peak observed in the previous STM-IETS experiments is dominated by the perpendicular mode of the adsorbed H atom, while the parallel one only makes a negligible contribution even when the STM tip is laterally displaced from the top position of the H atom. This propensity of the IETS is deeply rooted in the symmetry of the vibrational modes and the characteristics of the conduction channel of the Cu-H-Cu tunneling junction, which is mainly composed of the 4s and 4pz atomic orbitals of the Cu apex atom and the 1s orbital of the adsorbed H atom. These findings are helpful for deepening our understanding of the propensity rules for IETS and promoting IETS as a more popular spectroscopic tool for molecular devices.

  15. Observation of spin-glass behavior in nickel adsorbed few layer graphene

    SciTech Connect

    Mitra, Sreemanta; Mondal, Oindrila; Banerjee, Sourish; Chakravorty, Dipankar

    2013-01-14

    Nickel-adsorbed graphene was prepared by first synthesizing graphite oxide (GO) by modified Hummers' method and then reducing a solution containing both GO and Ni{sup 2+}. Energy dispersive X-ray spectroscopy analysis showed 31 at. % nickel was present. Magnetization measurements under both dc and ac magnetic fields were carried out in the temperature range 2 K to 300 K. The zero field cooled and field cooled magnetization data showed a pronounced irreversibility at a temperature around 20 K. The analysis of the ac susceptibility data was carried out by both Vogel-Fulcher as well as power law. From dynamic scaling analysis, the microscopic flipping time {tau}{sub 0}{approx}10{sup -13}s and critical exponent z{nu}=5.9{+-}0.1 were found, indicating the presence of conventional spin glass in the system. The spin glass transition temperature was estimated as 19.5 K. Decay of thermoremanent magnetization was explained by stretched exponential function with a value of the exponent as 0.6. From the results, it is concluded that nickel adsorbed graphene behaves like a spin-glass.

  16. Recombination of chlorine atoms on plasma-conditioned stainless steel surfaces in the presence of adsorbed Cl2

    NASA Astrophysics Data System (ADS)

    Stafford, Luc; Khare, Rohit; Guha, Joydeep; Donnelly, Vincent M.; Poirier, Jean-Sébastien; Margot, Joëlle

    2009-03-01

    We investigated the interactions of atomic and molecular chlorine with plasma-conditioned stainless steel surfaces through both experiments and modelling. The recombination of Cl during adsorption and desorption of Cl2 was characterized using a rotating-substrate technique in which portions of the cylindrical substrate surface are periodically exposed to an inductively coupled chlorine plasma and then to an Auger electron spectrometer in separate, differentially pumped chambers. After several hours of exposure to the Cl2 plasma, the stainless steel substrate became coated with a Si-oxychloride-based layer (Fe : Si : O : Cl ≈ 1 : 13 : 13 : 3) due to chlorine adsorption and the erosion of the silica discharge tube. Desorption of Cl2 from this surface was monitored through measurements of pressure rises in the Auger chamber as a function of substrate rotation frequency. Significant adsorption and desorption of Cl2 was observed with the plasma off, similar to that observed previously on plasma-conditioned anodized aluminium surfaces, but with much faster desorption rates that are most likely attributable to the smoother and non-porous stainless steel surface morphology. When the plasma was turned on, a much larger pressure rise was observed due to Langmuir-Hinshelwood recombination of Cl atoms. Recombination coefficients, γCl, ranged from 0.004 to 0.03 and increased with Cl-to-Cl2 number density ratio. This behaviour was observed previously for anodized aluminium surfaces, and was explained by the blocking of Cl recombination sites by adsorbed Cl2. Application of this variable recombination coefficient to the modelling of high-density chlorine plasmas gives a much better agreement with measured Cl2 percent dissociations compared with predictions obtained with a recombination coefficient that is independent of plasma conditions.

  17. Epitaxially guided assembly of collagen layers on mica surfaces.

    PubMed

    Leow, Wee Wen; Hwang, Wonmuk

    2011-09-01

    Ordered assembly of collagen molecules on flat substrates has potential for various applications and serves as a model system for studying the assembly process. While previous studies demonstrated self-assembly of collagen on muscovite mica into highly ordered layers, the mechanism by which different conditions affect the resulting morphology remains to be elucidated. Using atomic force microscopy, we follow the assembly of collagen on muscovite mica at a concentration lower than the critical fibrillogenesis concentration in bulk. Initially, individual collagen molecules adsorb to mica and subsequently nucleate into fibrils possessing the 67 nm D-periodic bands. Emergence of fibrils aligned in parallel despite large interfibril distances agrees with an alignment mechanism guided by the underlying mica. The epitaxial growth was further confirmed by the formation of novel triangular networks of collagen fibrils on phlogopite mica, whose surface lattice is known to have a hexagonal symmetry, whereas the more widely used muscovite does not. Comparing collagen assembly on the two types of mica at different potassium concentrations revealed that potassium binds to the negatively charged mica surface and neutralizes it, thereby reducing the binding affinity of collagen and enhancing surface diffusion. These results suggest that collagen assembly on mica follows the surface adsorption, diffusion, nucleation, and growth pathway, where the growth direction is determined at the nucleation step. Comparison with other molecules that assemble similarly on mica supports generality of the proposed assembly mechanism, the knowledge of which will be useful for controlling the resulting surface morphologies. PMID:21740026

  18. Surface shear rheology of saponin adsorption layers.

    PubMed

    Golemanov, Konstantin; Tcholakova, Slavka; Denkov, Nikolai; Pelan, Edward; Stoyanov, Simeon D

    2012-08-21

    Saponins are a wide class of natural surfactants, with molecules containing a rigid hydrophobic group (triterpenoid or steroid), connected via glycoside bonds to hydrophilic oligosaccharide chains. These surfactants are very good foam stabiliziers and emulsifiers, and show a range of nontrivial biological activities. The molecular mechanisms behind these unusual properties are unknown, and, therefore, the saponins have attracted significant research interest in recent years. In our previous study (Stanimirova et al. Langmuir 2011, 27, 12486-12498), we showed that the triterpenoid saponins extracted from Quillaja saponaria plant (Quillaja saponins) formed adsorption layers with unusually high surface dilatational elasticity, 280 ± 30 mN/m. In this Article, we study the shear rheological properties of the adsorption layers of Quillaja saponins. In addition, we study the surface shear rheological properties of Yucca saponins, which are of steroid type. The experimental results show that the adsorption layers of Yucca saponins exhibit purely viscous rheological response, even at the lowest shear stress applied, whereas the adsorption layers of Quillaja saponins behave like a viscoelastic two-dimensional body. For Quillaja saponins, a single master curve describes the data for the viscoelastic creep compliance versus deformation time, up to a certain critical value of the applied shear stress. Above this value, the layer compliance increases, and the adsorption layers eventually transform into viscous ones. The experimental creep-recovery curves for the viscoelastic layers are fitted very well by compound Voigt rheological model. The obtained results are discussed from the viewpoint of the layer structure and the possible molecular mechanisms, governing the rheological response of the saponin adsorption layers. PMID:22830458

  19. Shotgun proteomic analytical approach for studying proteins adsorbed onto liposome surface.

    PubMed

    Capriotti, Anna Laura; Caracciolo, Giulio; Cavaliere, Chiara; Crescenzi, Carlo; Pozzi, Daniela; Laganà, Aldo

    2011-09-01

    The knowledge about the interaction between plasma proteins and nanocarriers employed for in vivo delivery is fundamental to understand their biodistribution. Protein adsorption onto nanoparticle surface (protein corona) is strongly affected by vector surface characteristics. In general, the primary interaction is thought to be electrostatic, thus surface charge of carrier is supposed to play a central role in protein adsorption. Because protein corona composition can be critical in modifying the interactive surface that is recognized by cells, characterizing its formation onto lipid particles may serve as a fundamental predictive model for the in vivo efficiency of a lipidic vector. In the present work, protein coronas adsorbed onto three differently charged cationic liposome formulations were compared by a shotgun proteomic approach based on nano-liquid chromatography-high-resolution mass spectrometry. About 130 proteins were identified in each corona, with only small differences between the different cationic liposome formulations. However, this study could be useful for the future controlled design of colloidal drug carriers and possibly in the controlled creation of biocompatible surfaces of other devices that come into contact with proteins into body fluids. PMID:21725631

  20. Difference in Surface Properties between Insoluble Monolayer and Adsorbed Film from Kinetics of Water Evaporation and BAM Image.

    PubMed

    Moroi, Yoshikiyo; Rusdi, Muhammad; Kubo, Izumi

    2004-05-20

    The evaporation rate of water molecules across three kinds of interfaces (air/water interface (1), air/surfactant solution interface (2), and air/water interface covered by insoluble monolayer (3)) was examined using a remodeled thermogravimetric balance. There was no difference in both the evaporation rate and the activation energy for the first two interfaces for three types of surfactant solutions below and above the critical micelle concentration (cmc). This means that the molecular surface area from the Gibbs surface excess has nothing to do with the evaporation rate. In the third case, the insoluble monolayer of 1-heptadecanol decreased the evaporation rate and increased the activation energy, indicating a clear difference between an insoluble monolayer and an adsorbed film of soluble surfactant. This difference was substantiated by BAM images, too. The images of three surfactant solution interfaces were similar to that of just the water surface, while distinct structures of molecular assemblies were observed for the insoluble monolayer. The concentration profile of water molecules in an air/liquid interfacial region was derived by Fix's second law. The profile indicates that a definite layer just beneath the air/liquid interface of the surfactant solution is made mostly of water molecules and that the layer thickness is a few times the root-mean-square displacement %@mt;sys@%%@rl;;@%2%@ital@%Dt%@rsf@%%@rlx@%%@mx@% of the water molecules. The thickness was found to be more than a few nanometers, as estimated from several relaxation times derived from the other kinetics than evaporation of amphiphilic molecules in aqueous systems and a maximum evaporation rate of purified water. PMID:18950121

  1. Surface state and normal layer effects

    SciTech Connect

    Klemm, R.A.; Ledvij, M.; Liu, S.H.

    1995-08-01

    In addition to the conducting CuO{sub 2} (S) layers, most high-T{sub c} superconductors also contain other conducting (N) layers, which are only superconducting due to the proximity effect. The combination of S and N layers can give rise to complicated electronic densities of states, leading to quasilinear penetration depth and NMR relaxation rate behavior at low temperatures. Surface states can also complicate the analysis of tunneling and, photoemission measurements. Moreover, geometrical considerations and in homogeneously trapped flux axe possible explanations of the paramagnetic Meissner effect and of corner and ring SQUID experiments. Hence, all of the above experiments could be consistent with isotropic s-wave superconductivity within the S layers.

  2. Effects of surface topography on the collective diffusion of interacting adsorbed particles

    NASA Astrophysics Data System (ADS)

    Rodríguez, M. E. R.; Pasinetti, P. M.; Bulnes, F.; Ramirez-Pastor, A. J.

    2015-08-01

    Collective diffusion of particles with repulsive nearest-neighbor interactions on bivariate surfaces is studied through Monte Carlo simulation, in the framework of the Kubo-Green theory. Shallow and deep adsorbing sites form l × l patches distributed at random or in chessboard-like ordered domains on a two-dimensional square lattice. The influence of the energetic correlation and the lateral interactions on the jump and collective diffusion coefficients are analyzed by simulating the coverage fluctuations in the grand canonical ensemble and the mean-square displacements of particles in the canonical ensemble. The combination of topography and lateral coupling is shown to produce interesting effects such as different filling regimes as well as strong effects on the coverage dependence of the transport coefficients.

  3. Quantum Chemical Study of Raman Spectroscopy of Substituted Benzene Derivatives Adsorbed on Metal Surfaces

    NASA Astrophysics Data System (ADS)

    Wu, De-Yin; Tian, Zhong-Qun

    2011-06-01

    Surface-enhanced Raman spectroscopy (SERS) can be applied to obtain the information of molecules at the noble metal surfaces. But there are a number of difficulties to clearly correlate Raman spectra with microscopic molecular structures on metal surfaces. The main reason is that it is difficult to characterize unambiguously the metal surface structures and the influence of the binding interaction on SERS signals of the probe molecules. According to the surface selection rule of SERS, the electromagnetic enhancement will not change relative Raman intensities of vibrational modes with the same irreducible representation. Therefore, the change of the relative Raman intensities of the total symmetric modes may only originate from the chemical enhancement. In order to understand how the chemical interaction modulates the Raman intensity of individual modes, it is necessary to systematically investigate the Raman spectra of probe molecules themselves and the dependence of SERS signals on the binding interaction, adsorption sites, excitation wavelengths and metal property. Some probe molecules, including aniline, 1,4-benzenediamine, p-aminothiophenol, benzyl chlorine, and 4,4^'-bipyridine are investigated based on quantum chemical calculations. Raman spectra of these molecules and their adsorbed species were predicted and compared with experimentally measured spectra. The metal surfaces were mimicked using the metallic cluster model, where the silver or gold surfaces were replaced by silver or gold clusters, respectively. The density functional theory approach was employed to obtain the optimized structures and vibrational spectra by combining all-electron basis sets of 6-311+G** for atoms in the molecules and the poseudopotential basis set of LANL2DZ for metal atoms. The vibrational frequency shift and the relative Raman intensity are related to the adsorption configuration of the probe molecules. For all these molecules, the ring breathing mode and the C-C stretching

  4. LEED crystallography studies of the structure of clean and adsorbate-covered Ir, Pt and Rh crystal surfaces

    SciTech Connect

    Koestner, R.J.

    1982-08-01

    There have only been a few Low Energy Electron Diffraction (LEED) intensity analyses carried out to determine the structure of molecules adsorbed on metal surfaces; most surface crystallography studies concentrated on the structure of clean unreconstructed or atomic adsorbate-covered transition metal faces. The few molecular adsorption systems already investigated by dynamical LEED are CO on Ni(100), Cu(100) and Pd(100) as well as C/sub 2/H/sub 2/ and C/sub 2/H/sub 4/ adsorbed on Pt(111). The emphasis of this thesis research has been to extend the applicability of LEED crystallography to the more complicated unit cells found in molecular overlayers on transition metals or in there constructed surfaces of clean transition metals.

  5. The effect of surface modification on heavy metal ion removal from water by carbon nanoporous adsorbent

    NASA Astrophysics Data System (ADS)

    Baniamerian, M. J.; Moradi, S. E.; Noori, A.; Salahi, H.

    2009-12-01

    In this work, chemically oxidized mesoporous carbon (COMC) with excellent lead adsorption performance was prepared by an acid surface modification method from mesoporous carbon (MC) by wet impregnation method. The structural order and textural properties of the mesoporous materials were studied by XRD, SEM, and nitrogen adsorption. The presence of carboxylic functional groups on the carbon surface was confirmed by FT-IR analysis. Batch adsorption experiments were conducted to study the effect of adsorbent dose, initial concentration and temperature for the removal of Pb(II) from aqueous systems. The adsorption was maximum for the initial pH in the range of 6.5-8.0. The kinetic data were best fitted to the pseudo-second order model. The adsorption of chemically oxidized mesoporous carbon to Pb(II) fits to the Langmuir model. The larger adsorption capacity of chemically oxidized mesoporous carbon for Pb(II) is mainly due to the oxygenous functional groups formed on the surface of COMC which can react with Pb(II) to form salt or complex deposited on the surface of MC.

  6. Towards 1D nanolines on a monolayered supramolecular network adsorbed on a silicon surface

    NASA Astrophysics Data System (ADS)

    Makoudi, Younes; Beyer, Matthieu; Lamare, Simon; Jeannoutot, Judicael; Palmino, Frank; Chérioux, Frédéric

    2016-06-01

    The growth of 3D extended periodic networks made up of π-conjugated molecules on semi-conductor surfaces is of interest for the integration of nano-components in the future generations of smart devices. In the work presented in this article, we successfully achieved the formation of bilayered networks on a silicon surface including 1D-isolated nanolines in the second layer. Firstly, we observed the formation of a 2D large-scale supramolecular network in the plane of a silicon surface through the deposition of tailored molecules. Then using the same molecules, a second-layer, based on 1D nanolines, grew above the first layer, thanks to a template effect. Mono- or bi-layered networks were found to be stable from 100 K up to room temperature. These networks were investigated by scanning tunnel microscopy imaging under an ultra-high vacuum (UHV-STM).The growth of 3D extended periodic networks made up of π-conjugated molecules on semi-conductor surfaces is of interest for the integration of nano-components in the future generations of smart devices. In the work presented in this article, we successfully achieved the formation of bilayered networks on a silicon surface including 1D-isolated nanolines in the second layer. Firstly, we observed the formation of a 2D large-scale supramolecular network in the plane of a silicon surface through the deposition of tailored molecules. Then using the same molecules, a second-layer, based on 1D nanolines, grew above the first layer, thanks to a template effect. Mono- or bi-layered networks were found to be stable from 100 K up to room temperature. These networks were investigated by scanning tunnel microscopy imaging under an ultra-high vacuum (UHV-STM). Electronic supplementary information (ESI) available: Additional STM images showing submolecular details of the adsorption of molecules on the surface. See DOI: 10.1039/c6nr01826b

  7. A molecular surface science study of the structure of adsorbates on surfaces: Importance to lubrication

    SciTech Connect

    Mate, C.M.

    1986-09-01

    The interaction and bonding of atoms and molecules on metal surfaces is explored under ultra-high vacuum conditions using a variety of surface science techniques: high resolution electron energy loss spectroscopy (HREELS), low energy electron diffraction (LEED), thermal desorption spectroscopy (TDS), Auger electron spectroscopy (AES), work function measurements, and second harmonic generation (SHG). 164 refs., 51 figs., 3 tabs.

  8. Characteristics of the Martian atmosphere surface layer

    NASA Technical Reports Server (NTRS)

    Clow, G. D.; Haberle, R. M.

    1990-01-01

    Elements of various terrestrial boundary layer models are extended to Mars in order to estimate sensible heat, latent heat, and momentum fluxes within the Martian atmospheric surface ('constant flux') layer. The atmospheric surface layer consists of an interfacial sublayer immediately adjacent to the ground and an overlying fully turbulent surface sublayer where wind-shear production of turbulence dominates buoyancy production. Within the interfacial sublayer, sensible and latent heat are transported by non-steady molecular diffusion into small-scale eddies which intermittently burst through this zone. Both the thickness of the interfacial sublayer and the characteristics of the turbulent eddies penetrating through it depend on whether airflow is aerodynamically smooth or aerodynamically rough, as determined by the Roughness Reynold's number. Within the overlying surface sublayer, similarity theory can be used to express the mean vertical windspeed, temperature, and water vapor profiles in terms of a single parameter, the Monin-Obukhov stability parameter. To estimate the molecular viscosity and thermal conductivity of a CO2-H2O gas mixture under Martian conditions, parameterizations were developed using data from the TPRC Data Series and the first-order Chapman-Cowling expressions; the required collision integrals were approximated using the Lenard-Jones potential. Parameterizations for specific heat and binary diffusivity were also determined. The Brutsart model for sensible and latent heat transport within the interfacial sublayer for both aerodynamically smooth and rough airflow was experimentally tested under similar conditions, validating its application to Martian conditions. For the surface sublayer, the definition of the Monin-Obukhov length was modified to properly account for the buoyancy forces arising from water vapor gradients in the Martian atmospheric boundary layer. It was found that under most Martian conditions, the interfacial and surface

  9. A literature review of surface alteration layer effects on waste glass behavior

    SciTech Connect

    Feng, X.; Cunnane, J.C.; Bates, J.K.

    1993-01-01

    When in contact with an aqueous solution, nuclear waste glass is subject to a chemical attack that results in progressive alteration. During tills alteration, constituent elements of the glass pass into the solution; elements initially in solution diffuse into, or are adsorbed onto, the solid; and new phases appear. This results in the formation of surface layers on the reacted glass. The glass corrosion and radionuclide release can be better understood by investigating these surface layer effects. In the past decade, there have been numerous studies regarding the effects of surface layers on glass reactions. This paper presents a systematic analysis and summary of the past knowledge regarding the effects of surface layers on glass-water interaction. This paper describes the major formation mechanisms of surface layers; reviews the role of surface layers in controlling mass transport and glass reaction affinity (through crystalline phases, an amorphous silica, a gel layer, or all the components in the glass); and discusses how the surface layers contribute to the retention of radionuclides during glass dissolution.

  10. A literature review of surface alteration layer effects on waste glass behavior

    SciTech Connect

    Feng, X.; Cunnane, J.C.; Bates, J.K.

    1993-05-01

    When in contact with an aqueous solution, nuclear waste glass is subject to a chemical attack that results in progressive alteration. During tills alteration, constituent elements of the glass pass into the solution; elements initially in solution diffuse into, or are adsorbed onto, the solid; and new phases appear. This results in the formation of surface layers on the reacted glass. The glass corrosion and radionuclide release can be better understood by investigating these surface layer effects. In the past decade, there have been numerous studies regarding the effects of surface layers on glass reactions. This paper presents a systematic analysis and summary of the past knowledge regarding the effects of surface layers on glass-water interaction. This paper describes the major formation mechanisms of surface layers; reviews the role of surface layers in controlling mass transport and glass reaction affinity (through crystalline phases, an amorphous silica, a gel layer, or all the components in the glass); and discusses how the surface layers contribute to the retention of radionuclides during glass dissolution.

  11. Electronic structure of bacterial surface protein layers

    SciTech Connect

    Maslyuk, Volodymyr V.; Mertig, Ingrid; Bredow, Thomas; Mertig, Michael; Vyalikh, Denis V.; Molodtsov, Serguei L.

    2008-01-15

    We report an approach for the calculation of the electronic density of states of the dried two-dimensional crystalline surface protein layer (S layer) of the bacterium Bacillus sphaericus NCTC 9602. The proposed model is based on the consideration of individual amino acids in the corresponding conformation of the peptide chain which additively contribute to the electronic structure of the entire protein complex. The derived results agree well with the experimental data obtained by means of photoemission (PE), resonant PE, and near-edge x-ray absorption spectroscopy.

  12. A slowing down of proton motion from HPTS to water adsorbed on the MCM-41 surface.

    PubMed

    Alarcos, Noemí; Cohen, Boiko; Douhal, Abderrazzak

    2016-01-28

    We report on the steady-state and femtosecond-nanosecond (fs-ns) behaviour of 8-hydroxypyrene-1,3,6-trisulfonate (pyranine, HPTS) and its interaction with mesoporous silica based materials (MCM-41) in both solid-state and dichloromethane (DCM) suspensions in the absence and presence of water. In the absence of water, HPTS forms aggregates which are characterized by a broad emission spectrum and multiexponential behavior (τsolid-state/DCM = 120 ps, 600 ps, 2.2 ns). Upon interaction with MCM41, the aggregate population is found to be lower, leading to the formation of adsorbed monomers. In the presence of water (1%), HPTS with and without MCM41 materials in DCM suspensions undergoes an excited-state intermolecular proton-transfer (ESPT) reaction in the protonated form (ROH*) producing a deprotonated species (RO(-)*). The long-time emission decays of the ROH* in different systems in the presence of water are multiexponential, and are analysed using the diffusion-assisted geminate recombination model. The obtained proton-transfer and recombination rate constants for HPTS and HPTS/MCM41 complexes in DCM suspensions in the presence of water are kPT = 13 ns(-1), krec = 7.5 Å ns(-1), and kPT = 5.4 ns(-1), krec = 2.2 Å ns(-1), respectively, The slowing down of both processes in the latter case is explained in terms of specific interactions of the dye and of the water molecules with the silica surface. The ultrafast dynamics (fs-regime) of the HPTS/MCM41 complexes in DCM suspensions, without and with water, shows two components which are assigned to intramolecular vibrational-energy relaxation (IVR) (∼120 fs vs. ∼0.8 ps), and vibrational relaxation/cooling (VC), and charge transfer (CT) processes (∼2 ps without water and ∼5 ps with water) of the adsorbed ROH*. Our results provide new knowledge on the interactions and the proton-transfer reaction dynamics of HPTS adsorbed on mesoporous materials. PMID:26705542

  13. Dynamics of tungsten hexacarbonyl, dicobalt octacarbonyl, and their fragments adsorbed on silica surfaces

    SciTech Connect

    Muthukumar, Kaliappan; Valentí, Roser; Jeschke, Harald O.

    2014-05-14

    Tungsten and cobalt carbonyls adsorbed on a substrate are typical starting points for the electron beam induced deposition of tungsten or cobalt based metallic nanostructures. We employ first principles molecular dynamics simulations to investigate the dynamics and vibrational spectra of W(CO){sub 6} and W(CO){sub 5} as well as Co{sub 2}(CO){sub 8} and Co(CO){sub 4} precursor molecules on fully and partially hydroxylated silica surfaces. Such surfaces resemble the initial conditions of electron beam induced growth processes. We find that both W(CO){sub 6} and Co{sub 2}(CO){sub 8} are stable at room temperature and mobile on a silica surface saturated with hydroxyl groups (OH), moving up to half an Angström per picosecond. In contrast, chemisorbed W(CO){sub 5} or Co(CO){sub 4} ions at room temperature do not change their binding site. These results contribute to gaining fundamental insight into how the molecules behave in the simulated time window of 20 ps and our determined vibrational spectra of all species provide signatures for experimentally distinguishing the form in which precursors cover a substrate.

  14. Effects of electric field on a copper-dioxolene complex adsorbed on a gold surface

    NASA Astrophysics Data System (ADS)

    Kostyrko, T.; Ślusarski, T.

    2016-06-01

    A model of a copper-dioxolene complex linked to Au(1 1 1) surface with butanethiol linker is investigated using first-principles methods. It is shown that the complex adsorbed at the surface may appear in various locally stable structural forms differing in electron charge and spin density distribution, the symmetric high spin (HS) one and the twisted low spin (LS) structure. The electric field directed perpendicular to the surface controls the amount of the charge transfer between the complex and the substrate, starting from the zero-field value of Q = +0.18 |e| up to the value of Q = +0.94 |e| for the field strength of E = 0.5 V/Å. The field modifies also the mutual stability of the two structural forms, reducing the energy gap between the more energetically stable LS twisted form and the symmetrical HS one, from a value of Δ ∼ 0.29 eV in absence of the field to Δ ∼ 0.11 eV for the field strength of E = 0.35 V/Å.

  15. Surface enhanced raman spectroscopy on nucleic acids and related compounds adsorbed on colloidal silver particles

    NASA Astrophysics Data System (ADS)

    Kneipp, K.; Pohle, W.; Fabian, H.

    1991-04-01

    Various nucleic acids and related compounds have been investigated by surface enhanced Raman spectroscopy (SERS) on silver sol. The time delay between the addition of the various nucleic acids to the silver sol and the appearance of their SER spectra, i.e. the time needed by the various molecules to adsorb on an active site of the silver surface with an adsorption geometry which allows a SERS enhancement, shows strong differences. For instance, an immediate appearance of SER spectra has been found for DNA, whereas ribonucleic acids (RNAs) demonstrated a strong time delay (up to days) of the appearance of their SER spectra. This delay can be tentatively explained by the higher rigidity of RNA molecules compared with DNA. The more flexible DNA molecules are better adaptable to adsorption on silver than RNAs. The SER spectra of RNAs and DNAs showed strong changes within their relative line intensities as a function of time before they achieved stationary conditions, which indicates a protracted re-arrangement of the large molecules on the silver surface.

  16. Adsorbed sulfur-gas methods for both near-surface exploration and downhole logging

    SciTech Connect

    Farwell, S.O.; Barinaga, C.J.; Dolenc, M.R.; Farwell, G.H.

    1986-08-01

    The use of sulfur-containing gases in petroleum exploration is supported by (1) the idea that sulfur may play a role in petroleum genesis, (2) the corresponding existence of sulfur-containing compounds in petroleum and the potential for vertical migration of the low-molecular-weight sulfur species from these reservoirs, (3) the production of H/sub 2/S by anaerobic microorganism populations that develop in the subsurface areas overlying petroleum reservoirs due to the concomitant supply of hydrocarbon nutrients, (4) the recent discovery of near-surface accumulations of pyrite and marcasite as the source of induction potential anomalies over certain fields, and (5) the strong adsorptive affinities of sulfur gases to solid surfaces, which enhance both the concentration and localization of such sulfur-expressed anomalies. During the past 3 years, numerous near-surface soil samples and well cuttings from the Utah-Wyoming Overthrust belt have been analyzed for adsorbed sulfur-gas content by two novel analytical techniques: thermal desorption/metal foil collection/flash desorption/sulfur-selective detection (TD/MFC/FD/SSD) and thermal desorption/cryogenic preconcentration/high-resolution-gas chromatography/optimized-flame photometry (TD/CP/HRGC/OFP).

  17. Quantum chemical investigation on the role of Li adsorbed on anatase (101) surface nano-materials on the storage of molecular hydrogen.

    PubMed

    Srinivasadesikan, V; Raghunath, P; Lin, M C

    2015-06-01

    Lithiation of TiO2 has been shown to enhance the storage of hydrogen up to 5.6 wt% (Hu et al. J Am Chem Soc 128:11740-11741, 2006). The mechanism for the process is still unknown. In this work we have carried out a study on the adsorption and diffusion of Li atoms on the surface and migration into subsurface layers of anatase (101) by periodic density functional theory calculations implementing on-site Coulomb interactions (DFT+U). The model consists of 24 [TiO2] units with 11.097 × 7.655 Å(2) surface area. Adsorption energies have been calculated for different Li atoms (1-14) on the surface. A maximum of 13 Li atoms can be accommodated on the surface at two bridged O, Ti-O, and Ti atom adsorption sites, with 83 kcal mol(-1) adsorption energy for a single Li atom adsorbed between two bridged O atoms from where it can migrate into the subsurface layer with 27 kcal mol(-1) energy barrier. The predicted adsorption energies for H2 on the lithiated TiO2 (101) surface with 1-10 Li atoms revealed that the highest adsorption energies occurred on 1-Li, 5-Li, and 9-Li surfaces with 3.5, 4.4, and 7.6 kcal mol(-1), respectively. The values decrease rapidly with additional H2 co-adsorbed on the lithiated surfaces; the maximum H2 adsorption on the 9Li-TiO2(a) surface was estimated to be only 0.32 wt% under 100 atm H2 pressure at 77 K. The result of Bader charge analysis indicated that the reduction of Ti occurred depending on the Li atoms covered on the TiO2 surface. PMID:25966674

  18. Bionanocomposites based on layered silicates and cationic starch as eco-friendly adsorbents for hexavalent chromium removal.

    PubMed

    Koriche, Yamina; Darder, Margarita; Aranda, Pilar; Semsari, Saida; Ruiz-Hitzky, Eduardo

    2014-07-21

    Functional bionanocomposites based on two layered silicates, the commercial montmorillonite known as Cloisite®Na and a natural bentonite from Algeria, were prepared by intercalation of cationic starch, synthesized with two different degrees of substitution, 0.85 and 0.55. After characterization of the prepared bionanocomposites by XRD and zeta potential measurements, batch studies were conducted to evaluate the adsorption capacity of hexavalent chromium anions from aqueous solution. The adsorption isotherms, adsorption kinetics, and the effect of pH on the process were studied. The removal efficiency was evaluated in the presence of competing anions such as NO3(-), ClO4(-), SO4(2-) and Cl(-). In order to regenerate the adsorbent for its repeated use, the regeneration process was studied in two different extractant solutions, 0.1 M NaCl at pH 10 and 0.28 M Na2CO3 at pH 12. PMID:24658793

  19. An attenuated total reflectance IR study of silicic acid adsorbed onto a ferric oxyhydroxide surface

    NASA Astrophysics Data System (ADS)

    Swedlund, Peter J.; Miskelly, Gordon M.; McQuillan, A. James

    2009-07-01

    Silicic acid (H 4SiO 4) can have significant effects on the properties of iron oxide surfaces in both natural and engineered aquatic systems. Understanding the reactions of H 4SiO 4 on these surfaces is therefore necessary to describe the aquatic chemistry of iron oxides and the elements that associate with them. This investigation uses attenuated total reflectance infrared spectroscopy (ATR-IR) to study silicic acid in aqueous solution and the products formed when silicic acid adsorbs onto the surface of a ferrihydrite film in 0.01 M NaCl at pH 4. A spectrum of 1.66 mM H 4SiO 4 at pH 4 (0.01 M NaCl) has an asymmetric Si-O stretch at 939 cm -1 and a weak Si-O-H deformation at 1090 cm -1. ATR-IR spectra were measured over time (for up to 7 days) for a ferrihydrite film (≈1 mg) approaching equilibrium with H 4SiO 4 at concentrations between 0.044 and 0.91 mM. Adsorbed H 4SiO 4 had a broad spectral feature between 750 and 1200 cm -1 but the shape of the spectra changed as the amount of H 4SiO 4 adsorbed on the ferrihydrite increased. When the solid phase Si/Fe mole ratio was less than ≈0.01 the ATR-IR spectra had a maximum intensity at 943 cm -1 and the spectral shape suggests that a monomeric silicate species was formed via a bidentate linkage. As the solid phase Si/Fe mole ratio increased to higher values a discrete oligomeric silicate species was formed which had maximum intensity in the ATR-IR spectra at 1001 cm -1. The spectrum of this species suggests that it is larger than a dimer and it was tentatively identified as a cyclic tetramer. A small amount of a polymeric silica phase with a broad spectral feature centered at ≈1110 cm -1 was also observed at high surface coverage. The surface composition was estimated from the relative contribution of each species to the area of the ATR-IR spectra using multivariate curve resolution with alternating least squares. For a ferrihydrite film approaching equilibrium with 0.044, 0.14, 0.40 and 0.91 mM H 4SiO 4 the

  20. Regular surface layer of Azotobacter vinelandii.

    PubMed Central

    Bingle, W H; Doran, J L; Page, W J

    1984-01-01

    Washing Azotobacter vinelandii UW1 with Burk buffer or heating cells at 42 degrees C exposed a regular surface layer which was effectively visualized by freeze-etch electron microscopy. This layer was composed of tetragonally arranged subunits separated by a center-to-center spacing of approximately 10 nm. Cells washed with distilled water to remove an acidic major outer membrane protein with a molecular weight of 65,000 did not possess the regular surface layer. This protein, designated the S protein, specifically reattached to the surface of distilled-water-washed cells in the presence of the divalent calcium, magnesium, strontium, or beryllium cations. All of these cations except beryllium supported reassembly of the S protein into a regular tetragonal array. Although the surface localization of the S protein has been demonstrated, radioiodination of exposed envelope proteins in whole cells did not confirm this. The labeling behavior of the S protein could be explained on the basis of varying accessibilities of different tyrosine residues to iodination. Images PMID:6735982

  1. Photodissociation of methyl iodide adsorbed on low-temperature amorphous ice surfaces

    SciTech Connect

    DeSimone, Alice J.; Olanrewaju, Babajide O.; Grieves, Gregory A.; Orlando, Thomas M.

    2013-02-28

    Photodissociation dynamics of methyl iodide (CH{sub 3}I) adsorbed on both amorphous solid water (ASW) and porous amorphous solid water (PASW) has been investigated. The ejected ground-state I({sup 2}P{sub 3/2}) and excited-state I({sup 2}P{sub 1/2}) photofragments produced by 260- and 290-nm photons were detected using laser resonance-enhanced multiphoton ionization. In contrast to gas-phase photodissociation, (i) the I({sup 2}P{sub 3/2}) photofragment is favored compared to I({sup 2}P{sub 1/2}) at both wavelengths, (ii) I({sup 2}P{sub 3/2}) and I({sup 2}P{sub 1/2}) have velocity distributions that depend upon ice morphology, and (iii) I{sub 2} is produced on ASW. The total iodine [I({sup 2}P{sub 3/2})+I({sup 2}P{sub 1/2})+I{sub 2}] yield varies with substrate morphology, with greater yield from ASW than PASW using both 260- and 290-nm photons. Temperature-programmed desorption studies demonstrate that ice porosity enhances the trapping of adsorbed CH{sub 3}I, while pore-free ice likely allows monomer adsorption and the formation of two-dimensional CH{sub 3}I clusters. Reactions or collisions involving these clusters, I atomic fragments, or I-containing molecular fragments at the vacuum-surface interface can result in I{sub 2} formation.

  2. Theory of surface light scattering from a fluid-fluid interface with adsorbed polymeric surfactants

    NASA Astrophysics Data System (ADS)

    Buzza, D. M. A.; Jones, J. L.; McLeish, T. C. B.; Richards, R. W.

    1998-09-01

    We present a microscopic theory for the interfacial rheology of a fluid-fluid interface with adsorbed surfactant and calculate the effect of this on surface light scattering from the interface. We model the head and tail groups of the surfactant as polymer chains, a description that becomes increasingly accurate for large molecular weight surfactants, i.e., polymeric surfactants. Assuming high surface concentrations so that we have a double-sided polymer brush monolayer, we derive microscopic scaling expressions for the surface viscoelastic constants using the Alexander-deGennes model. Our results for the surface elastic constants agree with those in the literature, while the results for the viscous constants are new. We find that four elastic constants, i.e., γ (surface tension), ɛ (dilational elasticity), κ (bending modulus), λ (coupling constant), and three viscous constants, i.e., ɛ',κ',λ' (the viscous counterparts of ɛ, κ, and λ, respectively) are required for a general description of interfacial viscoelasticity (neglecting in-plane shear). In contrast to current phenomenological models, we find (1) there is no viscous counterpart to γ, i.e., γ'≡0; (2) there are two additional complex surface constants (i.e., λ+iωλ' and κ+iωκ') due to the finite thickness of the monolayer. Excellent agreement is found comparing our microscopic theory with measurements on diblock copolymer monolayers. We further derive the dispersion relation governing surface hydrodynamic modes and the power spectrum for surface quasielastic light scattering (SQELS) for a general interface parameterized by all the surface viscoelastic constants. Limiting results are presented for (1) liquid-air interfaces; (2) liquid-liquid interfaces with ultralow γ. The significant contribution of κ in the latter case opens up the possibility for a direct measurement of κ using SQELS for polymeric surfactant monolayers. Finally, we show that the coupling constant λ can lead to

  3. Influence of carboxylic ion-pairing reagents on retention of peptides in thin-layer chromatography systems with C18 silica-based adsorbents.

    PubMed

    Gwarda, Radosław Ł; Aletańska-Kozak, Monika; Klimek-Turek, Anna; Ziajko-Jankowska, Agnieszka; Matosiuk, Dariusz; Dzido, Tadeusz H

    2016-04-01

    One of the main problems related to chromatography of peptides concerns adverse interactions of their strong basic groups with free silanol groups of the silica based stationary phase. Influence of type and concentration of ion-pairing regents on peptide retention in reversed-phase high-performance liquid chromatography (RP-HPLC) systems has been discussed before. Here we present influence of these mobile phase additives on retention of some peptide standards in high-performance thin-layer chromatography (HPTLC) systems with C18 silica-based adsorbents. We prove, that due to different characteristic of adsorbents used in both techniques (RP HPLC and HPTLC), influence of ion-pairing reagents on retention of basic and/or amphoteric compounds also may be quite different. C18 silica-based HPTLC adsorbents provide more complex mechanism of retention and should be rather considered as mixed-mode adsorbents. PMID:26944833

  4. Surface layer effect on nuclear deformation energy

    NASA Astrophysics Data System (ADS)

    Kolomietz, V. M.; Sanzhur, A. I.; Reznychenko, B. V.

    2016-03-01

    In this paper, we apply the direct variational method to derive the nuclear deformation energy. The extended Thomas-Fermi approximation (ETFA) for the energy functional with Skyrme forces is used. We study the influence of the finite surface layer of the nuclear density profile function on the formation of the fission barrier and the scission configuration. Comparison of the variational approach with the traditional liquid drop model (LDM) is presented. We show the sensitivity of the numerical results to the surface diffuseness parameter.

  5. Effect of Oxygen Adsorbates on Terahertz Emission Properties of Various Semiconductor Surfaces Covered with Graphene

    NASA Astrophysics Data System (ADS)

    Bagsican, Filchito Renee; Zhang, Xiang; Ma, Lulu; Wang, Minjie; Murakami, Hironaru; Vajtai, Robert; Ajayan, Pulickel M.; Kono, Junichiro; Tonouchi, Masayoshi; Kawayama, Iwao

    2016-07-01

    We have studied coherent terahertz (THz) emission from graphene-coated surfaces of three different semiconductors—InP, GaAs, and InAs—to provide insight into the influence of O2 adsorption on charge states and dynamics at the graphene/semiconductor interface. The amplitude of emitted THz radiation from graphene-coated InP was found to change significantly upon desorption of O2 molecules by thermal annealing, while THz emission from bare InP was nearly uninfluenced by O2 desorption. In contrast, the amount of change in the amplitude of emitted THz radiation due to O2 desorption was essentially the same for graphene-coated GaAs and bare GaAs. However, in InAs, neither graphene coating nor O2 adsorption/desorption affected the properties of its THz emission. These results can be explained in terms of the effects of adsorbed O2 molecules on the different THz generation mechanisms in these semiconductors. Furthermore, these observations suggest that THz emission from graphene-coated semiconductors can be used for probing surface chemical reactions (e.g., oxidation) as well as for developing O2 gas sensor devices.

  6. Characteristics of the Martian atmosphere surface layer

    NASA Technical Reports Server (NTRS)

    Clow, G. D.; Haberle, R. M.

    1991-01-01

    Researchers extend elements of various terrestrial boundary layer models to Mars in order to estimate sensible heat, latent heat, and momentum fluxes within the Martian atmospheric surface layer. To estimate the molecular viscosity and thermal conductivity of a CO2-H2O gas mixture under Martian conditions, parameterizations were developed. Parameterizations for specific heat and and binary diffusivity were also determined. The Prandtl and Schmidt numbers derived from these thermophysical properties were found to range from 0.78 - 1.0 and 0.47 - 0.70, respectively, for Mars. Brutsaert's model for sensible and latent heat transport within the interfacial sublayer for both aerodynamically smooth and rough airflow was experimentally tested under similar conditions, validating its application to Martian conditions. For the surface sublayer, the researchers modified the definition of the Monin-Obukhov length to properly account for the buoyancy forces arising from water vapor gradients in the Martian atmospheric boundary layer. This length scale was then utilized with similarity theory turbulent flux profiles with the same form as those used by Businger et al. and others. It was found that under most Martian conditions, the interfacial and surface sublayers offer roughly comparable resistance to sensible heat and water vapor transport and are thus both important in determining the associated fluxes.

  7. Adsorbate-induced reconstruction of an array of atomic wires: Indium on the Si(553)-Au surface

    NASA Astrophysics Data System (ADS)

    Ahn, J. R.; Kang, P. G.; Byun, J. H.; Yeom, H. W.

    2008-01-01

    The In-induced surface reconstruction of the Si(553)-Au surface has been studied using the combined experiment of low-energy-electron diffraction, scanning tunneling microscopy, and angle-resolved photoemission spectroscopy. Low-energy-electron diffraction revealed that In adsorbates interact actively with the surface above 150°C , widening the terraces uniformly and forming a new atomic wire array. This wire structure has a ×2 period along the wires, where the phase coherence across the wires was much better than that of the pristine Si(553)-Au surface. The In-induced uniform terrace widening was confirmed by scanning tunneling microscopy. More interestingly, the In adsorbates alter the metallic atomic wires of the Si(553)-Au surface with highly dispersive one-dimensional bands into insulating ones with still large dispersion.

  8. Tuning of surface wettability of RGO-based aerogels for various adsorbates in water using different amino acids.

    PubMed

    Liu, Wenjun; Wang, Yongke; Li, Zhaohui

    2014-09-14

    RGO-based aerogels with varied and controllable surface wettability were fabricated using different amino acids. Hydrophobic cys-RGO aerogels prepared by L-cysteine exhibited an outstanding adsorption toward oils and organic solvents, while hydrophilic lys-RGO aerogels obtained from L-lysine can be used as adsorbents for heavy metal ions in water. PMID:25057754

  9. Thrombocyte adhesion and release of extracellular microvesicles correlate with surface morphology of adsorbent polymers for lipid apheresis.

    PubMed

    Weiss, René; Spittler, Andreas; Schmitz, Gerd; Fischer, Michael B; Weber, Viktoria

    2014-07-14

    Whole blood lipid apheresis is clinically applied to reduce low density lipoprotein cholesterol in patients with homozygous familial hypercholesterolemia. Here, we studied the correlation between physicochemical parameters, in particular, surface roughness and blood compatibility, of two polyacrylate-based and a dextran sulfate-based polymer for lipid apheresis. The adsorbent surface roughness was assessed by atomic force microscopy. Freshly isolated human thrombocytes were circulated over adsorbent columns downscaled equivalent to clinical use to study thrombocyte adhesion and microvesicle generation. Quantification of thrombocytes and microvesicles in the flow-through of the columns revealed that both thrombocyte adhesion and microvesicle generation increased with increasing adsorbent surface roughness. Activation of thrombocytes with thrombin receptor-activating peptide-6 favored their adhesion to the adsorbents, as demonstrated by preferential depletion of CD62(+) and PAC-1(+) thrombocytes. Taken together, enhanced polymer surface roughness fostered cell adhesion and microvesicle release, underscoring the role of extracellular microvesicles as markers of cellular activation and of blood compatibility. PMID:24844344

  10. Evaluation of the Effectiveness of Surfactants and Denaturants to Elute and Denature Adsorbed Protein on Different Surface Chemistries.

    PubMed

    Thyparambil, Aby A; Wei, Yang; Latour, Robert A

    2015-11-01

    The elution and/or denaturation of proteins from material surfaces by chemical excipients such as surfactants and denaturants is important for numerous applications including medical implant reprocessing, bioanalyses, and biodefense. The objective of this study was to develop and apply methods to quantitatively assess how surface chemistry and adsorption conditions influence the effectiveness of three commonly used surfactants (sodium dodecyl sulfate, n-octyl-β-d-glucoside, and 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate) and two denaturants (guanidium hydrochloride and urea) to elute protein (hen egg white lysozyme and bovine pancreatic ribonuclease A) from three different surface chemistries (silica glass, poly(methyl methacrylate), and high-density polyethylene). The structure and bioactivity of residual protein on the surface following elution were characterized using circular dichroism spectropolarimetry and enzyme assays to assess the extent of protein denaturation. Our results indicate that the denaturants were generally more effective than the surfactants in removing the adsorbed proteins from each type of surface. Also, the denaturing capacity of these excipients on the residual proteins on the surfaces was distinctly different from their influence on the proteins in solution and was unique for each of the adsorption conditions. Taken altogether, these results reveal that the effectiveness of surfactants and denaturants to elute and denature adsorbed protein is significantly influenced by surface chemistry and the conditions from which the protein was adsorbed. These results provide a basis for the selection, design, and further development of chemical agents for protein elution and surface decontamination. PMID:26449787

  11. Adsorbate-Induced Anchoring Transitions of Liquid Crystals on Surfaces Presenting Metal Salts with Mixed Anions

    PubMed Central

    Hunter, Jacob T.; Abbott, Nicholas L.

