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Sample records for adsorbed surface layers

  1. 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

  2. Characterization of the surface-active components of sugar beet pectin and the hydrodynamic thickness of the adsorbed pectin layer.

    PubMed

    Siew, Chee Kiong; Williams, Peter A; Cui, Steve W; Wang, Qi

    2008-09-10

    The fraction of sugar beet pectin (SBP) adsorbed onto limonene oil droplets during emulsification has been isolated, and its chemical and physicochemical characteristics have been determined. While the SBP sample itself was found to contain 2.67 and 1.06% protein and ferulic acid, respectively, the adsorbed fraction contained 11.10% protein and 2.16% ferulic acid. The adsorbed fraction was also found to have a higher degree of acetylation, notably at the C2 position on the galacturonic acid residues, and was also found to contain a higher proportion of neutral sugars, which are present in the ramified side chains of the pectin molecules. The thickness of the layer of SBP adsorbed onto polystyrene latex particles was studied by dynamic light scattering and was found to increase with increasing surface coverage. It was found to have a value of approximately 140 nm at plateau coverage, which closely corresponded to the hydrodynamic diameter of the pectin chains. The adsorbed layer thickness was found to be sensitive to pH and the presence of electrolyte. The thickness at a surface coverage of approximately 20 mg/m(2) in the absence of electrolyte at pH approximately 4 was 107 nm and at pH 8.8 was 70 nm, while at pH approximately 4 in the presence of 10 mM NaCl the thickness was found to be 70 nm. It was concluded that the SBP molecules form multilayers at the surface due to electrostatic interaction between the positively charged protein moieties and the galacturonic acid residues. The removal of calcium from the SBP had no effect on the adsorbed layer thickness; hence, multilayer formation due to calcium ion cross-linking was considered unlikely.

  3. 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.

  4. 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.

  5. Atomic force microscopy study of the interaction between adsorbed poly(ethylene oxide) layers: effects of surface modification and approach velocity.

    PubMed

    McLean, Scott C; Lioe, Hadi; Meagher, Laurence; Craig, Vincent S J; Gee, Michelle L

    2005-03-15

    The interaction forces between layers of the triblock copolymer Pluronic F108 adsorbed onto hydrophobic radio frequency glow discharge (RFGD) thin film surfaces and hydrophilic silica, in polymer-free 0.15 M NaCl solution, have been measured using the atomic force microscope (AFM) colloid probe technique. Compression of Pluronic F108 layers adsorbed on the hydrophobic RFGD surfaces results in a purely repulsive force due to the steric overlap of the layers, the form of which suggests that the PEO chains adopt a brush conformation. Subsequent fitting of these data to the polymer brush models of Alexander-de Gennes and Milner, Witten, and Cates confirms that the adsorbed Pluronic F108 adsorbs onto hydrophobic surfaces as a polymer brush with a parabolic segment density profile. In comparison, the interaction between Pluronic F108 layers adsorbed on silica exhibits a long ranged shallow attractive force and a weaker steric repulsion. The attractive component is reasonably well described by van der Waals forces, but polymer bridging cannot be ruled out. The weaker steric component of the force suggests that the polymer is less densely packed on the surface and is less extended into solution, existing as polymeric isolated mushrooms. When the surfaces are driven together at high piezo ramp velocities, an additional repulsive force is measured, attributable to hydrodynamic drainage forces between the surfaces. In comparing theoretical predictions of the hydrodynamic force to the experimentally obtained data, agreement could only be obtained if the flow profile of the aqueous solution penetrated significantly into the polymer brush. This finding is in line with the theoretical predictions of Milner and provides further evidence that the segment density profile of the adsorbed polymer brush is parabolic. A velocity dependent additional stepped repulsive force, reminiscent of a solvation oscillatory force, is also observed when the adsorbed layers are compressed under high

  6. Surface rheology of PEO-PPO-PEO triblock copolymers at the air-water interface: comparison of spread and adsorbed layers.

    PubMed

    Blomqvist, B Rippner; Wärnheim, T; Claesson, P M

    2005-07-01

    The dilatational rheological properties of monolayers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)-type block copolymers at the air-water interface have been investigated by employing an oscillating ring trough method. The properties of adsorbed monolayers were compared to spread layers over a range of surface concentrations. The studied polymers were PEO26-PPO39-PEO26 (P85), PEO103-PPO40-PEO103 (F88), and PEO99-PPO65-PEO99 (F127). Thus, two of the polymers have similar PPO block size and two of them have similar PEO block size, which allows us to draw conclusions about the relationship between molecular structure and surface dilatational rheology. The dilatational properties of adsorbed monolayers were investigated as a function of time and bulk solution concentration. The time dependence was found to be rather complex, reflecting structural changes in the layer. When the dilatational modulus measured at different concentrations was replotted as a function of surface pressure, one unique master curve was obtained for each polymer. It was found that the dilatational behavior of spread (Langmuir) and adsorbed (Gibbs) monolayers of the same polymer is close to identical up to surface concentrations of approximately 0.7 mg/m2. At higher coverage, the properties are qualitatively alike with respect to dilatational modulus, although some differences are noticeable. Relaxation processes take place mainly within the interfacial layers by a redistribution of polymer segments. Several conformational transitions were shown to occur as the area per molecule decreased. PEO desorbs significantly from the interface at segmental areas below 20 A(2), while at higher surface coverage, we propose that segments of PPO are forced to leave the interface to form a mixed sublayer in the aqueous region. PMID:15982044

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

    PubMed

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

    2015-09-14

    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. PMID:26374054

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

    PubMed

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

    2015-09-14

    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. Dynamics in Adsorbed Homopolymer Layers: Entanglements and Osmotic Effects

    NASA Astrophysics Data System (ADS)

    Santore, Maria; Mubarekyan, Ervin

    2001-03-01

    This work seeks the dynamic mechanism for the exchange of homopolymer chains between a dilute solution and a layer adsorbed at the solid-liquid interface. With the model system of polyethylene oxide (PEO) adsorbed onto silica from aqueous solution, it is shown that the behavior of saturated interfaces compared to starved layers reveals an interesting trend: The characteristic self exchange time is dependent only on coverage, not molecular weight, for chains of 100K or less. Therefore, it is concluded that classical entanglements do not play a role below 100K. For all molecular weights, when the coverage of 0.2 mg/m2 is exceeded, the interfacial dynamics become slow. At lower coverages, chains lie flat in train, with no loops or tails, and no lateral interactions either. The onset of slow dynamics at higher coverages may be a result of both surface crowding and the resistance of loops and tails to new chains approaching the layer.

  12. The origin and characterization of conformational heterogeneity in adsorbed polymer layers

    NASA Astrophysics Data System (ADS)

    Douglas, Jack F.; Schneider, Hildegard M.; Frantz, Peter; Lipman, Robert; Granick, Steve

    1997-09-01

    The equilibration of polymer conformations tends to be sluggish in polymer layers adsorbed onto highly attractive substrates, so the structure of these layers must be understood in terms of the layer growth process rather than equilibrium theory. Initially adsorbed chains adopt a highly flattened configuration while the chains which arrive later must adapt their configurations to the increasingly limited space available for adsorption. Thus, the chains adsorbed in the late stage of deposition are more tenuously attached to the surface. This type of non-equilibrium growth process is studied for polymethylmethacrylate (PMMA) adsorbed on oxidized silicon where the segmental attraction is strong (0953-8984/9/37/005/img7/segment) and for polystyrene (PS) adsorbed on oxidized silicon from a carbon tetrachloride solution where the segmental attraction is relatively weak (0953-8984/9/37/005/img8/segment). Measurements were based on Fourier transform infrared spectroscopy in attenuated total reflection (FTIR - ATR). In both cases, the chains arriving first adsorbed more tightly, became flattened (as measured by the dichroic ratio), and occupied a disproportionately large fraction of the surface. This non-uniform structure persisted indefinitely for the strongly adsorbed PMMA chains, while the PS chains exhibited a gradual evolution, presumably reflecting an equilibration of the adsorbed layer occurring after long times. On the theoretical side, the initial heterogeneity of these adsorbed polymer layers is modelled using a random sequential adsorption (RSA) model where the size of the adsorbing species is allowed to adapt to the surface space available at the time of adsorption. The inhomogeneity in the size of adsorbing species (hemispheres) in this model is similar to the distribution of chain contacts in our measurements on adsorbed polymer layers. Owing to extensive variance around the mean, conformations having the mean number of chain contacts are least probable, which

  13. Bowl inversion of surface-adsorbed sumanene.

    PubMed

    Jaafar, Rached; Pignedoli, Carlo A; Bussi, Giovanni; Aït-Mansour, Kamel; Groening, Oliver; Amaya, Toru; Hirao, Toshikazu; Fasel, Roman; Ruffieux, Pascal

    2014-10-01

    Bowl-shaped π-conjugated compounds offer the possibility to study curvature-dependent host-guest interactions and chemical reactivity in ideal model systems. For surface-adsorbed π bowls, however, only conformations with the bowl opening pointing away from the surface have been observed so far. Here we show for sumanene on Ag(111) that both bowl-up and bowl-down conformations can be stabilized. Analysis of the molecular layer as a function of coverage reveals an unprecedented structural phase transition involving a bowl inversion of one-third of the molecules. On the basis of scanning tunneling microscopy (STM) and complementary atomistic simulations, we develop a model that describes the observed phase transition in terms of a subtle interplay between inversion-dependent adsorption energies and intermolecular interactions. In addition, we explore the coexisting bowl-up and -down conformations with respect to host-guest binding of methane. STM reveals a clear energetic preference for methane binding to the concave face of sumanene. PMID:25181621

  14. Adsorbed layers and the origin of Amontons' laws

    NASA Astrophysics Data System (ADS)

    Robbins, Mark

    2000-03-01

    Three hundred years ago, Amontons wrote down phenomenogical friction laws that are still used today. They state that the friction is proportional to load, and independent of the dimensions of the contacting surfaces. The molecular underpinning of these laws has remained unclear. Indeed, exact analytic results and experiments in ultra-high vacuum indicate that the static friction between clean crystalline surfaces almost always vanishes in the thermodynamic limit. Of course any surface exposed to air is typically coated by a thin layer of hydrocarbons, water and other small molecules. Simulations are presented that show that these layers naturally produce static and kinetic friction forces that are consistent with Amontons' laws and other aspects of macroscopic experiments.(G. He, M. H. Muser and M. O. Robbins, Science 284, 1650 (1999).) For example, the friction is only weakly dependent on parameters that are not controlled in most experiments, such as the areal density of adsorbed molecules, their length, the orientation of the surfaces and the direction of sliding. The kinetic friction is of the same order as the static friction and varies only logarithmically with velocity.

  15. Activity of lactoperoxidase when adsorbed on protein layers.

    PubMed

    Haberska, Karolina; Svensson, Olof; Shleev, Sergey; Lindh, Liselott; Arnebrant, Thomas; Ruzgas, Tautgirdas

    2008-09-15

    Lactoperoxidase (LPO) is an enzyme, which is used as an antimicrobial agent in a number of applications, e.g., food technology. In the majority of applications LPO is added to a homogeneous product phase or immobilised on product surface. In the latter case, however, the measurements of LPO activity are seldom reported. In this paper we have assessed LPO enzymatic activity on bare and protein modified gold surfaces by means of electrochemistry. It was found that LPO rapidly adsorbs to bare gold surfaces resulting in an amount of LPO adsorbed of 2.9mg/m(2). A lower amount of adsorbed LPO is obtained if the gold surface is exposed to bovine serum albumin, bovine or human mucin prior to LPO adsorption. The enzymatic activity of the adsorbed enzyme is in general preserved at the experimental conditions and varies only moderately when comparing bare gold and gold surface pretreated with the selected proteins. The measurement of LPO specific activity, however, indicate that it is about 1.5 times higher if LPO is adsorbed on gold surfaces containing a small amount of preadsorbed mucin in comparison to the LPO directly adsorbed on bare gold.

  16. Infrared Analysis Of Enzymes Adsorbed Onto Model Surfaces

    NASA Astrophysics Data System (ADS)

    Story, Gloria M.; Rauch, Deborah S.; Brode, Philip F.; Marcott, Curtis A.

    1989-12-01

    The adsorption of the enzymes, subtilisin BPN' and lysozyme, onto model surfaces was examined using attenuated total reflectance (ATR) infrared (IR) spectroscopy. Using a cylindrical internal reflection (CIRcle) cell with a Germanium (Ge) internal reflection element (IRE), model hydrophilic surfaces were made by plasma cleaning the IRE and model hydrophobic surfaces were made by precoating the IRE with a thin film of polystyrene. Gas chromatography (GC)-IR data collection software was used to monitor adsorption kinetics during the first five minutes after injection of the enzyme into the CIRcle cell. It was found that for both lysozyme and BPN', most of the enzyme that was going to adsorb onto the model surface did so within ten seconds after injection. Nearly an order-of-magnitude more BPN' adsorbed on the hydrophobic Ge surface than the hydrophilic one, while lysozyme adsorbed somewhat more strongly to the hydrophilic Ge surface. Overnight, the lysozyme layer continued to increase in thickness, while BPN' maintained its initial coverage. The appearance of carboxylate bands in some of the adsorbed BPN' spectra suggests the occurrence of peptide bond hydrolysis. A Au/Pd coating on the CIRcle cell o-rings had a significant effect on the adsorption of BPN'. (This coating was applied in an attempt to eliminate interfering Teflon absorption bands.) An apparent electrochemical reaction occurred, involving BPN', Ge, Au/Pd, and the salt solution used to stabilize BPN'. The result of this reaction was enhanced adsorption of the enzyme around the coated o-rings, etching of the Ge IRE at the o-ring site, and some autolysis of the enzyme. No such reaction was observed with lysozyme.

  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. Surface properties of mesoporous carbon-silica gel adsorbents

    SciTech Connect

    Leboda, R.; Turov, V.V.; Charmas, B.; Skubiszewska-Zieba, J.; Gun'ko, V.M.

    2000-03-01

    Carbon/silica (carbosil) samples prepared utilizing mesoporous silica gel (Si-60) modified by methylene chloride pyrolysis were studied by nitrogen adsorption, quasi-isothermal thermogravimetry, p-nitrophenol adsorption from aqueous solution, and {sup 1}H NMR methods. The structural characteristics and other properties of carbosils depend markedly on the synthetic conditions and the amount of carbon deposited. The changes in the pore size distribution with increasing carbon concentration suggest grafting of carbon mainly in pores, leading to diminution of the mesopore radii. However, heating pure silica gel at the pyrolysis temperature of 550 C leads to an increase in the pore radii. The quasi-isothermal thermogravimetry and {sup 1}H NMR spectroscopy methods used to investigate the water layers on carbosils showed a significant capability of carbosils to adsorb water despite a relatively large content of the hydrophobic carbon deposit, which represents a nonuniform layer incompletely covering the oxide surface.

  19. 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.

  20. Structure of polymer layers adsorbed from concentrated solutions

    NASA Astrophysics Data System (ADS)

    Auvray, Loïc; Auroy, Philippe; Cruz, Margarida

    1992-06-01

    We study by neutron scattering the interfacial strucuture of poly(dimethylsiloxane) layers irreversibly adsorbed from concentrated solutions or melts. We first measure the thickness h of the layers swollen by a good solvent as a function of the chain polymerisation index N and of the polymer volume fraction in the initial solution Φ. The relation h ≈ N^{0.8}Φ^{0.3}, recently predicted from an analogy between irreversibly adsorbed layers and grafted polymer brushes, describes well our results. We can therefore deduce that there is at least one large loop of about N monomers per adsorbed chain. We also study the shape of the polymer concentration profile in the layers by measuring on two samples the polymer-solid partial structure factor, that is proportional to the Fourier transform of the profile. The model of pseudobrushes predicts a concentration decay varying with the distance of the wall z as z^{-2/5}. This power law profile accounts quantitatively for the angular variation of the polymer-solid cross structure factor but it is difficult to distinguish it without anbiguity from less singular profiles. It implies that the adsorption of PDMS onto silica is sufficiently strong and fast to quench completely the loop distribution in the initial layer. Nous étudions par diffusion de neutrons la structure interfaciale de couches de poly(diméthylsiloxane) irréversiblement adsorbées sur de la silice à partir de solutions semidiluées et de fondus. Nous mesurons d'abord l'épaisseur h des couches gonflées par un bon solvant en fonction du degré de polymérisation des chaînes N et de la fraction volumique dans la solution initiale Φ. La relation h≈ N^{0.8}Φ^{0.3} récemment prédite à partir de l'analogie entre couches irréversiblement adsorbées et brosses de polymères greffés décrit bien nos résultats. Nous en déduisons qu'il existe au moins une grande boucle d'environ N monomères par chaîne adsorbée. Nous étudions aussi la forme du profil de

  1. 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

  2. Compliant layer chucking surface

    DOEpatents

    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.

  3. 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.

  4. Surface atomic relaxation and magnetism on hydrogen-adsorbed Fe(110) surfaces from first principles

    NASA Astrophysics Data System (ADS)

    Chohan, Urslaan K.; Jimenez-Melero, Enrique; Koehler, Sven P. K.

    2016-11-01

    We have computed adsorption energies, vibrational frequencies, surface relaxation and buckling for hydrogen adsorbed on a body-centred-cubic Fe(110) surface as a function of the degree of H coverage. This adsorption system is important in a variety of technological processes such as the hydrogen embrittlement in ferritic steels, which motivated this work, and the Haber-Bosch process. We employed spin-polarised density functional theory to optimise geometries of a six-layer Fe slab, followed by frozen mode finite displacement phonon calculations to compute Fe-H vibrational frequencies. We have found that the quasi-threefold (3f) site is the most stable adsorption site, with adsorption energies of ∼3.0 eV/H for all coverages studied. The long-bridge (lb) site, which is close in energy to the 3f site, is actually a transition state leading to the stable 3f site. The calculated harmonic vibrational frequencies collectively span from 730 to 1220 cm-1, for a range of coverages. The increased first-to-second layer spacing in the presence of adsorbed hydrogen, and the pronounced buckling observed in the Fe surface layer, may facilitate the diffusion of hydrogen atoms into the bulk, and therefore impact the early stages of hydrogen embrittlement in steels.

  5. 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.

  6. 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

  7. Concentration and saturation effects of tethered polymer chains on adsorbing surfaces

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

    We consider end-grafted chains at an adsorbing surface under good solvent conditions using Monte Carlo simulations and scaling arguments. Grafting of chains allows us to fix the surface concentration and to study a wide range of surface concentrations from the undersaturated state of the surface up to the brushlike regime. The average extension of single chains in the direction parallel and perpendicular to the surface is analyzed using scaling arguments for the two-dimensional semidilute surface state according to Bouchaud and Daoud [J. Phys. (Paris) 48, 1991 (1987)]. We find good agreement with the scaling predictions for the scaling in the direction parallel to the surface and for surface concentrations much below the saturation concentration (dense packing of adsorption blobs). Increasing the grafting density we study the saturation effects and the oversaturation of the adsorption layer. In order to account for the effect of excluded volume on the adsorption free energy we introduce a new scaling variable related with the saturation concentration of the adsorption layer (saturation scaling). We show that the decrease of the single chain order parameter (the fraction of adsorbed monomers on the surface) with increasing concentration, being constant in the ideal semidilute surface state, is properly described by saturation scaling only. Furthermore, the simulation results for the chains' extension from higher surface concentrations up to the oversaturated state support the new scaling approach. The oversaturated state can be understood using a geometrical model which assumes a brushlike layer on top of a saturated adsorption layer. We provide evidence that adsorbed polymer layers are very sensitive to saturation effects, which start to influence the semidilute surface scaling even much below the saturation threshold.

  8. 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.

  9. 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.

  10. 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

  11. Adsorbate-catalyzed layer-by-layer metal dissolution in inert electrolyte: Pd(100)-c(2 × 2)-I

    NASA Astrophysics Data System (ADS)

    Schimpf, Jane A.; Abreu, Juan B.; Carrasquillo, Arnaldo; Soriaga, Manuel P.

    1994-08-01

    Studies on the corrosion of Pd in inert ( halide-free) H 2SO 4 solution, catalyzed by a single adsorbed layer of iodine, have been extended to a Pd(100) single-crystal electrode that contained an ordered c(2 × 2) adlattice of iodine. Experimental measurements were based upon a combination of linear-sweep voltammetry, potential-step coulometry, low-energy electron diffraction, and Auger electron spectroscopy. As was earlier noted with polycrystalline electrodes, Pd dissolution occurred only when iodine was present on the surface. More significantly, neither the coverage nor the ordered structure of the iodine adlattice was affected by the dissolution process. These observations strongly suggest that the iodine-catalyzed corrosion occurs one layer at a time.

  12. Bubble-surface interactions with graphite in the presence of adsorbed carboxymethylcellulose.

    PubMed

    Wu, Jueying; Delcheva, Iliana; Ngothai, Yung; Krasowska, Marta; Beattie, David A

    2015-01-21

    The adsorption of carboxymethylcellulose (CMC), and the subsequent effect on bubble-surface interactions, has been studied for a graphite surface. CMC adsorbs on highly oriented pyrolytic graphite (HOPG) in specific patterns: when adsorbed from a solution of low concentration it forms stretched, isolated and sparsely distributed chains, while upon adsorption from a solution of higher concentration, it forms an interconnected network of multilayer features. The amount and topography of the adsorbed CMC affect the electrical properties as well as the wettability of the polymer-modified HOPG surface. Adsorption of CMC onto the HOPG surface causes the zeta potential to be more negative and the modified surface becomes more hydrophilic. This increase in both the absolute value of zeta potential and the surface hydrophilicity originates from the carboxymethyl groups of the CMC polymer. The effect of the adsorbed polymer layer on wetting film drainage and bubble-surface/particle attachment was determined using high speed video microscopy to monitor single bubble-surface collision, and single bubble Hallimond tube flotation experiments. The time of wetting film drainage and the time of three-phase contact line spreading gets significantly longer for polymer-modified HOPG surfaces, indicating that the film rupture and three-phase contact line expansion were inhibited by the presence of polymer. The effect of longer drainage times and slower dewetting correlated with reduced flotation recovery. The molecular kinetic (MK) model was used to quantify the effect of the polymer on dewetting dynamics, and showed an increase in the jump frequency for the polymer adsorbed at the higher concentration.

  13. Volumetric Interpretation of Protein Adsorption: Interfacial Packing of Protein Adsorbed to Hydrophobic Surfaces from Surface-Saturating Solution Concentrations

    PubMed Central

    Kao, Ping; Parhi, Purnendu; Krishnan, Anandi; Noh, Hyeran; Haider, Waseem; Tadigadapa, Srinivas; Allara, David L.; Vogler, Erwin A.

    2010-01-01

    The maximum capacity of a hydrophobic adsorbent is interpreted in terms of square or hexagonal (cubic and face-centered-cubic, FCC) interfacial packing models of adsorbed blood proteins in a way that accommodates experimental measurements by the solution-depletion method and quartz-crystal-microbalance (QCM) for the human proteins serum albumin (HSA, 66 kDa), immunoglobulin G (IgG, 160 kDa), fibrinogen (Fib, 341 kDa), and immunoglobulin M (IgM, 1000 kDa). A simple analysis shows that adsorbent capacity is capped by a fixed mass/volume (e.g. mg/mL) surface-region (interphase) concentration and not molar concentration. Nearly analytical agreement between the packing models and experiment suggests that, at surface saturation, above-mentioned proteins assemble within the interphase in a manner that approximates a well-ordered array. HSA saturates a hydrophobic adsorbent with the equivalent of a single square-or-hexagonally-packed layer of hydrated molecules whereas the larger proteins occupy two-or-more layers, depending on the specific protein under consideration and analytical method used to measure adsorbate mass (solution depletion or QCM). Square-or-hexagonal (cubic and FCC) packing models cannot be clearly distinguished by comparison to experimental data. QCM measurement of adsorbent capacity is shown to be significantly different than that measured by solution depletion for similar hydrophobic adsorbents. The underlying reason is traced to the fact that QCM measures contribution of both core protein, water of hydration, and interphase water whereas solution depletion measures only the contribution of core protein. It is further shown that thickness of the interphase directly measured by QCM systematically exceeds that inferred from solution-depletion measurements, presumably because the static model used to interpret solution depletion does not accurately capture the complexities of the viscoelastic interfacial environment probed by QCM. PMID:21035180

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

    USGS Publications Warehouse

    Thomas, J.; 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.

  15. 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.

  16. Photoacoustic spectra of malachite green adsorbed on silica gel surface

    NASA Astrophysics Data System (ADS)

    Sikorska, Anna; Zachara, Stanislaw

    1992-11-01

    Photoacoustic spectra of malachite green adsorbed on silica gel were investigated at high dye concentrations. The measurements were carried out for two markedly differing layer thicknesses of dyed silica. The ratio of maxima of two characteristic dye bands at (lambda) equals 620 nm and (lambda) equals 425 nm was chosen as an indicator of concentration dependent changes in the shapes of the photoacoustic spectra investigated. The comparison of experimental data with the theoretical model implies that the changes observed in the shape of the spectrum result first of all from the mechanism of the signal generation in inhomogeneous medium.

  17. 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.

  18. Charge transfer during alkali-surface adsorbate collisions

    NASA Astrophysics Data System (ADS)

    Yang, Ye

    The study of charge transfer process between atomic particles and surface adsorbates is important, from both fundamental and practical points of view. Resonant charge transfer (RCT) process during the scattering of low-energy alkali ions from surfaces is proven to depend on the surface local electrostatic potential (LEP). This dissertation investigates the surface electronic environment around halogen and hydrogen adatoms on transition metal and silicon surfaces by using alkali ion scattering. Charge transfer in 7Li+ scattering from clean Si surfaces was shown to involve RCT between the Li 2s level and the Si dangling bonds. Hydrogen adsorption decreases the neutralization because it ties up the dangling bonds. The neutral fractions in 7Li + scattering from Cs/Si are also determined primarily by the dangling bond states, so that the surface LEP cannot be directly probed. Hydrogen adsorption on Cs/Si ties up the dangling bonds, thereby revealing the local potentials. The neutralization probabilities of Li+ backscattered from the hydrogen- and iodine-covered Ni(100) surface were measured. The neutral fraction does not change significantly on H-adsorbed surface. For iodine adsorption, however, unexpected high neutralization probabilities were found for Li scattered directly from iodine sites. Similar behavior were observed for Li+ scattering from I- and Br-covered Fe(100) and Fe(110). The neutralization of Li+ was measured as a function of the incident energy, adatom charge and coverage, and exit angle. It was found that the larger neutral fractions of Li scattered from the halogen sites are caused by a lower potential directly above the adatoms due to internal polarization. As the exit beam moves off-normal, the neutral fraction of Li scattered from iodine decreases. This is in contrast to Cs and Ag adsorbates where the neutral fractions increase for glancing exit trajectories. These angular-dependences are verified by a semi-quantitative theoretical analysis. To

  19. First-principles study of NO adsorbed Ni(100) surface.

    PubMed

    Mu, X; Sun, X; Li, H M; Ding, Z J

    2010-11-01

    The geometric, electronic and magnetic properties of NO molecules adsorbed on the Ni(100) surface are investigated by the first-principles calculation on the basis of the density functional theory (DFT). The NO molecules are predicted to be chemisorbed at hollow site with an upright configuration at 0.125 ML and 0.5 ML coverages. After adsorption, the magnetic moment is significantly suppressed for surface Ni atom and almost quenched for NO molecule. This behavior can be reasonably explained by the difference of the backdonation process between the spin-up and spin-down electronic states, which is demonstrated by the spin-resolved differential charge density map.

  20. 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

  1. 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.

  2. The Martian surface layer

    NASA Technical Reports Server (NTRS)

    Christensen, Philip R.; Moore, Henry J.

    1992-01-01

    The global characteristics of the Martian surface layer are discussed on the basis of thermal, albedo, color, and radar data for the region between approximately 60 deg S and 60 deg N. Thermal data reveal the presence of large low- and high-inertia regions of the northern hemisphere, with much of the south covered by material of moderate inertia. There is a strong anticorrelation between inertia and albedo, a correlation between inertia and rock abundance, and, over much of the planet, a correlation of radar-derived density with inertia. Viking Orbiter color data indicate the presence of three major surface materials: low-inertia, bright-red material that is presumably dust; high-inertia, dark-grey material interpreted to be lithic material mixed with palagonitelike dust; and moderate-inertia, dark-red material that is rough at subpixel scales and interpreted to be indurated. Observations from the Viking landing sites show rocks, fines of varying cohesion and crusts. These sites have indications of aeolian erosion and deposition in the recent past.

  3. 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.

  4. Scanning tunneling microscopy studies of organic monolayers adsorbed on the rhodium(111) crystal surface

    SciTech Connect

    Cernota, Paul D.

    1999-08-01

    Scanning Tunneling Microscopy studies were carried out on ordered overlayers on the (111) surface of rhodium. These adsorbates include carbon monoxide (CO), cyclohexane, cyclohexene, 1,4-cyclohexadiene, para-xylene, and meta-xylene. Coadsorbate systems included: CO with ethylidyne, CO with para- and meta-xylene, and para-xylene with meta-xylene. In the case of CO, the structure of the low coverage (2x2) overlayer has been observed. The symmetry of the unit cell in this layer suggests that the CO is adsorbed in the 3-fold hollow sites. There were also two higher coverage surface structures with ({radical}7x{radical}7) unit cells. One of these is composed of trimers of CO and has three CO molecules in each unit cell. The other structure has an additional CO molecule, making a total of four. This extra CO sits on a top site.

  5. 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.

  6. 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.

  7. Effects of surface trapped excess electrons on the dynamics of HCl adsorbed ice surfaces

    NASA Astrophysics Data System (ADS)

    Yoon, Yeohoon; Shin, Seokmin

    2007-05-01

    We report results of Car-Parrinello molecular dynamics simulations showing the effect of surface trapped electrons on the dynamics of HCl adsorbed ice surfaces. It is found that the existence of excess electrons can lead to extensive changes in structural and electronic properties of ice surfaces, which provide better environments for proton transfer. The results of simulations show rapid exchanging mechanism of the proton under such environment, suggesting the importance of interlayer proton transfer in the heterogeneous reaction of HCl adsorbed ice surfaces.

  8. Viscoelastic properties of adsorbed and cross-linked polypeptide and protein layers at a solid-liquid interface.

    PubMed

    Dutta, Amit K; Nayak, Arpan; Belfort, Georges

    2008-08-01

    The real-time changes in viscoelasticity of adsorbed poly(L-lysine) (PLL) and adsorbed histone (lysine rich fraction) due to cross-linking by glutaraldehyde and corresponding release of associated water were investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D) and attenuated total reflection Fourier transform infrared spectroscopy (ATR/FTIR). The kinetics of PLL and histone adsorption were measured through changes in mass adsorbed onto a gold-coated quartz surface from changes in frequency and dissipation and using the Voigt viscoelastic model. Prior to cross-linking, the shear viscosity and shear modulus of the adsorbed PLL layer were approximately 3.0 x 10(-3) Pas and approximately 2.5 x 10(5) Pa, respectively, while after cross-linking, they increased to approximately 17.5 x 10(-3) Pas and approximately 2.5 x 10(6) Pa, respectively. For the adsorbed histone layer, shear viscosity and shear modulus increased modestly from approximately 1.3 x 10(-3) to approximately 2.0 x 10(-3) Pas and from approximately 1.2 x 10(4) to approximately 1.6 x 10(4) Pa, respectively. The adsorbed mass estimated from the Sauerbrey equation (perfectly elastic) and the Voigt viscoelastic model differ appreciably prior to cross-linking whereas after cross-linking they converged. This is because trapped water molecules were released during cross-linking. This was confirmed experimentally via ATR/FTIR measurements. The variation in viscoelastic properties increased substantially after cross-linking presumably due to fluctuation of the randomly cross-linked network structure. An increase in fluctuation of the viscoelastic properties and the loss of imbibed water could be used as a signature of the formation of a cross-linked network and the amount of cross-linking, respectively. PMID:18508070

  9. 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.

  10. Vibrational Spectroscopic Studies of Adsorbates on Metal and Silicon Single Crystal Surfaces.

    NASA Astrophysics Data System (ADS)

    Horn, Andrew B.

    Available from UMI in association with The British Library. The design of an experiment to investigate the surface chemistry of silicon, with specific application to the study of intermediates formed during the chemical vapour deposition of silicon from silane homologues was considered in a theoretical manner using classical optical techniques, and experimental verification of the ability to detect multilayers of physically adsorbed species was performed. Both reflection-absorption infrared spectroscopy and transmission infrared spectroscopy were investigated. Some of the steps involved in the cleaning of a silicon wafer were investigated. Chemical etching of the wafers was simulated using hydrofluoric acid solutions and hydrogen peroxide/sulphuric acid rinses and monitored using transmission infrared spectroscopy. Thermal annealing and argon ion sputter etching were investigated using transmission infrared spectroscopy, Auger electron spectroscopy and low energy electron diffraction. The adsorption of disilane, Si_{z}H_{rm e} on Si(100) was investigated at a variety of temperatures. Contamination was demonstrated to be significant in the passivation of the surface to a point where little reactivity could be observed at room temperature. Physical adsorption was seen to occur in a dynamic pressure of disilane at ca. 130K. The adsorption of disilane at temperatures ranging from 100K to 300K was investigated on Ru(0001). At low temperatures, disilane was seen to adsorb molecularly at 100K, with partial decomposition in the first layer. Annealing to higher temperatures and adsorption at 160K was seen to produce adsorbed SiH_{n } (n = 1-3), which desorbed above 270K. At room temperature, disilane adsorbed dissociatively to form an SiH species which formed a variety of structures at increasing coverage, evidenced by complex LEED patterns. At higher temperatures, the adsorbed silicon reacted with the ruthenium crystal to form a ruthenium silicide as an incommensurate

  11. On the interplay between chemical reactions and phase transitions for molecules adsorbed on solid surfaces

    NASA Astrophysics Data System (ADS)

    Stiles, M.; Metiu, H.

    1986-02-01

    There is a large body of experimental evidence suggesting that the rate of product formation in a reaction between adsorbed molecules is deeply modified when one of the reagents undergoes a phase transition or, more broadly speaking, an aggregation of some kind. Specific examples are: H2 and CO oxidation; methanol transformation into a methoxy radical on O/Cu; the water reaction with oxygen to form 2OH; the decomposition of N2O on Pt(111) which is affected by a phase transition in the outermost Pt layer; and the oxidation of Ni7. It is suspected that similar effects might operate on supported metal catalysts. We use Monte Carlo simulations to examine the manner in which reagent aggregation affects the reaction rate between molecules adsorbed on a solid surface. We discuss the temperature and concentration dependence of the rate of product formation.

  12. Theory of Desorption and Vibrational Heating of Adsorbates at Surfaces

    NASA Astrophysics Data System (ADS)

    Saalfrank, Peter

    2000-03-01

    Adsorbate-surface bonds can be broken thermally and, more selectively and possibly with atomic resolution, also with scanning tunnelling microscopes (STMs) and ultrashort laser pulses. The microscopic unravelling of the mechanisms of bond-breaking at surfaces is of fundamental and of practical interest, e.g., for the microstructuring of materials. In this contribution we describe quantum-dynamical simulations for ultrafast bond-breaking enforced by STMs and lasers, which lead to the desorption of atoms or molecules from semiconductor or metal surfaces. Both DIET (Desorption Induced by Electronic Transitions) and DIMET (``M''=``Multiple'') have been investigated with the help of time-dependent open-system density matrix theory. For the example systems H/D/Si(100), NO/Pt(111), and NH_3,ND_3,/Cu(111), effects of thermal or photochemical vibrational preparation of the reactants, isotope effects, and possibilities and limitations for the active control of DIET and DIMET were considered and compared, where possible, to experiments.

