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Sample records for adsorbed surface layers

  1. Application of 1H NMR spectroscopy method for determination of characteristics of thin layers of water adsorbed on the surface of dispersed and porous adsorbents.

    PubMed

    Turov, V V; Leboda, R

    1999-02-01

    The paper presents 1H NMR spectroscopy as a perspective method of the studies of the characteristics of water boundary layers in the hydrated powders and aqueous dispergated suspensions of the adsorbents. The method involves measurements of temperature dependence proton signals intensity in the adsorbed water at temperatures lower than 273 K. Free energy of water molecules at the adsorbent/water interface is diminished due to the adsorption interactions causing the water dosed to the adsorbent surface freezes at T < 273 K. Thickness of a non-freezing layer of water can be determined from the intensity of the water signal of 1H NMR during the freezing-thawing process. Due to a disturbing action of the adsorbent surface, water occurs in the quasi-liquid state. As a result, it is observed in the 1H NMR spectra as a relatively narrow signal. The signal of ice is not registered due to great differences in the transverse relaxation times of the adsorbed water and ice. The method of measuring the free surface energy of the adsorbents from the temperature dependence of the signal intensity of non-freezing water is based on the fact that the temperature of water freezing decreases by the quantity which depends on the surface energy and the distance of the adsorbed molecules from the solid surface. The water at the interface freezes when the free energies of the adsorbed water and ice are equal. To illustrate the applicability of the method under consideration the series of adsorption systems in which the absorbents used differed in the surface chemistry and porous structure. In particular, the behaviour of water on the surface of the following adsorbents is discussed: non-porous and porous silica (aerosils, silica gels); chemically and physically modified non-porous and porous silica (silanization, carbonization, biopolymer deposition); and pyrogeneous Al2O3 and aluminasilicas. The effect of preliminary treatment of the adsorbent (thermal, high pressure, wetting with polar

  2. 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.

  3. Control of the dipole layer of polar organic molecules adsorbed on metal surfaces via different charge-transfer channels

    NASA Astrophysics Data System (ADS)

    Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Su, Kai-Jun; Wang, Chin-Yung; Pi, Tun-Wen; Metz, Sebastian; Papadopoulos, Theodoros A.; Chiang, T.-C.; Ishii, Hisao; Tang, S.-J.

    2017-02-01

    Organic molecules with a permanent electric dipole moment have been widely used as a template for further growth of molecular layers in device structures. Key properties of the resulting organic films such as energy level alignment (ELA), work function, and injection/collection barrier are linked to the magnitude and direction of the dipole moment at the interface. Using angle-resolved photoemission spectroscopy (ARPES), we have systematically investigated the coverage-dependent work function and spectral line shapes of occupied molecular energy states (MESs) of chloroaluminium-phthalocyanine (ClAlPc) grown on Ag(111). We demonstrate that the dipole orientation of the first ClAlPc layer can be controlled by adjusting the deposition rate and postannealing conditions, and we find that the ELA at the interface differs by ˜0.4 eV between the Cl up and down configurations of the adsorbed ClAlPc molecules. These observations are rationalized by density functional theory (DFT) calculations based on a realistic model of the ClAlPc/Ag(111) interface, which reveal that the different orientations of the ClAlPc dipole layer lead to different charge-transfer channels between the adsorbed ClAlPc and Ag(111) substrate. Our findings provide a useful framework toward method development for ELA tuning.

  4. Ultrathin calcium silicate hydrate nanosheets with large specific surface areas: synthesis, crystallization, layered self-assembly and applications as excellent adsorbents for drug, protein, and metal ions.

    PubMed

    Wu, Jin; Zhu, Ying-Jie; Chen, Feng

    2013-09-09

    A simple and low-cost solution synthesis is reported for low-crystalline 1.4 nm tobermorite-like calcium silicate hydrate (CSH) ultrathin nanosheets with a thickness of ~2.8 nm and with a large specific surface area (SSA), via a reaction-rate-controlled precipitation process. The BET SSA of the CSH ultrathin nanosheets can reach as high as 505 m(2) g(-1) . The CSH ultrathin nanosheets have little cytotoxicity and can be converted to anhydrous calcium silicate (ACS) ultrathin nanosheets with a well preserved morphology via a heat treatment process. The crystallinity of CSH ultrathin nanosheets can be improved by solvothermal treatment in water/ethanol binary solvents or a single solvent of water, producing well-crystalline 1.1 nm tobermorite-like CSH nanobelts or nanosheets. CSH ultrathin nanosheets acting as building blocks can self-assemble into layered nanostructures via three different routes. The CSH ultrathin nanosheets are investigated as promising adsorbents for protein (hemoglobin, Hb), drug (ibuprofen, IBU), and metal ions (Cr(3+) , Ni(2+) , Cu(2+) , Zn(2+) , Cd(2+) , Pb(2+) ). The highest adsorbed percentages of Hb and IBU are found to be 83% and 94%, respectively. The highest adsorption capacities of Hb and IBU are found to be as high as 878 milligram Hb per gram CSH and 2.2 gram IBU per gram CSH, respectively. The ppm level metal ions can be totally adsorbed from aqueous solution in just a few minutes. Thus, the CSH ultrathin nanosheets are a promising candidate as excellent adsorbents in the biomedical field and for waste water treatment. Several empirical laws are summarized based on the adsorption profiles of Hb and IBU using CSH ultrathin nanosheets as the adsorbent. Furthermore, the ACS ultrathin nanosheets as adsorbents for Hb protein and IBU drug are investigated.

  5. Accessing the structural and thermodynamic properties of ultra-thin layers of C32 adsorbed on a SiO2 surface

    NASA Astrophysics Data System (ADS)

    Gutierrez-Maldonado, Sebastian E.; Garate, Jose Antonio; Retamal, Maria Jose; Cisternas, Marcelo A.; Volkmann, Ulrich G.; Perez-Acle, Tomas

    2017-04-01

    Medium-chain alkanes are important molecules with applications in biology and industry. Notably, their structural properties are scarcely understood. To assess structural and thermodynamic properties of dotriacontane (C32) molecules adsorbed on a SiO2 surface, we conducted all-atom molecular dynamics (MD) simulations. By analyzing potentials of mean force, order parameters and self-diffusion, we compared the stability and preferential orientation between ordered and disordered systems. Our data confirm the presence of one parallel layer of C32 followed by a mixture of disordered C32 segments exhibiting no thermodynamic preference. This semi-ordered structural model shed light to the interactions between C32 and a SiO2 surface.

  6. IR investigations of surfaces and adsorbates

    SciTech Connect

    Gwyn Williams

    2001-12-10

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

  7. Do methanethiol adsorbates on the Au(111) surface dissociate?

    PubMed

    Zhou, Jian-Ge; Hagelberg, Frank

    2006-07-28

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

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

    NASA Astrophysics Data System (ADS)

    Zhou, Jian-Ge; Hagelberg, Frank

    2006-07-01

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

  9. 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.

  10. 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

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

    PubMed

    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/cm(2). 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/cm(2)) than on surfaces with a higher concentration of FGF-2 (120 ng/cm(2)).

  12. 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.

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

    PubMed

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

    2013-05-21

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

  14. Application of electron-stimulated desorption for studying adsorbed layers

    NASA Astrophysics Data System (ADS)

    Ageev, V. N.; Kuznetsov, Yu. A.; Potekhina, N. D.

    2013-06-01

    After a brief discussion of the main result of the research initiated by N.I. Ionov in his laboratory using electron-stimulated desorption for studying the surface layers of tungsten, we consider in greater detail recent results on layered coatings formed on the tungsten surface upon simultaneous adsorption of sodium (or cesium) and gold atoms on this surface, as well as the effect of sputtering of samarium atoms on the (Cs + Au)/W(100) surface that has already been formed at 300 K.

  15. Negatively charged ions on Mg(0001) surfaces: appearance and origin of attractive adsorbate-adsorbate interactions.

    PubMed

    Cheng, Su-Ting; Todorova, Mira; Freysoldt, Christoph; Neugebauer, Jörg

    2014-09-26

    Adsorption of electronegative elements on a metal surface usually leads to an increase in the work function and decrease in the binding energy as the adsorbate coverage rises. Using density-functional theory calculations, we show that Cl adsorbed on a Mg(0001) surface complies with these expectations, but adsorption of {N,O,F} causes a decrease in the work function and an increase in the binding energy. Analyzing the electronic structure, we show that the presence of a highly polarizable electron spill-out in front of Mg(0001) causes this unusual adsorption behavior and is responsible for the appearance of a hitherto unknown net-attractive lateral electrostatic interaction between same charged adsorbates.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. Dynamics of adsorbed polymers on attractive homogeneous surfaces

    PubMed Central

    Yang, Qing-Hui; Luo, Meng-Bo

    2016-01-01

    Dynamic behaviors of polymer chains adsorbed on an attractive, homogeneous surface are studied by using dynamic Monte Carlo simulations. The translational diffusion coefficient Dxy parallel to the surface decreases as the intra-polymer attraction strength EPP or the polymer-surface attraction strength EPS increases. The rotational relaxation time τR increases with EPS, but the dependence of τR on EPP is dependent on the adsorption state of the polymer. We find that τR decreases with increasing EPP for a partially adsorbed polymer but it increases with EPP for a fully adsorbed polymer. Scaling relations Dxy ~ N−α and τR ~ Nβ are found for long polymers. The scaling exponent α is independent of EPS for long polymers but increases with EPP from α = 1.06 at EPP = 0. While β ≈ 2.7 is also roughly independent of EPS for the adsorbed polymer at EPP = 0, but β increases with EPS at EPP > 0. Moreover, we find that β always decreases with increasing EPP. Our results reveal different effects of the attractive surface on the diffusion and rotation of adsorbed polymers. PMID:27849002

  1. The formation of standing cylinders in block copolymer films by irreversibly adsorbed polymer layers on substrates

    NASA Astrophysics Data System (ADS)

    Shang, Jun; Jiang, Naisheng; Endoh, Maya; Koga, Tadanori

    2013-03-01

    Block copolymers offer a simple and effective route to produce standing cylindrical nanostructures with regularity on the order of 10-100 nm, the length scale that is desirable for many advanced applications. However, these formations have been especially troublesome due to the fact that preferential interactions between one of the blocks and the surfaces will induce parallel alignment of the cylinders in order to minimize interfacial and surface energy. Here we introduce an alternative simple method utilizing an irreversibly adsorbed polymer layer (a ``Guiselin'' brush) as a neutral ``substrate'' formed on solid substrates for the arrangement of standing cylindrical nanostructures. The effect of polymer adsorbed layer on the long range ordering of asymmetric cylinder forming poly(styrene-block-ethylene/butylene-block-styrene) (SEBS) triblock copolymer thin films were investigated by using a combination of grazing incidence small angle x-ray scattering and atomic force microscopy techniques. We found that the SEBS, which forms cylinders lying parallel to the surface when prepared on silicon substrates, show standing cylindrical structures on selected Guiselin brush layers after prolong thermal annealing. The details will be discussed in the presentation. We acknowledges the financial support from NSF Grant No. CMMI-084626

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

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

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

  3. 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.

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

    NASA Astrophysics Data System (ADS)

    Lopinski, Gregory Peter

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

  5. Measurement of interactions between protein layers adsorbed on silica by atomic force microscopy

    NASA Astrophysics Data System (ADS)

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

    2004-07-01

    The present work, using an atomic force microscope and the colloid probe technique, investigates the interaction forces between bovine serum albumin (BSA) layers and between apoferritin layers adsorbed on silica surfaces. The measurements have been carried out in an aqueous medium at different pH values and NaCl concentrations. Similar behaviours have been found with both proteins. Electrostatic and steric forces dominate the interactions between the protein layers at low NaCl concentrations. However, a very strange behaviour is found as a function of pH at high NaCl concentrations. The results obtained under these conditions could be explained if the presence of hydration forces in these systems is assumed.

  6. Study for Reduction of Outgassing Property of Adsorbed Water Gas for Improved Surface Finished Titanium Material

    NASA Astrophysics Data System (ADS)

    Takeda, Masatoshi; Kurisu, Hiroki; Uchida, Takashi; Yamamoto, Setsuo; Ishizawa, Katsunobu; Nomura, Takeru; Eda, Takahiro; Murashige, Nobuyuki

    This paper addresses the development of the surface finishing for a titanium material and the study for the reduction of outgassing property of adsorbed water (H2O) molecules. Developed surface finishing is composed of the buffing for the reduction of the surface roughness and improved chemical polishing for the thick surface oxide layer compared with the chemical polishing so far. The surface roughness of the surface finished titanium material is reduced 35% and the thickness of the surface oxide layer increases by 30%. The total amount of thermal desorbed H2O gas for the new surface finished titanium is reduced 30%. It is considered that the origin for the decrease of the amount of desorption H2O gas is the reduction of the adsorption sites due to the decrease of the surface roughness and the reduction of adsorption energy of H2O gas due to the strong surface oxidation for a titanium material.

  7. 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.

  8. 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.

  9. Chemical speciation of adsorbed glycine on metal surfaces

    NASA Astrophysics Data System (ADS)

    Han, Jeong Woo; James, Joanna N.; Sholl, David S.

    2011-07-01

    Experimental studies have reported that glycine is adsorbed on the Cu(110) and Cu(100) surfaces in its deprotonated form at room temperature, but in its zwitterionic form on Pd(111) and Pt(111). In contrast, recent density functional theory (DFT) calculations indicated that the deprotonated molecules are thermodynamically favored on Cu(110), Cu(100), and Pd(111). To explore the source of this disagreement, we have tested three possible hypotheses. Using DFT calculations, we first show that the kinetic barrier for the deprotonation reaction of glycine on Pd(111) is larger than on Cu(110) or Cu(100). We then report that the presence of excess hydrogen would have little influence on the experimentally observed results, especially for Pd(111). Lastly, we perform Monte Carlo simulations to demonstrate that the aggregates of zwitterionic species on Pt(111) are energetically preferred to those of neutral species. Our results strongly suggest that the formation of aggregates with relatively large numbers of adsorbed molecules is favored under experimentally relevant conditions and that the adsorbate-adsorbate interactions in these aggregates stabilize the zwitterionic species.

  10. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  12. 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

  13. Effect of peptide secondary structure on adsorption and adsorbed film properties on end-grafted polyethylene oxide layers.

    PubMed

    Binazadeh, M; Zeng, H; Unsworth, L D

    2014-01-01

    Poly-l-lysine (PLL), in α-helix or β-sheet configuration, was used as a model peptide for investigating the effect of secondary structures on adsorption events to poly(ethylene oxide) (PEO) modified surfaces formed using θ solvents. Circular dichroism results showed that the secondary structure of PLL persisted upon adsorption to Au and PEO modified Au surfaces. Quartz crystal microbalance with dissipation (QCM-D) was used to characterize the chemisorbed PEO layer in different solvents (θ and good solvents), as well as the sequential adsorption of PLL in different secondary structures (α-helix or β-sheet). QCM-D results suggest that chemisorption of PEO 750 and 2000 from θ solutions led to brushes 3.8 ± 0.1 and 4.5 ± 0.1 nm thick with layer viscosities of 9.2 ± 0.8 and 4.8 ± 0.5 cP, respectively. The average number of H2O per ethylene oxides, while in θ solvent, was determined as ~0.9 and ~1.2 for the PEO 750 and 2000 layers, respectively. Upon immersion in good solvent (as used for PLL adsorption experiments), the number of H2O per ethylene oxides increased to ~1.5 and ~2.0 for PEO 750 and 2000 films, respectively. PLL adsorbed masses for α-helix and β-sheet on Au sensors was 231 ± 5 and 1087 ± 14 ng cm(-2), with layer viscosities of 2.3 ± 0.1 and 1.2 ± 0.1 cP, respectively; suggesting that the α-helix layer was more rigid, despite a smaller adsorbed mass, than that of β-sheet layers. The PEO 750 layer reduced PLL adsorbed amounts to ~10 and 12% of that on Au for α-helices and β-sheets respectively. The PLL adsorbed mass to PEO 2000 layers dropped to ~12% and 4% of that on Au, for α-helix and β-sheet respectively. No significant differences existed for the viscosities of adsorbed α-helix and β-sheet PLL on PEO surfaces. These results provide new insights into the fundamental understanding of the effects of secondary structures of peptides and proteins on their surface adsorption.

  14. 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.

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

    SciTech Connect

    Cernota, Paul Davis

    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 (√7x√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.

  16. Structures of multidomain proteins adsorbed on hydrophobic interaction chromatography surfaces.

    PubMed

    Gospodarek, Adrian M; Sun, Weitong; O'Connell, John P; Fernandez, Erik J

    2014-12-05

    In hydrophobic interaction chromatography (HIC), interactions between buried hydrophobic residues and HIC surfaces can cause conformational changes that interfere with separations and cause yield losses. This paper extends our previous investigations of protein unfolding in HIC chromatography by identifying protein structures on HIC surfaces under denaturing conditions and relating them to solution behavior. The thermal unfolding of three model multidomain proteins on three HIC surfaces of differing hydrophobicities was investigated with hydrogen exchange mass spectrometry (HXMS). The data were analyzed to obtain unfolding rates and Gibbs free energies for unfolding of adsorbed proteins. The melting temperatures of the proteins were lowered, but by different amounts, on the different surfaces. In addition, the structures of the proteins on the chromatographic surfaces were similar to the partially unfolded structures produced in the absence of a surface by temperature as well as by chemical denaturants. Finally, it was found that patterns of residue exposure to solvent on different surfaces at different temperatures can be largely superimposed. These findings suggest that protein unfolding on various HIC surfaces might be quantitatively related to protein unfolding in solution and that details of surface unfolding behavior might be generalized.