    2014-01-01

    We report that metal salts composed of mixtures of anions of differing coordination strength can be used to increase the sensitivity and selectivity of adsorbate-induced anchoring transitions of liquid crystals (LCs) supported on surfaces decorated with the metal salts. Specifically, the dynamics of anchoring transitions triggered by the adsorbate dimethyl methylphosphonate (DMMP) on surfaces of aluminum (III) salts were analyzed within the framework of a model for mass transport to reveal that the sensitivity of a nitrile-containing nematic LC to DMMP increased from 250 parts-per- billion (ppb) to 25 ppb when the composition of the (counter) anion was changed from 100% perchlorate to 90% nitrate and 10% perchlorate (by mole percent). To provide insight into these observations, Polarization-Modulation Infrared Reflectance-Absorbance Spectroscopy (PM-IRRAS) was used to show that the intensity of the absorption band in the IR spectrum corresponding to the coordinated state of the nitrile group (but not the position of the peak) decreased with increase in mole fraction of the strongly coordinating anion (nitrate) in the anion mixture, thus suggesting that the addition of the strongly coordinating anion decreased the number of coordination interactions (per unit area of the interface) but not the strength of the individual coordination interactions between the metal cation and the LC. We also measured the incorporation of the nitrate anion into the metal salt to decrease the effect of humidity on the dynamic response of the LC to DMMP, a result that is consistent with weaker interactions between the nitrate anion and water as compared to the perchlorate anion and water. Finally, the bidentate anion acetylacetonate was measured to cause a similar increase in sensitivity to DMMP when mixed with perchlorate in a 1:1 ratio (the resulting sensitivity of the system to DMMP was 100 ppb). Overall, these results suggest that tailoring the identity of the anion represents a

  12. Engineering topological superconductors using surface atomic-layer/molecule hybrid materials.

    PubMed

    Uchihashi, Takashi

    2015-08-28

    Surface atomic-layer (SAL) superconductors consisting of epitaxially grown metal adatoms on a clean semiconductor surface have been recently established. Compared to conventional metal thin films, they have two important features: (i) space-inversion symmetry-breaking throughout the system and (ii) high sensitivity to surface adsorption of foreign species. These potentially lead to manifestation of the Rashba effect and a Zeeman field exerted by adsorbed magnetic organic molecules. After introduction of the archetypical SAL superconductor Si(111)-(√7 × √3)-In, we describe how these features are utilized to engineer a topological superconductor with Majorana fermions and discuss its promises and expected challenges. PMID:26234824

  13. Engineering topological superconductors using surface atomic-layer/molecule hybrid materials

    NASA Astrophysics Data System (ADS)

    Uchihashi, Takashi

    2015-08-01

    Surface atomic-layer (SAL) superconductors consisting of epitaxially grown metal adatoms on a clean semiconductor surface have been recently established. Compared to conventional metal thin films, they have two important features: (i) space-inversion symmetry-breaking throughout the system and (ii) high sensitivity to surface adsorption of foreign species. These potentially lead to manifestation of the Rashba effect and a Zeeman field exerted by adsorbed magnetic organic molecules. After introduction of the archetypical SAL superconductor Si(111)-(√7 × √3)-In, we describe how these features are utilized to engineer a topological superconductor with Majorana fermions and discuss its promises and expected challenges.

  14. Surface rheology of saponin adsorption layers.

    PubMed

    Stanimirova, R; Marinova, K; Tcholakova, S; Denkov, N D; Stoyanov, S; Pelan, E

    2011-10-18

    Extracts of the Quillaja saponaria tree contain natural surfactant molecules called saponins that very efficiently stabilize foams and emulsions. Therefore, such extracts are widely used in several technologies. In addition, saponins have demonstrated nontrivial bioactivity and are currently used as essential ingredients in vaccines, food supplements, and other health products. Previous preliminary studies showed that saponins have some peculiar surface properties, such as a very high surface modulus, that may have an important impact on the mechanisms of foam and emulsion stabilization. Here we present a detailed characterization of the main surface properties of highly purified aqueous extracts of Quillaja saponins. Surface tension isotherms showed that the purified Quillaja saponins behave as nonionic surfactants with a relatively high cmc (0.025 wt %). The saponin adsorption isotherm is described well by the Volmer equation, with an area per molecule of close to 1 nm(2). By comparing this area to the molecular dimensions, we deduce that the hydrophobic triterpenoid rings of the saponin molecules lie parallel to the air-water interface, with the hydrophilic glucoside tails protruding into the aqueous phase. Upon small deformation, the saponin adsorption layers exhibit a very high surface dilatational elasticity (280 ± 30 mN/m), a much lower shear elasticity (26 ± 15 mN/m), and a negligible true dilatational surface viscosity. The measured dilatational elasticity is in very good agreement with the theoretical predictions of the Volmer adsorption model (260 mN/m). The measured characteristic adsorption time of the saponin molecules is 4 to 5 orders of magnitude longer than that predicted theoretically for diffusion-controlled adsorption, which means that the saponin adsorption is barrier-controlled around and above the cmc. The perturbed saponin layers relax toward equilibrium in a complex manner, with several relaxation times, the longest of them being around 3

  15. Outer-sphere Pb(II) adsorbed at specific surface sites on single crystal α-alumina

    USGS Publications Warehouse

    Bargar, John R.; Towle, Steven N.; Brown, Gordon E., Jr.; Parks, George A.

    1996-01-01

    Solvated Pb(II) ions were found to adsorb as structurally well-defined outer-sphere complexes at specific sites on the α-Al2O3 (0001) single crystal surface, as determined by grazing-incidence X-ray absorption fine structure (GI-XAFS) measurements. The XAFS results suggest that the distance between Pb(II) adions and the alumina surface is approximately 4.2 Å. In contrast, Pb(II) adsorbs as more strongly bound inner-sphere complexes on α-Al2O3 (102). The difference in reactivities of the two alumina surfaces has implications for modeling surface complexation reactions of contaminants in natural environments, catalysis, and compositional sector zoning of oxide crystals.

  16. Polarity of an MCM-41 adsorbent surface modified with methyl and phenyl groups based on data from gas chromatography

    NASA Astrophysics Data System (ADS)

    Sukhareva, D. A.; Gus'kov, V. Yu.; Karpov, S. I.; Kudasheva, F. Kh.; Roessner, F.; Borodina, E. V.

    2016-02-01

    The polarity of an MCM-41 adsorbent surface and organosilylated composites based on it with grafted trimethylsilane and dimethylphenylsilane groups is studied via inverse gas chromatography at infinite dilution. The dispersion and specific components of the value proportional to the Helmholtz adsorption energy are calculated, and a comparative analysis of the surface polarity of MCM-41 and its modified analogs relative to the commercially available C-120 silica gel is performed. The electrostatic and donor-acceptor components of the specific Helmholtz adsorption energy are calculated through linear decomposition of the adsorption energy. It is established that MCM-41 is less polar than C-120. The modification of the initial adsorbent surface leads to a reduction in polarity, due mainly to the weakening of induction and orientation interactions. It is concluded that the surfaces of the modified samples retain the ability to form hydrogen bonds.

  17. Interrogation of surfaces for the quantification of adsorbed species on electrodes: oxygen on gold and platinum in neutral media.

    PubMed

    Rodríguez-López, Joaquín; Alpuche-Avilés, Mario A; Bard, Allen J

    2008-12-17

    We introduce a new in situ electrochemical technique based on the scanning electrochemical microscope (SECM) operating in a transient feedback mode for the detection and direct quantification of adsorbed species on the surface of electrodes. A SECM tip generates a titrant from a reversible redox mediator that reacts chemically with an electrogenerated or chemically adsorbed species at a substrate of about the same size as the tip, which is positioned at a short distance from it (ca.1 microm). The reaction between the titrant and the adsorbate provides a transient positive feedback loop until the adsorbate is consumed completely. The sensing mechanism is provided by the contrast between positive and negative feedback, which allows a direct quantification of the charge neutralized at the substrate. The proposed technique allows quantification of the adsorbed species generated at the substrate at a given potential under open circuit conditions, a feature not attainable with conventional electrochemical methods. Moreover, the feedback mode allows the tip to be both the titrant generator and detector, simplifying notably the experimental setup. The surface interrogation technique we introduce was tested for the quantification of electrogenerated oxides (adsorbed oxygen species) on gold and platinum electrodes at neutral pH in phosphate and TRIS buffers and with two different mediator systems. Good agreement is found with cyclic voltammetry at the substrate and with previous results in the literature, but we also find evidence for the formation of "incipient oxides" which are not revealed by conventional voltammetry. The mode of operation of the technique is supported by digital simulations, which show good agreement with the experimental results. PMID:19053403

  18. Analysis of flexural rigidity of actin filaments propelled by surface adsorbed myosin motors.

    PubMed

    Bengtsson, Elina; Persson, Malin; Månsson, Alf

    2013-11-01

    Actin filaments are central components of the cytoskeleton and the contractile machinery of muscle. The filaments are known to exist in a range of conformational states presumably with different flexural rigidity and thereby different persistence lengths. Our results analyze the approaches proposed previously to measure the persistence length from the statistics of the winding paths of actin filaments that are propelled by surface-adsorbed myosin motor fragments in the in vitro motility assay. Our results suggest that the persistence length of heavy meromyosin propelled actin filaments can be estimated with high accuracy and reproducibility using this approach provided that: (1) the in vitro motility assay experiments are designed to prevent bias in filament sliding directions, (2) at least 200 independent filament paths are studied, (3) the ratio between the sliding distance between measurements and the camera pixel-size is between 4 and 12, (4) the sliding distances between measurements is less than 50% of the expected persistence length, and (5) an appropriate cut-off value is chosen to exclude abrupt large angular changes in sliding direction that are complications, e.g., due to the presence of rigor heads. If the above precautions are taken the described method should be a useful routine part of in vitro motility assays thus expanding the amount of information to be gained from these. PMID:24039103

  19. Electrical conductivity of reconstructed Si(111) surface with sodium-doped C{sub 60} layers

    SciTech Connect

    Tsukanov, D. A. Saranin, A. A.; Ryzhkova, M. V.; Borisenko, E. A.; Zotov, A. V.

    2015-01-05

    Electrical conductance of sodium-doped C{sub 60} ultra-thin layers (1–6 monolayers) grown on the Na-adsorbed Si(111)√3 × √3-Au surface has been studied in situ by four-point probe technique, combined with low-energy electron diffraction observations. Evidence of conductance channel formation through the C{sub 60} ultrathin layer is demonstrated as a result of Na dosing of 3 and 6 monolayers thick C{sub 60} layers. The observed changes in surface conductivity can be attributed to the formation of fulleride-like NaC{sub 60} and Na{sub 2}C{sub 60} compound layers.

  20. Surface roughness scattering in multisubband accumulation layers

    NASA Astrophysics Data System (ADS)

    Fu, Han; Reich, K. V.; Shklovskii, B. I.

    2016-06-01

    Accumulation layers with very large concentrations of electrons where many subbands are filled became recently available due to ionic liquid and other new methods of gating. The low-temperature mobility in such layers is limited by the surface roughness scattering. However, theories of roughness scattering so far dealt only with the small-density single subband two-dimensional electron gas (2DEG). Here we develop a theory of roughness-scattering limited mobility for the multisubband large concentration case. We show that with growing 2D electron concentration n the surface dimensionless conductivity σ /(2 e2/h ) first decreases as ∝n-6 /5 and then saturates as ˜(d aB/Δ2)≫1 , where d and Δ are the characteristic length and height of the surface roughness and aB is the effective Bohr radius. This means that in spite of the shrinkage of the 2DEG thickness and the related increase of the scattering rate the 2DEG remains a good metal.

  1. Diurnal ocean surface layer model validation

    NASA Technical Reports Server (NTRS)

    Hawkins, Jeffrey D.; May, Douglas A.; Abell, Fred, Jr.

    1990-01-01

    The diurnal ocean surface layer (DOSL) model at the Fleet Numerical Oceanography Center forecasts the 24-hour change in a global sea surface temperatures (SST). Validating the DOSL model is a difficult task due to the huge areas involved and the lack of in situ measurements. Therefore, this report details the use of satellite infrared multichannel SST imagery to provide day and night SSTs that can be directly compared to DOSL products. This water-vapor-corrected imagery has the advantages of high thermal sensitivity (0.12 C), large synoptic coverage (nearly 3000 km across), and high spatial resolution that enables diurnal heating events to be readily located and mapped. Several case studies in the subtropical North Atlantic readily show that DOSL results during extreme heating periods agree very well with satellite-imagery-derived values in terms of the pattern of diurnal warming. The low wind and cloud-free conditions necessary for these events to occur lend themselves well to observation via infrared imagery. Thus, the normally cloud-limited aspects of satellite imagery do not come into play for these particular environmental conditions. The fact that the DOSL model does well in extreme events is beneficial from the standpoint that these cases can be associated with the destruction of the surface acoustic duct. This so-called afternoon effect happens as the afternoon warming of the mixed layer disrupts the sound channel and the propagation of acoustic energy.

  2. Thermodynamic stability of a bi-layer of copper nitride on Cu(100) surface

    NASA Astrophysics Data System (ADS)

    Pushpa, Raghani; Williamson, Izaak; Jones, Barbara

    2011-08-01

    Ultrathin insulating films composed of a few atomic layers are being extensively used for controlling the electronic coupling of nanostructures deposited on a substrate. Ultrathin film, for example, a single layer of Cu2N deposited on a Cu(100) surface (known as Cu2N/Cu(100) surface) has been used to determine the spectral properties of nanomagnets using scanning tunneling spectroscopy. However, recent experiments that measure spin relaxation times in a single atom suggest that the single layer of Cu2N does not provide efficient electronic decoupling. In this work, we study the thermodynamic stability of a bi-layer of copper nitride on the Cu(100) surface. We calculate adsorption and co-adsorption energies of Cu and N as a function of their concentration on the Cu2N/Cu(100) surface using density functional theory. We find that the adsorption and co-adsorption energies of Cu and N on the Cu2N/Cu(100) surface are of the order of a few eV. This suggests that the bi-layer of copper nitride is thermodynamically stable on the Cu(100) surface. We also find that the work function of N-adsorbed Cu2N/Cu(100) increases with the N concentration, suggesting a better insulating character of the bi-layer of copper nitride on the Cu(100) surface.

  3. Surface Properties of PEMFC Gas Diffusion Layers

    SciTech Connect

    WoodIII, David L; Rulison, Christopher; Borup, Rodney

    2010-01-01

    The wetting properties of PEMFC Gas Diffusion Layers (GDLs) were quantified by surface characterization measurements and modeling of material properties. Single-fiber contact-angle and surface energy (both Zisman and Owens-Wendt) data of a wide spectrum of GDL types is presented to delineate the effects of hydrophobic post-processing treatments. Modeling of the basic sessile-drop contact angle demonstrates that this value only gives a fraction of the total picture of interfacial wetting physics. Polar forces are shown to contribute 10-20 less than dispersive forces to the composite wetting of GDLs. Internal water contact angles obtained from Owens-Wendt analysis were measured at 13-19 higher than their single-fiber counterparts. An inverse relationship was found between internal contact angle and both Owens-Wendt surface energy and % polarity of the GDL. The most sophisticated PEMFC mathematical models use either experimentally measured capillary pressures or the standard Young-Laplace capillary-pressure equation. Based on the results of the Owens-Wendt analysis, an advancement to the Young-Laplace equation is proposed for use in these mathematical models, which utilizes only solid surface energies and fractional surface coverage of fluoropolymer. Capillary constants for the spectrum of analyzed GDLs are presented for the same purpose.

  4. Quasielastic neutron scattering from adsorbed water molecules on pyrogenic silica surfaces

    NASA Astrophysics Data System (ADS)

    Tumanov, A. A.; Zarko, V. I.

    1994-04-01

    Quasielastic neutron scattering (QNS) from hydrated samples of high dispersion (Aerosil) and of porous dioxide silicon was investigated. The broadening of the QNS peak analysis permits one to obtain the effective diffusion coefficient D of adsorbed water molecules. It was obtained that the D-value increases with silica hydration. The mean square displacement of the water molecules from equilibrium < x2> equals approximately 0.1 Å 2 and does not depend on the quantity of adsorbed water.

  5. Study of the conformational change of adsorbed proteins on biomaterial surfaces using hydrogen-deuterium exchange with mass spectroscopy.

    PubMed

    Kim, Jinku

    2016-05-01

    There is no doubt that protein adsorption plays a crucial role in determining biocompatibility of biomaterials. Despite the information of the identity and composition of blood plasma/serum proteins adsorbed on surfaces of biomaterials to understand which proteins are involved in blood/biomaterial interactions, it still does not provide information about the conformations and orientations of adsorbed protein, which are very important in determining biological responses to biomaterials. Therefore, our laboratory has developed an experimental technology to probe protein conformations on materials that is applicable to mixtures of proteins. Herein, the new application of hydrogen/deuterium (H/D) exchange combined with mass spectrometry was applied to determine conformational changes of adsorbed proteins at biomaterial surfaces. The results suggest that there may be a significant conformational change in adsorbed proteins at 'low' bulk concentrations that leads to a large change in the kinetics of H/D exchange as compared to 'high' bulk concentrations. This technique may eventually be useful for the study of the kinetics of protein conformational changes. PMID:26896658

  6. Friction and transfer of copper, silver, and gold to iron in the presence of various adsorbed surface films

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1979-01-01

    Sliding friction experiments were conducted with the noble metals copper, silver, and gold and two binary alloys of these metals contacting iron in the presence of various adsorbates including, oxygen, methyl mercaptan, and methyl chloride. A pin on disk specimen configuration was used with a load of 100 grams, sliding velocity of 60 mm/min; at 25 C with the surfaces saturated with the adsorbates. Auger emission spectroscopy was used to monitor surface films. Results of the experiments indicate that friction and transfer characteristics are highly specific with respect to both the noble metal and surface film present. With all three metals and films transfer of the noble metal to iron occurred very rapidly. With all metals and films transfer of the noble metal to iron continuously increased with repeated passes except for silver and copper sliding on iron sulfide.

  7. Identification of salicylic acid using surface modified polyurethane film using an imprinted layer of polyaniline.

    PubMed

    Sreenivasan, K

    2007-02-01

    The surface of polyurethane (PU) was modified by coating a thin layer of polyaniline (PAN) by oxidizing aniline using ammonium persulfate. Affinity sites for salicylic acid (SA) were created in the coated layer by non-covalent imprinting method. The imprinted layer adsorbed SA five times more compared to the nonimprinted surface reflecting the creation of affinity sites specific to SA on the surface. The equilibrium was attained relatively faster indicating that a material of this kind is suitable for sensing applications. The selectivity in recognizing the print molecule by the imprinted surface was assessed by comparing the extent of uptake of other structurally resembling molecules namely O-amino benzoic acid and acetyl salicylic acid. The selectivity factor was found to be 22 and 16.5. The adsorbed SA was detected using the technique of Fourier transform attenuated total internal reflection infrared spectroscopy (FT-ATR-IR). The results show that molecularly imprinted surface in combination with FT-IR is a useful approach for the sensing applications. PMID:17386557

  8. Atmospheric boundary layer over steep surface waves

    NASA Astrophysics Data System (ADS)

    Troitskaya, Yuliya; Sergeev, Daniil A.; Druzhinin, Oleg; Kandaurov, Alexander A.; Ermakova, Olga S.; Ezhova, Ekaterina V.; Esau, Igor; Zilitinkevich, Sergej

    2014-08-01

    Turbulent air-sea interactions coupled with the surface wave dynamics remain a challenging problem. The needs to include this kind of interaction into the coupled environmental, weather and climate models motivate the development of a simplified approximation of the complex and strongly nonlinear interaction processes. This study proposes a quasi-linear model of wind-wave coupling. It formulates the approach and derives the model equations. The model is verified through a set of laboratory (direct measurements of an airflow by the particle image velocimetry (PIV) technique) and numerical (a direct numerical simulation (DNS) technique) experiments. The experiments support the central model assumption that the flow velocity field averaged over an ensemble of turbulent fluctuations is smooth and does not demonstrate flow separation from the crests of the waves. The proposed quasi-linear model correctly recovers the measured characteristics of the turbulent boundary layer over the waved water surface.

  9. Surface-induced changes in the conformation and glucan production of glucosyltransferase adsorbed on saliva-coated hydroxyapatite.

    PubMed

    Fears, Kenan P; Gonzalez-Begne, Mireya; Love, Corey T; Day, Delbert E; Koo, Hyun

    2015-04-28

    Glucosyltransferases (Gtfs) from S. mutans play critical roles in the development of virulent oral biofilms associated with dental caries disease. Gtfs adsorbed to the tooth surface produce glucans that promote local microbial colonization and provide an insoluble exopolysaccharides (EPS) matrix that facilitates biofilm initiation. Moreover, agents that inhibit the enzymatic activity of Gtfs in solution often have reduced or no effects on surface-adsorbed Gtfs. This study elucidated the mechanisms responsible for the differences in functionality that GtfB exhibits in solution vs surface-adsorbed. Upon adsorption to planar fused-quartz substrates, GtfB displayed a 37% loss of helices and 36% increase of β-sheets, as determined by circular dichroism (CD) spectroscopy, and surface-induced conformational changes were more severe on substrates modified with CH3- and NH2-terminated self-assembled monolayers. GtfB also underwent substantial conformation changes when adsorbing to hydroxyapatite (HA) microspheres, likely due to electrostatic interactions between negatively charged GtfB and positively charged HA crystal faces. Conformational changes were lessened when HA surfaces were coated with saliva (sHA) prior to GtfB adsorption. Furthermore, GtfB remained highly active on sHA, as determined by in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, producing glucans that were structurally different than GtfB in solution and known to increase the accumulation and virulence of biofilms. Our data provide the first insight into the structural underpinnings governing Gtf conformation and enzymatic function that occur on tooth surfaces in vivo, which may lead to designing potent new inhibitors and improved strategies to combat the formation of pathogenic oral biofilms. PMID:25867796

  10. Thermal characteristics of the lunar surface layer.

    NASA Technical Reports Server (NTRS)

    Cremers, C. J.; Birkebak, R. C.; White, J. E.

    1972-01-01

    The thermophysical properties of the fines from the Apollo 12 landing site have been determined as a function of their relevant parameters. These properties include the thermal conductivity, thermal diffusivity, directional reflectance and emittance. The density used was the same as that observed from the returned core-tube samples and so should be close to the true density of the surface layer at the Apollo 12 site. The measured properties are used to calculate the diurnal temperature variation of the moon's surface as well as for several depths below the surface. The maximum surface of 389 K is obtained at lunar noon while the minimum temperature of 86.1 K is obtained at sunrise. It is shown that the most significant effects on temperature, as compared with previous calculations, are caused by using the directional reflectance which controls the amount of solar energy absorption during the day in place of a constant hemispherical reflectance. The results are compared with previous analyses and remote measurements.

  11. In-plane conductance of thin films as a probe of surface chemical environment: Adsorbate effects on film electronic properties of indium tin oxide and gold

    NASA Astrophysics Data System (ADS)

    Swint, Amy Lynn

    Changes in the in-plane conductance of conductive thin films are observed as a result of chemical adsorption at the surface. Reaction of the indium tin oxide (ITO) surface with Bronsted acids (bases) leads to increases (decreases) in its in-plane conductance as measured by a four-point probe configuration. The conductance varies monotonically with pH suggesting that the degree of surface protonation or hydroxylation controls the surface charge density, which in turn affects the width of the n-type depletion layer, and ultimately the in-plane conductance. Measurements at constant pH with a series of tetraalkylammonium hydroxide species of varying cation size indicate that surface dipoles also affect ITO conductance by modulating the magnitude of the surface polarization. Modulating the double layer with varying aqueous salt solutions also affects ITO conductance, though not to the same degree as strong Bronsted acids and bases. Solvents of varying dielectric constant and proton donating ability (ethanol, dimethylformamide) decrease ITO conductance relative to H2O. In addition, changing solvent gives rise to thermally-derived conductance transients, which result from exothermic solvent mixing. The self-assembly of alkanethiols at the surface increases the conductance of ITO films, most likely through carrier population effects. In all cases examined the combined effects of surface charge, adsorbed dipole layer magnitude and carrier injection are responsible for altering the ITO conductance. Besides being directly applicable to the control of electronic properties, these results also point to the use of four-point probe resistance measurements in condensed phase sensing applications. Ultrasensitive conductance-based gas phase sensing of organothiol adsorption to gold nanowires is accomplished with a limit of detection in the 105 molecule range. Further refinement of the inherently low noise resistance measurement may lead to observation of single adsorption events at

  12. Extending the range of low energy electron diffraction (LEED) surface structure determination: Co-adsorbed molecules, incommensurate overlayers and alloy surface order studied by new video and electron counting LEED techniques

    SciTech Connect

    Ogletree, D.F.

    1986-11-01

    LEED multiple scattering theory is briefly summarized, and aspects of electron scattering with particular significance to experimental measurements such as electron beam coherence, instrument response and phonon scattering are analyzed. Diffuse LEED experiments are discussed. New techniques that enhance the power of LEED are described, including a real-time video image digitizer applied to LEED intensity measurements, along with computer programs to generate I-V curves. The first electron counting LEED detector using a ''wedge and strip'' position sensitive anode and digital electronics is described. This instrument uses picoampere incident beam currents, and its sensitivity is limited only by statistics and counting times. Structural results on new classes of surface systems are presented. The structure of the c(4 x 2) phase of carbon monoxide adsorbed on Pt(111) has been determined, showing that carbon monoxide molecules adsorb in both top and bridge sites, 1.85 +- 0.10 A and 1.55 +- 0.10 A above the metal surface, respectively. The structure of an incommensurate graphite overlayer on Pt(111) is analyzed. The graphite layer is 3.70 +- 0.05 A above the metal surface, with intercalated carbon atoms located 1.25 +- 0.10 A above hollow sites supporting it. The (2..sqrt..3 x 4)-rectangular phase of benzene and carbon monoxide coadsorbed on Pt(111) is analyzed. Benzene molecules adsorb in bridge sites parallel to and 2.10 +- 0.10 A above the surface. The carbon ring is expanded, with an average C-C bond length of 1.72 +- 0.15 A. The carbon monoxide molecules also adsorb in bridge sites. The structure of the (..sqrt..3 x ..sqrt..3) reconstruction on the (111) face of the ..cap alpha..-CuAl alloy has been determined.

  13. Modeling of Transmittance Degradation Caused by Optical Surface Contamination by Atomic Oxygen Reaction with Adsorbed Silicones

    NASA Technical Reports Server (NTRS)

    Snyder, Aaron; Banks, Bruce; Miller, Sharon; Stueber, Thomas; Sechkar, Edward

    2001-01-01

    A numerical procedure is presented to calculate transmittance degradation caused by contaminant films on spacecraft surfaces produced through the interaction of orbital atomic oxygen (AO) with volatile silicones and hydrocarbons from spacecraft components. In the model, contaminant accretion is dependent on the adsorption of species, depletion reactions due to gas-surface collisions, desorption, and surface reactions between AO and silicone producing SiO(x), (where x is near 2). A detailed description of the procedure used to calculate the constituents of the contaminant layer is presented, including the equations that govern the evolution of fractional coverage by specie type. As an illustrative example of film growth, calculation results using a prototype code that calculates the evolution of surface coverage by specie type is presented and discussed. An example of the transmittance degradation caused by surface interaction of AO with deposited contaminant is presented for the case of exponentially decaying contaminant flux. These examples are performed using hypothetical values for the process parameters.

  14. Density functional theory study of chemical sensing on surfaces of single-layer MoS{sub 2} and graphene

    SciTech Connect

    Mehmood, F.; Pachter, R.

    2014-04-28

    In this work, density functional theory (DFT) calculations have been used to investigate chemical sensing on surfaces of single-layer MoS{sub 2} and graphene, considering the adsorption of the chemical compounds triethylamine, acetone, tetrahydrofuran, methanol, 2,4,6-trinitrotoluene, o-nitrotoluene, o-dichlorobenzene, and 1,5-dicholoropentane. Physisorption of the adsorbates on free-standing surfaces was analyzed in detail for optimized material structures, considering various possible adsorption sites. Similar adsorption characteristics for the two surface types were demonstrated, where inclusion of a correction to the DFT functional for London dispersion was shown to be important to capture interactions at the interface of molecular adsorbate and surface. Charge transfer analyses for adsorbed free-standing surfaces generally demonstrated very small effects. However, charge transfer upon inclusion of the underlying SiO{sub 2} substrate rationalized experimental observations for some of the adsorbates considered. A larger intrinsic response for the electron-donor triethylamine adsorbed on MoS{sub 2} as compared to graphene was demonstrated, which may assist in devising chemical sensors for improved sensitivity.

  15. An Energy Conservation Approach to Adsorbate-Induced Surface Stress and the Extraction of Binding Energy Using Nanomechanics

    SciTech Connect

    Pinnaduwage, Lal A; Boiadjiev, Vassil I; Fernando, G. W.; Hawk, J. E.; Wijewardhana, L.C. R.; Gehl, Anthony C

    2008-01-01

    Microcantilevers are ideally-suited for the study of surface phenomena due to their large surface-to-volume ratios, which amplify surface effects. We show that when guest molecules bind to atoms/molecules on a microcantilever surface, the released binding energy is retained in the host surface, leading to a metastable state where the excess energy on the surface is manifested as an increase in surface stress leading to the bending of the microcantilever. When the excess energy is released, the microcantilever relaxes back to the original state, and the relaxation time depends on the particular binding process involved. Such experiments were conducted for three binding processes in vapor phase experiments: physisorption, hydrogen bonding, and chemisorption. To our knowledge, such an energy conservation approach has not been taken into account in adsorbate-induced surface effect investigations. Furthermore, these experiments illustrate that detailed molecular-level information on binding energies can be extracted from this simple micromechanical sensor.

  16. Scanning tunneling microscopy study: From clean surface to surfaces adsorbed with atom/cluster or metallic island

    NASA Astrophysics Data System (ADS)

    Zhang, Xieqiu

    2007-12-01

    Nanostructures, namely materials in the nanometer or sub-nanometer scales, can possess completely diRTMerent properties from their bulk counterparts. Due to the potential applications in different disciplines, the study of nanostructures has attracted extensive attention worldwide in recent years. Metal nanostructures grown on semiconductor substrates are a special group of nanostructures. Since these nanostructures can be prepared in ultrahigh vacuum with high controllability, one can use low-temperature scanning tunneling microscopy (STM) to obtain information in situ on both the structural and electronic properties of these nanostructures simultaneously. In this thesis, I will present the growth behavior of metal or semiconductor nanostructures at the initial stage and the novel electronic properties of some of these nanostructures. The study of single Ge atoms adsorbed on the Si(111)-7x7 surface shows that different deposition temperatures result in diRTMerent adsorption structures. We find Ge substitution for the Si adatoms during high temperature growth and simple Ge adsorption above the Si atoms during low temperature growth. Small Ag clusters, formed on the Si(111)-7x7 surface at controlled coverages, show a strong rectification effect, which is an indication of the initial stage of Schottky barrier formation and possibly the smallest Schottky diode. On the surfaces of heavily n-doped and p-doped Si substrates, although the 7x7 is metallic at room temperature, an energy gap opens at low temperatures. This energy gap is correlated well with the electronic localization induced by the doping impurities. For Pb nanoislands, a pseudogap was discovered at temperatures higher than the superconducting transition temperature. The strength of the pseudogap depends on the lateral size and temperature, which is speculated to originate from the weak electronic localization induced by structural disorder.

  17. Surface shear stress fluctuations in the atmospheric surface layer

    NASA Astrophysics Data System (ADS)

    Monty, Jason; Hutchins, Nick; Chong, Min

    2005-11-01

    A lightweight, high frequency response (25Hz), floating element sensor was used to measure wall shear stress fluctuations in the atmospheric surface layer formed over a salt flat at the SLTEST site, Utah, USA. The sensor uses a laser position measurement system to track the motion of the floating element which consisted of a 50mm diameter foam disc, as described by Heuer & Marusic (Meas. Sci. Tech., Vol. 16, 1644- -1649, 2005). The measurements were taken as part of an internationally coordinated experimental program designed to make extensive spatial and temporal measurements of velocity, temperature and wall shear stress of the surface layer. Velocity measurements were made with both a 30m high vertical array and a 100m wide horizontal array of sonic anemometers; 18 anemometers in total were employed. Cross-correlations of shear stress and streamwise velocity fluctuations were analysed in an attempt to identify structure angles in the flow. The results were also compared with experimental data from controlled, laboratory turbulent boundary layers having three orders of magnitude lower Reynolds number.

  18. The analysis of surface-adsorbed organic molecules by alkali-assisted MIES combined with UPS(He I)

    NASA Astrophysics Data System (ADS)

    Günster, J.; Ochs, D.; Dieckhoff, S.; Kempter, V.

    1996-12-01

    Metastable impact electron spectroscopy (MIES) in combination with UPS(He I) is applied to the study of s-triazine and triethoxytriazine molecules adsorbed on Si(100) either alone or in combination with cesium atoms. It is demonstrated that the presence of the Cs atoms facilitates the identification of the adsorbed species considerably. It is concluded that (i) non-dissociative adsorption of the studied organic molecules occurs whereby the basal rings of the molecules lie flat on the silicon surface, in accordance with previous studies by Bu and Lin, (ii) the binding of the molecules to the surface is mainly via the lone pair orbitals of the nitrogen in the ring, and (iii) s-triazine reacts strongly with oxygen which bonds to the carbon atoms of the triazine ring.

  19. Analysis of corrosion layers in ancient Roman silver coins with high resolution surface spectroscopic techniques

    NASA Astrophysics Data System (ADS)

    Keturakis, Christopher J.; Notis, Ben; Blenheim, Alex; Miller, Alfred C.; Pafchek, Rob; Notis, Michael R.; Wachs, Israel E.

    2016-07-01

    Determination of the microchemistry of surface corrosion layers on ancient silver alloy coins is important both in terms of understanding the nature of archaeological environmental conditions to which these ancient coins were exposed and also to help in their conservation. In this present study, five ancient silver alloy coins (225 BCE-244 CE) were used as test vehicles to measure their immediate surface microchemistry and evaluate the appropriateness and limitations of High Sensitivity-Low Energy Ion Scattering Spectroscopy (HS-LEIS, 0.3 nm depth analysis), High Resolution-X-ray Photoelectron Spectroscopy (HR-XPS, 1-3 nm depth analysis) and High Resolution-Raman Spectroscopy (HR-Raman, ∼1000 nm depth analysis). Additional information about the deeper corrosion layers, up to ∼300-1000 nm, was provided by dynamic HS-LEIS and HR-Raman spectroscopy. While not archeologically significant, the use of these coins of small commercial value provides data that is more representative of the weaker signals typically obtained from ancient corroded objects, which can be in stark contrast to pristine data often obtained from carefully prepared alloys of known composition. The oldest coins, from 225 to 214 BCE, possessed an outermost surface layer containing Cu2O, Na, Al, Pb, and adsorbed hydrocarbons, while the more recent coins, from 98 to 244 CE, contained Cu2O, Ag, N, F, Na, Al, S, Cl, and adsorbed hydrocarbons in similar corresponding surface layers. It thus appears that alloying with copper, even in small amounts, leads to the formation of an outer Cu2O layer. Depth profiling revealed the presence of K, Na, Cl, and S as key corrosion components for both sets of coins with S, most likely as Ag2S, concentrated towards the surface while the Cl, most likely as AgCl, penetrated deeper. Schema to understand the overall chemistry of the corrosion layers present on these silver alloy coins were developed from the equipment limitations encountered and are presented.

  20. Tailoring LaAlO3/SrTiO3 Interface Metallicity by Oxygen Surface Adsorbates.

    PubMed

    Dai, Weitao; Adhikari, Sanjay; Garcia-Castro, Andrés Camilo; Romero, Aldo H; Lee, Hyungwoo; Lee, Jung-Woo; Ryu, Sangwoo; Eom, Chang-Beom; Cen, Cheng

    2016-04-13

    We report an oxygen surface adsorbates induced metal-insulator transition at the LaAlO3/SrTiO3 interfaces. The observed effects were attributed to the terminations of surface Al sites and the resultant electron-accepting surface states. By controlling the local oxygen adsorptions, we successfully demonstrated the nondestructive patterning of the interface two-dimensional electron gas (2DEG). The obtained 2DEG structures are stable in air and also robust against general solvent treatments. This study provides new insights into the metal-insulator transition mechanism at the complex oxide interfaces and also a highly efficient technique for tailoring the interface properties. PMID:26928809

  1. Recombination of 5-eV O(3P) atoms with surface-adsorbed NO - Spectra and their dependence on surface material and temperature

    NASA Technical Reports Server (NTRS)

    Orient, O. J.; Martus, K. E.; Chutjian, A.; Murad, E.

    1992-01-01

    Measurements have been conducted of the 300-850 nm recombination spectra associated with 5-eV collisions of O(3P) atoms with NO adsorbed on surfaces of MgF2, Ni, and Ti. Attention is given to the dependence of chemiluminescence intensity on surface temperature over the 240-340 K range. While all three materials tend to emit at the lower temperatures, MgF2 exhibits the greatest tendency to chemiluminescence. Both results are reflective of the greater packing density of surface-adsorbed NO at the lower temperatures for each surface. The activation energy for each surface is independent of emission wavelength, so that the same species is emitting throughout the wavelength range.

  2. Surface-enhanced vibrational spectroscopy of adsorbates on microemulsion synthesized gold nanoparticles.

    PubMed

    Fasasi, Ayuba; Griffiths, Peter R; Pan, Horng-Bin; Wai, Chien M

    2011-07-01

    Very small (<10 nm) monodisperse gold nanoparticles (AuNPs) coated with a monolayer of decanethiol were prepared and their surface-enhanced infrared absorption (SEIRA) spectra were measured in the transmission mode. The AuNPs were prepared by the borohydride reduction of HAuCl(4) inside reverse micelles that were made by adding water to a hexane solution of sodium bis(2-ethylhexyl)sulfosuccinate (AOT). The gold nanoparticles were then stabilized by the addition of decanethiol. Subsequent addition of p-nitrothiophenol both facilitated the removal of excess AOT and showed that the gold surface was completely covered by the decanethiol. SEIRA spectra of decanethiol on gold particles prepared in AOT microemulsions were about twelve times more intense than corresponding layers on gold produced by electroless deposition and gave a significantly less noisy spectrum compared to the corresponding surface-enhanced Raman spectrum. The surface-enhanced Raman scattering (SERS) spectra of the same samples showed that the most intense spectrum was obtained from gold nanoparticles with a mean diameter of 2.5 nm. This result is in contrast to previous statements that SERS spectra could only be obtained from particles larger than 10 nm. PMID:21740634

  3. Surface-interface coupling in an oxide heterostructure: Impact of adsorbates on LaAlO3/SrTiO3

    NASA Astrophysics Data System (ADS)

    Scheiderer, P.; Pfaff, F.; Gabel, J.; Kamp, M.; Sing, M.; Claessen, R.

    2015-11-01

    The microscopic origin of the two-dimensional electron system (2DES) at the LaAlO3/SrTiO3 heterointerface remains a topic of debate. Among others, mechanisms involving surface defects acting as electron donors for the 2DES have been proposed recently. Since samples are usually investigated after exposure to air, adsorbates are a plausible candidate for such surface defects. We therefore used in situ photoelectron spectroscopy and in situ resistivity measurements to study the impact of adsorbates on the 2DES. The adsorbate coverage caused by storage in air is indeed found to induce additional charge carriers at the interface, compared to the adsorbate-free surface. In controlled adsorption experiments with water and hydrogen we identify adsorbed atomic hydrogen to induce additional charge carriers at the interface, differing from molecular water adsorption reported for samples exposed to macroscopically large volumes of water in air.

  4. Carbides composite surface layers produced by (PTA)

    SciTech Connect

    Tajoure, Meloud; Tajouri, Ali E-mail: dr.mokhtarphd@yahoo.com; Abuzriba, Mokhtar E-mail: dr.mokhtarphd@yahoo.com; Akreem, Mosbah

    2013-12-16

    The plasma transferred arc technique was applied to deposit a composite layer of nickel base with tungsten carbide in powder form on to surface of low alloy steel 18G2A type according to polish standard. Results showed that, plasma transferred arc hard facing process was successfully conducted by using Deloro alloy 22 plus tungsten carbide powders. Maximum hardness of 1489 HV and minimum dilution of 8.4 % were achieved by using an arc current of 60 A. However, when the current was further increased to 120 A and the dilution increases with current increase while the hardness decreases. Microstructure of the nickel base deposit with tungsten carbide features uniform distribution of reinforcement particles with regular grain shape half - dissolved in the matrix.

  5. Carbides composite surface layers produced by (PTA)

    NASA Astrophysics Data System (ADS)

    Tajoure, Meloud; Tajouri, Ali; Abuzriba, Mokhtar; Akreem, Mosbah

    2013-12-01

    The plasma transferred arc technique was applied to deposit a composite layer of nickel base with tungsten carbide in powder form on to surface of low alloy steel 18G2A type according to polish standard. Results showed that, plasma transferred arc hard facing process was successfully conducted by using Deloro alloy 22 plus tungsten carbide powders. Maximum hardness of 1489 HV and minimum dilution of 8.4 % were achieved by using an arc current of 60 A. However, when the current was further increased to 120 A & the dilution increases with current increase while the hardness decreases. Microstructure of the nickel base deposit with tungsten carbide features uniform distribution of reinforcement particles with regular grain shape half - dissolved in the matrix.

  6. Lysozyme adsorption at a silica surface using simulation and experiment: effects of pH on protein layer structure.

    PubMed

    Kubiak-Ossowska, Karina; Cwieka, Monika; Kaczynska, Agnieszka; Jachimska, Barbara; Mulheran, Paul A

    2015-10-01

    Hen Egg White Lysozyme (HEWL) is a widely used exemplar to study protein adsorption on surfaces and interfaces. Here we use fully atomistic Molecular Dynamics (MD) simulations, Multi-Parametric Surface Plasmon Resonance (MP-SPR), contact angle and zeta potential measurements to study HEWL adsorption at a silica surface. The simulations provide a detailed description of the adsorption mechanism and indicate that at pH7 the main adsorption driving force is electrostatics, supplemented by weaker hydrophobic forces. Moreover, they reveal the preferred orientation of the adsorbed protein and show that its structure is only slightly altered at the interface with the surface. This provides the basis for interpreting the experimental results, which indicate the surface adsorbs a close-packed monolayer at about pH10 where the surface has a large negative zeta potential and the HEWL is positively charged. At higher pH, the adsorption amount of the protein layer is greatly reduced due to the loss of charge on the protein. At lower pH, the smaller zeta potential of the surface leads to lower HEWL adsorption. These interpretations are complemented by the contact angle measurements that show how the hydrophobicity of the surface is greatest when the surface coverage is highest. The simulations provide details of the hydrophobic residues exposed to solution by the adsorbed HEWL, completing the picture of the protein layer structure. PMID:26315945

  7. Turbulent boundary layer over porous surfaces with different surface geometries

    NASA Technical Reports Server (NTRS)

    Kong, F. Y.; Schetz, J. A.

    1982-01-01

    The turbulent boundary layer over three porous walls with different surface geometries was studied in order to investigate the individual influences of porosity and small roughness, as well as their combined effects, on turbulent boundary layer behavior. The tests were conducted in a 2 m x 2 m tunnel on a large axisymmetric model at speeds corresponding to Re(L) = 5,000,000-6,000,000. The development of the turbulent boundary layer was compared for that of sintered metal, bonded screening, and perforated sheet and then to that for the flow over a solid smooth wall and a solid, sand-roughened wall. The comparisons reveal that the effect of porosity is to shift the logarithmic region of the wall law down by a certain amount from the solid wall results and to increase the skin friction values by about 30-40%. The downward shift of the logarithmic region of the wall law and the increase of the skin friction value by the combined effects of small roughness and porosity are found to be roughly the sum of their individual effects.

  8. Surface Layer Turbulence During a Frontal Passage

    SciTech Connect

    Piper, M; Lundquist, J K

    2004-06-15

    Some recent investigations have begun to quantify turbulence and dissipation in frontal zones to address the question of what physical mechanism counteracts the intensification of temperature and velocity gradients across a developing front. Frank (1994) examines the turbulence structure of two fronts that passed a 200m instrumented tower near Karlsruhe, Germany. In addition to showing the mean vertical structure of the fronts as they pass the tower, Frank demonstrates that there is an order of magnitude or more increase in turbulent kinetic energy across the frontal zone. Blumen and Piper (1999) reported turbulence statistics, including dissipation rate measurements, from the MICROFRONTS field experiment, where high-frequency turbulence data were collected from tower-mounted hotwire and sonic anemometers in a cold front and in a density current. Chapman and Browning (2001) measured dissipation rate in a precipitating frontal zone with high-resolution Doppler radar. Their measurements were conducted above the surface layer, to heights of 5km. The dissipation rate values they found are comparable to those measured in Kennedy and Shapiro (1975) in an upper-level front. Here, we expand on these recent studies by depicting the behavior of the fine scales of turbulence near the surface in a frontal zone. The primary objective of this study is to quantify the levels of turbulence and dissipation occurring in a frontal zone through the calculation of kinetic energy spectra and dissipation rates. The high-resolution turbulence data used in this study are taken during the cold front that passed the MICROFRONTS site in the early evening hours of 20 March 1995. These new measurements can be used as a basis for parameterizing the effects of surface-layer turbulence in numerical models of frontogenesis. We present three techniques for calculating the dissipation rate: direct dissipation technique, inertial dissipation technique and Kolmogorov's four-fifths law. Dissipation rate

  9. Reduction of electron accumulation at InN(0001) surfaces via saturation of surface states by potassium and oxygen as donor- or acceptor-type adsorbates

    SciTech Connect

    Eisenhardt, A.; Reiß, S.; Krischok, S. Himmerlich, M.