  13. The neutral surface layer above rough surfaces

    NASA Astrophysics Data System (ADS)

    Smedman, Ann-Sofi; Sahlee, Erik

    2014-05-01

    It is generally accepted that turbulent fluxes (momentum and scalar fluxes) are approx. constant with height above horizontal surfaces with low roughness. But what will happen when the roughness sub-layer is large as found over cities, forests and rough seas? In a study of the kinematic structure of the near neutral atmospheric surface layer, Högström, Hunt and Smedman, 2002, it was demonstrated that a model with detached eddies from above the surface layer impinging on to the surface (Hunt and Morison, 2000) could explain some of the observed features in the neutral atmospheric boundary layer. Thus the detached eddy model proved successful in explaining the dynamic structure of the near neutral atmospheric surface layer, especially the shape of the spectra of the wind components and scalars and corresponding fluxes. Here we make the hypothesis that the detached-eddy model can also be used to explain the experimental results related to the 3-dimensional turbulence structure above rough surfaces. Measurements are taken both over land (grass and forest) and over sea (Baltic Sea and hurricane Fabian in the Atlantic) above the roughness sub-layer. Analysis of the turbulence structure shows a striking similarity between the different sites. Hunt, J.C.R and Morrison, J.F., 2000: Eddy structure in turbulent boundary layers, Euro. J. Mech. B-Fluids, 19, 673-694. Högström, U., Hunt, J.C.R., and Smedman, A., 2002: Theory and measurements for turbulence spectra and variances in the atmospheric neutral surface layer, Bound.-Layer Meteorol., 103,101-124.

  14. 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.

  15. Surface enhanced Raman scattering of pyrazole adsorbed on silver colloids

    NASA Astrophysics Data System (ADS)

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

    1999-05-01

    SERS spectra of pyrazole adsorbed on silver hydrosol at different pH values and on silver colloidal substrate deposited on filters were obtained and interpreted on the basis of the existence of three forms in equilibrium, cationic, neutral and anionic. SERS data indicate that the neutral molecule is preferentially adsorbed in acidic environment, pyrazolide anion is instead favoured over all the other pH values. Addition of chloride anions induces the formation of reaction products when pyrazole is adsorbed on silver hydrosols, while this effect is missing on dry silver substrate.

  16. 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.

  17. Effect of Polarity of Activated Carbon Surface, Solvent and Adsorbate on Adsorption of Aromatic Compounds from Liquid Phase.

    PubMed

    Goto, Tatsuru; Amano, Yoshimasa; Machida, Motoi; Imazeki, Fumio

    2015-01-01

    In this study, introduction of acidic functional groups onto a carbon surface and their removal were carried out through two oxidation methods and outgassing to investigate the adsorption mechanism of aromatic compounds which have different polarity (benzene and nitrobenzene). Adsorption experiments for these aromatics in aqueous solution and n-hexane solution were conducted in order to obtain the adsorption isotherms for commercial activated carbon (BAC) as a starting material, its two types of oxidized BAC samples (OXs), and their outgassed samples at 900 °C (OGs). Adsorption and desorption kinetics of nitrobenzene for the BAC, OXs and OGs in aqueous solution were also examined. The results showed that the adsorption of benzene molecules was significantly hindered by abundant acidic functional groups in aqueous solution, whereas the adsorbed amount of nitrobenzene on OXs gradually increased as the solution concentration increased, indicating that nitrobenzene can adsorb favourably on a hydrophilic surface due to its high dipole moment, in contrast to benzene. In n-hexane solution, it was difficult for benzene to adsorb on any sample owing to the high affinity between benzene and n-hexane solvent. On the other hand, adsorbed amounts of nitrobenzene on OXs were larger than those of OGs in n-hexane solution, implying that nitrobenzene can adsorb two adsorption sites, graphene layers and surface acidic functional groups. The observed adsorption and desorption rate constants of nitrobenzene on the OXs were lower than those on the BAC due to disturbance of diffusion by the acidic functional groups.

  18. 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.

  19. Heavy meromyosin molecules extending more than 50 nm above adsorbing electronegative surfaces.

    PubMed

    Persson, Malin; Albet-Torres, Nuria; Ionov, Leonid; Sundberg, Mark; Höök, Fredrik; Diez, Stefan; Månsson, Alf; Balaz, Martina

    2010-06-15

    In the in vitro motility assay, actin filaments are propelled by surface-adsorbed myosin motors, or rather, myosin motor fragments such as heavy meromyosin (HMM). Recently, efforts have been made to develop actomyosin powered nanodevices on the basis of this assay but such developments are hampered by limited understanding of the HMM adsorption geometry. Therefore, we here investigate the HMM adsorption geometries on trimethylchlorosilane- [TMCS-] derivatized hydrophobic surfaces and on hydrophilic negatively charged surfaces (SiO(2)). The TMCS surface is of great relevance in fundamental studies of actomyosin and both surface substrates are important for the development of motor powered nanodevices. Whereas both the TMCS and SiO(2) surfaces were nearly saturated with HMM (incubation at 120 microg mL(-1)) there was little actin binding on SiO(2) in the absence of ATP and no filament sliding in the presence of ATP. This contrasts with excellent actin-binding and motility on TMCS. Quartz crystal microbalance with dissipation (QCM-D) studies demonstrate a HMM layer with substantial protein mass up to 40 nm above the TMCS surface, considerably more than observed for myosin subfragment 1 (S1; 6 nm). Together with the excellent actin transportation on TMCS, this strongly suggests that HMM adsorbs to TMCS mainly via its most C-terminal tail part. Consistent with this idea, fluorescence interference contrast (FLIC) microscopy showed that actin filaments are held by HMM 38 +/- 2 nm above the TMCS-surface with the catalytic site, on average, 20-30 nm above the surface. Viewed in a context with FLIC, QCM-D and TIRF results, the lack of actin motility and the limited actin binding on SiO(2) shows that HMM adsorbs largely via the actin-binding region on this surface with the C-terminal coiled-coil tails extending >50 nm into solution. The results and new insights from this study are of value, not only for the development of motor powered nanodevices but also for the

  20. Multi-layer graphene oxide alone and in a composite with nanosilica: Preparation and interactions with polar and nonpolar adsorbates

    NASA Astrophysics Data System (ADS)

    Gun'ko, V. M.; Turov, V. V.; Zarko, V. I.; Goncharuk, O. V.; Matkovsky, A. K.; Prykhod'ko, G. P.; Nychiporuk, Yu. M.; Pakhlov, E. M.; Krupska, T. V.; Balakin, D. Yu.; Charmas, B.; Andriyko, L. S.; Skubiszewska-Zięba, J.; Marynin, A. I.; Ukrainets, A. I.; Kartel, M. T.

    2016-11-01

    Freeze-dried multi-layer graphene oxide (MLGO), produced from natural flake graphite using ionic hydration method, demonstrates strong interactions of functionalized carbon sheets with polar or nonpolar adsorbates or co-adsorbates depending on the characteristics of dispersion media. Interactions of MLGO with a mixture of water and n-decane in chloroform media provide specific surface area (Su) in contact with unfrozen liquids greater than 1000 m2/g corresponding to stacks with 3-5 carbon layers. Electrostatic interactions between functionalized carbon sheets in dried MLGO are very strong. Therefore, nonpolar molecules (benzene, decane, nitrogen) cannot penetrate between the sheets. Water molecules can effectively penetrate between the sheets, especially if MLGO is located in weakly polar CDCl3 medium. In this case, n-decane molecules (co-adsorbate) can also penetrate into the sheet stacks and locate around nonpolar fragments of the sheets. The Su value of MLGO being in contact with unfrozen water can reach 360 m2/g, but upon co-adsorption of water with decane Su = 930 m2/g, i.e., hydrophobic interactions of the mentioned fragments with decane are stronger that with co-adsorbed water. Water alone (0.25 or 0.5 g/g) bound to MLGO in a mixture with fumed silica A-300 in air or CDCl3 media can provide Su = 30-50 m2/g. Pores in wetted MLGO or MLGO/A-300 mainly correspond to mesopores. Nanosilica does not provide significant opening of the MLGO sheet stacks during their mechanical mixing.

  1. Existence of hydration forces in the interaction between apoferritin molecules adsorbed on silica surfaces.

    PubMed

    Valle-Delgado, J J; Molina-Bolívar, J A; Galisteo-González, F; Gálvez-Ruiz, M J; Feiler, A; Rutland, M W

    2005-10-11

    The atomic force microscope, together with the colloid probe technique, has become a very useful instrument to measure interaction forces between two surfaces. Its potential has been exploited in this work to study the interaction between protein (apoferritin) layers adsorbed on silica surfaces and to analyze the effect of the medium conditions (pH, salt concentration, salt type) on such interactions. It has been observed that the interaction at low salt concentrations is dominated by electrical double layer (at large distances) and steric forces (at short distances), the latter being due to compression of the protein layers. The DLVO theory fits these experimental data quite well. However, a non-DLVO repulsive interaction, prior to contact of the protein layers, is observed at high salt concentration above the isoelectric point of the protein. This behavior could be explained if the presence of hydration forces in the system is assumed. The inclusion of a hydration term in the DLVO theory (extended DLVO theory) gives rise to a better agreement between the theoretical fits and the experimental results. These results seem to suggest that the hydration forces play a very important role in the stability of the proteins in the physiological media.

  2. Formation and composition of adsorbates on hydrophobic carbon surfaces from aqueous laccase-maltodextrin mixture suspension

    NASA Astrophysics Data System (ADS)

    Corrales Ureña, Yendry Regina; Lisboa-Filho, Paulo Noronha; Szardenings, Michael; Gätjen, Linda; Noeske, Paul-Ludwig Michael; Rischka, Klaus

    2016-11-01

    A robust procedure for the surface bio-functionalization of carbon surfaces was developed. It consists on the modification of carbon materials in contact with an aqueous suspension of the enzyme laccase from Trametes versicolor and the lyophilization agent maltodextrin, with the pH value adjusted close to the isoelectric point of the enzyme. We report in-situ investigations applying Quartz Crystal Microbalance with Dissipation (QCM-D) for carbon-coated sensor surfaces and, moreover, ex-situ measurements with static contact angle measurements, X-ray Photoelectron Spectroscopy (XPS) and Scanning Force Microscopy (SFM) for smooth Highly Oriented Pyrolytic Graphite (HOPG) substrates, for contact times between the enzyme formulation and the carbon material surface ranging from 20 s to 24 h. QCM-D studies reveals the formation of rigid layer of biomaterial, a few nanometers thin, which shows a strongly improved wettability of the substrate surface upon contact angle measurements. Following spectroscopic characterization, these layers are composed of mixtures of laccase and maltodextrin. The formation of these adsorbates is attributed to attractive interactions between laccase, the maltodextrin-based lyophilization agent and the hydrophobic carbon surfaces; a short-term contact between the aqueous laccase mixture suspension and HOPG surfaces is shown to merely result in de-wetting patterns influencing the results of contact angle measurements. The new enzyme-based surface modification of carbon-based materials is suggested to be applicable for the improvement of not only the wettability of low energy substrate surfaces with fluid formulations like coatings or adhesives, but also their adhesion in contact with hardened polymers.

  3. 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.

  4. 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.

  5. 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.

  6. Reaction Dynamics Following Ionization of Ammonia Dimer Adsorbed on Ice Surface.

    PubMed

    Tachikawa, Hiroto

    2016-09-22

    The ice surface provides an effective two-dimensional reaction field in interstellar space. However, how the ice surface affects the reaction mechanism is still unknown. In the present study, the reaction of an ammonia dimer cation adsorbed both on water ice and cluster surface was theoretically investigated using direct ab initio molecular dynamics (AIMD) combined with our own n-layered integrated molecular orbital and molecular mechanics (ONIOM) method, and the results were compared with reactions in the gas phase and on water clusters. A rapid proton transfer (PT) from NH3(+) to NH3 takes place after the ionization and the formation of intermediate complex NH2(NH4(+)) is found. The reaction rate of PT was significantly affected by the media connecting to the ammonia dimer. The time of PT was calculated to be 50 fs (in the gas phase), 38 fs (on ice), and 28-33 fs (on water clusters). The dissociation of NH2(NH4(+)) occurred on an ice surface. The reason behind the reaction acceleration on an ice surface is discussed. PMID:27588552

  7. 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.

  8. 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.

  9. 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

  10. Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry

    PubMed Central

    Silber, David; Kowalski, Piotr M.; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

    2016-01-01

    Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO2(110) surface. PMID:27686286

  11. Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry

    NASA Astrophysics Data System (ADS)

    Silber, David; Kowalski, Piotr M.; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

    2016-09-01

    Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO2(110) surface.

  12. 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.

  13. Surface properties and adsorption characteristics to methylene blue and iodine of adsorbents from sludge.

    PubMed

    Deng, L Y; Xu, G R; Li, G B

    2010-01-01

    Adsorbent materials created from wastewater sludge have unique surface characteristics and could be effective in adsorption applications. In this research, the sludge-adsorbents were generated by pyrolyzing mixtures of sewage sludge and H(2)SO(4). Scanning electron microscope (SEM), thermal analysis, X-ray diffraction (XRD) and X-ray photoelectron spectroscope (XPS) were used to analyze the properties of sludge-adsorbent. XPS results show that the adsorbent surface functional groups with high contents of oxygen-containing groups serve as active sites for the adsorption and affect the surface characteristics; the adsorption mechanism of methylene blue (MB) is mainly Brönsted acid-base reaction between the adsorbent surface and MB; and iodine atoms are bonded to the surface of the adsorbent mainly by dispersive interactions rather than by electrostatic interactions. The results also show that H(2)SO(4) level, pyrolysis temperature and sulfuric acid/sludge weight ratio actually affected the adsorption characteristics. Using the conditions (H(2)SO(4) level of 1-18 M, pyrolysis temperature of 650°C, and weight ratio of 0.8), the adsorption capacities for MB and iodine were 74.7-62.3 mg g(-1) and 169.5-209.3 mg g(-1), respectively.

  14. 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

  15. Layered double hydroxide-based nanomaterials as highly efficient catalysts and adsorbents.

    PubMed

    Li, Changming; Wei, Min; Evans, David G; Duan, Xue

    2014-11-01

    Layered double hydroxides (LDHs) are a class of anion clays consisting of brucite-like host layers and interlayer anions, which have attracted increasing interest in the fields of catalysis/adsorption. By virtue of the versatility in composition, morphology, and architecture of LDH materials, as well as their unique structural properties (intercalation, topological transformation, and self-assembly with other functional materials), LDHs display great potential in the design and fabrication of nanomaterials applied in photocatalysis, heterogeneous catalysis, and adsorption/separation processes. Taking advantage of the structural merits and various control synthesis strategies of LDHs, the active center structure (e.g., crystal facets, defects, geometric and electronic states, etc.) and macro-nano morphology can be facilely manipulated for specific catalytic/adsorbent processes with largely enhanced performances. In this review, the latest advancements in the design and preparation of LDH-based functional nanomaterials for sustainable development in catalysis and adsorption are summarized.

  16. 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.

  17. 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

  18. 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

  19. 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).

  20. UV-induced protonation of molecules adsorbed on ice surfaces at low temperature.

    PubMed

    Moon, Eui-Seong; Lee, Chang-Woo; Kim, Joon-Ki; Park, Seong-Chan; Kang, Heon

    2008-05-21

    UV irradiation of ice films adsorbed with methylamine molecules induces protonation of the adsorbate molecules at low temperature (50-130 K). The observation indicates that long-lived protonic defects are created in the ice film by UV light, and they transfer protons to the adsorbate molecules via tunneling mechanism at low temperature. The methylammonium ion formed by proton transfer remains to be stable at the ice surface. It is suggested that this solid-phase protonation might play a significant role in the production of molecular ions in interstellar clouds.

  1. 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

  2. Substrate-mediated interactions and intermolecular forces between molecules adsorbed on surfaces.

    PubMed

    Sykes, E Charles H; Han, Patrick; Kandel, S Alex; Kelly, Kevin F; McCarty, Gregory S; Weiss, Paul S

    2003-12-01

    Adsorbate interactions and reactions on metal surfaces have been investigated using scanning tunneling microscopy. The manners in which adsorbates perturb the surface electronic structure in their vicinity are discussed. The effects these perturbations have on other molecules are shown to be important in overlayer growth. Interactions of molecules with surface steps are addressed, and each molecule's electron affinity is shown to dictate its adsorption sites at step edges. Standing waves emanating from steps are demonstrated to effect transient molecular adsorption up to 40 A away from the step edge. Halobenzene derivatives are used to demonstrate how the surface is important in aligning reactive intermediates.

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

    PubMed

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

    2016-03-25

    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.

  4. Modeling the interaction of nanoparticles with mineral surfaces: adsorbed C60 on pyrophyllite.

    PubMed

    Zhu, Runliang; Molinari, Marco; Shapley, Thomas V; Parker, Stephen C

    2013-08-01

    We have applied DFT and molecular modeling to investigate the interaction between carbon-based nanoparticles (CNPs) and geosorbents using the adsorption of buckminsterfullerene (C60) on pyrophyllite and comparing it to the aggregation of C60 molecules. The approach is transferable and can be readily applied to more complex CNP-clay systems. We predict that C60 molecules adsorb preferably on the mineral surface and that the most stable adsorption site is the ditrigonal cavity of the surface. The free energy of adsorption on pyrophyllite was calculated to be more favorable than aggregation both in a vacuum (-0.47 vs -0.41 eV) and in water (-0.25 vs -0.19 eV). In aqueous environments, there are energy barriers as the C60 molecule approaches either a surface or another C60 molecule, and these occur upon disruption of the hydration layers that surround each component. There are also free energy minima that correspond to outer-sphere and more favorable inner-sphere complexes. We expect this adsorptive behavior to be a general feature of CNP-clay systems, and as clays are ubiquitous in the environment, it will offer an inexpensive remediative method to prevent the widespread impact of molecular C60 and CNPs. PMID:23815310

  5. 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.

  6. 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.

  7. 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

  8. The surface trans effect: influence of axial ligands on the surface chemical bonds of adsorbed metalloporphyrins.

    PubMed

    Hieringer, Wolfgang; Flechtner, Ken; Kretschmann, Andreas; Seufert, Knud; Auwärter, Willi; Barth, Johannes V; Görling, Andreas; Steinrück, Hans-Peter; Gottfried, J Michael

    2011-04-27

    The chemical bond between an adsorbed, laterally coordinated metal ion and a metal surface is affected by an additional axial ligand on the metal ion. This surface analogon of the trans effect was studied in detail using monolayers of various M(II)-tetraphenylporphyrins (MTTPs, M = Fe, Co, Zn) and their nitrosyl complexes on a Ag(111) surface. X-ray photoelectron spectroscopy (XPS) shows that the oxidation state of the Fe and Co (but not Zn) ions in the MTPP monolayers is reduced because of the interaction with the substrate. This partial reduction is accompanied by the appearance of new valence states in the UV photoelectron and scanning tunneling spectra (UPS and STS), revealing the covalent character of the ion-substrate bond. Subsequent coordination of nitric oxide (NO) to the metal ions (Fe, Co) reverses these surface-induced effects, resulting in an increase of the oxidation states and the disappearance of the new valence states. Removal of the NO ligands by thermal desorption restores the original spectroscopic features, indicating that the described processes are fully reversible. The NO coordination also changes the spin state and thus the magnetic properties of the metal ions. Density-functional theory (DFT) calculations on model systems provide structural and energetic data on the adsorbed molecules and the surface chemical bond. The calculations reveal that competition effects, similar to the trans effect, play a central role and lead to a mutual interference of the two axial ligands, NO and Ag, and their bonds to the metal center. These findings have important implications for sensor technology and catalysis using supported planar metal complexes, in which the activity of the metal center is sensitively influenced by the substrate.

  9. 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

  10. 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.

  11. In Situ Investigation the Photolysis of the PAHs Adsorbed on Mangrove Leaf Surfaces by Synchronous Solid Surface Fluorimetry

    PubMed Central

    Wang, Ping; Wu, Tun-Hua; Zhang, Yong

    2014-01-01

    An established synchronous solid surface fluorimetry (S-SSF) was utilized for in situ study the photolysis processes of anthracene (An) and pyrene (Py) adsorbed on the leaf surfaces of Kandelia obovata seedlings (Ko) and Aegiceras corniculata (L.) Blanco seedlings (Ac). Experimental results demonstrated that the photolysis of An and Py adsorbed on the leaf surfaces of two mangrove species under the laboratory conditions, followed first-order kinetics with their photolysis rates in the order of Ac>Ko. In addition, with the same amount of substances, the photolysis rate of An adsorbed on the same mangrove leaf surfaces was much faster than the adsorbed Py. In order to investigate further, the photolysis processes of An and Py in water were also studied for comparison. And the photolysis of An and Py in water also followed first-order kinetics. Moreover, for the same initial amount, the photolysis rate of the PAH in water was faster than that adsorbed on the leaf surfaces of two mangrove species. Therefore, photochemical behaviors of PAHs were dependent not only on their molecular structures but also the physical-chemical properties of the substrates on which they are adsorbed. PMID:24404158

  12. 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.

  13. Surface structure of GaAs with adsorbed Te

    NASA Astrophysics Data System (ADS)

    Feldman, R. D.; Austin, R. F.

    1986-10-01

    The surface structures that result from the adsorption of Te on (100) GaAs have been shown to affect the orientation of CdTe films on GaAs. Two structures are described here. A low-temperature (6×1) surface leads to (100) film growth. At 580 °C, a new surface results which is characterized by ordering along directions 60° from [011¯] and [01¯1], and leads to (111) growth of CdTe. Both surface structure and the interaction of the group II element with the surface are believed to be important in determining the orientation of the film.

  14. 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.

  15. 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.

  16. 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.

  17. Charged layer with undulated surface: configuration of electrical double layer.

    PubMed

    Lin, Sung-Hwa

    2010-06-15

    A charged layer with undulated surface exists commonly in natural entities (for example the biological membrane layer and the surface of charged colloid) and in artificial fabrications (for example the peripheral surface of ion-exchange membrane pores). When the micro- or nano-scale charged layer systems are concerned, the effect of undulation of charged layer surface on the electrical phenomenon may become great significant. In this work, using the perturbation method, the significance of undulated surface on a charged layer in the electrical phenomenon is investigated. Under assumptions that the undulation amplitude is small and that the Debye-Huckel approximation is applicable, the electrical potential field in three regions is solved simultaneously. Based on the analytical results it is found that, if compared with that in condition of flat surface, the undulation of charged layer surface decreases/increases the magnitude of electrical potential field near the wave crest/trough, due to the curvature of undulated surface. In addition, the surface potential on the undulated surface shows a wavelike distribution. The analytical results also show that, the significance of undulated surface is determined by the physical parameters, including the geometry of undulated surface, the amplitude and the period of undulation, and the fixed charge density in charged layer.

  18. 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.

  19. Activity of catalase adsorbed to carbon nanotubes: effects of carbon nanotube surface properties.

    PubMed

    Zhang, Chengdong; Luo, Shuiming; Chen, Wei

    2013-09-15

    Nanomaterials have been studied widely as the supporting materials for enzyme immobilization. However, the interactions between enzymes and carbon nanotubes (CNT) with different morphologies and surface functionalities may vary, hence influencing activities of the immobilized enzyme. To date how the adsorption mechanisms affect the activities of immobilized enzyme is not well understood. In this study the adsorption of catalase (CAT) on pristine single-walled carbon nanotubes (SWNT), oxidized single-walled carbon nanotubes (O-SWNT), and multi-walled carbon nanotubes (MWNT) was investigated. The adsorbed enzyme activities decreased in the order of O-SWNT>SWNT>MWNT. Fourier transforms infrared spectroscopy (FTIR) and circular dichrois (CD) analyses reveal more significant loss of α-helix and β-sheet of MWNT-adsorbed than SWNT-adsorbed CAT. The difference in enzyme activities between MWNT-adsorbed and SWNT-adsorbed CAT indicates that the curvature of surface plays an important role in the activity of immobilized enzyme. Interestingly, an increase of β-sheet content was observed for CAT adsorbed to O-SWNT. This is likely because as opposed to SWNT and MWNT, O-SWNT binds CAT largely via hydrogen bonding and such interaction allows the CAT molecule to maintain the rigidity of enzyme structure and thus the biological function.

  20. Extended triple layer modeling of arsenate and phosphate adsorption on a goethite-based granular porous adsorbent.

    PubMed

    Kanematsu, Masakazu; Young, Thomas M; Fukushi, Keisuke; Green, Peter G; Darby, Jeannie L

    2010-05-01

    The extended triple layer model (ETLM), which is consistent with spectroscopic and theoretical molecular evidence, is first systematically tested for its capability to model adsorption of arsenate and phosphate, a strong competitor, on a common goethite-based granular porous adsorptive media (Bayoxide E33 (E33)) in water treatment systems under a wide range of solution conditions. Deprotonated bidentate-binuclear, protonated bidentate-binuclear, and deprotonated monodentate complexes are chosen as surface species for both arsenate and phosphate. The estimated values of the ETLM parameters of arsenate for the adsorbent are close to those for pure goethite minerals previously determined by others. The ETLM predictions for arsenate and phosphate adsorption basically agree with experimental results over a wide range of pH, surface coverage, and solid concentrations. High background electrolyte concentration (i.e., I = 0.1 M), however, was found to strongly impact arsenate and phosphate adsorption on E33 probably because of the porous structure of the adsorbent, which cannot be observed for pure goethite minerals and could not be completely modeled by the ETLM. Prediction of phosphate adsorption isotherms at higher pH were relatively poor, and this may suggest searching for alternative surface species for phosphate. Since adsorption equilibrium constants of major coexisting ions encountered in water treatment systems for goethite minerals have been estimated by others, the application of ETLM theory to this common goethite-based adsorptive media will enable us to understand how those coexisting ions macroscopically and thermodynamically interact with arsenate and phosphate in the environment of adsorptive water treatment system in a way consistent with molecular and spectroscopic evidence.

  1. 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.

  2. 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

  3. Subharmonic excitation in amplitude modulation atomic force microscopy in the presence of adsorbed water layers

    SciTech Connect

    Santos, Sergio; Barcons, Victor; Verdaguer, Albert; Chiesa, Matteo

    2011-12-01

    In ambient conditions, nanometric water layers form on hydrophilic surfaces covering them and significantly changing their properties and characteristics. Here we report the excitation of subharmonics in amplitude modulation atomic force microscopy induced by intermittent water contacts. Our simulations show that there are several regimes of operation depending on whether there is perturbation of water layers. Single period orbitals, where subharmonics are never induced, follow only when the tip is either in permanent contact with the water layers or in pure noncontact where the water layers are never perturbed. When the water layers are perturbed subharmonic excitation increases with decreasing oscillation amplitude. We derive an analytical expression which establishes whether water perturbations compromise harmonic motion and show that the predictions are in agreement with numerical simulations. Empirical validation of our interpretation is provided by the observation of a range of values for apparent height of water layers when subharmonic excitation is predicted.

  4. Concentration-dependent surface-enhanced Raman scattering of 2-benzoylpyridine adsorbed on colloidal silver particles.

    PubMed

    Chowdhury, Joydeep; Ghosh, Manash

    2004-09-01

    Surface-enhanced Raman scattering (SERS) of 2-benzoylpyridine (2-BP) adsorbed on silver hydrosols has been investigated. It has been observed that with a small change in the adsorbate concentration, the SER spectra of 2-BP show significant change in their features, indicating different orientational changes of the different part of the flexible molecule on the colloidal silver surface with adsorbate concentration. The time dependence of the SER spectra of the molecule has been explained in terms of aggregation of colloidal silver particles and co-adsorption and replacement kinetics of the adsorbed solute and solvent molecules on the silver surface. The broad long-wavelength band in the absorption spectra of the silver sol due to solute-induced coagulation of colloidal silver particles is found to be red-shifted with the increase in adsorbate concentration. The surface-enhanced Raman excitation profiles indicate that the resonance of the Raman excitation radiation with the new aggregation band contributes more to the SERS intensity than that with the original sol band.

  5. 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

  6. 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.

  7. Siloxanes removal from biogas by high surface area adsorbents.

    PubMed

    Gislon, P; Galli, S; Monteleone, G

    2013-12-01

    Biogas utilized for energy production needs to be free from organic silicon compounds, as their burning has damaging effects on turbines and engines; organic silicon compounds in the form of siloxanes can be found in biogas produced from urban wastes, due to their massive industrial use in synthetic product, such as cosmetics, detergents and paints. Siloxanes removal from biogas can be carried out by various methods (Mona, 2009; Ajhar et al., 2010 May; Schweigkofler and Niessner, 2001); aim of the present work is to find a single practical and economic way to drastically and simultaneously reduce both the hydrogen sulphide and the siloxanes concentration to less than 1 ppm. Some commercial activated carbons previously selected (Monteleone et al., 2011) as being effective in hydrogen sulfide up taking have been tested in an adsorption measurement apparatus, by flowing the most volatile siloxane (hexamethyldisiloxane or L2) in a nitrogen stream, typically 100-200 ppm L2 over N2, through an activated carbon powder bed; the adsorption process was analyzed by varying some experimental parameters (concentration, grain size, bed height). The best activated carbon shows an adsorption capacity of 0.1g L2 per gram of carbon. The next thermogravimetric analysis (TGA) confirms the capacity data obtained experimentally by the breakthrough curve tests. The capacity results depend on L2 concentration. A regenerative carbon process is then carried out by heating the carbon bed up to 200 °C and flushing out the adsorbed L2 samples in a nitrogen stream in a three step heating procedure up to 200 °C. The adsorption capacity is observed to degrade after cycling the samples through several adsorption-desorption cycles.

  8. 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

  9. 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.

  10. Heterogeneous reactions of surface-adsorbed catechol with nitrogen dioxide: substrate effects for tropospheric aerosol surrogates.

    PubMed

    Woodill, Laurie A; Hinrichs, Ryan Z

    2010-09-28

    Surface-adsorbed organics can alter the chemistry of tropospheric aerosols 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 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. The dark heterogeneous reaction of NO(2) with NaCl-adsorbed catechol produced 4-nitrocatechol, 1,2-benzoquinone, and the ring-cleaved product muconic acid, with product yields of 88%, 8%, and 4% at relative humidity (RH) < 2%, respectively. The reaction was first-order with respect to both catechol and NO(2). The reactive uptake coefficient for NO(2) + NaCl-adsorbed catechol increased from 3 x 10(-6) at <2% RH to 7 x 10(-6) at 30% RH. These reactions were more than two orders of magnitude more reactive than NaCl without adsorbed catechol. The 4-nitrocatechol product yield was enhanced on NaF, while NaBr-adsorbed catechol produced considerably more 1,2-benzoquinone and muconic acid. This substrate effect is discussed in terms of each substrate's ability to polarize the phenol group and hinder hydrogen atom abstraction from intermediate o-semiquinone radicals. These dark heterogeneous reactions may alter the UV-visible absorbing properties of tropospheric aerosols and may also contribute as a dark source of NO(2)(-)/HONO. These results contrast prior observations which found pure catechol thin films unreactive with NO(2), highlighting the need to specifically consider substrate and matrix effects in laboratory systems.

  11. Fluctuations of surface-enhanced Raman spectra of CO adsorbed on gold substrates

    NASA Astrophysics Data System (ADS)

    Kudelski, Andrzej; Pettinger, Bruno

    2004-01-01

    Surface-enhanced Raman scattering (SERS) of CO adsorbed on roughened gold surfaces has been studied using a Raman microscope with high spatial resolution. Sequentially recorded SERS spectra showed variations of Raman lines in their number, intensity, frequency, and halfwidth. Sometimes, in addition to the band for CO adsorbed at top sites, Raman peaks for bridge-bonded CO appear, showing large intensity fluctuations. Obviously, SERS fluctuations represent a more general property of SERS and point to local restructuring of substrates that changes temporarily the character of adsorption sites and/or their contribution to SERS. The single molecule 'blinking' effect is also discussed.

  12. 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

  13. 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.

  14. Local electric field and configuration of CO molecules adsorbed on a nanostructured surface with nanocones

    NASA Astrophysics Data System (ADS)

    You, Rong-Yi; Huang, Xiao-Jing

    2009-09-01

    Based on the nanostructured surface model that the (platinum, Pt) nanocones grow out symmetrically from a plane substrate, the local electric field near the conical nanoparticle surface is computed and discussed. On the basis of these results, the adsorbed CO molecules are modelled as dipoles, and three kinds of interactions, i.e. interactions between dipoles and local electric field, between dipoles and dipoles, as well as between dipoles and nanostructured substrate, are taken into account. The spatial configuration of CO molecules adsorbed on the nanocone surface is then given by Monte-Carlo simulation. Our results show that the CO molecules adsorbed on the nanocone surface cause local agglomeration under the action of an external electric field, and this agglomeration becomes more compact with decreasing conical angle, which results in a stronger interaction among molecules. These results serve as a basis for explaining abnormal phenomena such as the abnormal infrared effect (AIRE), which was found when CO molecules were adsorbed on the nanostructured transit ion-metal surface.

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. Effects of Adsorbed Polyaniline on Redox Process on MoO3 Surface.

    PubMed

    de Farias RF; de Souza JM; de Melo JV; Airoldi

    1999-04-01

    The effects exhibited by adsorbed conducting polyaniline on the redox process on a molybdenum oxide surface were studied. Thermogravimetric results indicate a 4% polyaniline deposition. Cyclic voltammograms of the adsorbed polymer on MoO3 show that polyaniline exerts remarkable effects on the molybdenum blue oxidation-reduction process, with oxidation and reduction potentials of 0.33 and 0.18 V, respectively. This effect strongly enhances the electrode response, and can be used as an important tool in qualitative and/or quantitative determinations of molybdenum in solution as well as in any substrate. Copyright 1999 Academic Press.

  2. Ordering layers of [bmim][PF6] ionic liquid on graphite surfaces: molecular dynamics simulation.

    PubMed

    Maolin, Sha; Fuchun, Zhang; Guozhong, Wu; Haiping, Fang; Chunlei, Wang; Shimou, Chen; Yi, Zhang; Jun, Hu

    2008-04-01

    Microscopic structures of room temperature ionic liquid (IL) [bmim][PF6] on hydrophobic graphite surfaces have been studied in detail by molecular dynamics simulation. It is clearly shown that both the mass and electron densities of the surface adsorbed ionic liquid are oscillatory, and the first peak adjacent to the graphite surface is considerably higher than others, corresponding to a solidlike IL bottom layer of 6 angstroms thick. Three IL layers are indicated between the graphite surface and the inner bulk IL liquid. The individually simulated properties of single-, double-, and triple-IL layers on the graphite surface are very similar to those of the layers between the graphite surface and the bulk liquid, indicating an insignificant effect of vapor-IL interface on the ordered IL layers. The simulation also indicates that the imidazolium ring and butyl tail of the cation (bmim+) of the IL bottom layer lie flat on the graphite surface.

  3. Quantum Mechanical Calculations to Interpret Vibrational and NMR Spectra of Organic Compounds Adsorbed onto Mineral Surfaces

    NASA Astrophysics Data System (ADS)

    Kubicki, J. D.

    2008-12-01

    Vibrational (e.g., ATR FTIR and Raman) and nuclear magnetic resonance (NMR) spectroscopies provide excellent information on the bonding and atomic environment of adsorbed organic compounds. However, interpretation of observed spectra collected for organic compounds adsorbed onto mineral surfaces can be complicated by the lack of comparable analogs of known structure and uncertainties about the mineral surface structure. Quantum mechanical calculations provide a method for testing interpretations of observed spectra because models can be built to mimic predicted structures, and the results are independent of experimental parameters (i.e., no fitting to data is necessary). In this talk, methodologies for modeling vibrational frequencies and NMR chemical shifts of adsorbed organic compounds are discussed. Examples included salicylic acid (as an analog for important binding functional groups in humic acids) adsorbed onto aluminum oxides, organic phosphoryl compounds that represent herbicides and bacterial extracellular polymeric substances (EPS), and ofloxacin (a common agricultural antibiotic). The combination of the ability of quantum mechanical calculations to predict structures, spectroscopic parameters and energetics of adsorption with experimental data on these same properties allows for more definitive construction of surface complex models.

  4. 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

  5. Electrostatic model for treating long-range lateral interactions between polar molecules adsorbed on metal surfaces

    NASA Astrophysics Data System (ADS)

    Kokalj, Anton

    2011-07-01

    A classical polarizable point-dipole model for the adsorption of polar molecules on metal surfaces is presented. The main usefulness of the model is that lattice sums are represented by simple functions in closed form. This allows a simple extrapolation of adsorption energies of polar molecules—as calculated by first-principles calculations employing periodic boundary conditions—to the zero-coverage limit. Such an extrapolation is rather important for the proper evaluation of adsorption energy of highly polar molecules, because their long-range lateral interactions can extend beyond the nearest-neighbor distances of 50 bohrs. Moreover, the dependence of the adsorption energy on the orientation and configuration of molecular dipoles can be straightforwardly analyzed. It is demonstrated that an accumulation of polar molecules on the surface is favored provided that the molecular dipoles point parallel to the surface in the adsorbed state, whereas adsorbed molecules displaying dipoles oriented perpendicular to the surface would prefer to stay well separated due to repulsive lateral interactions. Further, the model is used to analyze the density-functional theory (DFT) calculated data of two polar molecules, triazole and benzotriazole, adsorbed onto Cu(111) surface. The DFT-calculated adsorption energies are about -0.5 eV, and it is shown that the main contribution to the molecule-surface bonding comes from the dipole-dipole electrostatic interactions.