  17. Speciation of adsorbed yttrium and rare earth elements on oxide surfaces

    NASA Astrophysics Data System (ADS)

    Piasecki, Wojciech; Sverjensky, Dimitri A.

    2008-08-01

    The distribution of yttrium and the rare earth elements (YREE) between natural waters and oxide mineral surfaces depends on adsorption reactions, which in turn depend on the specific way in which YREE are coordinated to mineral surfaces. Recent X-ray studies have established that Y 3+ is adsorbed to the rutile (1 1 0) surface as a distinctive tetranuclear species. However, the hydrolysis state of the adsorbed cation is not known from experiment. Previous surface complexation models of YREE adsorption have suggested two to four cation hydrolysis states coexisting on oxide surfaces. In the present study, we investigate the applicability of the X-ray results to rare earth elements and to several oxides in addition to rutile using the extended triple-layer surface complexation model. The reaction producing a hydrolyzed tetranuclear surface species 4>SOH+M+2HO=(>SOH)2_M(OH)2++4H was found to account for a significant fraction of the adsorbed Y 3+, La 3+, Nd 3+, Gd 3+, and Yb 3+ on rutile, hematite, alumina and silica over wide ranges of pH and ionic strength. Where adsorption data were available as a function of surface coverage for hematite and silica, an additional reaction involving a mononuclear species could be used to account for the higher surface coverages. However, it is also possible that some of the higher surface coverage data refer to surface precipitation rather than adsorption. The results of the present study provide an internally consistent basis for describing YREE adsorption which could be used to investigate more complex systems in which YREE compete both in aqueous solution and on mineral surfaces with alkaline earths and ligands such as carbonate, sulfate, chloride and organic species, in order to build a predictive adsorption model applicable to natural waters.

  18. Controlling the Electronic Structure of Graphene Using Surface-Adsorbate Interactions

    DTIC Science & Technology

    2015-07-21

    is cut-off from the substrate, and the band structure in Fig. 3(d). The hybridization is blocked by an atomic spacer of Na and thus there is only a...the underlying layer. 44. Gamo, Y., et al., Atomic structure of monolayer graphite formed on Ni(111). Surface Science, 1997. 374(1-3): p. 61-64. 45...1 Controlling the electronic structure of graphene using surface-adsorbate interactions Piotr Matyba, Adra V. Carr, Cong Chen, David L. Miller

  19. Hybrid magnetic amphiphilic composites based on carbon nanotube/nanofibers and layered silicates fragments as efficient adsorbent for ethynilestradiol.

    PubMed

    Purceno, Aluir D; Teixeira, Ana Paula C; de Souza, Nubia Janaína; Fernandez-Outon, Luis E; Ardisson, José D; Lago, Rochel M

    2012-08-01

    In this work, hybrid magnetic amphiphilic composites were prepared by the catalytic growth of carbon nanotubes (CNTs) and nanofibers CNF on layered silicates fragments. SEM, TEM, Raman, XRD, Mössbauer, TG/DTA showed that CVD with CH(4) at 800°C produced CNF and magnetic Fe cores fixed on the surface of microfragments of silicates layers. Due to the amphiphilic character, the composites can be easily dispersed in water and efficiently adsorb hydrophobic contaminant molecules. For example, the composites showed remarkable adsorption capacities for the hormone ethinylestradiol, e.g. 2-4 mg m(-2), compared to ca. 0.1 mg m(-2) obtained for high surface area activated carbon and multiwall CNT. These results are discussed in terms of a high hydrophobic exposed surface area of the CNT and CNF fixed on the layered silicates fragments surface. Moreover, the composites can be easily removed from water by a simple magnetic separation process.

  20. 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.

  1. 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.

  2. Structure of CO2 adsorbed on the KCl(100) surface.

    PubMed

    Traeger, Franziska; Hadnadjev, Milica; Vogt, Jochen; Weiss, Helmut

    2011-06-30

    The structure and dynamics of the adsorbate CO(2)/KCl(100) from a diluted phase to a saturated monolayer have been investigated with He atom scattering (HAS), low-energy electron diffraction (LEED), and polarization dependent infrared spectroscopy (PIRS). Two adsorbate phases with different CO(2) coverage have been found. The low-coverage phase is disordered at temperatures near 80 K and becomes at least partially ordered at lower temperatures, characterized by a (2√2×√2)R45° diffraction pattern. The saturated 2D phase has a high long-range order and exhibits (6√2×√2)R45° symmetry. Its isosteric heat of adsorption is 26 ± 4 kJ mol(-1). According to PIRS, the molecules are oriented nearly parallel to the surface, the average tilt angle in the saturated monolayer phase is 10° with respect to the surface plane. For both phases, structure models are proposed by means of potential calculations. For the saturated monolayer phase, a striped herringbone structure with 12 inequivalent molecules is deduced. The simulation of infrared spectra based on the proposed structures and the vibrational exciton approach gives reasonable agreement between experimental and simulated infrared spectra.

  3. 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.

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

    PubMed

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

    2004-09-15

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

  5. Long-term storage of surface-adsorbed protein machines.

    PubMed

    Albet-Torres, Nuria; Månsson, Alf

    2011-06-07

    The effective and simple long-term storage of complex functional proteins is critical in achieving commercially viable biosensors. This issue is particularly challenging in recently proposed types of nanobiosensors, where molecular-motor-driven transportation substitutes microfluidics and forms the basis for novel detection schemes. Importantly, therefore, we here describe that delicate heavy meromyosin (HMM)-based nanodevices (HMM motor fragments adsorbed to silanized surfaces and actin bound to HMM) fully maintain their function when stored at -20 °C for more than a month. The mechanisms for the excellent preservation of acto-HMM motor function upon repeated freeze-thaw cycles are discussed. The results are important to the future commercial implementation of motor-based nanodevices and are of more general value to the long-term storage of any protein-based bionanodevice.

  6. Accelerator analysis of tributyltin adsorbed onto the surface of a tributyltin resistant marine Pseudoalteromonas sp. cell.

    PubMed

    Mimura, Haruo; Sato, Ryusei; Sasaki, Yu; Furuyama, Yuichi; Taniike, Akira; Yoshida, Kazutoshi; Kitamura, Akira

    2008-10-01

    Tributyltin (TBT) released into seawater from ship hulls is a stable marine pollutant and obviously remains in marine environments. We isolated a TBT resistant marine Pseudoalteromonas sp. TBT1 from sediment of a ship's ballast water. The isolate (10(9.3 +/- 0.2) colony-forming units mL(-1)) adsorbed TBT in proportion to the concentrations of TBTCl externally added up to 3 mM, where the number of TBT adsorbed by a single cell was estimated to be 10(8.2). The value was reduced to about one-fifth when the lysozyme-treated cells were used. The surface of ethanol treated cells became rough, but the capacity of TBT adsorption was the same as that for native cells. These results indicate that the function of the cell surface, rather than that structure, plays an important role to the adsorption of TBT. The adsorption state of TBT seems to be multi-layer when the number of more than 10(6.8) TBT molecules is adsorbed by a single cell.

  7. Accelerator Analysis of Tributyltin Adsorbed onto the Surface of a Tributyltin Resistant Marine Pseudoalteromonas sp. Cell

    PubMed Central

    Mimura, Haruo; Sato, Ryusei; Sasaki, Yu; Furuyama, Yuichi; Taniike, Akira; Yoshida, Kazutoshi; Kitamura, Akira

    2008-01-01

    Tributyltin (TBT) released into seawater from ship hulls is a stable marine pollutant and obviously remains in marine environments. We isolated a TBT resistant marine Pseudoalteromonas sp. TBT1 from sediment of a ship’s ballast water. The isolate (109.3 ± 0.2 colony-forming units mL−1) adsorbed TBT in proportion to the concentrations of TBTCl externally added up to 3 mM, where the number of TBT adsorbed by a single cell was estimated to be 108.2. The value was reduced to about one-fifth when the lysozyme-treated cells were used. The surface of ethanol treated cells became rough, but the capacity of TBT adsorption was the same as that for native cells. These results indicate that the function of the cell surface, rather than that structure, plays an important role to the adsorption of TBT. The adsorption state of TBT seems to be multi-layer when the number of more than 106.8 TBT molecules is adsorbed by a single cell. PMID:19325731

  8. Surface diffusion of gold nanoclusters on Ru(0001): effects of cluster size, surface defects and adsorbed oxygen atoms.

    PubMed

    Stein, Ori; Ankri, Jonathan; Asscher, Micha

    2013-08-28

    Understanding thermal behavior of metallic clusters on their solid supports is important for avoiding sintering and aggregation of the active supported metallic particles in heterogeneous catalysis. As a model system we have studied the diffusion of gold nano-clusters on modified Ru(0001) single crystal surfaces, employing surface density grating formation via a laser induced ablation technique. Surface modifications included damage induced by varying periods of Ne(+) ion sputtering at a collision energy of 2.8 keV and the effect of pre-adsorbed oxygen on the clean, defect free ruthenium surface. High density of surface damage, obtained at long sputter times, has led to enhanced diffusivity with lower onset temperature for diffusion. It is attributed to reduced cluster-surface commensurability which gives rise to smaller effective activation energy for diffusion. The diffusion of gold nano-clusters, 2 nm in size, was found to be insensitive to the oxygen surface concentration. The adsorbed oxygen acted as an "atomic layer lubricant", reducing friction between the cluster and the underlying surface. This has led to lower diffusivity onset temperatures (150 K) of the nano-clusters, with a stronger effect on smaller clusters.

  9. Regulating the interactions of adsorbates on surfaces by scanning tunneling microscopy manipulation.

    PubMed

    Sun, Qiang; Xu, Wei

    2014-09-15

    Scanning tunneling microscopy (STM) manipulation has received wide attention in the surface science community since the pioneering work of Eigler to construct surface nanostructures in an atom by atom fashion. Lots of scientists have been inspired and devoted to study the surface issues with the help of STM manipulations and great achievements have been obtained. In this Minireview, we mainly describe the recent progress in applying STM manipulations to regulate the inter-adsorbate and adsorbate-substrate interactions on solid surfaces. It was shown that this technique could not only differentiate intermolecular interactions but also construct molecular nanostructures by regulating different kinds of inter-adsorbate interactions or adsorbate-substrate interactions.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  11. 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.

  12. 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.

  13. Surface layers of bacteria.

    PubMed Central

    Beveridge, T J; Graham, L L

    1991-01-01

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

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

    PubMed Central

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

    2015-01-01

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

  15. Effects of excluded surface area and adsorbate clustering on surface adsorption of proteins. II. Kinetic models.

    PubMed Central

    Minton, A P

    2001-01-01

    Models for equilibrium surface adsorption of proteins have been recently proposed (Minton, A. P., 2000. Biophys. Chem. 86:239-247) in which negative cooperativity due to area exclusion by adsorbate molecules is compensated to a variable extent by the formation of a heterogeneous population of monolayer surface clusters of adsorbed protein molecules. In the present work this concept is extended to treat the kinetics of protein adsorption. It is postulated that clusters may grow via two distinct kinetic pathways. The first pathway is the diffusion of adsorbed monomer to the edge of a preexisting cluster and subsequent accretion. The second pathway consists of direct deposition of a monomer in solution onto the upper (solution-facing) surface of a preexisting cluster ("piggyback" deposition) and subsequent incorporation into the cluster. Results of calculations of the time course of adsorption, carried out for two different limiting models of cluster structure and energetics, show that in the absence of piggyback deposition, enhancement of the tendency of adsorbate to cluster can reduce, but not eliminate, the negative kinetic cooperativity due to surface area exclusion by adsorbate. Apparently noncooperative (Langmuir-like) and positively cooperative adsorption progress curves, qualitatively similar to those reported in several published experimental studies, require a significant fraction of total adsorption flux through the piggyback deposition pathway. According to the model developed here and in the above-mentioned reference, the formation of surface clusters should be a common concomitant of non-site-specific surface adsorption of proteins, and may provide an important mechanism for assembly of organized "protein machines" in vivo. PMID:11259279

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

    PubMed

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

    2010-05-01

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

  17. Properties of competitively adsorbed BSA and fibrinogen from their mixture on mixed and hybrid surfaces

    NASA Astrophysics Data System (ADS)

    Pandey, Lalit M.; Pattanayek, Sudip K.

    2013-01-01

    We have studied the adsorption of BSA and fibrinogen from their mixture onto surfaces with mixed self-assembled monolayer (SAM) of amine and octyl (ratio 1:1) and hybrid SAM. The properties of adsorbed proteins obtained from individual protein solution differ considerably from the properties of the adsorbed proteins obtained from mixture of proteins at same total concentration. The adsorbed amount of proteins is lesser and the adsorbed protein is more elastic if it is adsorbing from mixture of proteins. It is found that with increasing total protein concentration, adsorbed amount increases and elasticity of the adsorbed proteins decreases. The apparent displacements of BSA with Fb are observed on the graphs of change in frequency with time, which are obtained from quartz crystal microbalance.

  18. Surface modification of chromatography adsorbents by low temperature low pressure plasma.

    PubMed

    Arpanaei, A; Winther-Jensen, B; Theodosiou, E; Kingshott, P; Hobley, T J; Thomas, O R T

    2010-10-29

    In this study we show how low temperature glow discharge plasma can be used to prepare bi-layered chromatography adsorbents with non-adsorptive exteriors. The commercial strong anion exchange expanded bed chromatography matrix, Q HyperZ, was treated with plasmas in one of two general ways. Using a purpose-designed rotating reactor, plasmas were employed to either: (i) remove anion exchange ligands at or close to the exterior surface of Q HyperZ, and replace them with polar oxygen containing functions ('plasma etching and oxidation'); or (ii) bury the same surface exposed ligands beneath thin polymer coatings ('plasma polymerization coating') using appropriate monomers (vinyl acetate, vinyl pyrrolidone, safrole) and argon as the carrier gas. X-ray photoelectron spectroscopy analysis (first ∼10 nm depth) of Q HyperZ before and after the various plasma treatments confirmed that substantial changes to the elemental composition of Q HyperZ's exterior had been inflicted in all cases. The atomic percent changes in carbon, nitrogen, oxygen, yttrium and zirconium observed after being exposed to air plasma etching were entirely consistent with: the removal of pendant Q (trimethylammonium) functions; increased exposure of the underlying yttrium-stabilised zirconia shell; and introduction of hydroxyl and carbonyl functions. Following plasma polymerization treatments (with all three monomers tested), the increased atomic percent levels of carbon and parallel drops in nitrogen, yttrium and zirconium provided clear evidence that thin polymer coats had been created at the exteriors of Q HyperZ adsorbent particles. No changes in adsorbent size and surface morphology, nor any evidence of plasma-induced damage could be discerned from scanning electron micrographs, light micrographs and measurements of particle size distributions following 3 h exposure to air (220 V; 35.8 W L(-1)) or 'vinyl acetate/argon' (170 V; 16.5 W L(-1)) plasmas. Losses in bulk chloride exchange capacity

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

  2. Adsorbate induced enhancement of secondary electron emission from the layered compound VSe 2

    NASA Astrophysics Data System (ADS)

    Starnberg, H. I.; Nilsson, P. O.; Hughes, H. P.

    1993-05-01

    It is demonstrated how adsorbates may drastically enhance the photoemission yield at low kinetic energies from VSe 2 surfaces. The reason for this enhancement seems to be that the adsorbate by reducing the work function φ creates a condition closely resembling negative electron affinity (NBA), i.e. the vacuum level is pulled down into an absolute band-gap. In contrast to true NBA systems, there are empty states (predominantly of V3d character) available below the vacuum level, but due to low probability for scattering into these states, the NEA-like behaviour prevails. Since the involved band minimum is located close to the K symmetry point of the Brillouin zone, adsorbate induced diffuse scattering is vital to the observed enhancement.

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

    PubMed

    Shimizu, Steven; Song, Changsik; Strano, Michael

    2011-03-15

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

  4. A computer modelling study of the interaction of organic adsorbates with fluorapatite surfaces

    NASA Astrophysics Data System (ADS)

    Mkhonto, Donald; Ngoepe, Phuti E.; Cooper, Timothy G.; de Leeuw, Nora H.