    2014-01-28

    The influence of selected donor- and acceptor-type adsorbates on the electronic properties of InN(0001) surfaces is investigated implementing in-situ photoelectron spectroscopy. The changes in work function, surface band alignment, and chemical bond configurations are characterized during deposition of potassium and exposure to oxygen. Although an expected opponent charge transfer characteristic is observed with potassium donating its free electron to InN, while dissociated oxygen species extract partial charge from the substrate, a reduction of the surface electron accumulation occurs in both cases. This observation can be explained by adsorbate-induced saturation of free dangling bonds at the InN resulting in the disappearance of surface states, which initially pin the Fermi level and induce downward band bending.

  10. Density functional study of TaSi n ( n = 1-3, 12) clusters adsorbed to graphene surface

    NASA Astrophysics Data System (ADS)

    Guo, Ping; Zheng, Lin; Zheng, Ji Ming; Zhang, Ruizhi; Yang, Luna; Ren, Zhaoyu

    2011-11-01

    A plane-wave density functional theory (DFT) calculations have been performed to investigate structural and electronic properties of TaSin (n = 1-3, 12) clusters supported by graphene surface. The resulting adsorption structures are described and discussed in terms of stability, bonding, and electron transfer between the cluster and the graphene. The TaSin clusters on graphene surface favor their free-standing ground-state structures. Especially in the cases of the linear TaSi2 and the planar TaSi3, the graphene surface may catalyze the transition of the TaSin clusters from an isomer of lower dimensionality into the ground-state structure. The adsorption site and configuration of TaSin on graphene surface are dominated by the interaction between Ta atom and graphene. Ta atom prefers to adsorb on the hollow site of graphene, and Si atoms tend to locate on the bridge site. Further, the electron transfer is found to proceed from the cluster to the surface for n = 1 and 2, while its direction reverses as n > 2. For the case of TaSi, chemisorption is shown to prevail over physisorption as the dominant mode of surface-adsorbate interaction by charge density analysis.

  11. Prediction of the speciation of alkaline earths adsorbed on mineral surfaces in salt solutions

    NASA Astrophysics Data System (ADS)

    Sverjensky, Dimitri A.

    2006-05-01

    Despite the fact that the bulk compositions of most low temperature natural surface waters, groundwaters, and porewaters are heavily influenced by alkaline earths, an understanding of the development of proton surface charge in the presence of alkaline earth adsorption on the surfaces of minerals is lacking. In particular, models of speciation at the mineral-water interface in systems involving alkaline earths need to be established for a range of different minerals. In the present study, X-ray standing wave results for Sr 2+ adsorption on rutile as a tetranuclear complex [Fenter, P., Cheng, L., Rihs, S., Machesky, M., Bedyzk, M.D., Sturchio, N.C., 2000. Electrical double-layer structure at the rutile-water interface as observed in situ with small-period X-ray standing waves. J. Colloid Interface Sci.225, 154-165] are used as constraints for all the alkaline earths in surface complexation simulations of proton surface charge, metal adsorption, and electrokinetic experiments referring to wide ranges of pH, ionic strength, surface coverage, and type of oxide. The tetranuclear reaction 4>SOH+M+H2O=(>SOH)2(>SO-)2_M(OH)++3H+ predominates for the large cations Sr 2+ and Ba 2+ (and presumably Ra 2+), consistent with X-ray results. In contrast, the mononuclear reaction >SOH+M+H2O=>SO-_M(OH)++2H+ predominates for the much smaller Mg 2+ (and presumably Be 2+), with minor amounts of the tetranuclear reaction. Both reaction types appear to be important for the intermediate size Ca 2+. For all the alkaline earths on all oxides, the proportions of the different reaction types vary systematically as a function of pH, ionic strength, and surface coverage. The application of Born solvation and crystal-chemical theory enables estimation of the equilibrium constants of adsorption of all the alkaline earths on all oxides. On high dielectric constant solids (rutile, magnetite, manganese dioxide), where the solvation contribution is negligable, ion adsorption correlates with crystal

  12. Separation of the attractive and repulsive contributions to the adsorbate-adsorbate interactions of polar adsorbates on Si(100)

    NASA Astrophysics Data System (ADS)

    Lin, Ying-Hsiu; Jeng, Horng-Tay; Lin, Deng-Sung

    2015-11-01

    Dissociative adsorption of H2O, NH3, CH3OH and CH3NH2 polar molecules on the Si(100) surface results in a 1:1 mixture of two adsorbates (H and multi-atomic fragment A = OH, NH2, CH3O, CH3NH, respectively) on the surface. By using density functional theory (DFT) calculations, the adsorption geometry, the total energies and the charge densities for various possible ordered structures of the mixed adsorbate layer have been found. Analyzing the systematic trends in the total energies unveils concurrently the nearest-neighbor interactions ENN and the next nearest-neighbor interactions ENNN between two polar adsorbates A. In going from small to large polar adsorbates, ENN's exhibit an attractive-to-repulsive crossover behavior, indicating that they include competing attractive and repulsive contributions. Exploration of the charge density distributions allows the estimation of the degree of charge overlapping between immediately neighboring A's, the resulting contribution of the steric repulsions, and that of the attractive interactions to the corresponding ENN's. The attractive contributions to nearest neighboring adsorbate-adsorbate interactions between the polar adsorbates under study are shown to result from hydrogen bonds or dipole-dipole interactions.

  13. Hybridization of poly(rI) with poly(rC) adsorbed to the carbon nanotube surface.

    PubMed

    Karachevtsev, Maksym V; Gladchenko, Galyna O; Leontiev, Victor S; Karachevtsev, Victor A

    2014-01-01

    Hybridization of homopolynucleotide poly(rC) adsorbed to the carbon nanotube surface with poly(rI) free in solution has been studied by absorption spectroscopy and molecular dynamics method. It was found that hybridization on the nanotube surface has a slow kinetics, the behavior of which differs essentially from fast hybridization of free polymers. The duplex obtained is characterized with the reduced thermostability and a lower hyperchromic coefficient than it was observed when the duplex was formed in the absence of the nanotube. These features point to the imperfectness in the structure of the duplex hybridized on the nanotube surface. Computer simulation showed that the strong interaction of nitrogen bases with the nanotube surface weakens significantly hybridization of two complementary oligomers, as the surface prevents the necessary conformational mobility of the polymer to be hybridized. PMID:24690381

  14. Hybridization of poly(rI) with poly(rC) adsorbed to the carbon nanotube surface

    PubMed Central

    2014-01-01

    Hybridization of homopolynucleotide poly(rC) adsorbed to the carbon nanotube surface with poly(rI) free in solution has been studied by absorption spectroscopy and molecular dynamics method. It was found that hybridization on the nanotube surface has a slow kinetics, the behavior of which differs essentially from fast hybridization of free polymers. The duplex obtained is characterized with the reduced thermostability and a lower hyperchromic coefficient than it was observed when the duplex was formed in the absence of the nanotube. These features point to the imperfectness in the structure of the duplex hybridized on the nanotube surface. Computer simulation showed that the strong interaction of nitrogen bases with the nanotube surface weakens significantly hybridization of two complementary oligomers, as the surface prevents the necessary conformational mobility of the polymer to be hybridized. PMID:24690381

  15. Hybridization of poly(rI) with poly(rC) adsorbed to the carbon nanotube surface

    NASA Astrophysics Data System (ADS)

    Karachevtsev, Maksym V.; Gladchenko, Galyna O.; Leontiev, Victor S.; Karachevtsev, Victor A.

    2014-04-01

    Hybridization of homopolynucleotide poly(rC) adsorbed to the carbon nanotube surface with poly(rI) free in solution has been studied by absorption spectroscopy and molecular dynamics method. It was found that hybridization on the nanotube surface has a slow kinetics, the behavior of which differs essentially from fast hybridization of free polymers. The duplex obtained is characterized with the reduced thermostability and a lower hyperchromic coefficient than it was observed when the duplex was formed in the absence of the nanotube. These features point to the imperfectness in the structure of the duplex hybridized on the nanotube surface. Computer simulation showed that the strong interaction of nitrogen bases with the nanotube surface weakens significantly hybridization of two complementary oligomers, as the surface prevents the necessary conformational mobility of the polymer to be hybridized.

  16. Quantitative proteomics analysis of adsorbed plasma proteins classifies nanoparticles with different surface properties and size

    SciTech Connect

    Zhang, Haizhen; Burnum, Kristin E.; Luna, Maria L.; Petritis, Brianne O.; Kim, Jong Seo; Qian, Weijun; Moore, Ronald J.; Heredia-Langner, Alejandro; Webb-Robertson, Bobbie-Jo M.; Thrall, Brian D.; Camp, David G.; Smith, Richard D.; Pounds, Joel G.; Liu, Tao

    2011-12-01

    In biofluids (e.g., blood plasma) nanoparticles are readily embedded in layers of proteins that can affect their biological activity and biocompatibility. Herein, we report a study on the interactions between human plasma proteins and nanoparticles with a controlled systematic variation of properties using stable isotope labeling and liquid chromatography-mass spectrometry (LC-MS) based quantitative proteomics. Novel protocol has been developed to simplify the isolation of nanoparticle bound proteins and improve the reproducibility. Plasma proteins associated with polystyrene nanoparticles with three different surface chemistries and two sizes as well as for four different exposure times (for a total of 24 different samples) were identified and quantified by LC-MS analysis. Quantitative comparison of relative protein abundances were achieved by spiking an 18 O-labeled 'universal reference' into each individually processed unlabeled sample as an internal standard, enabling simultaneous application of both label-free and isotopic labeling quantitation across the sample set. Clustering analysis of the quantitative proteomics data resulted in distinctive pattern that classifies the nanoparticles based on their surface properties and size. In addition, data on the temporal study indicated that the stable protein 'corona' that was isolated for the quantitative analysis appeared to be formed in less than 5 minutes. The comprehensive results obtained herein using quantitative proteomics have potential implications towards predicting nanoparticle biocompatibility.

  17. Preparation of a boron nitride single layer on a polycrystalline Rh surface

    NASA Astrophysics Data System (ADS)

    Kiss, János; Révész, Károly; Klivényi, Gábor; Solymosi, Frigyes

    2013-01-01

    The segregation of boron and its reactivity toward nitric oxide have been investigated by means of high-resolution Auger spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and thermal desorption spectroscopy (TDS). The segregation of boron from a Rh foil started from 700 K. Its presence altered the surface behaviors of Rh; the uptake of NO increased by about 30-37%. Whereas the dissociation of NO was about 3-10% on a clean, boron-free surface, the extent of dissociation (at saturation) at highest boron level was almost 98%. This feature strongly suggest a direct interaction between NO and boron on the surface. The presence of boron greatly stabilized the adsorbed nitrogen and oxygen formed in NO dissociation. Boron oxide (BO, B2O2) sublimated from the surface below 1000 K. Clean, single BN layer formed on the surface close to a monolayer regime, presumable in nanomash structure.

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

    NASA Astrophysics Data System (ADS)

    Drnec, Jakub

    Cesium adsorption on Pt(111) and its coadsorption with iodine and oxygen is studied in this dissertation. The work function during Cs dosing first decreases and at Deltaφ ≈ 3 eV (thetaCs = 0.15) the surface undergoes surface transition between a disordered anomalous state (Pt(111)(anom)-Cs) and islands of a Pt(111)(2x2)-Cs causing a change in the slope of the work function curve. The work function curve reaches minimum at --5.5 eV where the surface is fully covered with the Pt(111)(2 x 2)-Cs structure( thetaCs = 0.25). Further Cs dosing results in a work function increase and the surface undergoes a phase transition to Pt(111)(√3 x√3)-Cs. The Cs saturated structure (Pt(111)(ihcp)-Cs) has an hexagonal symmetry with the unit cell vector aligned with the (1, 0) direction of the substrate. Cs in the anomalous state desorbs from the surface in a high-temperature TDS peak (> 1000 K). When the lock-in TDS detection technique is used, this peak appears to be phase shifted by 180° when compared to the desorption peak of normally adsorbed Cs (thetaCs> 0.15) . This phase shift is a consequence of a positive charge of desorbing Cs. The TDS and work function behavior were explained by a Monte Carlo desorption model incorporating di¤erent desorption behavior for all four observed adsorption phases. When O2 is dosed on a Pt(111)-Cs surface, the maximum coverage of oxygen bonded to the surface is signi.cantly increased in comparison to Pt(111). Anomalously adsorbed Cs activates the O2 bond but does not interact strongly with coadsorbed O. However, when O2 is dosed on Pt(111)(ihcp)-Cs, the oxygen first adsorbs to a sub-layer adsorption site and strongly interacts with Cs. The oxygen in this state is responsible for thermal stabilization of coadsorbed Cs. When iodine is coadsorbed on a Pt(111)-Cs surface, it also strongly interacts with and thermally stabilizes Cs. During the desorption of Cs,I layers, some Cs and I desorb together in the form of a CsxIy cluster. The

  19. A [sup 13]C NMR study of ethylene adsorbed on reduced and oxygen-covered Ag surfaces

    SciTech Connect

    Plischke, J.K.; Benesi, A.J.; Vannice, M.A. )

    1992-11-01

    [sup 13]C-enriched ethylene was adsorbed on both clean and oxygen-covered Ag particles dispersed on [eta]-Al[sub 2]O[sub 3]. Irreversibly adsorbed C[sub 2]H[sub 4] on O-covered Ag exhibited an upfield shift of [minus]20 ppm relative to gas-phase C[sub 2]H[sub 4], whereas a narrower line and smaller shift of [minus]5 ppm occurred for C[sub 2]H[sub 4] reversibly adsorbed on reduced Ag. In addition to the resonance at 103 ppm for irreversibly adsorbed C[sub 2]H[sub 4], CP/MAS NMR spectra also gave resonances at 179, 170, 164, 159, and 19 ppm for the O-covered Ag sample. The CP/MAS spectrum for Ag acetate powder clearly identified the 179- and 19-ppm peaks as those associated with the carboxyl and methyl carbons of the acetate anion, and the peaks at 159, 164, and 170 ppm were assigned to oxalate, formate, and carbonate (or possibly acetic anhydride) species, respectively, based on previous studies. When heated to 473 K the adsorbed C[sub 2]H[sub 4] disappeared and only acetate and oxalate groups were observed, and continued heating to 573 K removed almost all resonances. No C[sub 2]H[sub 4]O was unambiguously detected, thus with this unpromoted Ag catalyst utilizing a high-surface-area alumina the observable surface species appeared to be those associated with complete combustion, with acetate and oxalate predominating during reaction. These results directly confirm the presence of an Ag acetate species which has been proposed previously to be an intermediate in complete combustion, and the presence of the other three species support earlier tentative assignments based on IR and TPR spectroscopy. Chemical shifts at 61, 28, and 13 ppm were indicative of alkoxy species formed on Bronsted-acid sites on the Al[sub 2]O[sub 3] surface. 58 refs., 8 figs., 4 tabs.

  20. Neutral surface layer turbulence over complex terrain

    SciTech Connect

    Bowen, B.M.

    1995-09-01

    Accurate turbulence estimates are important input to atmospheric dispersion models since they characterize downwind dispersion and hence, potential pollutant concentrations. When only basic wind information is available, an atmospheric modeler must first estimate roughness length (z{sub 0},) at the location of interest, ({mu}*) from similarity theory using average wind speed ({mu}) and z{sub 0}, and finally apply experimentally derived relationships to determine the turbulence intensities. Even when turbulence coefficients are measured, the turbulence profile must be estimated in the surface layer, using, for example, the power law recommended in a US Environmental Protection Agency guidance document. In this study, turbulent intensities and wind profiles are analyzed in eight direction sectors during near neutral stability. ``Local`` and ``regional`` roughness lengths are calculated from wind speed profiles and from longitudinal turbulence intensities ({sigma}{sub {mu}}) at both sites. With ``regional`` roughness length, complex terrain features are in effect the roughness elements. Profiles of median, 15-minute averaged turbulence intensities {sigma}{sub {mu}}, {sigma}{sub {nu}} and {sigma}{sub w} are calculated at both sites. Profiles of median {sigma}{sub {theta}} and {sigma}{sub {phi}} are also calculated using four mean values of regional z{sub 0} at both sites. Finally, differences between widely-used turbulence relationships and the relationships determined in this study, and their possible effect on model results, are discussed.

  1. A Turbulent Boundary Layer over Superhydrophobic Surfaces

    NASA Astrophysics Data System (ADS)

    Park, Hyunwook; Kim, John

    2015-11-01

    Direct numerical simulations of a spatially developing turbulent boundary layer (TBL) developing over superhydrophobic surfaces (SHS) were performed in order to investigate the underlying physics of turbulent flow over SHS. SHS were modeled through the shear-free boundary condition, assuming that the gas-liquid interfaces remained as non-deformable. Pattern-averaged turbulence statistics were examined in order to determine the effects of SHS on turbulence in no-slip and slip regions separately. Near-wall turbulence over the slip region was significantly affected by SHS due to insufficient mean shear required to sustain near-wall turbulence. SHS also indirectly affected near-wall turbulence over the no-slip region. In addition to the effects of the spanwise width of SHS on skin-friction drag reduction reported previously, spatial effects in the streamwise direction were examined. A guideline for optimal design of SHS geometry will be discussed. This research was supported by the ONR (Grant No. N000141410291).

  2. Site blocking effects on adsorbed polyacrylamide conformation

    NASA Astrophysics Data System (ADS)

    Brotherson, Brett A.

    ionic strength, and an adsorbed polymer on a surface functionalized with site blocking additives. This work investigated these scenarios using a low charge density high molecular weight cationic polyacrylamide. Three different substrates, for polymer adsorption were analyzed: mica, anionic latex, and glass. It was determined that, similar to previous studies, the adsorbed polymer layer thickness in water is relatively small even for high molecular weight polymers, on the order of tens of nanometers. The loop length distribution of a single polymer, experimentally verified for the first time, revealed a broad span of loop lengths as high as 1.5 microns. However, the bulk of the distribution was found between 40 and 260 nanometers. For the first time, previous theoretical predictions regarding the salt effect on adsorbed polymer conformation were confirmed experimentally. It was determined that the adsorbed polymer layer thickness expanded with increasing ionic strength of the solvent. Using atomic force microscopy, it was determined that the adsorbed polymer loop lengths and tail lengths increased with increasing ionic strength, supporting the results found using dynamic light scattering. The effect of the addition of site blocking additives on a single polymer's conformation was investigated for the first time. It was determined that the addition of site blocking additives caused strikingly similar results as the addition of salt to the medium. The changes in adsorbed polymer's loop lengths was found to be inconsistent and minimal. However, the changes in an adsorbed polymer's free tail length was found to increase with increasing site blocking additive levels. These results were obtained using either PDADMAC or cationic nanosilica as site blocking additives.

  3. Scanning electrochemical microscopy: surface interrogation of adsorbed hydrogen and the open circuit catalytic decomposition of formic acid at platinum.

    PubMed

    Rodríguez-López, Joaquín; Bard, Allen J

    2010-04-14

    The surface interrogation mode of scanning electrochemical microscopy (SECM) is extended to the in situ quantification of adsorbed hydrogen, H(ads), at polycrystalline platinum. The methodology consists of the production, at an interrogator electrode, of an oxidized species that is able to react with H(ads) on the Pt surface and report the amounts of this adsorbate through the SECM feedback response. The technique is validated by comparison to the electrochemical underpotential deposition (UPD) of hydrogen on Pt. We include an evaluation of electrochemical mediators for their use as oxidizing reporters for adsorbed species at platinum; a notable finding is the ability of tetramethyl-p-phenylenediamine (TMPD) to oxidize (interrogate) H(ads) on Pt at low pH (0.5 M H(2)SO(4) or 1 M HClO(4)) and with minimal background effects. As a case study, the decomposition of formic acid (HCOOH) in acidic media at open circuit on Pt was investigated. Our results suggest that formic acid decomposes at the surface of unbiased Pt through a dehydrogenation route to yield H(ads) at the Pt surface. The amount of H(ads) depended on the open circuit potential (OCP) of the Pt electrode at the time of interrogation; at a fixed concentration of HCOOH, a more negative OCP yielded larger amounts of H(ads) until reaching a coulomb limiting coverage close to 1 UPD monolayer of H(ads). The introduction of oxygen into the cell shifted the OCP to more positive potentials and reduced the quantified H(ads); furthermore, the system was shown to be chemically reversible, as several interrogations could be run consecutively and reproducibly regardless of the path taken to reach a given OCP. PMID:20225806

  4. Determination of Surface Potential and Electrical Double-Layer Structure at the Aqueous Electrolyte-Nanoparticle Interface

    NASA Astrophysics Data System (ADS)

    Brown, Matthew A.; Abbas, Zareen; Kleibert, Armin; Green, Richard G.; Goel, Alok; May, Sylvio; Squires, Todd M.

    2016-01-01

    The structure of the electrical double layer has been debated for well over a century, since it mediates colloidal interactions, regulates surface structure, controls reactivity, sets capacitance, and represents the central element of electrochemical supercapacitors. The surface potential of such surfaces generally exceeds the electrokinetic potential, often substantially. Traditionally, a Stern layer of nonspecifically adsorbed ions has been invoked to rationalize the difference between these two potentials; however, the inability to directly measure the surface potential of dispersed systems has rendered quantitative measurements of the Stern layer potential, and other quantities associated with the outer Helmholtz plane, impossible. Here, we use x-ray photoelectron spectroscopy from a liquid microjet to measure the absolute surface potentials of silica nanoparticles dispersed in aqueous electrolytes. We quantitatively determine the impact of specific cations (Li+ , Na+ , K+ , and Cs+ ) in chloride electrolytes on the surface potential, the location of the shear plane, and the capacitance of the Stern layer. We find that the magnitude of the surface potential increases linearly with the hydrated-cation radius. Interpreting our data using the simplest assumptions and most straightforward understanding of Gouy-Chapman-Stern theory reveals a Stern layer whose thickness corresponds to a single layer of water molecules hydrating the silica surface, plus the radius of the hydrated cation. These results subject electrical double-layer theories to direct and falsifiable tests to reveal a physically intuitive and quantitatively verified picture of the Stern layer that is consistent across multiple electrolytes and solution conditions.

  5. Effect of impurities in the description of surface nanobubbles: Role of nonidealities in the surface layer

    NASA Astrophysics Data System (ADS)

    Das, Siddhartha

    2011-06-01

    In a recent study [S. Das, J. H. Snoeijer, and D. Lohse, Phys. Rev. E1539-375510.1103/PhysRevE.82.056310 82, 056310 (2010)], we provided quantitative demonstration of the conjecture [W. A. Ducker, LangmuirLANGD50743-746310.1021/la902011v 25, 8907 (2009)] that the presence of impurities at the surface layer (or the air-water interface) of surface nanobubbles can substantially lower the gas-side contact angle and the Laplace pressure of the nanobubbles. Through an analytical model for any general air-water interface without nonideality effects, we showed that a large concentration of soluble impurities at the air-water interface of the nanobubbles ensures significantly small contact angles (matching well with the experimental results) and Laplace pressure (though large enough to forbid stability). In this paper this general model is extended to incorporate the effect of nonidealities at the air-water interface in impurity-induced alteration of surface nanobubble properties. Such nonideality effects arise from finite enthalpy or entropy of mixing or finite ionic interactions of the impurity molecules at the nanobubble air-water interface and ensure significant lowering of the nanobubble contact angle and Laplace pressure even at relatively small impurity coverage. In fact for impurity molecules that show enhanced tendency to get adsorbed at the nanobubble air-water interface from the bulk phase, impurity-induced lowering of the nanobubble contact angle is witnessed for extremely small bulk concentration. Surface nanobubble experiments being typically performed in an ultraclean environment, the bulk concentration of impurities is inevitably very small, and in this light the present calculations can be viewed as a satisfactory explanation of the conjecture that impurities, even in trace concentration, have significant impact on surface nanobubbles.

  6. Polyethyleneimine as a novel desorbent for anionic organic dyes on layered double hydroxide surface.

    PubMed

    Wang, Siming; Li, Zenghe; Lu, Chao

    2015-11-15

    Polyethyleneimine (PEI) is a positively charged polymer with hydrogen-bonding sites and hydrophobic chains. Therefore, it has been clearly established as an efficient adsorbent by means of these native properties in the literatures. However, there is apparently no good reason to disregard the use of PEI as a desired desorbent. Herein, using methyl orange as a model anionic dye, we investigated the desorption performances of PEI toward anionic dyes adsorbed on the surface of CO3-layered double hydroxides (LDHs) in a wide range of pH values. The experiment results showed that the positively charged PEI had very strong desorption capacity for anionic dyes at low pH values (<9.5) through electrostatic attraction between PEI and methyl orange because of the high degree of protonation of PEI. At high pH values (>9.5), PEI existed as neutral molecule, it could desorb methyl orange via hydrogen bonding between the amino groups of it and sulfonate group of methyl orange; simultaneously, the anion-exchange process occurred between abundant hydroxyl anions and anionic methyl orange. The adsorption capacity of the used LDH adsorbent was about 80% after five cycles of adsorption-desorption-regeneration, which was much higher than that conducted by 0.1M NaOH solution. These findings suggested that PEI could be regarded as a promising desorbent for enriching anionic dyes in wastewater and regenerating LDHs through surface adsorption-desorption cycles. PMID:26255712

  7. Angle resolved XPS of monomolecular layer of 5-chlorobenzotriazole on oxidized metallic surface

    NASA Astrophysics Data System (ADS)

    Kazansky, L. P.; Selyaninov, I. A.; Kuznetsov, Yu. I.

    2012-10-01

    Angle resolved XPS is used to study adsorption of 5-chlorobenzotriazole (5-chloroBTAH) on surfaces of the oxidized metals: mild steel, copper and zinc from borate buffer solution (pH 7.4). It is shown that for the metals studied the 5-chloroBTA anions, when adsorbed, form a monomolecular layer whose thickness is ∼6 Å comparable with the size of BTA. As XPS evidences adsorption proceeds with deprotonation of 5-chloroBTAH and formation of the coordination bonds between the lone pair of nitrogens and cation of a metal. Measuring XPS at two different angles unequivocally points out almost vertical arrangement of the anions toward the sample surface, when chlorine atoms form outmost virtual layer.

  8. Switching orientation of adsorbed molecules: Reverse domino on a metal surface

    NASA Astrophysics Data System (ADS)

    Braatz, C. R.; Esat, T.; Wagner, C.; Temirov, R.; Tautz, F. S.; Jakob, P.

    2016-01-01

    A thus far unknown phase of 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) on Ag(111), characterized by an all perpendicular orientation of the planar molecules and bound to the Ag substrate through the carboxyl oxygen atoms has been identified using infrared absorption spectroscopy and scanning tunneling microscopy. Its formation process requires second layer NTCDA to squeeze into empty spaces between relaxed monolayer NTCDA molecules. Remarkably, this process causes initially parallel oriented NTCDA to likewise adopt the new, highly inclined adsorption geometry. According to our SPA-LEED and STM findings, the new phase displays a distinct long range order and shows a pronounced tendency to form 1D rows or narrow islands. We suggest that extra NTCDA preferentially transforms into the upright configuration close to existing islands and attaches to them, i.e. the transformation process proceeds in a directed and recurrent manner (reverse domino scenario). Identical processing starting with a compressed NTCDA/Ag(111) monolayer leads to a purely parallel oriented bilayer, that is, the NTCDA monolayer phase is retained and merely acts as a passive template for bilayer NTCDA. The new vertical NTCDA phase represents an unusual molecular system with π-orbitals oriented parallel to a metal surface. A substantially reduced coupling of these orbitals to Ag(111) electronic levels is conjectured, which will have a major impact on intermolecular couplings and electronically excited state lifetimes.

  9. Removal of adsorbed gases with CO2 snow

    NASA Astrophysics Data System (ADS)

    Zito, Richard R.

    1991-09-01

    During the outgassing of orbiting astronomical observatories, the condensation of molecular species on optical surfaces can create difficulties for astronomers. The problem is particularly severe in ultraviolet astronomy where the adsorption of only a few atomic layers of some substances can be very damaging. In this paper the removal of adsorbed atomic layers using carbon dioxide snow is discussed. The rate of removal of adsorbed layers of isopropyl alcohol, Freon TF, and deionized distilled water on Teflon substrates was experimentally determined. The removal of fingerprints (containing fatty acids such as stearic acid) from optical surfaces is also demonstrated. The presence and rate of removal of the multilayers was monitored by detecting the molecular dipole field of adsorbed molecular species. For isopropyl alcohol, Freon TF (trichlorotrifluoroethane), and water adsorbed multilayers were removed in under 1.5 seconds. Fingerprint removal was much more difficult and required 20 seconds of spraying with a mixture of carbon dioxide snow flakes and atomized microdroplets of isopropyl alcohol.

  10. Angular Resolved X-Ray Absorption Near Edge Structure Investigation of Adsorbed Alkanethiol Monolayers on III-V(110) Surfaces

    NASA Astrophysics Data System (ADS)

    Chassé, T.; Zerulla, D.; Hallmeier, K. H.

    The structure of alkanethiol monolayers on III-V(110) surfaces was studied by analyzing the X-ray absorption near edge structure (XANES) of the carbon K edge. Pronounced absorption maxima were observed for special orientations of the polarization vector of the radiation as revealed from angular-dependent measurements, suggesting a rather well-defined molecular axis of the alkyl chains. From quantitative evaluations of these angular dependences the chains were found to be tilted from the normal towards the [001] direction of the (110) surfaces by 34° and 15° in the case of hexadecanethiol (HDT) adsorption on InP and GaP, respectively. The similarities as well as the differences in tilt angles between the substrates are dicussed in terms of constraints imposed by the surface structure and lattice constants as well as the space requirements of the van der Waals spheres of the adsorbed thiols. A unique feature observed on these monolayers is the nearly complete alignment of the alkyl chains with respect to the azimuthal orientation. We suggest that this adsorbate system represents the case of a single domain orientation within the organic monolayer.

  11. Surface-enhanced resonance hyper-Raman scattering and surface-enhanced resonance Raman scattering of dyes adsorbed on silver electrode and silver colloid: a comparison study

    NASA Astrophysics Data System (ADS)

    Li, Wu-Hu; Li, Xiao-Yuan; Yu, Nai-Teng

    1999-10-01

    Surface-enhanced resonance hyper-Raman scattering (SERHRS) and surface-enhanced resonance Raman scattering (SERRS) of three dyes, rhodamine 6G, crystal violet and basic fuchsin, are studied comparatively on electrochemically roughened silver electrode and silver colloid, respectively. All three dyes show a better SERHRS efficiency on the silver colloid than on the silver electrode, a phenomenon just opposite to what we have recently observed for pyridine and pyrazine [Chem. Phys. Lett. 305 (1999) 303]. These results suggest that the efficiency of SEHRS depends not only on the active surfaces employed (colloidal metals versus roughened electrodes) but also on the types of the adsorbed molecules.

  12. High-productivity membrane adsorbers: Polymer surface-modification studies for ion-exchange and affinity bioseparations

    NASA Astrophysics Data System (ADS)

    Chenette, Heather C. S.

    This dissertation centers on the surface-modification of macroporous membranes to make them selective adsorbers for different proteins, and the analysis of the performance of these membranes relative to existing technology. The common approach used in these studies, which is using membrane technology for chromatographic applications and using atom transfer radical polymerization (ATRP) as a surface modification technique, will be introduced and supported by a brief review in Chapter 1. The specific approaches to address the unique challenges and motivations of each study system are given in the introduction sections of the respective dissertation chapters. Chapter 2 describes my work to develop cation-exchange membranes. I discuss the polymer growth kinetics and characterization of the membrane surface. I also present an analysis of productivity, which measures the mass of protein that can bind to the stationary phase per volume of stationary phase adsorbing material per time. Surprisingly and despite its importance, this performance measure was not described in previous literature. Because of the significantly shorter residence time necessary for binding to occur, the productivity of these cation-exchange membrane adsorbers (300 mg/mL/min) is nearly two orders of magnitude higher than the productivity of a commercial resin product (4 mg/mL/min). My work studying membrane adsorbers for affinity separations was built on the productivity potential of this approach, as articulated in the conclusion of Chapter 2. Chapter 3 focuses on the chemical formulation work to incorporate glycoligands into the backbone of polymer tentacles grown from the surface of the same membrane stationary phase. Emphasis is given to characterizing and testing the working formulation for ligand incorporation, and details about how I arrived at this formulation are given in Appendix B. The plant protein, or lectin, Concanavalin A (conA) was used as the target protein. The carbohydrate affinity

  13. Polyethylenimine surface layer for enhanced virus immobilization on cellulose

    NASA Astrophysics Data System (ADS)

    Tiliket, Ghania; Ladam, Guy; Nguyen, Quang Trong; Lebrun, Laurent

    2016-05-01

    Thin regenerated cellulose films are prepared by hydrolysis of cellulose acetate (CA). A polycation, namely polyethylenimine (PEI), is then adsorbed onto the films. From QCM-D analysis, PEI readily adsorbs from a 0.1% w/v solution in NaCl 0.2 M (ca. 100 ng cm-2). Further PEI adsorption steps at higher PEI concentrations induce a linear growth of the PEI films, suggesting that free adsorption sites still exist after the initial adsorption. The adsorbed PEI chains are resistant to variations of the ionic strength up to NaCl 1 M. Promisingly, the adsorption of T4D bacteriophages are 15-fold more efficient onto the PEI-treated, compared to the native regenerated cellulose films, as measured by QCM-D. This confirms the strong affinity between the negatively charged viruses and PEI, even at low PEI concentration, probably governed by strong electrostatic attractive interactions. This result explains the remarkable improvement of the affinity of medical masks for virus droplets when one of their cellulose layers was changed by two-PEI-functionalized cellulose-based filters.

  14. Effects of water hardness and existence of adsorbent on toxic surface tension of surfactants for aquatic species.

    PubMed

    Oya, Masaru; Orito, Shintaro; Ishikawa, Yusuke; Iizuka, Tomoko

    2007-01-01

    We have studied the effectiveness of surface tension on surfactants risk assessment. gamma(tox) was defined as surface tension at a point where acute aquatic toxicity of a surfactant emerges. Oryzias latipes, Daphnia magna, and Podocopida were used for acute aquatic toxicity test of 7 surfactants and 3 detergents. Gamma(tox)values were plotted on surface tension curves, and the effect of water hardness on toxicity and surface tension were examined. Results showed that gamma(tox) varies greatly by kind of surfactant or detergent. Therefore, aquatic toxicity cannot only be explained by surface tension. The change of aquatic toxicity with varying water hardness, however, could be explained by the change of surface tension. Aquatic toxicity of LAS (Linear Alkylbenzene Sulphonate) increased and aquatic toxicity of SOAP decreased with an increase of water hardness, but both gamma(tox), values were constant. Aquatic toxicity was decreased by an addition of mud soil as adsorbent into surfactant solution. The toxicity change can be explained by the surface tension since gamma(tox) value of solution with and without mud soil were equal. These results showed that the change of aquatic toxicity of a surfactant caused by water property, such as water hardness, could be explained by the change of surface tension. PMID:17898487

  15. Polarizabilities of Halide Ions Co-Adsorbed on Silver Nanoparticles and Their Relationship to Increased Surface-Enhanced Raman Intensities of Rhodamine-6G and Pyridine

    NASA Astrophysics Data System (ADS)

    Cole, Michael; Jagodzinski, Paul

    2013-03-01

    Glaspell et. al. (2004), found a linear relationship between the intensities of surface-enhanced Raman (SER) signals of selected vibrational modes of rhodamine-6G (R6G) and the polarizabilities of co-adsorbed halide ions. Furthermore, they noticed that the slopes of intensity versus time plots for R6G also exhibit a linear relationship with the halide polarizabilities. We will present similar results from the SER signals from selected vibrational modes of pyridine and the polarizabilities of co-adsorbed halide ions. In addition, we will present a plausible relationship between the adsorbates and the electric field of the induced dipole of the halide ions.

  16. Surface heterogeneity of C{sub 60} as studied by infrared spectroscopy of adsorbed CO and adsorption potential calculations

    SciTech Connect

    Folman, M.; Fastow, M.; Kozirovski, Y.

    1997-03-05

    In our recent investigation of the IR spectrum of CO physically adsorbed on C{sub 60} films, two well-resolved absorption bands at 2135 and 2128 cm{sup -1} were found, suggesting that the molecule is adsorbed on two different sites. To determine the nature of these adsorption sites, calculations of adsorption potentials and spectral shifts for the CO/C{sub 60} system were performed. The calculations were done for the fcc (100), fcc (111) hcp (001), and hcp (111) surface planes. In the calculations the 6-exponential and the Lennard-Jones potentials were used. A number of adsorption sites were chosen. These included the void space between four, three, and two neighboring C{sub 60} molecules and the center of the hexagon and the pentagon on the C{sub 60} surface. The calculated potentials and spectral shifts clearly indicate that adsorption sites in the voids between the C{sub 60} molecules are energetically preferred over sites on top of single C{sub 60} molecules. Comparison is made between results obtained with the two potentials and with results obtained previously with the two other carbon allotropes: graphite and diamond. 11 refs., 4 figs., 3 tabs.

  17. The surface chemistry of GaAs atomic layer epitaxy

    SciTech Connect

    Creighton, J.R.; Banse, B.A.

    1991-01-01

    In this paper we review three proposed mechanisms for GaAs ALE and review or present data support or contradiction of these mechanisms. Surface chemistry results clearly demonstrated that TMGa irreversibly chemisorbs on the Ga-rich GaAs(100) surface. The reactive sticking coefficient (RSC) of TMGa on the adsorbate-free Ga-rich GaAs(100) surface was measured to be {approximately}0.5, conclusively demonstrating that the selective adsorption'' mechanism of ALE is not valid. We describe kinetic evidence for methyl radical desorption in support of the adsorbate inhibition'' mechanism. The methyl radical desorption rates determined by temperature programmed desorption (TPD) demonstrate that desorption is at least a factor of {approximately}10 faster from the As-rich c(2 {times} 8)/(2 {times} 4) surface than from the Ga-rich surface. It is disparity in CH{sub 3} desorption rates between the As-rich and Ga-rich surfaces that is largely responsible for GaAs ALE behavior. A gallium alkyl radical (e.g. MMGa) is also observed during TPD and molecular beam experiments, in partial support of the flux balance'' mechanism. Stoichiometry issues of ALE are also discussed. We have discovered that arsine exposures typical of atmospheric pressure and reduced pressure ALE lead to As coverages {ge} 1 ML, which provides the likely solution to the stoichiometry question regarding the arsine cycle. 32 refs., 6 figs.

  18. Layers of Porous Superhydrophobic Surfaces for Robust Water Repellency

    NASA Astrophysics Data System (ADS)

    Ahmadi, Farzad; Boreyko, Jonathan; Nature-Inspired Fluids; Interfaces Team

    2015-11-01

    In nature, birds exhibit multiple layers of superhydrophobic feathers that repel water. Inspired by bird feathers, we utilize porous superhydrophobic surfaces and compare the wetting and dewetting characteristics of a single surface to stacks of multiple surfaces. The superhydrophobic surfaces were submerged in water in a closed chamber. Pressurized gas was regulated to measure the critical pressure for the water to fully penetrate through the surfaces. In addition to using duck feathers, two-tier porous superhydrophobic surfaces were fabricated to serve as synthetic mimics with a controlled surface structure. The energy barrier for the wetting transition was modeled as a function of the number of layers and their orientations with respect to each other. Moreover, after partial impalement into a subset of the superhydrophobic layers, it was observed that a full dewetting transition was possible, which suggests that natural organisms can exploit their multiple layers to prevent irreversible wetting.

  19. Hydrogen storage on high-surface-area carbon monoliths for Adsorb hydrogen Gas Vehicle

    NASA Astrophysics Data System (ADS)

    Soo, Yuchoong; Pfeifer, Peter

    2014-03-01

    Carbon briquetting can increase hydrogen volumetric storage capacity by reducing the useless void volume resulting in a better packing density. It is a robust and efficient space-filling form for an adsorbed hydrogen gas vehicle storage tank. To optimize hydrogen storage capacity, we studied three fabrication process parameters: carbon-to-binder ratio, compaction temperature, and pyrolysis atmosphere. We found that carbon-to-binder ratio and pyrolysis atmosphere have influences on gravimetric excess adsorption. Compaction temperature has large influences on gravimetric and volumetric storage capacity. We have been able to optimize these parameters for high hydrogen storage. All monolith uptakes (up to 260 bar) were measured by a custom-built, volumetric, reservoir-type instrument.

  20. Zero-point vibration of hydrogen adsorbed on Si and Pt surfaces.

    PubMed

    Fukutani, K; Itoh, A; Wilde, M; Matsumoto, M

    2002-03-18

    Hydrogen atoms adsorbed on Si(111) and Pt(111) were investigated by nuclear reaction analysis (NRA) using 1H(15N,alphagamma)12C. From measurements of the NRA spectrum at normal and tilted ion incidences the zero-point vibrational energies of H on Si(111) in the perpendicular and parallel directions were found to be 123.4+/-4.6 and 44.6+/-6.2 meV, respectively, which are consistent with harmonic potentials. The zero-point energies obtained for Pt(111)-H were 80.8+/-3.9 and 62.1+/-6.0 meV for perpendicular and parallel directions, respectively. These results indicate that the stretching mode is harmonic, while the bending mode is strongly anharmonic. PMID:11909413

  1. Biotransformation of pink water TNT on the surface of a low-cost adsorbent pine bark.

    PubMed

    Chusova, O; Nõlvak, H; Odlare, M; Truu, J; Truu, M; Oopkaup, K; Nehrenheim, E

    2015-09-01

    This two-week anaerobic batch study evaluated 2,4,6-trinitrotoluene (TNT) removal efficiency from industrial pink water by (1) adsorption on low-cost adsorbent pine bark, and (2) adsorption coupled with TNT biotransformation by specialised microbial communities. Samples of the supernatant and acetonitrile extracts of pine bark were analysed by HPLC, while the composition of the bacterial community of the experimental batches, inocula and pine bark were profiled by high-throughput sequencing the V6 region of the bacterial 16S rRNA gene. Integrated adsorption and biotransformation proved to be the most efficient method for TNT removal from pink water. The type of applied inoculum had a profound effect on TNT removal efficiencies and microbial community structures, which were dominated by phylotypes belonging to the Enterobacteriaceae family. The analysis of acetonitrile extracts of pine bark supported the hypothesis that the microbial community indigenous to pine bark has the ability to degrade TNT. PMID:26142875

  2. Modeling of turbulent transport in the surface layer

    NASA Technical Reports Server (NTRS)

    Smith, G. L.

    1973-01-01

    The turbulence equations as written by Donaldson using the method of invariant modeling have been applied to the following limiting cases of the surface or constant flux layer of the planetary boundary layer: (1) Neutrally stable; (2) stable (above influence of surface roughness); (3) nearly neutrally stable; and (4) very unstable (free convection). For the neutrally stable case, the equations are shown to admit as a solution the familiar logarithmic profile. By use of this result, boundary conditions suitable for the surface layer are defined and are simple to apply to rough surfaces.

  3. Adsorbent and adsorbent bed for materials capture and separation processes

    SciTech Connect

    Liu, Wei

    2011-01-25

    A method device and material for performing adsorption wherein a fluid mixture is passed through a channel in a structured adsorbent bed having a solid adsorbent comprised of adsorbent particles having a general diameter less than 100 um, loaded in a porous support matrix defining at least one straight flow channel. The adsorbent bed is configured to allow passage of a fluid through said channel and diffusion of a target material into said adsorbent under a pressure gradient driving force. The targeted molecular species in the fluid mixture diffuses across the porous support retaining layer, contacts the adsorbent, and adsorbs on the adsorbent, while the remaining species in the fluid mixture flows out of the channel.

  4. Effects of surface adsorbed oxygen, applied voltage, and temperature on UV photoresponse of ZnO nanorods

    NASA Astrophysics Data System (ADS)

    Zong, Xian-Li; Zhu, Rong

    2015-10-01

    The ultraviolet (UV) photoresponses of ZnO nanorods directly grown on and between two micro Au-electrodes by using electric-field-assisted wet chemical method are measured comprehensively under different conditions, including ambient environment, applied bias voltage, gate voltage and temperature. Experimental results indicate that the photoresponses of the ZnO nanorods can be modulated by surface oxygen adsorptions, applied voltages, as well as temperatures. A model taking into account both surface adsorbed oxygen and electron-hole activities inside ZnO nanorods is proposed. The enhancement effect of the bias voltage on photoresponse is also analyzed. Experimental results shows that the UV response time (to 63%) of ZnO nanorods in air and at 59 °C could be shortened from 34.8 s to 0.24 s with a bias of 4 V applied between anode and cathode. Project supported by the National Natural Science Foundation of China (Grant No. 91123017).

  5. Iron phthalocyanine on Cu(111): Coverage-dependent assembly and symmetry breaking, temperature-induced homocoupling, and modification of the adsorbate-surface interaction by annealing.