  6. 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

  7. Synthesis of Au-CeO 2/SiO 2 catalyst via adsorbed-layer reactor technique combined with alcohol-thermal treatment

    NASA Astrophysics Data System (ADS)

    Jiang, Xin; Deng, Hui

    2011-10-01

    Au-CeO 2/SiO 2 was prepared via adsorbed-layer reactor technique combined with alcohol-thermal treatment. The catalytic performance in complete oxidation of benzene was investigated. TEM, Raman characterization showed that Au particles grew up obviously during alcohol-thermal process, while CeO 2 particles maintained 4 nm in diameter. The content of oxygen vacancies and adsorbed oxygen species on catalysts surface increased apparently. Alcohol-thermally treated Au-CeO 2/SiO 2 and CeO 2/SiO 2 showed similar change in catalytic performance, and were much superior to calcined CeO 2/SiO 2. Of alcohol-thermally treated and calcined CeO 2/SiO 2, initial temperatures of the reaction were 80 °C and 150 °C, respectively. The benzene conversions reached 85% and 40% at 300 °C.

  8. 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

  9. 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

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. The origin of 1560 cm-1 band in experimental IR spectra of water adsorbed on TiO2 surface: Ab initio assessment

    NASA Astrophysics Data System (ADS)

    Kevorkyants, Ruslan; Rudakova, Aida V.; Chizhov, Yuri V.; Bulanin, Kirill M.

    2016-10-01

    We present DFT study on vibrational spectrum of water layer on a surface of TiO2 which is modeled via Ti8O16 nanocluster. In contrast to ν2 mode's frequency of liquid water (1645 cm-1) for the water layer theory predicts considerably lower ν2 frequency (1570 cm-1) which matches experimentally observed shoulder in IR spectrum (1560 cm-1). We demonstrate that the calculated ν2 frequencies depend linearly on a distance between adsorbed water molecules and a surface of Ti8O16 nanocluster! We also show that hydrogen bonding strongly affects ν1 vibrational frequencies but leaves ν2 and ν3 ones almost intact.

  17. Dilatational rheology of beta-casein adsorbed layers at liquid-fluid interfaces.

    PubMed

    Maldonado-Valderrama, Julia; Fainerman, Valentin B; Galvez-Ruiz, M José; Martín-Rodriguez, Antonio; Cabrerizo-Vílchez, Miguel A; Miller, Reinhard

    2005-09-22

    The rheological behavior of beta-casein adsorption layers formed at the air-water and tetradecane-water interfaces is studied in detail by means of pendant drop tensiometry. First, its adsorption behavior is briefly summarized at both interfaces, experimentally and also theoretically. Subsequently, the experimental dilatational results obtained for a wide range of frequencies are presented for both interfaces. An interesting dependence with the oscillation frequency is observed via the comparative analysis of the interfacial elasticity (storage part) and the interfacial viscosity (loss part) for the two interfaces. The analysis of the interfacial elasticities provides information on the conformational transitions undergone by the protein upon adsorption at both interfaces. The air-water interface shows a complex behavior in which two maxima merge into one as the frequency increases, whereas only a single maximum is found at the tetradecane interface within the range of frequencies studied. This is interpreted in terms of a decisive interaction between the oil and the protein molecules. Furthermore, the analysis of the interfacial viscosities provides information on the relaxation processes occurring at both interfaces. Similarly, substantial differences arise between the gaseous and liquid interfaces and various possible relaxation mechanisms are discussed. Finally, the experimental elasticities obtained for frequencies higher than 0.1 Hz are further analyzed on the basis of a thermodynamic model. Accordingly, the nature of the conformational transition given by the maximum at these frequencies is discussed in terms of different theoretical considerations. The formation of a protein bilayer at the interface or the limited compressibility of the protein in the adsorbed state are regarded as possible explanations of the maximum.

  18. 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.

  19. 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).

  20. Photoacoustic spectroscopy of surface adsorbed molecules using a nanostructured coupled resonator array

    NASA Astrophysics Data System (ADS)

    Lee, Dongkyu; Kim, Seonghwan; Van Neste, C. W.; Lee, Moonchan; Jeon, Sangmin; Thundat, Thomas

    2014-01-01

    A rapid method of obtaining photoacoustic spectroscopic signals for trace amounts of surface adsorbed molecules using a nanostructured coupled resonator array is described. Explosive molecules adsorbed on a nanoporous anodic aluminum oxide cantilever, which has hexagonally ordered nanowells with diameters and well-to-well distances of 35 nm and 100 nm, respectively, are excited using pulsed infrared (IR) light with a frequency matching the common mode resonance frequency of the coupled resonator. The common mode resonance amplitudes of the coupled resonator as a function of illuminating IR wavelength present a photoacoustic IR absorption spectrum representing the chemical signatures of the adsorbed explosive molecules. In addition, the mass of the adsorbed molecules as an orthogonal signal for quantitative analysis is determined by measuring the variation of the localized, individual mode resonance frequency of a cantilever on the array. The limit of detection of the ternary mixture of explosive molecules (1:1:1 of trinitrotoluene (TNT), cyclotrimethylene trinitramine (RDX) and pentaerythritol tetranitrate (PETN)) is estimated to be ˜100 ng cm-2. These multi-modal signals enable us to perform quantitative and rapid chemical sensing and analysis in ambient conditions.

  1. 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.

  2. 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

  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. A prelude to surface chemical reaction: Imaging the induction period of sulfur interaction with a strained Cu layer

    SciTech Connect

    Hrbek, J.; Figuera, J. de la; Pohl, K.; Jirsak, T.; Rodriguez, J.A.; Schmid, A.K.; Bartelt, N.C.; Hwang, R.Q.

    1999-12-02

    The induction period of the chemical reaction between Cu and S was visualized with STM, revealing a complex interplay between strain relief and reaction mechanism. Copper sulfide formation, monitored by high-resolution soft X-ray photoemission, started only after adsorption of {approximately}0.2 ML of S on a two-atom thick Cu layer supported by a Ru(0001) substrate. The pre-sulfide stages of sulfur interaction were investigated by in situ STM. Sulfur decorated the Cu surface by adsorbing at pseudo 4-fold hollow sites of the striped Cu phase and restructured the Cu layer to create additional adsorption sites of this type. Several self-organized structures of adsorbed S on the dynamically responding strained Cu layer were observed. Significant structural changes of both adsorbate and adsorbent occurred within the induction period of this surface chemical reaction.

  6. 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

  7. Layer Control of WSe2 via Selective Surface Layer Oxidation.

    PubMed

    Li, Zhen; Yang, Sisi; Dhall, Rohan; Kosmowska, Ewa; Shi, Haotian; Chatzakis, Ioannis; Cronin, Stephen B

    2016-07-26

    We report Raman and photoluminescence spectra of mono- and few-layer WSe2 and MoSe2 taken before and after exposure to a remote oxygen plasma. For bilayer and trilayer WSe2, we observe an increase in the photoluminescence intensity and a blue shift of the photoluminescence peak positions after oxygen plasma treatment. The photoluminescence spectra of trilayer WSe2 exhibit features of a bilayer after oxygen plasma treatment. Bilayer WSe2 exhibits features of a monolayer, and the photoluminescence of monolayer WSe2 is completely absent after the oxygen plasma treatment. These changes are observed consistently in more than 20 flakes. The mechanism of the changes observed in the photoluminescence spectra of WSe2 is due to the selective oxidation of the topmost layer. As a result, N-layer WSe2 is reduced to N-1 layers. Raman spectra and AFM images taken from the WSe2 flakes before and after the oxygen treatment corroborate these findings. Because of the low kinetic energy of the oxygen radicals in the remote oxygen plasma, the oxidation is self-limiting. By varying the process duration from 1 to 10 min, we confirmed that the oxidation will only affect the topmost layer of the WSe2 flakes. X-ray photoelectron spectroscopy shows that the surface layer WOx of the sample can be removed by a quick dip in KOH solution. Therefore, this technique provides a promising way of controlling the thickness of WSe2 layer by layer. PMID:27391161

  8. Observation of the dynamical change in a water monolayer adsorbed on a ZnO surface.

    PubMed

    Dulub, Olga; Meyer, Bernd; Diebold, Ulrike

    2005-09-23

    A combined scanning tunneling microscopy and density-functional theory (DFT) study shows a rich structure of water monolayers adsorbed on ZnO(1010) at room temperature. Most of the water is in a lowest-energy configuration where every second molecule is dissociated. It coexists with an energetically almost degenerate configuration consisting of a fully molecular water monolayer. Parts of the layer continuously switch back and forth between these two states. DFT calculations reveal that water molecules repeatedly associate and dissociate in this sustained dynamical process. PMID:16197151

  9. 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.

  10. Direct imaging of Pt single atoms adsorbed on TiO2 (110) surfaces.

    PubMed

    Chang, Teng-Yuan; Tanaka, Yusuke; Ishikawa, Ryo; Toyoura, Kazuaki; Matsunaga, Katsuyuki; Ikuhara, Yuichi; Shibata, Naoya

    2014-01-01

    Noble metal nanoparticles (e.g., gold and platinum) supported on TiO2 surfaces are utilized in many technological applications such as heterogeneous catalysts. To fully understand their enhanced catalytic activity, it is essential to unravel the interfacial interaction between the metal atoms and TiO2 surfaces at the level of atomic dimensions. However, it has been extremely difficult to directly characterize the atomic-scale structures that result when individual metal atoms are adsorbed on the TiO2 surfaces. Here, we show direct atomic-resolution images of individual Pt atoms adsorbed on TiO2 (110) surfaces using aberration-corrected scanning transmission electron microscopy. Subangstrom spatial resolution enables us to identify five different Pt atom adsorption sites on the TiO2 (110) surface. Combining this with systematic density functional theory calculations reveals that the most favorable Pt adsorption sites are on vacancy sites of basal oxygen atoms that are located in subsurface positions relative to the top surface bridging oxygen atoms.

  11. 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.

  12. Intervalence transfer of ferrocene moieties adsorbed on electrode surfaces by a conjugated linkage

    NASA Astrophysics Data System (ADS)

    Chen, Wei; Brown, Lauren E.; Konopelski, Joseph P.; Chen, Shaowei

    2009-03-01

    Effective intervalence transfer occurred between the metal centers of ferrocene moieties that were adsorbed onto a ruthenium thin film surface by ruthenium-carbene π bonds, a direct verification of Hush's four-decade-old prediction. Electrochemical measurements showed two pairs of voltammetric peaks where the separation of the formal potentials suggested a Class II behavior. Additionally, the potential spacing increased with increasing ferrocene surface coverage, most probably as a consequence of the enhanced contribution from through-space electronic interactions between the metal centers. In contrast, the incorporation of a sp 3 carbon spacer into the ferrocene-ruthenium linkage led to the diminishment of interfacial electronic communication.

  13. Isocyanide ligands adsorbed on metal surfaces: applications in catalysis, nanochemistry, and molecular electronics.

    PubMed

    Angelici, Robert J; Lazar, Mihaela

    2008-10-20

    Knowledge of the coordination chemistry and reactivity of isocyanide ligands in transition-metal complexes forms the basis for understanding the adsorption and reactions of isocyanides on metal surfaces. In this overview, we explore reactions (often catalytic) of isocyanides adsorbed on metal surfaces that reflect their patterns of reactivity in metal complexes. We also examine applications of isocyanide adsorption to the stabilization of metal nanoparticles, the functionalization of metal electrodes, and the creation of conducting organic-metal junctions in molecule-scale electronic devices.

  14. Surface Enhanced Raman Scattering studies of L-amino acids adsorbed on silver nanoclusters

    NASA Astrophysics Data System (ADS)

    Botta, Raju; Rajanikanth, A.; Bansal, C.

    2015-01-01

    Silver nanocluster films were prepared using plasma inert gas phase condensation technique. These were used as Raman active substrates for Surface Enhanced Raman Scattering (SERS) studies of 19 standard L-amino acids adsorbed on the surface of Ag nanoclusters via Agsbnd N bonds. A detailed study of two essential aromatic amino acids viz. L-Phenylalanine and L-Tryptophan showed a correlation between the Raman intensity of the characteristic lines of phenol and indole side chains and their molar concentrations in the range 1 μM-1 mM. This indicates that Raman studies can be used for quantitative determination of the amino acids in proteins.

  15. 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.

  16. 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.

  17. Surface layer characterization at Paranal Observatory

    NASA Astrophysics Data System (ADS)

    Lombardi, G.; Melnick, J.; Hinojosa Goñi, R. H.; Navarrete, J.; Sarazin, M.; Berdja, A.; Tokovinin, A.; Wilson, R.; Osborn, J.; Butterley, T.; Shepherd, H.

    2010-07-01

    In this paper the Paranal Surface Layer characterization is presented. Causes, physics and behavior of the SL above Paranal surface are discussed. The analysis is developed using data from different turbulence profilers operated during several campaigns between 2007 and 2009. Instruments used are SL-SLODAR, DIMM, Elevated DIMM, MASS, Lunar Scintillometer and Ultrasonic Anemometers with temperature sensors positioned at different strategic heights.

  18. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    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 the 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 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. The work was supported by National Science Foundation.

  20. Effects of Adsorbed Polyaniline on Redox Processes on As(2)O(3) Surfaces.

    PubMed

    de Farias RF; de Souza JM; de Melo JV; Airoldi

    2000-07-01

    Polyaniline deposited on As(2)O(3) surface resulted in a new material, which was characterized by infrared spectoscopy, thermogravimetry, differential scanning calorimetry, scanning electron microscopy, X-ray diffraction, and cyclic voltammetry. The mass percentage of polymer deposited on oxide surface is approximately 13%. The scanning electron microscopy images as well as the X-ray diffraction patterns provided conclusive evidence that the oxide surface is coated by the polymer. The cyclic voltammograms of the polyaniline adsorbed on As(2)O(3) surface showed that the adsorbate exerts remarkable effects on redox processes on this oxide. The pure oxide exhibited two oxidation/reduction peaks at 0.25/-0.06 and 0.47/-0.25 V attributed tentatively to the processes As(2)O(3)(s)+6H(+)+6e(-)=2As(s)+3H(2)O and As(s)+3H(+)+3e(-)=AsH(3)(g), respectively. The polyaniline-coated sample exhibited a better-defined voltammogram in which the first oxidation peak of the oxide had its intensity increased about four times. Copyright 2000 Academic Press.

  1. 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.

  2. Paracrystalline surface layers of dairy propionibacteria.

    PubMed Central

    Lortal, S; Rouault, A; Cesselin, B; Sleytr, U B

    1993-01-01

    We examined 70 dairy propionibacteria and detected a crystalline surface layer (S-layer) in only 2 organisms (Propionibacterium freudenreichii CNRZ 722 and Propionibacterium jensenii CNRZ 87) by freeze-etching and sodium dodecyl sulfate-polyacrylamide electrophoresis (SDS-PAGE). Both S-layers exhibited oblique (p2) symmetry (a = 9.9 nm; b = 5.4 nm; gamma = 80 degrees) and completely covered the cell surface. Treatment for 15 min at the ambient temperature with 5 M guanidine hydrochloride or acidic conditions (250 mM ammonium acetate, pH 2.7) efficiently extracted the S-layer protein from intact cells of strain CNRZ 722, whereas treatment with 5 M guanidine hydrochloride at 100 degrees C for 15 min was necessary to isolate the S-layer protein of strain CNRZ 87. The precipitates obtained after dialysis of the extracting agents produced no regular patterns. The molecular masses of the two S-layer proteins, as estimated by SDS-PAGE, were 58.5 kDa for the strain CNRZ 722 and 67.3 kDa for the strain CNRZ 87. Mass spectrometry of the isolated S-layer protein of strain CNRZ 722 gave a molecular mass value close to the expected value (56,533 Da). The N-terminal sequences of the two purified S-layer proteins differed, as did their amino acid compositions, except that the same high hydrophobic amino acid content (52%) was observed. Images PMID:8304753

  3. Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface

    PubMed Central

    Hiebel, Fanny; Shong, Bonggeun; Chen, Wei; Madix, Robert J.; Kaxiras, Efthimios; Friend, Cynthia M.

    2016-01-01

    Weak inter-adsorbate interactions are shown to play a crucial role in determining surface structure, with major implications for its catalytic reactivity. This is exemplified here in the case of acetate bound to Au(110), where the small extra energy of the van der Waals interactions among the surface-bound groups drives massive restructuring of the underlying Au. Acetate is a key intermediate in electro-oxidation of CO2 and a poison in partial oxidation reactions. Metal atom migration originates at surface defects and is likely facilitated by weakened Au–Au interactions due to bonding with the acetate. Even though the acetate is a relatively small molecule, weak intermolecular interaction provides the energy required for molecular self-assembly and reorganization of the metal surface. PMID:27731407

  4. The dynamics of adsorption on clean and adsorbate-modified transition metal surfaces

    SciTech Connect

    Madix, R.J.

    1991-06-01

    Research is being carried out on both nondissociative and dissociative adsorption of gases on transition metal surfaces, with emphasis on alkanes. Particular attention is be placed on understanding the effects of adsorbed species on adsorption probabilities and on clarifying the role of energy exchange processes at the surface in both dissociative and nondissociative adsorption. Molecular beam methods are coupled with methods of surface science to gain the greatest control of the variables of the problem, including the incident kinetic energy, vibrational energy and angle of incidence of the incoming molecules. The dynamics of both direct and precursor-influenced dissociative adsorption routes are examined. Surface intermediates formed by activated adsorption are identified by vibrational spectroscopy and temperature programmed reaction. Emphasis is on comparative studies of low molecular weight alkanes in order to understand the origin of the differences in their reactivities on different metals.

  5. Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface

    NASA Astrophysics Data System (ADS)

    Hiebel, Fanny; Shong, Bonggeun; Chen, Wei; Madix, Robert J.; Kaxiras, Efthimios; Friend, Cynthia M.

    2016-10-01

    Weak inter-adsorbate interactions are shown to play a crucial role in determining surface structure, with major implications for its catalytic reactivity. This is exemplified here in the case of acetate bound to Au(110), where the small extra energy of the van der Waals interactions among the surface-bound groups drives massive restructuring of the underlying Au. Acetate is a key intermediate in electro-oxidation of CO2 and a poison in partial oxidation reactions. Metal atom migration originates at surface defects and is likely facilitated by weakened Au-Au interactions due to bonding with the acetate. Even though the acetate is a relatively small molecule, weak intermolecular interaction provides the energy required for molecular self-assembly and reorganization of the metal surface.

  6. 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.

  7. Ni 3+ adsorbate dynamics on a NiO(0 0 1) surface

    NASA Astrophysics Data System (ADS)

    Karakasidis, Theodoros E.; Vamvakopoulos, E.

    2006-05-01

    We present results concerning the dynamical behavior of a Ni 3+ adsorbate on a NiO(0 0 1) surface obtained by molecular dynamics simulations. In a first place, we examined at low temperature the position of the Ni 3+ ion as an adatom on the surface and the corresponding modification of its local environment as reflected on the pair-wise radial distribution function. The calculation of the vibrational properties of the adatom by means of the phonon local density of states (LDOS) shows that there is an anisotropic behavior both in the two principal in-plane directions as well as in the direction normal to the surface in accordance with the structural results. We compare the phonon LDOS of the Ni 3+ adatom with the corresponding results for the Ni 2+ adatom and the Ni 2+ surface cations. Static energetic calculations are indicative that the exchange of the Ni 3+ ion with a surface Ni 2+ ion could be favorable. Such a behavior is confirmed by results observed at temperatures higher than 700 K where the Ni 3+ adsorbate is located on a substitutional position on the surface and not on adatom position. The exchange takes place through simple or double exchange mechanisms. The structural and dynamical behavior of the Ni 3+ ion at the substitution position was investigated in the temperature range 700-2000 K through the calculation of the pair distribution function, the relaxed interlayer relative position (RIRP), mean-square displacements (MSDs) and phonon LDOS. Results show that in comparison with the Ni 2+ surface ions the Ni 3+ ion at substitution position is more tightly bound especially in the direction normal to the surface as is indicated by the local structure and the contraction it presents as well as its phonon LDOS. As temperature increases the binding of the Ni 3+ ion becomes less important as reflected on the physical properties mentioned above.

  8. First principles calculations on Na and K-adsorbed diamond(100) surface

    SciTech Connect

    Nie, JL; Xiao, H Y.; Zu, Xiaotao; Gao, Fei

    2006-08-01

    Self-consistent, periodic, density functional theory calculations, using PW91 functional, have been performed to investigate Na and K adsorption on the C(100)(2?1) surface. Our calculations showed that Na and K adatoms preferred to occupy valley-bridge sites at the coverage (?) of 0.5ML. For the coverage of 1ML, the combination of pedestal site and valley-bridge site turned out to be energetically favored. These findings are found to be consistent with those obtained for alkali-metal adsorption on silicon and germanium surfaces. Two desorption peaks named ? and ? for K adsorption have been observed and assigned to pedestal or bridge site and valley-bridge sites experimentally, while our results showed that the ? and ? states should be ascribed to pedestal site and valley-bridge sites and the combination of bridge and valley-bridge site is not the local minima. Work function analysis showed that when Na and K are adsorbed on diamond surface, the work function will decrease linearly with increasing coverage, up to a minimum, and finally increase again because of the depolarization of the adsorbate, agreeing well with experiments.

  9. Characterization and control of molecular ordering on adsorbate-induced reconstructed surfaces

    NASA Astrophysics Data System (ADS)

    Pai, Woei Wu; Hsu, C. L.; Lin, K. C.; Sin, L. Y.; Tang, Tong B.

    2005-02-01

    Understanding molecular ordering is a critical step in achieving molecular self-assembly for the fabrication of nanomaterials, and molecular ordering in the adsorption of large molecules on atomically flat surfaces can be characterized with precision by scanning tunneling microscopy (STM). Complications arise therein from the expanded possibility of various adsorption structures, conformations and surface reconstructions. Here we present two cases of C 60 adsorbed on Ag(1 0 0) and Cu(1 1 1) that illustrate the importance of competitive interactions in the presence of adsorbate-induced reconstruction. In both studies, strong STM contrasts derive from topographic features arising from reconstructed substrates. C 60/Ag(1 0 0) presents a unique uniaxially incommensurate molecular packing. We have also found that one can control molecular ordering with a stepped surface to produce a single-domain film. In C 60/Cu(1 1 1), we are able to obtain metastable, yet well-defined, molecular ordering with precise annealing procedures. These metastable states exhibit a clear correlation between molecular contrast patterns and the adlayer rotation angle, as a consequence of competitive interactions between optimizing C 60 bonding at preferred reconstructive sites and C 60-C 60 repulsion. Finer control of selective preparation of these metastable structures offers a plausible way of fabricating nanostructures by design.

  10. Efficient conformational sampling of peptides adsorbed onto inorganic surfaces: insights from a quartz binding peptide.

    PubMed

    Wright, Louise B; Walsh, Tiffany R

    2013-04-01

    Harnessing the properties of biomolecules, such as peptides, adsorbed on inorganic surfaces is of interest to many cross-disciplinary areas of science, ranging from biomineralisation to nanomedicine. Key to advancing research in this area is determination of the peptide conformation(s) in its adsorbed state, at the aqueous interface. Molecular simulation is one such approach for accomplishing this goal. In this respect, use of temperature-based replica-exchange molecular dynamics (T-REMD) can yield enhanced sampling of the interfacial conformations, but does so at great computational expense, chiefly because of the need to include an explicit representation of water at the interface. Here, we investigate a number of more economical variations on REMD, chiefly those based on Replica Exchange with Solvent Tempering (REST), using the aqueous quartz-binding peptide S1-(100) α-quartz interfacial system as a benchmark. We also incorporate additional implementation details specifically targeted at improving sampling of biomolecules at interfaces. We find the REST-based variants yield configurational sampling of the peptide-surface system comparable with T-REMD, at a fraction of the computational time and resource. Our findings also deliver novel insights into the binding behaviour of the S1 peptide at the quartz (100) surface that are consistent with available experimental data.

  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. 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

  13. 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.

  14. Surface free energy of polyimide aligning layers

    NASA Astrophysics Data System (ADS)

    Borycki, Jerzy; Okulska-Bozek, Malgorzata

    2000-05-01

    Polyimides from four selected dianhydrides and seven diamines were synthesized by two-step polycondensation method. During the first step 10% solutions of poly(amic acid)s in N,N-dimethylformamide and 1-methyl-2-pyrrolidinone were obtained. The thin polyimide layers on soda glass were prepared by thermal cyclodehydration. Contact angles of series of standard liquids for tested polyimide films were measured. The values of surface free energy and its components were calculated accordingly to Zisman, Owens et al. and van Oss equations. Some correlation between the surface properties and the chemical structure of polyimide aligning layers were presented.

  15. Electronic Structures of Hydrogen and Oxygen Adsorbed Tungsten (3, 2, 0) and Tungsten (8, 7, 0) Surfaces

    NASA Astrophysics Data System (ADS)

    Bao, Zhuo; Bostwick, Aaron; Rotenberg, Eli; Kevan, Stephen

    2011-03-01

    The Valence band electronic structues of Hydrogen adsorbed and Oxygen adsorbed Tungsten stepped surfaces, Tungsten (3, 2, 0) and (8, 7, 0) surface are investigated using angular-resolved photoemission techniques and ab-initio electronic structure calculation methods. The band features of surface states at different Hydrogen and Oxygen coverages are experimentally distinguished by using photon-energy scanning method. Quasi-one- dimensional band features are found in the surface states with saturated Oxygen coverages of both stepped surfaces. The effects of adsorbate coverages on dimensionalities of surface electronic states are studied using high-resolution band mapping methods and ab-initio calculation methods. Thanks to Department of Energy for the financial supporting of this project.

  16. 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.

  17. Validation of thermodesorption method for analysis of semi-volatile organic compounds adsorbed on wafer surface.

    PubMed

    Hayeck, Nathalie; Gligorovski, Sasho; Poulet, Irène; Wortham, Henri

    2014-05-01

    To prevent the degradation of the device characteristics it is important to detect the organic contaminants adsorbed on the wafers. In this respect, a reliable qualitative and quantitative analytical method for analysis of semi-volatile organic compounds which can adsorb on wafer surfaces is of paramount importance. Here, we present a new analytical method based on Wafer Outgassing System (WOS) coupled to Automated Thermal Desorber-Gas chromatography-Mass spectrometry (ATD-GC-MS) to identify and quantify volatile and semi-volatile organic compounds from 6", 8" and 12" wafers. WOS technique allows the desorption of organic compounds from one side of the wafers. This method was tested on three important airborne contaminants in cleanroom i.e. tris-(2-chloroethyl) phosphate (TCEP), tris-(2-chloroisopropyl) phosphate (TCPP) and diethyl phthalate (DEP). In addition, we validated this method for the analysis and quantification of DEP, TCEP and TCPP and we estimated the backside organic contamination which may contribute to the front side of the contaminated wafers. We are demonstrating that WOS/ATD-GC-MS is a suitable and highly efficient technique for desorption and quantitative analysis of organophosphorous compounds and phthalate ester which could be found on the wafer surface.

  18. Heterogeneous and Photochemical Reactions Involving Surface Adsorbed Organics: Common Lignin Pyrolysis Products With Nitrogen Dioxide.

    NASA Astrophysics Data System (ADS)

    Hinrichs, R. Z.; Nichols, B. R.; Rapa, C.; Costa, V.

    2009-05-01

    Solid-air interfaces, such as airborne particulate matter and ground level surfaces, provide unique supports for tropospheric heterogeneous chemistry. These interfaces commonly contain surface adsorbed organics, such as lignin pyrolysis products, that can significantly alter their physical and chemical properties. Attenuated total reflectance infrared spectroscopy (ATR-FTIR) provides an ideal tool for monitoring chemical changes in thin organic films during heterogeneous and photochemical reactions. Phenolic compounds, with and without co- adsorbed photosensitizers, were exposed to NO2 concentrations in the parts-per-billion range at 300 K and 20% relative humidity. Catechol, when mixed with benzophenone or dicyclohexylketone, formed 4- nitrocatechol as the dominant product under dark conditions. Deuterating the catechol alcohol groups caused the initial rate of reaction to decrease by a factor of 3.3±0.5, consistent with formation of the ortho- semiquinone radical as the rate determining step. The rate of 4-nitrocatechol formation did not increase under illuminated conditions, even with the presence of benzophenone a well known photosensitizer. UV-A/visible radiation did, however, initiate a photochemical reaction between benzophenone and 4-nitrocatechol, likely forming high molecular weight polymerization products. In contrast, 2-ethoxyphenol displayed no reactivity with NO2, even under illuminated conditions with a photosensitizer. Implications for the fate of lignin pyrolysis products, which are prevalent in biomass combustion smoke, will be discussed.

  19. Adsorbate induced mesoscopic surface reconstruction of the system Te/Pd(1 0 2)

    NASA Astrophysics Data System (ADS)

    Godzik, G.; Pfnür, H.

    2001-08-01

    Low energy electron diffraction (LEED) measurements have been carried out on the clean and Te covered Pd(1 0 2) surface. This is the surface into which the Pd(1 0 0) surface is reconstructed by a concentration of more than 0.5 ML of Te. The Pd(1 0 2) surface was produced with a terrace width of more than 1000 Å. Up to 0.5 ML the adsorption of Te takes place on the flat (1 0 2) surface, on which islands with (2×1) structure are formed coupled with a reduction of the terrace widths to about half the initial value. Above 0.5 ML, and up to 1 ML, the adsorbed Te atoms produce a structural change of the surface, i.e. a terrace structure is formed with a clear average terrace length that depends on Te concentration and with step edges in [ 2¯ 0 1] direction. As concluded from the characteristic splitting of LEED spots as a function of energy, these terraces occupy only two height levels in an alternating sequence and are separated by steps of single atomic height. The terrace width of the alternating terraces increases with increasing Te-concentration. Again a flat surface is formed at 1 ML of Te. A geometrical model is established and discussed.

  20. 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.

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. The refraction in the atmospheric surface layer

    NASA Astrophysics Data System (ADS)

    Golitsyn, G. S.

    1982-12-01

    An analytical theory of refraction for the atmospheric layer is developed in which the vertical profiles of the refraction are calculated based on the theory of Monin and Obukhov (1954). A similarity parameter is found for the refraction in such conditions. These results are used to clarify the idea of Moroz (1976) that the nearness of the horizon as recorded by the automatic stations on the surface of Venus can be explained by the decrease in the temperature at the very surface of the planet. In addition, several other optical phenomena which occur near the surface of the earth are examined.

  6. 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

  7. 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.

  8. Characteristics of the Martian atmosphere surface layer

    NASA Astrophysics Data System (ADS)

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

    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. 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.

  10. Manipulation of adsorbed atoms and creation of new structures on room-temperature surfaces with a scanning tunneling microscope.

    PubMed

    Whitman, L J; Stroscio, J A; Dragoset, R A; Celotta, R J

    1991-03-01

    A general method of manipulating adsorbed atoms and molecules on room-temperature surfaces with the use of a scanning tunneling microscope is described. By applying an appropriate voltage pulse between the sample and probe tip, adsorbed atoms can be induced to diffuse into the region beneath the tip. The field-induced diffusion occurs preferentially toward the tip during the voltage pulse because of the local potential energy gradient arising from the interaction of the adsorbate dipole moment with the electric field gradient at the surface. Depending upon the surface and pulse parameters, cesium (Cs) structures from one nanometer to a few tens of nanometers across have been created in this way on the (110) surfaces of gallium arsenide (GaAs) and indium antimonide (InSb), including structures that do not naturally occur.

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

    PubMed

    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 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Electronic and structural properties of nitrogen adsorbed Nb(100) surfaces: An ab initio study

    NASA Astrophysics Data System (ADS)

    Carvalho, P. A. S.; Miwa, R. H.

    2013-08-01

    We have performed an ab initio total energy investigation of the electronic and structural properties of nitrogen adsorbed Nb(100) surface, N/Nb(100). We find an energetic preference for the nitrogen adsorption on the hollow sites of the Nb(100) surface. Upon the presence of N adatoms, there is a reduction of the electronic density of states near the Fermi level. However, the metallic character of the Nb(100) surface has been maintained. The (occupied) electronic states of N adatoms are resonant within the valence band of Nb(100), mostly lying at 4 eV below the Fermi level. Further investigations reveal the formation of energetically stable N/Nb(100)-(n × 1) phase, being the (2 × 1), (5 × 1), and (10 × 1) the most likely ones. Those (n × 1) structures are composed by NbN stripes separated by N vacancy lines. Our scanning tunneling microscopy simulations indicate the formation of bright lines lying on the Nb atoms neighboring the (dark) N vacancy lines, giving rise to an anisotropic electronic structure on the N/Nb(100)-(n × 1) surface. That is, the metallic character of the surface has been strengthened along the vacancy-lines.

  17. 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.

  18. Tunneling spectroscopy of clean and adsorbate-covered gold surfaces in humid air, measured with fast bias voltage ramps

    NASA Astrophysics Data System (ADS)

    Rösch, Raphael; Schuster, Rolf

    2015-01-01

    The noise level of tunneling spectroscopic data can be significantly reduced by averaging the tunneling current over a large number of short bias voltage ramps, instead of recording over a single slow ramp. This effect is demonstrated for tunneling spectra of Au(111) by averaging over 200 consecutive bias voltage ramps, each 500 μs long. We attribute the improvement of the data quality to the frequency dependence of the current noise spectral density. Due to mechanical vibrations and tip instabilities the noise density is usually much higher for low frequencies ca. < 1 kHz than for the high frequencies relevant for measuring with fast bias ramps. The high data quality allowed for the routine detection of the Au(111) surface state and the investigation of the influence of steps in humid air, i.e., with a water-covered tunneling gap. For a CN covered Au surface in the presence of water we unexpectedly found additional electronic density of states at positive energies, around 0.6 eV, i.e., for unoccupied states. STS spectra of a (√{ 3} ×√{ 3}) R 30 ° Cu-UPD layer, formed by adsorbed sulfate and Cu species, indicate tunneling via the sulfate electronic density of states.

  19. Determination of surface properties of iron hydroxide-coated alumina adsorbent prepared for removal of arsenic from drinking water.

    PubMed

    Hlavay, József; Polyák, Klára

    2005-04-01

    A novel type adsorbent was prepared by in situ precipitation of Fe(OH)3 on the surface of activated Al2O3 as a support material. The iron content of the adsorbent was 0.31+/-0.003% m/m (56.1 mmol/g); its mechanical and chemical stability proved to be appropriate in solutions. The total capacity of the adsorbent was 0.12 mmol/g, and the pH of zero point of charge, pH(zpc) = 6.9+/-0.3. Depending on the pH of solutions, the adsorbent can be used for binding of both anions and cations, if pH(eq) < pH(zpc) anions are sorbed on the surface of adsorbent (S) through [SOH2+] and [SOH] groups. A graphical method was used for the determination of pH(iep) (isoelectric points) of the adsorbent and values of pH(iep) = 6.1+/-0.3 for As(III) and pH(iep) = 8.0+/-0.3 for As(V) ions were found. The amount of surface charged groups (Q) was about zero within the a pH range of 6.5-8.6, due to the practically neutral surface formed on the adsorption of As(V) ions. At acidic pH (pH 4.7), Q = 0.19 mol/kg was obtained. The adsorption of arsenate and arsenite ions from solutions of 0.1-0.4 mmol/L was represented by Langmuir-type isotherms. A great advantage of the adsorbent is that it can be used in adsorption columns, and low waste technology for removal of arsenic from drinking water can be developed.

  20. 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

  1. Surface characterization of adsorbents in ultrasound-assisted oxidative desulfurization process of fossil fuels.

    PubMed

    Etemadi, Omid; Yen, Teh Fu

    2007-09-01

    Surface properties of two different phases of alumina were studied through SEM images. Characterization of amorphous acidic alumina and crystalline boehmite by XRD explains the differences in adsorption capacities of each sample. Data from small angle neutron scattering (SANS) provide further results regarding the ordering in amorphous and crystalline samples of alumina. Quantitative measurements from SANS are used for pore size calculations. Higher disorder provides more topological traps, irregularities, and hidden grooves for higher adsorption capacity. An isotherm model was derived for adsorption of dibenzothiophene sulfone (DBTO) by amorphous acidic alumina to predict and calculate the adsorption of sulfur compounds. The Langmuir-Freundlich model covers a wide range of sulfur concentrations. Experiments prove that amorphous acidic alumina is the adsorbent of choice for selective adsorption in the ultrasound-assisted oxidative desulfurization (UAOD) process to produce ultra-low-sulfur fuel (ULSF).