    2006-08-01

    Computer modelling techniques were employed to investigate the adsorption of a selection of organic surfactant molecules to a range of fluorapatite surfaces, and new interatomic potential models for the apatite/adsorbate interactions are presented. The adsorbates coordinate mainly to the surfaces through interaction between their oxygen (or nitrogen) atoms to surface calcium ions, followed by hydrogen-bonded interactions to surface oxygen ions and, to a much lesser extent, surface fluorides. Bridging between two surface calcium ions is the preferred mode of adsorption, when the geometry of the adsorbates allows it, and multiple interactions between surfaces and adsorbate molecules lead to the largest adsorption energies. All adsorbates containing carbonyl and hydroxy groups interact strongly with the surfaces, releasing energies between approximately 100 and 215 kJ mol-1, but methylamine containing only the NH2 functional group adsorbs to the surfaces to a much lesser extent (25 95 kJ mol-1). Both hydroxy methanamide and hydroxy ethanal prefer to adsorb to some surfaces in an eclipsed conformation, which is a requisite for these functional groups. Sorption of the organic material by replacement of pre-adsorbed water at different surface features is calculated to be mainly exothermic for methanoic acid, hydroxy methanamide and hydroxy ethanal molecules, whereas methyl amine would not replace pre-adsorbed water at the fluorapatite surfaces. The efficacy of the surfactant molecules is calculated to be hydroxy aldehydes > alkyl hydroxamates > carboxylic acids ≫ alkyl amines. The results from this study suggest that computer simulations may provide a route to the identification or even design of particular organic surfactants for use in mineral separation by flotation.

  5. Direct Measurement of Core-Level Relaxation Dynamics on a Surface-Adsorbate System

    NASA Astrophysics Data System (ADS)

    Miaja-Avila, L.; Saathoff, G.; Mathias, S.; Yin, J.; La-O-Vorakiat, C.; Bauer, M.; Aeschlimann, M.; Murnane, M. M.; Kapteyn, H. C.

    2008-07-01

    The coupling between electronic states in a surface-adsorbate system is fundamental to the understanding of many surface interactions. In this Letter, we present the first direct time-resolved observations of the lifetime of core-excited states of an atom adsorbed onto a surface. By comparing laser-assisted photoemission from a substrate with a delayed Auger decay process from an adsorbate, we measure the lifetime of the 4d-1 core level of xenon on Pt(111) to be 7.1±1.1fs. This result opens up time-domain measurements of surface dynamics where energy-resolved measurements may provide incomplete information.

  6. Comparisons between Surface-Enhanced Raman and Surface Infrared Spectroscopies for Strongly Perturbed Adsorbates: Thiocyanate at Gold Electrodes.

    DTIC Science & Technology

    1986-07-30

    tu. 3. iptt FCSa, s CATALOG NUtof SBetween Surface -Enhanced Raman anj$ YEO EOTI EIDCvfr Surface Infared Spectroscopies for StrongiV Technical Report...REPORT 8 49 0Comparisons Between Surface-Enhanced Raman and Surface Infrared Spectroscopies for Strongly Perturbed Adsorbates: Thiocyanate at Gold...for thiocyanate adsorbed at the gold-aqueous interface is examined by both surface-enhanced Raman spectroscopy (SERS) and subtractively normalized

  7. Physically adsorbed fullerene layer on positively charged sites on zinc oxide cathode affords efficiency enhancement in inverted polymer solar cell.

    PubMed

    Cheng, Yu-Shan; Liao, Sih-Hao; Li, Yi-Lun; Chen, Show-An

    2013-07-24

    We present a novel idea for overcoming the drawback of poor contact between the ZnO cathode and active layer interface in an inverted polymer solar cell (i-PSC), simply by incorporating an electron-acceptor self-assembled monolayer (SAM)--tetrafluoroterephthalic acid (TFTPA)--on the ZnO cathode surface to create an electron-poor surface of TFTPA on ZnO. The TFTPA molecules on ZnO are anchored on the ZnO surface by reacting its carboxyl groups with hydroxyl groups on the ZnO surface, such that the tetrafluoroterephthalate moieties lay on the surface with plane-on electron-poor benzene rings acting as positive charge centers. Upon coating a layer of fullerenes on top of it, the fullerene molecules can be physically adsorbed by Coulombic interaction and facilitate a promoted electron collection from the bulk. The active layer is composed of the mid bandgap polymer poly(3-hexylthiophene) (P3HT) or low bandgap polymer, poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl) carbonyl]thieno[3,4-b]thiophenediyl

  8. 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.

  9. 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.

  10. Mars Surface Layers in Infrared

    NASA Technical Reports Server (NTRS)

    2002-01-01

    (Released 29 May 2002) Infrared imaging from NASA's Mars Odyssey spacecraft shows signs of layering exposed at the surface in a region of Mars called Terra Meridiani. The brightness levels show daytime surface temperatures, which range from about minus 20 degrees to zero degrees Celsius (minus 4 degrees to 32 degrees Fahrenheit). Many of the temperature variations are due to slope effects, with sun-facing slopes warmer than shaded slopes. However, several rock layers can be seen to have distinctly different temperatures, indicating that physical properties vary from layer to layer. These differences suggest that the environment on this part of Mars varied through time as these layers were formed. The image is a mosaic combining four exposures taken by the thermal emission imaging system aboard Odyssey during the first two months of the Odyssey mapping mission, which began in February 2002. The area shown is about 120 kilometers (75 miles) across, at approximately 358 degrees east (2 degrees west) longitude and 3 degrees north latitude.

  11. Mars Surface Layers in Infrared

    NASA Technical Reports Server (NTRS)

    2002-01-01

    Infrared imaging from NASA's Mars Odyssey spacecraft shows signs of layering exposed at the surface in a region of Mars called Terra Meridiani.

    The brightness levels show daytime surface temperatures, which range from about minus 20 degrees to zero degrees Celsius (minus 4 degrees to 32 degrees Fahrenheit). Many of the temperature variations are due to slope effects, with sun-facing slopes warmer than shaded slopes. However, several rock layers can be seen to have distinctly different temperatures, indicating that physical properties vary from layer to layer. These differences suggest that the environment on this part of Mars varied through time as these layers were formed.

    The image is a mosaic combining four exposures taken by the thermal emission imaging system aboard Odyssey during the first two months of the Odyssey mapping mission, which began in February 2002. The area shown is about 120 kilometers (75 miles) across, at approximately 358 degrees east (2 degrees west) longitude and 3 degrees north latitude.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The thermal emission imaging system was provided by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. Lockheed Martin Astronautics, Denver, is the prime contractor for the project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and JPL. JPL is a division of the California Institute of Technology in Pasadena.

  12. Direct measurement of core-level relaxation dynamics on a surface- adsorbate system

    NASA Astrophysics Data System (ADS)

    Yin, Jing; Miaja-Avila, Luis; Saathoff, Guido; La-O-Vorakiat, Chan; Murnane, Margaret; Kapteyn, Henry; Mathias, Stefan; Aeschlimann, Martin; Bauer, Michael

    2008-03-01

    Electronic coupling between an adsorbate and the surface on which it resides is fundamental to the understanding of many surface interactions. However, the interaction of highly-excited adsorbate states is an area that has been explored only indirectly to-date. In this work, we present the first direct time-resolved observations of the lifetime of core-excited states of an atom adsorbed onto a surface. By implementing laser-assisted Auger decay on an adsorbate/surface system, we directly measure the lifetime of the 4d-1 core level of Xenon on Pt(111) to be 7.1 ± 1.1 fs. This result opens up time domain measurements of highly-excited state dynamics in materials systems where, because of complex interactions, energy-resolved measurements provide incomplete information.

  13. Direct measurement of core-level relaxation dynamics on a surface- adsorbate system

    NASA Astrophysics Data System (ADS)

    Yin, Jing; Miaja-Avila, Luis; Saathoff, Guido; La-O-Vorakiat, Chan; Murnane, Margaret; Kapteyn, Henry; Mathias, Stefan; Aeschlimann, Martin; Bauer, Michael

    2008-05-01

    Electronic coupling between an adsorbate and the surface on which it resides is fundamental to the understanding of many surface interactions. However, the interaction of highly-excited adsorbate states is an area that has been explored only indirectly to-date. In this work, we present the first direct time-resolved observations of the lifetime of core-excited states of an atom adsorbed onto a surface. By implementing laser-assisted Auger decay on an adsorbate/surface system, we directly measure the lifetime of the 4d-1 core level of Xenon on Pt(111) to be 7.1 ± 1.1 fs. This result opens up time domain measurements of highly-excited state dynamics in materials systems where, because of complex interactions, energy-resolved measurements provide incomplete information.

  14. 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.

  15. Particle reflection and its energy spectrum from solid surfaces with adsorbate atoms

    NASA Astrophysics Data System (ADS)

    Yamamura, Y.

    1988-06-01

    Using the ACAT and ACOCT codes, the particle reflection coefficients and energy spectra reflected from solid surfaces covered with adsorbated atoms have been calculated in the low-energy region. It is found that the particle reflection coefficients of low energy ions are much reduced due to the collision between an incoming ion and an adsorbate atom, especially for M1 > M3 ( M1 and M3 being the atomic masses of an ion and an adsorbate atom, respectively), and the surface peak from a substrate atom becomes strongly suppressed as the coverage increases.

  16. 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.

  17. Structural Studies of Clean and Adsorbate-Covered Fcc Metal Surfaces

    NASA Astrophysics Data System (ADS)

    Statiris, Panayiotis Athanasiou

    We have used medium energy ion scattering (MEIS) to study the structural and vibrational properties of the clean metal surfaces of Ni(110) and Ag(111), the structural changes induced by the presence of small amounts ( {~}1 atomic layer) of heteroatoms on the Ni(001) and Ni(110) surfaces (Cs, K, K and CO on Ni(110) and Au on Ni(001)) as well as the arrangement of the heteroatoms on the surface. The thesis consists of five chapters two of which serve as an introduction and provide general information about metal surfaces and medium energy ion scattering (chapters 1 and 2) and three chapters (3, 4, 5) in which the experimental results are being presented, and structural models are proposed for the surfaces studied. The purpose of the material contained in chapter one is to familiarize the reader with the general concepts, and provide an overview of the progress (experimental and theoretical) in the field of clean and adsorbate covered metal surfaces. The second chapter contains an extensive discussion about the principles and applications of medium energy ion scattering. A study of the structure of the clean Ni(001) surface and the K/Ni(110) and K/CO/Ni(110) surfaces is presented in chapter 3. Both the K/Ni(110) and K/CO/Ni(110) exhibit the missing row reconstruction. The change in the surface unit cell observed upon adsorption of CO atoms on the K/Ni(110) surface observed with low energy electron diffraction is due to the ordering of the CO molecules. The growth and structure of thin Au films (0.35 -3 layers) deposited on the Ni(001) surface is the subject of chapter 4. Au forms an almost incommensurate overlayer with a c(2 times 8) unit cell whose structure resembles that of fcc Au(111). The Au atoms exhibit unusually high vibrational amplitudes, indicating the presence of a soft phonon mode as predicted by theoretical work. The growth mode resembles the Stranski-Krastanov mode without exactly following it. The temperature dependence of the vibrational amplitudes

  18. 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.

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

    PubMed

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

    2016-09-30

    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.

  20. 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

  1. 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.

  2. 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

  3. Surface properties of solids and surface acoustic waves: Application to chemical sensors and layer characterization

    NASA Astrophysics Data System (ADS)

    Krylov, V. V.

    1995-09-01

    A general phenomenological approach is given for the description of mechanical surface properties of solids and their influence on surface acoustic wave propogation. Surface properties under consideration may be changes of the stress distribution in subsurface atomic layers, the presence of adsorbed gas molecules, surface degradation as a result of impacts from an aggressive environment, damage due to mechanical manufacturing or polishing, deposition of thin films or liquid layers, surface corrugations, etc. If the characteristic thickness of the affected layers is much less than the wavelengths of the propagating surface waves, then the effects of all these irregularities can be described by means of non-classical boundary conditions incorporating the integral surface parameters such as surface tension, surface moduli of elasticity and surface mass density. The effect of surface properties on the propagation of Rayleigh surface waves is analysed in comparison with the results of traditional approaches, in particular with Auld's energy perturbation method. One of the important implications of the above-mentioned boudnary conditions is that they are adequate for the description of the effect of rarely distributed adsorbed atoms or molecules. This allows, in particular, to obtain a rigorous theoretical description of chemical sensors using surface acoustic waves and to derive analytical expressions for their sensitivity.

  4. 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

  5. Abstraction of sulfur from Pt( 1 1 1 ) surfaces with thermal H atoms toward adsorbed and gaseous H 2S

    NASA Astrophysics Data System (ADS)

    Güttler, A.; Kolovos-Vellianitis, D.; Zecho, T.; Küppers, J.

    2002-09-01

    Sulphur layers on Pt(1 1 1) surfaces with coverages of 0.25 and 0.33 were prepared by H 2S adsorption at 85 K and subsequent annealing. H 2S adsorption on Pt, S/Pt and H/Pt surfaces and S adsorbate layers were characterized by Auger electron and thermal desorption spectroscopies. Admission of thermal H atoms to S covered Pt(1 1 1) at 85 K leads to formation of gaseous (80%) as well as adsorbed H 2S (20%). The yield of adsorbed H 2S decreases due to its isothermal desorption above 90 K. The interaction of H(g) with S(a) involves three reaction steps: 1. H(g)+S(a)→SH(a), 2. H(g)+SH(a)→H 2S(g,a), and 3. H(g)+SH(a)→H 2(g)+S(a) with apparent cross-sections σ1=0.3 Å 2, σ2=0.6 Å 2 and σ3=0.03 Å 2. Above 140 K the hydrogenation of SH toward H 2S(a,g) is blocked by thermal decomposition of H 2S. Impact of D on coadsorbed S, SH, and H 2S leads to desorption of H 2S.

  6. 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.

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

    NASA Astrophysics Data System (ADS)

    Bharath, Satyaveda Chavi

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

  8. Parallel pore and surface diffusion of levulinic acid in basic polymeric adsorbents.

    PubMed

    Liu, Baojian; Yang, Yiwen; Ren, Qilong

    2006-11-03

    The equilibrium and kinetics of levulinic acid (LA) adsorption on two basic polymeric adsorbents, 335 (highly porous gel) and D315 (macroreticular), were investigated. Experimental adsorption rates in batch stirred vessels under a variety of operating conditions were described successfully by the parallel pore and surface diffusion model taking into account external mass transfer and nonlinear Toth isotherm. The film-pore diffusion model was matched with the rate data and the resulting apparent pore diffusivities were strongly concentration-dependent and approached to a constant value for 335 adsorbent. Thus, the constant value was taken as the accurate pore diffusivity, while the pore diffusivity in D315 was estimated from the particle porosity. The surface diffusivities decreased with increasing initial bulk concentration for both adsorbents. The inverse concentration dependence was correlated reasonably well to the change of isosteric heat of adsorption as amount adsorbed.

  9. On the HSAB based estimate of charge transfer between adsorbates and metal surfaces

    NASA Astrophysics Data System (ADS)

    Kokalj, Anton

    2012-01-01

    The applicability of the HSAB based electron charge transfer parameter, Δ N, is analyzed for molecular and atomic adsorbates on metal surfaces by means of explicit DFT calculations. For molecular adsorbates Δ N gives reasonable trends of charge transfer if work function is used for electronegativity of metal surface. For this reason, calculated work functions of low Miller index surfaces for 11 different metals are reported. As for reactive atomic adsorbates, e.g., N, O, and Cl, the charge transfer is proportional to the adatom valence times the electronegativity difference between the metal surface and the adatom, where the electronegativity of metal is represented by a linear combination of atomic Mulliken electronegativity and the work function of metal surface. It is further shown that the adatom-metal bond strength is linearly proportional to the metal-to-adatom charge transfer thus making the Δ N parameter a useful indicator to anticipate the corresponding adsorption energy trends.

  10. 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

  11. Universal singularities of multilayer adsorption isotherms and determination of surface area of adsorbents

    SciTech Connect

    Aranovich, G.L.; Donohue, M.D.

    1996-07-15

    The singularity in the adsorption isotherm for macroporous and nonporous adsorbents is considered as a universal function that can be characterized with two parameters: a coefficient of proportionality, K, and an exponent, d. It is shown that the value of K is proportional to the adsorbent surface area but does not depend on the nature of the adsorbent. This leads to a new method to determine the surface area of an adsorbent, S, that is independent of the form of the adsorption isotherm at low and moderate reduced pressures. Comparison with the BET areas for nitrogen shows that the new method gives the values of S which are very close to the BET results if K = 1.47 {times} 10{sup {minus}5} mol/m{sup 2} (for nitrogen). Analysis of adsorption data for macroporous adsorbents shows that the BET isotherm gives systematic deviations and that the experimental amount adsorbed is smaller than the value predicted by the BET equation (even in the range of the best agreement with experiment). These deviations lead to systematic error in the values of S of about 43%. Using K equal to K{sub f} = 1/{sigma}N{sub A} (=1.025 {times} 10{sup {minus}5} mol/m{sup 2} for nitrogen), the authors are able to eliminate systematic error in the surface area determination. Here {sigma} is the area occupied by one molecule and N{sub A} is the Avogadro number.