    PubMed

    Snezhkova, Olesia; Bischoff, Felix; He, Yuanqin; Wiengarten, Alissa; Chaudhary, Shilpi; Johansson, Niclas; Schulte, Karina; Knudsen, Jan; Barth, Johannes V; Seufert, Knud; Auwärter, Willi; Schnadt, Joachim

    2016-03-01

    We have examined the geometric and electronic structures of iron phthalocyanine assemblies on a Cu(111) surface at different sub- to mono-layer coverages and the changes induced by thermal annealing at temperatures between 250 and 320 °C by scanning tunneling microscopy, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy. The symmetry breaking observed in scanning tunneling microscopy images is found to be coverage dependent and to persist upon annealing. Further, we find that annealing to temperatures between 300 and 320 °C leads to both desorption of iron phthalocyanine molecules from the surface and their agglomeration. We see clear evidence of temperature-induced homocoupling reactions of the iron phthalocyanine molecules following dehydrogenation of their isoindole rings, similar to what has been observed for related tetrapyrroles on transition metal surfaces. Finally, spectroscopy indicates a modified substrate-adsorbate interaction upon annealing with a shortened bond distance. This finding could potentially explain a changed reactivity of Cu-supported iron phthalocyanine in comparison to that of the pristine compound. PMID:26957171

  6. Iron phthalocyanine on Cu(111): Coverage-dependent assembly and symmetry breaking, temperature-induced homocoupling, and modification of the adsorbate-surface interaction by annealing

    NASA Astrophysics Data System (ADS)

    Snezhkova, Olesia; Bischoff, Felix; He, Yuanqin; Wiengarten, Alissa; Chaudhary, Shilpi; Johansson, Niclas; Schulte, Karina; Knudsen, Jan; Barth, Johannes V.; Seufert, Knud; Auwärter, Willi; Schnadt, Joachim

    2016-03-01

    We have examined the geometric and electronic structures of iron phthalocyanine assemblies on a Cu(111) surface at different sub- to mono-layer coverages and the changes induced by thermal annealing at temperatures between 250 and 320 °C by scanning tunneling microscopy, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy. The symmetry breaking observed in scanning tunneling microscopy images is found to be coverage dependent and to persist upon annealing. Further, we find that annealing to temperatures between 300 and 320 °C leads to both desorption of iron phthalocyanine molecules from the surface and their agglomeration. We see clear evidence of temperature-induced homocoupling reactions of the iron phthalocyanine molecules following dehydrogenation of their isoindole rings, similar to what has been observed for related tetrapyrroles on transition metal surfaces. Finally, spectroscopy indicates a modified substrate-adsorbate interaction upon annealing with a shortened bond distance. This finding could potentially explain a changed reactivity of Cu-supported iron phthalocyanine in comparison to that of the pristine compound.

  7. Shear rheology of mixed protein adsorption layers vs their structure studied by surface force measurements.

    PubMed

    Danov, Krassimir D; Kralchevsky, Peter A; Radulova, Gergana M; Basheva, Elka S; Stoyanov, Simeon D; Pelan, Eddie G

    2015-08-01

    The hydrophobins are proteins that form the most rigid adsorption layers at liquid interfaces in comparison with all other investigated proteins. The mixing of hydrophobin HFBII with other conventional proteins is expected to reduce the surface shear elasticity and viscosity, E(sh) and η(sh), proportional to the fraction of the conventional protein. However, the experiments show that the effect of mixing can be rather different depending on the nature of the additive. If the additive is a globular protein, like β-lactoglobulin and ovalbumin, the surface rigidity is preserved, and even enhanced. The experiments with separate foam films indicate that this is due to the formation of a bilayer structure at the air/water interface. The more hydrophobic HFBII forms the upper layer adjacent to the air phase, whereas the conventional globular protein forms the lower layer that faces the water phase. Thus, the elastic network formed by the adsorbed hydrophobin remains intact, and even reinforced by the adjacent layer of globular protein. In contrast, the addition of the disordered protein β-casein leads to softening of the HFBII adsorption layer. Similar (an even stronger) effect is produced by the nonionic surfactant Tween 20. This can be explained with the penetration of the hydrophobic tails of β-casein and Tween 20 between the HFBII molecules at the interface, which breaks the integrity of the hydrophobin interfacial elastic network. The analyzed experimental data for the surface shear rheology of various protein adsorption layers comply with a viscoelastic thixotropic model, which allows one to determine E(sh) and η(sh) from the measured storage and loss moduli, G' and G″. The results could contribute for quantitative characterization and deeper understanding of the factors that control the surface rigidity of protein adsorption layers with potential application for the creation of stable foams and emulsions with fine bubbles or droplets. PMID:24828304

  8. Ozonolysis of surface-adsorbed methoxyphenols: kinetics of aromatic ring cleavage vs. alkene side-chain oxidation

    NASA Astrophysics Data System (ADS)

    O'Neill, E. M.; Kawam, A. Z.; Van Ry, D. A.; Hinrichs, R. Z.

    2014-01-01

    Lignin pyrolysis products, which include a variety of substituted methoxyphenols, constitute a major component of organics released by biomass combustion, and may play a central role in the formation of atmospheric brown carbon. Understanding the atmospheric fate of these compounds upon exposure to trace gases is therefore critical to predicting the chemical and physical properties of biomass burning aerosol. We used diffuse reflectance infrared spectroscopy to monitor the heterogeneous ozonolysis of 4-propylguaiacol, eugenol, and isoeugenol adsorbed on NaCl and α-Al2O3 substrates. Adsorption of gaseous methoxyphenols onto these substrates produced near-monolayer surface concentrations of 3 × 1018 molecules m-2. The subsequent dark heterogeneous ozonolysis of adsorbed 4-propylguaiacol cleaved the aromatic ring between the methoxy and phenol groups with the product conclusively identified by GC-MS and 1H-NMR. Kinetic analysis of eugenol and isoeugenol dark ozonolysis also suggested the formation of ring-cleaved products, although ozonolysis of the unsaturated substituent groups forming carboxylic acids and aldehydes was an order of magnitude faster. Average uptake coefficients for NaCl-adsorbed methoxyphenols were γ = 2.3 (± 0.8) × 10-7 and 2 (± 1) × 10-6 for ozonolysis of the aromatic ring and the unsaturated side chain, respectively, and reactions on α-Al2O3 were approximately two times slower. UV-visible radiation (λ > 300 nm) enhanced eugenol ozonolysis of the aromatic ring by a factor of 4(± 1) but had no effect on ozonolysis of the alkene side chain.

  9. ac conductance of surface layer in lithium tetraborate single crystals

    NASA Astrophysics Data System (ADS)

    Kim, Chung-Sik; Park, Jong-Ho; Moon, Byung Kee; Seo, Hyo-Jin; Choi, Byung-Chun; Hwang, Yoon-Hwae; Kim, Hyung Kook; Kim, Jung Nam

    2003-12-01

    ac conductance for the electrode effect in Li2B4O7 single crystal was investigated by use of a coplanar electrode applied on the surface of a (001) plate. A coplanar electrode in this material more clearly shows conduction of the electrode effect than a conventional parallel planar electrode. The electrode effect in ac conductance is likely to be controlled by the surface layer, which is a poorly conductive depletion layer possibly filled with vacancies of lithium ions. We found that the surface layer is not locally distributed near the electrodes, but, rather, on the broad area of the surface (001) plane of the material. So we conclude that the electrode effect in ac conduction of Li2B4O7 single crystal is mainly due to the poor conductive surface layer distributed over the whole surface of the (001) plane and is not a secondary phase formed by reaction with the electrode material.

  10. Segregation at the surfaces of CuxPd1 - x alloys in the presence of adsorbed S

    NASA Astrophysics Data System (ADS)

    Miller, James B.; Priyadarshini, Deepika; Gellman, Andrew J.

    2012-10-01

    The influence of adsorbed S on surface segregation in CuxPd1 - x alloys (S/CuxPd1 - x) was characterized over a wide range of bulk alloy compositions (x = 0.05 to 0.95) using high-throughput Composition Spread Alloy Film (CSAF) sample libraries. Top-surface and near-surface compositions of the CSAFs were measured as functions of bulk Cu composition, x, and temperature using spatially resolved low energy ion scattering spectroscopy (LEISS) and X-ray photoemission spectroscopy (XPS). Preferential segregation of Cu to the top-surface of the S/CuxPd1 - x CSAF was observed at all bulk compositions, x, but the extent of Cu segregation to the S/CuxPd1 - x surface was lower than the Cu segregation to the surface of a clean CuxPd1 - x CSAF, clear evidence of an S-induced "segregation reversal." The Langmuir-McLean formulation of the Gibbs isotherm was used to estimate the enthalpy and entropy of Cu segregation to the top-surface, ΔHseg(x) and ΔSseg(x), at saturation sulfur coverages. While Cu segregation to the top-surface of the clean CuxPd1 - x is exothermic (ΔHseg < 0) for all bulk Cu compositions, it is endothermic (ΔHseg > 0) for S/CuxPd1 - x. Segregation to the S/CuxPd1 - x surface is driven by entropy. Changes in segregation patterns that occur upon adsorption of S onto CuxPd1 - x appear to be related to formation of energetically favored Pdsbnd S bonds at the surface, which counterbalance the enthalpic driving forces for Cu segregation to the clean surface.

  11. Analysis of Chemical Reactions between Radical Growth Precursors Adsorbed on Plasma-Deposited Silicon Thin-Film Surfaces

    NASA Astrophysics Data System (ADS)

    Bakos, Tamas; Valipa, Mayur; Maroudas, Dimitrios

    2006-03-01

    The dominant precursor in the plasma deposition of hydrogenated amorphous silicon (a-Si:H) thin films is the SiH3 radical. In this presentation, we report results of first-principles density functional theory calculations on the crystalline Si(001)-(2x1):H surface and molecular-dynamics simulations on a-Si:H surfaces for the interactions between SiH3 radicals adsorbed on Si thin-film surfaces. The analysis reveals that two SiH3 radicals may either form disilane (Si2H6) that desorbs from the surface or undergo a disproportionation reaction producing an SiH2 radical that is incorporated in the film and a silane molecule that is released in the gas phase. The corresponding activation barriers depend on the local atomic coordination of the surface Si atoms; Si2H6 formation is barrierless if both radicals are bonded to overcoordinated surface Si atoms and exhibits barriers in excess of 1 eV for two chemisorbed SiH3 radicals.

  12. Surface-enhanced nonlinear optical effects and detection of adsorbed molecular monolayers

    SciTech Connect

    Shen, Y.R.; Chen, C.K.; Heinz, T.F.; Ricard, D.

    1981-01-01

    The observation of a number of surface-enhanced nonlinear optical effects is discussed. The feasibility of using second-harmonic generation to detect the adsorption of molecular monolayers on a metal surface in an electrolytic solution is shown.

  13. Surface and interface properties of thin pentacene and parylene layers

    NASA Astrophysics Data System (ADS)

    Vincze, Andrej; Jakabovič, Ján; Srnánek, Rudolf; Šatka, Alexander; Kováč, Jaroslav; Kováč, Jaroslav

    2009-06-01

    To improve Organic Thin Film Transistor (OTFT) properties we study OTFT semiconductor/dielectric interfacial properties via examination of the gate dielectric using thin Parylene C layer. Structural and morphology properties of pentacene layers deposited on parylene layer and SiO2/Si substrate structure were compared. The surface morphology was investigated using atomic force microscopy (AFM) and scanning electron microscopy (SEM). AFM topography of pentacene layer in non-contact mode confirmed the preferable pentacene grain formation on parylene surface in dependence on layer thickness. The distribution of chemical species on the surfaces and composition depth profiles were measured by secondary ion mass spectroscopy (SIMS) and surface imaging. The depth profiles of the analyzed structures show a homogenous pentacene layer, characterized with C or C2 ions. Relatively sharp interface between pentacene and parylene layers was estimated by characteristic increased intensity of CCl ions peak. For revealing the pentacene phases in the structures the Micro-Raman spectroscopy was utilized. Conformal coatings of parylene and pentacene layers without pinholes resulted from the deposition process as was confirmed by SIMS surface imaging. For the pentacene layers thicker than 20 nm, both thin and bulk pentacene phases were detected by Micro-Raman spectroscopy, while for the pentacene layer thickness of 5 and 10 nm the preferable thin phase was detected. The complete characterisation of pentacene layers deposited on SiO2 and parylene surface revealed that the formation of large grains suggests 3D pentacene growth at parylene layer with small voids between grains and more than one monolayer step growth. The results will be utilized for optimization of the deposition process.

  14. Preparation and Characterization of Chitosan/Feldspar Biohybrid as an Adsorbent: Optimization of Adsorption Process via Response Surface Modeling

    PubMed Central

    Yazdani, Maryam; Bahrami, Hajir; Arami, Mokhtar

    2014-01-01

    Chitosan/feldspar biobased beads were synthesized, characterized, and tested for the removal of Acid Black 1 dye from aquatic phases. A four-factor central composite design (CCD) accompanied by response surface modeling (RSM) and optimization was used to optimize the dye adsorption by the adsorbent (chitosan/feldspar composite) in 31 different batch experiments. Independent variables of temperature, pH, initial dye concentration, and adsorbent dose were used to change to coded values. To anticipate the responses, a quadratic model was applied. Analysis of variance (ANOVA) tested the significance of the process factors and their interactions. The adequacy of the model was investigated by the correlation between experimental and predicted data of the adsorption and the calculation of prediction errors. The results showed that the predicted maximum adsorption amount of 21.63 mg/g under the optimum conditions (pH 3, temperature 15°C, initial dye concentration 125 mg/L, and dose 0.2 g/50 mL) was close to the experimental value of 19.85 mg/g. In addition, the results of adsorption behaviors of the dye illustrated that the adsorption process followed the Langmuir isotherm model and the pseudo-second-order kinetic model. Langmuir sorption capacity was found to be 17.86 mg/g. Besides, thermodynamic parameters were evaluated and revealed that the adsorption process was exothermic and favourable. PMID:24587722

  15. Preservation of Archaeal Surface Layer Structure During Mineralization

    PubMed Central

    Kish, Adrienne; Miot, Jennyfer; Lombard, Carine; Guigner, Jean-Michel; Bernard, Sylvain; Zirah, Séverine; Guyot, François

    2016-01-01

    Proteinaceous surface layers (S-layers) are highly ordered, crystalline structures commonly found in prokaryotic cell envelopes that augment their structural stability and modify interactions with metals in the environment. While mineral formation associated with S-layers has previously been noted, the mechanisms were unconstrained. Using Sulfolobus acidocaldarius a hyperthermophilic archaeon native to metal-enriched environments and possessing a cell envelope composed only of a S-layer and a lipid cell membrane, we describe a passive process of iron phosphate nucleation and growth within the S-layer of cells and cell-free S-layer “ghosts” during incubation in a Fe-rich medium, independently of metabolic activity. This process followed five steps: (1) initial formation of mineral patches associated with S-layer; (2) patch expansion; (3) patch connection; (4) formation of a continuous mineral encrusted layer at the cell surface; (5) early stages of S-layer fossilization via growth of the extracellular mineralized layer and the mineralization of cytosolic face of the cell membrane. At more advanced stages of encrustation, encrusted outer membrane vesicles are formed, likely in an attempt to remove damaged S-layer proteins. The S-layer structure remains strikingly well preserved even upon the final step of encrustation, offering potential biosignatures to be looked for in the fossil record. PMID:27221593

  16. Preservation of Archaeal Surface Layer Structure During Mineralization.

    PubMed

    Kish, Adrienne; Miot, Jennyfer; Lombard, Carine; Guigner, Jean-Michel; Bernard, Sylvain; Zirah, Séverine; Guyot, François

    2016-01-01

    Proteinaceous surface layers (S-layers) are highly ordered, crystalline structures commonly found in prokaryotic cell envelopes that augment their structural stability and modify interactions with metals in the environment. While mineral formation associated with S-layers has previously been noted, the mechanisms were unconstrained. Using Sulfolobus acidocaldarius a hyperthermophilic archaeon native to metal-enriched environments and possessing a cell envelope composed only of a S-layer and a lipid cell membrane, we describe a passive process of iron phosphate nucleation and growth within the S-layer of cells and cell-free S-layer "ghosts" during incubation in a Fe-rich medium, independently of metabolic activity. This process followed five steps: (1) initial formation of mineral patches associated with S-layer; (2) patch expansion; (3) patch connection; (4) formation of a continuous mineral encrusted layer at the cell surface; (5) early stages of S-layer fossilization via growth of the extracellular mineralized layer and the mineralization of cytosolic face of the cell membrane. At more advanced stages of encrustation, encrusted outer membrane vesicles are formed, likely in an attempt to remove damaged S-layer proteins. The S-layer structure remains strikingly well preserved even upon the final step of encrustation, offering potential biosignatures to be looked for in the fossil record. PMID:27221593

  17. Structure of collagen adsorbed on a model implant surface resolved by polarization modulation infrared reflection-absorption spectroscopy.

    PubMed

    Brand, Izabella; Habecker, Florian; Ahlers, Michael; Klüner, Thorsten

    2015-03-01

    The polarization modulation infrared reflection-absorption spectra of collagen adsorbed on a titania surface and quantum chemical calculations are used to describe components of the amide I mode to the protein structure at a sub-molecular level. In this study, imino acid rich and poor fragments, representing the entire collagen molecule, are taken into account. The amide I mode of the collagen triple helix is composed of three absorption bands which involve: (i) (∼1690cm(-1)) the CO stretching modes at unhydrated groups, (ii) (1655-1673cm(-1)) the CO stretching at carbonyl groups at imino acids and glycine forming intramolecular hydrogen bonds with H atoms at both NH2 and, unusual for proteins, CH2 groups at glycine at a neighbouring chain and (iii) (∼1640cm(-1)) the CO stretching at carbonyl groups forming hydrogen bonds between two, often charged, amino acids as well as hydrogen bonds to water along the entire helix. The IR spectrum of films prepared from diluted solutions (c<50μgml(-1)) corresponds to solution spectra indicating that native collagen molecules interact with water adsorbed on the titania surface. In films prepared from solutions (c⩾50μgml(-1)) collagen multilayers are formed. The amide I mode is blue-shifted by 18cm(-1), indicating that intramolecular hydrogen bonds at imino acid rich fragments are weakened. Simultaneous red-shift of the amide A mode implies that the strength of hydrogen bonds at the imino acid poor fragments increases. Theoretically predicted distortion of the collagen structure upon adsorption on the titania surface is experimentally confirmed. PMID:25498816

  18. Novel adhesive properties of poly(ethylene-oxide) adsorbed nanolayers

    NASA Astrophysics Data System (ADS)

    Zeng, Wenduo

    Solid-polymer interfaces play crucial roles in the multidisciplinary field of nanotechnology and are the confluence of physics, chemistry, biology, and engineering. There is now growing evidence that polymer chains irreversibly adsorb even onto weakly attractive solid surfaces, forming a nanometer-thick adsorbed polymer layer ("adsorbed polymer nanolayers"). It has also been reported that the adsorbed layers greatly impact on local structures and properties of supported polymer thin films. In this thesis, I aim to clarify adhesive and tribological properties of adsorbed poly(ethylene-oxide) (PEO) nanolayers onto silicon (Si) substrates, which remain unsolved so far. The adsorbed nanolayers were prepared by the established protocol: one has to equilibrate the melt or dense solution against a solid surface; the unadsorbed chains can be then removed by a good solvent, while the adsorbed chains are assumed to maintain the same conformation due to the irreversible freezing through many physical solid-segment contacts. I firstly characterized the formation process and the surface/film structures of the adsorbed nanolayers by using X-ray reflectivity, grazing incidence X-ray diffraction, and atomic force microscopy. Secondly, to compare the surface energy of the adsorbed layers with the bulk, static contact angle measurements with two liquids (water and glycerol) were carried out using a optical contact angle meter equipped with a video camera. Thirdly, I designed and constructed a custom-built adhesion-testing device to quantify the adhesive property. The experimental results provide new insight into the microscopic structure - macroscopic property relationship at the solid-polymer interface.

  19. TEM studies of the nitrided Ni-Ti surface layer.

    PubMed

    Lelatko, J; Paczkowski, P; Wierzchoń, T; Morawiec, H

    2006-09-01

    The structure of surface layer, obtained on the nearly equiatomic Ni-Ti alloy after nitriding under glow discharge conditions at temperatures 700 or 800 degrees C, was investigated. The structural characterization of the intruded layer was performed on cross-sectional thin foils by the use of the transmission and scanning electron microscopes. The obtained results show that the nitrided layers consist mainly of the nanocrystalline TiN phase and small amount of Ti(2)N. Between the nitrided layers and beta-NiTi matrix an intermediate Ti(2)Ni phase layer was observed. PMID:17059538

  20. Generation and characterization of surface layers on acoustically levitated drops.

    PubMed

    Tuckermann, Rudolf; Bauerecker, Sigurd; Cammenga, Heiko K

    2007-06-15

    Surface layers of natural and technical amphiphiles, e.g., octadecanol, stearic acid and related compounds as well as perfluorinated fatty alcohols (PFA), have been investigated on the surface of acoustically levitated drops. In contrast to Langmuir troughs, traditionally used in the research of surface layers at the air-water interface, acoustic levitation offers the advantages of a minimized and contact-less technique. Although the film pressure cannot be directly adjusted on acoustically levitated drops, it runs through a wide pressure range due to the shrinking surface of an evaporating drop. During this process, different states of the generated surface layer have been identified, in particular the phase transition from the gaseous or liquid-expanded to the liquid-condensed state of surface layers of octadecanol and other related amphiphiles. Characteristic parameters, such as the relative permeation resistance and the area per molecule in a condensed surface layer, have been quantified and were found comparable to results obtained from surface layers generated on Langmuir troughs. PMID:17376468

  1. Observation of Surface Layering in a Nonmetallic Liquid

    SciTech Connect

    Mo,H.; Evmenenko, G.; Kewalramani, S.; Kim, K.; Ehrlich, S.; Dutta, P.

    2006-01-01

    Oscillatory density profiles (layers) have previously been observed at the free surfaces of liquid metals but not in other isotropic liquids. We have used x-ray reflectivity to study a molecular liquid, tetrakis(2-ethylhexoxy)silane. When cooled to T/T{sub c}{approx}0.25 (well above the freezing point for this liquid), density oscillations appear at the surface. Lateral order within the layers is liquidlike. Our results confirm theoretical predictions that a surface-layered state will appear even in dielectric liquids at sufficiently low temperatures, if not preempted by freezing.

  2. Improve oxidation resistance at high temperature by nanocrystalline surface layer.

    PubMed

    Xia, Z X; Zhang, C; Huang, X F; Liu, W B; Yang, Z G

    2015-01-01

    An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surface layer, which causes the fast oxidation in the initial oxidation stage. The formation of (Fe,Cr)2O3 inner layer would inhabit fast diffusion of alloy elements in the nanocrystalline surface layer of P91 steel in the later oxidation stage, and it causes a decrease in the parabolic oxidation rate compared with conventional specimens. This study provides a novel approach to improve the oxidation resistance of heat resistant steel without changing its Cr content. PMID:26269034

  3. Improve oxidation resistance at high temperature by nanocrystalline surface layer

    NASA Astrophysics Data System (ADS)

    Xia, Z. X.; Zhang, C.; Huang, X. F.; Liu, W. B.; Yang, Z. G.

    2015-08-01

    An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surface layer, which causes the fast oxidation in the initial oxidation stage. The formation of (Fe,Cr)2O3 inner layer would inhabit fast diffusion of alloy elements in the nanocrystalline surface layer of P91 steel in the later oxidation stage, and it causes a decrease in the parabolic oxidation rate compared with conventional specimens. This study provides a novel approach to improve the oxidation resistance of heat resistant steel without changing its Cr content.

  4. Improve oxidation resistance at high temperature by nanocrystalline surface layer

    PubMed Central

    Xia, Z. X.; Zhang, C.; Huang, X. F.; Liu, W. B.; Yang, Z. G.

    2015-01-01

    An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surface layer, which causes the fast oxidation in the initial oxidation stage. The formation of (Fe,Cr)2O3 inner layer would inhabit fast diffusion of alloy elements in the nanocrystalline surface layer of P91 steel in the later oxidation stage, and it causes a decrease in the parabolic oxidation rate compared with conventional specimens. This study provides a novel approach to improve the oxidation resistance of heat resistant steel without changing its Cr content. PMID:26269034

  5. The structures and dynamics of atomic and molecular adsorbates on metal surfaces by scanning tunneling microscopy and low energy electron diffraction

    SciTech Connect

    Yoon, Hyungsuk Alexander

    1996-12-01

    Studies of surface structure and dynamics of atoms and molecules on metal surfaces are presented. My research has focused on understanding the nature of adsorbate-adsorbate and adsorbate-substrate interactions through surface studies of coverage dependency and coadsorption using both scanning tunneling microscopy (STM) and low energy electron diffraction (LEED). The effect of adsorbate coverage on the surface structures of sulfur on Pt(111) and Rh(111) was examined. On Pt(111), sulfur forms p(2x2) at 0.25 ML of sulfur, which transforms into a more compressed ({radical}3x{radical}3)R30{degrees} at 0.33 ML. On both structures, it was found that sulfur adsorbs only in fcc sites. When the coverage of sulfur exceeds 0.33 ML, it formed more complex c({radical}3x7)rect structure with 3 sulfur atoms per unit cell. In this structure, two different adsorption sites for sulfur atoms were observed - two on fcc sites and one on hcp site within the unit cell.

  6. High-resolution electron-energy-loss spectroscopy and photoelectron-diffraction studies of the geometric structure of adsorbates on single-crystal metal surfaces

    SciTech Connect

    Rosenblatt, D.H.

    1982-11-01

    Two techniques which have made important contributions to the understanding of surface phenomena are high resolution electron energy loss spectroscopy (EELS) and photoelectron diffraction (PD). EELS is capable of directly measuring the vibrational modes of clean and adsorbate covered metal surfaces. In this work, the design, construction, and performance of a new EELS spectrometer are described. These results are discussed in terms of possible structures of the O-Cu(001) system. Recommendations for improvements in this EELS spectrometer and guidelines for future spectrometers are given. PD experiments provide accurate quantitative information about the geometry of atoms and molecules adsorbed on metal surfaces. The technique has advantages when used to study disordered overlayers, molecular overlayers, multiple site systems, and adsorbates which are weak electron scatterers. Four experiments were carried out which exploit these advantages.

  7. Adsorption of perfluoroalkyl acids by carbonaceous adsorbents: Effect of carbon surface chemistry.

    PubMed

    Zhi, Yue; Liu, Jinxia

    2015-07-01

    Adsorption by carbonaceous sorbents is among the most feasible processes to remove perfluorooctane sulfonic (PFOS) and carboxylic acids (PFOA) from drinking and ground waters. However, carbon surface chemistry, which has long been recognized essential for dictating performance of such sorbents, has never been considered for PFOS and PFOA adsorption. Thus, the role of surface chemistry was systematically investigated using sorbents with a wide range in precursor material, pore structure, and surface chemistry. Sorbent surface chemistry overwhelmed physical properties in controlling the extent of uptake. The adsorption affinity was positively correlated carbon surface basicity, suggesting that high acid neutralizing or anion exchange capacity was critical for substantial uptake of PFOS and PFOA. Carbon polarity or hydrophobicity had insignificant impact on the extent of adsorption. Synthetic polymer-based Ambersorb and activated carbon fibers were more effective than activated carbon made of natural materials in removing PFOS and PFOA from aqueous solutions. PMID:25827692

  8. "False" cytotoxicity of ions-adsorbing hydroxyapatite - Corrected method of cytotoxicity evaluation for ceramics of high specific surface area.

    PubMed

    Klimek, Katarzyna; Belcarz, Anna; Pazik, Robert; Sobierajska, Paulina; Han, Tomasz; Wiglusz, Rafal J; Ginalska, Grazyna

    2016-08-01

    An assessment of biomaterial cytotoxicity is a prerequisite for evaluation of its clinical potential. A material is considered toxic while the cell viability decreases under 70% of the control. However, extracts of certain materials are likely to reduce the cell viability due to the intense ions adsorption from culture medium (e.g. highly bioactive ceramics of high surface area). Thus, the standard ISO 10993-5 procedure is inappropriate for cytotoxicity evaluation of ceramics of high specific surface area because biomaterial extract obtained in this method (ions-depleted medium) is not optimal for cell cultures per se. Therefore, a simple test was designed as an alternative to ISO 10993-5 standard for cytotoxicity evaluation of the biomaterials of high surface area and high ions absorption capacity. The method, presented in this paper, included the evaluation of ceramics extract prepared according to corrected procedure. The corrected extract was found not cytotoxic (cell viability above 70%), suggesting that modified method for cytotoxicity evaluation of ions-adsorbing ceramics is more appropriate than ISO 10993-5 standard. For such biomaterials, the term "false" cytotoxicity is more suitable. Moreover, it was noted that NRU assay and microscopic observations should be recommended for cytotoxicity evaluation of ceramics of high surface area. PMID:27157729

  9. Elastic response of a protein monolayer adsorbed at decorated water surface

    NASA Astrophysics Data System (ADS)

    Singh, Amarjeet; Konovalov, Oleg

    2015-05-01

    Under the in-plane isothermal compression the self-assembled protein monolayer expand in the direction perpendicular to the applied force as a function of applied compression. The structure finally buckle beyond a critical compression, which finally returns to the initial structure when the compression force was removed, behaving like an elastic body. We modelled the layer as homogeneous elastic medium and calculated elastic constants. Young's modulus of the protein layer is 2 orders of magnitude smaller than the bulk lysozyme crystals. It is of fundamental significance to be able to predict the elastic properties of the proteins at air-water interface since protein remains in their natural environment unlike protein crystals.

  10. Process Conditions of Forming the Surface Layer of Aluminum Powder Product by Layer-by-layer Laser Sintering

    NASA Astrophysics Data System (ADS)

    Saprykina, N. A.; Saprykin, A. A.; Ibragimov, E. A.; Arkhipova, D. A.

    2016-07-01

    The paper presents data on state of the art in selective laser sintering of products. Layer-by-layer sintering is shown to be a future-oriented technology, making it possible to synthesize products of metal powder materials. Factors, influencing the quality of a sintered product, are revealed in the paper. It presents outcomes of experiments, focused on the dependence of surface layer thickness of sintered aluminum powder PA-4 on laser processing conditions. Basic factors, influencing the quality of a sintered surface layer include laser power, speeds of scanning and moving the laser beam on the layer of powder. Thickness of the sintered layer varies from 0.74 to 1.55 mm, as the result of changing the laser processing conditions.

  11. Thin gold layer in Ni electroforming process: optical surface characterization

    NASA Astrophysics Data System (ADS)

    Sironi, G.; Spiga, D.; Pareschi, G.; Missaglia, N.; Paganini, L.

    2009-08-01

    Mandrel replication by Nickel electroforming is a well-suited process to manufacture X-ray mirrors, making use of Gold layer playing the twofold role of release agent and reflective coating. To increase the optical performances of mirrors it is crucial to minimize the impact of X-ray scattering effects related to surface microroughness, especially when the mirror is intended to operate in hard X-rays. In this case, the Gold layer simply acts as release agent because the reflection is demanded to interferential over-coatings. Even though the replicated optical surface is usually believed to reproduce the smooth topography of the master, a surface degradation is commonly observed. Such a worsening can also suffer from a contribution from the spontaneous roughness growth of the Gold layer itself: if this is the case, the mirror's optical quality could potentially benefit from the utilization of a thin Gold layer (< 100 nm) instead of the traditional thick gold layer (> 100 nm). To prove the effectiveness of the Gold thickness reduction, a microroughness characterization of replicated thin gold layers has been achieved. We report here a preliminary roughness study of 3 electroformed Ni samples replicated from a super-polished Zerodur flat master with various Gold layer thicknesses, in the spectral range 0.02-1000 μm. The study is organized as follows: (a) characterization of the 3 replicated samples; (b) comparison of the Gold roughness for thin vs. thick layers; (c) comparison of the two sides of Gold layers.

  12. Subgrid-scale Modeling in the Atmospheric Surface Layer^1

    NASA Astrophysics Data System (ADS)

    Khanna, S.; Wyngaard, J. C.; Brasseur, J. G.

    1996-11-01

    Subgrid-scale (SGS) modeling is crucial in the surface layer of wall-bounded flows where the vertical velocity fluctuations cannot be well resolved. We focus on the distinct characteristics of the surface layer of the atmospheric boundary layer (ABL), and analyze, from a highly resolved surface-layer field of a moderately convective ABL, the extent to which Smagorinsky-based SGS models predict these characteristics. The fields were generated using a nested-mesh large-eddy simulation (LES) with the finest mesh having an effective grid resolution of 512^3 covering 1/16^th of the boundary-layer depth. At a height where the fine mesh resolves 90 % of the total fluxes and variances, the resolved fields were treated as surrogate fully resolved fields that were filtered onto a coarser mesh to get ``resolvable'' and ``subgrid'' fields. Preliminary results show that Smagorinsky-based models fail to capture many of the distinctive characteristics of the ABL surface layer. For example, they do not capture the anisotropic distribution of subgrid-scale energy among the horizontal and the vertical components, and they grossly underestimate the SGS horizontal temperature flux. Currently we are focusing on more suitable closures for the atmospheric surface layer. A DNS-based study is also underway and will be used to supplement this analysis. ^1 supported by ARO (# DAAL03-92-G-0117) and ONR (# N00014-92-J-1688)

  13. CORRELATIONS FOR THE DETERMINATION OF SURFACE DIFFUSIVITIES OF ORGANIC CHEMICALS ADSORBED ONTO GRANULAR ACTIVATED CARBON

    EPA Science Inventory

    Differential column batch reactor (DCBR) experiments in organic-free water were conducted for the following volatile organic compounds (VOCs): trichloroethene, tetrachloroethene, cis-1,2 dichlorethene, and toluene. Surface diffusion was required to explain the rate of uptake for ...

  14. The origin of inverse absorption bands observed in the far-infrared RAIRS spectra of SnCl 4 and SnBr 4 adsorbed on thin-film SnO 2 surfaces

    NASA Astrophysics Data System (ADS)

    Awaluddin, A.; Pilling, M. J.; Wincott, P. L.; LeVent, S.; Surman, M.; Pemble, M. E.; Gardner, P.

    2002-04-01

    The adsorption of SnCl 4 and SnBr 4 on polycrystalline SnO 2 has been studied using synchrotron radiation based far-infrared reflection absorption infrared spectroscopy FIR-RAIRS. In order to exploit the sensitivity advantages of the buried metal layer method, the SnO 2 is in the form of a thin film deposited on a tungsten foil substrate. Adsorption of SnCl 4 and SnBr 4 on an oxygen sputtered surface at 120 K results in spectra characteristic of condensed multilayers. In addition, both spectra exhibit an inverse absorption band centred at 355 cm -1. Modified 4-layer, wavelength-dependent, Greenler calculations show that this inverse absorption band is induced by the presence of the adsorbate but is characteristic of the SnO 2 layer. The lack of any frequency shift upon changing the adsorbate from SnCl 4 to SnBr 4 rules out the possibility that the inverse absorption band is due to a dipole-forbidden parallel mode of the molecule excited via the interaction with free electron oscillations in the metal, resulting from the radiation induced oscillating electric field just below the surface.

  15. Ethylene and oxygen species adsorbed on a defect oxidized surface Ag(1 1 1) . Theoretical analysis by DFT method

    NASA Astrophysics Data System (ADS)

    Avdeev, Vasilii I.; Zhidomirov, Georgii M.

    2001-10-01

    We suggest a cluster model AS v→Ag12-3O of the oxidized surface Ag(1 1 1) with a defect. The defect is simulated by cationic vacancy V. Density functional theory (B3LYP/LANL1MB approximation) is used to calculate ethylene and oxygen adsorption on the regular (AS r) and defect (AS d) sites on the Ag(1 1 1). Oxygen interaction with site AS r produces atomic oxygen species (AS r-O). Oxygen adsorption on site AS d is accompanied by its association with subsurface oxygen atoms to form a quasimolecular structure of metal ozonide type -Ag-O-O ep-O-Ag-, containing electrophilic oxygen O ep. Energies of atomic oxygen binding to the regular and defect surfaces are found to be approximately equal. On the regular surface, ethylene forms a π-complex with binding energy Eπ(Ag-C 2H 4)=14.2 kcal/mol. On the defect surface, ethylene produces a metal-ethylene-peroxide cycle such as Ag-O-O-C 2H 4-Ag. Determined are the frequencies of normal vibration for ethylene and oxygen species, adsorbed on the regular and defect surfaces. In the case of associative oxygen species and complete isotope replacement 16O→ 18O, the main frequency at 1000 cm -1 shifts by Δν=57-61 cm -1, but this shift decreases to Δν=25-30 cm -1 for isotope mixtures 16O/ 18O. For the adsorbed species of ethylene-oxygen mixtures, IR spectra show the frequencies within which 170-180 cm -1 are associated with stretching of bond Ag-C. Frequencies at 300-490 cm -1 are assigned to mode ν(Ag-O) of the functional group Ag-O-O ep-O-Ag. The most intensive modes at 950 and 600 cm -1 are likely to stretching and bending of the functional groups containing the O-O-O and O-O-C bonds.

  16. Investigation of surface charge density on solid-liquid interfaces by modulating the electrical double layer.

    PubMed

    Moon, Jong Kyun; Song, Myung Won; Pak, Hyuk Kyu

    2015-05-20

    A solid surface in contact with water or aqueous solution usually carries specific electric charges. These surface charges attract counter ions from the liquid side. Since the geometry of opposite charge distribution parallel to the solid-liquid interface is similar to that of a capacitor, it is called an electrical double layer capacitor (EDLC). Therefore, there is an electrical potential difference across an EDLC in equilibrium. When a liquid bridge is formed between two conducting plates, the system behaves as two serially connected EDLCs. In this work, we propose a new method for investigating the surface charge density on solid-liquid interfaces. By mechanically modulating the electrical double layers and simultaneously applying a dc bias voltage across the plates, an ac electric current can be generated. By measuring the voltage drop across a load resistor as a function of bias voltage, we can study the surface charge density on solid-liquid interfaces. Our experimental results agree very well with the simple equivalent electrical circuit model proposed here. Furthermore, using this method, one can determine the polarity of the adsorbed state on the solid surface depending on the material used. We expect this method to aid in the study of electrical phenomena on solid-liquid interfaces. PMID:25923410

  17. Poly(ethylene oxide) Mushrooms Adsorbed at Silica-Ionic Liquid Interfaces Reduce Friction.

    PubMed

    Sweeney, James; Webber, Grant B; Atkin, Rob

    2016-03-01

    The adsorbed layer conformation and lubricity of 35, 100, and 300 kDa PEO adsorbed to ionic liquid (IL)-silica interfaces from 0.01 wt % solutions have been investigated using colloid probe atomic force microscopy. The ILs used were propylammonium nitrate (PAN) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), which are protic and aprotic ILs, respectively. Normal force curves reveal steric interactions consistent with adsorbed polymer layers which are best fit using the mushroom model. Friction measurements show that the adsorbed polymer layer markedly reduces friction compared to surfaces sliding in the pure ILs and that lubricity increases with polymer length. When polymer is adsorbed to the sliding surfaces, friction is controlled by the creation and disruption of intermolecular interactions between entangled chains and the dragging of polymer chains through the interpenetration region. These experiments show that added polymer can reduce friction while maintaining the useful properties of ILs as lubricants. PMID:26844589

  18. Evolution of the surface area of a snow layer

    SciTech Connect

    Hanot, L.; Domine, F.

    1999-12-01

    Atmospheric trace gases can partition between the atmosphere and the snow surface. Because snow has a large surface-to-volume ratio, an important interaction potential between ice and atmospheric trace gases exists. Quantifying this partitioning requires the knowledge of the surface area (SA) of snow. Eleven samples were taken from a 50 cm thick snow fall at Col de Porte, near Grenoble (French Alps) between January 20 and February 4, 1998. Fresh snow and 3, 8, and 15-day-old snow were sampled at three different depths. Surface hoar, formed after the fall, was also sampled. Air and surface snow temperature, snow density, and snow fall rate were measured. Snow temperature always remained below freezing. Snow SA was measured using methane adsorption at 77.15 K. Values ranged from 2.25 m{sup 2}/g for fresh snow to 0.25 m{sup 2}/g for surface hoar and surface snow after 15 days. These values are much too high to be explained by the macroscopic aspect of snow crystals, and microstructures such as small rime droplets must have been present. Large decrease in SA with time were observed. The first meter of snowpack had a total surface area of about 50,000 m{sup 2} per m{sup 2} of ground. Reduction in SA will lead to the emission of adsorbed species by the snowpack, with possible considerable increase in atmospheric concentrations.

  19. Speciation of adsorbates on surface of solids by infrared spectroscopy and chemometrics.

    PubMed

    Vilmin, Franck; Bazin, Philippe; Thibault-Starzyk, Frédéric; Travert, Arnaud

    2015-09-01

    Speciation, i.e. identification and quantification, of surface species on heterogeneous surfaces by infrared spectroscopy is important in many fields but remains a challenging task when facing strongly overlapped spectra of multiple adspecies. Here, we propose a new methodology, combining state of the art instrumental developments for quantitative infrared spectroscopy of adspecies and chemometrics tools, mainly a novel data processing algorithm, called SORB-MCR (SOft modeling by Recursive Based-Multivariate Curve Resolution) and multivariate calibration. After formal transposition of the general linear mixture model to adsorption spectral data, the main issues, i.e. validity of Beer-Lambert law and rank deficiency problems, are theoretically discussed. Then, the methodology is exposed through application to two case studies, each of them characterized by a specific type of rank deficiency: (i) speciation of physisorbed water species over a hydrated silica surface, and (ii) speciation (chemisorption and physisorption) of a silane probe molecule over a dehydrated silica surface. In both cases, we demonstrate the relevance of this approach which leads to a thorough surface speciation based on comprehensive and fully interpretable multivariate quantitative models. Limitations and drawbacks of the methodology are also underlined. PMID:26388366

  20. Surface hopping dynamics of direct trans --> cis photoswitching of an azobenzene derivative in constrained adsorbate geometries

    NASA Astrophysics Data System (ADS)

    Floß, Gereon; Granucci, Giovanni; Saalfrank, Peter

    2012-12-01

    With ongoing miniaturization of electronic devices, the need for individually addressable, switchable molecules arises. An example are azobenzenes on surfaces which have been shown to be switchable between trans and cis forms. Here, we examine the "direct" (rather than substrate-mediated) channel of the trans → cis photoisomerization after ππ* excitation of tetra-tert-butyl-azobenzene physisorbed on surfaces mimicking Au(111) and Bi(111), respectively. In spirit of the direct channel, the electronic structure of the surface is neglected, the latter merely acting as a rigid platform which weakly interacts with the molecule via Van-der-Waals forces. Starting from thermal ensembles which represent the trans-form, sudden excitations promote the molecules to ππ*-excited states which are non-adiabatically coupled among themselves and to a nπ*-excited and the ground state, respectively. After excitation, relaxation to the ground state by internal conversion takes place, possibly accompanied by isomerization. The process is described here by "on the fly" semiclassical surface hopping dynamics in conjunction with a semiempirical Hamiltonian (AM1) and configuration-interaction type methods. It is found that steric constraints imposed by the substrate lead to reduced but non-vanishing, trans → cis reaction yields and longer internal conversion times than for the isolated molecule. Implications for recent experiments for azobenzenes on surfaces are discussed.

  1. Turbulent boundary layer on a convex, curved surface

    NASA Technical Reports Server (NTRS)

    Gillis, J. C.; Johnston, J. P.; Kays, W. M.; Moffat, R. J.

    1980-01-01

    The effects of strong convex curvature on boundary layer turbulence were investigated. The data gathered on the behavior of Reynolds stress suggested the formulation of a simple turbulence model. Three sets of data were taken on two separate facilities. Both rigs had flow from a flat surface, over a convex surface with 90 deg of turning, and then onto a flat recovery surface. The geometry was adjusted so that, for both rigs, the pressure gradient along the test surface was zero - thus avoiding any effects of streamwise acceleration on the wall layers. Results show that after a sudden introduction of curvature, the shear stress in the outer part of the boundary layer is sharply diminished and is even slightly negative near the edge. The wall shear also drops off quickly downstream. In contrast, when the surface suddenly becomes flat again, the wall shear and shear stress profiles recover very slowly towards flat wall conditions.

  2. C,N-bipyrazole receptor grafted onto a porous silica surface as a novel adsorbent based polymer hybrid.

    PubMed

    Radi, Smaail; Attayibat, Ahmed; El-Massaoudi, Mohamed; Bacquet, Maryse; Jodeh, Shehdeh; Warad, Ismail; Al-Showiman, Salim S; Mabkhot, Yahia N

    2015-10-01

    A simple heterogeneous synthesis of pure adsorbent based polymer hybrid made by condensing a functionalized C,N-bipyrazole with a 3-glycidoxypropyl-trimethoxysilane silylant agent, previously anchored on a silica surface was developed. The formed material (SG2P) was characterized through elemental analysis, FT-IR spectroscopy, (13)C NMR of solid state, scanning electron microscope (SEM), and was studied and evaluated by determination of the surface area using the BET equation, the adsorption and desorption capability using the isotherm of nitrogen and B.J.H. pore sizes. The new material exhibits good thermal stability determined by thermogravimetry curves and good chemical stability was examined in various acidic and buffer solutions (pH 1-7). The binding and adsorption abilities of SG2P were investigated for Hg(2+), Cd(2+), Pb(2+), Zn(2+), K(+), Na(+) and Li(+) cations and compared to the results of classical liquid-liquid extraction with the unbound C,N-bipyrazole compound. The grafting at the surface of silica does not affect complexing properties of the ligand and the SG2P exhibits a high selectivity toward Hg(2+) ion with no complexation being observed towards zinc and alkali metals. The extracted and the complexing cation percentages were determined by atomic absorption measurements. PMID:26078121

  3. The Role of Non-Bonded Interactions in the Conformational Dynamics of Organophosphorous Hydrolase Adsorbed onto Functionalized Mesoporous Silica Surfaces

    SciTech Connect

    Gomes, Diego Enry B.; Lins, Roberto D.; Pascutti, Pedro G.; Lei, Chenghong; Soares, Thereza A.

    2010-01-14

    The enzyme organophosphorous hydrolase (OPH) catalyzes the hydrolysis of a wide variety of organophosphorous compounds with high catalytic efficiency and broad substrate specificity. The immobilization of OPH in functionalized mesoporous silica surfaces increases significantly its catalytic specific activity compared to the enzyme in solution with important applications for the detection and decontamination of insecticides and chemical warfare agents. Experimental measurements of immobilization efficiency as function of the charge and coverage percentage of different functional groups have been interpreted as electrostatic forces being the predominant interactions underlying the adsorption of OPH onto functionalized mesoporous silica surfaces. Explicit solvent molecular dynamics simulations have been performed for OPH in bulk solution and adsorbed onto two distinct interaction potential models of the mesoporous silica functional groups in order to investigate the relative contributions of non-bonded interactions to the conformational dynamics and adsorption of the protein. Our results support the conclusion that while electrostatic interactions are responsible for the specific binding of OPH to the FMS surface, van der Waals forces are detrimental for enhanced interfacial adhesion. Key-words: molecular dynamics simulations; bacterial phosphotriesterase; conformational changes; confined environments; coarse-grain and atomistic models; silanol molecular model.