  2. Surface characterization of adsorbents in ultrasound-assisted oxidative desulfurization process of fossil fuels.

    PubMed

    Etemadi, Omid; Yen, Teh Fu

    2007-09-01

    Surface properties of two different phases of alumina were studied through SEM images. Characterization of amorphous acidic alumina and crystalline boehmite by XRD explains the differences in adsorption capacities of each sample. Data from small angle neutron scattering (SANS) provide further results regarding the ordering in amorphous and crystalline samples of alumina. Quantitative measurements from SANS are used for pore size calculations. Higher disorder provides more topological traps, irregularities, and hidden grooves for higher adsorption capacity. An isotherm model was derived for adsorption of dibenzothiophene sulfone (DBTO) by amorphous acidic alumina to predict and calculate the adsorption of sulfur compounds. The Langmuir-Freundlich model covers a wide range of sulfur concentrations. Experiments prove that amorphous acidic alumina is the adsorbent of choice for selective adsorption in the ultrasound-assisted oxidative desulfurization (UAOD) process to produce ultra-low-sulfur fuel (ULSF). PMID:17543320

  3. 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.

  4. Surface-enhanced Raman spectroscopy of amino acids adsorbed on an electrochemically prepared silver surface

    NASA Astrophysics Data System (ADS)

    Stewart, S.; Fredericks, P. M.

    1999-07-01

    An electrochemically roughened silver surface, in conjunction with a Raman microprobe spectrometer, was used to obtain SER spectra of a suite of 19 L-amino acids. The spectra obtained were very different from previously reported SER spectra obtained from silver hydrosols of amino acids. Analysis of the spectra showed that adsorption of all amino acids was via the ionised carboxylate group, and that the side chain of most of the molecules was also in close proximity to the surface. The spectra also indicated that, in contrast, the amine terminus was protonated and relatively far from the surface. Sulfur-containing amino acids also interacted with the silver surface through their sulfur atoms.

  5. 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.

  6. X-ray Reflectivity Studies of Adsorbed Proteins on Langmuir Layers

    NASA Astrophysics Data System (ADS)

    Málková, Šárka; Pingali, Sai V.; Long, Fei; Cho, Wonhwa; Schlossman, Mark L.

    2002-03-01

    Synchrotron X-ray reflectivity is used to study the interaction of the C2 domain of cytosolic phospholipase A2 (cPLA_2-C2) with a phospholipid membrane. SOPC (1-steraoyl-2-oleoyl-sn-glycero-3-phosphocholine) monolayer has been chosen as our model membrane. SOPC monolayer is supported on a buffered, Ca^2+ containing aqueous solution. The original phospholipid layer, which can be described by a two layer model roughened by capillary wave theory, is modified and a three layer model is necessary to fit the data after the protein is injected. The data analysis indicates that a third layer attached to the phospholipid headgroup region is formed. This additional layer corresponds to proteins bound to the phospholipid. The mechanism of the protein binding to the lipid depends on the initial lipid pressure with adsorption being less pronounced at higher pressures. Two control experiments are performed. Buffer containing no Ca^2+ is used in the first and F35/L39A mutant of cPLA_2-C2 (the mutation is in the region containing ligands for multiple Ca^2+ ions) is used in the second. Reflectivity curves do not show any evidence of protein adsorption to the phospholipid monolayer in any of our two control experiments. Our results thus support the idea that the initial pressure of the lipid, Ca^2+ ions and Ca^2+ binding sites of cPLA_2-C2 are important factors for the membrane binding of this protein.

  7. 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.

  8. Theoretical Study on Surface-Enhanced Raman Spectra of Water Adsorbed on Noble Metal Cathodes of Nanostructures

    NASA Astrophysics Data System (ADS)

    Wu, De-Yin; Pang, Ran; Tian, Zhong-Qun

    2016-06-01

    The observed surface-enhanced Raman scattering (SERS) spectra of water adsorbed on metal film electrodes of silver, gold, and platinum nanoparticles were used to infer interfacial water structures. The basis is the change of the electrochemical vibrational Stark tuning rates and the relative Raman intensity of the stretching and bending modes. How it is not completely understood the reason why the relative Raman intensity ratio of the bending and stretching vibrations of interfacial water increases at the very negative potential region. Density functional theory calculations provide the conceptual model. The specific enhancement effect for the bending mode was closely associated with the water adsorption structure in a hydrogen bonded configuration through its H-end binding to surface sites with large polarizability due to strong cathodic polarization. The present theoretical results allow us to propose that interfacial water molecules exist on these metal cathodes with different hydrogen bonding interactions, the HO-H…Ag(Au) for silver and gold. In acidic solution, a surface electron-hydronium ion-pair was proposed as an adsorption configuration of interfacial water structures on silver and gold cathodes based on density functional theory (DFT) calculations. The EHIP is in the configuration of H3O+(H2O)ne-, where the hydronium H3O+ and the surface electron is separated by water layers. The electron bound in the EHIP can first be excited under light irradiation, subsequently inducing a structural relaxation into a hydrated hydrogen atom. Thus, Raman intensities of the interfacial water in the EHIP species are signifcantly enhanced due to the cathodic polarization on silver and gold electrodes.

  9. 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

  10. Attenuated total reflectance Fourier-transform infrared spectroscopy of carboxylic acids adsorbed onto mineral surfaces

    NASA Astrophysics Data System (ADS)

    Kubicki, J. D.; Schroeter, L. M.; Itoh, M. J.; Nguyen, B. N.; Apitz, S. E.

    1999-09-01

    A suite of naturally-occurring carboxylic acids (acetic, oxalic, citric, benzoic, salicylic and phthalic) and their corresponding sodium salts were adsorbed onto a set of common mineral substrates (quartz, albite, illite, kaolinite and montmorillonite) in batch slurry experiments. Solution pH's of approximately 3 and 6 were used to examine the effects of pH on sorption mechanisms. Attenuated total reflectance Fourier-transform infrared (ATR FTIR) spectroscopy was employed to obtain vibrational frequencies of the organic ligands on the mineral surfaces and in solution. UV/visible spectroscopy on supernatant solutions was also employed to confirm that adsorption from solution had taken place for benzoic, salicylic and phthalic acids. Molecular orbital calculations were used to model possible surface complexes and interpret the experimental spectra. In general, the tectosilicates, quartz and albite feldspar, did not chemisorb (i.e., strong, inner-sphere adsorption) the carboxylate anions in sufficient amounts to produce infrared spectra of the organics after rinsing in distilled water. The clays (illite, kaolinite and montmorillonite) each exhibited similar ATR FTIR spectra. However, the illite sample used in this study reacted to form strong surface and aqueous complexes with salicylic acid before being treated to remove free Fe-hydroxides. Chemisorption of carboxylic acids onto clays is shown to be limited without the presence of Fe-hydroxides within the clay matrix.

  11. 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.

  12. Interpretation of the excess adsorption isotherms of organic eluent components on the surface of reversed-phase adsorbents. Effect on the analyte retention.

    PubMed

    Kazakevich, Y V; LoBrutto, R; Chan, F; Patel, T

    2001-04-13

    The excess adsorption isotherms of acetonitrile, methanol and tetrahydrofuran from water on reversed-phase packings were studied, using 10 different columns packed with C1-C6, C8, C10, C12, and C18 monomeric phases, bonded on the same type of silica. The interpretation of isotherms on the basis of the theory of excess adsorption shows significant accumulation of the organic eluent component on the adsorbent surface on the top of "collapsed" bonded layer. The accumulated amount was shown to be practically independent of the length of alkyl chains bonded to the silica surface. A model that describes analyte retention on a reversed-phase column from a binary mobile phase is developed. The retention mechanism involves a combination of analyte distribution between the eluent and organic adsorbed layer, followed by analyte adsorption on the surface of the bonded phase. A general retention equation for the model is derived and methods for independent measurements of the involved parameters are suggested. The theory was tested by direct measurement of analyte retention from the eluents of varied composition and comparison of the values obtained with those theoretically calculated values. Experimental and theoretically calculated values are in good agreement.

  13. 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

  14. Controlled surface photochemistry: Bond- and isotope-selective photodesorption of neutrals by adsorbate vibrational preparation with infrared laser pulses

    NASA Astrophysics Data System (ADS)

    Saalfrank, Peter; Paramonov, Guennaddi K.

    1997-12-01

    The possibility of controlling surface photochemistry by the selective vibrational preparation of adsorbates with infrared (ir) laser pulses is investigated theoretically. In particular, the selective ir plus ultraviolet (uv) light-induced desorption of different isotopomeric neutral adsorbates from metal surfaces is studied with the help of nuclear density matrix theory. As a concrete example the system NH3/ND3/Cu(111) is chosen. In a first step of the "vibrationally mediated chemistry" advocated here, based on computed two-mode dipole functions and model potentials, optimal infrared laser pulses are designed to selectively excite the umbrella mode ν2 of either adsorbed NH3 or ND3. In a second step, an uv/visible photon enforces an electronic transition, leading, after ultrafast quenching, to desorption induced by electronic transitions (DIET). It is argued that despite strong dissipation, the proper vibrational preparation not only increases desorption yields substantially, but also allows for an almost complete separation of both isotopomers.

  15. 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.

  16. Rate of evolution of the specific surface area of surface snow layers.

    PubMed

    Cabanes, Axel; Legagneux, Loïc; Dominé, Florent

    2003-02-15

    The snowpack can impact atmospheric chemistry by exchanging adsorbed or dissolved gases with the atmosphere. Modeling this impact requires the knowledge of the specific surface area (SSA) of snow and its variations with time. We have therefore measured the evolution of the SSA of eight recent surface snow layers in the Arctic and the French Alps, using CH4 adsorption at liquid nitrogen temperature (77 K). The SSA of fresh snow layers was found to decrease with time, from initial values in the range 613-1540 cm2/g to values as low as 257 cm2/g after 6 days. This is explained by snow metamorphism, which causes modifications in crystal shapes, here essentially crystal rounding and the disappearance of microstructures. A parametrization of the rate of SSA decrease is proposed. We fit the SSA decrease to an exponential law and find that the time constant alpha(exp) (day(-1)) depends on temperature according to alpha(exp) = 76.6 exp (-1708/7), with Tin kelvin. Our parametrization predicts that the SSA of a snow layer evolving at -40 degrees C will decrease by a factor of 2 after 14 days, while a similar decrease at -1 degrees C will only require 5 days. Wind was found to increase the rate of SSA decrease, but insufficient data did not allow a parametrization of this effect. PMID:12636262

  17. 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

  18. Investigations on HONO formation from photolysis of adsorbed HNO3 on quartz glass surfaces.

    PubMed

    Laufs, Sebastian; Kleffmann, Jörg

    2016-04-14

    During the last few decades, nitrous acid (HONO) has attracted significant attention as a major source of the OH radical, the detergent of the atmosphere. However, the different daytime sources identified in the laboratory are still the subject of controversial discussion. In the present study, one of these postulated HONO sources, the heterogeneous photolysis of nitric acid (HNO3), was studied on quartz glass surfaces in a photo flow-reactor under atmospherically relevant conditions. In contrast to other investigations, a very low HNO3 photolysis frequency for HONO formation of J(HNO3→ HONO) = 2.4 × 10(-7) s(-1) (0° SZA, 50% r.h.) was determined. If these results can be translated to atmospheric surfaces, HNO3 photolysis cannot explain the significant HONO levels in the daytime atmosphere. In addition, it is demonstrated that even the small measured yields of HONO did not result from the direct photolysis of HNO3 but rather from the consecutive heterogeneous conversion of the primary photolysis product NO2 on the humid surfaces. The secondary NO2 conversion was not photo-enhanced on pure quartz glass surfaces in good agreement with former studies. A photolysis frequency for the primary reaction product NO2 of J(HNO3→ NO2) = 1.1 × 10(-6) s(-1) has been calculated (0° SZA, 50% r.h.), which indicates that renoxification by photolysis of adsorbed HNO3 on non-reactive surfaces is also a minor process in the atmosphere. PMID:26997156

  19. 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.

  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. 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.

  2. Layer structured graphite oxide as a novel adsorbent for humic acid removal from aqueous solution.

    PubMed

    Hartono, Tri; Wang, Shaobin; Ma, Qing; Zhu, Zhonghua

    2009-05-01

    Layer structured graphite oxide (GO) was prepared from graphite using the Hummers-Offeman method, characterised using N(2) adsorption, XRD, XPS, SEM(TEM), and FT-IR, and tested for humic acid (HA) adsorption in aqueous solution. XRD, XPS, and FT-IR measurements indicate the formation of layered structure with strong functional groups of GO. It is also found that the GO exhibits strong and much higher adsorption capacity of HA than graphite. The maximum adsorption capacity of the GO from the Langmuir isotherm is 190 mg/g, higher than activated carbon. For the adsorption, several parameters will affect the adsorption such as solid loading and pH. HA adsorption will decrease with increasing pH and an optimum GO loading is required for maximum adsorption. PMID:19233379

  3. Mechanisms for aqueous photolysis of adsorbed benzoate, oxalate, and succinate on iron oxyhydroxide (goethite) surfaces

    USGS Publications Warehouse

    Cunningham, K.M.

    1988-01-01

    Photolysis of carboxylate anions adsorbed onto highly crystalline goethite (??-FeOOH) with 300-400-nm light produces Fe2+(aq) and ??OH from surface and solution redox reactions. The production of Fe2+(aq) and ??OH was studied in N2-purged and aerated aqueous suspensions, respectively, of goethite containing equimolar (10-3 M) concentrations of oxalate and benzoate (ob + g), succinate and benzoate (sb + g), benzoate alone (b + g), and goethite alone (g). The hydroxyl radical was measured by fluorescence analysis of salicylate formed in a reaction between benzoate and ??OH. Fe2+(aq) was determined colorimetrically. A proposed reaction mechanism includes the photoexcitation of Fe(III) surface complexes with OH-, HCO3-, and RCOO- ligands to form Fe2+(aq) and corresponding ligand radicals. Additional ??OH is made by the O2 oxidation of Fe2+(aq) (Haber-Weiss mechanism). Comparison of Fe2+(aq) and ??OH yields permitted an estimate of the relative importance of pathways leading to ??OH.

  4. Characteristics of PAHs adsorbed on street dust and the correlation with specific surface area and TOC.

    PubMed

    Wang, Chengkun; Li, Yingxia; Liu, Jingling; Xiang, Li; Shi, Jianghong; Yang, Zhifeng

    2010-10-01

    Street dust was collected from five roads with different traffic volumes in the metropolitan area of Beijing and separated into five size fractions. Concentrations of polycyclic aromatic hydrocarbons (PAHs) adsorbed on street dust in different size ranges and their correlation with specific surface area and total organic carbon (TOC) were investigated. Results show that the concentration of 16-PAHs of sieved samples ranges from 0.27 to 1.30 mg/kg for all the sampling sites. Particles smaller than 40 mum in diameter have the highest 16-PAHs concentration among all of the size ranges for street dust from the four sampling sites with vehicles running on. PAHs with three or four rings account for 68% of the overall 16-PAHs on average. Remarkable positive correlation exists between 16-PAHs concentration and specific surface area with R(2) values from 0.7 to 0.96 for the four sampling sites with vehicles running on. The relationship between the concentration of 16-PAHs and TOC is less clear.

  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

    2016-11-01

    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. 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.

  7. Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

    NASA Astrophysics Data System (ADS)

    Waychunas, G. A.; Rea, B. A.; Fuller, C. C.; Davis, J. A.

    1993-05-01

    EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, α (goethite), β (akaganeite), and γ (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface ( 3.28 ±0.01 Å) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces ( 3.25 ± 0.02 Å). Mono-dentate arsenate linkages ( 3.60 ± 0.03 Å) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As/Fe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ± 0.01 Å. Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As/Fe ratio is increased. Coherent crystallite size is probably no more than 10 Å in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As/Fe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As/Fe) indicates ferrihydrite units consisting mainly of Fe

  8. Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

    USGS Publications Warehouse

    Waychunas, G.A.; Rea, B.A.; Fuller, C.C.; Davis, J.A.

    1993-01-01

    EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, ?? (goethite), ?? (akaganeite), and ?? (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface (3.28 ??0.01 A ??) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces (3.25 ?? 0.02 A ??). Mono-dentate arsenate linkages (3.60 ?? 0.03 A ??) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As Fe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ?? 0.01 A ??. Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As Fe ratio is increased. Coherent crystallite size is probably no more than 10 A?? in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As Fe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As Fe) indicates ferrihydrite units consisting mainly

  9. 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.

  10. Are atmospheric surface layer flows ergodic?

    NASA Astrophysics Data System (ADS)

    Higgins, Chad W.; Katul, Gabriel G.; Froidevaux, Martin; Simeonov, Valentin; Parlange, Marc B.

    2013-06-01

    The transposition of atmospheric turbulence statistics from the time domain, as conventionally sampled in field experiments, is explained by the so-called ergodic hypothesis. In micrometeorology, this hypothesis assumes that the time average of a measured flow variable represents an ensemble of independent realizations from similar meteorological states and boundary conditions. That is, the averaging duration must be sufficiently long to include a large number of independent realizations of the sampled flow variable so as to represent the ensemble. While the validity of the ergodic hypothesis for turbulence has been confirmed in laboratory experiments, and numerical simulations for idealized conditions, evidence for its validity in the atmospheric surface layer (ASL), especially for nonideal conditions, continues to defy experimental efforts. There is some urgency to make progress on this problem given the proliferation of tall tower scalar concentration networks aimed at constraining climate models yet are impacted by nonideal conditions at the land surface. Recent advancements in water vapor concentration lidar measurements that simultaneously sample spatial and temporal series in the ASL are used to investigate the validity of the ergodic hypothesis for the first time. It is shown that ergodicity is valid in a strict sense above uniform surfaces away from abrupt surface transitions. Surprisingly, ergodicity may be used to infer the ensemble concentration statistics of a composite grass-lake system using only water vapor concentration measurements collected above the sharp transition delineating the lake from the grass surface.

  11. Comparative study of normal and branched alkane monolayer films adsorbed on a solid surface. I. Structure

    NASA Astrophysics Data System (ADS)

    Enevoldsen, A. D.; Hansen, F. Y.; Diama, A.; Criswell, L.; Taub, H.

    2007-03-01

    The structure of a monolayer film of the branched alkane squalane (C30H62) adsorbed on graphite has been studied by neutron diffraction and molecular dynamics (MD) simulations and compared with a similar study of the n-alkane tetracosane (n-C24H52). Both molecules have 24 carbon atoms along their backbone and squalane has, in addition, six methyl side groups. Upon adsorption, there are significant differences as well as similarities in the behavior of these molecular films. Both molecules form ordered structures at low temperatures; however, while the melting point of the two-dimensional (2D) tetracosane film is roughly the same as the bulk melting point, the surface strongly stabilizes the 2D squalane film such that its melting point is 91K above its value in bulk. Therefore, squalane, like tetracosane, will be a poor lubricant in those nanoscale devices that require a fluid lubricant at room temperature. The neutron diffraction data show that the translational order in the squalane monolayer is significantly less than in the tetracosane monolayer. The authors' MD simulations suggest that this is caused by a distortion of the squalane molecules upon adsorption on the graphite surface. When the molecules are allowed to relax on the surface, they distort such that all six methyl groups point away from the surface. This results in a reduction in the monolayer's translational order characterized by a decrease in its coherence length and hence a broadening of the diffraction peaks. The MD simulations also show that the melting mechanism in the squalane monolayer is the same footprint reduction mechanism found in the tetracosane monolayer, where a chain melting drives the lattice melting.

  12. Comparative study of normal and branched alkane monolayer films adsorbed on a solid surface. I. Structure.

    PubMed

    Enevoldsen, A D; Hansen, F Y; Diama, A; Criswell, L; Taub, H

    2007-03-14

    The structure of a monolayer film of the branched alkane squalane (C30H62) adsorbed on graphite has been studied by neutron diffraction and molecular dynamics (MD) simulations and compared with a similar study of the n-alkane tetracosane (n-C24H52). Both molecules have 24 carbon atoms along their backbone and squalane has, in addition, six methyl side groups. Upon adsorption, there are significant differences as well as similarities in the behavior of these molecular films. Both molecules form ordered structures at low temperatures; however, while the melting point of the two-dimensional (2D) tetracosane film is roughly the same as the bulk melting point, the surface strongly stabilizes the 2D squalane film such that its melting point is 91 K above its value in bulk. Therefore, squalane, like tetracosane, will be a poor lubricant in those nanoscale devices that require a fluid lubricant at room temperature. The neutron diffraction data show that the translational order in the squalane monolayer is significantly less than in the tetracosane monolayer. The authors' MD simulations suggest that this is caused by a distortion of the squalane molecules upon adsorption on the graphite surface. When the molecules are allowed to relax on the surface, they distort such that all six methyl groups point away from the surface. This results in a reduction in the monolayer's translational order characterized by a decrease in its coherence length and hence a broadening of the diffraction peaks. The MD simulations also show that the melting mechanism in the squalane monolayer is the same footprint reduction mechanism found in the tetracosane monolayer, where a chain melting drives the lattice melting.

  13. Effect of biomass addition on the surface and adsorption characterization of carbon-based adsorbents from sewage sludge.

    PubMed

    Wu, Changzi; Song, Min; Jin, Baosheng; Wu, Yimin; Huang, Yaji

    2013-02-01

    Sewage sludge with the additive corn cob was used as prescusor to prepare sludge-based carbon adsorbents by pyrolysis method. And then, the carbonizated products were activated with potassium hydroxide. The mixing ratio of the corn cob to sewage sludge was investigated. The surface area and pore size distribution, elemental composition, surface chemistry structure and the surface physical morphology were determined and compared. The results demonstrated that the addition of corn cob into the sewage sludge sample could effectively improve the surface area (from 287 to 591 m2/g) and the microporosity (from 5% to 48%) of the carbon based adsorbent, thus enhancing the adsorption behavior. The sulfur dioxide adsorption capacity was measured according to breakthrough test. It was found that the sulfur dioxide adsorption capacity of the adsorbents was obviously enhanced after the addition of the corn cob. It is presumed that not only highly porous adsorbents, but also a high metallic content of these materials are required to achieve good performances. PMID:23596963

  14. 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.

  15. 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

  16. 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

  17. Deuterium Magic Angle Spinning NMR Used to Study the Dynamics of Peptides Adsorbed onto Polystyrene and Functionalized Polystyrene Surfaces

    PubMed Central

    Breen, Nicholas F.; Li, Kun; Olsen, Gregory L.; Drobny, Gary P.

    2011-01-01

    LKα14 is a 14 amino acid peptide with a periodic sequence of leucine and lysine residues consistent with an amphipathic α-helix. This “hydrophobic periodicity” has been found to result in an α-helical secondary structure at air-water interfaces and on both polar and non-polar solid polymer surfaces. In this paper the dynamics of LKα14 peptides, selectively deuterated at a single leucine and adsorbed onto polystyrene and carboxylated polystyrene beads, are studied using 2H Magic Angle Spinning (MAS) solid state NMR over a 100 degree temperature range. We first demonstrate the sensitivity enhancement possible with 2H MAS techniques, which in turn enables us to obtain high quality 2H NMR spectra for selectively deuterated peptides adsorbed onto solid polymer surfaces. An extensive literature shows that the dynamics of leucine side chains are sensitive to the local structural environment of the protein. Therefore the degree to which the dynamics of leucine side chains and the backbone of the peptide LKα14 are influenced by surface proximity and surface chemistry is studied as a function of temperature with 2H MAS NMR. It is found that the dynamics of the leucine side chains in LKα14 depend strongly upon the orientation of the polymer on the surface, which in turn depends on whether the LKα14 peptide adsorbs onto a polar or non-polar surface. 2H MAS line shapes therefore permit probes of surface orientation over a wide temperature range. PMID:21650191

  18. pH-Dependent Surface-Enhanced Raman Scattering of 8-Hydroxy Quinoline Adsorbed on Silver Hydrosol.

    PubMed

    Chowdhury; Ghosh; Misra

    2000-08-15

    Surface-enhanced Raman scattering (SERS) of 8-hydroxy quinoline (HQ) adsorbed on silver hydrosols are compared with the FTIR and normal Raman spectrum in the bulk and in solution. Definite evidence of the charge transfer interaction to the overall contribution in the SER enhancement has been reported. The excitation profile study also supports the evidence of a charge transfer interaction. The effect of pH variation on the SER band intensity is explained in terms of chemisorption of the molecule on bare and chlorinated silver surfaces. The apparent enhancement factor calculations of the principal Raman bands indicate that in the surface-adsorbed state, an HQ molecule is oriented neither flat nor vertical to the silver surface but is tilted. Copyright 2000 Academic Press.

  19. Outer-sphere Pb(II) adsorbed at specific surface sites on single crystal {alpha}-alumina

    SciTech Connect

    Bargar, J.R.; Towle, S.N.; Parks, G.A.

    1996-09-01

    Solvated Pb(II) ions were found to adsorb as structurally well-defined outer-sphere complexes at specific sites on the {alpha}-Al{sub 2}O{sub 3} (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 {angstrom}. In contrast, Pb(II) adsorbs as more strongly bound inner-sphere complexes on {alpha}-Al{sub 2}O{sub 3} (1102). 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. 29 refs., 3 figs., 1 tab.

  20. 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.

  1. 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.; 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.

  2. Adsorption of proteins at physiological concentrations on pegylated surfaces and the compatibilizing role of adsorbed albumin with respect to other proteins according to optical waveguide lightmode spectroscopy (OWLS).

    PubMed

    Leclercq, Laurent; Modena, Enrico; Vert, Michel

    2013-01-01

    In literature, contacts between pegylated compounds and blood proteins are generally discussed in terms of excluded volume-related repulsions although adsorption and compatibility have been reported for some of these proteins occasionally. The major problem to investigate the behavior of blood in contact with pegylated surfaces is the complexity of the medium and especially the presence of albumin in large excess. In a model approach, optical waveguide lightmode spectroscopy (OWLS) was used to monitor the fate of albumin, fibrinogen, and γ-globulins at physiological concentrations in pH = 7.4 isotonic HEPES buffer after contact with SiTiO2 chips coated with diblock poly(DL-lactic acid)-block-poly(ethylene oxide)s and triblock poly(DL-lactic acid)-block-poly(ethylene oxide)-block-poly(DL-lactic acid) copolymers. Corresponding homopolymers were used as controls. The three protein systems were investigated separately, as a mixture and when added successively according to different orders of addition. OWLS gave access to the mass and the thickness of adhering protein layers that resist washing with HEPES buffer. Protein depositions were detected regardless of the presence of poly(ethylene glycol) segments on surfaces. Adsorption depended on the protein, on the surface and also on the presence of the other proteins. Unexpectedly any surface coated with a layer of adsorbed albumin prevented deposition of other proteins, including albumin itself. This outstanding finding suggests that it was the presence of albumin adsorbed on a surface, pegylated or not, that made that surface compatible with other proteins. As a consequence, dipping a device to be in contact with the blood of a patient in a solution of albumin could be a very simple means to avoid further protein deposition and maybe platelets adhesion after in vivo implantation.

  3. Zeta potential, contact angles, and AFM imaging of protein conformation adsorbed on hybrid nanocomposite surfaces.

    PubMed

    Pinho, Ana C; Piedade, Ana P

    2013-08-28

    The sputtering deposition of gold (Au) and poly(tetrafluoroethylene) (PTFE) was used to prepare a nanocomposite hybrid thin film suitable for protein adsorption while maintaining the native conformation of the biological material. The monolithic PTFE and the nanocomposite PTFE/Au thin films, with Au content up to 1 at %, were co-deposited by r.f. magnetron sputtering using argon as a discharge gas and deposited onto 316L stainless steel substrates, the most commonly used steel in biomaterials. The deposited thin films, before and after bovine serum albumin (BSA) adsorption, were thoroughly characterized with special emphasis on the surface properties/characteristics by atomic force microscopy (AFM), zeta potential, and static and dynamic contact angle measurements, in order to assess the relationship between structure and conformational changes. The influence of a pre-adsorbed peptide (RGD) was also evaluated. The nanotopographic and chemical changes induced by the presence of gold in the nanocomposite thin films enable RGD bonding, which is critical for the maintenance of the BSA native conformation after adsorption.

  4. Theory of Covalent Adsorbate Frontier Orbital Energies on Functionalized Light-Absorbing Semiconductor Surfaces.

    PubMed

    Yu, Min; Doak, Peter; Tamblyn, Isaac; Neaton, Jeffrey B

    2013-05-16

    Functional hybrid interfaces between organic molecules and semiconductors are central to many emerging information and solar energy conversion technologies. Here we demonstrate a general, empirical parameter-free approach for computing and understanding frontier orbital energies - or redox levels - of a broad class of covalently bonded organic-semiconductor surfaces. We develop this framework in the context of specific density functional theory (DFT) and many-body perturbation theory calculations, within the GW approximation, of an exemplar interface, thiophene-functionalized silicon (111). Through detailed calculations taking into account structural and binding energetics of mixed-monolayers consisting of both covalently attached thiophene and hydrogen, chlorine, methyl, and other passivating groups, we quantify the impact of coverage, nonlocal polarization, and interface dipole effects on the alignment of the thiophene frontier orbital energies with the silicon band edges. For thiophene adsorbate frontier orbital energies, we observe significant corrections to standard DFT (∼1 eV), including large nonlocal electrostatic polarization effects (∼1.6 eV). Importantly, both results can be rationalized from knowledge of the electronic structure of the isolated thiophene molecule and silicon substrate systems. Silicon band edge energies are predicted to vary by more than 2.5 eV, while molecular orbital energies stay similar, with the different functional groups studied, suggesting the prospect of tuning energy alignment over a wide range for photoelectrochemistry and other applications.

  5. Enhanced Durability of Antisticking Layers by Recoating a Silica Surface with Fluorinated Alkylsilane Derivatives by Chemical Vapor Surface Modification

    NASA Astrophysics Data System (ADS)

    Kohno, Akihiro; Sakai, Nobuji; Matsui, Shinji; Nakagawa, Masaru

    2010-06-01

    Adsorbed monolayers from (3,3,3-trifluoropropyl)trimethoxysilane (FAS3), (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane (FAS13), (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane (FAS17), and (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trichlorosilane (FAS17-Cl) were formed by chemical vapor surface modification (CVSM) on silica lens surfaces cleaned by exposure to vacuum ultraviolet (VUV) light at 172 nm. Changes in monolayer-modified lens surfaces concomitant with repeating a cycle of curing to induce the radical polymerization of a UV-curable resin and detaching the UV-cured resin were monitored by contact angle measurement with water and atomic force microscopy to investigate the property of the adsorbed monolayers as antisticking layers in UV nanoimprint lithography. A decrease of the contact angle for water with increasing the number of repeated cycles was mainly responsible for the removal of surface impurities in the form of nanoparticles on detaching the cured resin repeatedly. It was found that recoating the silica lens surface with monolayers from FAS13, FAS17, and FAS17-Cl after cleaning by VUV-light exposure resulted in the suppression of the decrease in the contact angle. These results indicate that the durability of an antisticking layer in UV nanoimprint lithography is markedly improved by the recoating.

  6. Desorption Induced by Excited Electrons from Semiconductor Surfaces (I)
    —Desorption Induced by Electron-/hole-injection into Halogen-adsorbed Silicon Surfaces—

    NASA Astrophysics Data System (ADS)

    Shudo, Kenichi; Tanaka, Masatoshi

    We review excited-electron-induced desorption from halogen-adsorbed semiconductor surfaces, focusing on desorption processes associated with electron-beam irradiation using an electron gun and hole-injection using a scanning tunneling microscope. Recent studies on halogen-adsorbed silicon surfaces, i.e., typical etching systems, are described from the viewpoint of desorption induced by electronic transitions (DIET).

  7. Speciation of trace metals in natural waters: the influence of an adsorbed layer of natural organic matter (NOM) on voltammetric behaviour of copper.

    PubMed

    Louis, Yoann; Cmuk, Petra; Omanović, Dario; Garnier, Cédric; Lenoble, Véronique; Mounier, Stéphane; Pizeta, Ivanka

    2008-01-01

    The influence of an adsorbed layer of the natural organic matter (NOM) on voltammetric behaviour of copper on a mercury drop electrode in natural water samples was studied. The adsorption of NOM strongly affects the differential pulse anodic stripping voltammogram (DPASV) of copper, leading to its distortion. Phase sensitive ac voltammetry confirmed that desorption of adsorbed NOM occurs in general at accumulation potentials more negative than -1.4V. Accordingly, an application of negative potential (-1.6V) for a very short time at the end of the accumulation time (1% of total accumulation time) to remove the adsorbed NOM was introduced in the measuring procedure. Using this protocol, a well-resolved peak without interferences was obtained. It was shown that stripping chronopotentiogram of copper (SCP) in the depletive mode is influenced by the adsorbed layer in the same manner as DPASV. The influence of the adsorbed NOM on pseudopolarographic measurements of copper and on determination of copper complexing capacity (CuCC) was demonstrated. A shift of the peak potential and the change of the half-peak width on the accumulation potential (for pseudopolarography) and on copper concentration in solution (for CuCC) were observed. By applying a desorption step these effects vanished, yielding different final results.

  8. 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.

  9. Density functional theory study of chemical sensing on surfaces of single-layer MoS2 and graphene

    NASA Astrophysics Data System (ADS)

    Mehmood, F.; Pachter, R.

    2014-04-01

    In this work, density functional theory (DFT) calculations have been used to investigate chemical sensing on surfaces of single-layer MoS2 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 SiO2 substrate rationalized experimental observations for some of the adsorbates considered. A larger intrinsic response for the electron-donor triethylamine adsorbed on MoS2 as compared to graphene was demonstrated, which may assist in devising chemical sensors for improved sensitivity.

  10. 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.

  11. 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.

  12. Energy loss in gas-surface dynamics: Electron-hole pair and phonon excitation upon adsorbate relaxation

    NASA Astrophysics Data System (ADS)

    Novko, D.; Blanco-Rey, M.; Juaristi, J. I.; Alducin, M.

    2016-09-01

    We study the effect of electron and phonon degrees of freedom on the relaxation dynamics of adsorption processes in gas-surface systems by using ab initio molecular dynamics that incorporates an electronic friction force (AIMDEF). As representative cases we have chosen three systems with different adsorption energies and adsorbate-to-surface atom mass ratios: H on Pd(1 0 0), N on Ag(1 1 1), and N2 on Fe(1 1 0). We show, through inspection of the total energies and trajectories of the hot adsorbates on the surface, that electron-hole (e-h) pair excitations dominate relaxation of the light gas species, while the phonon channel is dominant for the heavy species. In the latter case e-h pairs become more important at the final thermalization stages.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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

  19. Nucleation and mobility model of Agn clusters adsorbed on perfect and oxygen vacancy MgO surfaces.

    PubMed

    Liu, Yongfei; Wang, Yan; Chen, Guangju

    2011-05-01

    The structures and energy properties for Ag(n) (n = 1-8) metal clusters adsorbed on the perfect and oxygen vacancy MgO surfaces have been studied by using the DFT/UB3LYP method with an embedded cluster model. The nucleation and mobility model for the Ag(n) (n = 1-8) clusters on the perfect and oxygen vacancy MgO(100) surfaces was investigated. The results show that the Ag atoms locate initially at the surface oxygen vacancy sites; then, with the growth of Ag cluster sizes, the large Ag clusters move possibly out of the vacancy sites by a rolling model, and diffuse on the MgO surface under a certain temperature condition. The relative energies needed for moving out of the oxygen vacancy region for the adsorbed Ag(n) clusters with the rolling model have been predicted. The even-odd oscillation behaviors for the cohesive energies, nucleation energies, first ionization potentials and HOMO-LUMO gaps of the adsorbed Ag(n) clusters with the variation of cluster sizes have also been discussed.

  20. 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.

  1. Quantum resolved studies of electron-stimulated reactions on adsorbate covered Pt(111) surfaces

    NASA Astrophysics Data System (ADS)

    Orlando, T. M.; Burns, A. R.; Stechel, E. B.; Jennison, D. R.