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

    PubMed

    Rubasinghege, Gayan; Grassian, Vicki H

    2013-04-18

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

  13. Surface alloy formation of noble adatoms adsorbed on Si(111)-\\sqrt {3}\\times \\sqrt {3} -Pb surface: a first-principles study

    NASA Astrophysics Data System (ADS)

    Li, Chong; Wang, Fei; Sun, Q.; Jia, Yu

    2011-07-01

    The geometric structures, stability and electronic properties of initial stages of surface alloy formation for noble atoms adsorbed on Si(111)-\\sqrt {3}\\times \\sqrt {3} -Pb surfaces have been comparatively and extensively studied by using first-principles calculations within density functional theory. Our results revealed that an Au trimer rather than a tetramer adsorption induces a surface alloy by combining with Pb atoms in covalent bonds, exhibiting semiconducting characteristics due to the localization of surface states. The stability of the two-dimensional (2D) surface alloy obeys the Hume-Rothery rule. The electronic structures of the 2D surface alloy are sensitive to the number of Au adatoms and can be modulated by the quantity of Au adatoms. Unlike the Au atoms, our further calculations indicated that adsorption of Ag or Cu atoms on the surface cannot form a surface alloy with Pb atoms in the surface layer due to a weaker interaction or smaller radius.

  14. 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

  15. Effects due to adsorbed atoms upon angular and energy distributions of surface produced negative hydrogen ions

    NASA Astrophysics Data System (ADS)

    Wada, M.; Bacal, M.; Kasuya, T.; Kato, S.; Kenmotsu, T.; Sasao, M.

    2013-02-01

    Exposure to Cs added hydrogen discharge makes surface of plasma grid of a negative hydrogen ion source covered with Cs and hydrogen. A Monte-Carlo particle simulation code ACAT was run to evaluate the effects due to adsorbed Cs and H atoms upon the angular and energy distributions of H atoms leaving the surface. Accumulation of H atoms on the surface reduces particle reflection coefficients and the mean energy of backscattered H atoms. Angular distributions of H atoms reflected from the hydrogen covered surface tend to be under-cosine at lower energies. Desorption of adsorbed H atoms is more efficient for hydrogen positive ions than for Cs positive ions at lower incident energy. At higher energy more than 100 eV, Cs ions desorb adsorbed H atoms more efficiently than hydrogen ions.

  16. 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.

  17. Resonant electron scattering by molecules adsorbed on a surface: N2-Ag system

    NASA Astrophysics Data System (ADS)

    Teillet-Billy, D.; Djamo, V.; Gauyacq, J. P.

    1992-05-01

    A model study of resonant electron scattering by static molecules adsorbed on a metal surface is presented, using the recently developed coupled angular mode (CAM) method. It is applied to the case of N2 molecules adsorbed on an Ag surface. The N2-2πg resonance characteristics (energy position and width) are determined and shown to be modified by the presence of the surface in qualitative agreement with the experimental results of Demuth et al. [Phys. Rev. Lett. 47 (1981) 1166].

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

    SciTech Connect

    Sun, Yun

    2010-06-07

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

  19. Chemical Raman Enhancement of Organic Adsorbates on Metal Surfaces

    DTIC Science & Technology

    2011-02-25

    system with an ordered monolayer of about one BTmolecule per nm2 bonded to a flat periodic Au(111) slab. A 400 eV plane-wave cutoff and 2 2 1 Monkhorst...cm 1 width. (B) Binding geometries. Our supercell consists of 5 atomic layers of Au stacked along [111] with 16 atoms per layer, with 30 Å of vacuum... 1 ] M. Fleischman, P. J. Hendra, and A. McQuillan, Chem. Phys. Lett. 26, 163 (1974). [2] D. L. Jeanmaire and R. P. V . Duyne, J. Electroanal. Chem. 84

  20. 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.

  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. 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.

  5. New surfaces stabilized by adsorbate-induced faceting

    NASA Astrophysics Data System (ADS)

    Kaghazchi, Payam; Jacob, Timo; Ermanoski, Ivan; Chen, Wenhua; Madey, Theodore E.

    2012-07-01

    Faceting is a form of self-assembly of single-crystal surfaces at the nanometer-scale in which an initially planar surface converts to a ‘hill-and-valley’ structure, exposing new faces of low-index surfaces. Our recent studies revealed that, upon annealing in O2, three-sided nanoscale pyramids form on Ir(210) exposing smooth {311} and partially restructured (110) faces. Through a combination of scanning tunneling microscopy and density functional theory, we identify this structure to be a stepped double-missing-row reconstruction, which is only stable on nanopyramidal facets, not on a planar Ir(110) surface. This faceting-enabled stabilization of a hitherto unstable surface points to a new approach to prepare nanoscale model catalysts for structure-sensitivity studies in heterogeneous (electro-)catalysis with high selectivity and reactivity.

  6. Adherence of platelets to in situ albumin-binding surfaces under flow conditions: role of surface-adsorbed albumin.

    PubMed

    Guha Thakurta, Sanjukta; Miller, Robert; Subramanian, Anuradha

    2012-08-01

    Surfaces that preferentially bind human serum albumin (HSA) were generated by grafting albumin-binding linear peptide (LP1) onto silicon surfaces. The research aim was to evaluate the adsorption pattern of proteins and the adhesion of platelets from platelet-poor plasma and platelet-rich plasma, respectively, by albumin-binding surfaces under physiological shear rate (96 and 319 s(-1)) conditions. Bound proteins were quantified using enzyme-linked immunosorbent assays (ELISAs) and two-dimensional gel electrophoresis. A ratio of ∼1000:100:1 of adsorbed HSA, human immunoglobulin (HIgG) and human fibrinogen (HFib) was noted, respectively, on LP1-functionalized surfaces, and a ratio of ∼5:2:1 of the same was noted on control surfaces, as confirmed by ELISAs. The surface-adsorbed von Willebrand factor was undetectable by sensitive ELISAs. The amount of adhered platelets correlated with the ratio of adsorbed HSA/HFib. Platelet morphology was more rounded on LP1-functionalized surfaces when compared to control surfaces. The platelet adhesion response on albumin-binding surfaces can be explained by the reduction in the co-adsorption of other plasma proteins in a surface environment where there is an excess of albumin molecules, coupled with restrictions in the conformational transitions of other surface-adsorbed proteins into hemostatically active forms.

  7. Melt crystallization/dewetting of ultrathin PEO films via carbon dioxide annealing: the effects of polymer adsorbed layers.

    PubMed

    Asada, Mitsunori; Jiang, Naisheng; Sendogdular, Levent; Sokolov, Jonathan; Endoh, Maya K; Koga, Tadanori; Fukuto, Masafumi; Yang, Lin; Akgun, Bulent; Dimitriou, Michael; Satija, Sushil

    2014-09-14

    The effects of CO2 annealing on the melting and subsequent melt crystallization processes of spin-cast poly(ethylene oxide) (PEO) ultrathin films (20-100 nm in thickness) prepared on Si substrates were investigated. By using in situ neutron reflectivity, we found that all the PEO thin films show melting at a pressure as low as P = 2.9 MPa and at T = 48 °C which is below the bulk melting temperature (Tm). The films were then subjected to quick depressurization to atmospheric pressure, resulting in the non-equilibrium swollen state, and the melt crystallization (and/or dewetting) process was carried out in air via subsequent annealing at given temperatures below Tm. Detailed structural characterization using grazing incidence X-ray diffraction, atomic force microscopy, and polarized optical microscopy revealed two unique aspects of the CO2-treated PEO films: (i) a flat-on lamellar orientation, where the molecular chains stand normal to the film surface, is formed within the entire film regardless of the original film thickness and the annealing temperature; and (ii) the dewetting kinetics for the 20 nm thick film is much slower than that for the thicker films. The key to these phenomena is the formation of irreversibly adsorbed layers on the substrates during the CO2 annealing: the limited plasticization effect of CO2 at the polymer-substrate interface promotes polymer adsorption rather than melting. Here we explain the mechanisms of the melt crystallization and dewetting processes where the adsorbed layers play vital roles.

  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. Vibrational Spectroscopic Studies of Adsorbates on Bimetallic Surfaces.

    DTIC Science & Technology

    1992-12-01

    sublimed. Prior to use, the metal evaporator was outgassed extensively. No measurable contaminants accumulated on the surface during metal deposition...substrate was an annealed c(2X2) S/Mo(110) surface which can be thought of as roughly approximating the surface of a MoS2 crystallite. Increasing Co...catalytic activity of Co promoted MoS2 would be that the active site is a Co promoted Mo-S site. As a final point, it is notewoi chy that in all the co

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

    PubMed

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

    2015-07-01

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

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  13. Induced rupture of vesicles adsorbed on glass by pore formation at the surface-bilayer interface.

    PubMed

    Kataoka-Hamai, Chiho; Yamazaki, Tomohiko

    2015-02-03

    Supported lipid bilayers (SLBs) are often formed by spontaneous vesicle rupture and fusion on a solid surface. A well-characterized rupture mechanism for isolated vesicles is pore nucleation and expansion in the solution-exposed nonadsorbed area. In contrast, pore formation in the adsorbed bilayer region has not been investigated to date. In this work, we studied the detailed mechanisms of asymmetric rupture of giant unilamellar vesicles (GUVs) adsorbed on glass using fluorescence microscopy. Asymmetric rupture is the pathway where a rupture pore forms in a GUV near the edge of the glass-bilayer interface with high curvature and then expansion of the pore yields a planar bilayer patch. We show that asymmetric rupture occasionally resulted in SLB patches bearing a defect pore. The defect formation probability depended on lipid composition, salt concentration, and pH. Approximately 40% of negatively charged GUVs under physiological conditions formed pore-containing SLB patches, while negatively charged GUVs at low salt concentration or pH 4.0 and positively charged GUVs exhibited a low probability of defect inclusion. The edge of the defect pore was either in contact with (on-edge) or away from (off-edge) the edge of the planar bilayer. On-edge pores were predominantly formed over off-edge defects. Pores initially formed in the glass-adsorbed region before rupture, most frequently in close contact with the edge of the adsorbed region. When a pore formed near the edge of the adsorbed area or when the edge of a pore reached that of the adsorbed area by pore expansion, asymmetric rupture was induced from the defect site. These induced rupture mechanisms yielded SLB patches with an on-edge pore. In contrast, off-edge pores were produced when defect pore generation and subsequent vesicle rupture were uncoupled. The current results demonstrate that pore formation in the surface-adsorbed region of GUVs is not a negligible event.

  14. 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.

  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. Gas-Solid Dynamics at Disordered and Adsorbate Covered Surfaces.

    DTIC Science & Technology

    1987-05-15

    Schrodinger equation . Specific numerical results are presented for pulses of area equal to v, 21r, 31r, 4r and 51r for both symmetric and asymmetric... Semiclassical Perturbation Theory for Atom Scattering from Surfaces with Defects 1 Presented here is an extension of semiclassical perturbation theory (SCP...Involved in solving the AWM equations in equivalent to that Involved for elastic scattering in the same formulation. As an initial Illustration, expUclt

  17. Nanoengineering Catalyst Supports via Layer-by Layer Surface Functionalization

    SciTech Connect

    Yan, Wenfu; Mahurin, Shannon Mark; Overbury, Steven {Steve} H; Dai, Sheng

    2006-01-01

    Recent progress in the layer-by-layer surface modification of oxides for the preparation of highly active and stable gold nanocatalysts is briefly reviewed. Through a layer-by-layer surface modification approach, the surfaces of various catalyst supports including both porous and nonporous silica materials and TiO{sub 2} nanoparticles were modified with monolayers or multilayers of distinct metal oxide ultra-thin films. The surface-modified materials were used as supports for Au nanoparticles, resulting in highly active nanocatalysts for low-temperature CO oxidation. Good stability against sintering under high-temperature treatment was achieved for a number of the Au catalysts through surface modification of the support material. The surface modification of supports can be a viable route to control both the composition and structure of support and nanoparticle interfaces, thereby tailoring the stability and activity of the supported catalyst systems.

  18. 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.

  19. The influence of surface chemistry on adsorbed fibrinogen conformation, orientation, fiber formation and platelet adhesion.

    PubMed

    Zhang, Liudi; Casey, Brendan; Galanakis, Dennis K; Marmorat, Clement; Skoog, Shelby; Vorvolakos, Katherine; Simon, Marcia; Rafailovich, Miriam H

    2017-03-02

    Thrombosis is a clear risk when any foreign material is in contact with the bloodstream. Here we propose an immunohistological stain-based model for non-enzymatic clot formation that enables a facile screen for the thrombogenicity of blood-contacting materials. We exposed polymers with different surface chemistries to protease-free human fibrinogen. We observed that on hydrophilic surfaces, fibrinogen is adsorbed via αC regions, while the γ400-411 platelet-binding dodecapeptide on the D region becomes exposed, and fibrinogen fibers do not form. In contrast, fibrinogen is adsorbed on hydrophobic surfaces via the relatively hydrophobic D and E regions, exposing the αC regions while rendering the γ400-411 inaccessible. Fibrinogen adsorbed on hydrophobic surfaces is thus able to recruit other fibrinogen molecules through αC regions and polymerize into large fibrinogen fibers, similar to those formed in vivo in the presence of thrombin. Moreover, the γ400-411 is available only on the large fibers not elsewhere throughout the hydrophobic surface after fibrinogen fiber formation. When these surfaces were exposed to gel-sieved platelets or platelet rich plasma, a uniform monolayer of platelets, which appeared to be activated, was observed on the hydrophilic surfaces. In contrast, large agglomerates of platelets were clustered on fibers on the hydrophobic surfaces, resembling small nucleating thrombi. Endothelial cells were also able to adhere to the monomeric coating of fibrinogen on hydrophobic surfaces. These observations reveal that the extent and type of fibrinogen adsorption, as well as the propensity of adsorbed fibrinogen to bind platelets, may be modulated by careful selection of surface chemistry.

  20. Semiconducting electronic property of graphene adsorbed on (0001) surfaces of SiO2.

    PubMed

    Nguyen, Thanh Cuong; Otani, Minoru; Okada, Susumu

    2011-03-11

    First-principles total energy calculations are performed to investigate the energetics and electronic structures of graphene adsorbed on both an oxygen-terminated SiO2 (0001) surface and a fully hydroxylated SiO2 (0001) surface. We find that there are several stable adsorption sites for graphene on both O-terminated and hydroxylated SiO2 surfaces. The binding energy in the most stable geometry is found to be 15 meV per C atom, indicating a weak interaction between graphene and SiO2 (0001) surfaces. We also find that the graphene adsorbed on SiO2 is a semiconductor irrespective of the adsorption arrangement due to the variation of on-site energy induced by the SiO2 substrate.

  1. 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

  2. Effects of surface curvature and surface chemistry on the structure and activity of proteins adsorbed in nanopores.

    PubMed

    Sang, Lung-Ching; Coppens, Marc-Olivier

    2011-04-14

    The interactions of proteins with the surface of cylindrical nanopores are systematically investigated to elucidate how surface curvature and surface chemistry affect the conformation and activity of confined proteins in an aqueous, buffered environment. Two globular proteins, lysozyme and myoglobin, with different catalytic functions, were used as model proteins to analyze structural changes in proteins after adsorption on ordered mesoporous silica SBA-15 and propyl-functionalized SBA-15 (C(3)SBA-15) with carefully controlled pore size. Liquid phase ATR-FTIR spectroscopy was used to study the amide I and II bands of the adsorbed proteins. The amide I bands showed that the secondary structures of free and adsorbed protein molecules differ, and that the secondary structure of the adsorbed protein is influenced by the local geometry as well as by the surface chemistry of the nanopores. The conformation of the adsorbed proteins inside the nanopores of SBA-15 and C(3)SBA-15 is strongly correlated with the local geometry and the surface properties of the nanoporous materials, which results in different catalytic activities. Adsorption by electrostatic interaction of proteins in nanopores of an optimal size provides a favorably confining and protecting environment, which may lead to considerably enhanced structural stability and catalytic activity.

  3. Spin-polarized metastable-atom deexcitation spectroscopy study of Xenon-adsorbed iron surfaces

    NASA Astrophysics Data System (ADS)

    Yamauchi, Yasushi; Kurahashi, Mitsunori; Suzuki, Taku; Sun, Xia; Wang, Zhongping

    2007-03-01

    The electron spin polarization at the interface between nonmagnetic and ferromagnetic medias is one of the essential factors that may alter the spin transport phenomena. To investigate fundamental aspects of induced spin polarization we have examined the adsorbate-covered magnetic surfaces by means of spin polarized metastable-atom deexcitation spectroscopy (SPMDS). Use of spin-polarized metastable helium atoms in triplet states moving at thermal energies gives rise to the ultimate surface sensitivity. Although Xenon can adsorb on surfaces at low temperatures by the van der Waals force, no electron exchange with surfaces, especially no spin interaction, is expected because of its closed shell structure. SPMDS spectra measured for Xenon-adsorbed iron surfaces show three prominent peaks that are the same as those previously reported for other surfaces by D. M. Oro, et al. [Phys. Rev. A 49 (1994) 4703]. Two peaks (^2P1/2, ^2P3/2) at higher kinetic energies exhibit clear spin asymmetries while the other low energy peak has no appreciable spin asymmetry. The spin asymmetries will be discussed on the basis of spin polarization and deexcitation processes of metastable atoms.

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

    NASA Astrophysics Data System (ADS)

    Olsen, R.