  4. Surface activity of Janus particles adsorbed at fluid-fluid interfaces: Theoretical and experimental aspects.

    PubMed

    Fernandez-Rodriguez, Miguel Angel; Rodriguez-Valverde, Miguel Angel; Cabrerizo-Vilchez, Miguel Angel; Hidalgo-Alvarez, Roque

    2016-07-01

    Since de Gennes coined in 1992 the term Janus particle (JP), there has been a continued effort to develop this field. The purpose of this review is to present the most relevant theoretical and experimental results obtained so far on the surface activity of amphiphilic JPs at fluid interfaces. The surface activity of JPs at fluid-fluid interfaces can be experimentally determined using two different methods: the classical Langmuir balance or the pendant drop tensiometry. The second method requires much less amount of sample than the first one, but it has also some experimental limitations. In all cases collected here the JPs exhibited a higher surface or interfacial activity than the corresponding homogeneous particles. This reveals the significant advantage of JPs for the stabilization of emulsions and foams. PMID:26094083

  5. Nanoshells made easy: improving Au layer growth on nanoparticle surfaces.

    PubMed

    Brinson, Bruce E; Lassiter, J Britt; Levin, Carly S; Bardhan, Rizia; Mirin, Nikolay; Halas, Naomi J

    2008-12-16

    The growth of a continuous, uniform Au layer on a dielectric nanoparticle is the critical step in the synthesis of nanoparticles such as nanoshells or nanorice, giving rise to their unique geometry-dependent plasmon resonant properties. Here, we report a novel, streamlined method for Au layer metallization on prepared nanoparticle surfaces using carbon monoxide as the reducing agent. This approach consistently yields plasmonic nanoparticles with highly regular shell layers and is immune to variations in precursor or reagent preparation. Single particle spectroscopy combined with scanning electron microscopy reveal that thinner, more uniform shell layers with correspondingly red-shifted optical resonances are achievable with this approach. PMID:19360963

  6. Hierarchical Porous and High Surface Area Tubular Carbon as Dye Adsorbent and Capacitor Electrode.

    PubMed

    Chen, Long; Ji, Tuo; Brisbin, Logan; Zhu, Jiahua

    2015-06-10

    Hierarchically porous tubular carbon (HPTC) with large surface area of 1094 m(2)/g has been successfully synthesized by selectively removing lignin from natural wood. No templates or chemicals are involved during the process. By further KOH activation, surface area of activated HPTC reaches up to 2925 m(2)/g. These materials show unprecedented high adsorption capacity toward organic dyes (methylene blue, 838 mg/g; methyl orange, 264 mg/g) and large electrochemical capacitance of >200 F/g. The sustainable feature of the wood precursor and demonstrated superior adsorption and energy storage properties allow promising applications of the processed materials in energy and environmental related fields. PMID:25980528

  7. Superwetting of TiO2 by light-induced water-layer growth via delocalized surface electrons

    PubMed Central

    Lee, Kunyoung; Kim, QHwan; An, Sangmin; An, JeongHoon; Kim, Jongwoo; Kim, Bongsu; Jhe, Wonho

    2014-01-01

    Titania, which exhibits superwetting under light illumination, has been widely used as an ideal material for environmental solution such as self-cleaning, water–air purification, and antifogging. There have been various studies to understand such superhydrophilic conversion. The origin of superwetting has not been clarified in a unified mechanism yet, which requires direct experimental investigation of the dynamic processes of water-layer growth. We report in situ measurements of the growth rate and height of the photo-adsorbed water layers by tip-based dynamic force microscopy. For nanocrystalline anatase and rutile TiO2 we observe light-induced enhancement of the rate and height, which decrease after O2 annealing. The results lead us to confirm that the long-range attraction between water molecules and TiO2, which is mediated by delocalized electrons in the shallow traps associated with O2 vacancies, produces photo-adsorption of water on the surface. In addition, molecular dynamics simulations clearly show that such photo-adsorbed water is critical to the zero contact angle of a water droplet spreading on it. Therefore, we conclude that this “water wets water” mechanism acting on the photo-adsorbed water layers is responsible for the light-induced superwetting of TiO2. Similar mechanism may be applied for better understanding of the hydrophilic conversion of doped TiO2 or other photo-catalytic oxides. PMID:24711400

  8. Dusty boundary layer in a surface-burst explosion

    SciTech Connect

    Kuhl, A.L.; Ferguson, R.E.; Chien, K.Y.; Collins, J.P.

    1993-08-01

    Dusty boundary layers are an inherent feature of explosions over ground surfaces. Detailed knowledge of dusty boundary layer characteristics is needed in explosion safety analysis (e.g., to calculate the drag loads on structures). Also, to predicct the amount of dust in the rising fireball of an explsion, one must know the dusty boundary layer swept up during the positive and negative phases of the blast wave and how much of this boundary layer dust is entrained into the stem of the dust cloud. This paper describes the results of numerical simulations of the dusty boundary layer created by a surface burst explosion. The evolution of the flow was calculated by a high-order Godunov code that solves the nonsteady conservation laws.

  9. Thermocapillary convection in two immiscible liquid layers with free surface

    NASA Technical Reports Server (NTRS)

    Doi, Takao; Koster, Jean N.

    1993-01-01

    Thermocapillary convection is studied in two immiscible liquid layers with one free surface, one liquid/liquid interface, and differential heating applied parallel to the interfaces. An analytical solution is introduced for infinite horizontal layers. The defining parameter for the flow pattern is lambda, the ratio of the temperature coefficient of the interfacial tension to that of the surface tension. Four different flow patterns exist under zero gravity conditions. 'Halt' conditions which halt the fluid motion in the lower encapsulated liquid layer have been found. A numerical experiment is carried out to study effects of vertical end walls on the double layer convection in a 2D cavity. The halt condition obtained from the analytical study is found to be valid in the limit of small Reynolds numbers. The flow in the encapsulated liquid layer can be suppressed substantially.

  10. Segregation at the surfaces of CuxPd1-x alloys in the presence of adsorbed S

    SciTech Connect

    Miller, James B.; Priyadarshini, Deepika; Gellman, Andrew J.

    2012-10-01

    The influence of adsorbed S on surface segregation in Cu{sub x}Pd{sub 1 - x} alloys (S/Cu{sub x}Pd{sub 1 - x)} was characterized over a wide range of bulk alloy compositions (x = 0.05 to 0.95) using high-throughput Composition Spread Alloy Film (CSAF) sample libraries. Top-surface and near-surface compositions of the CSAFs were measured as functions of bulk Cu composition, x, and temperature using spatially resolved low energy ion scattering spectroscopy (LEISS) and X-ray photoemission spectroscopy (XPS). Preferential segregation of Cu to the top-surface of the S/Cu{sub x}Pd{sub 1 - x} CSAF was observed at all bulk compositions, x, but the extent of Cu segregation to the S/Cu{sub x}Pd{sub 1 - x} surface was lower than the Cu segregation to the surface of a clean Cu{sub x}Pd{sub 1 - x} CSAF, clear evidence of an S-induced “segregation reversal.” The Langmuir–McLean formulation of the Gibbs isotherm was used to estimate the enthalpy and entropy of Cu segregation to the top-surface, ΔH{sub seg}(x) and ΔS{sub seg}(x), at saturation sulfur coverages. While Cu segregation to the top-surface of the clean Cu{sub x}Pd{sub 1 - x} is exothermic (ΔH{sub seg} < 0) for all bulk Cu compositions, it is endothermic (ΔH{sub seg} > 0) for S/Cu{sub x}Pd{sub 1 - x}. Segregation to the S/Cu{sub x}Pd{sub 1 - x} surface is driven by entropy. Changes in segregation patterns that occur upon adsorption of S onto Cu{sub x}Pd{sub 1 - x} appear to be related to formation of energetically favored Pd{single bond}S bonds at the surface, which counterbalance the enthalpic driving forces for Cu segregation to the clean surface.

  11. Eley-Rideal surface chemistry: Direct reactivity of gas phase atomic hydrogen with adsorbed species

    SciTech Connect

    Weinberg, W.H.

    1996-10-01

    Selected examples of Eley-Rideal surface chemistry are presented in order to review this field. Reactions on Ru(100) only are considered. The specific examples employed are: (i) hydrogenation of oxygen atoms, (ii) hydrogenation of CO, (iii) formation of dihydrogen, and (iv) hydrogenation of formate. 80 refs., 8 figs.

  12. Tunable surface charge of ZnS : Cu nano-adsorbent induced the selective preconcentration of cationic dyes from wastewater

    NASA Astrophysics Data System (ADS)

    Wang, Yongjing; Chen, Dagui; Wang, Yandi; Huang, Feng; Hu, Qichang; Lin, Zhang

    2012-05-01

    A novel environmentally friendly nano-adsorbent is developed by doping Cu+ cations into the lattice of ZnS microspheres. The adsorbent shows selective adsorbability for cationic dyes in low concentrations in wastewater. The adsorbed dye could be successfully eluted with alcohol, resulting in a 1000 fold enrichment of the dye solution.A novel environmentally friendly nano-adsorbent is developed by doping Cu+ cations into the lattice of ZnS microspheres. The adsorbent shows selective adsorbability for cationic dyes in low concentrations in wastewater. The adsorbed dye could be successfully eluted with alcohol, resulting in a 1000 fold enrichment of the dye solution. Electronic supplementary information (ESI) available: Synthesis, structural details of ZnS : Cu, adsorption isotherm of RhB on ZnS : Cu, control experiments for the adsorption measurements, pH effect on the adsorbability, and preliminary assessment of the adsorption efficiency for real industrial wastewater. See DOI: 10.1039/c2nr30689a

  13. Boundary Layer Flow Over a Moving Wavy Surface

    NASA Astrophysics Data System (ADS)

    Hendin, Gali; Toledo, Yaron

    2016-04-01

    Boundary Layer Flow Over a Moving Wavy Surface Gali Hendin(1), Yaron Toledo(1) January 13, 2016 (1)School of Mechanical Engineering, Tel-Aviv University, Israel Understanding the boundary layer flow over surface gravity waves is of great importance as various atmosphere-ocean processes are essentially coupled through these waves. Nevertheless, there are still significant gaps in our understanding of this complex flow behaviour. The present work investigates the fundamentals of the boundary layer air flow over progressive, small-amplitude waves. It aims to extend the well-known Blasius solution for a boundary layer over a flat plate to one over a moving wavy surface. The current analysis pro- claims the importance of the small curvature and the time-dependency as second order effects, with a meaningful impact on the similarity pattern in the first order. The air flow over the ocean surface is modelled using an outer, inviscid half-infinite flow, overlaying the viscous boundary layer above the wavy surface. The assumption of a uniform flow in the outer layer, used in former studies, is now replaced with a precise analytical solution of the potential flow over a moving wavy surface with a known celerity, wavelength and amplitude. This results in a conceptual change from former models as it shows that the pressure variations within the boundary layer cannot be neglected. In the boundary layer, time-dependent Navier-Stokes equations are formulated in a curvilinear, orthogonal coordinate system. The formulation is done in an elaborate way that presents additional, formerly neglected first-order effects, resulting from the time-varying coordinate system. The suggested time-dependent curvilinear orthogonal coordinate system introduces a platform that can also support the formulation of turbulent problems for any surface shape. In order to produce a self-similar Blasius-type solution, a small wave-steepness is assumed and a perturbation method is applied. Consequently, a

  14. Momentum resolved electron stimulated desorption ion angular distribution, a new technique, probing the low frequency motion of adsorbed molecules on single crystal surfaces

    SciTech Connect

    Ahner, J.; Mocuta, D.; Yates, J.T. Jr.

    1999-07-01

    A new technique, momentum resolved electron stimulated desorption ion angular distribution (ESDIAD), provides a method for taking snapshots of the zero-point position and lateral momentum of particles adsorbed on crystalline surfaces. By employing state-of-the-art electronics and computer technology it is possible to record for each desorbing particle the desorption direction together with the flight time. High momentum and directional resolved images are obtained, with time-of-flight resolution in the picosecond range and data acquisition rates up to 100 kHz. This enables us to deconvolute spatial and momentum contributions to the ESDIAD pattern and to map the low frequency motion of the adsorbed particles. These maps reflect the adsorbate interactions with the substrate and with neighboring species on the substrate. For selected examples it is demonstrated that by measuring the three dimensional momentum vector for each desorbing particle it is possible to probe the lowest energy states of adsorbed species, as well as to measure the momentum distribution when the adsorbed species gains thermal energy. Such information can be used as a basis for thinking about anisotropies in lateral motion of particles on surfaces. One major opportunity involves the study of dissimilar chemisorbed species which, when imaged together in momentum and real space, give new insights into the first stages of interaction between the species, leading ultimately to a chemical reaction. {copyright} {ital 1999 American Vacuum Society.}

  15. Surface-Adsorbed Long G-Quadruplex Nanowires Formed by G:C Linkages.

    PubMed

    Troha, Tinkara; Drevenšek-Olenik, Irena; Webba da Silva, Mateus; Spindler, Lea

    2016-07-19

    G-quadruplexes connected into long, continuous nanostructures termed G-wires show properties superior to dsDNA when applied in nanotechnology. Using AFM imaging, we systematically studied surface adsorption of a set of G-rich oligonucleotides with GC-termini for their ability to form long G-wires through G:C pairing. We investigated the effects of increasing sequence length, the type of nucleotide in the side loops, and removal of the CG-3' terminus. We found that sequences with adenine in the side loops most readily form G-wires. The role of magnesium as an efficient surface-anchoring ion was also confirmed. Conversely, as resolved from dynamic light scattering measurements, magnesium had no ability to promote G-quadruplex formation in solution. These insights may help in selecting prosperous candidates for construction of G-quadruplex based nanowires and to explore them for their electronic properties. PMID:27392201

  16. Control of Electronic Conduction at an Oxide Heterointerface using Surface Polar Adsorbates

    SciTech Connect

    Bell, Christopher

    2011-08-19

    We study the effect of the surface adsorption of a variety of common laboratory solvents on the conductivity at the interface between LaAlO{sub 3} and SrTiO{sub 3}. This interface possesses a range of intriguing physics, notably a proposed connection between the surface state of the LaAlO{sub 3} and the conductivity buried in the SrTiO{sub 3}. We show that the application of chemicals such as acetone, ethanol, and water can induce a large change (factor of three) in the conductivity. This phenomenon is observed only for polar solvents. These data provide experimental evidence for a general polarization-facilitated electronic transfer mechanism.

  17. Time-resolved spectroscopy at surfaces and adsorbate dynamics: Insights from a model-system approach

    NASA Astrophysics Data System (ADS)

    Boström, Emil; Mikkelsen, Anders; Verdozzi, Claudio

    2016-05-01

    We introduce a model description of femtosecond laser induced desorption at surfaces. The substrate part of the system is taken into account as a (possibly semi-infinite) linear chain. Here, being especially interested in the early stages of dissociation, we consider a finite-size implementation of the model (i.e., a finite substrate), for which an exact numerical solution is possible. By time-evolving the many-body wave function, and also using results from a time-dependent density functional theory description for electron-nuclear systems, we analyze the competition between several surface-response mechanisms and electronic correlations in the transient and longer time dynamics under the influence of dipole-coupled fields. Our model allows us to explore how coherent multiple-pulse protocols can impact desorption in a variety of prototypical experiments.

  18. Effects of the surface mobility on the oxidation of adsorbed CO on platinum electrodes in alkaline media. The role of the adlayer and surface defects.

    PubMed

    Herrero, Enrique; Chen, Qing-Song; Hernández, Javier; Sun, Shi-Gang; Feliu, Juan M

    2011-10-01

    The oxidation of adsorbed CO on Pt single crystal electrodes has been studied in alkaline media. The surfaces used in this study were the Pt(111) electrode and vicinal stepped and kinked surfaces with (111) terraces. The kinked surfaces have either (110) steps broken by (100) kinks or (100) steps broken by (110) kinks and different kink densities. The voltammetric profiles for the CO stripping on those electrodes show peaks corresponding to the oxidation of CO on the (111) terraces, on the (100) steps/kinks and on the (110) steps/kinks at very distinctive potentials. Additionally, the stripping voltammograms always present a prewave. The analysis of the results with the different stepped and kinked surfaces indicates that the presence of the prewave is not associated with defects or kinks in the electrode surface. Also, the clear separation of the CO stripping process in different peak contributions indicates that the mobility of CO on the surface is very low. Using partial CO stripping experiments and studies at different pH, it has been proposed that the low mobility is a consequence of the negative absolute potential at which the adlayers are formed in alkaline media. Also, the surface diffusion coefficient for CO in these media has been estimated from the dependence of the stripping charge of the peaks with the scan rate of the voltammetry. PMID:21863178

  19. Surface charge and wetting characteristics of layered silicate minerals.

    PubMed

    Yin, Xihui; Gupta, Vishal; Du, Hao; Wang, Xuming; Miller, Jan D

    2012-11-01

    The surface characteristics, including surface charge and wettability, of layered silicates are reviewed based on experimental results and molecular dynamics simulation (MDS) results. The surface charge features of important layered silicates including mica, talc, and kaolinite are described from atomic force microscopy (AFM) measurements, electrophoresis measurements, and/or results from potentiometric titration. In addition, the wetting characteristics of the silica tetrahedral surface which is common to all layered silicates are examined with different experimental techniques and results are discussed. The wettability of trilayer silicates and bilayer silicates is discussed, particularly the wettability of the silica tetrahedral face and alumina octahedral face of kaolinite based on MDS results as well as recent AFM results. PMID:22809732

  20. Adsorbent phosphates

    NASA Technical Reports Server (NTRS)

    Watanabe, S.

    1983-01-01

    An adsorbent which uses as its primary ingredient phosphoric acid salts of zirconium or titanium is presented. Production methods are discussed and several examples are detailed. Measurements of separating characteristics of some gases using the salts are given.

  1. Magnetized graphene layers synthesized on the carbon nanofibers as novel adsorbent for the extraction of polycyclic aromatic hydrocarbons from environmental water samples.

    PubMed

    Rezvani-Eivari, Mostafa; Amiri, Amirhassan; Baghayeri, Mehdi; Ghaemi, Ferial

    2016-09-23

    The application of magnetized graphene (G) layers synthesized on the carbon nanofibers (CNFs) (m-G/CNF) was investigated as novel adsorbent for the magnetic solid-phase extraction (MSPE) of polycyclic aromatic hydrocarbons (PAHs) in water samples followed by gas chromatography-flame ionization detector (GC-FID). Six important parameters, affecting the extraction efficiency of PAHs, including: amount of adsorbent, adsorption and desorption times, type and volume of the eluent solvent and salt content of the sample were evaluated. The optimum extraction conditions were obtained as: 5min for extraction time, 20mg for sorbent amount, dichloromethane as desorption solvent, 1mL for desorption solvent volume, 5min for desorption time and 15% (w/v) for NaCl concentration. Good performance data were obtained at the optimized conditions. The calibration curves were linear over the concentration ranges from 0.012 to 100ngmL(-1) with correlation coefficients (r) between 0.9950 and 0.9967 for all the analytes. The limits of detection (LODs, S/N=3) of the proposed method for the studied PAHs were 0.004-0.03ngmL(-1). The relative standard deviations (RSDs) for five replicates at two concentration levels (0.1 and 50ngmL(-1)) of PAHs were ranged from 3.4 to 5.7%. Appropriate relative recovery values, in the range of 95.5-99.9%, were also obtained for the real water sample analysis. PMID:27578405

  2. Phthalocyaninato complexes with peripheral alkylthio chains: disk-like adsorbate species for the vertical anchoring of ligands on gold surfaces

    PubMed Central

    Siemeling, Ulrich; Schirrmacher, Christian; Glebe, Ulrich; Bruhn, Clemens; Baio, Joe E.; Árnadóttir, Líney; Castner, David G.; Weidner, Tobias

    2011-01-01

    Thin metalorganic films were prepared on gold by self-assembly of thioether-functionalised phthalocyaninato complexes from solution. The phthalocyaninato ligands used contain eight peripheral, β-positioned, alkylthio substituents SR (1a: R = n-C8H17, 1b: R = n-C12H25), which serve as headgroups for surface binding and promote lateral assembly, while the disk-like phthalocyaninato core offers the scope for the attachment of axial ligands to the adsorbed molecules. This process was mimicked by coordination of pyridine (Py) to [Zn(1a)] and [Zn(1b)], respectively. The crystal structures of the products [Zn(1a)(Py)] and [Zn(1b)(Py)] were determined. The crystal structures of 4,5-bis(octylthio)phthalodinitrile and 4,5-bis(dodecylthio)phthalodinitrile were also determined. The films fabricated from [Mn(1a)Cl] and [Mn(1b)Cl] on gold were characterised by XPS, ToF-SIMS and NEXAFS spectroscopy, which revealed the presence of well-defined and homogeneous self-assembled monolayers (SAMs), whose constituents are bound to the substrate by thioether–gold linkages. The orientation of the macrocycles is predominantly parallel to the surface. Strong electronic interaction of the manganese(III) centre with the substrate leads to Cl loss upon adsorption and its reduction to MnII. PMID:21857743

  3. Modification of surfaces and surface layers by non equilibrium processes

    NASA Astrophysics Data System (ADS)

    Beamson, G.; Brennan, W. J.; Clark, D. T.; Howard, J.

    1988-01-01

    Methods for using plasma in the synthesis and modification of materials in ways impossible by conventional routes are introduced. The equipment used in these methods is described. The chemical analysis of polymer surfaces undergoing modification by inert gas, hydrogen or oxygen plasmas is shown to give physical information regarding the relative roles of diffusion of active species and direct and radiative energy transfer from the plasma. Surface modification by plasma depositing a new material onto an existing substrate is discussed with particular reference to the deposition of amorphous carbon films. Applications of the unique properties of these films are outlined together with current understanding of these properties based on chemical and physical methods of analysis of both the films and the plasmas producing them. Finally, surface modification by ion beams is briefly illustrated using examples from the electronics and metals industries.

  4. Vapor layer evolution during drop impact on a heated surface

    NASA Astrophysics Data System (ADS)

    Lee, Sanghyeon; Lee, Sangjun; Lee, Jisan; Fezzaa, Kamel; Je, Jung Ho

    2015-11-01

    When a liquid drop impacts on a sufficiently hot surface above the boiling point, a vapor layer is formed between the drop and the surface, preventing direct contact between them and as a result levitating the drop, known as the Leidenfrost effect. Understanding the evolution of the vapor layer is largely unexplored despite its importance in estimating heat transfer in cooling systems of thermal or nuclear power plants. The side-profile visualization of the vapor layer, as absolutely required for investigating its evolution, has been however unavailable by conventional optical microscopy. In this study, by employing ultrafast X-ray phase contrast imaging, we directly visualize the profiles of the vapor layers during liquid drop impact on a hot surface and elucidate the evolution of the vapor layers during spreading and retraction of the drop as functions of impact height and surface temperature. We reveal that the evolution is governed by the propagation of capillary waves generated in retraction and the wavelength of capillary waves λ is inversely proportional to the impact height h with a relation ~σ/ρh ~We-1 where We is weber number. Capillary waves that converge at the center of the vapor layers are linked to the bouncing behavior of the drop.

  5. Mitigating nutrient leaching with a sub-surface drainage layer of granulated tires.

    PubMed

    Lisi, R D; Park, J K; Stier, J C

    2004-01-01

    Markets for scrap tires have expanded since the early 1990s with the development of value-added applications such as tire-derived fuel and crumb-rubber-amended asphalt. Granulated tires have also displayed the ability to adsorb volatile organic compounds, indicating that the rubber material can be a useful filter media. Sand-based root zones, typically used for golf course putting green and athletic field construction, lack sufficient cation exchange capacity to restrict nitrogen and phosphorus migration through the root zone and into sub-surface drainage systems. Therefore, the adsorptive properties of tire rubber for retaining nitrogen and phosphorus were studied when applied as a distinct sub-surface drainage or intermediate layer in golf course putting greens. A statistically significant reduction in the concentration of nitrate in leachate was achieved by replacing traditional pea gravel with equally sized granulated tires for the drainage layer media, although the mechanism of nitrate mitigation remains unclear. The results indicate that using granulated tires as a drainage layer or fill material beneath sand-based root zones does not compromise the function of the profile or quality of the vegetation while creating an environmentally beneficial and value-added option for scrap tire reuse. PMID:15381235

  6. The structure of N2 adsorbed on the rumpled NaCl(100) surface--a combined LEED and DFT-D study.

    PubMed

    Vogt, Jochen

    2012-11-01

    The structure of N(2) physisorbed on the NaCl(100) single crystal surface is investigated by means of quantitative low-energy electron diffraction (LEED) in combination with dispersion corrected density functional theory (DFT-D). In the temperature range between 20 K and 45 K, a p(1 × 1) structure is observed in the LEED experiment. According to the structure analysis based on the measured diffraction spot intensity profiles, the N(2) molecules are adsorbed over the topmost Na(+) ions. The experimental distance of the lower nitrogen to the Na(+) ion underneath is (2.55 ± 0.07) Å; the corresponding DFT-D value is 2.65 Å. The axes of the molecules are tilted (26 ± 3)° with respect to the surface normal, while in the zero Kelvin optimum structure from DFT-D, the molecules have a perpendicular orientation. The experimental monolayer heat of adsorption, deduced from a Fowler-Guggenheim kinetic model of adsorption is -(13.6 ± 1.6) kJ mol(-1), including a lateral molecule-molecule interaction energy of -(2.0 ± 0.4) kJ mol(-1). The zero Kelvin adsorption energy from DFT-D, including zero point energy correction, is -15.6 kJ mol(-1); the molecule-molecule interaction is -2.4 kJ mol(-1). While the rumpling of the NaCl(100) surface is unchanged upon adsorption of nitrogen, the best-fit root mean square thermal displacements of the ions in the topmost substrate layer are significantly reduced. PMID:23145740

  7. Targeted Mutagenesis and Combinatorial Library Screening Enables Control of Protein Orientation on Surfaces and Increased Activity of Adsorbed Proteins.

    PubMed

    Cruz-Teran, Carlos A; Carlin, Kevin B; Efimenko, Kirill; Genzer, Jan; Rao, Balaji M

    2016-08-30

    While nonspecific adsorption is widely used for immobilizing proteins on solid surfaces, the random nature of protein adsorption may reduce the activity of immobilized proteins due to occlusion of the active site. We hypothesized that the orientation a protein assumes on a given surface can be controlled by systematically introducing mutations into a region distant from its active site, thereby retaining activity of the immobilized protein. To test this hypothesis, we generated a combinatorial protein library by randomizing six targeted residues in a binding protein derived from highly stable, nonimmunoglobulin Sso7d scaffold; mutations were targeted in a region that is distant from the binding site. This library was screened to isolate binders that retain binding to its cognate target (chicken immunoglobulin Y, cIgY) as well as exhibit adsorption on unmodified silica at pH 7.4 and high ionic strength conditions. A single mutant, Sso7d-2B5, was selected for further characterization. Sso7d-2B5 retained binding to cIgY with an apparent dissociation constant similar to that of the parent protein; both mutant and parent proteins saturated the surface of silica with similar densities. Strikingly, however, silica beads coated with Sso7d-2B5 could achieve up to 7-fold higher capture of cIgY than beads coated with the parent protein. These results strongly suggest that mutations introduced in Sso7d-2B5 alter its orientation relative to the parent protein, when adsorbed on silica surfaces. Our approach also provides a generalizable strategy for introducing mutations in proteins so as to improve their activity upon immobilization, and has direct relevance to development of protein-based biosensors and biocatalysts. PMID:27490089

  8. Method for producing functionally graded nanocrystalline layer on metal surface

    DOEpatents

    Ajayi, Oyelayo O.; Hershberger, Jeffrey G.

    2010-03-23

    An improved process for the creation or formation of nanocrystalline layers on substrates' surfaces is provided. The process involves "prescuffing" the surface of a substrate such as a metal by allowing friction to occur on the surface by a load-bearing entity making rubbing contact and moving along and on the substrate's surface. The "prescuffing" action is terminated when the coefficient of friction between the surface and the noise is rising significantly. Often, the significant rise in the coefficient of friction is signaled by a change in pitch of the scuffing action sound emanating from the buffeted surface. The "prescuffing" gives rise to a harder and smoother surface which withstands better any inadequate lubrication that may take place when the "prescuffed" surface is contacted by other surfaces.

  9. Directional dependence of surface morphological stability of heteroepitaxial layers

    NASA Astrophysics Data System (ADS)

    Obayashi, Y.; Shintani, K.

    1998-09-01

    Surface morphological stability in coherent heteroepitaxial layers is analyzed focusing on the directional dependence of surface undulations created by surface diffusion. The critical stability condition is defined in terms of the free energy of the system which is assumed to be the sum of the elastic strain energy and the surface free energy. The displacement and stress fields of the semi-infinite anisotropic solid with the slightly undulating surface are calculated by using the surface admittance tensor and the vector complex potential function. Numerical results for the Si1-xGex/Si systems show that the critical wavelength of the <100> surface undulations is smaller than that of the <110> surface undulations, which means that surface undulations are likely to be formed in the <100> directions. It is also found that the critical wavelength decreases with the increase of Ge fraction. These tendencies are in good agreement with the observations in annealing experiments for the Si1-xGex/Si systems in the literature. If the substrate is assumed to be rigid, the range of layer thickness where the system is absolutely stable against a surface undulation of any wavelength exists. Finally, the growth rate of the amplitude of surface undulations is estimated from an evolution equation for the surface shape. It is shown that even if anisotropy is taken into account, the growth rate of the amplitude takes the maximum value when the wavelength is 4/3 times the critical wavelength, which is the same as in the isotropic approximation.

  10. Surface properties and work function changes induced by atomic oxygen adsorbed on HfC(1 1 1) surface

    NASA Astrophysics Data System (ADS)

    Wang, Jian; Wang, Shao-qing

    2015-12-01

    Hafnium carbide (HfC) is regarded as one of the most promising cathode materials for field emission. But the experimental results did not provide a detail picture of the surface properties. In this work, we perform an ab initio study of the surface energies and work functions for the (1 0 0), (1 1 0), (1 1 1), (2 1 0), (3 1 0) and (3 1 1) surfaces of hafnium carbide. For the polar surface of (1 1 1) and (3 1 1) plane, a new method is taken to calculate the surface energy of the different surface terminations. The results indicate that the Hf termination surface is most stable, which are consistent with the experimental results. Additionally, we focused in particular on oxygen atom induced work function changes on HfC(1 1 1) plane as a function of coverage. An unexpected decrease of the work function is found at low coverage, and a reasonable resolution for this anomaly is given based on the method of Roman et al.

  11. Surface-enhanced Raman spectroscopy study of indolic molecules adsorbed on gold colloids

    NASA Astrophysics Data System (ADS)

    Tu, Qiang; Eisen, Jonathan; Chang, Chang

    2010-03-01

    Serotonin is both a ubiquitous neurotransmitter in the central nervous system and an important immunomodulator involved in various immune responses. The ability to unambiguously detect serotonin is therefore imperative in biomedical research. However, detection of serotonin and related indoles using immunohistochemistry has been largely limited by their small molecular size and the resultant uncertainty in antibody specificity. Here we show that surface-enhanced Raman spectroscopy (SERS) can be used to detect and distinguish serotonin from its various closely related precursors and metabolites. Compared with traditional antibody-based methods, SERS is highly specific and capable of real-time detection. We also quantify the relative concentration of serotonin against a background of other indoles using SERS. We expect this optical detection method to directly benefit a variety of immune and nervous systems studies involving serotonin.

  12. Magnetism of ultrathin wires suspended in free space and adsorbed on vicinal surfaces

    NASA Astrophysics Data System (ADS)

    Spišák, D.; Hafner, J.

    2003-06-01

    On the basis of total-energy calculations within density functional theory the possibility of magnetic ordering in ultrathin, one or two atom wide nanowires is studied. Specifically, we investigate nanowires composed of fifth and sixth row elements, which are nonmagnetic in the solid phase. At first, the unsupported straight wires are discussed and then, similar to experimental conditions, the wires are placed along step ledges of vicinal surfaces of copper and silver. Free-standing wires show only a weak tendency towards magnetic ordering at the equilibrium bond length. In analogy with their 3d homologues Mo, Tc, W, Re are found to order antiferromagnetically, Ru, Rh, and Ir ferromagnetically. Surprisingly, ferromagnetism is also predicted for the early transition metals Zr and Ta and for the simple metals In and Tl. This picture is profoundly modified for supported wires, where the expansion of the bond length enforced through the epitaxial relationship with the substrate favors magnetic ordering but hybridization with the substrate electrons tends to quench magnetism. It turns out that wires on a Cu substrate prefer a ferromagnetic order, whereas on a Ag substrate most elements tend to antiferromagnetism. A second row of atoms added to the wires destroys the magnetism in wires on a Cu substrate, and reduces it in wires on a Ag substrate, except for the late transition metals (Rh, Ir) where an enhancement of magnetic moments is observed. Two possible growth modes of nanowires — a row-by-row growth and island growth — are explored. The results allow us to suggest that Ru, Rh, and Os wires on Ag stepped surfaces are the most promising systems in which magnetism could be verified experimentally.

  13. Atomic and molecular layer deposition for surface modification

    SciTech Connect

    Vähä-Nissi, Mika; Sievänen, Jenni; Salo, Erkki; Heikkilä, Pirjo; Kenttä, Eija; Johansson, Leena-Sisko; Koskinen, Jorma T.; Harlin, Ali

    2014-06-01

    Atomic and molecular layer deposition (ALD and MLD, respectively) techniques are based on repeated cycles of gas–solid surface reactions. A partial monolayer of atoms or molecules is deposited to the surface during a single deposition cycle, enabling tailored film composition in principle down to molecular resolution on ideal surfaces. Typically ALD/MLD has been used for applications where uniform and pinhole free thin film is a necessity even on 3D surfaces. However, thin – even non-uniform – atomic and molecular deposited layers can also be used to tailor the surface characteristics of different non-ideal substrates. For example, print quality of inkjet printing on polymer films and penetration of water into porous nonwovens can be adjusted with low-temperature deposited metal oxide. In addition, adhesion of extrusion coated biopolymer to inorganic oxides can be improved with a hybrid layer based on lactic acid. - Graphical abstract: Print quality of a polylactide film surface modified with atomic layer deposition prior to inkjet printing (360 dpi) with an aqueous ink. Number of printed dots illustrated as a function of 0, 5, 15 and 25 deposition cycles of trimethylaluminum and water. - Highlights: • ALD/MLD can be used to adjust surface characteristics of films and fiber materials. • Hydrophobicity after few deposition cycles of Al{sub 2}O{sub 3} due to e.g. complex formation. • Same effect on cellulosic fabrics observed with low temperature deposited TiO{sub 2}. • Different film growth and oxidation potential with different precursors. • Hybrid layer on inorganic layer can be used to improve adhesion of polymer melt.

  14. Multi-layer surface profiling using gated wavefront sensing

    NASA Astrophysics Data System (ADS)

    Wang, Xin; Nordin, Nur Dalilla; Tik, Eddy Chow Mun; Tan, ChingSeong; Chew, Kuew Wai; Menoni, Carmen

    2015-01-01

    Recently, multi-layer surface profiling and inspection has been considered an emerging topic that can be used to solve various manufacturing inspection problems, such as graded index lenses, TSV (Thru-Silicon Via), and optical coating. In our study, we proposed a gated wavefront sensing approach to estimate the multi-layer surface profile. In this paper, we set up an experimental platform to validate our theoretical models and methods. Our test bed consists of pulse laser, collimator, prism, well-defined focusing lens, testing specimen, and gated wavefront sensing assembly (e.g., lenslet and gated camera). Typical wavefront measurement steps are carried out for the gated system, except the reflectance is timed against its time of flight as well as its intensity profile. By synchronizing the laser pulses to the camera gate time, it is possible to discriminate a multi-layer wavefront from its neighbouring discrete layer reflections.

  15. Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations

    NASA Astrophysics Data System (ADS)

    Meng, Qingyong; Meyer, Hans-Dieter

    2015-10-01

    Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed.

  16. Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations

    SciTech Connect

    Meng, Qingyong; Meyer, Hans-Dieter

    2015-10-28

    Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed.

  17. Photon-exposure-dependent photon-stimulated desorption for obtaining photolysis cross section of molecules adsorbed on surface by monochromatic soft x-ray photons.

    PubMed

    Chou, L-C; Jang, C-Y; Wu, Y-H; Tsai, W-C; Wang, S-K; Chen, J; Chang, S-C; Liu, C-C; Shai, Y; Wen, C-R

    2008-12-01

    Photon-exposure-dependent positive- and negative-ion photon-stimulated desorption (PSD) was proposed to study the photoreactions and obtain the photolysis cross sections of molecules adsorbed on a single-crystal surface by monochromatic soft x-ray photons with energy near the core level of adsorbate. The changes in the F(+) and F(-) PSD ion yields were measured from CF(3)Cl molecules adsorbed on Si(111)-7x7 at 30 K (CF(3)Cl dose=0.3x10(15) molecules/cm(2), approximately 0.75 monolayer) during irradiation of monochromatic soft x-ray photons near the F(1s) edge. The PSD ion yield data show the following characteristics: (a) The dissociation of adsorbed CF(3)Cl molecules is due to a combination of direct photodissociation via excitation of F(1s) core level and substrate-mediated dissociation [dissociative attachment and dipolar dissociation induced by the photoelectrons emitting from the silicon substrate]. (b) the F(+) ion desorption is associated with the bond breaking of the surface CF(3)Cl, CF(2)Cl, CFCl, and SiF species. (c) the F(-) yield is mainly due to DA and DD of the adsorbed CF(3)Cl molecules. (d) The surface SiF is formed by reaction of the surface Si atom with the neutral fluorine atom, F(+), or F(-) ion produced by scission of C-F bond of CF(3)Cl, CF(2)Cl, or CFCl species. A kinetic model was proposed for the explanation of the photolysis of this submonolayer CF(3)Cl-covered surface. Based on this model and the variation rates of the F(+)F(-) signals during fixed-energy monochromatic photon bombardment at 690.2 and 692.6 eV [near the F(1s) edge], the photolysis cross section was deduced as a function of energy. PMID:19063541

  18. Surface stress of graphene layers supported on soft substrate

    PubMed Central

    Du, Feng; Huang, Jianyong; Duan, Huiling; Xiong, Chunyang; Wang, Jianxiang

    2016-01-01

    We obtain the surface stress of a single layer and multilayers of graphene supported on silicone substrates by measuring the deformation of the graphene-covered substrates induced by the surface tension of liquid droplets together with the Neumann’s triangle concept. We find that the surface stress of the graphene-covered substrate is significant larger than that of the bare substrate, and it increases with increasing graphene layers, and finally reaches a constant value of about 120 mN/m on three and more layers of graphene. This work demonstrates that the apparent surface stress of graphene-substrate systems can be tuned by the substrate and the graphene layers. The surface stress and the tuning effect of the substrate on it may have applications in design and characterization of graphene-based ultra-sensitive sensors and other devices. Moreover, the method may also be used to measure the surface stress of other ultrathin films supported on soft substrates. PMID:27166087

  19. Surface stress of graphene layers supported on soft substrate.

    PubMed

    Du, Feng; Huang, Jianyong; Duan, Huiling; Xiong, Chunyang; Wang, Jianxiang

    2016-01-01

    We obtain the surface stress of a single layer and multilayers of graphene supported on silicone substrates by measuring the deformation of the graphene-covered substrates induced by the surface tension of liquid droplets together with the Neumann's triangle concept. We find that the surface stress of the graphene-covered substrate is significant larger than that of the bare substrate, and it increases with increasing graphene layers, and finally reaches a constant value of about 120 mN/m on three and more layers of graphene. This work demonstrates that the apparent surface stress of graphene-substrate systems can be tuned by the substrate and the graphene layers. The surface stress and the tuning effect of the substrate on it may have applications in design and characterization of graphene-based ultra-sensitive sensors and other devices. Moreover, the method may also be used to measure the surface stress of other ultrathin films supported on soft substrates. PMID:27166087

  20. Surface stress of graphene layers supported on soft substrate

    NASA Astrophysics Data System (ADS)

    Du, Feng; Huang, Jianyong; Duan, Huiling; Xiong, Chunyang; Wang, Jianxiang

    2016-05-01

    We obtain the surface stress of a single layer and multilayers of graphene supported on silicone substrates by measuring the deformation of the graphene-covered substrates induced by the surface tension of liquid droplets together with the Neumann’s triangle concept. We find that the surface stress of the graphene-covered substrate is significant larger than that of the bare substrate, and it increases with increasing graphene layers, and finally reaches a constant value of about 120 mN/m on three and more layers of graphene. This work demonstrates that the apparent surface stress of graphene-substrate systems can be tuned by the substrate and the graphene layers. The surface stress and the tuning effect of the substrate on it may have applications in design and characterization of graphene-based ultra-sensitive sensors and other devices. Moreover, the method may also be used to measure the surface stress of other ultrathin films supported on soft substrates.

  1. Atomic layer deposition in nanostructured photovoltaics: tuning optical, electronic and surface properties

    NASA Astrophysics Data System (ADS)

    Palmstrom, Axel F.; Santra, Pralay K.; Bent, Stacey F.

    2015-07-01

    Nanostructured materials offer key advantages for third-generation photovoltaics, such as the ability to achieve high optical absorption together with enhanced charge carrier collection using low cost components. However, the extensive interfacial areas in nanostructured photovoltaic devices can cause high recombination rates and a high density of surface electronic states. In this feature article, we provide a brief review of some nanostructured photovoltaic technologies including dye-sensitized, quantum dot sensitized and colloidal quantum dot solar cells. We then introduce the technique of atomic layer deposition (ALD), which is a vapor phase deposition method using a sequence of self-limiting surface reaction steps to grow thin, uniform and conformal films. We discuss how ALD has established itself as a promising tool for addressing different aspects of nanostructured photovoltaics. Examples include the use of ALD to synthesize absorber materials for both quantum dot and plasmonic solar cells, to grow barrier layers for dye and quantum dot sensitized solar cells, and to infiltrate coatings into colloidal quantum dot solar cell to improve charge carrier mobilities as well as stability. We also provide an example of monolayer surface modification in which adsorbed ligand molecules on quantum dots are used to tune the band structure of colloidal quantum dot solar cells for improved charge collection. Finally, we comment on the present challenges and future outlook of the use of ALD for nanostructured photovoltaics.

  2. The Turbulent Boundary Layer on a Rough Curvilinear Surface

    NASA Technical Reports Server (NTRS)

    Droblenkov, V. F.

    1958-01-01

    A number of semiempirical approximate methods exist for determining the characteristics of the turbulent boundary layer on a curvilinear surface. At present, among these methods, the one proposed by L. G. Loitsianskii is given frequent practical application. This method is sufficiently effective and permits, in the case of wing profiles with technically smooth surfaces, calculating the basic characteristics of the boundary layer and the values of the overall drag with an accuracy which suffices for practical purposes. The idea of making use of the basic integral momentum equation ((d delta(sup xx))/dx) + ((V' delta(sup xx))/V) (2 + H) = (tau(sub 0))/(rho V(exp 2)) proves to be fruitful also for the solution of the problems in the determination of the characteristics of the turbulent boundary layer on a rough surface.

  3. An experimental investigation of turbulent boundary layers along curved surfaces

    NASA Technical Reports Server (NTRS)

    So, R. M. C.; Mellor, G. L.

    1972-01-01

    A curved wall tunnel was designed, and an equilibrium turbulent boundary layer was set up on the straight section preceding the curved test section. Turbulent boundary layer flows with uniform and adverse pressure distributions along convex and concave walls were investigated. Hot-wire measurements along the convex surface indicated that turbulent mixing between fluid layers was very much reduced. However, the law of the wall held and the skin friction, thus determined, correlated well with other measurements. Hot-wire measurements along the concave test wall revealed a system of longitudinal vortices inside the boundary layer and confirmed that concave curvature enhances mixing. A self-consistent set of turbulent boundary layer equations for flows along curved surfaces was derived together with a modified eddy viscosity. Solution of these equations together with the modified eddy viscosity gave results that correlated well with the present data on flows along the convex surface with arbitrary pressure distribution. However, it could only be used to predict the mean characteristics of the flow along concave walls because of the existence of the system of longitudinal vortices inside the boundary layer.

  4. Chemical Potential of Triethylene Glycol Adsorbed on Surfaces Relevant to Gas Transport and Processing - Studies Using Molecular Dynamics Simulations

    NASA Astrophysics Data System (ADS)

    Kvamme, B.; Olsen, R.; Sjöblom, S.; Leirvik, K. N.; Kuznetsova, T.

    2014-12-01

    Natural gas will inevitably contain trace amounts of water and other impurities during different stages of processing and transport. Glycols, such as triethylene glycol (TEG), will in many cases follow the water. The glycol contents of the gas can originate from preceding glycol-drying units or it can be a residue from the direct injection of glycols used to prevent hydrate formation. Thus, it is important to know how glycol contents will affect the different paths leading to hydrate formation. Glycols may in some cases dominate the condensed water phase. If this occurs, it will lead to the well-documented shift in the hydrate stability curve, due to the altered activity of the water. A great deal of information on the molecular path of a glycol through the system can be obtained from calculating the chemical potential. Due to difficulties in measuring interfacial chemical potentials, these often need to be estimated using theoretical tools. We used molecular dynamics (MD) to study how TEG behaves in the vicinity of mineral surfaces such as calcite and hematite. Many methods exist for estimating chemical potentials based on MD trajectories. These include techniques such as free energy perturbation theory (FEP) and thermodynamic integration (TI). Such methods require sufficient sampling of configurations where free energy is to be estimated. Thus, it can be difficult to estimate chemical potentials on surfaces. There are several methods to circumvent this problem, such as blue moon sampling and umbrella sampling. These have been considered and the most important have been used to estimate chemical potentials of TEG adsorbed on the mineral surfaces. The resulting chemical potentials were compared to the chemical potential of TEG in bulk water, which was estimated using temperature thermodynamic integration.

  5. Anomalous thermal denaturing of proteins adsorbed to nanoparticles

    NASA Astrophysics Data System (ADS)

    Teichroeb, J. H.; Forrest, J. A.; Ngai, V.; Jones, L. W.