    1991-06-01

    Using laser resonance-enhanced ionisation spectroscopy, we have studied electron (6-350 eV) stimulated dissociation of NO 2 coadsorbed with up to 0.75 monolayer of atomic O on Pt(111). Several dramatic effects on NO 2 dissociation occur due to the presence of O. There is a large ( × 26) enhancement in the specific dissociation yield, a narrowing of the NO translational energy distributions, and a distinct propensity ( > 4:1 at low J) for populating the upper Ω = {3}/{2} NO spin-orbit level over the Ω = {1}/{2} level. The spin-orbit state distribution of the O( 3PJ) dissociation fragment is (5.0): (2.5): (1.0) for J = 2, 1 and 0, which is within experimental error of the statistical ( T → ∞) 2 J + 1 limit. The enhanced yield probably results from an increased excited state lifetime due to a reduction in substrate charge-transfer screening. We have also detected O( 3PJ = 2,1,0) andNO X2 Π {3}/{2}, {1}/{2}(v = 5) above an electron (6-350 eV) beam irradiated Pt(111) surface containing coadsorbed O 2 and NO at 90 K. We conclude that both O( 3PJ) andNO(v = 5) are laser-induced photodissociation fragments of NO 2desorbates. The NO 2 is probably the reaction product of a collision between an O atom (created by electron-stimulated dissociation of adsorbed O 2) and an NO(a). We correlate the 10 eV NO 2 production threshold with the dissociative ionization of the 3σ g molecular bonding orbital of O 2(a).

  2. Influence of Polymers on the Crystal Growth Rate of Felodipine: Correlating Adsorbed Polymer Surface Coverage to Solution Crystal Growth Inhibition.

    PubMed

    Schram, Caitlin J; Taylor, Lynne S; Beaudoin, Stephen P

    2015-10-20

    The bioavailability of orally administered drugs that exhibit poor aqueous solubility can be enhanced with the use of supersaturating dosage forms. Stabilization of these forms by preventing or inhibiting crystallization in solution is an important area of study. Polymers can be used to stabilize supersaturated systems; however, the properties that impact their effectiveness as crystal growth rate inhibitors are not yet fully understood. In this study, the impact of various polymers on the crystal growth rate of felodipine and the conformation of these polymers adsorbed to crystalline felodipine was investigated in order to gain a mechanistic understanding of crystal growth inhibition. It was determined that polymer hydrophobicity impacted polymer adsorption as well as adsorbed polymer conformation. Polymer conformation impacts its surface coverage, which was shown to directly correlate to the polymer's effectiveness as a growth rate inhibitor. By modeling this correlation, it is possible to predict polymer effectiveness given the surface coverage of the polymer.

  3. 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.

  4. Turbulent transport process in atmospheric surface layer

    NASA Astrophysics Data System (ADS)

    Hayashi, T.; Awasaki, T.

    2012-04-01

    The organized motion or the coherent motion can be detected in wind tunnel and water channel experiments and those motions play an important role for the production of turbulent energy and transport of turbulent fluxes. Similar phenomena can be found in the atmospheric surface layer (Gao et al., 1989). The purpose of this study is to clarify the transport structure and process of turbulent fluxes, especially heat, water vapor and carbon dioxide. The organized motions are detected by using the wavelet transform analysis as well as the conventional statistical method such as Fourier spectral analysis. We consider the dependency of transport process by the organized motion to the atmospheric stability in the surface layer. The observation was carried out at the test field of Shionomisaki Wind Effect Laboratory, where two sets of the combination of sonic anemometer thermometer and open path H2O/CO2 analyzer were mounted at 2m and 20m height. The evident ramp and inverse ramp structures can be found in the time series of temperature, water vapor and CO2 in the unstable stability, using the Mexican hut wavelet transform analysis. The co-spectral density in wavelet analysis is considered as the flux at each time scale. The large amount of fluxes is transported at the sudden decrease in scalar ramp structure and the sudden increase in inverse ramp structure in several tens of seconds. The scalar and vertical wind velocity are completely either in phase or out of phase, which means that the turbulent transport by the organized motion occurs at time scales of several tens of seconds. The quadrant analysis of turbulent flux shows that the rate of the transport amount of scalar by ejection and sweep to the total transport flux increases according to the increase of the atmospheric stability. At 2m height, the transport by ejection is dominant in unstable condition, and that by sweep is larger in the stable condition. At 20m height, transport by ejection is larger than that by

  5. In situ investigation into surfactant effects on the clearance of polycyclic aromatic hydrocarbons adsorbed onto soybean leaf surfaces.

    PubMed

    Sun, Haifeng; Wang, Weipeng; Guo, Shuai; Zhang, Yong

    2016-03-01

    The partitioning of polycyclic aromatic hydrocarbons (PAHs) in agricultural crop leaves, contributes to the exposure of organisms to these chemicals through the dietary pathway. To precisely predict the fate of PAHs and crop safety, the clearance of three-ringed phenanthrene (Phe) and four-ringed pyrene (Pyr) adsorbed individually onto living soybean leaf surfaces, as well as the effects of two surfactants, namely, an ionic surfactant (sodium dodecylbenzene sulfonate, SDBS) and a non-ionic surfactant (polyoxyethyleneglycol dodecyl ether, Brij35), were investigated in situ using the laser-induced nanosecond time-resolved fluorescence (LITRF) method. The effects varied significantly with surfactant types primarily in terms of the elimination rates and the final residues of PAH chemicals. With increasing SDBS and Brij35 concentrations, volatilization rate constants (kC) of both Phe and Pyr initially decreased at fast rates and then at more moderate rates later on, resulting from the plasticizing effect of surfactants adsorbed on leaf surfaces. In addition, the photolysis rate constants (kP) decreased with the presence of SDBS but increased with the presence of Brij35. Overall, the total clearance rates of PAHs (kT) adsorbed onto living soybean leaf surfaces were inhibited by the presence of SDBS but promoted by the presence of Brij35. These observations show that surfactants may significantly alter the clearance of PAHs in agricultural systems, and the potential impact of surfactants on crop safety is closely related to surfactant types in natural environments.

  6. Concentration-dependent surface-enhanced resonance Raman scattering of a porphyrin derivative adsorbed on colloidal silver particles.

    PubMed

    Chowdhury, Joydeep; Ghosh, Manash; Pal, Prabir; Misra, T N

    2003-07-01

    Surface-enhanced Raman spectra (SERS) of 5,10,15,20-tetrakis(1-decylpyridium-4-yl)-21H,23H-porphintetrabromide or Por 10 (H(2)Tdpyp) adsorbed on silver hydrosols are compared with the FTIR and resonance Raman spectrum (RRS) in the bulk and in solution. Comparative analysis of the RR and the FTIR spectra indicate that the molecule, in its free state, has D(2h) symmetry rather than C(2v). The SERS spectra, obtained on adsorption of this molecule on borohydride-reduced silver sol, indicate the formation of silver porphyrin. With the change in the adsorbate concentration, the SERS shows that the molecule changes its orientation on the colloidal silver surface. The appearance of longer wavelength band in the electronic absorption spectra of the sol has been attributed to the coagulation of colloidal silver particles in the sol. The long wavelength band is found to be red-shifted with the decrease in adsorbate concentration. The excitation profile study indicates that the resonance of the Raman excitation radiation with the original sol band is more important than that with the new aggregation band for the SERS activity. This indicates a large contribution of electromagnetic effect to surface enhancement.

  7. Speciation of Adsorbed Phosphate at Gold Electrodes: A Combined Surface-Enhanced Infrared Absorption Spectroscopy and DFT Study.

    PubMed

    Yaguchi, Momo; Uchida, Taro; Motobayashi, Kenta; Osawa, Masatoshi

    2016-08-18

    Despite the significance of phosphate buffer solutions in (bio)electrochemistry, detailed adsorption properties of phosphate anions at metal surfaces remain poorly understood. Herein, phosphate adsorption at quasi-Au(111) surfaces prepared by a chemical deposition technique has been systematically investigated over a wide range of pH by surface-enhanced infrared absorption spectroscopy in the ATR configuration (ATR-SEIRAS). Two different pH-dependent states of adsorbed phosphate are spectroscopically detected. Together with DFT calculations, the present study reveals that pKa for adsorbed phosphate species at the interface is much lower than that for phosphate species in the bulk solution; the dominant phosphate anion, H2PO4(-) at 2 < pH < 7 or HPO4(2-) at 7 < pH < 12, undergoes deprotonation upon adsorption and transforms into the adsorbed HPO4 or PO4, respectively. This study leads to a conclusion different than earlier spectroscopic studies have reached, highlighting the capability of the ATR-SEIRAS technique at electrified metal-solution interfaces. PMID:27453430

  8. Electron structure of AgCl nanocrystal with silver ion adsorbed on atomic-rough surface and quantum transitions

    NASA Astrophysics Data System (ADS)

    Timoshenko, Yury K.; Shunina, Valentina A.

    2009-08-01

    Adsorption was considered as on the atomically-rough surface (near the step and step fracture) as on the smooth surface. The electron structure of AgCl nanocrystals with the adsorbed silver ion were calculated by semiempirical tight-binding method relying on a self-consistent approach for the effective charges and dipole moments of the ions and in frame of DFT method B3LYP/HW. The quantum transitions were investigated in semiempirical approach. Visualization of the wave functions was performed for the localized states. Basing on the obtained data a conclusion is specically made that one can expect an enhancement of photoelectron localization with a decrease of the anions number in the substrate nearest to the adsorbed ion. It means that the most ecient trapping of photoelectron should occur under adsorption on a smooth surface rather than near the steps and their fractures as it was assumed previously. Also probabilities of quantum transitions for AgCl : J nanocrystal with the adsorbed silver ion were been discussed. This work is a continuation of paper [1].

  9. Effectiveness of the statistical potential in the description of fermions in a worm-algorithm path-integral Monte Carlo simulation of 3He atoms placed on a 4He layer adsorbed on graphite.

    PubMed

    Ghassib, Humam B; Sakhel, Asaad R; Obeidat, Omar; Al-Oqali, Amer; Sakhel, Roger R

    2012-01-01

    We demonstrate the effectiveness of a statistical potential (SP) in the description of fermions in a worm-algorithm path-integral Monte Carlo simulation of a few 3He atoms floating on a 4He layer adsorbed on graphite. The SP in this work yields successful results, as manifested by the clusterization of 3He, and by the observation that the 3He atoms float on the surface of 4He. We display the positions of the particles in 3D coordinate space, which reveal clusterization of the 3He component. The correlation functions are also presented, which give further evidence for the clusterization.

  10. Neutron diffraction and quasielastic neutron scattering studies of films of intermediate-length alkanes adsorbed on a graphite surface

    NASA Astrophysics Data System (ADS)

    Diama, Armand

    Over the past several years, we have conducted a variety of elastic neutron diffraction and quasielastic neutron scattering experiments to study the structure and the dynamics of films of two intermediate-length alkane molecules (C nH2n+2), adsorbed on a graphite basal-plane surface. The two molecules are the normal alkane n-tetracosane [n-CH 3(CH2)22CH3] and the branched alkane squalane (C30H62 or 2, 6, 10, 15, 19, 23-hexamethyltetracosane) whose carbon backbone is the same length as teteracosane. The temperature dependence of the monolayer structure of tetracosane and squalane was investigated using elastic neutron diffraction and evidence of two phase transitions was observed. Both the low-coverage tetracosane (C 24H50) and squalane (C30H62) monolayers have crystalline-to-"smectic" and "smectic"-to-isotropic fluid phase transitions upon heating. The diffusive motion in the tetracosane and squalane monolayers has been investigated by quasielastic neutron scattering. Two different quasielastic neutron scattering spectrometers at the Center for Neutron Research, National Institute of Standards and Technology (NIST) have been used. The spectrometers differ in both their dynamic range and energy resolution allowing molecular motions to be investigated on time scales in the range 10-13--10 -9 s. On these time scales, we observe evidence of translational, rotational, and intermolecular diffusive motions in the tetracosane and squalane monolayers. We conclude that the molecular diffusive motion in the two monolayers is qualitatively similar. Thus, despite the three methyl sidegroups at each end of the squalane molecule, its monolayer structure, phase transitions, and dynamics are qualitatively similar to that of a monolayer of the unbranched tetracosane molecules. With the higher resolution spectrometer at NIST, we have also investigated the molecular diffusive motion in multilayer tetracosane films. The analysis of our measurements indicates slower diffusive motion in

  11. 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.

  12. Phosphonic Acid Adsorbates Tune the Surface Potential of TiO2 in Gas and Liquid Environments.

    PubMed

    Rivest, Jessy B; Li, Guo; Sharp, Ian D; Neaton, Jeffrey B; Milliron, Delia J

    2014-07-17

    Controlled attachment of molecules to the surface of a material can alter the band structure energies with respect to the surrounding environment via a combination of intrinsic and bonding-induced dipoles. Here, we demonstrate that the surface potential of an application-relevant material, anatase TiO2, can be tuned over a broad energy range of ∼1 eV using a family of dipolar phosphonic acid-based adsorbates. Using TiO2 as an example, we show with photoelectron spectroscopy that these adsorbates are stable in a liquid environment (propylene carbonate). More interestingly, the tunability is substantially retained and follows trends in the computed bound dipole. The electrochemical surface potential is shown to vary over 600 meV, the highest range in electrolytes to the best of our knowledge. Using density functional theory calculations, we rationalize the measured trends and show that the effective dipole upon molecular adsorption and not the intrinsic dipole of the isolated molecules correlates with observed changes in surface potential. Control of the effective dipole, through judicious choice of robust surface species, can allow in situ tuning of energy levels and functionality at active surfaces for energy conversion and storage, biosensing, and molecular electronics.

  13. 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.

  14. Trypsin immobilization on to polymer surface through grafted layer and its reaction with inhibitors.

    PubMed

    Kulik, E A; Kato, K; Ivanchenko, M I; Ikada, Y

    1993-08-01

    Trypsin was covalently immobilized and physically adsorbed on to the surface of poly(ethylene terephthalate) fibres using poly(acrylic acid) (PAAc) chains grafted on to the ozonized fibres. The covalent immobilization was accomplished through amide formation between amino groups of trypsin and carboxyl groups of grafted PAAc chains, with the use of water-soluble carbodiimide. A set of samples with surface concentrations of grafted polymer ranging from 0.03 to 2.5 micrograms/cm2 was used to study the effects of grafted layer on the enzymatic activity of immobilized trypsin and its inhibition by trypsin inhibitors of different molecular sizes. The amount of immobilized trypsin increased linearly with an increase in graft yield of fibres, but the activity of immobilized enzyme reached saturation at a certain graft yield, probably because of diffusion limitation for the transport of enzyme substrate molecules into the grafted PAAc layer. The reduction of inhibition with an increase in graft yield and in molecular weight of inhibitors was attributed to enhancement of steric hindrance and enzyme inactivation in the dense grafted layer. We also found that the adsorbed trypsin was inhibited more easily than the covalently immobilized at any concentration of the grafted PAAc and for any type of inhibitor used.

  15. Changes in the adsorbate dipole layer with changing d-filling of the metal (II) (Co, Ni, Cu) phthalocyanines on Au(111).

    PubMed

    Xiao, Jie; Dowben, Peter A

    2009-02-01

    In combined photoemission and inverse photoemission spectroscopy studies, we observe changes in the metal phthalocyanine molecular orbital offsets with respect to the conducting gold substrate Fermi level, with the changing d-electron filling of the metal (II) (Co, Ni, Cu) phthalocyanines. The implication is that the interfacial dipole layer depends upon the choice of metal (Co, Ni, Cu) centers within the metal (II) phthalocyanines adsorbed on Au(111).

  16. 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

  17. 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.

  18. Dry layer formation? Solvent polarity at hydrophobic solid-liquid surfaces

    NASA Astrophysics Data System (ADS)

    Walker, Robert; Zhang, Xiaoyi; Esenturk, Okan

    2002-03-01

    From low-wear, "friction-free" materials to reverse phase chromatography columns to specific protein domains, hydrophobic surfaces are ubiquitous in physics, chemistry and biology. Our efforts to understand how hydrophobic surfaces influence the solvating properties of an adjacent solvent have led us to investigate solvent polarity at a number of weakly associating, solid-liquid interfaces. Second-order nonlinear optical spectroscopy enables experiments to probe the solvent-sensitive excitation energies of adsorbed probe molecules. Comparisons to probe behavior in bulk solution allow us to infer how hydrophobic surfaces have altered properties inside of the solute cavity. Boundaries formed between hydrophobic surfaces and associating or hydrogen bonding solvents show significantly reduced solvent polarity, consistent with proposed models of dry-layer formation. Polar, aprotic liquid-hydrophobic solid interfaces show no evidence of this effect. We can understand this behavior based on the relative imbalance in forces between the solid and liquid phases.

  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. Multiple-overtone resonance Raman scattering and fluorescence from I{sub 2} species adsorbed on silver surfaces

    SciTech Connect

    Sibbald, M.S.; Chumanov, G.; Small, G.; Cotton, T.M.

    1998-07-01

    A detailed excitation profile of a Raman progression consisting of up to six overtones and a fundamental band at 123 cm{sup {minus}1} observed from iodide adsorbed on an electrochemically roughened silver surface at 20 K is analyzed. The excitation profile was constructed from 77 spectra obtained by tuning the laser wavelength in {approximately}0.25 nm steps through the spectral range 409 nm{endash}433 nm. The shift between resonances in the excitation profile, corresponding to the spacing between vibronic levels in the excited state, is also equal to 123 cm{sup {minus}1} indicating that the ground state and excited state potential energy surfaces have the same shape. Only two distinct resonances spaced three vibrational quanta apart were evident in the profile for each band in the progression. Curve fitting of the Raman band shapes indicates that each overtone is composed of one sharp and one broad band, whereas the fundamental contains only one sharp component. The measured width of the fundamental was less than 2.5 cm{sup {minus}1} FWHM, limited by the instrument function. It is proposed that the sharp Raman bands represent a normal vibrational mode of a surface-adsorbed I{sub 2}-like species with the width determined by the intrinsic vibrational dephasing in the ground state. On the other hand, the broad Raman bands reflect vibronic coupling between different I{sub 2}-like species adsorbed on the same Ag cluster. The broad bandwidths result from both dephasing associated with the vibronic coupling and the intrinsic vibrational dephasing. Other weak emission bands are attributed to resonance fluorescence corresponding to direct transitions from higher vibronic levels of the excited state to the ground state. An emission at 429.9 nm is assigned to exciton recombination in small silver iodide clusters which are formed after spontaneous oxidation of the iodide-modified silver surface. {copyright} {ital 1998 American Institute of Physics.}

  1. The dynamics of adsorption on clean and adsorbate-modified transition metal surfaces. [Progress report, 1989--1991

    SciTech Connect

    Madix, R.J.

    1991-06-01

    Research is being carried out on both nondissociative and dissociative adsorption of gases on transition metal surfaces, with emphasis on alkanes. Particular attention is be placed on understanding the effects of adsorbed species on adsorption probabilities and on clarifying the role of energy exchange processes at the surface in both dissociative and nondissociative adsorption. Molecular beam methods are coupled with methods of surface science to gain the greatest control of the variables of the problem, including the incident kinetic energy, vibrational energy and angle of incidence of the incoming molecules. The dynamics of both direct and precursor-influenced dissociative adsorption routes are examined. Surface intermediates formed by activated adsorption are identified by vibrational spectroscopy and temperature programmed reaction. Emphasis is on comparative studies of low molecular weight alkanes in order to understand the origin of the differences in their reactivities on different metals.

  2. 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.

  3. 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.

  4. Contact mechanics for layered materials with randomly rough surfaces.

    PubMed

    Persson, B N J

    2012-03-01

    The contact mechanics model of Persson is applied to layered materials. We calculate the M function, which relates the surface stress to the surface displacement, for a layered material, where the top layer (thickness d) has different elastic properties than the semi-infinite solid below. Numerical results for the contact area as a function of the magnification are presented for several cases. As an application, we calculate the fluid leak rate for laminated rubber seals.

  5. 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.

  6. Kinetics of Initial Layer-by-Layer Oxidation of Si(001) Surfaces

    NASA Astrophysics Data System (ADS)

    Watanabe, Heiji; Kato, Koichi; Uda, Tsuyoshi; Fujita, Ken; Ichikawa, Masakazu; Kawamura, Takaaki; Terakura, Kiyoyuki

    1998-01-01

    Layer-by-layer oxidation of Si(001) surfaces has been studied by scanning reflection electron microscopy (SREM). The oxidation kinetics of the top and second layers were independently investigated from the change in oxygen Auger peak intensity calibrated from the SREM observation. A barrierless oxidation of the first subsurface layer, as well as oxygen chemisorption onto the top layer, occurs at room temperature. The energy barrier of the second-layer oxidation was found to be 0.3 eV. The initial oxidation kinetics are discussed based on first-principles calculations.

  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.

  8. Characterization and use of crystalline bacterial cell surface layers

    NASA Astrophysics Data System (ADS)

    Sleytr, Uwe B.; Sára, Margit; Pum, Dietmar; Schuster, Bernhard

    2001-10-01

    Crystalline bacterial cell surface layers (S-layers) are one of the most common outermost cell envelope components of prokaryotic organisms (archaea and bacteria). S-layers are monomolecular arrays composed of a single protein or glycoprotein species and represent the simplest biological membranes developed during evolution. S-layers as the most abundant of prokaryotic cellular proteins are appealing model systems for studying the structure, synthesis, genetics, assembly and function of proteinaceous supramolecular structures. The wealth of information existing on the general principle of S-layers have revealed a broad application potential. The most relevant features exploited in applied S-layer research are: (i) pores passing through S-layers show identical size and morphology and are in the range of ultrafiltration membranes; (ii) functional groups on the surface and in the pores are aligned in well-defined positions and orientations and accessible for chemical modifications and binding functional molecules in very precise fashion; (iii) isolated S-layer subunits from a variety of organisms are capable of recrystallizing as closed monolayers onto solid supports (e.g., metals, polymers, silicon wafers) at the air-water interface, on lipid films or onto the surface of liposomes; (iv) functional domains can be incorporated in S-layer proteins by genetic engineering. Thus, S-layer technologies particularly provide new approaches for biotechnology, biomimetics, molecular nanotechnology, nanopatterning of surfaces and formation of ordered arrays of metal clusters or nanoparticles as required for nanoelectronics.

  9. 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

  10. Quenching of magnetic excitations in single adsorbates at surfaces: Mn on CuN/Cu(100)

    NASA Astrophysics Data System (ADS)

    Novaes, Frederico D.; Lorente, Nicolás; Gauyacq, Jean-Pierre

    2010-10-01

    The lifetimes of spin excitations of Mn adsorbates on CuN/Cu(100) are computed from first principles. The theory is based on a strong-coupling approach that evaluates the decay of a spin excitation due to electron-hole pair creation. Using a previously developed theory [Phys. Rev. Lett. 103, 176601 (2009)10.1103/PhysRevLett.103.176601 and Phys. Rev. B 81, 165423 (2010)10.1103/PhysRevB.81.165423], we compute the excitation rates by a tunneling current for all the Mn spin states. A rate equation approach permits us to simulate the experimental results by Loth and co-workers [Nat. Phys. 6, 340 (2010)]10.1038/nphys1616 for large tunneling currents, taking into account the finite population of excited states. Our simulations give us insight into the spin dynamics, in particular, in the way polarized electrons can reveal the existence of an excited-state population. In addition, it reveals that the excitation process occurs in a way very different from the deexcitation one. Indeed, while excitation by tunneling electrons proceeds via the s and p electrons of the adsorbate, deexcitation mainly involves the d electrons.

  11. Density matrix treatment of combined instantaneous and delayed dissipation for an electronically excited adsorbate on a solid surface

    NASA Astrophysics Data System (ADS)

    Leathers, Andrew S.; Micha, David A.; Kilin, Dmitri S.

    2009-10-01

    The interaction of an excited adsorbate with a medium undergoing electronic and vibrational transitions leads to fast dissipation due to electronic energy relaxation and slow (or delayed) dissipation from vibrational energy relaxation. A theoretical and computational treatment of these phenomena has been done in terms of a reduced density matrix satisfying a generalized Liouville-von Neumann equation, with instantaneous dissipation constructed from state-to-state transition rates, and delayed dissipation given by a memory term derived from the time-correlation function (TCF) of atomic displacements in the medium. Two representative applications are presented here, where electronic excitation may enhance vibrational relaxation of an adsorbate. They involve femtosecond excitation of (a) a CO molecule adsorbed on the Cu(001) metal surface and (b) a metal cluster on a semiconductor surface, Ag3Si(111):H, both electronically excited by visible light and undergoing electron transfer and dissipative dynamics by electronic and vibrational relaxations. Models have been parametrized in both cases from electronic structure calculations and known TCFs for the medium, which are slowly decaying in case (a) and fast decaying in case (b). This requires different numerical procedures in the solution of the integrodifferential equations for the reduced density matrix, which have been solved with an extension of the Runge-Kutta algorithm. Results for the populations of vibronic states versus time show that they oscillate due to vibrational coupling through dissipative interaction with the substrate and show quantum coherence. The total population of electronic states is, however, little affected by vibrational motions. Vibrational relaxation is important only at very long times to establish thermal equilibrium.

  12. 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

  13. Ameriflux data used for verification of surface layer parameterizations

    NASA Astrophysics Data System (ADS)

    Tassone, Caterina; Ek, Mike

    2015-04-01

    The atmospheric surface-layer parameterization is an important component in a coupled model, as its output, the surface exchange coefficients for momentum, heat and humidity, are used to determine the fluxes of these quantities between the land-surface and the atmosphere. An accurate prediction of these fluxes is therefore required in order to provide a correct forecast of the surface temperature, humidity and ultimately also the precipitation in a model. At the NOAA/NCEP Environmental Modeling Center, a one-dimensional Surface Layer Simulator (SLS) has been developed for simulating the surface layer and its interface. Two different configurations of the SLS exist, replicating in essence the way in which the surface layer is simulated in the GFS and the NAM, respectively. Input data for the SLS are the basic atmospheric quantities of winds, temperature, humidity and pressure evaluated at a specific height above the ground, surface values of temperature and humidity, and the momentum roughness length z0. The output values of the SLS are the surface exchange coefficients for heat and momentum. The exchange coefficients computed by the SLS are then compared with independent estimates derived from measured surface heat fluxes. The SLS is driven by a set of Ameriflux data acquired at 22 stations over a period of several years. This provides a large number of different vegetation characteristics and helps ensure statistical significance. Even though there are differences in the respective surface layer formulations between the GFS and the NAM, they are both based on similarity theory, and therefore lower boundary conditions, i.e. roughness lengths for momentum and heat, and profile functions are among the main components of the surface layer that need to be evaluated. The SLS is a very powerful tool for this type of evaluation. We present the results of the Ameriflux comparison and discuss the implications of our results for the surface layer parameterizations of the NAM

  14. Temperature Dependence of Surface Layering in a Dielectric Liquid

    SciTech Connect

    Mo,H.; Kewalramani, S.; Evmenenko, G.; Kim, K.; Ehrlich, S.; Dutta, P.

    2007-01-01

    The temperature dependence of the density oscillations (layers) at the free surface of tetrakis(2-ethylhexoxy)silane, a nonmetallic molecular liquid, was investigated using x-ray reflectivity. Below {approx}215K , the layer parameters weakly vary with temperature, if at all. Above this temperature, the layer spacings and intrinsic layer widths increase continuously, until there is no identifiable layering above 230K . This transition occurs at T/{Tc}{approx}0.23 , a temperature region that is usually accessible in metallic liquids but is preempted by freezing in many dielectric liquids.

  15. 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.

  16. 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

  17. 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.

  18. Observation of surface layering in a nonmetallic liquid.

    PubMed

    Mo, Haiding; Evmenenko, Guennadi; Kewalramani, Sumit; Kim, Kyungil; Ehrlich, Steven N; Dutta, Pulak

    2006-03-10

    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/Tc approximately 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.

  19. 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

  20. 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

  1. Modeling adsorption: Investigating adsorbate and adsorbent properties

    NASA Astrophysics Data System (ADS)

    Webster, Charles Edwin

    1999-12-01

    Surface catalyzed reactions play a major role in current chemical production technology. Currently, 90% of all chemicals are produced by heterogeneously catalyzed reactions. Most of these catalyzed reactions involve adsorption, concentrating the substrate(s) (the adsorbate) on the surface of the solid (the adsorbent). Pore volumes, accessible surface areas, and the thermodynamics of adsorption are essential in the understanding of solid surface characteristics fundamental to catalyst and adsorbent screening and selection. Molecular properties such as molecular volumes and projected molecular areas are needed in order to convert moles adsorbed to surface volumes and areas. Generally, these molecular properties have been estimated from bulk properties, but many assumptions are required. As a result, different literature values are employed for these essential molecular properties. Calculated molar volumes and excluded molecular areas are determined and tabulated for a variety of molecules. Molecular dimensions of molecules are important in the understanding of molecular exclusion as well as size and shape selectivity, diffusion, and adsorbent selection. Molecular dimensions can also be used in the determination of the effective catalytic pore size of a catalyst. Adsorption isotherms, on zeolites, (crystalline mineral oxides) and amorphous solids, can be analyzed with the Multiple Equilibrium Analysis (MEA) description of adsorption. The MEA produces equilibrium constants (Ki), capacities (ni), and thermodynamic parameters (enthalpies, ΔHi, and entropies, ΔSi) of adsorption for each process. Pore volumes and accessible surface areas are calculated from the process capacities. Adsorption isotherms can also be predicted for existing and new adsorbate-adsorbent systems with the MEA. The results show that MEA has the potential of becoming a standard characterization method for microporous solids that will lead to an increased understanding of their behavior in gas

  2. The Cold Surface Layer of Kahiltna Glacier, Central Alaska Range

    NASA Astrophysics Data System (ADS)

    Harrison, W. D.; Gusmeroli, A.; Arendt, A. A.; Atwood, D. K.; Kampes, B.; Sanford, M.; Young, J. C.; Aschwanden, A.; Truffer, M.; Herreid, S. J.; Hock, R. M.

    2011-12-01

    In Arctic, sub-Arctic and high-Alpine settings the ablation area of many mountain glaciers is rarely entirely temperate, and a cold near-surface layer of variable thickness, whose temperature remains below freezing throughout the year, can be found. This occurs when summer ablation rates do not melt the near-surface ice enough to remove the cold layer from the previous winter. A cold near-surface layer is a useful climatological parameter because, for example, its thinning over time can be related to climatic warming. In April 2011 we conducted several 100 MHz ground penetrating radar (GPR) surveys in the upper ablation area (˜1200 m a.s.l.) of the Kahiltna glacier, in the central Alaska Range. Surface ice temperatures, measured continuously during the preceding winter remained at ˜-4°C for 6 months. The GPR data showed the presence of a spatially variable, ˜20 m thick, transparent layer which we interpret to be the cold surface layer. A layer of similar thickness was retrieved by airborne IFSAR P-band radar surveys on several Alaskan glaciers. We use these observations to discuss the occurrence of a cold-surface layer in the Alaska Range and its usefulness for glacier monitoring studies.

  3. Calculation of vibrational frequencies of atoms adsorbed on metal surfaces: H, O, and S on Ni(100) and Ni(111) as examples

    SciTech Connect

    Black, J.E.; Bopp, P.; Luetzenkirchen, K.; Wolfsberg, M.

    1982-06-15

    We present vibrational frequencies calculated for H, O, and S atoms adsorbed on Ni(111) and Ni(100) surfaces. The calculations are done for a single atom adsorbed on nickel clusters, and also for a single atom and periodic arrangements of atoms on an infinite nickel substrate. We are able to indicate under what conditions a simple cluster calculation will yield vibrational frequencies suitable for comparison with experiment.

  4. Surface speciation of Eu3+ adsorbed on kaolinite by time-resolved laser fluorescence spectroscopy (TRLFS) and parallel factor analysis (PARAFAC).

    PubMed

    Ishida, Keisuke; Saito, Takumi; Aoyagi, Noboru; Kimura, Takaumi; Nagaishi, Ryuji; Nagasaki, Shinya; Tanaka, Satoru

    2012-05-15

    Time-resolved laser fluorescence spectroscopy (TRLFS) is an effective speciation technique for fluorescent metal ions and can be further extended by the parallel factor analysis (PARAFAC). The adsorption of Eu(3+) on kaolinite as well as gibbsite as a reference mineral was investigated by TRLFS together with batch adsorption measurements. The PAFAFAC modeling provided the fluorescence spectra, decay lifetimes, and relative intensity profiles of three Eu(3+) surface complexes with kaolinite; an outer-sphere (factor A) complex and two inner-sphere (factors B and C) complexes. Their intensity profiles qualitatively explained the measured adsorption of Eu(3+). Based on the TRLFS results in varied H(2)O/D(2)O media, it was shown that the outer-sphere complex exhibited more rapid fluorescence decay than Eu(3+) aquo ion, because of the energy transfer to the surface. Factor B was an inner-sphere complex, which became dominant at relatively high pH, high salt concentration and low Eu(3+) concentration. Its spectrum and lifetime were similar to those of Eu(3+) adsorbed on gibbsite, suggesting its occurrence on the edge face of the gibbsite layer of kaolinite. From the comparison with the spectra and lifetimes of crystalline or aqueous Eu(OH)(3), factor C was considered as a poly-nuclear surface complex of Eu(3+) formed at relatively high Eu(3+) concentration.

  5. 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.

  6. 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).

  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.

    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.

  8. Effect of side by side interactions on the thermodynamic properties of adsorbed CO molecules on the Ni(111) surface: a cluster model study

    NASA Astrophysics Data System (ADS)

    Shamkhali, Amir N.; Parsafar, Gholamabbas

    2010-05-01

    The effect of electrostatic interactions on vibrational frequencies and thermodynamic properties of CO adsorbate on the Ni(111) surface is calculated by taking the first and second nearest-neighbour interactions into account. In order to obtain reasonable results, the cluster model of various surface adsorption sites with CO adsorbate is partially optimized, using Density Functional Theory and also the MP2 method for the hcp site. Comparison between DFT and MP2 results shows that DFT results are more reliable for this system. The stretching and bending frequencies of CO adsorbate are calculated using both Partial Hessian Analysis and Cluster-Adsorbate Coupling methods. Stretching and bending frequencies are both shifted by the side by side interactions. The coupling of surface phonons and adsorbate vibrations reduces the side effects. The largest side effects on the vibrational internal energy, isochoric heat capacity, entropy and total Helmholtz free energy of adsorbed CO molecule calculated using the CAC method are found for 0.5 ML coverage. The results of the CAC method are better, but the PHA method can be used as a simple upper bound estimation. The adsorptive phase acts as an intelligent material in such a way that it changes its configuration in order to reduce the side effects.

  9. Assembly and function of the tRNA-modifying GTPase MnmE adsorbed to surface functionalized bioactive glass.

    PubMed

    Gruian, C; Boehme, S; Simon, S; Steinhoff, H-J; Klare, J P

    2014-05-28

    Protein adsorption onto solid surfaces is a common phenomenon in tissue engineering related applications, and considerable progress was achieved in this field. However, there are still unanswered questions or contradictory opinions concerning details of the protein's structure, conformational changes, or aggregation once adsorbed onto solid surfaces. Electron paramagnetic resonance (EPR) spectroscopy and site-directed spin labeling (SDSL) were employed in this work to investigate the conformational changes and dynamics of the tRNA-modifying dimeric protein MnmE from E. coli, an ortholog of the human GTPBP3, upon adsorption on bioactive glass mimicking the composition of the classical 45S5 Bioglass. In addition, prior to protein attachment, the bioactive glass surface was modified with the protein coupling agent glutaraldehyde. Continuous wave EPR spectra of different spin labeled MnmE mutants were recorded to assess the dynamics of the attached spin labels before and after protein adsorption. The area of the continuous wave (cw)-EPR absorption spectrum was further used to determine the amount of the attached protein. Double electron-electron resonance (DEER) experiments were conducted to measure distances between the spin labels before and after adsorption. The results revealed that the contact regions between MnmE and the bioactive glass surface are located at the G domains and at the N-terminal domains. The low modulation depths of all DEER time traces recorded for the adsorbed single MnmE mutants, corroborated with the DEER measurements performed on MnmE double mutants, show that the adsorption process leads to dissociation of the dimer and alters the tertiary structure of MnmE, thereby abolishing its functionality. However, glutaraldehyde reduces the aggressiveness of the adsorption process and improves the stability of the protein attachment.