    2015-12-01

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

  5. Photomanipulation of the anchoring strength using a spontaneously adsorbed layer of azo dendrimers.

    PubMed

    Nádasi, Hajnalka; Stannarius, Ralf; Eremin, Alexey; Ito, Atsuki; Ishikawa, Ken; Haba, Osamu; Yonetake, Koichiro; Takezoe, Hideo; Araoka, Fumito

    2017-03-15

    We systematically studied the photoinduced anchoring transition in a nematic liquid crystal containing azo dendrimers. Because the azo dendrimers in the trans-isomer state were spontaneously adsorbed at substrate surfaces, which was confirmed by optical second-harmonic generation (SHG), a homeotropic orientation was established at the first stage. Ultraviolet (UV) light irradiation triggered a transition into a planar state which was accompanied by a suppression of the SH generation. The monotonic decrease of the effective scalar order parameter with increasing UV light intensity was determined by polarized attenuated total reflection infrared (ATR-IR) spectroscopy. The variation of anchoring strength and extrapolation length was evaluated by observing the Fréedericksz transition as a function of UV light intensity at a certain visible (VIS) light intensity. Such a photoinduced variation can be interpreted as a variation of the anchoring strength depending on the trans/cis ratio at the surfaces based on a modified Rapini-Papoular model. Thus, this system provides the opportunity for a controlled change in the anchoring strength.

  6. General trend for adsorbate-induced segregation of subsurface metal atoms in bimetallic surfaces

    NASA Astrophysics Data System (ADS)

    Menning, Carl A.; Chen, Jingguang G.

    2009-05-01

    It is well known that the unique chemical properties of transition metal alloys depend on the configuration of metal atoms of the bimetallic surfaces. Using density functional theory calculations, the thermodynamic potential for segregation of an admetal from the subsurface to surface configuration is shown to correlate linearly with the difference in occupied d-band center, Δɛd, between these two configurations for a wide range of bimetallic systems. The thermodynamic potential for segregation is also shown to increase with the Pauling electronegativity for several adsorbates, including atomic H, O, C, N, S, and Se. A generalized equation is provided to predict the stable surface configuration for the bimetallic systems with different adsorbates.

  7. Rough SERS substrate based on gold coated porous silicon layer prepared on the silicon backside surface

    NASA Astrophysics Data System (ADS)

    Dridi, H.; Haji, L.; Moadhen, A.

    2017-04-01

    We report in this paper a novel method to elaborate rough Surface Enhanced Raman Scattering (SERS) substrate. A single layer of porous silicon was formed on the silicon backside surface. Morphological characteristics of the porous silicon layer before and after gold deposition were influenced by the rough character (gold size). The reflectance measurements showed a dependence of the gold nano-grains size on the surface nature, through the Localized Surface Plasmon (LSP) band properties. SERS signal of Rhodamine 6G used as a model analyte, adsorbed on the rough porous silicon layer revealed a marked enhancement of its vibrational modes intensities.

  8. 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

  9. Effects of dilution of poly(ethylvinylbenzene-divinylbenzene) adsorbent on the adsorption of aliphatic, alicyclic, and aromatic hydrocarbon adsorbates from effective zero to finite surface coverage

    SciTech Connect

    Djordjevic, N.M.; Laub, R.J.

    1988-01-15

    The chromatographic measurement and systematic interpretation of the solidgas partition coefficients K/sub s/ and related thermodynamic properties of a number of hydrocarbon adsorbates (n-pentane through n-octane, cyclohexane, methylcyclohexane, benzene, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, thiophene, and acetone) at effective zero surface coverage with a 1:10 admixture of the title adsorbent-inert diluent from 393 to 443 K are reported. Despite a difference of an order of magnitude in the surface areas of bulk and admixed packings, the adsorbate relative retentions were in good agreement with those found in previous work with neat Porapak Q. The heats of adsorption also coincided to within an experimental error of ca. +- 5%. The GSC technique of elution by characteristic point was then used to derive the finite-concentration adsorption isotherms and isosteric heats of adsorption on n-hexane, cyclohexane, benzene, carbon tetrachloride, and acetone adsorbates with diluted Porapak Q over the temperature range 393-433 K. All exhibited BET Type IV isotherms, as well as changes in the respective isotherm temperature coefficients. The latter is said to be a consequence of the microporous substructure of this adsorbent.

  10. 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.

  11. Collision-induced migration of adsorbates on solid surfaces: an experimental approach.

    PubMed

    Danziger, I M; Asscher, M

    2006-07-13

    Collision-induced migration (CIM) is a process in which energetic gas-phase atoms or molecules at the tail of the Boltzmann distribution enhance surface migration of adsorbates upon collision. It is believed to exist and play an important role in any realistic high pressure-high-temperature heterogeneous catalytic system. Combining supersonic beam-surface collision setup with in-situ optical second harmonic generation diffraction technique from a coverage grating, we have shown, for the first time, that indeed energetic collisions (Kr seeded in He) promote surface mobility of CO-K surface complex on Ru(001) with a threshold total kinetic energy of 3 eV. An average migration distance/collision of more than 30 adsorption sites was estimated from the experimental data at Kr total energy of 3.8 eV. This long-range migration distance per collision is understood in terms of a cascade migration mechanism, where adsorbed CO molecules collide and push their neighbors from high to low coverage areas, in a direction dictated by the collision momentum vector. A similar mechanism has recently been suggested to explain adsorbate mobility at high coverage induced by an STM tip.

  12. 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.

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2003-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  16. MOF-Graphite Oxide Nanocomposites: Surface Characterization and Evaluation as Adsorbents of Ammonia

    DTIC Science & Technology

    2009-01-01

    July 2009 DOI: 10.1039/b908862h Metal-organic framework (MOF-5)–graphite oxide (GO) composite was synthesized using a solvothermal synthesis route. The...restacked and their degree of orientation depends on the method of drying. Our recent studies demonstrate that graphite oxide can be an efficient adsorbent...parent materials and the nanocomposite is fol- lowed by their surface characterization using a range of experi- mental methods . Then, their

  17. Controlling the Electronic Structure of Graphene Using Surface-adsorbate Interactions

    DTIC Science & Technology

    2015-07-21

    before and after adsorption [in Fig. 4(a)] and structural changes to Gr/Ni(111) [in Fig. 4(b)]. Before adsorption, the atomic orbitals of graphene (pz...RAPID COMMUNICATIONS PHYSICAL REVIEW B 92, 041407(R) (2015) Controlling the electronic structure of graphene using surface-adsorbate interactions...manuscript received 3 May 2015; published 21 July 2015) Hybridization of atomic orbitals in graphene on Ni(111) opens up a large energy gap of ≈2.8 eV

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

    PubMed

    Haryanto, Bode; Chang, Chien-Hsiang

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-02-01

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

  20. 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.

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

    SciTech Connect

    Peterson, Eric Scott

    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.

  2. Comparative study of the surface layer density of liquid surfaces

    NASA Astrophysics Data System (ADS)

    Chacón, E.; Fernández, E. M.; Duque, D.; Delgado-Buscalioni, R.; Tarazona, P.

    2009-11-01

    Capillary wave fluctuations blur the inherent structure of liquid surfaces in computer simulations. The intrinsic sampling method subtracts capillary wave fluctuations and yields the intrinsic surface structure, leading to a generic picture of the liquid surface. The most relevant magnitude of the method is the surface layer density ns that may be consistently determined from different properties: the layering structure of the intrinsic density profiles, the turnover rate for surface layer particles, and the hydrodynamic damping rate of capillary waves. The good agreement among these procedures provides evidence for the physical consistency of the surface layering hypothesis, as an inherent physical property of the liquid surfaces. The dependence of the surface compactness, roughness, and exchange rate with temperature is analyzed for several molecular interaction models.

  3. 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.

  4. Structural characterization of irreversibly adsorbed polymer layers at the polymer/solid interface - In-situ grazing incidence angle x-ray scattering studies

    NASA Astrophysics Data System (ADS)

    Jiang, Naisheng; Chen, Fen; Chen, Xiameng; Han, Zexi; Liang, Chen; Gin, Peter; Asada, Mitsunori; Endoh, Maya; Koga, Tad

    2012-02-01

    In recent years, great attention has been paid to irreversibly adsorbed polymer layers formed on solid substrates since they can modify various properties of polymeric materials confined at the nanometer scale. In this talk, by the combined use of in-situ grazing incidence small angle x-ray scattering and x-ray reflectivity techniques, we aim to characterize the detailed structures of the adsorbed layers composed of different homopolymers (polystyrene, polybutadiene, poly (ethylene oxide), and poly (methyl methacrylate)) prepared on silicon substrates. We will highlight the generality/differences in the structures, leading to a better understanding of the formation process of the adsorbed layers at the impenetrable solid interfaces.

  5. Leidenfrost Vapor Layer Stabilization on Superhydrophobic Surfaces

    NASA Astrophysics Data System (ADS)

    Vakarelski, Ivan; Patankar, Neelesh; Marston, Jeremy; Chan, Derek; Thoroddsen, Sigurdur

    2012-11-01

    We have performed experiments to investigate the influence of the wettability of a superheated metallic sphere on the stability of a thin vapor layer during the cooling of a sphere immersed in water. For high enough sphere temperatures, a continuous vapor layer (Leidenfrost regime) is observed on the surface of non-superhydrophobic spheres, but below a critical sphere temperature the layer becomes unstable and explosively switches to nuclear boiling regime. In contrast, when the sphere surface is textured and superhydrophobic, the vapor layer is stable and gradually relaxes to the sphere surface until the complete cooling of the sphere, thus avoiding the nuclear boiling transition altogether. This finding could help in the development of heat exchange devices and of vapor layer based drag reducing technologies.

  6. 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

    2014-01-08

    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.

  7. 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.

  8. The reaction of propylene with ordered and disordered oxygen atoms adsorbed on the Ag(110) surface

    NASA Astrophysics Data System (ADS)

    Ranney, Jeffrey T.; Bare, Simon R.

    1997-06-01

    The adsorption and reaction of propylene on oxygen covered Ag(110) was investigated using temperature programmed desorption spectroscopy. Propylene oxidation was compared on the oxygen reconstructed (ordered) Ag(110) surface and on the unreconstructed (disordered) oxygen dosed surface. Oxygen atoms adsorbed < 185 K do not incorporate into long silver-oxygen chains on the (110) surface and are referred to as disordered. Propylene desorbs from clean Ag(110) with an activation energy of 9.8 kcal mol -1. The desorption activation energy increases by 30% as the coverage of oxygen is increased up to 0.33 monolayers. While the desorption activation energy increase was the same on the reconstructed and unreconstructed surface, the reactivity of the adsorbed oxygen for propylene oxidation was quite different. Disordered oxygen adatoms were determined to be at least ten times more active for propylene oxidation than ordered oxygen atoms on the reconstructed surface. The decrease in activity of the oxygen atoms is attributed to the embedding of the oxygen adatoms into long silver-oxygen chains at higher temperatures. With increasing propylene coverage on the oxygen pre-covered surface the water yield increases and the yield of carbon dioxide decreases, indicating that water formation through hydrogen abstraction consumes the bulk of the oxygen at higher propylene coverages.

  9. 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.

  10. 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.

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

    NASA Astrophysics Data System (ADS)

    Schafer, Robert; Xu, Jun; Mohideen, Umar

    2016-01-01

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

  12. Surface layering effect of diluted Intralipid

    NASA Astrophysics Data System (ADS)

    Foschum, F.; Bodenschatz, N.; Krauter, P.; Nothelfer, S.; Liemert, A.; Simon, E.; Kröner, S.; Kienle, A.

    2015-07-01

    In this study the formation of a surface layer on top of an Intralipid dilution was studied. By use of spatial frequency reflectance and spatially resolved reflectance the surface layer could be characterized. The influence on the determination of the optical properties assuming a semi-infinite medium in the theory was investigated. By use of an angularly resolved reflectance device the formation even on a horizontally orientated glass slide could be shown.

  13. Detrimental adsorbate fields in experiments with cold Rydberg gases near surfaces

    NASA Astrophysics Data System (ADS)

    Hattermann, H.; Mack, M.; Karlewski, F.; Jessen, F.; Cano, D.; Fortágh, J.

    2012-08-01

    We observe the shift of Rydberg levels of rubidium close to a copper surface when atomic clouds are repeatedly deposited on it. We measure transition frequencies of rubidium to S and D Rydberg states with principal quantum numbers n between 31 and 48 using the technique of electromagnetically induced transparency. The spectroscopic measurement shows a strong increase of electric fields towards the surface that evolves with the deposition of atoms. Starting with a clean surface, we measure the evolution of electrostatic fields in the range between 30 and 300 μm from the surface. We find that after the deposition of a few hundred atomic clouds, each containing ˜106 atoms, the field of adsorbates reaches 1 V/cm for a distance of 30 μm from the surface. This evolution of the electrostatic field sets serious limitations on cavity QED experiments proposed for Rydberg atoms on atom chips.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2007-03-01

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

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

    PubMed

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

    2014-07-14

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

  17. Formation of Adsorbed Oxygen Radicals on Minerals at the Martian Surface and the Decomposition of Organic Molecules

    NASA Technical Reports Server (NTRS)

    Yen, A. S.; Kim, S. S.; Freeman, B. A.; Hecht, M. H.

    2000-01-01

    We present experimental evidence that superoxide ions form on mineral grains at the martian surface and show that these adsorbates can explain the unusual reactivity of the soil as well as the apparent absence of organic molecules.

  18. Investigations on the Q and CT Bands of Cytochrome c Submonolayer Adsorbed on an Alumina Surface Using Broadband Spectroscopy with Single-Mode Integrated Optical Waveguides.

    PubMed

    Wiederkehr, Rodrigo S; Hoops, Geoffrey C; Aslan, Mustafa M; Byard, Courtney L; Mendes, Sergio B

    2009-05-14

    In this work, we report experimental results on the molar absorptivity of cytochrome c adsorbed at different submonolayer levels onto an aluminum oxide waveguide surface; our data show a clear dependence of the protein optical properties on its surface density. The measurements were performed using the broadband, single-mode, integrated optical waveguide spectroscopic technique, which is an extremely sensitive tool able to reach submonolayer levels of detection required for this type of studies. This investigation focuses on the molar absorptivity at the Q-band (centered at 525 nm) and, for the first time to our knowledge, the weak charge transfer (CT) band (centered at 695 nm) of surface-adsorbed cyt c. Polarized light in the spectral region from 450 to 775 nm was all-coupled into an alumina thin film, which functioned as a single-mode planar optical waveguide. The alumina thin-film waveguide used for this work had a thickness of 180 nm and was deposited on a glass substrate by the atomic layer deposition process. The protein submonolayer was formed on the alumina waveguide surface through electrostatic adsorption from an aqueous buffer solution at neutral pH. The optical properties of the surface-adsorbed cyt c were investigated for bulk protein concentrations ranging from 5 nM to 8200 nM in the aqueous buffer solution. For a protein surface density of 2.3 pmol/cm(2), the molar absorptivity measured at the charge transfer band was 335 M(-1) cm(-1), and for a surface density of 15 pmol/cm(2) was 720 M(-1) cm(-1), which is much closer to the value of cyt c dissolved in an aqueous neutral buffer (830 M(-1) cm(-1)). The modification of the protein molar absorptivity and its dependence on the surface density can most likely be attributed to conformational changes of the surface-adsorbed species.

  19. Utilization of microfluidic V-junction device to prepare surface itraconazole adsorbed nanospheres.

    PubMed

    Kucuk, Israfil; Ahmad, Zeeshan; Edirisinghe, Mohan; Orlu-Gul, Mine

    2014-09-10

    Itraconazole is widely used as an anti-fungal drug to treat infections. However, its poor aqueous solubility results in low bioavailability. The aim of the present study was to improve the drug release profile by preparing surface itraconazole adsorbed polymethylsilsesquioxane (PMSQ) nanospheres using a V-junction microfluidic (VJM) device. In order to generate nanospheres with rough surface, the process flow rate of perfluorohexane (PFH) was set between 50 and 300 μl min(-1) while the flow rate of PMSQ and itraconazole solution were constant at 300 μl min(-1). Variations in the PFH flow rate enable the controlled size generation of nanospheres. PMSQ nanospheres adsorbing itraconazole were characterized by SEM, FTIR and Zetasizer. The release of itraconazole from PMSQ nanosphere surface was measured using UV spectroscopy. Nanosphere formulations with a range of sphere size (120, 320 and 800 nm diameter) were generated and drug release was studied. 120 nm itraconazole coated PMSQ nanospheres were found to present highest drug encapsulation efficiency and 13% drug loading in a more reproducible manner compared to 320 nm and 800 nm sized nanosphere formulations. Moreover, 120 nm itraconazole coated PMSQ nanospheres (encapsulation efficiency: 88%) showed higher encapsulation efficiency compared to 320 nm (encapsulation efficiency: 74%) and 800 nm (encapsulation efficiency: 62%) sized nanosphere formulations. The itraconazole coated PMSQ nanospheres were prepared continuously at the rate of 2.6 × 10(6) per minute via VJM device. Overall the VJM device enabled the preparation of monodisperse surface itraconazole adsorbed nanospheres with controlled in vitro drug release profile.