    2006-09-01

    We have used localized surface plasmon resonance (LSPR) to monitor the structural changes that accompany thermal denaturing of bovine serum albumin (BSA) adsorbed onto gold nanospheres of size 5nm-60nm. The effect of the protein on the LSPR was monitored by visible extinction spectroscopy. The position of the resonance is affected by the conformation of the adsorbed protein layer, and as such can be used as a very sensitive probe of thermal denaturing that is specific to the adsorbed protein. The results are compared to detailed calculations and show that full calculations can lead to significant increases in knowledge where gold nanospheres are used as biosensors. Thermal denaturing on spheres with diameter > 20 nm show strong similarity to bulk calorimetric studies of BSA in solution. BSA adsorbed on nanospheres with d ⩽ 15nm shows a qualitative difference in behavior, suggesting a sensitivity of denaturing characteristics on local surface curvature. This may have important implications for other protein-nanoparticle interactions.

  6. Assessment of surface turbulent fluxes using geostationary satellite surface skin temperatures and a mixed layer planetary boundary layer scheme

    NASA Technical Reports Server (NTRS)

    Diak, George R.; Stewart, Tod R.

    1989-01-01

    A method is presented for evaluating the fluxes of sensible and latent heating at the land surface, using satellite-measured surface temperature changes in a composite surface layer-mixed layer representation of the planetary boundary layer. The basic prognostic model is tested by comparison with synoptic station information at sites where surface evaporation climatology is well known. The remote sensing version of the model, using satellite-measured surface temperature changes, is then used to quantify the sharp spatial gradient in surface heating/evaporation across the central United States. An error analysis indicates that perhaps five levels of evaporation are recognizable by these methods and that the chief cause of error is the interaction of errors in the measurement of surface temperature change with errors in the assigment of surface roughness character. Finally, two new potential methods for remote sensing of the land-surface energy balance are suggested which will relay on space-borne instrumentation planned for the 1990s.

  7. Surface reactions on thin layers of silane coupling agents

    SciTech Connect

    Kurth, D.G.; Bein, T. )

    1993-11-01

    The reactivity of immobilized functional groups in thin layers of (3-aminopropyl)triethoxysilane (APS), (3-mercaptopropyl)trimethoxysilane, (3-bromopropyl)trimethoxysilane, and (8-bromooctyl)trimethoxysilane on oxidized aluminum substrates was studied with reflection-adsorption infrared spectroscopy (RAIR), optical ellipsometry and contact-angle measurements. Mass changes on the surface associated with the surface-confined reactions were measured with the quartz crystal microbalance (QCM). Single layers of (3-aminopropyl)triethoxysilane on oxidized aluminum react with chlorodimethylsilane to give [(-O)[sub 3]Si(CH[sub 2])[sub 3]NH[sub 2][sup +]SiMe[sub 2]H]Cl[sup [minus

  8. The hydrophobic character of nonsulfide mineral surfaces as influenced by double-bond reactions of adsorbed unsaturated collector species

    SciTech Connect

    Miller, J.D.

    1991-07-01

    A unique in-situ sampling technique has been developed which allowed for real-time analysis of surfactant adsorption processes on mineral single crystals. This technique couples FT-IR spectroscopy and internal reflection spectroscopy (FT-IR/IRS) and the mineral single crystal is referred to as a reactive'' internal reflect element (IRE). The single crystal is reactive in the sense that the adsorption occurs directly upon the surface of the IRE, which also serves to transmit IR electromagnetic radiation. The in-situ FT-IR/IRS method was previously demonstrated for the fluorite (CaF{sub 2})/oleate flotation system. Information obtained from this system included adsorption density (from mid- and near-infrared spectra), adsorption state and reactivity of adsorbed collector, and alkyl chain conformational analysis. In the second budget period, similar analyses have been performed for three other mineral systems. These systems are as follows: Insoluble Oxides: sapphire ({alpha}-Al{sub 2}O{sub 3})/sodium dodecylsulfate; Soluble Salts: sylvite (KCl)/n-octylamine; and Semisoluble Salts: calcite (CaCO{sub 3})/sodium oleate and fluorite (CaF{sub 2})/sodium oleate.

  9. Toward quantitative STM: Scanning tunneling microscopy study of structure and dynamics of adsorbates on transition metal surfaces

    SciTech Connect

    Dunphy, J.C.

    1995-05-01

    STM was applied to chemisorbed S layers on Re(000l) and Mo(100) surfaces. As function of coverage on both these surfaces, S orders into several different overlayer structures, which have been studied by dynamic LEED. STM images of all these structures were obtained. Approximate location of S atoms in the structures was determined by inspecting the images, especially the regions containing defects. Results are in agreement with LEED except for the p(2{times}l) overlayer of sulfur on Mo(100). The STM images were compared to calculations made with Electron Scattering Quantum Chemistry (ESQC) theory. Variation of contrast in experimental images is explained as a result of changes in STM tip termination structure. STM image contrast is a result of changes in the interference between different paths for the tunneling electrons. The simplest structure on the Mo(100) surface was used as a model for developing and testing a method of quantitative structure determination with the STM. Experimental STM images acquired under a range of tunneling conditions were compared to theoretical calculations of the images as a function of surface structure to determine the structure which best fit. Results matched within approximately 0.1 Angstroms a LEED structural determination. At lower S coverage, diffusion of S atoms over the Re(0001) surface and the lateral interaction between these atoms were investigated by application of a new image analysis technique. The interaction between the S and a coadsorbed CO layer was also studied, and CO was found to induce compression of the S overlayer. A similar result was found for Au deposited on the sulfur covered Mo(100) surface. The interaction between steps on the Mo surface was found to be influenced by S adsorption and this observation was interpreted with the theory of equilibrium crystal shape. Design of an STM instrument which operates at cryogenic and variable sample temperatures, and its future applications, are described.

  10. Progress in our understanding of structure bonding and reactivity of metal surfaces and adsorbed monolayers at the molecular level: A 25 year perspective

    NASA Astrophysics Data System (ADS)

    Somorjai, G. A.

    1995-12-01

    Over fifty techniques have been developed during the past 25 years that permit molecular level investigation of structure and bonding of the surface monolayer. Among them, low-energy electron diffraction surface crystallography and vibrational spectroscopies using photons and electrons have contributed the lion's share of quantitative experimental data. (Most of these investigations have utilized small area (~1 cm 2) external surfaces, although microporous large internal surface area samples were also scrutinized.) From these studies, the physical picture of the surface which emerges is one of a separate phase with distinct structure, composition, and bonding that is distinguishable from the solid bulk. The new surface phenomena which were discovered include clean surface reconstruction, adsorbate-induced restructuring, ordering and reactivity of surface defects (steps and kinks), cluster-like bonding, the large mobility of adsorbates, and the coadsorption bond. Techniques were also developed that permit in situ molecular level study of surfaces during reactions at high pressures and temperatures with good time resolution (10 -12-10 -3 sec). Molecular surface science has had a great impact in major applications involving surface phenomena-selective adsorption, heterogeneous catalysis, coatings, microelectronics, electrochemistry, and tribology-and spawned new surface technologies. The demands of these applications focus attention on the behavior of the buried interface, both solid-liquid and solid-solid.

  11. Surface chemistry of the atomic layer deposition of metals and group III oxides

    NASA Astrophysics Data System (ADS)

    Goldstein, David Nathan

    low impurities and a good growth rate. The second section of this thesis focuses on two metal ALD systems. One major drawback of metal ALD systems is their inability to nucleate on many oxide surfaces. This greatly limits the applications of metal ALD for interconnects and flexible electrodes. The first emphasis is an on a new palladium ALD system using palladium (II) hexafluoroacetylaceonate (Pd(hfac)2) and formalin. FT-IR studies show that the Pd(hfac)2 dissociatively adsorbs, releasing free hfacH molecules that bind to Lewis acid sites on the alumina. The observed nucleation period of Pd is linked to surface poisoning by hfacH. In a related experiment, I use trimethylaluminum exposures to remove excess hfacH from the surface. Trimethylaluminum is able to ligand exchange an easier to remove methyl group with the surface hfacH, This treatment causes palladium to nucleate much more rapidly and deposit at lower temperatures. Finally, I examine ToRuS, a new precursor solution for Ru ALD. ToRuS, a solution of RuO4 in perfluoroethers, deposits ruthenium faster and at lower temperatures than all other Ru precursors. The mechanism for deposition and role of the perfluoroethers, however, is poorly understood. In the first study, I couple FT-IR spectroscopy with ab-initio calculations to identify the surface species formed when the perfluoroether solvent adsorbs on alumina. These surface species bind strongly to the alumina surface, creating a nonpolar, fluorinated layer. I then use these results to understand how ToRuS deposits Ru films. The fluorinated layer solvates RuO4, stabilizing it near the surface until it can be reduced by H2 gas. FT-IR and XPS analysis shows that the fluorinated layer does not leave carbonaceous impurities on the ruthenium surface or impedes metal deposition.

  12. Evolving surface cusps during strained-layer epitaxy

    SciTech Connect

    Jesson, D.E.; Pennycook, S.J.; Baribeau, J.M.; Houghton, D.C.

    1993-04-01

    We have combined Z-contrast imaging and Ge marker layer experiments to study the evolving surface morphology of Si{sub x}Ge{sub 1-x} alloys grown by molecular beam epitaxy (MBE). Surface cusps are seen to arise as the intersection lines between coherent islands. The potential implications of stress concentrations associated with cusps are considered with a view to strain relaxation in the film via dislocation nucleation.

  13. Surface morphological evolution during annealing of epitaxial Cu(001) layers

    SciTech Connect

    Purswani, J. M.; Gall, D.

    2008-08-15

    Single crystal Cu(001) layers were grown on MgO(001) by ultrahigh vacuum magnetron sputtering at T{sub s}=100 deg. C. Quantitative surface morphological analyses by in situ scanning tunneling microscopy show that the surfaces exhibit self-affine mound structures with a scaling exponent of 0.82{+-}0.03 and a mound radius r{sub c} that increases from 31{+-}8 to 39{+-}6 nm for increasing layer thickness t=24-120 nm. In situ annealing at 200 and 300 deg. C leads to a thermodynamically driven mass transport that minimizes the surface step density, resulting in broader mounds and a smaller root mean square surface roughness {sigma}. This effect is most pronounced for t=24 nm, for which r{sub c} increases from 31{+-}8 to 70{+-}20 nm and {sigma} decreases from 1.3{+-}0.1 to 0.74{+-}0.08 nm, resulting in a decrease in the average surface slope from {chi}=7 deg. to 2 deg. and an increase in the average terrace width w{sub T} by more than a factor of 4. In contrast, w{sub T} increases by only 20% for t=120 nm. This remarkable difference between 'thin' and 'thick' layers is attributed to diverging surface morphological pathways during annealing: The strong smoothening for t=24 nm is due to a competitive coalescence process where some mounds grow laterally at the expense of their smaller neighbors, which die out. In contrast, the initially wider mounds of thicker layers (t=120 nm) combine to form a quasistable surface morphology that exhibits anisotropic mound structures, which limit mass transport and stabilize the surface step density.

  14. The hydrophobic character of nonsulfide mineral surfaces as influenced by double-bond reactions of adsorbed unsaturated collector species. Progress report, 15 December 1992--14 December 1993

    SciTech Connect

    Miller, J.D.

    1993-07-01

    Different collector adsorption phenomena including adsorption density, adsorption state, and conformation have been examined for soluble salt, semi-soluble salt and insoluble oxide mineral systems. In the case of the soluble salt system, the influence of crystal lattice defects on the surface charge of KCl and its flotation response was studied. In the case of semi-soluble salt minerals, the behavior of fatty acid collectors adsorbed at the surfaces of calcite and fluorite was determined by in-situ Fourier transform infrared internal reflection spectroscopy (FT-IR/IRS), multichannel laser Raman spectroscopy (MLRS), and Langmuir-Blodgett (LB) techniques. Finally, changes in the hydrophobic character of the insoluble oxide mineral surfaces of sapphire and quartz were examined with respect to the aggregative nature of the adsorbed collector phase. A number of papers and presentations were prepared from this research and these contributions are listed at the end of this progress report.

  15. Mechanism of formation of humus coatings on mineral surfaces 3. Composition of adsorbed organic acids from compost leachate on alumina by solid-state 13C NMR

    USGS Publications Warehouse

    Wershaw, R. L.; Llaguno, E.C.; Leenheer, J.A.

    1996-01-01

    The adsorption of compost leachate DOC on alumina is used as a model for elucidation of the mechanism of formation of natural organic coatings on hydrous metal oxide surfaces in soils and sediments. Compost leachate DOC is composed mainly of organic acid molecules. The solid-state 13C NMR spectra of these organic acids indicate that they are very similar in composition to aquatic humic substances. Changes in the solid-state 13C NMR spectra of compost leachate DOC fractions adsorbed on alumina indicate that the DOC molecules are most likely adsorbed on metal oxide surfaces through a combination of polar and hydrophobic interaction mechanisms. This combination of polar and hydrophobic mechanism leads to the formation of bilayer coatings of the leachate molecules on the oxide surfaces.

  16. Optical luminescence studies of diffusion times at the potassium ethyl xanthate adsorption layer on the surface of sphalerite minerals

    NASA Astrophysics Data System (ADS)

    Todoran, R.; Todoran, D.; Anitas, E. M.; Szakács, Zs

    2016-08-01

    We propose reflectance measurements as a method for the evaluation of the kinetics of adsorption processes, to compute the diffusion times of the adsorption products at the thin layers formed at the sphalerite natural mineral-potassium ethyl xanthate solution interface. The method is based on the intensity measurement of the reflected monochromatic radiation obtained from the mineral-xanthate thin layer as a function of time. These determinations were made at the thin layer formed between the sphalerite or activated sphalerite natural minerals with potassium ethyl xanthate, for different solutions concentrations and pH values at constant temperature. Diffusion times of desorbed molecular species into the liquid bring important information about the global kinetics of the ions in this phase during adsorption processes at interfaces. Analysing the time dependence of this parameter one concluded on the diffusion properties of the xanthate molecule in the solution depending on its concentration and pH, knowing that at the initial time these molecules had a uniform spread. This method enabled us to determine that, in time interval of approximately 35 minutes to achieve dynamic equilibrium in the formation of the interface layer, one had three different kinetic behaviours of our systems. In the first 5-8 min one had highly adsorbent character, the state of equilibrium is followed by low adsorbent properties. Gaining information on the adsorption kinetics in the case of xanthate on mineral surface leads to the optimization of the industrial froth flotation process.

  17. Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer

    DOE PAGESBeta

    Dell'Angela, M.; Anniyev, T.; Beye, M.; Coffee, R.; Föhlisch, A.; Gladh, J.; Kaya, S.; Katayama, T.; Krupin, O.; Nilsson, A.; et al

    2015-03-01

    Vacuum space charge-induced kinetic energy shifts of O 1s and Ru 3d core levels in femtosecond soft X-ray photoemission spectra (PES) have been studied at a free electron laser (FEL) for an oxygen layer on Ru(0001). We fully reproduced the measurements by simulating the in-vacuum expansion of the photoelectrons and demonstrate the space charge contribution of the high-order harmonics in the FEL beam. Employing the same analysis for 400 nm pump-X-ray probe PES, we can disentangle the delay dependent Ru 3d energy shifts into effects induced by space charge and by lattice heating from the femtosecond pump pulse.

  18. Synthesis, Development, and Testing of High-Surface-Area Polymer-Based Adsorbents for the Selective Recovery of Uranium from Seawater

    DOE PAGESBeta

    Oyola, Yatsandra; Janke, Christopher J.; Dai, Sheng

    2016-02-29

    The ocean contains uranium with an approximate concentration of 3.34 ppb, which can serve as an incredible supply source to sustain nuclear energy in the United States. Unfortunately, technology currently available to recover uranium from seawater is not efficient enough and mining uranium on land is still more economical. For this study, we have developed polymer-based adsorbents with high uranium adsorption capacities by grafting amidoxime onto high-surface-area polyethylene (PE) fibers. Various process conditions have been screened, in combination with developing a rapid testing protocol (<24 h), to optimize the process. These adsorbents are synthesized through radiation-induced grafting of acrylonitrile (AN)more » and methacrylic acid (MAA) onto PE fibers, followed by the conversion of nitriles to amidoximes and basic conditioning. In addition, the uranium adsorption capacity, measured in units of gU/kgads, is greatly increased by reducing the diameter of the PE fiber or changing its morphology. An increase in the surface area of the PE polymer fiber allows for more grafting sites that are positioned in more-accessible locations, thereby increasing access to grafted molecules that would normally be located in the interior of a fiber with a larger diameter. Polymer fibers with hollow morphologies are able to adsorb beyond 1 order of magnitude more uranium from simulated seawater than current commercially available adsorbents. Finally, several high-surface-area fibers were tested in natural seawater and were able to extract 5–7 times more uranium than any adsorbent reported to date.« less

  19. Entropy-Driven Conformational Control of α,ω-Difunctional Bidentate-Dithiol Azo-Based Adsorbates Enables the Fabrication of Thermally Stable Surface-Grafted Polymer Films.

    PubMed

    Lee, Han Ju; Jamison, Andrew C; Lee, T Randall

    2016-06-22

    Thermally stable radical initiator monolayers were prepared from uniquely designed α,ω-difunctional adsorbates with bidentate headgroups for the growth of nanoscale polymer films on metal surfaces. The length of the spacer separating the bidentate headgroups was varied to afford 4,4'-(diazene-1,2-diyl)bis(N-(16-(3,5-bis(mercaptomethyl)phenoxy)hexadecyl)-4-cyanopentanamide) (B16), 4,4'-(diazene-1,2-diyl)bis(N-(16-(3,5-bis(mercapto-methyl)phenoxy)decyl)-4-cyanopentanamide) (B10), and 4,4'-(diazene-1,2-diyl)bis(N-(4-(3,5-bis(mercaptomethyl)phenoxy)butyl)-4-cyanopentanamide) (B4). The structural features of the self-assembled monolayers (SAMs) derived from B16, B10, and B4 were characterized by X-ray photoelectron spectroscopy (XPS), ellipsometry, and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and compared to those derived from an analogous α,ω-difunctional adsorbate with monodentate headgroups, 4,4'-(diazene-1,2-diyl)bis(4-cyano-N-(16-mercaptohexadecyl)pentanamide (M). These studies demonstrate that the conformation (i.e., hairpin vs standing up) of the bidentate initiator adsorbates on gold surfaces was easily controlled by adjusting the concentration of the adsorbates in solution. The results of solution-phase thermal desorption tests revealed that the radical initiator monolayers generated from B16, B10, and B4 exhibit an enhanced thermal stability when compared to those generated from M. Furthermore, a study of the growth of polymer films was performed to evaluate the utility of these new bidentate adsorbate SAMs as film-development platforms for new functional materials and devices. Specifically, surface-grafted polystyrene films were successfully generated from SAMs derived from B16. In contrast, attempts to grow polystyrene films from SAMs derived from M under a variety of analogous conditions were unsuccessful. PMID:27219525

  20. A scheme for computing surface layer turbulent fluxes from mean flow surface observations

    NASA Technical Reports Server (NTRS)

    Hoffert, M. I.; Storch, J.

    1978-01-01

    A physical model and computational scheme are developed for generating turbulent surface stress, sensible heat flux and humidity flux from mean velocity, temperature and humidity at some fixed height in the atmospheric surface layer, where conditions at this reference level are presumed known from observations or the evolving state of a numerical atmospheric circulation model. The method is based on coupling the Monin-Obukov surface layer similarity profiles which include buoyant stability effects on mean velocity, temperature and humidity to a force-restore formulation for the evolution of surface soil temperature to yield the local values of shear stress, heat flux and surface temperature. A self-contained formulation is presented including parameterizations for solar and infrared radiant fluxes at the surface. Additional parameters needed to implement the scheme are the thermal heat capacity of the soil per unit surface area, surface aerodynamic roughness, latitude, solar declination, surface albedo, surface emissivity and atmospheric transmissivity to solar radiation.

  1. SERS and in situ SERS spectroscopy of riboflavin adsorbed on silver, gold and copper substrates. Elucidation of variability of surface orientation based on both experimental and theoretical approach

    NASA Astrophysics Data System (ADS)

    Dendisová-Vyškovská, Marcela; Kokaislová, Alžběta; Ončák, Milan; Matějka, Pavel

    2013-04-01

    Surface-enhanced Raman scattering and in situ surface-enhanced Raman scattering spectra have been collected to study influences of (i) used metal and (ii) applied electrode potential on orientation of adsorbed riboflavin molecules. Special in situ SERS spectroelectrochemical cell was used to obtain in situ SERS spectra of riboflavin adsorbed on silver, gold and copper nanostructured surfaces. Varying electrode potential was applied in discrete steps forming a cycle from positive values to negative and backward. Observed spectral features in in situ SERS spectra, measured at alternate potentials, have been changing very significantly and the spectra have been compared with SERS spectra of riboflavin measured ex situ. Raman spectra of single riboflavin molecule in the vicinity to metal (Ag, Au and Cu) clusters have been calculated for different mutual positions. The results demonstrate significant changes of bands intensities which can be correlated with experimental spectra measured at different potentials. Thus, the orientation of riboflavin molecules adsorbed on metal surfaces can be elucidated. It is influenced definitely by the value of applied potential. Furthermore, the riboflavin adsorption orientation on the surface depends on the used metal. Adsorption geometries on the copper substrates are more diverse in comparison with the orientations on silver and gold substrates.

  2. Laminarization of Turbulent Boundary Layer on Flexible and Rigid Surfaces

    NASA Technical Reports Server (NTRS)

    Maestrello, Lucio

    2001-01-01

    An investigation of the control of turbulent boundary layer flow over flexible and rigid surfaces downstream of a concave-convex geometry has been made. The concave-convex curvature induces centrifugal forces and a pressure gradient on the growth of the turbulent boundary layer. The favorable gradient is not sufficient to overcome the unfavorable; thus, the net effect is a destabilizing, of the flow into Gortler instabilities. This study shows that control of the turbulent boundary layer and structural loading can be successfully achieved by using localized surface heating because the subsequent cooling and geometrical shaping downstream over a favorable pressure gradient is effective in laminarization of the turbulence. Wires embedded in a thermally insulated substrate provide surface heating. The laminarized velocity profile adjusts to a lower Reynolds number, and the structure responds to a lower loading. In the laminarization, the turbulent energy is dissipated by molecular transport by both viscous and conductivity mechanisms. Laminarization reduces spanwise vorticity because of the longitudinal cooling gradient of the sublayer profile. The results demonstrate that the curvature-induced mean pressure gradient enhances the receptivity of the flow to localized surface heating, a potentially viable mechanism to laminarize turbulent boundary layer flow; thus, the flow reduces the response of the flexible structure and the resultant sound radiation.

  3. Surface modification of layered zirconium phosphate with PNIPAM.

    PubMed

    Wang, Xuezhen; Zhao, Di; Medina, Ilse B Nava; Diaz, Agustin; Wang, Huiliang; Clearfield, Abraham; Mannan, M Sam; Cheng, Zhengdong

    2016-04-01

    A new method was reported to modify layered zirconium phosphate (ZrP) with thermoresponsive polymer PNIPAM (poly N-isopropylacrylamide). PNIPAM was proved to be covalently grafted onto ZrP. (60)Co γ-rays irradiation produced peroxide groups on the surface which, upon heating, initiated free radical polymerization and subsequent attachment of PNIPAM. PMID:26966882

  4. NMR of thin layers using a meanderline surface coil

    DOEpatents

    Cowgill, Donald F.

    2001-01-01

    A miniature meanderline sensor coil which extends the capabilities of nuclear magnetic resonance (NMR) to provide analysis of thin planar samples and surface layer geometries. The sensor coil allows standard NMR techniques to be used to examine thin planar (or curved) layers, extending NMRs utility to many problems of modern interest. This technique can be used to examine contact layers, non-destructively depth profile into films, or image multiple layers in a 3-dimensional sense. It lends itself to high resolution NMR techniques of magic angle spinning and thus can be used to examine the bonding and electronic structure in layered materials or to observe the chemistry associated with aging coatings. Coupling this sensor coil technology with an arrangement of small magnets will produce a penetrator probe for remote in-situ chemical analysis of groundwater or contaminant sediments. Alternatively, the sensor coil can be further miniaturized to provide sub-micron depth resolution within thin films or to orthoscopically examine living tissue. This thin-layer NMR technique using a stationary meanderline coil in a series-resonant circuit has been demonstrated and it has been determined that the flat meanderline geometry has about he same detection sensitivity as a solenoidal coil, but is specifically tailored to examine planar material layers, while avoiding signals from the bulk.

  5. Mercurian megaregolith layer and surface heat flows constraints

    NASA Astrophysics Data System (ADS)

    Egea-Gonzalez, Isabel; Ruiz, Javier

    2013-04-01

    Mercury is covered by a thermally insulating megaregolith layer. Despite the fact that it is known that this poor conducting layer has important influences on surface heat flows, most thermal modeling studies have overlooked it. Mercurian megaregolith is not very well known, but data provided by MESSENGER suggest that mercurian megaregolith is less insulating than its lunar counterpart. This information together with brittle-ductile transition (BDT) depths, estimated from the analysis of fault geometries associated with lobate scarps, allow us to constrain the surface heat flow on Mercury at the time of scarps formation. In this work, we have solved the heat conduction equation in order to constrain surface heat flows. Firstly, we obtain an upper limit in surface heat flows by using published values of the BDT depth and by neglecting the megaregolith layer. Then, we calculate a lower limit by including in the heat equation a top layer with thermal properties representative of the lunar megaregolith. In our calculations we have taken into account volumetric heat production rates obtained from the surface abundances of radioactive elements provided by MESSENGER. Heat equation solutions constrain surface heat flows to a range of 6 - 29 mWm-2. These results suggest the possibility that surface heat flows could be lower than those calculated in previous works, which is in agreement with the small amount of radial contraction detected on Mercury. Furthermore, the procedure followed in this article can be easily applied to other planets and satellites, which will improve our knowledge about the thermal evolution of these bodies.

  6. Hierarchy of adhesion forces in patterns of photoreactive surface layers

    NASA Astrophysics Data System (ADS)

    Hlawacek, Gregor; Shen, Quan; Teichert, Christian; Lex, Alexandra; Trimmel, Gregor; Kern, Wolfgang

    2009-01-01

    Precise control of surface properties including electrical characteristics, wettability, and friction is a prerequisite for manufacturing modern organic electronic devices. The successful combination of bottom up approaches for aligning and orienting the molecules and top down techniques to structure the substrate on the nano- and micrometer scale allows the cost efficient fabrication and integration of future organic light emitting diodes and organic thin film transistors. One possibility for the top down patterning of a surface is to utilize different surface free energies or wetting properties of a functional group. Here, we used friction force microscopy (FFM) to reveal chemical patterns inscribed by a photolithographic process into a photosensitive surface layer. FFM allowed the simultaneous visualization of at least three different chemical surface terminations. The underlying mechanism is related to changes in the chemical interaction between probe and film surface.

  7. Enhancing the mechanical and biological performance of a metallic biomaterial for orthopedic applications through changes in the surface oxide layer by nanocrystalline surface modification

    NASA Astrophysics Data System (ADS)

    Bahl, Sumit; Shreyas, P.; Trishul, M. A.; Suwas, Satyam; Chatterjee, Kaushik

    2015-04-01

    Nanostructured metals are a promising class of biomaterials for application in orthopedics to improve the mechanical performance and biological response for increasing the life of biomedical implants. Surface mechanical attrition treatment (SMAT) is an efficient way of engineering nanocrystalline surfaces on metal substrates. In this work, 316L stainless steel (SS), a widely used orthopedic biomaterial, was subjected to SMAT to generate a nanocrystalline surface. Surface nanocrystallization modified the nature of the oxide layer present on the surface. It increased the corrosion-fatigue strength in saline by 50%. This increase in strength is attributed to a thicker oxide layer, residual compressive stresses, high strength of the surface layer, and lower propensity for intergranular corrosion in the nanocrystalline layer. Nanocrystallization also enhanced osteoblast attachment and proliferation. Intriguingly, wettability and surface roughness, the key parameters widely acknowledged for controlling the cellular response remained unchanged after nanocrystallization. The observed cellular behavior is explained in terms of the changes in electronic properties of the semiconducting passive oxide film present on the surface of 316L SS. Nanocrystallization increased the charge carrier density of the n-type oxide film likely preventing denaturation of the adsorbed cell-adhesive proteins such as fibronectin. In addition, a net positive charge developed on the otherwise neutral oxide layer, which is known to facilitate cellular adhesion. The role of changes in the electronic properties of the oxide films on metal substrates is thus highlighted in this work. This study demonstrates the advantages of nanocrystalline surface modification by SMAT for processing metallic biomaterials used in orthopedic implants.

  8. Enhancing the mechanical and biological performance of a metallic biomaterial for orthopedic applications through changes in the surface oxide layer by nanocrystalline surface modification.

    PubMed

    Bahl, Sumit; Shreyas, P; Trishul, M A; Suwas, Satyam; Chatterjee, Kaushik

    2015-05-01

    Nanostructured metals are a promising class of biomaterials for application in orthopedics to improve the mechanical performance and biological response for increasing the life of biomedical implants. Surface mechanical attrition treatment (SMAT) is an efficient way of engineering nanocrystalline surfaces on metal substrates. In this work, 316L stainless steel (SS), a widely used orthopedic biomaterial, was subjected to SMAT to generate a nanocrystalline surface. Surface nanocrystallization modified the nature of the oxide layer present on the surface. It increased the corrosion-fatigue strength in saline by 50%. This increase in strength is attributed to a thicker oxide layer, residual compressive stresses, high strength of the surface layer, and lower propensity for intergranular corrosion in the nanocrystalline layer. Nanocrystallization also enhanced osteoblast attachment and proliferation. Intriguingly, wettability and surface roughness, the key parameters widely acknowledged for controlling the cellular response remained unchanged after nanocrystallization. The observed cellular behavior is explained in terms of the changes in electronic properties of the semiconducting passive oxide film present on the surface of 316L SS. Nanocrystallization increased the charge carrier density of the n-type oxide film likely preventing denaturation of the adsorbed cell-adhesive proteins such as fibronectin. In addition, a net positive charge developed on the otherwise neutral oxide layer, which is known to facilitate cellular adhesion. The role of changes in the electronic properties of the oxide films on metal substrates is thus highlighted in this work. This study demonstrates the advantages of nanocrystalline surface modification by SMAT for processing metallic biomaterials used in orthopedic implants. PMID:25833718

  9. Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer

    PubMed Central

    Dell'Angela, M.; Anniyev, T.; Beye, M.; Coffee, R.; Föhlisch, A.; Gladh, J.; Kaya, S.; Katayama, T.; Krupin, O.; Nilsson, A.; Nordlund, D.; Schlotter, W. F.; Sellberg, J. A.; Sorgenfrei, F.; Turner, J. J.; Öström, H.; Ogasawara, H.; Wolf, M.; Wurth, W.

    2015-01-01

    Vacuum space charge induced kinetic energy shifts of O 1s and Ru 3d core levels in femtosecond soft X-ray photoemission spectra (PES) have been studied at a free electron laser (FEL) for an oxygen layer on Ru(0001). We fully reproduced the measurements by simulating the in-vacuum expansion of the photoelectrons and demonstrate the space charge contribution of the high-order harmonics in the FEL beam. Employing the same analysis for 400 nm pump-X-ray probe PES, we can disentangle the delay dependent Ru 3d energy shifts into effects induced by space charge and by lattice heating from the femtosecond pump pulse. PMID:26798795

  10. Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer.

    PubMed

    Dell'Angela, M; Anniyev, T; Beye, M; Coffee, R; Föhlisch, A; Gladh, J; Kaya, S; Katayama, T; Krupin, O; Nilsson, A; Nordlund, D; Schlotter, W F; Sellberg, J A; Sorgenfrei, F; Turner, J J; Öström, H; Ogasawara, H; Wolf, M; Wurth, W

    2015-03-01

    Vacuum space charge induced kinetic energy shifts of O 1s and Ru 3d core levels in femtosecond soft X-ray photoemission spectra (PES) have been studied at a free electron laser (FEL) for an oxygen layer on Ru(0001). We fully reproduced the measurements by simulating the in-vacuum expansion of the photoelectrons and demonstrate the space charge contribution of the high-order harmonics in the FEL beam. Employing the same analysis for 400 nm pump-X-ray probe PES, we can disentangle the delay dependent Ru 3d energy shifts into effects induced by space charge and by lattice heating from the femtosecond pump pulse. PMID:26798795

  11. Effects of mesoscale surface inhomogeneities on atmospheric boundary layer transfer

    SciTech Connect

    Shaw, W.J.; Doran, J.C.; Hubbe, J.M.

    1992-09-01

    Defining the nature of turbulent transfer over horizontally inhomogeneous surfaces remains one of the challenges in meteorology. Because the transfer of energy and momentum through the atmospheric boundary layer forms part of the lower boundary condition for global climate models (GCMs), the problem is important. Over the last two decades, advances in sensor and computer technology wave made good point measurements of turbulent fluxes fairly routine. A fundamental question with respect to climate models, however, is how such point measurements are related to average fluxes over the area of a GCM grid box. In this paper we will use data from the field program to depict the evolution of the boundary layer over adjacent, sharply contrasting surface types on two separate occasions. We will then use simple scaling based on the observations to argue that sub-gridscale motions would often be likely to significantly alter the estimates and resulting parameterizations of GCM-scale surface fluxes in the region.

  12. Nucleation and Early Stages of Layer-by-Layer Growth of Metal Organic Frameworks on Surfaces

    PubMed Central

    2015-01-01

    High resolution atomic force microscopy (AFM) is used to resolve the evolution of crystallites of a metal organic framework (HKUST-1) grown on Au(111) using a liquid-phase layer-by-layer methodology. The nucleation and faceting of individual crystallites is followed by repeatedly imaging the same submicron region after each cycle of growth and we find that the growing surface is terminated by {111} facets leading to the formation of pyramidal nanostructures for [100] oriented crystallites, and triangular [111] islands with typical lateral dimensions of tens of nanometres. AFM images reveal that crystallites can grow by 5–10 layers in each cycle. The growth rate depends on crystallographic orientation and the morphology of the gold substrate, and we demonstrate that under these conditions the growth is nanocrystalline with a morphology determined by the minimum energy surface. PMID:26709359

  13. Ultrastructure of the Bacteroides nodosus cell envelope layers and surface.

    PubMed Central

    Every, D; Skerman, T M

    1980-01-01

    The surface structure and cell envelope layers of various virulent Bacteroides nodosus strains were examined by light microscopy and by electron microscopy by using negative staining, thin-section, and freeze-fracture-etch techniques. Three surface structures were described: pili and a diffuse material, both of which emerged from one or both poles of the bacteria (depending on the stage of growth and division), and large rodlike structures (usually 30 to 40 nm in diameter) associated with a small proportion of the bacterial population. No capsule was detected. The cell envelope consisted of four layers: a plasma membrane, a peptidoglycan layer, an outer membrane, and an outermost additional layer. The additional layer was composed of subunits, generally hexagonally packed with center-to-center spacing of 6 to 7 nm. The outer membrane and plasma membrane freeze-fractured through their hydrophobic regions revealing four fracture faces with features similar to those of other gram-negative bacteria. However, some unusual features were seen on the fracture faces of the outer membrane: large raised ring structure (11 to 12 nm in diameter) on cw 3 at the poles of the bacteria; complementary pits or ring-shaped depressions on cw 2; and small raised ring structures (7 to 8 nm in diameter) all over cw 2. Images PMID:6154040

  14. Friedel oscillations at the surfaces of rhombohedral N -layer graphene

    NASA Astrophysics Data System (ADS)

    Dutreix, C.; Katsnelson, M. I.

    2016-01-01

    The low-energy physics of rhombohedral N -layer graphene mainly arises on the external layers, where most of the π electrons are located. Their Bloch band structure defines a two-band semimetal; the dispersion relation scales as ±qN with the momentum norm q in the vicinity of two nonequivalent valleys. In this paper, we address the problem of elastic scattering through a localized impurity located either on the surface of the material or within the bulk, and focus on the quantum interferences it induces on the two external layers. It is apprehended in the framework of a T -matrix approach, both numerically and analytically, regardless of the impurity magnitude, which enables the description of realistic scatters. In rhombohedral multilayer graphene, the impurity induces Friedel oscillations that always decay as 1 /r . As a result, monolayer graphene is the only material of the rhombohedral class that exhibits 1 /r2 -decaying Friedel oscillations. The interference patterns are subsequently analyzed in momentum space. This analysis enables a clear distinction between monolayer graphene and multilayer graphene. It also shows that the interference pattern reveals the whole Bloch band structure, and highlights the number of layers stacked in the material, as well as the π -quantized Berry phases that characterize the existence of nodal points in the semimetallic spectrum. Experimentally, these features may be probed from scanning tunneling microscopy, when imaging the local density of states at the surfaces of suspended rhombohedral N -layer graphene.

  15. The Role of Surface Layer Processes in Solid Propellant Combustion.

    NASA Astrophysics Data System (ADS)

    Chakravarthy, Satyanarayanan R.

    The qualitative multidimensional theory of composite solid propellant combustion based on the sandwich burning methodology was applied to certain specific problems: (a) burning rate enhancement by ferric oxide, (b) plateau burning behavior caused by binder melt flow effects, and (c) characterization of the combustion of new energetic oxidizers--ADN and HNIW. Exothermic reactions at the interfacial contact lines between AP particles and the binder in the surface layer of the burning propellant assume significance in the presence of ferric oxide, and control the burning rate. Binder melt flow covers adjacent AP particle surfaces increasingly at higher pressures, and disperses the O/F leading edge flames attached to coarse particles. It also causes fine AP/binder matrix areas on the surface not to support a steady premixed flame at intermediate pressures, resulting in an overall decrease in the burning rate with increasing pressure, which implies plateau or mesa effects. ADN self -deflagration rate is significantly higher than that of AP, and controls the sandwich burning rate to a great extent. The O/F flame of ADN and binder still behaves as rate limiting, although strongly supported by ADN self-deflagration. ADN melts and vaporizes substantially before the binder, allowing for the possibility of complex physical processes in the surface layer. The strong exothermic decomposition of HNIW at moderate temperatures causes the oxidizer particles in the surface layer to be the sites of burning rate control. The problems addressed in this study combinedly point to the significance of crucial surface layer processes under the situations of interest, and signal a need to characterize such processes directly and in greater detail.

  16. Oxygen inhibition layer of composite resins: effects of layer thickness and surface layer treatment on the interlayer bond strength.

    PubMed

    Bijelic-Donova, Jasmina; Garoushi, Sufyan; Lassila, Lippo V J; Vallittu, Pekka K

    2015-02-01

    An oxygen inhibition layer develops on surfaces exposed to air during polymerization of particulate filling composite. This study assessed the thickness of the oxygen inhibition layer of short-fiber-reinforced composite in comparison with conventional particulate filling composites. The effect of an oxygen inhibition layer on the shear bond strength of incrementally placed particulate filling composite layers was also evaluated. Four different restorative composites were selected: everX Posterior (a short-fiber-reinforced composite), Z250, SupremeXT, and Silorane. All composites were evaluated regarding the thickness of the oxygen inhibition layer and for shear bond strength. An equal amount of each composite was polymerized in air between two glass plates and the thickness of the oxygen inhibition layer was measured using a stereomicroscope. Cylindrical-shaped specimens were prepared for measurement of shear bond strength by placing incrementally two layers of the same composite material. Before applying the second composite layer, the first increment's bonding site was treated as follows: grinding with 1,000-grit silicon-carbide (SiC) abrasive paper, or treatment with ethanol or with water-spray. The inhibition depth was lowest (11.6 μm) for water-sprayed Silorane and greatest (22.9 μm) for the water-sprayed short-fiber-reinforced composite. The shear bond strength ranged from 5.8 MPa (ground Silorane) to 36.4 MPa (water-sprayed SupremeXT). The presence of an oxygen inhibition layer enhanced the interlayer shear bond strength of all investigated materials, but its absence resulted in cohesive and mixed failures only with the short-fiber-reinforced composite. Thus, more durable adhesion with short-fiber-reinforced composite is expected. PMID:25556290

  17. Plasma behavior in the boundary layer near a railgun surface

    SciTech Connect

    Kang, S.W.; McCallen, R. )

    1989-01-01

    Viscous flow and thermal characteristics are theoretically analyzed for the plasma behind a moving projectile inside a railgun. When only convective effects are included in the turbulent boundary layer analysis, the results suggest a temperature maximum in the wall region for very high velocity flows. The case of radiative as well as convective transport has also been investigated for an optically thick boundary layer flow by application of an approximate method. Results show a sizable effect of radiation on the flow characteristics, especially on the heat transfer rate to the railgun surface.

  18. Plasma behavior in the boundary layer near a railgun surface

    SciTech Connect

    Kang, Sang-Wook; McCallen, R.E.

    1988-03-01

    Viscous flow and thermal characteristics are theoretically analyzed for the plasma behind a moving projectile inside a railgun. When only convective effects are included in the turbulent boundary layer analysis, the results suggest a temperature maximum in the wall region for very high velocity flows. The case of radiative as well as convective transport has also been investigated for an optically-thick boundary layer flow by application of an approximate method. Results show a sizable effect of radiation on the flow characteristics, especially on the heat-transfer rate to the railgun surface. 7 refs., 2 figs.

  19. Photodegradation of Stearic Acid Adsorbed on Superhydrophilic TiO2 Surface: In Situ FT-IR and LDI Study.

    PubMed

    Smirnova, Natalia; Fesenko, Tatiana; Zhukovsky, Maxim; Goworek, Jacek; Eremenko, Anna

    2015-12-01

    TiO2 films prepared by template-assisted sol-gel method were characterized by X-ray diffraction spectroscopy, scanning and atomic force electron microscopy, and Fourier transform infrared (FT-IR) spectroscopy. Based on the hexane adsorption-desorption analysis, the films have a surface area of 390-540 m(2)/g with pore size distribution narrowly centered around 10 nm. Optimal component ratio and condition of heat treatment of mesoporous titania films have been found. Photocatalytic activity of the coatings was determined by the destruction of stearic acid layers, monitored using FT-IR spectroscopy and laser desorption-ionization (LDI) mass spectrometry. Under UV illumination, all the used films reach hydrophilicity with water contact angle of 0°. As the result, hydrophobic fat acid molecules undergo self-association and active desorption from the hydrophilic surface during mass-spectrometric experiment. PMID:26714862

  20. Photodegradation of Stearic Acid Adsorbed on Superhydrophilic TiO2 Surface: In Situ FT-IR and LDI Study

    NASA Astrophysics Data System (ADS)

    Smirnova, Natalia; Fesenko, Tatiana; Zhukovsky, Maxim; Goworek, Jacek; Eremenko, Anna

    2015-12-01

    TiO2 films prepared by template-assisted sol-gel method were characterized by X-ray diffraction spectroscopy, scanning and atomic force electron microscopy, and Fourier transform infrared (FT-IR) spectroscopy. Based on the hexane adsorption-desorption analysis, the films have a surface area of 390-540 m2/g with pore size distribution narrowly centered around 10 nm. Optimal component ratio and condition of heat treatment of mesoporous titania films have been found. Photocatalytic activity of the coatings was determined by the destruction of stearic acid layers, monitored using FT-IR spectroscopy and laser desorption-ionization (LDI) mass spectrometry. Under UV illumination, all the used films reach hydrophilicity with water contact angle of 0°. As the result, hydrophobic fat acid molecules undergo self-association and active desorption from the hydrophilic surface during mass-spectrometric experiment.

  1. Modification of Surface Layers by Surfacing Intermetallic Coatings with Variable Properties

    NASA Astrophysics Data System (ADS)

    Makeev, D. N.; Zakharov, O. V.; Vinogradov, A. N.; Kochetkov, A. V.

    2016-02-01

    The paper considers the possibility of forming coating layers for parts within wide limits of microhardness. The technology uses surfacing of intermetallic coatings provided by a unique experimental setup. Theoretical and experimental dependence of the coating layer microhardness on the filler concentration using the changes in the speed of the filler wire feed and current intensity were determined.

  2. Infrared spectroscopy of adsorbed CO2 as a probe for the surface heterogeneity of diamond C(111)-1 × 1:H

    NASA Astrophysics Data System (ADS)

    Chang, H.-C.; Lin, J.-C.

    1995-10-01

    Infrared polarization spectroscopy of the stretching motion of physisorbed CO2 has been used as a probe for the heterogeneity of hydrogen-terminated diamond single crystal surfaces. At the substrate temperature of 83 K, band shape, photometry, and isotherm measurements all indicate that the CO2 molecules are first adsorbed on defect sites, followed by adsorption on terraces that yields a single sharp spectral feature at 2333 cm-1 with FWHM=6 cm-1. Nearly 20% of the surface sites on the as-polished C(111)-1×1:H surfaces are defects

  3. Adsorption mechanism of ester phosphate on baryum titanate in organic medium. Preliminary results on the structure of the adsorbed layer

    NASA Astrophysics Data System (ADS)

    Le Bars, N.; Tinet, D.; Faugère, A. M.; van Damme, H.; Levitz, P.

    1991-05-01

    The purpose of this work is to evidence the adsorption mechanism and the structure of commercial phosphate ester surfactant stabilized BaTiO3 in organic suspension, and to relate these characteristics to rheological behaviour. Binders and plasticizers are omitted to reduce the number of system components. Firstly adsorption isotherm were determined by inductively coupled argon plasma technique and interpretated based on transmission electron microscopy and ^{31}P nuclear magnetic resonance studies. Preliminary rheological measurements were then performed and related to suspension structure. Structure of the adsorption layer is critically discussed. L'objectif de cette étude est la compréhension du mécanisme d'adsorption d'agents dispersants phosphatés dans des suspensions organiques de BaTiO3, ainsi que la caractérisation de la structure, et du comportement rhéologique de ces suspensions. Liants et plastifiants ne sont pas utilisés, afin de réduire le nombre de composants dans le système. Dans un premier temps, l'isotherme d'adsorption est établie par dosage en émission plasma, puis interprétée sur la base de résultats de Microscopie Eloctronique à Transmission, et de spectroscopie par Résonance Magnétique Nucléaire du ^{31}P. Des mesures rhéologiques préliminaires sont effectuées pour caractériser la structure des suspensions.

  4. Surface morphological evolution of epitaxial CrN(001) layers

    SciTech Connect

    Frederick, J.R.; Gall, D.