  10. Assembly and function of the tRNA-modifying GTPase MnmE adsorbed to surface functionalized bioactive glass.

    PubMed

    Gruian, C; Boehme, S; Simon, S; Steinhoff, H-J; Klare, J P

    2014-05-28

    Protein adsorption onto solid surfaces is a common phenomenon in tissue engineering related applications, and considerable progress was achieved in this field. However, there are still unanswered questions or contradictory opinions concerning details of the protein's structure, conformational changes, or aggregation once adsorbed onto solid surfaces. Electron paramagnetic resonance (EPR) spectroscopy and site-directed spin labeling (SDSL) were employed in this work to investigate the conformational changes and dynamics of the tRNA-modifying dimeric protein MnmE from E. coli, an ortholog of the human GTPBP3, upon adsorption on bioactive glass mimicking the composition of the classical 45S5 Bioglass. In addition, prior to protein attachment, the bioactive glass surface was modified with the protein coupling agent glutaraldehyde. Continuous wave EPR spectra of different spin labeled MnmE mutants were recorded to assess the dynamics of the attached spin labels before and after protein adsorption. The area of the continuous wave (cw)-EPR absorption spectrum was further used to determine the amount of the attached protein. Double electron-electron resonance (DEER) experiments were conducted to measure distances between the spin labels before and after adsorption. The results revealed that the contact regions between MnmE and the bioactive glass surface are located at the G domains and at the N-terminal domains. The low modulation depths of all DEER time traces recorded for the adsorbed single MnmE mutants, corroborated with the DEER measurements performed on MnmE double mutants, show that the adsorption process leads to dissociation of the dimer and alters the tertiary structure of MnmE, thereby abolishing its functionality. However, glutaraldehyde reduces the aggressiveness of the adsorption process and improves the stability of the protein attachment. PMID:24785159

  11. 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.

  12. 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.

  13. Surface Layer Accretion in Transitional and Conventional Disks: From Polycyclic Aromatic Hydrocarbons to Planets

    NASA Astrophysics Data System (ADS)

    Perez-Becker, Daniel; Chiang, Eugene

    2011-01-01

    "Transitional" T Tauri disks have optically thin holes with radii gsim10 AU, yet accrete up to the median T Tauri rate. Multiple planets inside the hole can torque the gas to high radial speeds over large distances, reducing the local surface density while maintaining accretion. Thus multi-planet systems, together with reductions in disk opacity due to grain growth, can explain how holes can be simultaneously transparent and accreting. There remains the problem of how outer disk gas diffuses into the hole. Here it has been proposed that the magnetorotational instability (MRI) erodes disk surface layers ionized by stellar X-rays. In contrast to previous work, we find that the extent to which surface layers are MRI-active is limited not by ohmic dissipation but by ambipolar diffusion, the latter measured by Am: the number of times a neutral hydrogen molecule collides with ions in a dynamical time. Simulations by Hawley & Stone showed that Am ~ 100 is necessary for ions to drive MRI turbulence in neutral gas. We calculate that in X-ray-irradiated surface layers, Am typically varies from ~10-3 to 1, depending on the abundance of charge-adsorbing polycyclic aromatic hydrocarbons, whose properties we infer from Spitzer observations. We conclude that ionization of H2 by X-rays and cosmic rays can sustain, at most, only weak MRI turbulence in surface layers 1-10 g cm-2 thick, and that accretion rates in such layers are too small compared to observed accretion rates for the majority of disks.

  14. Surface properties of polyimide layers used in microelectronics

    NASA Astrophysics Data System (ADS)

    Borycki, Jerzy; Okulska-Bozek, Malgorzata

    1998-01-01

    Dozens of poly(amic acids) from selected aromatic diamines and dianhydrides were prepared in the first step of the classical two-step polycondensation. Polyimide layers on different surfaces were obtained by the poly(amic acids) imidization. Some of mechanical properties of these layers were tested. Some correlations between these properties and chemical structure of them wee noticed and discussed.

  15. 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.

  16. 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.

  17. 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.

  18. Concentrating materials covered by molecular imprinted nanofiltration layer with reconfigurability prepared by a surface sol-gel process for gas-selective detection.

    PubMed

    Imahashi, Masahiro; Hayashi, Kenshi

    2013-09-15

    Sensors that recognize molecules are acquired for the comprehensive detection of great many kinds of gases. Adsorbents with high molecular recognition and condensation ability were developed for selective gas sensing with a molecular imprinting technique. Developed adsorbents have multilayer structures consisted of a chemically modified polymer layer on the surface of a substrate covered by a TiO2 gel monolayer by the surface sol-gel process. Ellipsometry measurements showed that the 6-nm-thick layers deposited on the substrate. Cavities of molecular templates were imprinted on these layers, and thus, the film acts as a molecular gas filter without concentrating ability, which could form specific binding sites for various molecules that confirmed using solid-phase microextraction and gas chromatography-mass spectrometry. Gases were selectively absorbed into an accumulating adsorption layer and other gas molecules were blocked by the nanofiltration. These developed adsorbents enabled effective concentration ability and the filtration of gases or odors. In addition, these filters possess the flexibility to be easily configured with specific surface properties to interact with volatile molecules under appropriate conditions. A successful multiplex filter, imprinted simultaneously on an adsorbent with different sites, was demonstrated.

  19. Acid drainage response to surface limestone layers

    SciTech Connect

    Geidel, G.; Caruccio, F.T.

    1982-12-01

    A 150 acre drainage basin in an unreclaimed coal strip mine in east-central Ohio was studied and extensively monitored to determine the effect of a surface application of limestone on the ground water quality. Prior to the limestone treatment the ground and surface water of the basin was acidic due to pyrite oxidation in the spoil. In order to assess the effect of the limestone application the basin was divided into seven sub-basins, five of which were treated and two which served as controls. The seeps from the treated sub-basins with low acid concentrations became alkaline due to neutralization but after a long dry period, they returned to their acid condition. The moderately and highly acidic seeps showed a decline in the acid concentrations which could be attributed to a combination of neutralization and a decrease in the rate of pyrite oxidation. The results of this field study and simultaneous laboratory experiments showed that under natural conditions, with no limestone application, the acidity generated by pyrite oxidation in a backfill decreased. A surface application of limestone slightly enhanced the decrease in acidity by both neutralization and decreasing the rate of pyrite oxidation. However, the limestone application did not provide sufficient alkalinity to produce either neutral or alkaline discharges from the abandoned coal strip mine site.

  20. In situ determination of the depuration of three- and four-ringed polycyclic aromatic hydrocarbons co-adsorbed onto mangrove leaf surfaces.

    PubMed

    Sun, Haifeng; Shi, Jing; Guo, Shuai; Zhang, Yong; Duan, Lusha

    2016-01-01

    A dual-wavelength fiber-optic fluorimetry for the in situ simultaneous determinations of fluorene (Flu), phenanthrene (Phe) and pyrene (Pyr) adsorbed onto the leaf surfaces of living Avicennia marina (Am) seedling were developed and used to study the depuration kinetics of the three PAHs, adsorbed individually or mixed together, onto living Am leaf surfaces. Limits of detection for the in situ measurements of adsorbed Flu, Phe and Pyr were 4.62, 2.75 and 1.38 ng spot(-1), respectively. The depuration kinetics of the three selected polycyclic aromatic hydrocarbons (PAHs) are divided into rapid and slow phases; both phases followed the same first-order kinetics with relative clearance rates of Flu > Phe > Pyr during the rapid phase, and a clearance rate order of Pyr > Flu > Phe during the slow phase. For the three PAHs co-adsorbed on living Am leaf surfaces, a significant synergistic effect was detected during the rapid phase clearance; conversely, an antagonistic effect was observed during the slow phase. However, the synergistic effect dominated during both phases of the depuration process, and the co-adsorption of PAHs promoted the clearance of all three compounds from the mangrove leaf surfaces. These findings demonstrate a novel analytical method for in situ characterization of multiple PAHs adsorbed onto the plant surfaces.

  1. 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

  2. Study of surface charge density on solid/liquid interfaces by modulating the electrical double layer

    NASA Astrophysics Data System (ADS)

    Pak, Hyuk Kyu; Moon, Jong Kyun

    2014-11-01

    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 difference between the plates 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 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. This work was supported by Center for Soft and Living Matter through IBS program in Korea.

  3. 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.

  4. Investigation of surface charge density on solid-liquid interfaces by modulating the electrical double layer

    NASA Astrophysics Data System (ADS)

    Moon, Jong Kyun; Song, Myung Won; Pak, Hyuk Kyu

    2015-05-01

    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.

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

    NASA Astrophysics Data System (ADS)

    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) (∼1690 cm-1) the Cdbnd O stretching modes at unhydrated groups, (ii) (1655-1673 cm-1) the Cdbnd O 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) (∼1640 cm-1) the Cdbnd O 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 < 50 μg ml-1) corresponds to solution spectra indicating that native collagen molecules interact with water adsorbed on the titania surface. In films prepared from solutions (c ⩾ 50 μg ml-1) collagen multilayers are formed. The amide I mode is blue-shifted by 18 cm-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.

  6. Structure and dynamics of monolayer films of squalane molecules adsorbed on a solid surface

    NASA Astrophysics Data System (ADS)

    D. T Enevoldsen, A.; Hansen, F. Y.; Diama, A.; Taub, H.

    2003-03-01

    Squalane is a branched alkane (C_30H_62). It consists of a straight chain with 24 carbon atoms, as in tetracosane (C_24H_50), and has six methyl side groups. Branched polymers such as squalane are thought to be better lubricants than n-alkanes. At low temperature, our molecular dynamics (MD) simulations show that the molecules form an ordered monolayer which melts at approximately 325 K compared to the tetracosane monolayer melting point of ˜ 340 K. Our MD simulations indicate the same melting mechanism in the squalane monolayer that was found previously for tetracosane (F. Y. Hansen and H. Taub, Phys. Rev. Lett. 69, 652 (1992).) They also show that the adsorbed molecules are distorted from an all-trans carbon backbone in contrast to what was found for tetracosane. This may explain why the Bragg diffraction peaks were observed to be broader for the squalane monolayer than for tetracosane (D. Fuhrmann, A. P. Graham, L. Criswell, H. Mo, B. Matthies, K. W. Herwig, and H. Taub, Surf. Sci. 482-485, 77 (2001).). The diffusive motion in a squalane monolayer has been investigated by both quasielastic neutron scattering and MD simulations and compared to the dynamics in tetracosane monolayers. Focus will be on differences in the dynamics.

  7. 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.

  8. Boundary layer flow visualisation patterns on a riblet surface

    NASA Astrophysics Data System (ADS)

    Clark, D. G.

    Boundary layer flow visualization methods, developed at Queen Mary and Westfield College, have been applied to a riblet surface. The results reveal cellular crossflows developing in the grooves between the riblets. These local flor regimes appear to have little direct effect on the flow in the wall layers immediately adjacent to them. Qualitatively, the behavior of the wall layers appears to be that which would be expected if a virtual surface existed at a level slightly above the riblet tops, but a tendency for the origin of longitudinal eddy pairs to become anchored to the top of a riblet is noted.

  9. 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

  10. 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.

  11. Adsorbed polyelectrolyte coatings decrease Fe(0) nanoparticle reactivity with TCE in water: conceptual model and mechanisms.

    PubMed

    Phenrat, Tanapon; Liu, Yueqiang; Tilton, Robert D; Lowry, Gregory V

    2009-03-01

    The surfaces of reactive nanoscale zerovalent iron (NZVI) particles used for in situ groundwater remediation are modified with polymers or polyelectrolytes to enhance colloidal stability and mobility in the subsurface. However, surface modification decreases NZVI reactivity. Here, the TCE dechlorination rate and reaction products are measured as a function of adsorbed polyelectrolyte mass for three commercially available polyelectrolytes used for NZVI surface modification including poly(styrene sulfonate) (PSS), carboxymethyl cellulose (CMC), and polyaspartate (PAP). The adsorbed mass, extended layer thickness, and TCE-polyelectrolyte partition coefficient are measured and used to explain the effect of adsorbed polyelectrolyte on NZVI reactivity. For all modifiers, the dechlorination rate constant decreased nonlinearly with increasing surface excess, with a maximum of a 24-fold decrease in reactivity. The TCE dechlorination pathways were not affected. Consistent with Scheutjens-Fleer theory for homopolymer adsorption, the nonlinear relationship between the dechlorination rate and the surface excess of adsorbed polyelectrolyte suggests that adsorbed polyelectrolyte decreases reactivity primarily by blocking reactive surface sites at low surface excess where they adsorb relatively flat onto the NZVI surface, and by a combination of site blocking and decreasing the aqueous TCE concentration at the NZVI surface due to partitioning of TCE to adsorbed polyelectrolytes. This explanation is also consistent with the effect of adsorbed polyelectrolyte on acetylene formation. This conceptual model should apply to other medium and high molecular weight polymeric surface modifiers on nanoparticles, and potentially to adsorbed natural organic matter.

  12. 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.

  13. 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.

  14. Two-photon photoemission investigation of electronic and dynamical properties of alkali atoms adsorbed on noble metal surfaces

    NASA Astrophysics Data System (ADS)

    Sametoglu, Vahit

    We present a systematic time-resolved two-photon photoemission study of the electronic and dynamical properties of Li through Cs adsorbed on Cu(111) and Ag(111) surfaces. A fundamental problem in surface science is how to describe the electronic structure of a chemisorption interface based on the intrinsic properties of the interacting materials. Because of their simple s-electron structure, elements of the alkali atom group comprise paradigmatic adsorbates in many theories of chemisorption, whereas the complementary experimental studies are sparse and incomplete. Through a combination of spectroscopic and femtosecond time-resolved surface measurements, we are able to probe systematically the binding energies, symmetries, and electron and nuclear relaxation dynamics of the initially unoccupied alkali atom resonances. As a prelude, we study the two-photon photoemission process occurring at the bare Ag(111) surface. We develop a quantitative model for two-photon photoemission process, where the nonresonant and k-dependent two-photon absorption between the lower and upper sp-bands is modeled by the optical Bloch equations, and the angle-dependent intensities are described by the Fresnel equations. Our two-photon photoemission spectra of Li through Cs chemisorbed Cu(111) and Ag(111) surfaces reveal two resonances with the m = 0 and m = +/-1 symmetry ('m' is the projection of the orbital angular momentum 'l' onto the surface plane). For the m = 0 resonance, which is derived from the hybridization of the ns and npz orbitals of alkali atoms, we find a binding energy of 1.84--1.99 eV below the vacuum level, which is independent of the alkali atom period, and tunes with coverage in a universal manner. At 0.3--0.7 eV higher energy, we discover and identify the m = +/-1 resonance by its characteristic angular intensity distribution, which derives from the antisymmetry of the npx and npy orbitals. We implement a quantitative model for the alkali atom chemisorption based on the

  15. 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.

  16. 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

  17. Comparative study of normal and branched alkane monolayer films adsorbed on a solid surface. II. Dynamics

    NASA Astrophysics Data System (ADS)

    Enevoldsen, A. D.; Hansen, F. Y.; Diama, A.; Taub, H.; Dimeo, R. M.; Neumann, D. A.; Copley, J. R. D.

    2007-03-01

    The dynamics of monolayer films of the n-alkane tetracosane (n-C24H52) and the branched alkane squalane (C30H62) adsorbed on graphite have been studied by quasielastic and inelastic neutron scattering and molecular dynamics (MD) simulations. Both molecules have 24 carbon atoms along their carbon backbone, and squalane has an additional six methyl side groups symmetrically placed along its length. The authors' principal objective has been to determine the influence of the side groups on the dynamics of the squalane monolayer and thereby assess its potential as a nanoscale lubricant. To investigate the dynamics of these monolayers they used both the disk chopper spectrometer (DCS) and the high flux backscattering spectrometer (HFBS) at the National Institute of Standards and Technology. These instruments made it possible to study dynamical processes such as molecular diffusive motions and vibrations on very different time scales: 1-40ps (DCS) and 0.1-4ns (HFBS). The MD simulations were done on corresponding time scales and were used to interpret the neutron spectra. The authors found that the dynamics of the two monolayers are qualitatively similar on the respective time scales and that there are only small quantitative differences that can be understood in terms of the different masses and moments of inertia of the two molecules. In the course of this study, the authors developed a procedure to separate out the low-frequency vibrational modes in the spectra, thereby facilitating an analysis of the quasielastic scattering. They conclude that there are no major differences in the monolayer dynamics caused by intramolecular branching. It remains to be seen whether this similarity in monolayer dynamics also holds for the lubricating properties of these molecules in confined geometries.

  18. 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.

  19. 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.

  20. Surface-enhanced Raman scattering spectra of adsorbates on Cu2O nanospheres: charge-transfer and electromagnetic enhancement

    NASA Astrophysics Data System (ADS)

    Jiang, Li; You, Tingting; Yin, Penggang; Shang, Yang; Zhang, Dongfeng; Guo, Lin; Yang, Shihe

    2013-03-01

    Surface-enhanced Raman scattering (SERS) spectra of 4-mercaptobenzoic acid (4-MBA) have been investigated on the surface of Cu2O nanospheres. The SERS signals were believed to originate from the static chemical enhancement, resonant chemical enhancement and electromagnetic enhancement. The coupling between the adsorbates and the semiconductor, evidenced by the shift in absorption spectrum of modified Cu2O and the enhancement of non-totally symmetric modes of the 4-MBA and 4-mercaptopyridine (4-MPY) molecules, were invoked to explain the experimental results. Furthermore, simulations were employed to investigate the nature of the enhancement mechanisms operative between the molecules and the semiconductor. Density functional theory (DFT) calculations suggested a charge transfer (CT) transition process between the molecules and the Cu2O nanospheres. Three-dimensional finite-difference time domain (3D-FDTD) simulations were conducted to map out the electromagnetic field around the Cu2O nanospheres. The experimental and simulation results have revealed the promise of the Cu2O nanospheres as a good SERS substrate and the prospect of using the SERS substrate as a valuable tool for in situ investigation and assay of the adsorption behavior on semiconductor surfaces.Surface-enhanced Raman scattering (SERS) spectra of 4-mercaptobenzoic acid (4-MBA) have been investigated on the surface of Cu2O nanospheres. The SERS signals were believed to originate from the static chemical enhancement, resonant chemical enhancement and electromagnetic enhancement. The coupling between the adsorbates and the semiconductor, evidenced by the shift in absorption spectrum of modified Cu2O and the enhancement of non-totally symmetric modes of the 4-MBA and 4-mercaptopyridine (4-MPY) molecules, were invoked to explain the experimental results. Furthermore, simulations were employed to investigate the nature of the enhancement mechanisms operative between the molecules and the semiconductor

  1. Optical detection of adsorbed CO2 and other gases on ferroelectric surfaces using second harmonic generation (SHG)

    NASA Astrophysics Data System (ADS)

    Cabrera, Guerau; Chen, Disheng; Jambunathan, Karthik; Xu, Ruijuan; Cabrera, Alejandro; Martin, Lane; Holcomb, Mikel

    2013-03-01

    Due to their polar surfaces, ferroelectrics may provide an ideal way to detect and collect gas molecules, useful for applications such as gas sensing and pollution mitigation. Since ferroelectric materials have a high reliability (at least 109 switching cycles) these sensors could be used for prolonged periods of time without failure. Second harmonic generation (SHG) allows us to determine the spatial orientation of surface adsorbates and to monitor in realtime the kinetics of adsorption/desorption. In preliminary experiments we see a variation of SHG signal from the surface of PbZrTiO3 (PZT) (100 nm film 20% Zr, 80% Ti) when dosed with 1 atm of N2 or CO2. There is a 21% increase in signal when dosed with N2 with respect to signal in vacuum and there is a 19.9% increase in signal when dosed with CO2 with respect to signal in vacuum. Further studies will be performed to determine the orientation of these molecules on the surface of this device. Experiments will also be performed while polarizing the device with an external electric field to determine the effect of polarization on adsorption/desorption of molecules.

  2. "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

  3. "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.

  4. 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.

  5. XPS study of distribution of elements between surface and volume in aluminosilicate catalysts and adsorbents

    SciTech Connect

    Chukin, G.D.; Grishin, S.A.; Kulikov, A.S.; Nefedov, B.K.; Surin, S.A.

    1986-02-01

    X-ray photoelectron spectroscopy (XPS) has been used in an investigation of the distribution of aluminum and sodium on the surface and in the volume of amorphous aluminosilicates. It has been shown that in the Na form of the aluminosilicates, the sodium and aluminum ions are localized preferentially on the surface. When the Na/sup +/ ions are replaced by protons, there is a change in the electronic state of the near-surface atoms in the aluminosilicates. Information on acidic centers that has been obtained by IR spectroscopy is consistent with the XPS data.

  6. Layer-by-layer deposition of oppositely charged polyelectrolytes on the surface of condensed DNA particles.

    PubMed Central

    Trubetskoy, V S; Loomis, A; Hagstrom, J E; Budker, V G; Wolff, J A

    1999-01-01

    DNA can be condensed with an excess of poly-cations in aqueous solutions forming stable particles of submicron size with positive surface charge. This charge surplus can be used to deposit alternating layers of polyanions and polycations on the surface surrounding the core of condensed DNA. Using poly-L-lysine (PLL) and succinylated PLL (SPLL) as polycation and polyanion, respectively, we demonstrated layer-by-layer architecture of the particles. Polyanions with a shorter carboxyl/backbone distance tend to disassemble binary DNA/PLL complexes by displacing DNA while polyanions with a longer carboxyl/backbone distance effectively formed a tertiary complex. The zeta potential of such complexes became negative, indicating effective surface recharging. The charge stoichiometry of the DNA/PLL/SPLL complex was found to be close to 1:1:1, resembling poly-electrolyte complexes layered on macrosurfaces. Recharged particles containing condensed plasmid DNA may find applications as non-viral gene delivery vectors. PMID:10454604

  7. Layer-by-layer deposition of oppositely charged polyelectrolytes on the surface of condensed DNA particles.

    PubMed

    Trubetskoy, V S; Loomis, A; Hagstrom, J E; Budker, V G; Wolff, J A

    1999-08-01

    DNA can be condensed with an excess of poly-cations in aqueous solutions forming stable particles of submicron size with positive surface charge. This charge surplus can be used to deposit alternating layers of polyanions and polycations on the surface surrounding the core of condensed DNA. Using poly-L-lysine (PLL) and succinylated PLL (SPLL) as polycation and polyanion, respectively, we demonstrated layer-by-layer architecture of the particles. Polyanions with a shorter carboxyl/backbone distance tend to disassemble binary DNA/PLL complexes by displacing DNA while polyanions with a longer carboxyl/backbone distance effectively formed a tertiary complex. The zeta potential of such complexes became negative, indicating effective surface recharging. The charge stoichiometry of the DNA/PLL/SPLL complex was found to be close to 1:1:1, resembling poly-electrolyte complexes layered on macrosurfaces. Recharged particles containing condensed plasmid DNA may find applications as non-viral gene delivery vectors.

  8. 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.

  9. Soft X-Ray Spectroscopy of Glycyl-Glycine Adsorbed on Cu(110) Surface

    NASA Astrophysics Data System (ADS)

    Feyer, V.; Plekan, O.; Lyamayev, V.; Skala, T.; Prince, K. C.; Chab, V.; Tsud, N.; Matolin, V.; Carravetta, V.

    2010-06-01

    Studies of the interaction between organic compounds and surfaces are motivated by their application as bio sensors, and their relevance to biocompatibility of implants and the origin of life. In the present work interaction of the simplest peptide, glycyl-glycine, with the Cu surface has been studied. Multilayer, monolayer and sub-monolayer films of this dipeptide on the clean and oxygen modified Cu(110) surface were prepared by thermal evaporation in high vacuum. The techniques used were soft X-ray photoelectron spectroscopy, near edge X-ray absorption fine structure spectroscopy and density functional theory calculations. By comparing the experimental and theoretical spectra, detailed models of the electronic structure and adsorption geometry for each coverage have been proposed, which are in good agreement with the theoretical calculations. The carboxylic acid group of glycyl-glycine loses hydrogen and the molecule is coordinated via the carboxylate oxygen atoms to the surface. At low coverage the amino group bonds to the surface via a hydrogen atom, while at higher coverage the bonding is via the nitrogen lone pair. The peptide group is not involved in the bonding to the surface.

  10. Using localized surface plasmon resonances to probe the nanoscopic origins of adsorbate-driven ordering transitions of liquid crystals in contact with chemically functionalized gold nanodots.

    PubMed

    Koenig, Gary M; Gettelfinger, Brian T; de Pablo, Juan J; Abbott, Nicholas L

    2008-08-01

    We report that localized surface plasmon resonances (LSPRs) of gold nanodots immersed under liquid crystals (LCs) can be used to characterize adsorbate-induced ordering transitions of the LCs on the surfaces of the nanodots. The nanoscopic changes in ordering of the LCs, as measured by LSPR, were shown to give rise to macroscopic ordering transitions of the LCs that were observed by polarized light microscopy. The results reported herein suggest that (i) LCs may be useful for enhancing the sensitivity of LSPR-based detection of binding events and (ii) that LSPR measurements of gold nanodots provide a means to characterize the nanoscopic origins of macroscopic, adsorbate-induced LC ordering transitions.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. Anomalous surface fatigue in a nano-layered material.

    PubMed

    Yang, Liu; Czajkowsky, Daniel M; Sun, Jielin; Hu, Jun; Shao, Zhifeng

    2014-10-01

    Nanoscale materials fatigue within a single 7 Å layer of a 2D nano-layered material, muscovite mica, resembles fatigue in macroscopic systems except for two remarkable properties: first, there is an Å-scale precision in the depth of the damage and second, there are sharply defined "magical" stresses, beyond yield, at which the surface remains intact regardless of the number of applications of stress.

  17. 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.

  18. Alternative barrier layers for surface covers in dry climates

    SciTech Connect

    Stormont, J.C.

    1994-09-01

    Surface covers are one of the most widespread remediation and waste management options in all climates. Barrier layers to limit percolation through cover systems are principal features of engineered, multi-component cover designs. Conventional barrier layer components developed for humid climates have limitations in dry climates. One alternative barrier layer is a capillary barrier, which consists of a fine-over-coarse soil arrangement. The capacity of capillary barrier to laterally divert downward moving water is the key to their success. Another alternative is a dry barrier, in which atmospheric air is circulated through a coarse layer within the cover to remove water vapor. Incorporating a coarse layer which stores water for subsequent removal by air flow reduces the requirements for the air flow velocity and increases the applicability of the dry barrier.

  19. 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

  20. Biphasic surface amorphous layer lubrication of articular cartilage.

    PubMed

    Graindorge, Simon; Ferrandez, Wendy; Jin, Zhongmin; Ingham, Eileen; Grant, Colin; Twigg, Peter; Fisher, John

    2005-12-01

    The biphasic nature of articular cartilage has been acknowledged for some time and is known to play an important role in many of the biomechanical functions performed by this unique tissue. From the lubrication point of view however, a simple biphasic model is unable to account for the extremely low friction coefficients that have been recorded experimentally, particularly during start-up. In addition, research over the last decade has indicated the presence of a surface amorphous layer on top of articular cartilage. Here, we present results from a finite element model of articular cartilage that includes a thin, soft, biphasic surface amorphous layer (BSAL). The results of this study show that a thin BSAL, with lower elastic modulus, dramatically altered the load sharing between the solid and liquid phases of articular cartilage, particularly in the near-surface regions of the underlying bulk cartilage and within the surface amorphous layer itself where the fluid load support exceeded 85%. By transferring the load from the solid phase to the fluid phase, the biphasic surface layer improves lubrication and reduces friction, whilst also protecting the underlying cartilage surface by 'shielding' the solid phase from elevated stresses. The increase in lubrication effectiveness is shown to be greatest during short duration loading scenarios, such as shock loads.

  1. Metastable-atom deexcitation spectroscopy of clean and Ag-adsorbed Si (111) surfaces

    NASA Astrophysics Data System (ADS)

    Nishigaki, S.; Takao, K.; Yamada, T.; Arimoto, M.; Komatsu, T.

    1985-07-01

    Electron energy spectra upon incidence of He ∗ metastables on a clean Si(111)7 × 7 surface are obtained, which demonstrate the operation of the surface Penning ionization mechanism for the metastable-atom deexcitation (MD). Dangling bond orbitals are detected at about -0.5 and -1.5 eV below EF in the MD spectra. They are compared with previous UPS results. The adsorption process of Ag on Si(111) is studied by MDS and AES. In a MD spectrum for a Ag-deposited surface at room temperature with θ = {2}/{3} a peak appears at -5.2 below EF which belongs to Ag 4d orbitals. For a surface with the 3× 3 structure (deposited at 300°C with θ = {2}/{3}), however, the intensity of the Ag 4d peak is rather weak and its energy shifts by about -0.4 eV from the room-temperature value. These results support the embedded-Ag model for the Si(111) 3Ag structure.

  2. [Surface-enhanced Raman spectroscopy of biopolymers: membrane proteins, bacteriorhodopsin and rhodopsin adsorbed on silver electrodes and silver hydrosols].

    PubMed

    Nabiev, I R; Efremov, R G; Chumanov, G D

    1986-01-01

    Surface-enhanced Raman (SER) spectra of purple membranes of Halobacterium halobium and photoreceptor disks of the rod outer segments adsorbed on silver hydrosols were analysed. It has been shown that the intensity of SER spectra of bacterial and visual rhodopsins increases 5 X 10(4) times at adsorption. Concentration relationship of the signal intensity of SER spectra has the maximum at bacteriorhodopsin concentration about 2 X 10(-7) M. It has been shown that adsorption on silver hydrosol leads to fixation of light-induced photochemical transformations in bacterial and visual rhodopsins. Adsorption on the "smooth" electrodes at the potential of the zero charge of silver does not affect the photocycle of bacteriorhodopsin. An increase or decrease of the electrode potential relative to the zero charge point of silver leads to the accumulation of kinetic intermediate K610 and a decrease of the concentration of the form BRh570. It has been shown that on the "smooth" electrode primarily the long-range component of the SER mechanism is realized. Bands corresponding to the vibrations of the atom groups directly contacting with the metal are mainly intensified after redox cycle which increases the concentration of chemosorption centres. A conclusion is drawn that the method of SER spectroscopy of biomolecules adsorbed on "smooth" electrodes, permits obtaining information similar to that obtained from the analysis of Raman spectra of unadsorbed molecules, but at concentrations by two orders less. Adsorption on the electrodes treated with the help of redox cycle permits to obtain highly oriented preparations and to study topography of biopolymers in water solutions and suspensions.

  3. Structural rearrangements in self-assembled surfactant layers at surfaces

    SciTech Connect

    Sushko, Maria L.; Liu, Jun

    2010-03-25

    The transition from compact to extended configuration in ionic surfactant layers under the influence of salt, surfactant surface density and temperature is studied using the classical density functional theory (cDFT). The increase in ionic strength of aqueous salt solution or in surfactant surface density leads to the transition from the hemicylindrical to the perpendicular monolayer configuration of the molecules. Although producing the same structural rearrangement in the surfactant layer the origin of the effect of salt and surface density is different. While the addition of salt increases the out-of-plane attractive interactions with the solvent, the increase in density results in the increase in the in-plane repulsion in surfactant layer. The temperature effects are subtler and are mainly manifested in the reduction of the solution structuring at elevated temperatures.

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. Spectromicroscopy of C60 and azafullerene C59N: Identifying surface adsorbed water

    NASA Astrophysics Data System (ADS)

    Erbahar, Dogan; Susi, Toma; Rocquefelte, Xavier; Bittencourt, Carla; Scardamaglia, Mattia; Blaha, Peter; Guttmann, Peter; Rotas, Georgios; Tagmatarchis, Nikos; Zhu, Xiaohui; Hitchcock, Adam P.; Ewels, Chris P.

    2016-10-01

    C60 fullerene crystals may serve as important catalysts for interstellar organic chemistry. To explore this possibility, the electronic structures of free-standing powders of C60 and (C59N)2 azafullerenes are characterized using X-ray microscopy with near-edge X-ray adsorption fine structure (NEXAFS) spectroscopy, closely coupled with density functional theory (DFT) calculations. This is supported with X-ray photoelectron spectroscopy (XPS) measurements and associated core-level shift DFT calculations. We compare the oxygen 1s spectra from oxygen impurities in C60 and C59N, and calculate a range of possible oxidized and hydroxylated structures and associated formation barriers. These results allow us to propose a model for the oxygen present in these samples, notably the importance of water surface adsorption and possible ice formation. Water adsorption on C60 crystal surfaces may prove important for astrobiological studies of interstellar amino acid formation.

  9. 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.

  10. Spectromicroscopy of C60 and azafullerene C59N: Identifying surface adsorbed water

    PubMed Central

    Erbahar, Dogan; Susi, Toma; Rocquefelte, Xavier; Bittencourt, Carla; Scardamaglia, Mattia; Blaha, Peter; Guttmann, Peter; Rotas, Georgios; Tagmatarchis, Nikos; Zhu, Xiaohui; Hitchcock, Adam P.; Ewels, Chris P.

    2016-01-01

    C60 fullerene crystals may serve as important catalysts for interstellar organic chemistry. To explore this possibility, the electronic structures of free-standing powders of C60 and (C59N)2 azafullerenes are characterized using X-ray microscopy with near-edge X-ray adsorption fine structure (NEXAFS) spectroscopy, closely coupled with density functional theory (DFT) calculations. This is supported with X-ray photoelectron spectroscopy (XPS) measurements and associated core-level shift DFT calculations. We compare the oxygen 1s spectra from oxygen impurities in C60 and C59N, and calculate a range of possible oxidized and hydroxylated structures and associated formation barriers. These results allow us to propose a model for the oxygen present in these samples, notably the importance of water surface adsorption and possible ice formation. Water adsorption on C60 crystal surfaces may prove important for astrobiological studies of interstellar amino acid formation. PMID:27748425

  11. 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

  12. Atomic layer deposition in nanostructured photovoltaics: tuning optical, electronic and surface properties.

    PubMed

    Palmstrom, Axel F; Santra, Pralay K; Bent, Stacey F

    2015-08-01

    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.

  13. Sputtered silver oxide layers for surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Büchel, D.; Mihalcea, C.; Fukaya, T.; Atoda, N.; Tominaga, J.; Kikukawa, T.; Fuji, H.

    2001-07-01

    We present results of reactively sputtered silver oxide thin films as a substrate material for surface-enhanced Raman spectroscopy (SERS). Herein, we show that deposited layers develop an increasingly strong SERS activity upon photoactivation at 488 nm. A benzoic acid/2-propanol solution was used to demonstrate that the bonding of molecules to SERS active sites at the surface can be followed by investigating temporal changes of the corresponding Raman intensities. Furthermore, the laser-induced structural changes in the silver oxide layers lead to a fluctuating SERS activity at high laser intensities which also affects the spectral features of amorphous carbon impurities.

  14. 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

  15. Effect of nanoconfinement on polymer dynamics: surface layers and interphases.

    PubMed

    Krutyeva, M; Wischnewski, A; Monkenbusch, M; Willner, L; Maiz, J; Mijangos, C; Arbe, A; Colmenero, J; Radulescu, A; Holderer, O; Ohl, M; Richter, D

    2013-03-01

    We present neutron spin echo experiments that address the much debated topic of dynamic phenomena in polymer melts that are induced by interacting with a confining surface. We find an anchored surface layer that internally is highly mobile and not glassy as heavily promoted in the literature. The polymer dynamics in confinement is, rather, determined by two phases, one fully equal to the bulk polymer and another that is partly anchored at the surface. By strong topological interaction, this phase confines further chains with no direct contact to the surface. These form the often invoked interphase, where the full chain relaxation is impeded through the interaction with the anchored chains. PMID:23521308

  16. 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

  17. Meteoric cosmogenic Beryllium-10 adsorbed to river sediment and soil: Applications for Earth-surface dynamics

    NASA Astrophysics Data System (ADS)

    Willenbring, Jane K.; von Blanckenburg, Friedhelm

    2010-01-01

    Rainfall scavenges meteoric cosmogenic 10Be from the atmosphere. 10Be falls to the Earth's surface, where it binds tightly to sediment particles in non-acidic soils over the life-span of those soils. As such, meteoric 10Be has the potential to be an excellent geochemical tracer of erosion and stability of surfaces in a diverse range of natural settings. Meteoric 10Be has great potential as a recorder of first-order erosion rates and soil residence times. Even though this tracer was first developed in the late 1980s and showed great promise as a geomorphic tool, it was sidelined in the past two decades with the rise of the "sister nuclide", in situ10Be, which is produced at a known rate inside quartz minerals. Since these early days, substantial progress has been made in several areas that now shed new light on the applicability of the meteoric variety of this cosmogenic nuclide. Here, we revisit the potential of this tracer and we summarize the progress: (1) the atmospheric production and fallout is now described by numeric models, and agrees with present-day measurements and paleo-archives such as from rain and ice cores; (2) short-term fluctuations in solar modulation of cosmic rays or in the delivery of 10Be are averaged out over the time scale soils accumulate; (3) in many cases, the delivery of 10Be is not dependent on the amount of precipitation; (4) we explore where 10Be is retained in soils and sediment; (5) we suggest a law to account for the strong grain-size dependence that controls adsorption and the measured nuclide concentrations; and (6) we present a set of algebraic expressions that allows calculation of both soil or sediment ages and erosion rates from the inventory of meteoric 10Be distributed through a vertical soil column. The mathematical description is greatly simplified if the accumulation of 10Be is at a steady state with its export through erosion. In this case, a surface sample allows for the calculation of an erosion rate. Explored

  18. 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

  19. 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.