  20. Characterization of silver ions adsorbed on gold nanorods: surface analysis by using surface-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Niidome, Yasuro; Nakamura, Yuki; Honda, Kanako; Akiyama, Yasuyuki; Nishioka, Koji; Kawasaki, Hideya; Nakashima, Naotoshi

    2009-04-07

    Surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-MS) indicated AgBr2-, which adsorbed on gold nanorod surfaces, was a key material to control the anisotropic growth of gold nanorods.

  1. Surface layering properties of Intralipid phantoms.

    PubMed

    Bodenschatz, Nico; Krauter, Philipp; Foschum, Florian; Nothelfer, Steffen; Liemert, André; Simon, Emanuel; Kröner, Sabrina; Kienle, Alwin

    2015-02-07

    Intralipid has become an extensively studied and widely used reference and calibration phantom for diffuse optical imaging technologies. In this study we call attention to the layering properties of Intralipid emulsions, which are commonly assumed to have homogeneous optical properties. By measurement of spatial frequency domain reflectance in combination with an analytical solution of the radiative transfer equation for two-layered media, we make quantitative investigations on the formation of a surface layer on different dilutions of Intralipid. Our findings are verified by an independent spatially resolved reflectance setup giving evidence of a time dependent, thin and highly scattering surface layer on top of Intralipid-water emulsions. This layer should be considered when using Intralipid as an optical calibration or reference phantom.

  2. Surface layering properties of Intralipid phantoms

    NASA Astrophysics Data System (ADS)

    Bodenschatz, Nico; Krauter, Philipp; Foschum, Florian; Nothelfer, Steffen; Liemert, André; Simon, Emanuel; Kröner, Sabrina; Kienle, Alwin

    2015-02-01

    Intralipid has become an extensively studied and widely used reference and calibration phantom for diffuse optical imaging technologies. In this study we call attention to the layering properties of Intralipid emulsions, which are commonly assumed to have homogeneous optical properties. By measurement of spatial frequency domain reflectance in combination with an analytical solution of the radiative transfer equation for two-layered media, we make quantitative investigations on the formation of a surface layer on different dilutions of Intralipid. Our findings are verified by an independent spatially resolved reflectance setup giving evidence of a time dependent, thin and highly scattering surface layer on top of Intralipid-water emulsions. This layer should be considered when using Intralipid as an optical calibration or reference phantom.

  3. Development of drug adsorbates onto soluble inorganic silicate glass surface: example with acetaminophen.

    PubMed

    Hristova, Yoanna; Djambaski, Peter; Samuneva, Biserka; Rangelova, Nadya; Bogdanova, Svetla

    2008-02-01

    A ternary melt-derived inorganic glass system (Igl) of composition corresponding to 62SiO(2), 35Na(2)O, 3Al(2)O(3 )(wt.%) has been formulated and studied as a drug carrier. The [Al(2)O(3)/Na(2)O] ratio is less than one and the aluminium ion is a network former that retards the glass dissolution. The processing conditions lead to a brittle, easily grinding, amorphous product. The Igl structure was proven by IR-spectroscopy, energy-dispersive spectrometry, X-ray diffraction, scanning electron microscopy. A very important fact established is that the Igl corrosion (dissolution) is pH-dependent. Inorganic glass system was transformed into model acetaminophen (APH) adsorbate (APH/Igla 1:1(w/w)) with mild experimental conditions and evaluated as a drug carrier. No interactions between Igl and APH during the processing were proven. Besides, APH settles onto the glass surface as crystalline phase. A lower extent of corrosion, apparent solubility and delayed in vitro APH release from the adsorbate in water and artificial gastric juice in comparison to the samples untreated drug and APH/Iglm physical mixture were established. It is hypothesized that the glass decomposition products, formed into contact with a solvent, initiate interactions with APH at the glass/solution interface. Similar behaviour of the Igl and its drug adsorbates could be expected in gastro-intestinal tract.

  4. 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.

  5. 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

  6. 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.

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

    PubMed

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

    2015-05-19

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

  8. Surface Chemistry in Electrochemical Atomic Layer Processing

    DTIC Science & Technology

    2007-11-02

    example, where a thin film of a material is formed an atomic layer at a time. That is, surface limited reactions are used to deposit individual atomic...The present studies were designed to investigate these surface limited reactions. To determine what the structures of the deposits were, and how that structure influenced subsequent deposition .

  9. Longitudinal vortices in concave surface boundary layer

    NASA Astrophysics Data System (ADS)

    Crane, R. I.,; Winoto, S. H.

    1980-01-01

    Local measurements of mean and fluctuating velocity by laser anemometer were made inside the developing concave surface boundary layer in a free surface water channel at Reynolds numbers up to 16000. Concave surface radius was 3.5 times channel width and the ratio of spanwise mean boundary layer thickness to surface radius ranged between 0.03 and 0.11. Systems of longtitudinal vortices developed without artificial triggering. Vortex wavelength varied across the span by as much as a factor of 2, but mean wavelength was typically 1.3 times the boundary layer thickness and did not vary significantly in the flow direction. Continuous vortex growth at Reynolds number = 9800 contrasted with apparent breakup of the vortices at Reynolds number = 16000.

  10. Chemical effects on vibrational properties of adsorbed molecules on metal surfaces: Coverage dependence

    NASA Astrophysics Data System (ADS)

    Ueba, H.

    1987-10-01

    Vibrational properties of chemisorbed molecules on metal surfaces are studied with a focus on the coverage dependent chemical shift of the frequencies. Available experimental data of a CO adsorption on transition metal and noble metal surfaces are analyzed in the light of the coverage dependent back-donation into the 2 π* orbitals of chemisorbed CO molecules. The vibrational frequency ωCO of the intramolecular stretching mode exhibits a downward shift of varying magnitude, depending on the amount of back-donation into the 2 π* orbitals of the chemisorbed CO. On increasing the coverage θ, ωCO usually increases due to the dipole-dipole interaction. On Cu surfaces, however, the shifts are relatively small, or in some cases, negative. So far, this anomalous frequency shift with θ is understood as a result of competitive effect between the upward dipole Ωdip and the downward chemical shift Ωchem associated with back-donation. The purpose of this paper is to establish the possible origin of the downward frequency shift through the electronic properties of an incomplete monolayer of adsorbates. The adsorbate density of states ρa is calculated by means of the coherent potential approximation, in which the electron hopping between the adsorbates (band formation effect) and the depolarization effect due to the proximity of ionized adsorbed molecules are taken into account. The change of the occupied portion of ρa and ρa ( ɛF) at the Fermi level ɛF with increasing θ then manifests itself in the coverage dependent Ωchem not only due to the static back-donation, but also due to the dynamical charge fluctuation during vibrational excitation. It is found that in a weakly chemisorbed system, such as CO/Cu, the negative Ωchem amounts to Ωdip at low θ. Consequently the apparent total frequency shift remains almost constant. As the coverage increases, Ωchem becomes larger than Ωdip due to the band effect. It is also shown that the variation of the back

  11. 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.

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

    PubMed

    Wright, Louise B; Walsh, Tiffany R

    2013-04-07

    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.

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed

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

    2013-01-01

    Finding appropriate systems with a large spin splitting of metallic surface-state band which can be fabricated on silicon using routine technique is an essential step in combining Rashba-effect based spintronics with silicon technology. We have found that originally poor structural and electronic properties of the Au/Si(111) √3 x √3 surface can be substantially improved by adsorbing small amounts of suitable species (e.g., Tl, In, Na, Cs). The resultant surfaces exhibit a highly-ordered atomic structure and spin-split metallic surface-state band with a momentum splitting of up to 0.052 Å(-1) and an energy splitting of up to 190 meV at the Fermi level. The family of adsorbate-modified Au/Si(111) √3 x √3 surfaces, on the one hand, is thought to be a fascinating playground for exploring spin-splitting effects in the metal monolayers on a semiconductor and, on the other hand, expands greatly the list of material systems prospective for spintronics applications.

  16. Infrared spectral investigations of UV irradiated nucleobases adsorbed on mineral surfaces

    NASA Astrophysics Data System (ADS)

    Fornaro, Teresa; Brucato, John Robert; Pace, Emanuele; Guidi, Mariangela Cestelli; Branciamore, Sergio; Pucci, Amaranta

    2013-09-01

    The interaction between electromagnetic radiation and bio-molecules in heterogeneous environments is a prebiotically relevant process. Minerals may have a pivotal role in the prebiotic evolution of complex chemical systems, mediating the effects of electromagnetic radiation, influencing the photostability of bio-molecules, catalyzing important chemical reactions and/or protecting molecules against degradation. In particular, nucleobases are relevant bio-molecules to investigate both in the prebiotic context, because they are coding components of nucleic acids, and from the standpoint of the survival of biological systems in space conditions. Several studies on the photodynamics of nucleobases suggest that their structure could have been naturally selected for the ability to dissipate electronic energy through ultrafast photophysical decay. Considering the putative involvement of minerals in the prebiotic chemistry, it is necessary to study the photostability of nucleobases under space conditions in the presence of mineral matrices, to investigate both the prebiotic processes that might have had a role in the development of the first living entities on Earth and the physical and chemical processes occurring in extraterrestrial environments. We focused our study on the characterization of the nature of the interaction between nucleobases and the surface of the minerals magnesium oxide and forsterite by infrared vibrational spectroscopy. We observed that most of the characteristic bands of pure nucleobases vanished when adsorbed on magnesium oxide. On the contrary, in the case of adenine and uracil adsorbed on forsterite, very intense nucleobase absorption peaks appeared. This phenomenon pertains to the surface selection rules changes related to molecular orientation. Moreover, based on the vibrational shifts, we deduced the molecular interaction sites with the mineral surfaces. Furthermore, we investigated the photostability of nucleobases adsorbed on such minerals

  17. Three-dimensional hierarchical flower-like Mg-Al-layered double hydroxides: highly efficient adsorbents for As(v) and Cr(vi) removal

    NASA Astrophysics Data System (ADS)

    Yu, Xin-Yao; Luo, Tao; Jia, Yong; Xu, Ren-Xia; Gao, Chao; Zhang, Yong-Xing; Liu, Jin-Huai; Huang, Xing-Jiu

    2012-05-01

    3D hierarchical flower-like Mg-Al-layered double hydroxides (Mg-Al-LDHs) were synthesized by a simple solvothermal method in a mixed solution of ethylene glycol (EG) and water. The formation mechanism of the flower-like Mg-Al-LDHs was proposed. After calcination, the flower-like morphology could be completely preserved. With relatively high specific surface areas, Mg-Al-LDHs and calcined Mg-Al-LDHs with 3D hierarchical nanostructures were tested for their application in water purification. When tested as adsorbents in As(v) and Cr(vi) removal, the as-prepared calcined Mg-Al-LDHs showed excellent performance, and the adsorption capacities of calcined Mg-Al-LDHs for As(v) and Cr(vi) were better than those of Mg-Al-LDHs. The adsorption isotherms, kinetics and mechanisms for As(v) and Cr(vi) onto calcined Mg-Al-LDHs were also investigated. The high uptake capability of the as-prepared novel 3D hierarchical calcined Mg-Al-LDHs make it a potentially attractive adsorbent in water purification. Also, this facile strategy may be extended to synthesize other LDHs with 3D hierarchical nanostructures, which may find many other applications due to their novel structural features.3D hierarchical flower-like Mg-Al-layered double hydroxides (Mg-Al-LDHs) were synthesized by a simple solvothermal method in a mixed solution of ethylene glycol (EG) and water. The formation mechanism of the flower-like Mg-Al-LDHs was proposed. After calcination, the flower-like morphology could be completely preserved. With relatively high specific surface areas, Mg-Al-LDHs and calcined Mg-Al-LDHs with 3D hierarchical nanostructures were tested for their application in water purification. When tested as adsorbents in As(v) and Cr(vi) removal, the as-prepared calcined Mg-Al-LDHs showed excellent performance, and the adsorption capacities of calcined Mg-Al-LDHs for As(v) and Cr(vi) were better than those of Mg-Al-LDHs. The adsorption isotherms, kinetics and mechanisms for As(v) and Cr(vi) onto calcined

  18. Topical Meeting on Microphysics of Surfaces, Beams and Adsorbates held at Santa Fe, New Mexico on 4 - 6 February 1985

    NASA Astrophysics Data System (ADS)

    Quinn, J. W.

    1985-12-01

    The Topical Meeting on Microphysics of Surfaces, Beams, and Adsorbates was organized within the interdisciplinary area of molecule/surface interactions induced, or studied, by laser and ion beam techniques. Especially emphasized was the molecular physics and electromagnetism of beam activated chemical reactions for applications in fabrication of semiconductor devices, in photocatalysis, and in optical recording. Emphasis was on the laser spectroscopy of molecular collision and reaction processes on surfaces, new sensitive or high resolution spectroscopies for studies of adsorbates, and optical methods applied to surface characterization.

  19. Infrared spectral investigations of UV irradiated nucleobases adsorbed on mineral surfaces

    NASA Astrophysics Data System (ADS)

    Brucato, J. R.; Fornaro, T.

    2014-04-01

    Spectroscopic studies of the effects of UV radiation on biomolecules such as nucleobases in heterogeneous environments are particularly relevant in prebiotic chemistry to unravel the role of minerals in the transformation/preservation of biomolecules in abiotic environments. Minerals may have a pivotal role in the prebiotic evolution of complex chemical systems, mediating the effects of electromagnetic radiation, influencing the photostability of biomolecules, catalyzing important chemical reactions and/or protecting molecules against degradation. Studies on the photodegradation of biomolecules adsorbed on minerals have applications also in the life detection context to identify potential biomarkers for future space mission and hence to develop suitable sample-extraction protocols for bioanalytical instruments [1]. Moreover, the characterization of the spectroscopic features of biomolecules-mineral complexes provides a support in remote sensing spectroscopy for detecting organic compounds on planetary surfaces or cometary grains and asteroid surfaces. In this context we will present laboratory results on UV photostability of nucleobases adsorbed on magnesium oxide and forsterite minerals and analysed with infrared spectroscopic [2,3].

  20. ``QM/Me'' - a novel embedding approach for adsorbate dynamics on metal surfaces

    NASA Astrophysics Data System (ADS)

    Meyer, Jörg; Reuter, Karsten

    2010-03-01

    The dissociative adsorption of oxygen molecules on metal surfaces is a commonly known, highly exothermic reaction and in its slow or fast form of great importance for corrosion or oxidation catalysis, respectively. However, knowledge about atomistic details of the heat dissipation, a central conceptual concern, is very limited at best. Even on the level of Born-Oppenheimer potential energy surfaces, accurate dynamical ab-initio descriptions of such reactions are quite challenging from a computational point of view: Modeling the excitations of substrate phonons within periodic boundary conditions requires huge supercells, whereas traditional ``QM/MM'' embedding schemes would need unfeasibly large metal clusters. In the novel ``QM/Me'' approach presented here, the adsorbate- interaction is obtained from periodic first-principles calculations in convenient supercells and combined with the description of a 'bath-like' substrate based on classical potentials, which are parametrized to seamlessly fit the first-principles data. We apply our approach to the dissociative adsorption of O2 and H2 on Pd(100) using density-functional theory and a modified embedded atom potential. In both cases, a dominant fraction of the released chemisorption energy is dissipated into the bulk already on a femtosecond time scale. Implications for the adsorbate dynamics will be discussed.

  1. Classical dynamics of adsorbate-surface systems: Application to nonthermal desorption

    NASA Astrophysics Data System (ADS)

    Dzegilenko, Fedor; Herbst, Eric

    1994-06-01

    The classical trajectory approach has been used to study the nonthermal desorption of CO from a variety of model surfaces to which it is weakly adsorbed. In addition to three degrees of freedom for the CO adsorbate (bond stretching, physisorption, libration), a significant number of lattice degrees of freedom have been included using the generalized Langevin approximation. Nonthermal amounts of energy have been put into both the CO stretching and librational modes at t=0. We find that for initial values of the stretching quantum number vstr=0-10, desorption does not take place at all within 12.5 ps unless there is also significant librational excitation. The detailed mechanism by which librational energy causes desorption is discussed. The role of the surface is also explored; we find that the probability of desorption is a nonmonotonic function of the Debye frequency of the solid in the range 28-915 cm-1, and is larger for lattices with either ``high'' or ``low'' Debye frequencies than for lattices with ``intermediate'' Debye frequencies. This result is partially explained in terms of resonances between low frequency libration and physisorption modes and high frequency phonon modes.

  2. 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.

  3. 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

  4. 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.

  5. Adsorption of aliphatic, alicyclic, and aromatic hydrocarbons on poly(ethylvinylbenzene-divinylbenzene) adsorbent at from effective zero to finite adsorbate surface coverage

    SciTech Connect

    Djordjevic, N.M.; Laub, R.J.; Kopecni, M.M.; Milonjic, S.K.