    2005-09-01

    CrN layers, 57 and 230 nm thick, were grown on MgO(001) at T{sub s}=600-800 deg. C by ultrahigh-vacuum magnetron sputter deposition in pure N{sub 2} discharges from an oblique deposition angle {alpha}=80 deg. . Layers grown at 600 deg. C nucleate as single crystals with a cube-on-cube epitaxial relationship with the substrate. However, rough surfaces with cauliflower-type morphologies cause the nucleation of misoriented CrN grains that develop into cone-shaped grains that protrude out of the epitaxial matrix to form triangular faceted surface mounds. The surface morphology of epitaxial CrN(001) grown at 700 deg. C is characterized by dendritic ridge patterns extending along the orthogonal <110> directions superposed by square-shaped super mounds with <100> edges. The ridge patterns are attributed to a Bales-Zangwill instability while the supermounds form due to atomic shadowing which leads to the formation of epitaxial inverted pyramids that are separated from the surrounding layer by tilted nanovoids. Growth at 800 deg. C yields complete single crystals with smooth surfaces. The root-mean-square surface roughness for 230-nm-thick layers decreases from 18.8 to 9.3 to 1.1 nm as T{sub s} is raised from 600 to 700 to 800 deg. C. This steep decrease is due to a transition in the roughening mechanism from atomic shadowing to kinetic roughening. Atomic shadowing is dominant at 600 and 700 deg. C, where misoriented grains and supermounds, respectively, capture a larger fraction of the oblique deposition flux in comparison to the surrounding epitaxial matrix, resulting in a high roughening rate that is described by a power law with an exponent {beta}>0.5. In contrast, kinetic roughening controls the surface morphology for T{sub s}=800 deg. C, as well as the epitaxial fraction of the layers grown at 600 and 700 deg. C, yielding relatively smooth surfaces and {beta}{<=}0.27.

  5. Electrografted diazonium salt layers for antifouling on the surface of surface plasmon resonance biosensors.

    PubMed

    Zou, Qiongjing; Kegel, Laurel L; Booksh, Karl S

    2015-02-17

    Electrografted diazonium salt layers on the surface of surface plasmon resonance (SPR) sensors present potential for a significant improvement in antifouling coatings. A pulsed potential deposition profile was used in order to circumvent mass-transport limitations for layer deposition rate. The influence of number of pulses with respect to antifouling efficacy was evaluated by nonspecific adsorption surface coverage of crude bovine serum proteins. Instead of using empirical and rough estimated values, the penetration depth and sensitivity of the SPR instrument were experimentally determined for the calculation of nonspecific adsorption surface coverage. This provides a method to better examine antifouling surface coatings and compare crossing different coatings and experimental systems. Direct comparison of antifouling performance of different diazonium salts was facilitated by a tripad SPR sensor design. The electrografted 4-phenylalanine diazonium chloride (4-APhe) layers with zwitterionic characteristic demonstrate ultralow fouling. PMID:25526646

  6. Arctic Cloud-driven Mixed Layers and Surface Coupling State

    NASA Astrophysics Data System (ADS)

    Shupe, M.; Persson, O. P.; Solomon, A.; de Boer, G.

    2013-12-01

    Arctic low-level clouds interact with the atmosphere and underlying surface via many inter-related processes. The balance of cloud radiative warming and cooling effects imparts a strong control on the net surface energy budget. Cloud-driven atmospheric circulations can impact surface turbulent heat fluxes and influence the vertical mixing of atmospheric state parameters and aerosols. Large-scale advection of heat and moisture provides the background context within which these local interactions unfold. Importantly, these radiative, dynamical, and advective processes also contribute to a complex web of self-sustaining cloud processes that can promote cloud maintenance over long periods of time. We examine many of these processes, with a specific focus on the dynamical linkages between Arctic clouds and the surface that influence low-level atmospheric structure and mixing. Comprehensive, ground-based observations from meteorological towers, remote-sensors, and radiosondes are used to simultaneously characterize surface fluxes, atmospheric structure, cloud properties, in-cloud motions, and the depth of the cloud-driven mixed layer in multiple Arctic environments. Relationships among these parameters are explored to elucidate the properties of the system that determine the degree of vertical atmospheric mixing and the coupling state between cloud and surface. The influence of temperature and moisture inversions on this system is also explored. Transitions in the coupling state are utilized to illustrate the relative roles of different processes. Cases from a coastal Arctic site at Barrow, Alaska and a station embedded in the Arctic sea-ice pack are used to contrast conditional influences related to season and surface type. It is found that over sea-ice, where surface turbulent fluxes are weak, the coupling of cloud-level processes to the surface layer is largely due to proximity of the cloud-driven mixed layer to the surface, which appears to be primarily influenced by

  7. Polydopamine meets porous membrane: A versatile platform for facile preparation of membrane adsorbers.

    PubMed

    Fan, Jinxin; Luo, Jianquan; Chen, Xiangrong; Wan, Yinhua

    2016-05-27

    Polydopamine, as an intermediate layer coated on PES membrane, was applied to fabricate various membrane adsorbers. Anion-exchange, hydrophobic interaction and affinity membrane adsorbers prepared by this facile method exhibited a high selectivity in fractionation of IgG (immunoglobulin)/HSA (human serum albumin) mixture. The anion-exchange membrane adsorber containing polyethylenimine (PEI) improved the HSA purity from 17.7% to 96.7%; The hydrophobic interaction membrane adsorber with Dodecyl mercaptan (DDM) as ligand obtained an IgG purity of 94.6%; Histidine attached affinity membrane chromatography achieved nearly a 100% purity of IgG. The present work indicated that the polydopamine layer not only activated membrane surface to attach various adsorptive ligands under the mild condition, but also reduced non-specific adsorption. Due to the versatile conjunction function, this facile mussel-inspired coating is also promising for the preparation of diverse membrane adsorbers. PMID:27131962

  8. Characterization of carbides composite surface layers produced by PTA

    NASA Astrophysics Data System (ADS)

    Tajoure, M.; Tajouri, A.

    2015-03-01

    Composite surface layer of nickel base with titanium carbide in powder form was deposited on to surface of low alloy steel 18G2A type according to polish standard by using plasma transferred arc technique. Results showed that, plasma transferred arc hardfacin process was successfully conducted by using PMNICr50P alloy plus titanium carbide powders. Maximum hardness of 754 HV and minimum dilution of 4.6 % were achieved by using an arc current of 80 A. However, when the current was further increased to 120 A& the dilution increases with current increase while the hardness decreases. Microstructure of the nickel base with titanium carbide feature uniform distribution of reinforcement particles with irregular grain shape and relatively small particles size, and regular boundary line between the substrate and over layer with presence of black area along the boundary line. A few micro - porosities are located in the matrix.

  9. On the Effects of Surface Roughness on Boundary Layer Transition

    NASA Technical Reports Server (NTRS)

    Choudhari, Meelan M.; Li, Fei; Chang, Chau-Lyan; Edwards, Jack

    2009-01-01

    Surface roughness can influence laminar-turbulent transition in many different ways. This paper outlines selected analyses performed at the NASA Langley Research Center, ranging in speed from subsonic to hypersonic Mach numbers and highlighting the beneficial as well as adverse roles of the surface roughness in technological applications. The first theme pertains to boundary-layer tripping on the forebody of a hypersonic airbreathing configuration via a spanwise periodic array of trip elements, with the goal of understanding the physical mechanisms underlying roughness-induced transition in a high-speed boundary layer. The effect of an isolated, finite amplitude roughness element on a supersonic boundary layer is considered next. The other set of flow configurations examined herein corresponds to roughness based laminar flow control in subsonic and supersonic swept wing boundary layers. A common theme to all of the above configurations is the need to apply higher fidelity, physics based techniques to develop reliable predictions of roughness effects on laminar-turbulent transition.

  10. Continuous-time core-level photon-stimulated desorption spectroscopy for monitoring soft x-ray-induced reactions of molecules adsorbed on a single-crystal surface

    SciTech Connect

    Chou, L.-C.; Wen, C.-R.

    2006-05-15

    Continuous-time core-level photon-stimulated desorption (PSD) spectroscopy was proposed for monitoring the soft x-ray-induced reactions of molecules adsorbed on a single-crystal surface. Monochromatic synchrotron radiation was used as a soft x-ray light source in the photon-induced reactions of CF{sub 3}Cl adsorbed on a Si(111)-7x7 surface at 30 K and also as a probe for studying the produced fluorination states of the bonding surface Si atom in the positive-ion PSD spectroscopy. The F{sup +} PSD spectrum was obtained by monitoring the F{sup +} signal as a function of incident photon energy near the Si(2p) edge (98-110 eV). Sequential F{sup +} PSD spectra were measured as a function of photon exposure at four adsorbate coverages (the first dose=0.3x10{sup 15} molecules/cm{sup 2}, the second dose=0.8x10{sup 15} molecules/cm{sup 2}, the third dose=2.2x10{sup 15} molecules/cm{sup 2}, and the fourth dose=3.2x10{sup 15} molecules/cm{sup 2}). For the first and second CF{sub 3}Cl-dosed surfaces, the sequential F{sup +} PSD spectra show the variation of their shapes with photon exposure and indicate the formation of surface SiF species. The sequential F{sup +} PSD spectra for the third and fourth CF{sub 3}Cl-dosed surfaces also show the variation of their shapes with photon exposure and depict the production of surface SiF and SiF{sub 3} species.

  11. Rotating compact bodies with a disk surface layer

    NASA Astrophysics Data System (ADS)

    Haggag, Salah

    2016-03-01

    The Senovilla family for a subclass of Petrov type-D stationary axisymmetric differentially rotating perfect fluids is considered. A scheme is presented to construct from a solution an interior of a rotating compact body satisfying dominant energy conditions and with a boundary of vanishing pressure. The equatorial disk of the body is a surface layer due to a jump in the second fundamental form. However, unlike previous results, the body is free from curvature singularities.

  12. Surface-plasmons lasing in double-graphene-layer structures

    SciTech Connect

    Dubinov, A. A.; Aleshkin, V. Ya.; Ryzhii, V.; Shur, M. S.; Otsuji, T.

    2014-01-28

    We consider the concept of injection terahertz lasers based on double-graphene-layer (double-GL) structures with metal surface-plasmon waveguide and study the conditions of their operation. The laser under consideration exploits the resonant radiative transitions between GLs. This enables the double-GL laser room temperature operation and the possibility of voltage tuning of the emission spectrum. We compare the characteristics of the double-GL lasers with the metal surface-plasmon waveguides with those of such laser with the metal-metal waveguides.

  13. Vibrational spectra of CO adsorbed on oxide thin films: A tool to probe the surface defects and phase changes of oxide thin films

    SciTech Connect

    Savara, Aditya

    2014-03-15

    Thin films of iron oxide were grown on Pt(111) single crystals using cycles of physical vapor deposition of iron followed by oxidative annealing in an ultrahigh vacuum apparatus. Two procedures were utilized for film growth of ∼15–30 ML thick films, where both procedures involved sequential deposition+oxidation cycles. In procedure 1, the iron oxide film was fully grown via sequential deposition+oxidation cycles, and then the fully grown film was exposed to a CO flux equivalent to 8 × 10{sup −7} millibars, and a vibrational spectrum of adsorbed CO was obtained using infrared reflection-absorption spectroscopy. The vibrational spectra of adsorbed CO from multiple preparations using procedure 1 show changes in the film termination structure and/or chemical nature of the surface defects—some of which are correlated with another phase that forms (“phase B”), even before enough of phase B has formed to be easily detected using low energy electron diffraction (LEED). During procedure 2, CO vibrational spectra were obtained between deposition+oxidation cycles, and these spectra show that the film termination structure and/or chemical nature of the surface defects changed as a function of sequential deposition+oxidation cycles. The authors conclude that measurement of vibrational spectra of adsorbed CO on oxide thin films provides a sensitive tool to probe chemical changes of defects on the surface and can thus complement LEED techniques by probing changes not visible by LEED. Increased use of vibrational spectra of adsorbed CO on thin films would enable better comparisons between films grown with different procedures and by different groups.

  14. Moored surface buoy observations of the diurnal warm layer

    NASA Astrophysics Data System (ADS)

    Prytherch, J.; Farrar, J. T.; Weller, R. A.

    2013-09-01

    An extensive data set is used to examine the dynamics of diurnal warming in the upper ocean. The data set comprises more than 4700 days of measurements at five sites in the tropics and subtropics, obtained from surface moorings equipped to make comprehensive meteorological, incoming solar and infrared radiation, and high-resolution subsurface temperature (and, in some cases, velocity) measurements. The observations, which include surface warmings of up to 3.4°C, are compared with a selection of existing models of the diurnal warm layer (DWL). A simple one-layer physical model is shown to give a reasonable estimate of both the magnitude of diurnal surface warming (model-observation correlation 0.88) and the structure and temporal evolution of the DWL. Novel observations of velocity shear obtained during 346 days at one site, incorporating high-resolution (1 m) upper ocean (5-15 m) acoustic Doppler current profile measurements, are also shown to be in reasonable agreement with estimates from the physical model (daily maximum shear model-observation correlation 0.77). Physics-based improvements to the one-layer model (incorporation of rotation and freshwater terms) are discussed, though they do not provide significant improvements against the observations reported here. The simplicity and limitations of the physical model are used to discuss DWL dynamics. The physical model is shown to give better model performance under the range of forcing conditions experienced across the five sites than the more empirical models.

  15. Surface-cooling effects on compressible boundary-layer instability

    NASA Technical Reports Server (NTRS)

    Seddougui, Sharon O.; Bowles, R. I.; Smith, F. T.

    1990-01-01

    The influence of surface cooling on compressible boundary layer instability is discussed theoretically for both viscous and inviscid modes, at high Reynolds numbers. The cooling enhances the surface heat transfer and shear stress, creating a high heat transfer sublayer. This has the effect of distorting and accentuating the viscous Tollmien-Schlichting modes to such an extent that their spatial growth rates become comparable with, and can even exceed, the growth rates of inviscid modes, including those found previously. This is for moderate cooling, and it applies at any Mach number. In addition, the moderate cooling destabilizes otherwise stable viscous or inviscid modes, in particular triggering outward-traveling waves at the edge of the boundary layer in the supersonic regime. Severe cooling is also discussed as it brings compressible dynamics directly into play within the viscous sublayer. All the new cooled modes found involve the heat transfer sublayer quite actively, and they are often multi-structured in form and may be distinct from those observed in previous computational and experimental investigations. The corresponding nonlinear processes are also pointed out with regard to transition in the cooled compressible boundary layer. Finally, comparisons with Lysenko and Maslov's (1984) experiments on surface cooling are presented.

  16. Laser-Based Transient Surface Acceleration of Thermoelastic Layers

    NASA Astrophysics Data System (ADS)

    CETINKAYA, CETIN; WU, CUNLI; LI, CHEN

    2000-03-01

    The removal of particles from elastic substrates has been an important practical problem in the electronics industry especially as the sizes of electronic units shrink. In recent years, there has been an interest in removingsubmicron level particles from surfaces. The use of traditional surface cleaning methods, such as ultrasonically induced fluid flow, vibrational methods, centrifugal techniques, is limited to particles that require surface acceleration lower than 107m/s2. For the effective removal of submicron particles, a higher level surface acceleration is needed since the adhesion forces (mainly van der Waals force for dry surfaces) are related to the particle size and increase approximately linearly as the characteristic radius of small particles that are to be removed decreases. In current work, based on the generalized dynamic theory of thermoelasticity reported, a transfer matrix formulation including the second sound effect is developed for a thermoelastic layer. The transfer matrix for axisymmetric wave propagation in a thermoelastic layer is obtained by adopting a double integral transform approach. The second sound effect is included to eliminate the thermal wave travelling with infinite velocity as predicted by the diffusion heat transfer model, and, consequently, the immediate arrival of waves. Using the current formulation and the periodic systems framework, a transfer function formulation for calculating the accelerations is developed for transient analysis. A double integral transform inversion method is used for transient response calculations. Acceleration levels, sufficient for submicron particle removal, are reported. Various processes such as thermoelastic stresses, surface evaporation, and optical breakdown may be responsible for surface acceleration components and particle removal. In current work, only the surface acceleration due to transient thermoelastic wave propagation is under investigation.

  17. Photon-exposure-dependent photon-stimulated desorption for obtaining photolysis cross section of molecules adsorbed on surface by monochromatic soft x-ray photons

    SciTech Connect

    Chou, L.-C.; Jang, C.-Y.; Wu, Y.-H.; Tsai, W.-C.; Wang, S.-K.; Chen, J.; Chang, S.-C.; Liu, C.-C.; Shai, Y.; Wen, C.-R.

    2008-12-07

    Photon-exposure-dependent positive- and negative-ion photon-stimulated desorption (PSD) was proposed to study the photoreactions and obtain the photolysis cross sections of molecules adsorbed on a single-crystal surface by monochromatic soft x-ray photons with energy near the core level of adsorbate. The changes in the F{sup +} and F{sup -} PSD ion yields were measured from CF{sub 3}Cl molecules adsorbed on Si(111)-7x7 at 30 K (CF{sub 3}Cl dose=0.3x10{sup 15} molecules/cm{sup 2}, {approx}0.75 monolayer) during irradiation of monochromatic soft x-ray photons near the F(1s) edge. The PSD ion yield data show the following characteristics: (a) The dissociation of adsorbed CF{sub 3}Cl molecules is due to a combination of direct photodissociation via excitation of F(1s) core level and substrate-mediated dissociation [dissociative attachment and dipolar dissociation induced by the photoelectrons emitting from the silicon substrate]. (b) the F{sup +} ion desorption is associated with the bond breaking of the surface CF{sub 3}Cl, CF{sub 2}Cl, CFCl, and SiF species. (c) the F{sup -} yield is mainly due to DA and DD of the adsorbed CF{sub 3}Cl molecules. (d) The surface SiF is formed by reaction of the surface Si atom with the neutral fluorine atom, F{sup +}, or F{sup -} ion produced by scission of C-F bond of CF{sub 3}Cl, CF{sub 2}Cl, or CFCl species. A kinetic model was proposed for the explanation of the photolysis of this submonolayer CF{sub 3}Cl-covered surface. Based on this model and the variation rates of the F{sup +}/F{sup -} signals during fixed-energy monochromatic photon bombardment at 690.2 and 692.6 eV[near the F(1s) edge], the photolysis cross section was deduced as a function of energy.

  18. Atomic scale control of hexaphenyl molecules manipulation along functionalized ultra-thin insulating layer on the Si(1 0 0) surface at low temperature (9 K).

    PubMed

    Chiaravalloti, Franco; Dujardin, Gérald; Riedel, Damien

    2015-02-11

    Ultra-thin CaF2 layers are grown on the Si(1 0 0) surface by using a Knudsen cell evaporator. These epitaxial structures are studied with a low temperature (9 K) scanning tunneling microscope and used to electronically decouple hexaphenyl molecules from the Si surface. We show that the ultra-thin CaF2 layers exhibit stripe structures oriented perpendicularly to the silicon dimer rows and have a surface gap of 3.8 eV. The ultra-thin semi-insulating layers are also shown to be functionalized, since 80% of the hexaphenyl molecules adsorbed on these structures self-orients along the stripes. Numerical simulations using time-dependent density functional theory allow comparison of computed orbitals of the hexaphenyl molecule with experimental data. Finally, we show that the hexaphenyl molecules can be manipulated along or across the stripes, enabling the molecules to be arranged precisely on the insulating surface. PMID:25414151

  19. Tailored surface engineering of pigments by layer-by-layer coating.

    PubMed

    Dähne, Lars; Schneider, Julia; Lewe, Dirk; Petersen, Henrik

    2015-01-01

    We have evaluated the feasibility of layer-by-layer encapsulation technology for the improvement of dye pigments used for tattoos or permanent make-up. The formation of core-shell structures is possible by coating pigments with thin films of several different polyelectrolytes using this technology. The physicochemical surface properties, such as charge density and chemical functionality, can be reproducibly varied in a wide range. Tailoring the surface properties independently from the pigment core allows one to control the rheological behaviour of pigment suspensions, to prevent aggregation between different pigments, to reduce the cytotoxicity, and to influence the response of phagocytes in order to have similar or the same uptake and bioclearance for all pigments. These properties determine the durability and colour tone stability of tattoos and permanent make-up. PMID:25833634

  20. Time-resolved surface infrared spectroscopy during atomic layer deposition of TiO{sub 2} using tetrakis(dimethylamido)titanium and water

    SciTech Connect

    Sperling, Brent A. Hoang, John; Kimes, William A.; Maslar, James E.; Steffens, Kristen L.; Nguyen, Nhan V.

    2014-05-15

    Atomic layer deposition of titanium dioxide using tetrakis(dimethylamido)titanium (TDMAT) and water vapor is studied by reflection-absorption infrared spectroscopy (RAIRS) with a time resolution of 120 ms. At 190 °C and 240 °C, a decrease in the absorption from adsorbed TDMAT is observed without any evidence of an adsorbed product. Ex situ measurements indicate that this behavior is not associated with an increase in the impurity concentration or a dramatic change in the growth rate. A desorbing decomposition product is consistent with these observations. RAIRS also indicates that dehydroxylation of the growth surface occurs only among one type of surface hydroxyl groups. Molecular water is observed to remain on the surface and participates in reactions even at a relatively high temperature (110 °C) and with long purge times (30 s)

  1. Effects of sodium chloride on the properties of chlorophyll a submonolayer adsorbed onto hydrophobic and hydrophilic surfaces using broadband spectroscopy with single-mode integrated optical waveguides

    NASA Astrophysics Data System (ADS)

    Wiederkehr, Rodrigo S.; Hoops, Geoffrey C.; Mendes, Sergio B.

    2011-07-01

    In this work, we experimentally investigated the effects of sodium chloride on the molar absorptivity and surface density of a submonolayer of chlorophyll a adsorbed onto hydrophilic and hydrophobic solid/liquid interfaces. Those investigations were made possible by a broadband spectroscopic platform based on single-mode, integrated optical waveguides, which allows for extremely sensitive spectroscopic detection of analytes immobilized at submonolayer levels. Chlorophyll a with a constant bulk concentration (1.4 μM) was dissolved in phosphate buffer solutions (7 mM) of neutral pH, but with different sodium chloride concentrations. For a buffer solution of 1 mM of sodium chloride, the measured surface density of chlorophyll a was 0.209 pmol/cm2 for a hydrophilic and 0.125 pmol/cm2 for a hydrophobic surface. For a phosphate buffer solution of 10 mM of sodium chloride, the measured surface density of chlorophyll a was 0.528 pmol/cm2 for a hydrophilic and 0.337 pmol/cm2 for a hydrophobic surface. Additionally, a hypsochromic shift of the Soret band was observed for the adsorbed pigment in correlation with an increase in buffer ionic strength. The adsorption of chlorophyll a onto different surfaces can play an important role to elucidate several processes found in nature and provide a rationale for bio-inspired new material technologies.

  2. Turbulence effects on concentration statistics in the atmospheric surface layer

    SciTech Connect

    Biltoft, C.; Bowers, J.; Yee, E.; Klewicki, J.; Metzger, M.

    1996-12-31

    The dispersion of windborne material released near the earth`s surface is strongly influenced by this impenetrable boundary, which inhibits downward mixing and creates sharp vertical gradients in wind, temperature, turbulence. These strong gradients and the continuous creation of turbulence at the surface cause a rapid evolution of the vertical concentration structure for material released into the atmospheric surface layer (ASL). Recent developments in fast-response instrumentation and an increased realization of potential hazards from the release of common industrial chemicals into the ASL have led to a series of tripartite (US, UK, Canada) field experiments at the US Army Dugway Proving Ground, Utah. This paper contains a preliminary analysis of the data from the most recent follow-on experiments, which included measurements of the vertical profiles of mean and peak concentrations.

  3. Linear stability of a layered fluid with mobile surface plates

    NASA Technical Reports Server (NTRS)

    Buffett, B. A.; Gable, C. W.; O'Connell, R. J.

    1994-01-01

    We develop a general method of calculating the linear stability of a fluid with homogeneous layers that is heated from below. The method employs a propagator technique to obtain expressions for the fluid velocity, stress, and temperature. The principal advantage of the method is the ease with which solutions are adapted to a wide variety of boundary conditions and fluid properties. We demonstrate the utility of the method using three examples which quantify the effects of (1) rheological layering, (2) mobile plates at the surface, and (3) multiple phase transitions. Each example is presented in the context of Earth's mantle. In the first example, we predict that convection becomes confined to the upper mantle once the viscosity increase between the upper and lower mantle exceeds a factor of 2000, consistent with the nonlinear calculations of Davies (1977). In the second example we find that the heat flux variations in a convecting fluid with variably sized, surface plates can be attributed, in part, to changes in the critical Rayleigh number. The linear stability of a fluid with multiple phase transitions is significantly affects by the locations of the transitions. We find that phase transitions have their largest effect when they are located at the center of the fluid layer and become much less important when they are located near the exterior boundaries.

  4. Multi-layer topological transmissions of spoof surface plasmon polaritons.

    PubMed

    Pan, Bai Cao; Zhao, Jie; Liao, Zhen; Zhang, Hao Chi; Cui, Tie Jun

    2016-01-01

    Spoof surface plasmon polaritons (SPPs) in microwave frequency provide a high field confinement in subwavelength scale and low-loss and flexible transmissions, which have been widely used in novel transmission waveguides and functional devices. To play more important roles in modern integrated circuits and systems, it is necessary and helpful for the SPP modes to propagate among different layers of devices and chips. Owing to the highly confined property and organized near-field distribution, we show that the spoof SPPs could be easily transmitted from one layer into another layer via metallic holes and arc-shaped transitions. Such designs are suitable for both the ultrathin and flexible single-strip SPP waveguide and double-strip SPP waveguide for active SPP devices. Numerical simulations and experimental results demonstrate the broadband and high-efficiency multi-layer topological transmissions with controllable absorption that is related to the superposition area of corrugated metallic strips. The transmission coefficient of single-strip SPP waveguide is no worse than -0.8 dB within frequency band from 2.67 GHz to 10.2 GHz while the transmission of double-strip SPP waveguide keeps above -1 dB within frequency band from 2.26 GHz to 11.8 GHz. The proposed method will enhance the realizations of highly complicated plasmonic integrated circuits. PMID:26939995

  5. Multi-layer topological transmissions of spoof surface plasmon polaritons

    PubMed Central

    Pan, Bai Cao; Zhao, Jie; Liao, Zhen; Zhang, Hao Chi; Cui, Tie Jun

    2016-01-01

    Spoof surface plasmon polaritons (SPPs) in microwave frequency provide a high field confinement in subwavelength scale and low-loss and flexible transmissions, which have been widely used in novel transmission waveguides and functional devices. To play more important roles in modern integrated circuits and systems, it is necessary and helpful for the SPP modes to propagate among different layers of devices and chips. Owing to the highly confined property and organized near-field distribution, we show that the spoof SPPs could be easily transmitted from one layer into another layer via metallic holes and arc-shaped transitions. Such designs are suitable for both the ultrathin and flexible single-strip SPP waveguide and double-strip SPP waveguide for active SPP devices. Numerical simulations and experimental results demonstrate the broadband and high-efficiency multi-layer topological transmissions with controllable absorption that is related to the superposition area of corrugated metallic strips. The transmission coefficient of single-strip SPP waveguide is no worse than −0.8 dB within frequency band from 2.67 GHz to 10.2 GHz while the transmission of double-strip SPP waveguide keeps above −1 dB within frequency band from 2.26 GHz to 11.8 GHz. The proposed method will enhance the realizations of highly complicated plasmonic integrated circuits. PMID:26939995

  6. Summer surface layer thermal response to surface gravity waves in the Yellow Sea

    NASA Astrophysics Data System (ADS)

    Zhang, Xuefeng; Han, Guijun; Wang, Dongxiao; Deng, Zengan; Li, Wei

    2012-07-01

    The Princeton Ocean Model (POM) with generalized coordinate system (POMgcs) is used to study the summer surface-layer thermal response to surface gravity waves in the Yellow Sea (YS). The parameterization schemes of wave breaking developed by Mellor and Blumberg (J Phys Oceanogr 34:693-698, 2004) and Kantha and Clayson (Ocean Model 6:101-124, 2004), respectively, and Stokes production developed by Kantha and Clayson (Ocean Model 6:101-124, 2004) are both included in the Mellor-Yamada turbulence closure model Mellor and Yamada (Rev Geophys 20:851-875, 1982) of POMgcs. Numerical results show that surface gravity waves impact the depth of surface mixed layer of temperature in the YS in summer. The surface mixed layer in the YS cannot be reproduced well and has a visible difference from the observation if the parameterization schemes are not included. A diagnostic analysis of turbulent kinetic energy suggests that both Stokes production and wave breaking play key roles in enhancing the turbulent mixing near the sea surface in the YS. Stokes production seems to have a greater impact throughout the upper mixed layer in the YS in summer than that of wave breaking. In addition, a diagnostic analysis of the momentum balance shows that Coriolis-Stokes forcing has a significant effect on the momentum budget in the upper layer in the YS, and surface gravity waves are able to reduce the velocity of mean flow near the surface and make the mean flow near the surface more homogeneous vertically in the YS.

  7. Density-functional theory with screened van der Waals interactions applied to atomic and molecular adsorbates on close-packed and non-close-packed surfaces

    NASA Astrophysics Data System (ADS)

    Ruiz, Victor G.; Liu, Wei; Tkatchenko, Alexandre

    2016-01-01

    Modeling the adsorption of atoms and molecules on surfaces requires efficient electronic-structure methods that are able to capture both covalent and noncovalent interactions in a reliable manner. In order to tackle this problem, we have developed a method within density-functional theory (DFT) to model screened van der Waals interactions (vdW) for atoms and molecules on surfaces (the so-called DFT+vdWsurf method). The relatively high accuracy of the DFT+vdWsurf method in the calculation of both adsorption distances and energies, as well as the high degree of its reliability across a wide range of adsorbates, indicates the importance of the collective electronic effects within the extended substrate for the calculation of the vdW energy tail. We examine in detail the theoretical background of the method and assess its performance for adsorption phenomena including the physisorption of Xe on selected close-packed transition metal surfaces and 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) on Au(111). We also address the performance of DFT+vdWsurf in the case of non-close-packed surfaces by studying the adsorption of Xe on Cu(110) and the interfaces formed by the adsorption of a PTCDA monolayer on the Ag(111), Ag(100), and Ag(110) surfaces. We conclude by discussing outstanding challenges in the modeling of vdW interactions for studying atomic and molecular adsorbates on inorganic substrates.

  8. Surface-enhanced Raman scattering of amorphous silica gel adsorbed on gold substrates for optical fiber sensors

    NASA Astrophysics Data System (ADS)

    Degioanni, S.; Jurdyc, A. M.; Cheap, A.; Champagnon, B.; Bessueille, F.; Coulm, J.; Bois, L.; Vouagner, D.

    2015-10-01

    Two kinds of gold substrates are used to produce surface-enhanced Raman scattering (SERS) of amorphous silica obtained via the sol-gel route using tetraethoxysilane Si(OC2H5)4 (TEOS) solution. The first substrate consists of a gold nanometric film elaborated on a glass slide by sputter deposition, controlling the desired gold thickness and sputtering current intensity. The second substrate consists of an array of micrometer-sized gold inverted pyramidal pits able to confine surface plasmon (SP) enhancing electric field, which results in a distribution of electromagnetic energy inside the cavities. These substrates are optically characterized to observe SPR with, respectively, extinction and reflectance spectrometries. Once coated with thin layers of amorphous silica (SiO2) gel, these samples show Raman amplification of amorphous SiO2 bands. This enhancement can occur in SERS sensors using amorphous SiO2 gel as shells, spacers, protective coatings, or waveguides, and represents particularly a potential interest in the field of Raman distributed sensors, which use the amorphous SiO2 core of optical fibers as a transducer to make temperature measurements.

  9. Adsorbate-induced demagnetization and restructuring of ultrathin magnetic films: CO chemisorbed on γ-Fe/Cu(100)

    NASA Astrophysics Data System (ADS)

    Spišák, D.; Hafner, J.

    2001-09-01

    First-principles local-spin-density (LSD) investigations of the structural, magnetic, and electronic properties of clean and CO-adsorbed ultrathin γ-iron films epitaxially grown on Cu(100) surfaces demonstrate that both the geometrical and the magnetic structures of the films are profoundly modified by the adsorption of CO. The enhanced magnetic moments of the top-layer atoms are strongly quenched by the presence of the adsorbate. Due to the pronounced magnetovolume effect, this leads also to a correlated change in the interlayer relaxations. Strikingly, the adsorbate-induced demagnetization is primarily limited to those surface atoms directly bonded to the adsorbate. This leads to the formation of an in-plane magnetic pattern in a partially adsorbate-covered film. The comparison of the calculated vibrational eigenfrequencies of the CO adsorbate with experiment confirms the picture based on the LSD calculations.

  10. Soil moisture sensor calibration for organic soil surface layers

    NASA Astrophysics Data System (ADS)

    Bircher, S.; Andreasen, M.; Vuollet, J.; Vehviläinen, J.; Rautiainen, K.; Jonard, F.; Weihermüller, L.; Zakharova, E.; Wigneron, J.-P.; Kerr, Y. H.

    2015-12-01

    This paper's objective is to present generic calibration functions for organic surface layers derived for the soil moisture sensors Decagon ECH2O 5TE and Delta-T ThetaProbe ML2x, using material from northern regions, mainly from the Finish Meteorological Institute's Arctic Research Center in Sodankylä and the study area of the Danish Center for Hydrology HOBE. For the Decagon 5TE sensor such a function is currently not reported in literature. Data were compared with measurements from underlying mineral soils including laboratory and field measurements. Shrinkage and charring during drying were considered. For both sensors all field and lab data showed consistent trends. For mineral layers with low soil organic matter (SOM) content the validity of the manufacturer's calibrations was demonstrated. Deviating sensor outputs in organic and mineral horizons were identified: for the Decagon 5TE apparent relative permittivities at a given moisture content decreased for increased SOM content, which was attributed to an increase of bound water in organic materials with large surface areas compared to the studied mineral soils. ThetaProbe measurements from organic horizons showed stronger non-linearity in the sensor response and signal saturation in the high level data. The derived calibration fit functions between sensor response and volumetric water content hold for samples spanning a wide range of humus types with differing SOM characteristics. This strengthens confidence in their validity under various conditions, rendering them highly suitable for large-scale applications in remote sensing and land surface modeling studies. Agreement between independent Decagon 5TE and ThetaProbe time series from an organic surface layer at the Sodankylä site was significantly improved when the here proposed fit functions were used. Decagon 5TE data also well-reflected precipitation events. Thus, Decagon 5TE network data from organic surface layers at the Sodankylä and HOBE sites are

  11. Soil moisture sensor calibration for organic soil surface layers

    NASA Astrophysics Data System (ADS)

    Bircher, Simone; Andreasen, Mie; Vuollet, Johanna; Vehviläinen, Juho; Rautiainen, Kimmo; Jonard, François; Weihermüller, Lutz; Zakharova, Elena; Wigneron, Jean-Pierre; Kerr, Yann H.

    2016-04-01

    This paper's objective is to present generic calibration functions for organic surface layers derived for the soil moisture sensors Decagon ECH2O 5TE and Delta-T ThetaProbe ML2x, using material from northern regions, mainly from the Finnish Meteorological Institute's Arctic Research Center in Sodankylä and the study area of the Danish Center for Hydrology (HOBE). For the Decagon 5TE sensor such a function is currently not reported in the literature. Data were compared with measurements from underlying mineral soils including laboratory and field measurements. Shrinkage and charring during drying were considered. For both sensors all field and lab data showed consistent trends. For mineral layers with low soil organic matter (SOM) content the validity of the manufacturer's calibrations was demonstrated. Deviating sensor outputs in organic and mineral horizons were identified. For the Decagon 5TE, apparent relative permittivities at a given moisture content decreased for increased SOM content, which was attributed to an increase of bound water in organic materials with large specific surface areas compared to the studied mineral soils. ThetaProbe measurements from organic horizons showed stronger nonlinearity in the sensor response and signal saturation in the high-level data. The derived calibration fit functions between sensor response and volumetric water content hold for samples spanning a wide range of humus types with differing SOM characteristics. This strengthens confidence in their validity under various conditions, rendering them highly suitable for large-scale applications in remote sensing and land surface modeling studies. Agreement between independent Decagon 5TE and ThetaProbe time series from an organic surface layer at the Sodankylä site was significantly improved when the here-proposed fit functions were used. Decagon 5TE data also well-reflected precipitation events. Thus, Decagon 5TE network data from organic surface layers at the Sodankylä and

  12. Changes in the surfaces on DDOAB organoclays adsorbed with paranitrophenol-An XRD, TEM and TG study

    SciTech Connect

    Zhou Qin; He Hongping; Frost, Ray L. Xi Yunfei

    2008-12-01

    The adsorption of paranitrophenol on organoclays synthesised by the ion exchange of the surfactant molecule dimethyldioctadecylammonium bromide (DDOAB) of formula (CH{sub 3}(CH{sub 2}){sub 17}){sub 2}NBr(CH{sub 3}){sub 2} has been studied by X-ray diffraction (XRD), transmission electron microscopy (TEM) and thermogravimetric analysis. The expansion of the montmorillonite depends on the loading of the montmorillonite with dimethyldioctadecylammonium bromide and is related to the arrangement of the surfactant molecules within the clay interlayer. This expansion is altered by the adsorbed paranitrophenol and is observed in the transmission electron microscopic images of the organoclay with adsorbed paranitrophenol. Changes in the surfactant molecular arrangements were analysed by thermogravimetry. The paranitrophenol is sublimed simultaneously with the loss of surfactant. The dehydroxylation temperature of the montmorillonite is decreased upon adsorption of the paranitrophenol indicating a bonding between the paranitrophenol and the hydroxyl units of the montmorillonite.

  13. Atmospheric surface and boundary layers of the Amazon Basin

    NASA Technical Reports Server (NTRS)

    Garstang, Michael

    1987-01-01

    Three phases of work were performed: design of and preparation for the Amazon Boundary Layer Experiment (ABLE 2-A); execution of the ABLE 2-A field program; and analysis of the ABLE 2-A data. Three areas of experiment design were dealt with: surface based meteorological measurements; aircraft missions; and project meteorological support. The primary goal was to obtain a good description of the structure of the atmosphere immediately above the rain forest canopy (top of canopy to a few thousand meters), to describe this region during the growing daytime phase of the boundary layer; and to examine the nighttime stratified state. A secondary objective was to examine the role that deep convective storms play in the vertical transport of heat, water vapor, and other trace gases. While significant progress was made, much of the analysis remains to be done.

  14. Construction of a functional S-layer fusion protein comprising an immunoglobulin G-binding domain for development of specific adsorbents for extracorporeal blood purification.

    PubMed

    Völlenkle, Christine; Weigert, Stefan; Ilk, Nicola; Egelseer, Eva; Weber, Viktoria; Loth, Fritz; Falkenhagen, Dieter; Sleytr, Uwe B; Sára, Margit

    2004-03-01

    The chimeric gene encoding a C-terminally-truncated form of the S-layer protein SbpA from Bacillus sphaericus CCM 2177 and two copies of the Fc-binding Z-domain was constructed, cloned, and heterologously expressed in Escherichia coli HMS174(DE3). The Z-domain is a synthetic analogue of the B-domain of protein A, capable of binding the Fc part of immunoglobulin G (IgG). The S-layer fusion protein rSbpA(31-1068)/ZZ retained the specific properties of the S-layer protein moiety to self-assemble in suspension and to recrystallize on supports precoated with secondary cell wall polymer (SCWP), which is the natural anchoring molecule for the S-layer protein in the bacterial cell wall. Due to the construction principle of the S-layer fusion protein, the ZZ-domains remained exposed on the outermost surface of the protein lattice. The binding capacity of the native or cross-linked monolayer for human IgG was determined by surface plasmon resonance measurements. For batch adsorption experiments, 3-microm-diameter, biocompatible cellulose-based, SCWP-coated microbeads were used for recrystallization of the S-layer fusion protein. In the case of the native monolayer, the binding capacity for human IgG was 5.1 ng/mm(2), whereas after cross-linking with dimethyl pimelimidate, 4.4 ng of IgG/mm(2) was bound. This corresponded to 78 and 65% of the theoretical saturation capacity of a planar surface for IgGs aligned in the upright position, respectively. Compared to commercial particles used as immunoadsorbents to remove autoantibodies from sera of patients suffering from an autoimmune disease, the IgG binding capacity of the S-layer fusion protein-coated microbeads was at least 20 times higher. For that reason, this novel type of microbeads should find application in the microsphere-based detoxification system. PMID:15006773

  15. Pyrocarbons prepared by carbonisation of polymers adsorbed or synthesised on a surface of silica and mixed oxides

    NASA Astrophysics Data System (ADS)

    Gun'ko, V. M.; Skubiszewska-Zi ęba, J.; Leboda, R.; Voronin, E. F.; Zarko, V. I.; Levitskaya, S. I.; Brei, V. V.; Guzenko, N. V.; Kazakova, O. A.; Seledets, O.; Janusz, W.; Chibowski, S.

    2004-04-01

    Initial oxides fumed silica, alumina/silica and titania/silica and silica gel and hybrid adsorbents with pyrocarbon formed on these oxide substrates by carbonisation of immobilised (adsorbed or synthesised) polymers such as starch, methyl cellulose, polyvinylpyrrolidone, polystyrene, and polybutylvinyl ether were studied by adsorption, AFM, TEM, and FTIR methods. Polymer/oxide materials were investigated by nitrogen and Pb(II) adsorption, FTIR, and potentiometric titration methods. Analysis of nitrogen adsorption-desorption isotherms by different methods, FTIR spectra, AFM and TEM images of the initial and hybrid adsorbents reveals that the morphology of the substrates significantly changes on carbonisation of oxygen-containing polymers because of hydrothermal treatment of them by water eliminated as a product of pyrolysis. Contribution of own microporosity of pyrocarbon deposits formed on carbonisation of immobilised polymers is greater (dependent on reaction conditions) than that on pyrolysis of low-molecular compounds at the same oxide substrates. Pyrocarbon particles formed on silica gel are larger than those formed on fumed oxides and larger than those formed on silica gel on pyrolysis of low-molecular compounds.

  16. Seaglider observations of surface mixed layer physics and biogeochemistry

    NASA Astrophysics Data System (ADS)

    Damerell, Gillian; Heywood, Karen; Thompson, Andrew; Henson, Stephanie; Rumyantseva, Anya

    2013-04-01

    The Ocean Surface Mixing, Ocean Sub-mesoscale Interaction Study (OSMOSIS) aims to develop new, physically-based parameterisations of processes that deepen and shoal the ocean surface boundary layer. As part of this project, 2 Seagliders were deployed in September 2012 at the Porcupine Abyssal Plain (PAP) site in the North Atlantic, to measure the structure and evolution of the ocean surface boundary layer over the seasonal cycle. The gliders measured temperature, salinity, dissolved oxygen, dive-averaged currents, chlorophyll fluorescence, CDOM fluorescence and PAR. We present results from the first 6 months of the Seaglider deployments, examining particular case studies of deepening/shoaling events and their impact on the biogeochemistry. Shoaling events appear to be more abrupt than deepening events. We also discuss the water masses found in the area, in particular, the occurrences of Mediterranean Water observed at a depth of approximately 800 m. As a contribution to the GROOM project, we assess the advantages and challenges of maintaining a continuous glider-based multidisciplinary observing system at the PAP site, with 2 gliders being turned around approximately every 4 months.

  17. Recognition of silver nanoparticles surface-adsorbed citrate anions by macrocyclic polyammonium cations: a spectrophotometric approach to study aggregation kinetics and evaluation of association constant.

    PubMed

    Choudhury, Rupasree; Purkayastha, Atanu; Debnath, Diptanu; Misra, Tarun Kumar

    2016-09-01

    In this report, we have studied the recognition of citrate anions adsorbed on the surface of silver nanoparticles (cit-Ag-NPs), by macrocyclic polyammonium cations (MCPACs): Me6 [14]ane-N4 H8 (4+) (Tet-A/Tet-B cations) and [32]ane-N8 H16 (8+) , which are well reputed anion recognizers and are treated as to mimic of biological polyamines. The study was monitored on ultraviolet-visible spectroscopy by performing a titration of the aqueous dispersion of the cit-Ag-NPs by the aqueous solution of MCPACs. The ultraviolet-visible time-scan plots over the reduction of the absorption band of surface plasmon resonance of cit-Ag-NPs at 390 nm are well fitted with fourth-order polynomial equation and are employed to determine the initial aggregation rate constants. It has been stated that the aggregation is the result in electrostatic attraction followed by H-bond formation between the surface-adsorbed citrate anions and added MCPACs. The atomic force microscopy results have evidenced aggregation of cit-Ag-NPs in presence of MCPACs. The evaluated H-bonded association constant (Kasso ) using Benesi-Hildebrand method reveals that [32]ane-N8 H16 (8+) cations form stronger association complex, as expected, with the citrate anions than the Me6 [14]ane-N4 H8 (4+) cations. The study would thus provide the insight of molecular interactions involved in nanoparticle surface-adsorbed anions with biological polyamines. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27146323

  18. Oblique surface Josephson plasma waves in layered superconductors

    NASA Astrophysics Data System (ADS)

    Averkov, Yu. O.; Yakovenko, V. M.; Yampol'skii, V. A.; Nori, Franco

    2013-02-01

    We have theoretically studied oblique surface waves (OSWs) which propagate along the interface between a dielectric and a layered superconductor. We assume that this interface is perpendicular to the superconducting layers, and OSWs at the interface can propagate at an arbitrary angle with respect to them. The electromagnetic field of the OSWs in a layered superconductor is a superposition of an ordinary wave (with its electric field parallel to the layers) and an extraordinary wave (with its magnetic field parallel to the layers). We have derived the dispersion equation for the OSWs and shown that the dispersion curves have end points where the extraordinary mode transforms from evanescent wave to bulk wave, propagating deep into the superconductor. In addition, we have analytically solved the problem of the resonance excitation of the OSWs by the attenuated-total-reflection method using an additional dielectric prism. Due to the strong current anisotropy in the boundary of the superconductor, the excitation of the OSWs is accompanied by an additional important phenomenon: The electromagnetic field component with the orthogonal polarization appears in the wave reflected from the bottom of the prism. We show that, for definite optimal combinations of the problem parameters (the wave frequency, the direction of the incident wave vector, the thickness of the gap between dielectric prism and superconductor, etc.), there is a complete suppression of the reflected wave with its polarization coinciding with the polarization of the incident wave. Contrary to the isotropic case, this phenomenon can be observed even in the dissipationless limit. In such a regime, the complete transformation of the incident wave into a reflected wave with orthogonal polarization can be observed.