  20. Enhanced Raman scattering by molecules adsorbed at the surface of colloidal spheroids

    NASA Astrophysics Data System (ADS)

    Wang, D.-S.; Kerker, M.

    1981-08-01

    Equations are derived and calculations are presented for the electrodynamic mechanism of enhanced Raman scattering by molecules at the surface of prolate and oblate spheroids in the small-particle limit. The molecules may be arbitrarily distributed; the particles may be arbitrarily oriented. Calculations are presented for a monolayer distributed over randomly oriented spheroids. The effects of particle shape are considered for Ag, Au, and Cu hydrosols. The peak enhancement moves to longer wavelengths, and in the case of Au and Cu the magnitude of the enhancement increases strikingly as the eccentricity increases. The relation between the dependence of the Raman enhancement upon excitation wavelength and the extinction spectra is discussed, including the precariousness of extrapolating such relations beyond the small-particle limit.

  1. 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.

  2. Nano-materials for adhesive-free adsorbers for bakable extreme high vacuum cryopump surfaces

    DOEpatents

    Stutzman, Marcy; Jordan, Kevin; Whitney, Roy R.

    2016-10-11

    A cryosorber panel having nanomaterials used for the cryosorption material, with nanomaterial either grown directly on the cryopanel or freestanding nanomaterials attached to the cryopanel mechanically without the use of adhesives. Such nanomaterial cryosorber materials can be used in place of conventional charcoals that are attached to cryosorber panels with special low outgassing, low temperature capable adhesives. Carbon nanotubes and other nanomaterials could serve the same purpose as conventional charcoal cryosorbers, providing a large surface area for cryosorption without the need for adhesive since the nanomaterials can be grown directly on a metallic substrate or mechanically attached. The nanomaterials would be capable of being fully baked by heating above 100.degree. C., thereby eliminating water vapor from the system, eliminating adhesives from the system, and allowing a full bake of the system to reduce hydrogen outgassing, with the goal of obtaining extreme high vacuum where the pump can produce pressures below 1.times.10.sup.-12 Torr.

  3. 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.

  4. Super-hydrophobic surfaces of layer-by-layer structured film-coated electrospun nanofibrous membranes

    NASA Astrophysics Data System (ADS)

    Ogawa, Tasuku; Ding, Bin; Sone, Yuji; Shiratori, Seimei

    2007-04-01

    We have recently fabricated super-hydrophobic membrane surfaces based on the inspiration of self-cleaning silver ragwort leaves. This biomimetic super-hydrophobic surface was composed of fluoroalkylsilane (FAS)-modified layer-by-layer (LBL) structured film-coated electrospun nanofibrous membranes. The rough fibre surface caused by the electrostatic LBL coating of TiO2 nanoparticles and poly(acrylic acid) (PAA) was used to imitate the rough surface of nanosized grooves along the silver ragwort leaf fibre axis. The results showed that the FAS modification was the key process for increasing the surface hydrophobicity of the fibrous membranes. Additionally, the dependence of the hydrophobicity of the membrane surfaces upon the number of LBL coating bilayers was affected by the membrane surface roughness. Moreover, x-ray photoelectron spectroscopy (XPS) results further indicated that the surface of LBL film-coated fibres absorbed more fluoro groups than the fibre surface without the LBL coating. A (TiO2/PAA)10 film-coated cellulose acetate nanofibrous membrane with FAS surface modification showed the highest water contact angle of 162° and lowest water-roll angle of 2°.

  5. 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.

  6. Estimating Active Layer Thickness from Remotely Sensed Surface Deformation

    NASA Astrophysics Data System (ADS)

    Liu, L.; Schaefer, K. M.; Zhang, T.; Wahr, J. M.

    2010-12-01

    We estimate active layer thickness (ALT) from remotely sensed surface subsidence during thawing seasons derived from interferometric synthetic aperture radar (InSAR) measurements. Ground ice takes up more volume than ground water, so as the soil thaws in summer and the active layer deepens, the ground subsides. The volume of melted ground water during the summer thaw determines seasonal subsidence. ALT is defined as the maximum thaw depth at the end of a thawing season. By using InSAR to measure surface subsidence between the start and end of summer season, one can estimate the depth of thaw over a large area (typically 100 km by 100 km). We developed an ALT retrieval algorithm integrating InSAR-derived surface subsidence, observed soil texture, organic matter content, and moisture content. We validated this algorithm in the continuous permafrost area on the North Slope of Alaska. Based on InSAR measurements using ERS-1/2 SAR data, our estimated values match in situ measurements of ALT within 1--10 cm at Circumpolar Active Layer Monitoring (CALM) sites within the study area. The active layer plays a key role in land surface processes in cold regions. Current measurements of ALT using mechanical probing, frost/thaw tubes, or inferred from temperature measurements are of high quality, but limited in spatial coverage. Using InSAR to estimate ALT greatly expands the spatial coverage of ALT observations.

  7. Luna 9 photographs: Evidence for a fragmental surface layer

    USGS Publications Warehouse

    Gault, D.E.; Quaide, W.L.; Oberbeck, V.R.; Moore, H.J.

    1966-01-01

    The morphological features of the lunar surface photographed by Luna 9 indicate a surficial layer of weakly cohesive to noncohesive fragmental material. Most of this material is finer than a centimeter and probably finer than a few millimeters, although objects of centimeter size and larger are plentiful.

  8. 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.

  9. Surface-enhanced Raman spectroscopy of organic molecules adsorbed on metallic nanoparticles.

    PubMed

    Heleg-Shabtai, Vered; Zifman, Adi; Kendler, Shai

    2012-01-01

    The improvements in Raman instrumentation have led to the development of -portable, simple to operate, Raman instruments that can be used for on-site analysis of substances relevant for homeland security purposes such as chemical and biological warfare and explosives materials.Raman spectroscopy, however, suffers from limited sensitivity which can be overcome by Surface-Enhanced Raman Spectroscopy (SERS). SERS can enhance the Raman signal of a target molecule by 6-10 orders of magnitude. The increased sensitivity, together with Raman's molecular recognition capabilities and the availability of portable Raman instruments make SERS a powerful analytical tool for on site detection.In this work we studied the effect of target molecules and SERS-active substrate properties on the obtained SERS, using a field portable Raman spectrometer. Also reported herein is the SERS detection of the chemical warfare agent sulfur mustard (HD, 2,2 dichloroethyl sulfide). This study may serve as a basis for the development of SERS platform for homeland security purposes.

  10. 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.

  11. 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.

  12. 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.

  13. Identification of the properties of a complex layer deposited on the surface of a quartz crystal microbalance (QCM) by the impedance measurement

    NASA Astrophysics Data System (ADS)

    Wakatsuki, N.; Kagawa, Y.

    2007-01-01

    The quartz crystal microbalance (QCM) is a quartz crystal plate resonator for measuring a minute mass according to the resonant frequency change. In some applications, an adsorbing layer must be formed on the resonator surface, which adsorbs the material whose mass is measured. This layer affects not only the resonant frequency but also its damping as the layer is viscoelastic. Its presence cannot simply be ignored but should be included in the modelling. In our previous work, the algorithm to characterize the viscoelastic layer's properties was developed, in which the multiple resonant frequencies and the corresponding resonant resistances were considered including the overtone operation of the quartz crystal plate (Wakatsuki N, Wada S, Kagawa Y and Haba M 2003 Inverse Problems in Engineering Mechanics vol 4 (Oxford: Elsevier) pp 121-6). It is unrealistic however to assume that the layer's properties are unchanged for such a wide frequency range. In the present paper, no overtone resonance is considered. Mass of the adsorbed material and the thickness of the viscoelastic layer are identified by means of Newton's method.

  14. 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

  15. 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.

  16. Defatted algal biomass as a non-conventional low-cost adsorbent: surface characterization and methylene blue adsorption characteristics.

    PubMed

    Sarat Chandra, T; Mudliar, S N; Vidyashankar, S; Mukherji, S; Sarada, R; Krishnamurthi, K; Chauhan, V S

    2015-05-01

    The present study investigates the use of defatted algal biomass (DAB) as a non-conventional low cost adsorbent. The maximum adsorption capacity of biomass (raw, defatted and sulfuric acid pretreated DAB) was determined by liquid phase adsorption studies in batch mode for the removal of methylene blue present at various concentrations (1, 2, 3, 4, and 5 mg L(-1)) from aqueous solutions. The data was well fitted with Langmuir and Freundlich isotherms. The maximum adsorption capacity for raw, defatted and sulfuric acid pretreated DAB was found to be 6.0, 7.73 and 7.80 mg g(-1), respectively. The specific surface area of raw, defatted and sulfuric acid pretreated DAB was estimated to be 14.70, 18.94, and 19.10 m(2) g(-1), respectively. To evaluate the kinetic mechanism that controls the adsorption process, pseudo-first order, pseudo-second order, intraparticle diffusion and particle diffusion has been tested. The data fitted quite well with pseudo-second order kinetic model.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  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. Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer

    DOE PAGES

    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.

  3. 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.

  4. 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.

  5. Adsorption of HSA, IgG and laminin-1 on model titania surfaces--effects of glow discharge treatment on competitively adsorbed film composition.

    PubMed

    Santos, Olga; Svendsen, Ida E; Lindh, Liselott; Arnebrant, Thomas

    2011-10-01

    This study investigated the effect of glow discharge treatment of titania surfaces on plasma protein adsorption, by means of ellipsometry and mechanically assisted SDS elution. The adsorption and film elution of three plasma proteins, viz. human serum albumin (HSA), human immunoglobulin G (IgG) and laminin-1, as well as competitive adsorption from a mixture of the three proteins, showed that the adsorbed amount of the individual proteins after 1 h increased in the order HSA adsorbed films. No difference in the total adsorbed amounts of individual proteins, or from the mixture, was observed between untreated and glow discharge treated titania surfaces. However, the composition of the adsorbed films from the mixture differed between the untreated and glow discharge treated substrata. On glow discharge-treated titania the fraction of HSA increased, the fraction of laminin-1 decreased and the fraction of IgG was unchanged compared to the adsorption on the untreated titania, which was attributed to protein-protein interactions and competitive/associative adsorption behaviour.

  6. Detection of molecular oxygen adsorbate during room-temperature oxidation of Si(100)2 × 1 surface: In situ synchrotron radiation photoemission study

    NASA Astrophysics Data System (ADS)

    Yoshigoe, Akitaka; Yamada, Yoichi; Taga, Ryo; Ogawa, Shuichi; Takakuwa, Yuji

    2016-10-01

    Synchrotron radiation photoelectron spectroscopy during the oxidation of a Si(100)2 × 1 surface at room temperature revealed the existence of molecularly adsorbed oxygen, which was considered to be absent. The O 1s spectrum of such oxidation was found to be similar to that of Si(111)7 × 7 surface oxidation. Also, molecular oxygen appeared after the initial surface oxides were formed, indicating that it was not a precursor for dissociation oxygen adsorption on a clean surface. Considering this finding, we have proposed presumable structural models for atomic configurations, where molecular oxygen resided on the oxidized silicon with two oxygen atoms at the backbonds.

  7. Synthesis, Development, and Testing of High-Surface-Area Polymer-Based Adsorbents for the Selective Recovery of Uranium from Seawater

    DOE PAGES

    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

  8. 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.

  9. 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.

  10. Air-sea fluxes and surface layer turbulence around a sea surface temperature front

    NASA Technical Reports Server (NTRS)

    Friehe, C. A.; Shaw, W. J.; Davidson, K. L.; Rogers, D. P.; Large, W. G.; Stage, S. A.; Crescenti, G. H.; Khalsa, S. J. S.; Greenhut, G. K.; Li, F.

    1991-01-01

    The observed effects of sharp changes in sea surface temperature (SST) on the air-sea fluxes, surface roughness, and the turbulence structure in the surface layer and the marine atmospheric boundary layer are discussed. In situ flux and turbulence observations were carried out from three aircraft and two ships within the FASINEX framework. Three other aircraft used remote sensors to measure waves, microwave backscatter, and lidar signatures of cloud tops. Descriptions of the techniques, intercomparison of aircraft and ship flux data, and use of different methods for analyzing the fluxes from the aircraft data are described. Changing synoptic weather on three successive days yielded cases of wind direction both approximately parallel and perpendicular to a surface temperature front. For the wind perpendicular to the front, wind over both cold-to-warm and warm-to-cold surface temperatures occurred. Model results consistent with the observations suggest that an internal boundary layer forms at the SST.

  11. 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.

  12. 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

  13. 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.

  14. A comparison of didodecyldimethylammonium bromide adsorbed at mica/water and silica/water interfaces using neutron reflection.

    PubMed

    Griffin, Lucy R; Browning, Kathryn L; Truscott, Chris L; Clifton, Luke A; Webster, John; Clarke, Stuart M

    2016-09-15

    The layer structure of the dichain alkyl ammonium surfactant, didodecyldimethylammonium bromide (DDAB), adsorbed from water on to silica and mica surfaces has been determined using neutron reflection. Although sometimes considered interchangeable surfaces for study, we present evidence of significant differences in the adsorbed layer structure below the critical micelle concentration. A complete DDAB bilayer was assembled at the water/mica interface at concentrations below the critical micelle concentration (CMC). In contrast it is not until the CMC was reached that the complete bilayer structure formed on the oxidised silicon crystal. Removal of the complete bilayer on both surfaces was attempted by both washing and ion exchange yet the adsorbed structure proved tenacious.

  15. Layer-by-layer assembly of polymersomes and polyelectrolytes on planar surfaces and microsized colloidal particles.

    PubMed

    Coustet, Marcos; Irigoyen, Joseba; Garcia, Teodoro Alonso; Murray, Richard A; Romero, Gabriela; Susana Cortizo, M; Knoll, Wolfgang; Azzaroni, Omar; Moya, Sergio E

    2014-05-01

    Hybrid polyelectrolyte multilayer systems were fabricated on top of planar surfaces and colloidal particles via layer by layer (LbL) assembly of polystyrene sulphonate (PSS) and polybenzyl methacrylate-block-poly(dimethylamino)ethyl methacrylate (PBzMA-b-PDMAEMA) polymersomes. Polymersomes were prepared by self assembly of PBzMA-b-PDMAEMA copolymer, synthesised by group transfer polymerisation. Polymersomes display a diameter of 270 nm and a shell thickness of 11nm. Assembly on planar surfaces was followed by means of the Quartz Crystal Microbalance with Dissipation (QCM-D) and Atomic Force Microscopy (AFM). Detailed information on the assembly mechanism and surface topology of the polymersome/polyelectrolyte films was thereby obtained. The assembly of polymersomes and PSS on top of silica particles of 500 nm in diameter was confirmed by ζ-potential measurements. Confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that polymersome/PSS coated silica particles increase in total diameter up to 3-5μm. This hints toward the formation of densely packed polymersome layers. In addition, CLSM showed that polymersome/PSS films exhibit a high loading capacity that could potentially be used for encapsulation and delivery of diverse chemical species. These results provide an insight into the formation of multilayered films with compartmentalised hydrophilic/hydrophobic domains and may lead to the successful application of polymersomes in surface-engineered colloidal systems.

  16. Kondo screening and spin excitation in few-layer CoPc molecular assembly stacking on Pb(111) surface: A DFT+HEOM study

    NASA Astrophysics Data System (ADS)

    Wang, Yu; Zheng, Xiao; Yang, Jinlong

    2016-10-01

    Transition metal phthalocyanine molecules adsorbed on a metal substrate exhibit rich spin-related phenomena such as magnetic anisotropy, spin excitation, and Kondo effect. In this work, we investigate theoretically few-layer cobalt phthalocyanine (CoPc) molecular assembly stacking on Pb(111) surface with the use of a combined density functional theory (DFT) and hierarchical equations of motion (HEOM) approach. Calculation results indicate that the local spin properties of CoPc/Pb(111) composites depend critically on the number of adsorption layers. The first layer of CoPc on the Pb(111) surface serves as a spin-insulating buffer, while the CoPc molecules in the second layer exhibit spin-1/2 Kondo effect with a Kondo temperature of about 22 K. In a triple-layer CoPc assembly stacking on Pb(111), the antiferromagnetic coupling between the second and third layers leads to local spin-flip excitations under finite bias voltages, which gives rise to characteristic signatures in the differential conductance spectra. The DFT+HEOM approach thus provides a practical means for investigating the local electronic and spin properties of two-dimensional molecular assemblies adsorbed on the metal surface. The insights obtained from the first-principles based simulations could be useful for experimental manipulation or design of magnetic composite systems.

  17. Magnetic Or Optical Surface Layer Would Indicate Strain

    NASA Technical Reports Server (NTRS)

    Heyman, Joseph S.

    1995-01-01

    In proposed method of obtaining information on strain at surface of material specimen, magnetic coat (like that on magnetic tape) or optical coat (like that on compact disk) applied to all or part of surface monitored. Coating layer and associated measuring equipment, taken together, constitute system called "material strain monitor" (MSM). MSM important in research in materials and mechanics; in particular, expected to compete strongly with systems based on image-analysis and laser techniques now being developed to obtain information on strain fields.

  18. Surface alloys as interfacial layers between quasicrystalline and periodic materials

    NASA Astrophysics Data System (ADS)

    Duguet, T.; Ledieu, J.; Dubois, J. M.; Fournée, V.

    2008-08-01

    Low adhesion with normal metals is an intrinsic property of many quasicrystalline surfaces. Although this property could be useful to develop low friction or non-stick coatings, it is also responsible for the poor adhesion of quasicrystalline coatings on metal substrates. Here we investigate the possibility of using complex metallic surface alloys as interface layers to enhance the adhesion between quasicrystals and simple metal substrates. We first review some examples where such complex phases are formed as an overlayer. Then we study the formation of such surface alloys in a controlled way by annealing a thin film deposited on a quasicrystalline substrate. We demonstrate that a coherent buffer layer consisting of the γ-Al4Cu9 approximant can be grown between pure Al and the i-Al-Cu-Fe quasicrystal. The interfacial relationships between the different layers are defined by [111]_{\\mathrm {Al}}\\parallel [110]_{\\mathrm {Al_4Cu_9}}\\parallel [5\\mathrm {f}]_{i\\mbox {-}\\mathrm {Al\\mbox {--}Cu \\mbox {--}Fe}} .

  19. 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.

  20. Selective surface adsorption and pore trapping for ethanol-water mixtures near single-layer polyporous graphynes

    NASA Astrophysics Data System (ADS)

    Liu, Fang; Yang, Jie; Xu, Zhijun; Yang, Xiaoning

    2016-11-01

    The interfacial behavior of ethanol-water mixtures with various concentrations near single-layer polyporous γ-graphyne (Graphyne-n, n = 3,4,5) surfaces were investigated using molecular dynamics simulation. Comprehensive energetic analysis and structure properties, including density profiles, radial distribution functions, orientation distributions, and surface two-dimensional densities, have been simulated to quantify the surface-induced effect. Our simulation results illustrate micro-phase demixing phenomenon with ethanol molecules preferential adsorbing on the graphyne surfaces. This surface-induced demixing behavior is enhanced as the pore area decreases for the γ-graphynes, that is, G-3 surface induces the strongest demixing of ethanol-water mixture. Meanwhile, when in contacting with the graphyne-4 and graphyne-5 surfaces, ethanol molecules from the mixture are able to predominately occupy the nanopores of graphynes, and display selective ethanol penetration through single-layer graphynes. This unique interface behavior could be attributed to the enhanced hydrophobic interaction between amphiphilic ethanol molecules and graphyne carbon surfaces.

  1. Lotus-leaf-like topography predominates over adsorbed ECM proteins in poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) surface/cell interactions.

    PubMed

    Zheng, Jun; Li, Dan; Yuan, Lin; Liu, Xiaoli; Chen, Hong

    2013-06-26

    It is well-known that extracellular matrix (ECM) proteins mediate cell/surface interactions. However, introduction of a specific surface topography may disturb the correlation between ECM proteins adsorption and cells adhesion on a given surface. In present study, lotus-leaf-like topography was introduced on the surface of a biodegradable material, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx). Protein adsorption and cell interactions with this lotus-leaf-like surface (designated PHBHHx-L) were investigated. Water contact angle data indicated that the hydrophobicity of PHBHHx was enhanced by the introduction of lotus-leaf-like topography. The adsorption of extracellular matrix proteins (fibronectin and vitronectin) on PHBHHx-L was measured by enzyme linked immunosorbent assay (ELISA). Compared with flat PHBHHx, adsorption on the PHBHHx-L surface increased by ~260% for fibronectin and ~40% for vitronectin. In contrast, fibroblast and endothelial cell adhesion and proliferation were reduced on the PHBHHx-L compared to the flat polymer surface. These results suggest that the inhibition of cell adhesion and proliferation caused by the lotus-leaf-like topography dominates over the effect of the adsorbed adhesive proteins in promoting adhesion and proliferation. It can be concluded that the lotus-leaf-like topography plays a dominant role in cell/PHBHHx-L interactions. The present findings indicate the complexity of the interplay among surface topography, adsorbed proteins, and cell-surface interactions.

  2. 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.

  3. 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.

  4. Molecular dynamics simulations of SDS, DTAB, and C12E8 monolayers adsorbed at the air/water surface in the presence of DSEP.

    PubMed

    Pang, Jinyu; Wang, Yajing; Xu, Guiying; Han, Tingting; Lv, Xin; Zhang, Jian

    2011-03-24

    The properties of adsorbed monolayers of three hydrocarbon surfactants with the same hydrophobic tail, sodium dodecyl sulfate (SDS), dodecyltrimethylammonium bromide (DTAB) and octaethylene glycol dodecyl ether (C(12)E(8)) at the air/water surface in the absence and presence of a dimethylsiloxane ethoxylate-propoxylate (DSEP) were studied via molecular dynamics simulations to compare the effect of the headgroups on the aggregation behaviors of surfactant mixtures. The structures and dynamical properties of the monolayers were greatly affected after adding DSEP. In the presence of DSEP, SDS monolayer was better ordered and more compact, whereas C(12)E(8) monolayer was relatively disordered. Some DTAB molecules immerged into water, and the others adsorbed at the surface were in less compact but well-ordered arrangement. The reason for the appearance of different types of monolayers was also discussed, with the goal of providing a theoretical approach for their further applications.

  5. A study of phenylalanine side-chain dynamics in surface-adsorbed peptides using solid-state deuterium NMR and rotamer library statistics.

    PubMed

    Li, Kun; Emani, Prashant S; Ash, Jason; Groves, Michael; Drobny, Gary P

    2014-08-13

    Extracellular matrix proteins adsorbed onto mineral surfaces exist in a unique environment where the structure and dynamics of the protein can be altered profoundly. To further elucidate how the mineral surface impacts molecular properties, we perform a comparative study of the dynamics of nonpolar side chains within the mineral-recognition domain of the biomineralization protein salivary statherin adsorbed onto its native hydroxyapatite (HAP) mineral surface versus the dynamics displayed by the native protein in the hydrated solid state. Specifically, the dynamics of phenylalanine side chains (viz., F7 and F14) located in the surface-adsorbed 15-amino acid HAP-recognition fragment (SN15: DpSpSEEKFLRRIGRFG) are studied using deuterium magic angle spinning ((2)H MAS) line shape and spin-lattice relaxation measurements. (2)H NMR MAS spectra and T1 relaxation times obtained from the deuterated phenylalanine side chains in free and HAP-adsorbed SN15 are fitted to models where the side chains are assumed to exchange between rotameric states and where the exchange rates and a priori rotameric state populations are varied iteratively. In condensed proteins, phenylalanine side-chain dynamics are dominated by 180° flips of the phenyl ring, i.e., the "π flip". However, for both F7 and F14, the number of exchanging side-chain rotameric states increases in the HAP-bound complex relative to the unbound solid sample, indicating that increased dynamic freedom accompanies introduction of the protein into the biofilm state. The observed rotameric exchange dynamics in the HAP-bound complex are on the order of 5-6 × 10(6) s(-1), as determined from the deuterium MAS line shapes. The dynamics in the HAP-bound complex are also shown to have some solution-like behavioral characteristics, with some interesting deviations from rotameric library statistics.

  6. Surface plasmon resonance and electrochemistry characterization of layer-by-layer self-assembled DNA and Zr4+ thin films, and their interaction with cytochrome c.

    PubMed

    Wang, Jianlong; Wang, Fuan; Xu, Zhiai; Wang, Yizhe; Dong, Shaojun

    2007-11-15

    Through electrostatic layer-by-layer (LbL) assembly, negatively charged calf thymus double stranded DNA (CTds-DNA), and positively charged Zr4+ ions were alternately deposited on gold substrate modified with chemisorbed cysteamine. Thus-prepared three-dimensional DNA networks were characterized by surface plasmon resonance (SPR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IR-RAS). SPR spectroscopy indicates that the effective thickness of DNA monolayer in the (DNA/Zr4+)(1) bilayer was 1.5+/-0.1 nm, which corresponds to the surface coverage of 79% of its full packed monolayer. At the same time, a linear increase of film thickness with increasing number of layers was also confirmed by SPR characterizations. The data of XPS and IR-RAS show that Zr4+ ions interact with both the phosphate groups and nitrogenous bases of DNA and load into the framework of DNA. Furthermore, the interactions between this composite film and heme protein cytochrome c (Cyt c) were investigated by SPR spectroscopy and electrochemistry. Compared with the adsorption of Cyt c on DNA monolayer, this composite multilayer film can obviously enhance the amount of immobilized Cyt c confirmed by SPR reflectivity-incident angle (R-theta) curves. Cyclic voltammetry (CV) indicates the Cyt c adsorbed on the composite film is electroactive, and the enhancement of peak current in CV indirectly verifies the increase of the amount of immobilized Cyt c.

  7. Nanoscale Structuring of Surfaces by Using Atomic Layer Deposition.

    PubMed

    Sobel, Nicolas; Hess, Christian

    2015-12-01

    Controlled structuring of surfaces is interesting for a wide variety of areas, including microelectronic device fabrication, optical devices, bio(sensing), (electro-, photo)catalysis, batteries, solar cells, fuel cells, and sorption. A unique feature of atomic layer deposition (ALD) is the possibility to form conformal uniform coatings on arbitrarily shaped materials with controlled atomic-scale thickness. In this Minireview, we discuss the potential of ALD for the nanoscale structuring of surfaces, highlighting its versatile application to structuring both planar substrates and powder materials. Recent progress in the application of ALD to porous substrates has even made the nanoscale structuring of high-surface-area materials now feasible, thereby enabling novel applications, such as those in the fields of catalysis and alternative energy.

  8. Surface Dynamics of Segregation Layer in Blockcopolymer Films

    NASA Astrophysics Data System (ADS)

    Song, Sanghoon; Cha, Wonsuk; Jiang, Zhang; Narayanan, Suresh; Ruehm, Adrian; Sinha, Sunil K.; Kim, Hyunjung

    2009-03-01

    We have investigated the surface dynamics of supported block copolymer films of poly(styrene)-b-poly(dimethylsiloxane) (PS-b- PDMS) in the spherical phase, i.e., PDMS cores surrounded by PS shells by x-ray photon correlation spectroscopy (XPCS) in grazing angle geometry. The experiment was performed at the beamline 8ID-I in Advanced Photon Source. We found that the PDMS-rich layer near the surface appears at the temperature higher than the glass transition temperature. We applied the modified theory for bilayer model with surface capillary waves on simple viscoelastic liquid films. The viscosity obtained in this study is compared with that from the rheology measurement for bulk.

  9. 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.

  10. Multi-layer topological transmissions of spoof surface plasmon polaritons

    NASA Astrophysics Data System (ADS)

    Pan, Bai Cao; Zhao, Jie; Liao, Zhen; Zhang, Hao Chi; Cui, Tie Jun

    2016-03-01

    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.

  11. Inelastic neutron scattering (INS) observations of rotational tunneling within partially deuterated methane monolayers adsorbed on MgO(1 0 0) surfaces

    NASA Astrophysics Data System (ADS)

    Hicks, Andy S.; Larese, J. Z.

    2013-12-01

    High resolution inelastic neutron scattering (INS) measurements of the low temperature (T ∼ 2.0 K) rotational dynamics of isotopically substituted methane monolayers adsorbed on MgO(1 0 0) are presented. These spectra, obtained using BASIS at SNS, represent the most detailed measurements available for surface-adsorbed monolayer films of methane. Distinct excitations are readily observed at 15, 31, 45 and 127 μeV for the CH2D2 on MgO monolayer and at 40, 51, 95 and 138 μeV for CH3D/MgO. These features are attributed to tunneling transitions between sublevels within the ground librational state and are interpreted using the pocket state (PS) formalism first proposed by Hüller. This theoretical analysis employs the findings of earlier studies of CH4 on MgO(1 0 0) which suggest that molecules adsorb with their C2v axes normal to the surface plane. The comparison between theory and experiment provides direct insight into the impact of molecular versus surface symmetry on the observed tunneling spectra.

  12. 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)

  13. Composition, microstructure, and surface barrier layer development during brine salting.

    PubMed

    Melilli, C; Carcò, D; Barbano, D M; Tumino, G; Carpino, S; Licitra, G

    2005-07-01

    The goal of this study was to characterize the changes in chemical composition, porosity, and structure that occur at the surface of a block of brine-salted cheese and their relationship to the rate at which salt is taken up from the brine. To create a difference in composition, salt uptake, and barrier layer properties, identical blocks of Ragusano cheese were placed in saturated and 18% salt brine at 18 degrees C for 12 d. The overall moisture content and porosity decreased, whereas salt and salt in moisture content increased near the surface of blocks of brine-salted Ragusano cheese for all treatments. The general appearance of the microstructure of the surface of the blocks of brine-salted cheese was much more compact than the microstructure 1 mm inside the block at both brine concentrations. Large differences in porosity of the barrier layer were produced by brine-salting cheese in 18% vs. saturated brine, with cheese in saturated brine having much lower porosity at the surface and taking up much less salt during brining. The macro network of water channels within the microstructure of the cheese was less open near the surface of the block for cheese in both saturated and 18% brine after 4 d. However, no large differences in the size of the macro channels in the cheese structure due to the difference in brine concentration were observed by scanning electron microscopy. It is possible that the shrinkage of the much smaller pore structure within the casein matrix of the cheese is more important and will become more limiting to the rate of salt diffusion. Further microstructure work at higher resolution is needed to answer this question. The calculated decrease in porosity at the exterior 1-mm portion of the block was 50.8 and 29.2% for cheeses that had been in saturated vs. 18% brine for 12 d, respectively. The difference in brine concentration had a very large impact on the salt in moisture content of the cheese. The exterior of the cheese in 18% brine reached

  14. 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

  15. 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

  16. 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.

  17. Double-layer interaction between two plates with hairy surfaces.

    PubMed

    Huang, Haohao; Ruckenstein, Eli

    2004-05-01

    In most theoretical treatments of colloidal particles with hairy surfaces, only the steric effect is taken into account. The steric force is a short-range interaction and acts only when the chains on different particles begin to interpenetrate each other. However, since the hairy chains are extended into the continuous phase, they constrain the orientation of the water molecules near the surface and, as a result, the dielectric constant in that region can become very different from that in the bulk. The low dielectric constant affects the distributions of ion concentrations and the gradient of the electric field. Therefore, the double-layer interactions between two plates with hairy surfaces cannot be calculated on the basis of the classical Gouy-Chapman theory, which involves a uniform dielectric constant in the Poisson-Boltzmann equation. A model which accounts for the difference in dielectric constants in the hairy region and outside that region is therefore proposed. The ion specificity is also taken into account by using Born's expression for the free energy of hydration of ions. The repulsive forces calculated via the Gouy-Chapman theory and via the new model are compared. The hairy region can have a long range effect on the repulsive double-layer interactions.

  18. 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.

  19. Contact Angle Measurements by AFM on Droplets of Intermediate-Length Alkanes Adsorbed on SiO2 Surfaces

    NASA Astrophysics Data System (ADS)

    Bai, M.; Taub, H.; Knorr, K.; Volkmann, U. G.; Hansen, F. Y.

    2007-03-01

    We have recently discovered that films of intermediate-length alkanes (n-CnH2n+2; 24 < n < 40) do not completely wet a SiO2 surface on a nanometer length scale [2]. In a narrow temperature range near the bulk melting point Tb, we observe a single layer of molecules oriented with their long axis perpendicular to the surface. On heating just above Tb, these molecules undergo a delayering transition to three-dimensional droplets that remain present up to their evaporation point. Here we report measurements by noncontact Atomic Force Microscopy of the contact angle of these droplets for a film of hexatriacontane (n-C36H74 or C36). Our preliminary measurements indicate that there is a weak maximum in the contact angle at ˜Tb + 3 C. Further measurements are planned to investigate whether the weak maximum in the contact angle is consistent with the droplets supporting a surface freezing effect as at the bulk fluid/air interface. ^2M. Bai, K. Knorr, M. J. Simpson, S. Trogisch, H. Taub, S. N. Ehrlich, H. Mo, U. G. Volkmann, F. Y. Hansen, cond-mat/0611497.

  20. Quantitative coverage and stability of hydrogen-passivation layers on HF-etched Si(1-x)Gex surfaces

    NASA Astrophysics Data System (ADS)

    Wilde, Markus; Fukutani, Katsuyuki; Koh, Shinji; Sawano, Kentarou; Shiraki, Yasuhiro

    2005-07-01

    This study investigates the stability of surface hydride layers passivating silicon-germanium alloys against contamination in ambient conditions after treatment in dilute hydrofluoric acid (HF), which is of central importance to the fabrication of SiGe-based semiconductor devices. We report quantitative hydrogen coverages on HF-etched Si(1-x)Gex surfaces (x=0,0.30,0.60,0.82), determined after air-to-vacuum transfer by H-specific H1(N15,αγ)C12 nuclear reaction analysis. Combination of this coverage information with analysis of the zero-point vibrational properties and N15-ion-induced desorption kinetics of the surface H atoms enables the distinction of well-passivated SiGe surfaces terminated exclusively by hydrides of Si and Ge from those partially covered by contaminating adsorbates. It is found that the resistance of HF-etched Si(1-x)Gex alloys against recontamination is drastically reduced at increasing Ge contents. Pure Si(100)-H is stably passivated at least up to 1week in air by a layer of 1.3±0.1 monolayer total H coverage. Si0.70Ge0.30 initially resembles H-passivated Si(100) but shows indications of moderate contamination after 1week in air. The HF treatment does not produce stable passivation layers on Ge-rich alloys (x⩾0.60), which suffer heavy recontamination within minutes after removal from the HF solution.

  1. The structure, energetics, and nature of the chemical bonding of phenylthiol adsorbed on the Au(111) surface: implications for density-functional calculations of molecular-electronic conduction.