    1986-06-01

    The solid/gas partition coefficients, K/sub s/, and related thermodynamic properties of a number of hydrocarbon adsorbates at effective zero surface coverage on commercial samples of the title adsorbent, Porapak Q, were measured over the temperature range 293-443 K. The enthalpies of adsorption derived from the averaged absolute K/sub s/ gave incremental ..delta..H/sub s//sup 0/ of -7.5 kJ mol/sup -1/ for aliphatic and alicyclic -CH/sub 2/-, as well as aromatic -CH=, and -12 kJ mol/sup -1/ for -CH/sub 3/, while the differential entropies calculated in terms of translational motions were found to predict correctly the trends observed in the experimental ..delta..S/sub s//sup 0/. The technique of elution by characteristic point (ECP) was then used to derive the finite concentration adsorption isotherms and isosteric heats of adsorption of n-hexane, n-heptane, cyclohexane, benzene, carbon tetrachloride, and acetone at fractional adsorbate pressures, p/p/sup 0/, of no greater than 10/sup -2/ on a particular sample of the title absorbent at 20/sup 0/ intervals over the temperature range 413-493 K.

  6. 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.

  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. β-Cristobalite (001) surface as 4-formaminoantipyrine adsorbent: First principle study of the effect on adsorption of surface modification.

    PubMed

    Simonetti, S; Compañy, A Díaz; Brizuela, G; Juan, A

    2016-12-01

    Silica based materials find applications as excipients and particularly as drug delivery agents for pharmaceutical drugs. Their performance can be crucially affected by surface treatments, as it can modify the adsorption (and release) of these formulations. The role of surface modification on the features of 4-formaminoantipyrine (FAA) adsorbed on β-cristobalite (001) surface is studied by means of simulations based on the Density Functional Theory (DFT). Starting from the results of FAA in interaction with a dehydroxylated surface; a fully hydroxylated surface and a functionalized surface with benzalkonium chloride (BC) surfactant have been added to study the configurational landscape. Calculations suggest that the trend for FAA preferential adsorption on silica surfaces is: dehydroxylated>hydroxylated>BC-functionalized. The potential for hydrogen bonding causes the main contribution to the bonding while dispersion forces present an additional contribution independently of whether the drug is hydrogen-bonded or BC-bonded to the surface. Adsorption takes mainly place through nitrogen atoms in the heterocyclic ring, the carbonyl and amine functional groups. Associated mode's shifts and concurrent changes in bond length are also observed showing accordance between electronic and geometrical structure results. BC surfactant reduces the number of formed H-bonds and lowers the attractive molecule-surface interaction being it useful to prevent particle agglomeration and could favor drug release in therapies that requires faster but controlled delivery.

  9. Surface enhanced Raman scattering of pyridine adsorbed on Au@Pd core/shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Yang, Zhilin; Li, Yan; Li, Zhipeng; Wu, Deyin; Kang, Junyong; Xu, Hongxing; Sun, Mengtao

    2009-06-01

    Surface enhanced Raman scattering (SERS) of pyridine adsorbed on Au@Pd core/shell nanoparticles has been investigated theoretically with quantum chemical method, generalized Mie theory and three-dimensional finite-difference time domain (3D-FDTD) method. We first studied the influence of the coated Pd on the electronic structure of Au nanoparticle, and compared the electronic structure of Au20 cluster with that of Au10Pd10 (core/shell) cluster. Second, we studied SERS spectroscopy of pyridine on Au@Pd core/shell nanoparticles, which revealed the rate of static chemical enhancement and electromagnetic enhancement in the experimental reports. Third, the influence of the Pd shell thickness to the optical absorption of Au@Pd core/shell nanoparticles was investigated with generalized Mie theory. Fourth, we studied the influence of the shell thickness to the local electric field enhancement with 3D-FDTD method. The theoretical results reveal that the static chemical enhancement and electromagnetic enhancement are in the order of 10 and 103, respectively. These theoretical studies promote the deeper understanding of the electronic structure and optical absorption properties of Au@Pd, and the mechanisms for SERS of molecule adsorbed on Au@Pd.

  10. 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.

  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. Impacts of surface adsorbed catechol on tropospheric aerosol surrogates: heterogeneous ozonolysis and its effects on water uptake.

    PubMed

    Woodill, Laurie A; O'Neill, Erinn M; Hinrichs, Ryan Z

    2013-07-11

    Surface adsorbed organics are ubiquitous components of inorganic tropospheric aerosols and have the potential to alter aerosol chemical and physical properties. To assess the impact of adsorbed organics on water uptake by inorganic substrates, we used diffuse reflectance infrared spectroscopy to compared water adsorption isotherms for uncoated NaCl and α-Al2O3 samples, samples containing a monolayer of adsorbed catechol, and adsorbed catechol samples following ozonolysis. Adsorption of gaseous catechol on to the inorganic substrates produced vibrational features indicating physisorption on NaCl and displacement of surface hydroxyl groups forming binuclear bidentate catecholate on α-Al2O3, with surface concentrations of 2-3 × 10(18) molecules m(-2). Subsequent heterogeneous ozonolysis produced muconic acid at a rate 4-5 times faster on NaCl compared to α-Al2O3, with predicted atmospheric lifetimes of 4.3 and 18 h, respectively, assuming a tropospheric ozone concentration of 40 ppb. Water adsorption isotherms for all NaCl samples were indistinguishable within experimental uncertainty, indicating that these organic monolayers had negligible impact on coadsorbed water surface concentrations for these systems. α-Al2O3-catechol samples exhibited dramatically less water uptake compared to uncoated α-Al2O3, while oxidation of surface adsorbed catechol had no effect on the extent of water uptake. For both substrates, adsorbed organics increased the relative abundance of "ice-like" versus "liquid-like" water, with the effect larger for catechol than oxidized ozonolysis products. These results highlight the importance of aerosol substrate in understanding the heterogeneous ozonolysis of adsorbed polyphenols and suggest such coatings may impair ice nucleation by aluminosilicate mineral aerosol.

  13. Surface packing determines the redox potential shift of cytochrome c adsorbed on gold.

    PubMed

    Zanetti-Polzi, Laura; Daidone, Isabella; Bortolotti, Carlo Augusto; Corni, Stefano

    2014-09-17

    Thermodynamic and dynamic properties of iso-1-cytochrome c covalently bound to a bare gold surface are here investigated by large scale atomistic simulations. The reduction potential of the protein for low and high surface concentrations is calculated showing a good agreement with experimental estimates. The origin of the dependence of the reduction potential on the surface concentration is investigated and is demonstrated to stem from the changing polarizability of the environment surrounding the protein, a mechanism reminiscent of crowding effects. Moreover, structural analyses are performed revealing relevant changes induced by the presence of the electrode on the dynamic properties of cytochrome c. In particular, one of the two cavities previously identified on the protein surface [Bortolotti et al. J. Am. Chem. Soc., 2012, 134, 13670], and that reversibly open in cytochrome c freely diffusing in solution, is found to be deformed when the protein is adsorbed on gold. This modification exemplifies a mechanism that potentially leads to changes in the protein properties by surface-induced modification of its dynamical behavior.

  14. 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.

  15. Oscillating electric-field effects on adsorbed-water at rutile- and anatase-TiO2 surfaces

    NASA Astrophysics Data System (ADS)

    Futera, Zdenek; English, Niall J.

    2016-11-01

    We have performed non-equilibrium molecular dynamics simulations of various TiO2/water interfaces at ambient temperature in presence of oscillating electric fields in frequency range 20-100 GHz and RMS intensities 0.05-0.25 V/Å. Although the externally applied fields are by one order of magnitude lower than the intrinsic electric field present on the interfaces (˜1.5-4.5 V/Å), significant non-thermal coupling of rotational and translational motion of water molecules was clearly observed. Enhancement of the motion, manifested by increase of diffusivity, was detected in the first hydration layer, which is known to be heavily confined by adsorption to the TiO2 surface. Interestingly, the diffusivity increases more rapidly on anatase than on rutile facets where the adsorbed water was found to be more organized and restrained. We observed that the applied oscillating field reduces number of hydrogen bonds on the interface. The remaining H-bonds are weaker than those detected under zero-field conditions; however, their lifetime increases on most of the surfaces when the low-frequency fields are applied. Reduction of adsorption interaction was observed also in IR spectra of interfacial water where the directional patterns are smeared as the intensities of applied fields increase.

  16. 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.

  17. 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.

  18. 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.

  19. Pseudo Order Kinetics Model to Predict the Adsorption Interaction of Corn-Stalk Adsorbent Surface with Metal Ion Adsorbate Cu (II) and Fe (II)

    NASA Astrophysics Data System (ADS)

    Haryanto, B.; Singh, W. B.; Barus, E. S.; Ridho, A.; Rawa, M. R.

    2017-01-01

    The adsorption process using cornstalk as adsorbent was used to remove the single metal ion such as copper ion and cadmium ion. The adsorption kinetics of each contaminant then used to predict the interaction type of metal ion on surface of corn stalk by calculating pseudo order 1st and 2nd. The identification type as chemically or physically interaction was predicted from the quality of r2 by plotting the adsorption capacity (q) and time (t). The r2 were 0.01 and 0.99 for pseudo order 1st and 2nd respectively for Fe (II). The r2 were 0.26 and 0.999 for pseudo order 1st and 2nd respectively for Cu (II). The result of adsorption interaction of metal ion and surface function of corn stalk is chemical type. SEM/EDX confirmed the Cu2+ presence on cornstalk surface.

  20. 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.

  1. Self-avoiding walks adsorbed at a surface and pulled at their mid-point

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

    We consider a self-avoiding walk on the d-dimensional hypercubic lattice, terminally attached to an impenetrable hyperplane at which it can adsorb. When a force is applied the walk can be pulled off the surface and we consider the situation where the force is applied at the middle vertex of the walk. We show that the temperature dependence of the critical force required for desorption differs from the corresponding value when the force is applied at the end-point of the walk. This is of interest in single molecule pulling experiments since it shows that the required force can depend on where the force is applied. We also briefly consider the situation when the force is applied at other interior vertices of the walk.

  2. Redox kinetics of adriamycin adsorbed on the surface of graphite and mercury electrodes.

    PubMed

    Komorsky-Lovrić, Sebojka

    2006-09-01

    Kinetics of the surface redox reactions of adriamycin (doxorubicin hydrochloride) adsorbed on paraffin-impregnated graphite electrode (PIGE) and on mercury electrode is measured by square-wave voltammetry. In 0.9 mol/L KNO3 buffered to pH 4.65, the standard electrode reaction rate constants of the first quinone/hydroquinone redox couple (see Scheme 2) on PIGE and mercury are k(s1)=49+/-12 s(-1) and k(s1)=147+/-36 s(-1), respectively. Under the same conditions, the standard rate constant of the second redox couple on the PIGE is smaller than 4 s(-1) and the electron transfer coefficient of the reduction is alpha2=0.35.

  3. Ultrafast photo-induced electron-transfer from coumarin dyes adsorbed on semiconductor nanoclusters surfaces

    SciTech Connect

    Castner, E.W. Jr.; Murakoshi, Kei; Yanagida, Shozo

    1997-12-31

    Photosensitizers adsorbed directly on semiconductor surfaces provide the basis for solar photoelectrochemical devices. Semiconductor nanoclusters in solution allow for simple preparation of the photosensitized surface, with very large surface area. To optimize the efficiency of the photoelectrochemical cycle, one must know the rates of forward and reverse electron-transfer from the excited state dye to the semiconductor conduction band. We present measurements of the ultrafast forward electron-transfer rates for three coumarin dyes (Coumarins 343, D-1421, and D-126) bound by the carboxylic acid group to the metal cationic sites of TiO{sub 2} and ZnO semiconductor nanocluster surfaces. These rates are obtained directly from the ultrafast fluorescence dynamics, measured using the femotosecond upconversion technique. Coumarins 343 and D-1421 on TiO{sub 2} nanoclusters in aqueous solution display very rapid forward electron-transfer with rate constants exceeding 10{sup 13} s{sup -1}. Substantially slower rates are observed for the same coumarin TiO{sub 2} systems in methanol solution.

  4. Helium diffraction from adsorbate-covered surfaces: A study of the O-Ni(001) system

    NASA Astrophysics Data System (ADS)

    Batra, Inder P.; Barker, J. A.

    1984-05-01

    Elastic helium-atom-surface scattering is currently being used to obtain important structural information from adsorbate-covered surfaces. Since our earlier work on helium diffraction from p(2×2) and c(2×2) phases of oxygen on Ni(001) there have been three new developments. These are (i) the suggestion by Rieder of a prolate charge distribution on oxygen, (ii) the pseudobridge site proposal of Demuth et al., and (iii) the self-consistent calculation of the helium-surface interaction potential due to Lang and Nørskov. In this paper we present results for a wide range of calculational parameters for the c(2×2) phase of oxygen on Ni(001) and comment on the above developments. Specifically, based on the results in (iii), we are able to explore the implications of the use of the Esbjerg-Nørskov-Lang relation with and without helium averaged surface-charge density. We conclude that the prolate charge distribution produces a shape function in better agreement with experiment. Changes in corrugation coefficients introduced by shifting to the pseudobridge site from the centered site are noted to be small.

  5. Positron States at Li- and O-adsorbed Fe(001) Ferromagnetic Surfaces Studied by Two-Component Density Functional Theory

    NASA Astrophysics Data System (ADS)

    Hagiwara, Satoshi; Watanabe, Kazuyuki

    2016-11-01

    The positron states for Li- and O-adsorbed Fe(001) ferromagnetic surfaces are studied by using two-component density functional theory. Positron surface lifetimes and positron binding energies are found to be sensitive to changes in the surface structure and the dipole barrier induced by adatoms, which can be understood by the positron density distribution and surface potential. Spin-dependent positron lifetime fractions are in excellent agreement with spin-polarization fractions at the topmost surface, because the localized positrons at the surface are sensitive to the surface magnetic state. Therefore, the present results show that spin-polarized positron annihilation spectroscopy can extract the outermost surface magnetic state.

  6. Microthermal Instrument for Measuring Surface Layer Seeing

    NASA Astrophysics Data System (ADS)

    Li, Xue-Bao; Zheng, Yan-Fang; Deng, Lin Hua; Xu, Guang

    2012-02-01

    Microthermal fluctuations are introduced by atmospheric turbulence very near the ground. In order to detect microthermal fluctuations at Fuxian Solar Observatory (FSO), a microthermal instrument has been developed. The microthermal instrument consists of a microthermal sensor, which is based on a Wheatstone bridge circuit and uses fine tungsten filaments as resistance temperature detectors, an associated signal processing unit, and a data collection, & communication subsystem. In this paper, after a brief introduction to surface layer seeing, we discuss the instrumentation behind the microthermal detector we have developed and then present the results obtained. The results of the evaluation indicate that the effect of the turbulent surface boundary layer to astronomical seeing would become sufficiently small when installing a telescope at a height of 16m or higher from the ground at FSO.

  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. Dynamic air layer on textured superhydrophobic surfaces.

    PubMed

    Vakarelski, Ivan U; Chan, Derek Y C; Marston, Jeremy O; Thoroddsen, Sigurdur T

    2013-09-03

    We provide an experimental demonstration that a novel macroscopic, dynamic continuous air layer or plastron can be sustained indefinitely on textured superhydrophobic surfaces in air-supersaturated water by a natural gas influx mechanism. This type of plastron is an intermediate state between Leidenfrost vapor layers on superheated surfaces and the equilibrium Cassie-Baxter wetting state on textured superhydrophobic surfaces. We show that such a plastron can be sustained on the surface of a centimeter-sized superhydrophobic sphere immersed in heated water and variations of its dynamic behavior with air saturation of the water can be regulated by rapid changes of the water temperature. The simple experimental setup allows for quantification of the air flux into the plastron and identification of the air transport model of the plastron growth. Both the observed growth dynamics of such plastrons and millimeter-sized air bubbles seeded on the hydrophilic surface under identical air-supersaturated solution conditions are consistent with the predictions of a well-mixed gas transport model.

  9. 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.