  19. Characteristics of turbulent structures in the unstable atmospheric surface layer

    NASA Astrophysics Data System (ADS)

    Schols, J. L. J.; Jansen, A. E.; Krom, J. G.

    1985-10-01

    An atmospheric surface-layer (ASL) experiment conducted at a meteorological site in the Oostelijk-Flevoland polder of the Netherlands is described. Turbulent fluctuations of wind velocity, air temperature and static pressure were measured, using three 10 m towers. Simultaneous turbulent signals at several heights on the towers were used to investigate the properties of the turbulent structures which contribute most significantly to the turbulent vertical transports in the unstable ASL. These turbulent structures produce between 30 and 50% of the mean turbulent vertical transport of horizontal alongwind momentum and they contribute to between 40 and 50% of the mean turbulent vertical heat transport; in both cases this occurs during 15 to 20% of the total observation time. The translation speed of the turbulent structures equals the wind speed averaged over the depth of the ASL, which scales on the surface friction velocity. The inclination angle of the temperature interface at the upstream edge of the turbulent structures to the surface is significantly smaller than that of the internal shear layer, which is associated with the temperature interface. The turbulent structures in the unstable ASL are determined by a large-scale temperature field: Convective motions, which encompass the whole depth of the planetary boundary layer (PBL), penetrate into the ASL. The curvature of the vertical profile of mean horizontal alongwind velocity forces the alignment of the convective cells in the flow direction (Kuettner, 1971), which have an average length of several hundreds of metres and an average width of a few tens of metres. This mechanism leads to the formation of turbulent structures, which extend throughout the depth of the ASL.

  20. Surface activation of CNT Webs towards layer by layer assembly of biosensors.

    PubMed

    Musameh, Mustafa; Huynh, Chi P; Hickey, Mark; Kyratzis, Ilias Louis

    2016-04-25

    Several surface activation methods such as chemical, electrochemical and plasma have been used for enhancing the electrochemical performance of carbon based electrodes for various applications. However, some of these surface activation methods may not be useful depending on the chemical and physical properties of the activated surface. Herein we investigate the surface activation of carbon nanotube (CNT) webs by electrochemical and plasma techniques to enhance their electrochemical performance and enable the fabrication of a biosensor using the layer-by-layer (LBL) approach. The pretreated CNT webs were characterized by SEM, TEM, Raman, XPS and electrochemical methods. TEM images and Raman analysis showed an increase in the level of surface defects upon pretreatment with higher number of defects after electrochemical pretreatment. XPS analysis showed an increase in the level of oxygen functional groups after pretreatment (4 to 5 times increase) which resulted in enhanced water wettability especially for plasma pretreated CNT webs. The pretreated CNT web electrodes also showed an enhanced electrochemical activity towards the oxidation and reduction of different redox probes with higher sensitivity for the electrochemically pretreated CNT web electrode that was accompanied by a higher level of noise in amperometric measurements. A highly linear response was obtained for the untreated and the electrochemically pretreated CNT web electrodes towards the amperometric detection of NADH (R(2) of 0.9996 and 0.9986 respectively) while a non-linear response was observed for the plasma pretreated CNT web electrode (R(2) of 0.8538). The pretreated CNT web electrodes enabled the fabrication of a LBL biosensor for alcohol detection with highest operational stability obtained for the plasma pretreated CNT web surface. PMID:26818435

  1. Boundary layer flow of nanofluid over an exponentially stretching surface

    PubMed Central

    2012-01-01

    The steady boundary layer flow of nanofluid over an exponential stretching surface is investigated analytically. The transport equations include the effects of Brownian motion parameter and thermophoresis parameter. The highly nonlinear coupled partial differential equations are simplified with the help of suitable similarity transformations. The reduced equations are then solved analytically with the help of homotopy analysis method (HAM). The convergence of HAM solutions are obtained by plotting h-curve. The expressions for velocity, temperature and nanoparticle volume fraction are computed for some values of the parameters namely, suction injection parameter α, Lewis number Le, the Brownian motion parameter Nb and thermophoresis parameter Nt. PMID:22289390

  2. Effect of van der Waals interaction on the geometric and electronic properties of DNA nucleosides adsorbed on Cu(111) surface: a DFT study.

    PubMed

    Bogdan, Diana; Morari, Cristian

    2013-06-01

    The geometrical properties and electronic structure of DNA nucleosides (deoxyadenosine, thymidine, deoxyguanosine, deoxycytidine) adsorbed on a metallic surface of Cu(111) are determined using density functional theory computations. In order to assess the effect of the long-range interaction upon the results of the DFT simulations, we compare the results of a standard GGA exchange-correlation functional with those produced by the newly developed van der Waals exchange-correlation functional. The most striking difference between the two sets of results occurs for the adsorption energies: standard functional predicts values representing about 30% of those obtained when van der Waals interaction is taken into account. The standard GGA functional favors slightly tilted orientation of the DNA bases with respect to the surface, while the inclusion of the van der Waals effect leads to an almost parallel orientation of the bases with the surface. On the other hand, the position of the sugar pucker is less influenced by the type of the exchange-correlation used. According to our studies, in the presence of long-range interactions, the molecule-surface charge transfer is qualitatively affected. Standard functional predicts a decrease of the electronic population of the adsorbate, while the presence of long-range interaction leads to an opposite effect. PMID:23647023

  3. Nanofilms of hyaluronan/chitosan assembled layer-by-layer: An antibacterial surface for Xylella fastidiosa.

    PubMed

    Hernández-Montelongo, Jacobo; Nascimento, Vicente F; Murillo, Duber; Taketa, Thiago B; Sahoo, Prasana; de Souza, Alessandra A; Beppu, Marisa M; Cotta, Monica A

    2016-01-20

    In this work, nanofilms of hyaluronan/chitosan (HA/CHI) assembled layer by layer were synthesized; their application as a potential antimicrobial material was demonstrated for the phytopathogen Xylella fastidiosa, a gram-negative bacterium, here used as a model. For the synthesis, the influence of pH and ionic strength of these natural polymer stem-solutions on final characteristics of the HA/CHI nanofilms was studied in detail. The antibacterial effect was evaluated using widefield fluorescence microscopy. These results were correlated with the chemical properties of the nanofilms, studied by FTIR and Raman spectroscopy, as well as with their morphology and surface properties characterized using SEM and AFM. The present findings can be extended to design and optimize HA/CHI nanofilms with enhanced antimicrobial behavior for other type of phytopathogenic gram-negative bacteria species, such as Xanthomonas citri, Xanthomas campestri and Ralstonia solanacearum. PMID:26572322

  4. Trapping surface electrons on graphene layers and islands

    NASA Astrophysics Data System (ADS)

    Niesner, D.; Fauster, Th.; Dadap, J. I.; Zaki, N.; Knox, K. R.; Yeh, P.-C.; Bhandari, R.; Osgood, R. M.; Petrović, M.; Kralj, M.

    2012-02-01

    We report the use of time- and angle-resolved two-photon photoemission to map the bound, unoccupied electronic structure of the weakly coupled graphene/Ir(111) system. The energy, dispersion, and lifetime of the lowest three image-potential states are measured. In addition, the weak interaction between Ir and graphene permits observation of resonant transitions from an unquenched Shockley-type surface state of the Ir substrate to graphene/Ir image-potential states. The image-potential-state lifetimes are comparable to those of midgap clean metal surfaces. Evidence of localization of the excited electrons on single-atom-layer graphene islands is provided by coverage-dependent measurements.

  5. Layer by Layer, Nano-particle "Only" Surface Modification of Filtration Membranes

    NASA Astrophysics Data System (ADS)

    Escobar-Ferrand, Luis

    Layer by Layer (LbL) deposition using primarily inorganic silica nanoparticles is employed for the modification of polymeric micro and ultrafiltration (MF/UF) membranes to produce thin film composites (TFC) with potential nanofiltration (NF) and reverse osmosis (RO) capabilities.. A variety of porous substrate membranes with different membrane surface characteristics are employed, but exhibiting in common that wicking of water does not readily occur into the pore structure, including polycarbonate track etched (PCTE), polyethersulfone (PES) and sulfonated PES (SPEES) MF/UF membranes. Both spherical (cationic/anionic) and eccentric elongated (anionic) silica nanoparticles are deposited using conditions similar to those reported by Lee et al. Appropriate selection of the pH's for anionic and cationic particle deposition enables the construction of nanoparticle only layers 100--1200 nm in thickness atop the original membrane substrates. The surface layer thickness varies monotonically with the number of bilayers (anionic/cationic deposition cycles) as expected. The deposition process is optimized to eliminate drying induced cracking and to improve mechanical durability via thickness control and post-deposition hydro-thermal treatment. The hydrodynamic permeability of these TFC membranes is measured to evaluate their performance under typical NF operating conditions using dead-end permeation experiments and their performance compared quantitatively with realistic hydrodynamic models, with favorable results. For track etched polycarbonate MF substrates, surface modification causes a permeability reduction of approximately two orders of magnitude with respect to the bare substrates, to values comparable to those for typical commercial NF membranes. Good quantitative agreement with hydrodynamic models with no adjustable parameters was also established for this case, providing indirect confirmation that the LbL deposited surface layers are largely defect (crack) free

  6. What is really driving cell-surface interactions? Layer-by-layer assembled films may help to answer questions concerning cell attachment and response to biomaterials.

    PubMed

    Sergeeva, Yulia N; Huang, Tongtong; Felix, Olivier; Jung, Laura; Tropel, Philippe; Viville, Stephane; Decher, Gero

    2016-06-01

    Layer-by-layer (LbL) assembled multicomponent films offer the opportunity to control and to fine-tune cell attachment and behavior on solid surfaces [Layer-by-Layer Films for Biomedical Applications, edited by Picart et al. (Wiley, Weinheim, 2014) and El-Khouri et al., "Multifunctional layer-by-layer architectures for biological applications," in Functional Polymeric Ultrathin Films, edited by Advincula and Knoll (Wiley, Weinheim, 2011), Vol. 1]. At the same time, these films allow for quite detailed physicochemical characterization of static and dynamic surface properties that are typically not available in classic cell culture. In this report, the authors investigate cell adhesion and cytocompatibility of compositionally and morphologically similar thin films composed of oppositely charged synthetic or natural polyelectrolytes in which different physical parameters such as surface charge or water content are varied through chemical composition and deposition conditions. Human adult dermal fibroblasts were chosen as a model because of the need for chemically defined matrix in the field of primary cell amplification. The growth and the stability of the multilayer films in the incubation media were studied dissipation-enhanced quartz crystal micobalance (QCM-D) and ellipsometry. The QCM-D signals observed during the film deposition were analyzed qualitatively to estimate the viscoelastic properties of the films. The authors used contact angle measurements with water to study the contribution of the chemical functionalities to wetting behavior of the films. Most importantly, they also studied the interaction of the films with serum components. Our results underline that cell adhesion is a highly complex process which is not only governed by the functionality of a surface but also by its morphology, its affinity for serum components, and also by changes of surface properties brought about by adsorbing molecules. Of the many LbL-films tested, poly(4-styrenesulfonate

  7. Controlling the hydrophilicity and contact resistance of fuel cell bipolar plate surfaces using layered nanoparticle assembly

    NASA Astrophysics Data System (ADS)

    Wang, Feng

    Hybrid nanostructured coatings exhibiting the combined properties of electrical conductivity and surface hydrophilicity were obtained by using Layer-by-Layer (LBL) assembly of cationic polymer, silica nanospheres, and carbon nanoplatelets. This work demonstrates that by controlling the nanoparticle zeta (zeta) potential through the suspension parameters (pH, organic solvent type and amount, and ionic content) as well as the assembly sequence, the nanostructure and composition of the coatings may be adjusted to optimize the desired properties. Two types of silica nanospheres were evaluated as the hydrophilic component: X-TecRTM 3408 from Nano-X Corporation, with a diameter of about 20 nm, and polishing silica from Electron Microscopy Supply, with diameter of about 65 nm. Graphite nanoplatelets with a thickness of 5~10nm (Aquadag RTM E from Acheson Industries) were used as electrically conductive filler. A cationic copolymer of acrylamide and a quaternary ammonium salt (SuperflocRTM C442 from Cytec Corporation) was used as the binder for the negatively charged nanoparticles. Coatings were applied to gold-coated stainless steel substrates presently used a bipolar plate material for proton exchange membrane (PEM) fuel cells. Coating thickness was found to vary nearly linearly with the number of polymer-nanoparticle layers deposited while a monotonic increase in coating contact resistance was observed for all heterogeneous and pure silica coatings. Thickness increased if the difference in the oppositely charged zeta potentials of the adsorbing components was enhanced through alcohol addition. Interestingly, an opposite effect was observed if the zeta potential difference was increased through pH variation. This previously undocumented difference in adsorption behavior is herein related to changes to the surface chemical heterogeneity of the nanoparticles. Coating contact resistance and surface wettability were found to have a more subtle dependence on the assembly

  8. In vivo Measurement of the Mouse Pulmonary Endothelial Surface Layer

    PubMed Central

    Yang, Yimu; Yang, Gaoqing; Schmidt, Eric P.

    2013-01-01

    The endothelial glycocalyx is a layer of proteoglycans and associated glycosaminoglycans lining the vascular lumen. In vivo, the glycocalyx is highly hydrated, forming a substantial endothelial surface layer (ESL) that contributes to the maintenance of endothelial function. As the endothelial glycocalyx is often aberrant in vitro and is lost during standard tissue fixation techniques, study of the ESL requires use of intravital microscopy. To best approximate the complex physiology of the alveolar microvasculature, pulmonary intravital imaging is ideally performed on a freely-moving lung. These preparations, however, typically suffer from extensive motion artifact. We demonstrate how closed-chest intravital microscopy of a freely-moving mouse lung can be used to measure glycocalyx integrity via ESL exclusion of fluorescently-labeled high molecular weight dextrans from the endothelial surface. This non-recovery surgical technique, which requires simultaneous brightfield and fluorescent imaging of the mouse lung, allows for longitudinal observation of the subpleural microvasculature without evidence of inducing confounding lung injury. PMID:23462690

  9. Thermal stability of nanocrystalline layers fabricated by surface nanocrystallization

    NASA Astrophysics Data System (ADS)

    Mai, Yong-jin; Jie, Xiao-hua; Liu, Li-li; Yu, Neng; Zheng, Xiang-xin

    2010-01-01

    A nanocrystalline layer with ultrafine grains (about 30-40 nm) on the surface of 7050 aluminum alloy was fabricated by a new technique called High Pressure Shot Peening (HPSP) which is the combination of common Shot Peening equipment with a pressurizing vessel. Relationship between hot flow and temperature was observed by Differential Scanning Calorimetry (DSC) and the activation energy, calculated by Kisssinger equation, of the as-treated sample increased 26.6 kJ/mol when it is compared with the as-reserved sample. The Bragg peaks of the as-prepared samples, respectively treated with various annealing treatments were characterized by XRD and the microhardness distribution along the depth from the treated surface were measured at the same time, which indicated that the broadening of Bragg peaks decreased with the increasing of anneal temperature; the grain size, calculated by Scherrer-Wilson equation, increased obviously during 180-220 °C, accordingly, the microhardness obviously decreased. According to the results of DSC, XRD and microhardness, it is reasonable to deduce that the temperature range of thermal stability for aluminum alloy nanocrystalline layer is lower than 200 °C.

  10. Surface enhanced fluorescence of anti-tumoral drug emodin adsorbed on silver nanoparticles and loaded on porous silicon

    PubMed Central

    2012-01-01

    Fluorescence spectra of anti-tumoral drug emodin loaded on nanostructured porous silicon have been recorded. The use of colloidal nanoparticles allowed embedding of the drug without previous porous silicon functionalization and leads to the observation of an enhancement of fluorescence of the drug. Mean pore size of porous silicon matrices was 60 nm, while silver nanoparticles mean diameter was 50 nm. Atmospheric and vacuum conditions at room temperature were used to infiltrate emodin-silver nanoparticles complexes into porous silicon matrices. The drug was loaded after adsorption on metal surface, alone, and bound to bovine serum albumin. Methanol and water were used as solvents. Spectra with 1 μm spatial resolution of cross-section of porous silicon layers were recorded to observe the penetration of the drug. A maximum fluorescence enhancement factor of 24 was obtained when protein was loaded bound to albumin, and atmospheric conditions of inclusion were used. A better penetration was obtained using methanol as solvent when comparing with water. Complexes of emodin remain loaded for 30 days after preparation without an apparent degradation of the drug, although a decrease in the enhancement factor is observed. The study reported here constitutes the basis for designing a new drug delivery system with future applications in medicine and pharmacy. PMID:22748115

  11. Luminescence of quantum-dimensional centers with spatially ordered molecules of organic compunds adsorbed on their surfaces

    SciTech Connect

    Belous, V.M.

    1995-11-01

    A dimensional effect in the luminescence of a narrow-band silver sulfide semiconductor (with the width of the forbidden band E{sub g} = 0.9 eV) was discovered in 1977, when a luminescent method was used to study the nature and functions of the centers appearing as a result of sulfur sensitization of halogen-silver photographic emulsions. As is known, during the indicated sensitization, certain sulfur-containing compounds (usually, sodium thiosulfate) are introduced into a melted emulsion containing microcrystals of silver halide, thus promoting an increase in the photosensitivity of the emulsion layers. The reason for the observed increase in photosensitivity is the fact that during the interaction between sulfur-containing compounds and silver halide silver-sulfide centers arise on the surface of the emulsion microcrystals, which serve as deep traps for electrons and therefore determine the possibility for silver centers of latent image to be formed near them by a two-stage electron-ion mechanism. Measurement of the low-temperature (T = 77 K) luminescence spectra of different photographic emulsions containing AgBr, AgBr (I), or AgCl microcrystals made it possible to establish that the introduction of sulfur sensitizers (sodium thiosulfate or thiourea) into emulsion to increase its photosensitivity is accompanied by the appearance of new luminescence bands in the near IR spectral region.

  12. Photochemistry on surfaces: Fluorescence emission of monomers and dimers and triplet state absorption of acridine orange adsorbed on microcrystalline cellulose

    NASA Astrophysics Data System (ADS)

    Wilkinson, F.; Worrall, D. R.; Ferreira, L. F. Vieira

    1992-02-01

    Prompt fluorescence as well as delayed fluorescence emission of acridine orange was detected at room temperature from samples where this dye is adsorbed on microcrystalline cellulose. Ground state absorption studies provided evidence for dimer formation of the dye when adsorbed on cellulose, and the equilibrium constant for dimerisation was determined as 1.6±0.1 × 10 6mol -1g. At low loadings of acridine orange on cellulose (<1 μmol g -1) the fluorescence emission is mainly due to the monomer and is similar to that observed in ethanolic solutions where little aggregation occurs, and peaks at 530 nm. A linear dependence of the fluorescence intensity on the amount of light absorbed by the dye was established for these "diluted" samples. However, at higher loadings (>20 μmol g -1), the fluorescence intensity decreases, and the emission is broad with its maximum at 620 nm, and is mainly due to the dimer. By assuming that the excited monomer and dimer of acridine orange are the only emitting species, it was possible to determine the fluorescence quantum yields for these two species when adsorbed on microcrystalline cellulose as 0.95±0.05 and 0.40±0.10, respectively. Pulsed emission studies at room temperature in the millisecond time-range also revealed monomer and dimer emissions on this longer time-scale. These are shown to be due to thermally activated delayed fluorescence arising from the triplet states of monomer and dimer acridine orange as confirmed by diffuse reflectance transient absorption studies.

  13. Atomic layer deposition of ultrathin platinum films on tungsten atomic layer deposition adhesion layers: Application to high surface area substrates

    SciTech Connect

    Clancey, Joel W.; Cavanagh, Andrew S.; Kukreja, Ratandeep S.; Kongkanand, Anusorn; George, Steven M.

    2015-01-15

    Platinum (Pt) atomic layer deposition (ALD) usually yields Pt nanoparticles during initial film growth. In contrast, deposition of continuous and ultrathin Pt films is needed for many important applications, such as the oxygen reduction reaction in polymer electrolyte membrane (PEM) fuel cells. A continuous and high radius of curvature Pt film is more stable and has a higher area-specific activity than the Pt nanoparticles commonly used in PEM fuel cells. However, the Pt film must be ultrathin and have a large surface area to be cost effective. In this paper, a review of earlier Pt ALD studies on flat substrates is presented that demonstrates that tungsten, with a higher surface energy than platinum, can serve as an adhesion layer to achieve Pt ALD films that are continuous at ultrathin thicknesses of ∼1.5 nm. This work utilized MeCpPtMe{sub 3} and H{sub 2} plasma as the Pt ALD reactants. The deposition of continuous and ultrathin Pt ALD films using MeCpPtMe{sub 3} and H{sub 2} plasma as the reactants is then studied on two high surface area substrate materials: TiO{sub 2} nanoparticles and 3M nanostructured thin film (NSTF). Transmission electron microscopy (TEM) showed uniform and continuous Pt films with thicknesses of ∼4 nm on the TiO{sub 2} nanoparticles. TEM with electron energy loss spectroscopy analysis revealed W ALD and Pt ALD films with thicknesses of ∼3 nm that were continuous and conformal on the high aspect ratio NSTF substrates. These results demonstrate that cost effective use of Pt ALD on high surface area substrates is possible for PEM fuel cells.

  14. Conformational properties of an adsorbed charged polymer.

    PubMed

    Cheng, Chi-Ho; Lai, Pik-Yin

    2005-06-01

    The behavior of a strongly charged polymer adsorbed on an oppositely charged surface of a low-dielectric constant is formulated by the functional integral method. By separating the translational, conformational, and fluctuational degrees of freedom, the scaling behaviors for both the height of the polymer and the thickness of the diffusion layer are determined. Unlike the results predicted by scaling theory, we identified the continuous crossover from the weak compression to the compression regime. All the analytical results are found to be consistent with Monte Carlo simulations. Finally, an alternative (operational) definition of a charged polymer adsorption is proposed. PMID:16089715

  15. Real-time assessment of surface interactions with titanium passivation layer by surface plasmon resonance

    PubMed Central

    Hirata, Isao; Yoshida, Yasuhiro; Nagaoka, Noriyuki; Hiasa, Kyou; Abe, Yasuhiko; Maekawa, Kenji; Kuboki, Takuo; Akagawa, Yasumasa; Suzuki, Kazuomi; Van Meerbeek, Bart; Messersmith, Phillip B.; Okazaki, Masayuki

    2011-01-01

    The high corrosion resistance and strength-to-density ratio makes titanium widely used in major industry, but also in a gamut of medical applications. Here we report for the first time on our development of a titanium passivation layer sensor that makes use of surface plasmon resonance (SPR). The deposited titanium metal layer on the sensor was passivated in air, like titanium medical devices. Our ‘Ti-SPR sensor’ enables analysis of biomolecules interactions with the passivated surface of titanium in real time. As a proof of concept, corrosion of titanium passivation layer exposed to acid was monitored in real time. Also, the Ti-SPR sensor can accurately measure the time-dependence of protein adsorption onto titanium passivation layer with a sub-nanogram per square millimeter accuracy. Besides such SPR analyses, an SPR-imaging (SPRI) enables real-time assessment of chemical surface processes that occur simultaneously at ‘multiple independent spots’ on the Ti-SPR sensor, such as acid-corrosion or adhesion of cells. Our Ti-SPR sensor will therefore be very useful to study titanium-corrosion phenomena and biomolecular titanium-surface interactions with application in a broad range of industrial and biomedical fields. PMID:22154862

  16. Cryogenic adsorber design in a helium refrigeration system

    NASA Astrophysics Data System (ADS)

    Hu, Zhongjun; Zhang, Ning; Li, Zhengyu; Li, Q.

    2012-06-01

    The cryogenic adsorber is specially designed to eliminate impurities in gaseous helium such as O2, and N2 which is normally difficult to remove, based on the reversible cryotrapping of impurities on an activated carbon bed. The coconut shell activated carbon is adopted because of its developed micropore structure and specific surface area. This activated carbon adsorption is mostly determined by the micropore structure, and the adsorption rate of impurities is inversely proportional to the square of the particle sizes. The active carbon absorber's maximum permissible flow velocity is 0.25 m/s. When the gas flow velocity increases, the adsorption diffusion rate of the adsorbent is reduced, because an increase in the magnitude of the velocity resulted in a reduced amount of heat transfer to a unit volume of impure gas. According to the numerical simulation of N2 adsorption dynamics, the appropriate void tower link speed and the saturated adsorption capacity are determined. Then the diameter and height of the adsorber are designed. The mass transfer length should be taken into account in the adsorber height design. The pressure decrease is also calculated. The important factors that influence the adsorber pressure decrease are the void tower speed, the adsorbed layer height, and the active carbon particle shape and size.

  17. Crystalline Bacterial Surface Layer (S-Layer) Opens Golden Opportunities for Nanobiotechnology in Textiles.

    PubMed

    Asadi, Narges; Chand, Nima; Rassa, Mehdi

    2015-12-01

    This study focuses on the successful recrystallization of bacterial S-layer arrays of the Lactobacillus acidophilus ATCC 4356 at textile surfaces to create a novel method and material. Optimum bacterial growth was obtained at approximately 45 °C, pH 5.0, and 14 h pi. The cells were resuspended in guanidine hydrochloride and the 43 kDa S-protein was dialyzed and purified. The optimum reassembly on the polypropylene fabric surface in terms of scanning electron microscopy (SEM), reflectance, and uniformity (spectrophotometry) was obtained at 30 °C, pH 5.0 for 30 minutes in the presence of 2 gr/l (liquor ratio; 1:40) of the S-protein. Overall, our data showed that the functional aspects and specialty applications of the fabric would be very attractive for the textile and related sciences, and result in advanced technical textiles. PMID:26552090

  18. Numerical Computations of Hypersonic Boundary-Layer over Surface Irregularities

    NASA Technical Reports Server (NTRS)

    Chang, Chau-Lyan; Choudhari, Meelan M.; Li, Fei

    2010-01-01

    Surface irregularities such as protuberances inside a hypersonic boundary layer may lead to premature transition on the vehicle surface. Early transition in turn causes large localized surface heating that could damage the thermal protection system. Experimental measurements as well as numerical computations aimed at building a knowledge base for transition Reynolds numbers with respect to different protuberance sizes and locations have been actively pursued in recent years. This paper computationally investigates the unsteady wake development behind large isolated cylindrical roughness elements and the scaled wind-tunnel model of the trip used in a recent flight measurement during the reentry of space shuttle Discovery. An unstructured mesh, compressible flow solver based on the space-time conservation element, solution element (CESE) method is used to perform time-accurate Navier-Stokes calculations for the flow past a roughness element under several wind-tunnel conditions. For a cylindrical roughness element with a height to the boundary-layer thickness ratio from 0.8 to 2.5, the wake flow is characterized by a mushroom-shaped centerline streak and horse-shoe vortices. While time-accurate solutions converged to a steady-state for a ratio of 0.8, strong flow unsteadiness is present for a ratio of 1.3 and 2.5. Instability waves marked by distinct disturbance frequencies were found in the latter two cases. Both the centerline streak and the horse-shoe vortices become unstable downstream. The oscillatory vortices eventually reach an early breakdown stage for the largest roughness element. Spectral analyses in conjunction with the computed root mean square variations suggest that the source of the unsteadiness and instability waves in the wake region may be traced back to possible absolute instability in the front-side separation region.

  19. In situ modification of chromatography adsorbents using cold atmospheric pressure plasmas

    NASA Astrophysics Data System (ADS)

    Olszewski, P.; Willett, T. C.; Theodosiou, E.; Thomas, O. R. T.; Walsh, J. L.

    2013-05-01

    Efficient manufacturing of increasingly sophisticated biopharmaceuticals requires the development of new breeds of chromatographic materials featuring two or more layers, with each layer affording different functions. This letter reports the in situ modification of a commercial beaded anion exchange adsorbent using atmospheric pressure plasma generated within gas bubbles. The results show that exposure to He-O2 plasma in this way yields significant reductions in the surface binding of plasmid DNA to the adsorbent exterior, with minimal loss of core protein binding capacity; thus, a bi-layered chromatography material exhibiting both size excluding and anion exchange functionalities within the same bead is produced.

  20. Density functional theory study of SO2-adsorbed Ni(1 1 1) and hydroxylated NiO(1 1 1) surface

    NASA Astrophysics Data System (ADS)

    Wei, Xin; Dong, Chaofang; Chen, Zhanghua; Xiao, Kui; Li, Xiaogang

    2015-11-01

    Spin polarized, DFT + U periodic calculation is used as an effective way to model the adsorption process of SO2 on hydroxylated NiO(1 1 1) surface. The adsorption of atomic O and O2 on the clean Ni(1 1 1) surface is calculated to investigate the forming process of passive film. The molecular and dissociated adsorptions of H2O on NiO(1 1 1) surface are evaluated to construct defect-free hydroxylated NiO(1 1 1) surface. The adsorption of SO2 and atomic O on clean Ni(1 1 1) surface is also investigated to compare with the adsorption capacity between passive film and substrate. With respect to the single adsorption process of SO2 on defect-free hydroxylated NiO(1 1 1) surface, the effects of O vacancy of surface and atomic O closed to the surface are investigated. The calculation results show that there is no chemical adsorption of SO2 on the defect-free hydroxylated NiO(1 1 1) surface with or without atomic O. Either single SO2 or SO2 with atomic O prefer adsorbing on the hydroxylated NiO(1 1 1) surface with O vacancies. The adsorption behavior is strengthened with the increase of percentage of surface O vacancy. The existence of atomic O leads to the production of SO3 on the hydroxylated NiO(1 1 1) surface and strengthens the adsorption capacity of SO2. Furthermore, the results also reveal the relationship between the charge transfer and the adsorption energy of SO2 and atomic O on the hydroxylated NiO(1 1 1) surface and clean Ni(1 1 1) surface. We inferred that broken passive film susceptibility to corrosion compare with substrate when surface O vacancies aggregate and its concentration large enough.

  1. Characterization and seasonal variations of surface active substances in the natural sea surface micro-layers of the coastal Middle Adriatic stations

    NASA Astrophysics Data System (ADS)

    Frka, Sanja; Kozarac, Zlatica; Ćosović, Božena

    2009-12-01

    Surface micro-layer (ML) samples were collected in different seasons over a long time period in the coastal area of the Middle Adriatic Sea including the seawater Rogoznica lake location and the semi-enclosed estuarine Martinska station. Natural surface micro-layers were studied as original samples and as ex-situ reconstructed films after previous extraction by organic solvents of different polarities ( n-hexane and dichloromethane). Using alternating current (AC) voltammetry (out-of-phase mode) the concentration of surface active substances (SAS) in original ML of both locations was determined, and the enrichment factor (EF) in the ML was related to the underlayer water (ULW) samples collected at 0.5 m depth. Seasonal variability of SAS concentrations of the ML was observed at both locations. The ex-situ films were studied using a modified AC voltammetry method (out-of-phase mode) transferring an organic extract of natural micro-layers spread onto electrolyte from the air-water interface to the mercury electrode surface. The comparison of adsorption characteristics for model lipids of different polarities and those of transferred ex-situ reconstructed films has revealed that different types of lipid material were present in each ex-situ film of the same micro-layer. Additional characterization of the surface active material of natural MLs was carried out by AC voltammetry (in-phase mode) using cathodic reduction of cadmium ions as an indicator of permeability of different films adsorbed at the mercury electrode. The SAS of ML of both investigated locations induced an inhibition effect to the reduction of cadmium ions. Seasonal variations of inhibition have also been noticed. The electrochemical study contributed to the physicochemical characterization of the surface active matter of the surface micro-layer with the emphasis to the role of lipids which, although they represent a minor fraction of the total micro-layer organic material, contribute considerably to

  2. In situ transmission infrared spectroscopy of high-kappa oxide atomic layer deposition onto silicon surfaces

    NASA Astrophysics Data System (ADS)

    Ho, Ming-Tsung

    Ultra-thin aluminum oxide (Al2O3) and hafnium oxide (HfO2) layers have been grown by atomic layer deposition (ALD) using tri-methyl-aluminum (TMA) and tetrakis-ethyl-methyl-amino-hafnium (TEMAH) respectively with heavy water (D2O) as the oxidizing agent. Several different silicon surfaces were used as substrates such as hydrogen terminated silicon (H/Si), SC2 (or RCA 2) cleaned native silicon oxide (SiO 2/Si), and silicon (oxy)nitride. In-situ transmission Fourier transform infrared spectroscopy (FTIR) has been adopted for the study of the growth mechanisms during ALD of these films. The vibrational spectra of gas phase TEMAH and its reaction byproducts with oxidants have also been investigated. Density functional theory (DFT) normal mode calculations show a good agreement with the experimental data when it is combined with linear wave-number scaling method and Fermi resonance mechanism. Ether (-C-O-C-) and tertiary alkylamine (N(R1R 2R3)) compounds are the two most dominant products of TEMAH reacting with oxygen gas and water. When ozone is used as the oxidant, gas phase CH2O, CH3NO2, CH3-N=C=O and other compounds containing -(C=O)- and --C-O-C- (or --O-C-) segments are observed. With substrate temperatures less than 400°C and 300°C for TMA and TEMAH respectively, Al oxide and Hf oxide ALD can be appropriately performed on silicon surfaces. Thin silicon (oxy)nitride thermally grown in ammonia on silicon substrate can significantly reduce silicon oxide interlayer formation during ALD and post-deposition annealing. The crystallization temperature of amorphous ALD grown HfO2 on nitridized silicon is 600°C, which is 100°C higher than on the other silicon surfaces. When HfO2 is grown on H/Si(111) at 100°C deposition temperature, minimum 5--10 ALD cycles are required for the full surface coverage. The steric effect can be seen by the evolution of the H-Si stretching mode at 2083 cm-1. The observed red shift of H-Si stretching to ˜ 2060 cm-1 can be caused by Si

  3. Fabricating electrospun cellulose nanofibre adsorbents for ion-exchange chromatography

    PubMed Central

    Dods, Stewart R.; Hardick, Oliver; Stevens, Bob; Bracewell, Daniel G.

    2015-01-01

    Protein separation is an integral step in biopharmaceutical manufacture with diffusion-limited packed bed chromatography remaining the default choice for industry. Rapid bind-elute separation using convective mass transfer media offers advantages in productivity by operating at high flowrates. Electrospun nanofibre adsorbents are a non-woven fibre matrix of high surface area and porosity previously investigated as a bioseparation medium. The effects of compression and bed layers, and subsequent heat treatment after electrospinning cellulose acetate nanofibres were investigated using diethylaminoethyl (DEAE) or carboxylate (COO) functionalisations. Transbed pressures were measured and compared by compression load, COO adsorbents were 30%, 70% and 90% higher than DEAE for compressions 1, 5 and 10 MPa, respectively, which was attributed to the swelling effect of hydrophilic COO groups. Dynamic binding capacities (DBCs) at 10% breakthrough were measured between 2000 and 12,000 CV/h (2 s and 0.3 s residence times) under normal binding conditions, and DBCs increased with reactant concentration from 4 to 12 mg BSA/mL for DEAE and from 10 to 21 mg lysozyme/mL for COO adsorbents. Comparing capacities of compression loads applied after electrospinning showed that the lowest load tested, 1 MPa, yielded the highest DBCs for DEAE and COO adsorbents at 20 mg BSA/mL and 27 mg lysozyme/mL, respectively. At 1 MPa, DBCs were the highest for the lowest flowrate tested but stabilised for flowrates above 2000 CV/h. For compression loads of 5 MPa and 10 MPa, adsorbents recorded lower DBCs than 1 MPa as a result of nanofibre packing and reduced surface area. Increasing the number of bed layers from 4 to 12 showed decreasing DBCs for both adsorbents. Tensile strengths were recorded to indicate the mechanical robustness of the adsorbent and be related to packing the nanofibre adsorbents in large scale configurations such as pleated cartridges. Compared with an

  4. Exploring the bronzing effect at the surface of ink layers

    NASA Astrophysics Data System (ADS)

    Hébert, Mathieu; Mallet, Maxime; Deboos, Alexis; Chavel, Pierre; Kuang, Deng-Feng; Hugonin, Jean-Paul; Besbes, Mondher; Cazier, Anthony

    2015-03-01

    We investigate the optical phenomenon responsible for the colored shine that sometimes appears at the surface of ink layers in the specular direction, often called bronzing or gloss differential. It seems to come from the wavelength-dependent refractive index of the ink, which induces a wavelength-dependent reflectance of the ink-air interface. Our experiments on cyan and magenta inkjet inks confirm this theory. Complex refractive indices can be obtained from measurements of the spectral reflectance and transmittance of a transparency film coated with the ink. We propose a correction of the classical Clapper-Yule model in order to include the colored gloss in the prediction of the spectral reflectance of an inked paper. We also explored effects of scattering by the micrometric or nanometric roughness of the ink surface. The micrometric roughness, easy to model with a geometrical optics model, can predict the spreading of the colored gloss over a large cone. Electromagnetic models accounting for the effect of the nanometric roughness of the surface also predict the attenuation of short wavelengths observed under collimated illumination.

  5. Characterization of cathode keeper wear by surface layer activation

    NASA Technical Reports Server (NTRS)

    Polk, James E.

    2003-01-01

    In this study, the erosion rates of the discharge cathode keeper in a 30 cm NSTAR configuration ion thruster were measured using a technique known as Surface Layer Activation (SLA). This diagnostic technique involves producing a radioactive tracer in a given surface by bombardment with high energy ions. The decrease in activity of the tracer material may be monitored as the surface is subjected to wear processes and correlated to a depth calibration curve, yielding the eroded depth. Analysis of the activities was achieved through a gamma spectroscopy system. The primary objectives of this investigation were to reproduce erosion data observed in previous wear studies in order to validate the technique, and to determine the effect of different engine operating parameters on erosion rate. The erosion profile at the TH 15 (23 kw) setting observed during the 8200 hour Life Demonstration Test (LDT) was reproduced. The maximum keeper erosion rate at this setting was determined to be 0.085 pm/hr. Testing at the TH 8 (1.4 kw) setting demonstrated lower erosion rates than TH 15, along with a different wear profile. Varying the keeper voltage was shown to have a significant effect on the erosion, with a positive bias with respect to cathode potential decreasing the erosion rate significantly. Accurate measurements were achieved after operating times of only 40 to 70 hours, a significant improvement over other erosion diagnostic methods.

  6. Modelling boundary layer flow over barnacle-fouled surfaces

    NASA Astrophysics Data System (ADS)

    Sadique, Jasim; Yang, Xiang; Meneveau, Charles; Mittal, Rajat

    2014-11-01

    Macro-biofouling is a critical concern for the marine industry. However, there is little data on flow and drag over such surfaces. Accurate modelling of such multi-scale flows remains a big challenge. Such simulations are vital in providing insights into the fundamental flow physics, and they can be used to estimate the timing, need and effectiveness of measures used to counteract bio-fouling. This talk focuses on the use of a sharp-interface immersed boundary method coupled with a wall model and large-eddy simulations to carry out accurate simulations of a turbulent boundary layer flow over macro-fouled surfaces. For the current study, high resolution scans of barnacles were used to create simple geometrical representations. Simulations were then carried out to test how well these simpler geometric models mimic the flow over actual barnacles. Simulations of array of modeled barnacles, with different barnacle densities have also been carried out and we present results on the effect distribution density on the flow physics and drag on the surfaces. This work is funded by ONR Grant N00014-12-1-0582.

  7. Surface plasma source with anode layer plasma accelerator

    SciTech Connect

    Dudnikov, Vadim

    2012-02-15

    Proposed plasma generation system can be used for high current negative ion beam production and for directed deposition by flux of sputtered neutrals and negative ions. The main mechanism of negative ion formation in surface plasma sources is the secondary emission from low work function surface bombarded by a flux of positive ion or neutrals. The emission of negative ions is enhanced significantly by introducing a small amount of cesium or other substance with low ionization potential. In the proposed source are used positive ions generated by Hall drift plasma accelerator (anode layer plasma accelerator or plasma accelerator with insulated channel, with cylindrical or race track configuration of emission slit). The target-emitter is bombarded by the ion beam accelerated in crossed ExB fields. Negative ions are extracted from the target surface with geometrical focusing and are accelerated by negative voltage applied between emitter and plasma, contacting with the plasma accelerator. Hall drift ion source has a special design with a space for passing of the emitted negative ions and sputtered particles through the positive ion source.

  8. Conformational changes of adsorbed proteins

    NASA Astrophysics Data System (ADS)

    Allen, Scott

    2005-03-01

    The adsorption of bovine serum albumin (BSA) and pepsin to gold surfaces has been studied using surface plasmon resonance (SPR). Proteins are adsorbed from solution onto a gold surface and changes in the conformation of the adsorbed proteins are induced by changing the buffer solution. We selected pH and ionic strength values for the buffer solutions that are known from our circular dichroism measurements to cause conformational changes of the proteins in bulk solution. We find that for both BSA and pepsin the changes in conformation are impeded by the interaction of the protein with the gold surface.

  9. Can mobilization of the coarse surface layer release fine sediment trapped beneath the surface?

    NASA Astrophysics Data System (ADS)

    Wydzga, M. A.; Venditti, J. G.; Dunne, T.

    2006-12-01

    The U.S. EPA estimates that 40 percent of U.S. rivers are ecologically impaired by sedimentation. On dam- controlled rivers that are impaired by sedimentation, flushing flows with the potential to flush the fine sediments are commonly prescribed to improve ecological conditions. One goal of these flushing flows is to mobilize the riverbed's coarse surface layer and thus to create the potential to release fine sediment trapped beneath the surface. Given the economical value of water, releasing flows large enough to generate shear stresses adequate to mobilize the coarse surface can be difficult. Gravel augmentation using fine gravel has been recently demonstrated as a viable alternative to mobilizing coarse surface layers. This occurs because sheets of fine gravel smooth the bed, increasing the local shear stress available to move the grains. Does the mobilization of the coarse surface layer by fine gravel increase the depth to which fines are selectively removed or decrease the amount of fine sediment in the bed subsurface? To answer this question we conducted two series of laboratory experiments designed to flush or selectively remove fine sediment from the bed subsurface in a 28 m long and 0.86 m wide gravel-bedded flume channel. Before each experiment, we fed fine sediment (2,000 g/min; D50 = 0.4 mm) into the flume to saturate the gravel bed (D50 = 10 mm). The flow during the infiltration period was competent to transport the sand as bedload but not to suspend it (Q = 0.05 m3/s). In the first series of experiments, we attempted to flush the fine sediment from a non-mobile bed with a steady flow that was not competent to mobilize the coarse surface layer (Q = 0.205 m3/s). In the second set of experiments, the magnitude (Q = 0.205 m3/s) and duration of the flow conditions were the same; however, we fed fine gravel into the flume that moved thru the flume as bedload sheets and mobilized the coarse surface layer. After each experiment, we photographed the bed

  10. Force constants and bond polarizabilities of thiocyanate ion adsorbed on the silver electrode as interpreted from the surface enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Huang, Yi; Wu, Guozhen

    1989-01-01

    The surface enhanced Raman spectra of the thiocyanate ion is studied in two ways. First, normal mode analysis is employed to determine the force constants of the adsorbed thiocyanate ion. The result shows that the force constant for the CN bond becomes larger while that for the SC bond smaller in the adsorbed state. The adatom model with an effective silver mass of 0.1 mAg ( mAg being the mass of the silver atom) is adequate for the analysis. This implies that the silver adatom is bound to the bulk electrode surface. The adsorption is also shown to be physical. Second, the SER intensifies are analyzed to obtain the molecular polarizability derivatives. The result shows that the polarizability derivative of the CN stretching motion is most responsive to the applied voltage. The polarizability derivative of the SC stretching motion is much smaller than that of the CN bond as compared in the solution. This conclusion is attributed to the adsorption center at the sulfur atom. In general, molecular polarizability derivatives are functions of the frequencies of the exciting lasers and the applied voltages on the electrode.

  11. The theoretical model of atmospheric turbulence spectrum in surface layer

    NASA Astrophysics Data System (ADS)

    Liu, Shida; Liu, Shikuo; Xin, Guojun; Liang, Fuming

    1994-12-01

    It is shown that the slope of energy spectrum obtained from the velocity solution of Kdv—Burgers equation lies between —5/3 and—2 in the dilogarithmic coordinates paper. The spectrum is very close to one of Kolmogorov's isotropic turbulence and Frisch's intermittent turbulence in inertial region. In this paper, the Kdv-Burgers equation to describe atmospheric boundary layer turbulence is obtained. In the equation, the 1 / R e corresponds to dissipative coefficient v, R /2 t to dispersive coefficient β, then ( v/2 β)2 corresponds to 1 / R 2 e • Ri. We prove that the wave number corresponding to maximum energy spectrum S(k) decreases with the decrease of stability (i.e., the increase of ( v / 2 β)2 in eddy—containing region. And the spectrim amplitude decreases with the increase of ( v / 2 β)2 (i.e., the decrease of stability). These results are consistent with actual turbulence spectrum of atmospheric surface layer from turbulence data.

  12. GYROSCOPIC PUMPING IN THE SOLAR NEAR-SURFACE SHEAR LAYER

    SciTech Connect

    Miesch, Mark S.; Hindman, Bradley W.

    2011-12-10

    We use global and local helioseismic inversions to explore the prevailing dynamical balances in the solar near-surface shear layer (NSSL). The differential rotation and meridional circulation are intimately linked, with a common origin in the turbulent stresses of the upper solar convection zone. The existence and structure of the NSSL cannot be attributed solely to the conservation of angular momentum by solar surface convection, as is often supposed. Rather, the turbulent angular momentum transport accounts for the poleward meridional flow while the often overlooked meridional force balance is required to maintain the mid-latitude rotational shear. We suggest that the base of the NSSL is marked by a transition from baroclinic to turbulent stresses in the meridional plane which suppress Coriolis-induced circulations that would otherwise establish a cylindrical rotation profile. The turbulent angular momentum transport must be nondiffusive and directed radially inward. Inferred mean flows are consistent with the idea that turbulent convection tends to mix angular momentum but only if the mixing efficiency is inhomogeneous and/or anisotropic. The latitudinal and longitudinal components of the estimated turbulent transport are comparable in amplitude and about an order of magnitude larger than the vertical component.