    PubMed

    Bilić, Ante; Reimers, Jeffrey R; Hush, Noel S

    2005-03-01

    The adsorption of phenylthiol on the Au(111) surface is modeled using Perdew and Wang density-functional calculations. Both direct molecular physisorption and dissociative chemisorption via S-H bond cleavage are considered as well as dimerization to form disulfides. For the major observed product, the chemisorbed thiol, an extensive potential-energy surface is produced as a function of both the azimuthal orientation of the adsorbate and the linear translation of the adsorbate through the key fcc, hcp, bridge, and top binding sites. Key structures are characterized, the lowest-energy one being a broad minimum of tilted orientation ranging from the bridge structure halfway towards the fcc one. The vertically oriented threefold binding sites, often assumed to dominate molecular electronics measurements, are identified as transition states at low coverage but become favored in dense monolayers. A similar surface is also produced for chemisorption of phenylthiol on Ag(111); this displays significant qualitative differences, consistent with the qualitatively different observed structures for thiol chemisorption on Ag and Au. Full contours of the minimum potential energy as a function of sulfur translation over the crystal face are described, from which the barrier to diffusion is deduced to be 5.8 kcal mol(-1), indicating that the potential-energy surface has low corrugation. The calculated bond lengths, adsorbate charge and spin density, and the density of electronic states all indicate that, at all sulfur locations, the adsorbate can be regarded as a thiyl species that forms a net single covalent bond to the surface of strength 31 kcal mol(-1). No detectable thiolate character is predicted, however, contrary to experimental results for alkyl thiols that indicate up to 20%-30% thiolate involvement. This effect is attributed to the asymptotic-potential error of all modern density functionals that becomes manifest through a 3-4 eV error in the lineup of the adsorbate and

  2. 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.

  3. Formation of a supramolecular gel between alpha-cyclodextrin and free and adsorbed PEO on the surface of colloidal silica: effect of temperature, solvent, and particle size.

    PubMed

    Dreiss, Cécile A; Cosgrove, Terence; Newby, Francisco N; Sabadini, Edvaldo

    2004-10-12

    Aqueous solutions of alpha-cyclodextrin (alpha-CD) complex spontaneously with poly(ethylene oxide) (PEO), forming a supramolecular structure known as pseudopolyrotaxane. We have studied the formation of the complex obtained from the threading of alpha-CD onto PEO, both free in solution and adsorbed on colloidal silica. The kinetics of the reaction were studied by gravimetric methods and determined as a function of temperature and solvent composition for the PEO free in solution. PEO was then adsorbed on the surface of colloidal silica particles, and the monomers were displaced by systematically varying the degree of complexation, the concentration of particles, and the molecular weight of the polymer. The effect of the size of the silica particles on the yield of the reaction was also studied. With the adsorbed PEO, the complexation was found to be partial and to take place from the tails of the polymer. The formation of a gel network containing silica at high degrees of complexation was observed. Small-angle X-ray and neutron scattering experiments were performed to study the configuration of the polymeric chains and confirmed the partial desorption of the polymer from the surface of the silica upon complexation.

  4. 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

  5. Chemical-state-resolved x-ray standing-wave analysis of Te-adsorbed GaAs(001)-(2×1) surface

    NASA Astrophysics Data System (ADS)

    Sugiyama, Munehiro; Maeyama, Satoshi

    1998-03-01

    A Te-adsorbed GaAs(001)-(2×1) surface is studied by back-reflection x-ray standing-wave analysis, and average position of adsorbed Te atoms on GaAs(001) is found to be close to the As atomic site and bond with Ga atoms. Chemical-state-resolved x-ray standing-wave analysis using chemical shift in Te 3d5/2 core-level photoelectron spectra suggest that Te atoms in two different chemical states correspond to two different distributions. Te atoms in a lower binding-energy chemical state are found to be in higher atomic positions and to be less ordered, whereas those in a higher binding-energy chemical state are found to be in lower atomic position and are highly ordered.

  6. 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

  7. Porphyrin adsorbed on the (101[combining macron]0) surface of the wurtzite structure of ZnO--conformation induced effects on the electron transfer characteristics.

    PubMed

    Niskanen, Mika; Kuisma, Mikael; Cramariuc, Oana; Golovanov, Viacheslav; Hukka, Terttu I; Tkachenko, Nikolai; Rantala, Tapio T

    2013-10-28

    Electron transfer at the adsorbate-surface interface is crucial in many applications but the steps taking place prior to and during the electron transfer are not always thoroughly understood. In this work a model system of 4-(porphyrin-5-yl)benzoic acid adsorbed as a corresponding benzoate on the ZnO wurtzite (101[combining macron]0) surface is studied using density functional theory (DFT) and time-dependent DFT. Emphasis is on the initial photoexcitation of porphyrin and on the strength of coupling between the porphyrin LUMO or LUMO + 1 and the ZnO conduction band that plays a role in the electron transfer. Firstly, ZnO wurtzite bulk is optimized to minimum energy geometry and the properties of the isolated ZnO (101[combining macron]0) surface model and the porphyrin model are discussed to gain insight into the combined system. Secondly, various orientations of the model porphyrin on the ZnO surface are studied: the porphyrin model standing perpendicularly to the surface and gradually brought close to the surface by tilting the linker in a few steps. The porphyrin model approaches the surface either sideways with hydrogen atoms of the porphyrin ring coming down first or twisted in a ca. 45° angle, giving rise to π-interactions of the porphyrin ring with ZnO. Because porphyrins are closely packed and near the surface, emerging van der Waals (vdW) interactions are examined using Grimme's D2 method. While the orientation affects the initial excitation of porphyrin only slightly, the coupling between the LUMO and LUMO + 1 of porphyrin and the conduction band of ZnO increases considerably if porphyrin is close to the surface, especially if the π-electrons are interacting with the surface. Based on the results of coupling studies, not only the distance between porphyrin and the ZnO surface but also the orientation of porphyrin can greatly affect the electron transfer. PMID:24022239

  8. Possible Albedo Proton Signature of Hydrated Lunar Surface Layer

    NASA Astrophysics Data System (ADS)

    Schwadron, N.; Wilson, J. K.; Looper, M. D.; Jordan, A.; Spence, H. E.; Blake, J. B.; Case, A. W.; Iwata, Y.; Kasper, J. C.; Farrell, W. M.; Lawrence, D. J.; Livadiotis, G.; Mazur, J. E.; Petro, N. E.; Pieters, C. M.; Robinson, M. S.; Smith, S. S.; Townsend, L. W.; Zeitlin, C. J.

    2015-12-01

    We find evidence for a surface layer of hydrated material in the lunar regolith using "albedo protons" measured by the Cosmic Ray Telescope for the Effects of Radiation (CRaTER) on the Lunar Reconnaissance Orbiter (LRO). Fluxes of these albedo protons, which are emitted from the regolith due to steady bombardment by high-energy radiation (Galactic Cosmic Rays), are observed to peak near the poles, and cannot be accounted for by either heavy element enrichment (e.g., enhanced Fe abundance), or by deeply buried (> 50 cm) hydrogenous material. The latitudinal distribution of albedo protons does not correlate with that of epithermal or high-energy neutrons. The high latitude enhancement may be due to the conversion of upward directed secondary neutrons from the lunar regolith into tertiary protons due to neutron-proton collisions in a thin (~ 1-10 cm) layer of hydrated regolith near the surface that is more prevalent near the poles. The CRaTER instrument thus provides critical measurements of volatile distributions within lunar regolith and potentially, with similar sensors and observations, at other bodies within the Solar System.

  9. 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.

  10. 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

    2016-03-10

    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

  11. 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

  12. Surface electrochemistry of CO2 reduction and CO oxidation on Sm-doped CeO(2-x): coupling between Ce(3+) and carbonate adsorbates.

    PubMed

    Feng, Zhuoluo A; Machala, Michael L; Chueh, William C

    2015-05-14

    The efficient electro-reduction of CO2 to chemical fuels and the electro-oxidation of hydrocarbons for generating electricity are critical toward a carbon-neutral energy cycle. The simplest reactions involving carbon species in solid-oxide fuel cells and electrolyzer cells are CO oxidation and CO2 reduction, respectively. In catalyzing these reactions, doped ceria exhibits a mixed valence of Ce(3+) and Ce(4+), and has been employed as a highly active and coking-resistant electrode. Here we report an operando investigation of the surface reaction mechanism on a ceria-based electrochemical cell using ambient pressure X-ray photoelectron spectroscopy. We show that the reaction proceeds via a stable carbonate intermediate, the coverage of which is coupled to the surface Ce(3+) concentration. Under CO oxidation polarization, both the carbonate and surface Ce(3+) concentration decrease with overpotential. Under CO2 reduction polarization, on the other hand, the carbonate coverage saturates whereas the surface Ce(3+) concentration increases with overpotential. The evolution of these reaction intermediates was analyzed using a simplified two-electron reaction scheme. We propose that the strong adsorbate-adsorbate interaction explains the coverage-dependent reaction mechanism. These new insights into the surface electrochemistry of ceria shed light on the optimization strategies for better fuel cell electrocatalysts.

  13. 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

  14. Quantum theory of IR spectroscopy of dipole-forbidden vibrational modes of adsorbed molecules on the surface of a metal in the frequency range of the anomalous skin effect

    SciTech Connect

    Volokitin, A.I.; Persson, B.N.J.

    1995-09-01

    A completely quantum-mechanical calculation of the IR spectrum for the dipole-forbidden vibrational modes of adsorbed molecules on a metal surface is performed. IT is shown for broad-band metals with a simple band structure that the asymmetry of the line shape is determined by nonlocal effects, while the nonadiabaticity makes a small contribution. In the region of the limiting anomalous skin effect ({omega}/{omega}{sub 1}{much_lt} 1, where {omega} is the frequency of the IR radiation, {omega}{sub 1}={upsilon}{sub F}/{delta}, {upsilon}{sub F} is the Fermi velocity, {delta}=c/{omega}{sub p} is the depth of the skin layer, and {omega}{sub p} is the plasma frequency) the broad-band absorption spectrum caused by the adsorbed molecules has an asymptotic limit {omega}{sup O}. The theory is compared with new absolute measurements of the IR spectrum of the CO/Cu(100) system. 20 refs., 2 figs.

  15. Solid-surface luminescence interactions of nitrogen heterocycles adsorbed on silica gel chromatoplates submerged in chloroform/n-hexane solvents

    SciTech Connect

    Burrell, G.J.; Hurtubise, R.J.

    1988-03-15

    The room-temperature fluorescence (RTF) and room-temperature phosphorescence (RTP) of benzo(f)quinoline and benzo(h)quinoline, obtained from the samples adsorbed on silica gel chromatoplates submerged in chloroform/n-hexane solvents, revealed several of the interactions of the nitrogen heterocycles with the solid matrix. The RTP results showed the emitting phosphor was protected from collisional deactivation by the matrix and that the adsorbed chloroform minimally disrupted the phosphor adsorption interactions. In addition, at least two populations of phosphors were indicated. The RTF data and RTP data showed that different interactions were occurring in the singlet state compared to the triplet state. A comparison of RTF intensity and TRP intensity as a function of chromatographic solvent strength indicated that the protonated forms of the nitrogen heterocycles in their triplet states were interacting with the matrix more strongly than the protonated forms of the nitrogen heterocycles in their singlet states.

  16. 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.

  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. Alignment of valence photoemission, x-ray absorption, and substrate density of states for an adsorbate on a semiconductor surface

    NASA Astrophysics Data System (ADS)

    Schnadt, J.; O'Shea, J. N.; Patthey, L.; Krempaský, J.; Mårtensson, N.; Brühwiler, P. A.

    2003-06-01

    A method for determining the placement of x-ray absorption data into an experimental density of states for an adsorbate-semiconductor system is motivated and illustrated with the cases of bi-isonicotinic acid, isonicotinic acid, and benzoic acid on rutile TiO2(110). Special attention is paid to experimental aspects, as well as the role of Z+1 effects and the choice of reference level.

  19. Surface-imprinted nanostructured layer-by-layer film for molecular recognition of theophylline derivatives.

    PubMed

    Niu, Jia; Liu, Zhihua; Fu, Long; Shi, Feng; Ma, Hongwei; Ozaki, Yukihiro; Zhang, Xi

    2008-10-21

    In this article we report the introduction of the cooperativity of various specific interactions combined with photo-cross-linking of the interlayers to yield binding sites that can realize better selectivity and imprinting efficiency of a surface molecularly imprinted LbL film (SMILbL), thus providing a new approach toward fabrication of nanostructured molecularly imprinted thin films. It involves preassembly of poly(acrylic acid) (PAA) conjugated of the theophylline residue template via a disulfide bridge, denoted as PAAtheo 15, in solution, and layer-by-layer (LbL) assembly of PAAtheo 15 and a positively charged photoreactive diazo resin (DAR) to form multilayer thin film with designed architecture. After photo-cross-linking of the film and template removal, binding sites specific to 7-(beta-hydroxyethyl)theophylline (Theo-ol) molecules are introduced within the film. Binding assay demonstrates that the SMILbL has a high selectivity of SMILbL to Theo-ol over caffeine. A control experiment demonstrates that the selectivity of SMILbL derives from nanostructured recognition sites among the layers. The imprinting amount per unit mass of the film can be 1 order of magnitude larger than that of the conventional bulk molecular imprinting systems. As this concept of construction SMILbL can be easily extended to the other molecules by the following similar protocol: its applications in building many other different molecular recognition systems are greatly anticipated. PMID:18788771

  20. 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.

  1. Layer-by-Layer Surface Molecular Imprinting on Polyacrylonitrile Nanofiber Mats.

    PubMed

    Liu, Yuxuan; Cao, Bing; Jia, Peng; An, Junhu; Luo, Chao; Ma, Lijing; Chang, Jiao; Pan, Kai

    2015-06-25

    Surface molecular imprinting in layer-by-layer (SMI-LbL) film is known as a facile and effective strategy to build imprinting sites that are more accessible to template molecules compared with molecular imprinting in polymers. Herein, we accomplished the formation of SMI-LbL film on electrospun nanofibers for the first time. The SMI-LbL nanofibers were prepared by a template-induced LbL process on the polyacrylonitrile (PAN) nanofiber substrates, followed by postinfiltrating and photo-cross-linking of photosensitive agent 4,4'-diazostilbene-2,2'-disulfonic acid disodium salt (DAS). The obtained nanofiber mat maintained the nanofibrous structure and showed rapid absorption and extraction of template molecules of meso-tetra(4-carboxyphenyl)-porphine (Por). The binding capacity of Por reached 2.1 mg/g when 3.5 bilayers were deposited on the nanofibers. After six cycles of extraction and reabsorption, the binding capacity of Por remained at 83%. Moreover, the absorption results of the targeted templated molecule of Por and the control molecule of Fast Green, which had a very similar chemical structure and charge status to Por, indicated the specific absorption for template molecule of Por. Thus, a surface molecular imprinted nanofiber mat with high selectivity of the templated molecule has been demonstrated. PMID:26038802

  2. Generic Nitric Oxide (NO) Generating Surface by Immobilizing Organoselenium Species via Layer-by-Layer Assembly

    PubMed Central

    Yang, Jun; Welby, Jenna L.; Meyerhoff, Mark E.

    2010-01-01

    A universal nitric oxide (NO) generating surface is assembled via Layer-by-Layer (LbL) deposition of sodium alginate (Alg) and organoselenium modified polyethyleneimine (SePEI) on quartz and polymeric substrates. The immobilized SePEI species is capable of catalytically decomposing S-nitrosothiol species (RSNO) to NO in the presence of thiol reducing agents (e.g., glutathione, cysteine, etc.). The stepwise buildup of the multilayer films is monitored by UV-Vis spectroscopy, SEM and surface contact angle measurements. X-ray photoelectron spectroscopy is used to study the stoichiometry between the polyanion and polycation, and also the presence of Se in the catalytic LbL film. A reductive annealing process is necessary to improve the stability of freshly coated multilayer films via chain rearrangement. Chemiluminescence measurements illustrate the ability of the LbL films to generate NO from S-nitrosoglutathione (GSNO) in the presence of S-glutathione (GSH). Enhanced NO fluxes can be achieved by increasing the number of catalytic (SePEI/Alg) bilayers coated on the substrates. Nitric oxide generation is observed even after prolonged contact with sheep whole blood. Preliminary applications of this LbL on silicone rubber tubings and polyurethane catheters reveal similar NO generation behavior from these biomedical grade polymeric substrates. PMID:18710268

  3. 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

  4. 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.

  5. 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.

  6. 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.

  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. Surface molecular imprinting in layer-by-layer films on silica particles.

    PubMed

    Gauczinski, Jan; Liu, Zhihua; Zhang, Xi; Schönhoff, Monika

    2012-03-01

    An improvement to molecular imprinting in polymers, where bulk systems often suffer from slow dynamics of release and uptake, is the formation of thin films with imprinting sites that are more rapid to access by guest molecules. Based on our previous development of surface molecular imprinting layer-by-layer (LbL) films (SMILbL), the present paper presents selective imprinted sites in a surface film on dispersed silica particles, thus designing a SMILbL system with maximized active area and in addition allowing studies with bulk techniques. The multilayer is designed to include the template during the LbL buildup and to form a cross-linked network upon UV-irradiation for enhanced stability. A theophylline moiety is grafted to poly(acrylic acid) as the template, while a UV-sensitive diazo polycation cross-links the polymers after irradiation. Electrophoretic measurements prove the successful buildup of the multilayers by an alternating sign of the zeta potential. Template release is achieved by cleavage of the grafted template. The released amount of template is quantified in solution by (1)H NMR spectra and is in good agreement with the prediction from surface coverage calculations. Rebinding studies of template to the now empty imprinted binding sites show a high affinity for a theophylline derivative with a rebound amount on the order of the original template content. In contrast to theophylline, caffeine with a very similar chemical structure-only differing in one functional group-shows very different binding properties due to a thiol moiety in the binding site. Thus, a particle system with very selective molecular imprinting sites is demonstrated. PMID:22324368

  9. Layer-dependent surface potential of phosphorene and anisotropic/layer-dependent charge transfer in phosphorene-gold hybrid systems.

    PubMed

    Xu, Renjing; Yang, Jiong; Zhu, Yi; Yan, Han; Pei, Jiajie; Myint, Ye Win; Zhang, Shuang; Lu, Yuerui

    2016-01-01

    The surface potential and the efficiency of interfacial charge transfer are extremely important for designing future semiconductor devices based on the emerging two-dimensional (2D) phosphorene. Here, we directly measured the strong layer-dependent surface potential of mono- and few-layered phosphorene on gold, which is consistent with the reported theoretical prediction. At the same time, we used an optical way photoluminescence (PL) spectroscopy to probe charge transfer in the phosphorene-gold hybrid system. We firstly observed highly anisotropic and layer-dependent PL quenching in the phosphorene-gold hybrid system, which is attributed to the highly anisotropic/layer-dependent interfacial charge transfer.

  10. Amorphous chalcogenide layers and nanocomposites for direct surface patterning

    NASA Astrophysics Data System (ADS)

    Molnar, Sandor; Bohdan, Roland; Csarnovics, Istvan; Burunkova, Iulia; Kokenyesi, Sandor

    2015-03-01

    Homogeneous, 200 - 3000 nm thick layers of chalcogenide glasses, 1 - 2 mm thick plane-parallel plates as well as nanocomposite structures, containing gold nanoparticles have been produced and used for in situ surface optical and geometrical relief fabrication by optical- or electron-, ion-beam recording. Investigations were focused on the formation of giant (height modulation from nanometers up to micrometers) geometrical reliefs and elements (dots, lines and diffractive elements) applicable in the 0.5 - 10 micrometer spectral range. Recording parameters were compared with available data on acrylic polymer nanocomposites. The mechanism of the recording processes, which include thermal, electron and mass-transport components were explained and the selection of the materials from As(Ge)-S(Se) binary systems with best recording parameters was done.

  11. Surface enhanced fluorescence of anti-tumoral drug emodin adsorbed on silver nanoparticles and loaded on porous silicon

    NASA Astrophysics Data System (ADS)

    Hernandez, Margarita; Recio, Gonzalo; Martin-Palma, Raul J.; Garcia-Ramos, Jose V.; Domingo, Concepcion; Sevilla, Paz

    2012-07-01

    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.

  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. We estimate that it requires 2%-4% of the solar luminosity to maintain the solar NSSL against the inertia of the mean flow. Most of this energy is associated with the turbulent transport of angular momentum out of the layer, with a spin-down timescale of {approx}600 days. We also address implications of these results for numerical modeling of the NSSL.

  13. Gyroscopic Pumping in the Solar Near-surface Shear Layer

    NASA Astrophysics Data System (ADS)

    Miesch, Mark S.; Hindman, Bradley W.

    2011-12-01

    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. We estimate that it requires 2%-4% of the solar luminosity to maintain the solar NSSL against the inertia of the mean flow. Most of this energy is associated with the turbulent transport of angular momentum out of the layer, with a spin-down timescale of ~600 days. We also address implications of these results for numerical modeling of the NSSL.

  14. Heat transfer to the adsorbent in solar adsorption cooling device

    NASA Astrophysics Data System (ADS)

    Pilat, Peter; Patsch, Marek; Papucik, Stefan; Vantuch, Martin

    2014-08-01

    The article deals with design and construction of solar adsorption cooling device and with heat transfer problem in adsorber. The most important part of adsorption cooling system is adsorber/desorber containing adsorbent. Zeolith (adsorbent) type was chosen for its high adsorption capacity, like a coolant was used water. In adsorber/desorber occur, at heating of adsorbent, to heat transfer from heat change medium to the adsorbent. The time required for heating of adsorber filling is very important, because on it depend flexibility of cooling system. Zeolith has a large thermal resistance, therefore it had to be adapted the design and construction of adsorber. As the best shows the tube type of adsorber with double coat construction. By this construction is ensured thin layer of adsorbent and heating is quick in all volume of adsorbent. The process of heat transfer was experimentally measured, but for comparison simulated in ANSYS, too.

  15. Controlling surface enrichment in polymeric hole extraction layers to achieve high-efficiency organic photovoltaic cells.

    PubMed

    Kim, Dong-Hun; Lim, Kyung-Geun; Park, Jong Hyeok; Lee, Tae-Woo

    2012-10-01

    Hole extraction in organic photovoltaic cells (OPVs) can be modulated by a surface-enriched layer formed on top of the conducting polymer-based hole extraction layer (HEL). This tunes the surface work function of the HEL to better align with the ionization potential of the polymeric photoactive layer. Results show noticeable improvement in device power conversion efficiencies (PCEs) in OPVs. We achieved a 6.1 % PCE from the OPV by optimizing the surface-enriched layer.

  16. Raman scattering spectra of insect virus PrGV-VP and their surface-enhanced Raman scattering spectra adsorbed on silver

    NASA Astrophysics Data System (ADS)

    Bao, PeiDi; Huang, TianQuan; Liu, XinMing; Wu, Tieqiao

    1998-04-01

    The ordinary Raman scattering (ORS) spectra of virion protein of Granulosis Virus of Cabbage Butterfly Preris rapae (PrGV-VP) and their surface-enhanced Raman scattering (SERS) spectra adsorbed on the surface of silver colloid particles have been found that the Raman signal in the SERS spectra was enhanced by a factor of about 8 X 102. In ORS spectra of PrGV-VP, it indicates that PrGV-VP has a predominantly random-coil secondary structures. All tyrosine residues are exposed. And the PrGV-VP has a gauche-gauche- gauche configuration of the C-C-S-S-C-C linkage. In SERS spectra of PrGV-VP, the intensities of bands related to COO group and NH2 group vibrations are relatively strong. We interpret that the PrGV-VP are adsorbed on the Ag surface through both the carboxylate groups and the amino groups. The efficient enhancement of amide I and amide II vibrations are impeded, because the peptide groups of PrGV-VP are screened by the side-chains amino acid residues. The Raman enhancement of PrGV-VP has a short-range mechanism. The chemisorption is a main mechanism on Ag hydrosols of PrGV- VP.

  17. In situ investigation of the mechanisms of the transport to tissues of polycyclic aromatic hydrocarbons adsorbed onto the root surface of Kandelia obovata seedlings.

    PubMed

    Li, Ruilong; Zhu, Yaxian; Zhang, Yong

    2015-06-01

    A novel method for in situ determination of the polycyclic aromatic hydrocarbons (PAHs) adsorbed onto the root surface of Kandelia obovata seedlings was established using laser-induced time-resolved nanosecond fluorescence spectroscopy (LITRF). The linear dynamic ranges for the established method were 1.5-1240ng/spot for phenanthrene, 1.0-1360ng/spot for pyrene and 5.0-1220ng/spot for benzo[a]pyrene. Then, the mechanisms of PAHs transport from the Ko root surface to tissues were investigated. The three-phase model including fast, slow and very slow fractions was superior to the single or dual-phase model to describe the PAHs transport processes. Moreover, the fast fraction of PAHs transport process was mainly due to passive movement, while the slow and very slow fractions were not. Passive movement was the main process of B[a]P adsorbed onto Ko root surface transport to tissues. In addition, the extent of the PAHs transport to Ko root tissues at different salinity were evaluated.

  18. Water Surface Ripples Generated by the Turbulent Boundary Layer of a Surface-Piercing Moving Wall

    NASA Astrophysics Data System (ADS)

    Washuta, N.; Masnadi, N.; Duncan, J. H.

    2014-11-01

    Free surface ripples created by subsurface turbulence along a surface-piercing moving wall are studied experimentally. In this experiment, a meter-wide stainless steel belt travels horizontally in a loop around two rollers with vertically oriented axes, which are separated by 7.5 meters. One of the two 7.5-m-long belt sections between the rollers is in contact with the water in a large open-surface water tank and the water level is adjusted so that the top of the belt pierces the water free surface. The belt is launched from rest with a 3 g acceleration in order to quickly reach a steady state velocity. This belt motion creates a temporally evolving boundary layer analogous to the spatially evolving boundary layer created along the side of a ship hull moving at the belt velocity, with a length equivalent to the length of belt that has passed the measurement region. The water surface ripples generated by the subsurface turbulence are measured in a plane normal to the belt using a cinematic LIF technique. It is found that the overall RMS surface fluctuations increase linearly with belt speed and that the spatial distributions of the fluctuations show a sharp increase near the wall. The support of the Office of Naval Research is gratefully acknowledged.

  19. Surface Roughness and Dislocation Distribution in Compositionally Graded Relaxed SiGe Buffer Layer with Inserted Strained Si Layers

    NASA Astrophysics Data System (ADS)

    Yoon, Tae-Sik

    2005-03-01

    We report the experimental investigation of surface roughness and dislocation distribution of 1 μm-thick, compositionally graded, relaxed SiGe buffer layer with a final Ge surface content of 30%. Tensile-strained Si layers are inserted at various locations in the graded buffer during SiGe epitaxial growths. Slight reduction in surface roughness from about 10.3 nm to about 7.8 nm by inserting two 20 nm thick tensile-strained Si layers followed by SiGe growths. It turns out that majority of the residual surface roughness is developed during the SiGe growths on top of the topmost strain Si layer. The surface immediately after the growth of tensile strained Si is very flat with about 1.1 nm RMS roughness and without crosshatch morphology. Cross-sectional TEM shows clear signs of increased interaction between dislocation half-loops at the top surface of the strained Si layers. Our observation shows that although thin Si layers under tensile-strain are effective in reducing cross-hatch, they could in the meantime impede dislocation propagation leading to higher threading dislocation density. Considerations for an optimized scheme exploiting the flattening function of tensile-strained layers will be discussed.

  20. 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

  1. Global ocean wind power sensitivity to surface layer stability

    NASA Astrophysics Data System (ADS)

    Capps, Scott B.; Zender, Charles S.

    2009-05-01

    Global ocean wind power has recently been assessed (W. T. Liu et al., 2008) using scatterometry-based 10 m winds. We characterize, for the first time, wind power at 80 m (typical wind turbine hub height) above the global ocean surface, and account for the effects of surface layer stability. Accounting for realistic turbine height and atmospheric stability increases mean global ocean wind power by +58% and -4%, respectively. Our best estimate of mean global ocean wind power is 731 W m-2, about 50% greater than the 487 W m-2 based on previous methods. 80 m wind power is 1.2-1.5 times 10 m power equatorward of 30° latitude, between 1.4 and 1.7 times 10 m power in wintertime storm track regions and >6 times 10 m power in stable regimes east of continents. These results are relatively insensitive to methodology as wind power calculated using a fitted Weibull probability density function is within 10% of power calculated from discrete wind speed measurements over most of the global oceans.

  2. Thin hydroxyapatite surface layers on titanium produced by ion implantation

    NASA Astrophysics Data System (ADS)

    Baumann, H.; Bethge, K.; Bilger, G.; Jones, D.; Symietz, I.

    2002-11-01

    In medicine metallic implants are widely used as hip replacement protheses or artificial teeth. The biocompatibility is in all cases the most important requirement. Hydroxyapatite (HAp) is frequently used as coating on metallic implants because of its high acceptance by the human body. In this paper a process is described by which a HAp surface layer is produced by ion implantation with a continuous transition to the bulk material. Calcium and phosphorus ions are successively implanted into titanium under different vacuum conditions by backfilling oxygen into the implantation chamber. Afterwards the implanted samples are thermally treated. The elemental composition inside the implanted region was determined by nuclear analysis methods as (α,α) backscattering and the resonant nuclear reaction 1H( 15N,αγ) 12C. The results of X-ray photoelectron spectroscopy indicate the formation of HAp. In addition a first biocompatibility test was performed to compare the growing of marrow bone cells on the implanted sample surface with that of titanium.

  3. 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.

  4. The role of Cu atoms on silver electrodes in surface enhanced Raman scattering from pyridine: Giant enhancement by a minority of adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Moerl, Ludwig; Pettinger, Bruno

    1982-08-01

    Surface enhanced Raman scattering (SERS) has been studied for pyridine molecules adsorbed at Ag electrodes covered with submonolayers of Cu ( θ = 0.003 - 0.1). Depending on the amount of Cu coverage the frequencies of the breathing vibrations shift, and new breathing modes appear. Obviously two types of pyridine complexes are formed, differing in the nature of the bonding provided either by copper or silver surface atoms. The generation and quenching behaviour of SERS at rough electrodes evidence the importance of metastable atomic surface structures for SERS and indicate the cooperation of local and non-local enhancement processes. Since active sites can be stabilized with traces of Cu at the silver electrode, the enhancement factor on a molecular basis appears to be by one order of magnitude larger than earlier anticipated, and ranges from 2 × 10 6 to 1.6 × 10 7 for an exciting wavelength at 514.5 nm or 647.1 nm, respectively.

  5. 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.

  6. Precise control of surface electrostatic forces on polymer brush layers with opposite charges for resistance to protein adsorption.

    PubMed

    Sakata, Sho; Inoue, Yuuki; Ishihara, Kazuhiko

    2016-10-01

    Various molecular interaction forces are generated during protein adsorption process on material surfaces. Thus, it is necessary to control them to suppress protein adsorption and the subsequent cell and tissue responses. A series of binary copolymer brush layers were prepared via surface-initiated atom transfer radical polymerization, by mixing the cationic monomer unit and anionic monomer unit randomly in various ratios. Surface characterization revealed that the constructed copolymer brush layers exhibited an uniform super-hydrophilic nature and different surface potentials. The strength of the electrostatic interaction forces operating on these mixed-charge copolymer brush surfaces was evaluated quantitatively using force-versus-distance (f-d) curve measurements by atomic force microscopy (AFM) and probes modified by negatively charged carboxyl groups or positively charged amino groups. The electrostatic interaction forces were determined based on the charge ratios of the copolymer brush layers. Notably, the surface containing equivalent cationic/anionic monomer units hardly interacted with both the charged groups. Furthermore, the protein adsorption force and the protein adsorption mass on these surfaces were examined by AFM f-d curve measurement and surface plasmon resonance measurement, respectively. To clarify the influence of the electrostatic interaction on the protein adsorption behavior on the surface, three kinds of proteins having negative, positive, and relatively neutral net charges under physiological conditions were used in this study. We quantitatively demonstrated that the amount of adsorbed proteins on the surfaces would have a strong correlation with the strength of surface-protein interaction forces, and that the strength of surface-protein interaction forces would be determined from the combination between the properties of the electrostatic interaction forces on the surfaces and the charge properties of the proteins. Especially, the

  7. Characterization of Floating Surface Layers of Lipids and Lipopolymers by Surface-Sensitive Scattering

    NASA Astrophysics Data System (ADS)

    Krüger, Peter; Lösche, Mathias

    Nanotechnology and molecular (bio-)engineering are making ever deepening inroads into everybodys daily life. Physicochemical and biotechnological achievements in the design of physiologically active supramolecular assemblies have brought about the quest for their submolecular-level characterization. We employ surface-sensitive scattering techniques for the investigation of planar lipid membranes - floating monolayers on aqueous surfaces - to correlate structural, functional and dynamic aspects of biomembrane models. This chapter surveys recent work on the submolecular structure of floating phospholipid monolayers - where the advent of third-generation synchrotron X-ray sources has driven the development of realistic, submolecular-scale quasi-chemical models - as well as of more complex systems: cation binding to anionic lipid surfaces; conformational changes of lipopolymers undergoing phase transitions; the conformational organization of phosphatidylinositol and phosphatidylinositides, as examples of physiologically important lipids; and the adsorption of peptides (neuropeptide Y, NPY) or solvents (dimethylsulfoxide, DMSO) onto phospholipid surface layers.

  8. Extending the Diffuse Layer Model of Surface Acidity Constant Behavior: IV. Diffuse Layer Charge/Potential Relationships

    EPA Science Inventory

    Most current electrostatic surface complexation models describing ionic binding at the particle/water interface rely on the use of Poisson - Boltzmann (PB) theory for relating diffuse layer charge densities to diffuse layer electrostatic potentials. PB theory is known to contain ...

  9. 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

  10. New Material Development for Surface Layer and Surface Technology in Tribology Science to Improve Energy Efficiency

    NASA Astrophysics Data System (ADS)

    Ismail, R.; Tauviqirrahman, M.; Jamari, Jamari; Schipper, D. J.

    2009-09-01

    This paper reviews the development of new material and surface technology in tribology and its contribution to energy efficiency. Two examples of the economic benefits, resulted from the optimum tribology in the transportation sector and the manufacturing industry are discussed. The new materials are proposed to modify the surface property by laminating the bulk material with thin layer/coating. Under a suitable condition, the thin layer on a surface can provide a combination of good wear, a low friction and corrosion resistance for the mechanical components. The innovation in layer technology results molybdenum disulfide (MoS2), diamond like carbon (DLC), cubic boron nitride (CBN) and diamond which perform satisfactory outcome. The application of the metallic coatings to carbon fibre reinforced polymer matrix composites (CFRP) has the capacity to provide considerable weight and power savings for many engineering components. The green material for lubricant and additives such as the use of sunflower oil which possesses good oxidation resistance and the use of mallee leaves as bio-degradable solvent are used to answer the demand of the environmentally friendly material with good performance. The tribology research implementation for energy efficiency also touches the simple things around us such as: erasing the laser-print in a paper with different abrasion techniques. For the technology in the engineering surface, the consideration for generating the suitable surface of the components in running-in period has been discussed in order to prolong the components life and reduce the machine downtime. The conclusion, tribology can result in reducing manufacturing time, reducing the maintenance requirements, prolonging the service interval, improving durability, reliability and mechanical components life, and reducing harmful exhaust emission and waste. All of these advantages will increase the energy efficiency and the economic benefits.

  11. Intermixed adatom and surface-bound adsorbates in regular self-assembled monolayers of racemic 2-butanethiol on Au(111).

    PubMed

    Ouyang, Runhai; Yan, Jiawei; Jensen, Palle S; Ascic, Erhad; Gan, Shiyu; Tanner, David; Mao, Bingwei; Niu, Li; Zhang, Jingdong; Tang, Chunguang; Hush, Noel S; Reimers, Jeffrey R; Ulstrup, Jens

    2015-04-01

    In situ scanning tunneling microscopy combined with density functional theory molecular dynamics simulations reveal a complex structure for the self-assembled monolayer (SAM) of racemic 2-butanethiol on Au(111) in aqueous solution. Six adsorbate molecules occupy a (10×√3)R30° cell organized as two RSAuSR adatom-bound motifs plus two RS species bound directly to face-centered-cubic and hexagonally close-packed sites. This is the first time that these competing head-group arrangements have been observed in the same ordered SAM. Such unusual packing is favored as it facilitates SAMs with anomalously high coverage (30%), much larger than that for enantiomerically resolved 2-butanethiol or secondary-branched butanethiol (25%) and near that for linear-chain 1-butanethiol (33%).

  12. Surface-layer protein from Caulobacter crescentus: expression, purification and X-ray crystallographic analysis.

    PubMed

    Jones, Michael D; Chan, Anson C K; Nomellini, John F; Murphy, Michael E P; Smit, John

    2016-09-01

    Protein surface layers are self-assembling, paracrystalline lattices on the surface of many prokaryotes. Surface-layer proteins have not benefited from widespread structural analysis owing to their resistance to crystallization. Here, the successful expression of a truncated version of RsaA, the surface-layer protein from Caulobacter crescentus,