  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. Electron Scattering at Surfaces of Epitaxial Metal Layers

    NASA Astrophysics Data System (ADS)

    Chawla, Jasmeet Singh

    and without thin epitaxial TiN(001) wetting layers and are studied for structure, crystalline quality, surface morphology, density and composition by a combination of x-ray diffraction theta-2theta scans, o-rocking curves, pole figures, reciprocal space mapping, Rutherford backscattering, x-ray reflectometry and transmission electron microscopy. The TiN(001) surface suppresses Cu and Ag dewetting, yielding lower defect density, no twinning, and smaller surface roughness than if grown on MgO(001). Textured polycrystalline Cu(111) layers 25-50-nm-thick are deposited on a stack of 7.5-nm-Ta on SiO2/Si(001), and subsequent in situ annealing at 350°C followed by sputter etching in Ar plasma yields Cu layers with independently variable thickness and grain size. Cu nanowires, 75 to 350 nm wide, are fabricated from Cu layers with different average grain size using a subtractive patterning process. In situ electron transport measurements at room temperature in vacuum and at 77 K in liquid nitrogen for single-crystal Cu and Ag layers is consistent with the Fuchs-Sondheimer (FS) model and indicates specular scattering at the metal-vacuum boundary with an average specularity parameter p = 0.8 and 0.6, respectively. In contrast, layers measured ex situ show diffuse surface scattering due to sub-monolayer oxidation. Also, addition of Ta atoms on Cu(001) surface perturbs the smooth interface potential and results in completely diffuse scattering at the Cu-Ta interface, and in turn, a higher resistivity of single-crystal Cu layers. In situ exposure of Cu(001) layers to O2 between 10 -3 and 105 Pa-s results in a sequential increase, decrease and increase of the electrical resistance which is attributed to specular surface scattering for clean Cu(001) and for surfaces with a complete adsorbed monolayer, but diffuse scattering at partial coverage and after chemical oxidation. Electron transport measurements for polycrystalline Cu layers and wires show a 10-15% and 7-9% decrease in

  12. Infrared-Laser Excitation of the Internal Vibrational Mode of a Diatomic Molecule Adsorbed on a Metal Surface.

    DTIC Science & Technology

    1986-11-01

    Excitation of the Internal Vibrational Mode of a Diatomic Molecule Adsorbed on a Metal Surface m by ’ Andre Peremans, Jacques Darville , Jean-Marie...Andre Peremans, Jacques Darville , Jean-Marie Gilles and Thomas F. George 13. TYPE OF REPORT 13b. TIME COVERED 14. DATE OF REPORT (Yr. Mo.. Dayl As...ON A METAL SURFACE h Andr& Peremans , Jacques Darville and Jean-Marie Gilles _ _ _ _ Laboratoire de Spectroscopie Mol6culaire de Surface Accesnion

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

    NASA Astrophysics Data System (ADS)

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

    1998-09-01

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

  14. Adsorbed poly(ethyleneoxide)-poly(propyleneoxide) copolymers on synthetic surfaces: spectroscopy and microscopy of polymer structures and effects on adhesion of skin-borne bacteria.

    PubMed

    Marsh, Lorraine H; Coke, Mark; Dettmar, Peter W; Ewen, Richard J; Havler, Michael; Nevell, Thomas G; Smart, John D; Smith, James R; Timmins, Barry; Tsibouklis, John; Alexander, Cameron

    2002-09-15

    Poly(ethyleneoxide)-copoly(propyleneoxide) (PEO-PPO) polymer coatings were evaluated for their resistance to the attachment of the marker organism Serratia marcescens and the skin-borne bacteria Staphylococcus epidermidis. The copolymers were adsorbed onto poly(styrene) films-chosen as simplified physicochemical models of skin surfaces-and their surface characteristics probed by contact angle goniometry, attenuated total reflectance-Fourier transform infrared (ATR-FTIR), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). These functional surfaces were then presented to microbial cultures, bacterial attachment was assessed by fluorescence microscopy and AFM, and the structures of the polymer films examined again spectroscopically. Surface characterization data suggest that the adsorbed copolymer was partially retained at the surface and resisted bacterial attachment for 24 h. Quantitative evaluation of cell attachment was carried out by scintillation counting of (14)C-labeled microorganisms in conjunction with plate counts. The results show that a densely packed layer of PEO-PPO copolymer can reduce attachment of skin commensals by an order of magnitude, even when the coating is applied by a simple adsorptive process. The work supports the hypothesis that adhesion of microorganisms to biological substrates can be reduced if a pretreatment with an appropriate copolymer can be effected in vivo.

  15. Modeling of transmittance degradation caused by optical surface contamination by atomic oxygen reaction with adsorbed silicones

    NASA Astrophysics Data System (ADS)

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

    2000-09-01

    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 silicon producing SiOx (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.

  16. 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.

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

    NASA Astrophysics Data System (ADS)

    Uchihashi, Takashi

    2015-08-01

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

  18. 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.

  19. Surface-enhanced Raman scattering of Ethyl carbamate adsorbed on Ag20 cluster: Enhancement mechanism

    NASA Astrophysics Data System (ADS)

    Du, Junmei; Wang, Hongyan; Wang, Hui; Chen, Yuanzheng; Guo, Chunsheng; Gan, Liyong; Du, Muying

    2017-03-01

    The normal and surface-enhanced Raman scattering of EC are studied by using the M06-2X functional. Different contributions to Raman enhancements of EC adsorbed on Ag20 cluster are analyzed in detail to explore the enhancement mechanism. The adsorption of EC on Ag20 cluster involves the static chemical enhancement with enhancements factor (EF) of 10 by forming a new EC-Ag20 complex. The charge-transfer enhancement with EF of 104 is found when a 352 nm wavelength, corresponding to the absorption maximum of EC-Ag20 complex, is taken as an incident light. The electromagnetic enhancement EF of 3.6 × 106 due to the localized surface plasmon resonance (LSPR) of Ag nanosphere at the same excitation wavelength are acquired by the discrete dipole approximation (DDA) method. The combined effect of the chemical and electromagnetic enhancement results in the total relative enhancements factor up to 3.6 × 1010. The enhancement mechanisms are successfully explained by the combination of ab initio calculation and discrete dipole appropriation method.

  20. 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

  1. Surface-enhanced raman spectra and molecular orientation of phthalazine adsorbed on a silver electrode

    NASA Astrophysics Data System (ADS)

    Takahashi, Machiko; Fujita, Masato; Ito, Masatoki

    1984-08-01

    SERS from phthalazine adsorbed on an Ag electrode was investigated under several conditions of applied voltage and solution concentration. Spectral assignments of the Raman bands were successfully performed and two differently oriented adsorbates, i.e. flat and end-on species, were identified. The contribution of the image field to the SERS intensity was considerable.

  2. 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.

  3. 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.

  4. In situ UV-visible reflection absorption wavelength modulation spectroscopy of species irreversibly adsorbed on electrode surfaces

    SciTech Connect

    Kim, Sunghyun; Scherson, D.A. )

    1992-12-15

    A method is herein described for the in situ detection of species adsorbed on electrode surfaces which employs a vibrating grating to modulate the wavelength of the incident light. This technique denoted as reflection absorption wavelength modulation spectroscopy (RAWMS) has made it possible to obtain at a fixed electrode potential normalized, differential UV-visible spectra of a single, irreversibly adsorbed monolayer of cobalt tetrasulfonated phthalocyanine (Co[sup II]TsPc) on the basal plane of highly oriented pyrolytic graphite (HOPG(bp)) and of methylene blue (MB) on graphite. The (wavelength) integrated difference RAWMS spectra for these adsorbed species were remarkably similar to those observed for the same compounds in aqueous solutions when present in the monomeric form. Complementary wavelength modulation experiments involving a conventional transmission geometry have shown that the instrument involved in the in situ RAWMS measurements is capable of resolving absorbance changes on the order of 0.002 units. 20 refs.

  5. 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.

  6. 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.

  7. Effect of Amine Surface Coverage on the Co-Adsorption of CO2 and Water: Spectral Deconvolution of Adsorbed Species.

    PubMed

    Didas, Stephanie A; Sakwa-Novak, Miles A; Foo, Guo Shiou; Sievers, Carsten; Jones, Christopher W

    2014-12-04

    Three primary amine materials functionalized onto mesoporous silica with low, medium, and high surface amine coverages are prepared and evaluated for binary CO2/H2O adsorption under dilute conditions. Enhancement of amine efficiency due to humid adsorption is most pronounced for low surface amine coverage materials. In situ FT-IR spectra of adsorbed CO2 on these materials suggest this enhancement may be associated with the formation of bicarbonate species during adsorption on materials with low surface amine coverage, though such species are not observed on high surface coverage materials. On the materials with the lowest amine loading, bicarbonate is observed on longer time scales of adsorption, but only after spectral contributions from rapidly forming alkylammonium carbamate species are removed. This is the first time that direct evidence for bicarbonate formation, which is known to occur in liquid aqueous amine solutions, has been presented for CO2 adsorption on solid amine adsorbents.

  8. 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.

  9. 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.

  10. Electrochemical hydrogenation of a homogeneous nickel complex to form a surface adsorbed hydrogen-evolving species.

    PubMed

    Martin, Daniel J; McCarthy, Brian D; Donley, Carrie L; Dempsey, Jillian L

    2015-03-28

    A Ni(II) complex degrades electrochemically in the presence of acid in acetonitrile to form an electrode adsorbed film that catalytically evolves hydrogen. Comparison with a similar compound permitted investigation of the degradation mechanism.

  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. Light harvesting, energy transfer and electron cycling of a native photosynthetic membrane adsorbed onto a gold surface.

    PubMed

    Magis, Gerhard J; den Hollander, Mart-Jan; Onderwaater, Willem G; Olsen, John D; Hunter, C Neil; Aartsma, Thijs J; Frese, Raoul N

    2010-03-01

    Photosynthetic membranes comprise a network of light harvesting and reaction center pigment-protein complexes responsible for the primary photoconversion reactions: light absorption, energy transfer and electron cycling. The structural organization of membranes of the purple bacterial species Rb. sphaeroides has been elucidated in most detail by means of polarized light spectroscopy and atomic force microscopy. Here we report a functional characterization of native and untreated membranes of the same species adsorbed onto a gold surface. Employing fluorescence confocal spectroscopy and light-induced electrochemistry we show that adsorbed membranes maintain their energy and electron transferring functionality. Gold-adsorbed membranes are shown to generate a steady high photocurrent of 10 microA/cm(2) for several minutes and to maintain activity for up to three days while continuously illuminated. The surface-adsorbed membranes exhibit a remarkable functionality under aerobic conditions, even when exposed to light intensities well above that of direct solar irradiation. The component at the interface of light harvesting and electron cycling, the LH1 complex, displays exceptional stability, likely contributing to the robustness of the membranes. Peripheral light harvesting LH2 complexes show a light intensity dependent decoupling from photoconversion. LH2 can act as a reversible switch at low-light, an increased emitter at medium light and photobleaches at high light.

  14. Atomic Layer Epitaxy Group IV Materials: Surface Processes, Thin Films, Devices and Their Characterization

    DTIC Science & Technology

    1991-06-01

    carbide, SiH 2 Cb1, 14PRC CD adsorbtion , desorption 01.PIECD J7. S(CURITY CLASSI;ICATION 1S SECURITY C.AS’IfICAIION 19. SECURITY CLASSIFICATION 20...the hydrogen atoms break away from the molecule as the SiH 2 CI2 nears or is adsorbed onto the heated substrate and a monolayer of Si having a...terminating layer formed by the remaining chlorine atoms now resides on the Si surface. This molecular surface configuration now prevents the adsorbtion of

  15. 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.

  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. 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.

  18. 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.

  19. Sorption of organic molecules on surfaces of a microporous polymer adsorbent modified with different quantities of uracil

    NASA Astrophysics Data System (ADS)

    Gus'kov, V. Yu.; Ganieva, A. G.; Kudasheva, F. Kh.

    2016-11-01

    The sorption of organic molecules on the surfaces of a number of adsorbents based on a microporous copolymer of styrene and divinylbenzene modified with different quantities of uracil is studied by means of inverse gas chromatography at infinite dilution. Samples containing 10-6, 10-5, 10-4, 10-3, 10-2, and 0.5 × 10‒1 weight parts of uracil (the pC of uracil ranges from 1.3 to 6) are studied. The contributions from different intermolecular interactions to the Helmholtz energy of sorption are calculated via the linear free energy relationship. It is found that as the concentration of uracil on the surface of the polymer adsorbent grows, the contributions from different intermolecular interactions and the conventional polarity of the surface have a bend at pC = 3, due probably to the formation of a supramolecular structure of uracil. Based on the obtained results, it is concluded that the formation of the supramolecular structure of uracil on the surface of the polymer adsorbent starts when pC < 3.

  20. STM observation of the chemical reaction of atomic hydrogen on the N-adsorbed Cu(001) surface

    NASA Astrophysics Data System (ADS)

    Hattori, Takuma; Yamada, Masamichi; Komori, Fumio

    2017-01-01

    Chemical reaction of atomic hydrogen with the N-adsorbed Cu(001) surfaces was investigated at room temperature by scanning tunnel microscopy. At the low exposure of atomic hydrogen, it reacted with the N atoms and turned to be the NH species on the surface. The reaction rate is proportional to the amount of the unreacted N atoms. By increasing the exposure of atomic hydrogen from this condition, the amount of nitrogen species on the surface decreased. This is attributed to the formation of ammonia and its desorption from the surface. The NH species on the surface turn to NH3 through the surface NH2 species by atomic hydrogen. Coexistence of the clean Cu surface enhances the rate of ammonia formation owing to atomic hydrogen migrating on the clean surface.

  1. 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.

  2. Acoustic tomography in the atmospheric surface layer

    NASA Astrophysics Data System (ADS)

    Ziemann, A.; Arnold, K.; Raabe, A.

    1999-01-01

    Acoustic tomography is presented as a technique for remote monitoring of meteorological quantities. This method and a special algorithm of analysis can directly produce area-averaged values of meteorological parameters. As a result consistent data will be obtained for validation of numerical atmospheric micro-scale models. Such a measuring system can complement conventional point measurements over different surfaces. The procedure of acoustic tomography uses the horizontal propagation of sound waves in the atmospheric surface layer. Therefore, to provide a general overview of sound propagation under various atmospheric conditions a two-dimensional ray-tracing model according to a modified version of Snell's law is used. The state of the crossed atmosphere can be estimated from measurements of acoustic travel time between sources and receivers at different points. Derivation of area-averaged values of the sound speed and furthermore of air temperature results from the inversion of travel time values for all acoustic paths. Thereby, the applied straight ray two-dimensional tomographic model using SIRT (simultaneous iterative reconstruction technique) is characterised as a method with small computational requirements, satisfactory convergence and stability properties as well as simple handling, especially, during online evaluation.

  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. 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

  5. Hydrogen Bonding Controls the Dynamics of Catechol Adsorbed on a TiO2(110) Surface

    NASA Astrophysics Data System (ADS)

    Diebold, Ulrike; Li, Shao-Chun; Chu, Li-Na; Gong, Xue-Qing

    2011-03-01

    Direct studies of how organic molecules diffuse on metal oxide surfaces can provide insights into catalysis and molecular assembly processes. We studied individual catechol molecules, C6 H4 (OH)2 , on a rutile Ti O2 (110) surface with scanning tunnelingmicroscopy. Surface hydroxyls enhanced the diffusivity of adsorbed catecholates. The capture and release of a proton caused individual molecules to switch between mobile and immobile states within a measurement period of minutes. Density functional theory calculations showed that the transfer of hydrogen from surface hydroxyls to the molecule and its interaction with surface hydroxyls substantially lowered the activation barrier for rotational motion across the surface. Hydrogen bonding can play an essential role in the initial stages of the dynamics of molecular assembly.

  6. 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.

  7. Study of interface formation on the cleavage surfaces of A3{B}6 layered semiconductors

    NASA Astrophysics Data System (ADS)

    Galiy, P. V.; Nenchuk, T. M.; Stakhira, J. M.

    2001-01-01

    The adsorption activity of In4Se3, In4Se3(Ag), InSe, GaSe and TlGaSe2 semiconductor crystal interlayer cleavage surfaces relatively to N2, O2, CO gases and water vapour has been studied by Auger electron spectroscopy and mass spectrometry. It has been determined that atomically clean layered crystal surfaces do not adsorb N2 and water vapour but reveal a low activity with respect to O2. The kinetics of CO adsorption on surfaces obtained by cleavage in an UHV have been investigated. Indium and gallium selenides adsorb CO with the tendency increasing in the sequence GaSe→TlGaSe2→ InSe→In4Se3 crystals; In4Se3 is essentially more active than the others. The adsorption model with dissociations of the CO molecule and carbon adsorption resulting from the layered structure and peculiarities in the electron-energy spectra of the crystals and their surfaces is discussed with the In4Se3 crystal serving as example.

  8. Derivatization and fluorescence detection of amino acids and peptides with 9-fluorenylmethyl chloroformate on the surface of a solid adsorbent.

    PubMed

    Shangguan, D; Zhao, Y; Han, H; Zhao, R; Liu, G

    2001-05-01

    An approach that exploits the surface of a solid adsorbent is proposed for precolumn FMOC derivatization of amino acids and peptides. Amino acids (Ser, Glu, GABA, Val, Phe, Lys) and two neuropeptides (substance P and Leuenkephalin) were adsorbed on alkaline silica gel cartridges. After drying, they were reacted with 9-fluorenyl-methyl chloroformate (FMOC-Cl) in toluene. After washing off the excess FMOC-Cl with ethyl acetate, the derivatives were eluted with aqueous eluant. The eluates were separated and detected by means of HPLC with fluorescence detection. Compared with the traditional derivatization in the liquid phase, the extent of formation of byproducts of FMOC-Cl with water was greatly decreased, and the excess FMOC-Cl was eliminated completely.

  9. 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

    2009-02-04

    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).

  10. Optimization of operating parameters of novel composite adsorbent for organic pollutants removal from POME using response surface methodology.

    PubMed

    Adeleke, A O; Latiff, Ab Aziz Ab; Al-Gheethi, A A; Daud, Zawawi

    2017-05-01

    The present work aimed to develop a novel composite material made up of activated cow bone powder (CBP) as a starting material for reducing chemical oxygen demand (COD) and ammonia-nitrogen (NH3N) from palm oil mill effluent (POME). The optimization of the reduction efficiency was investigated using response surface methodology (RSM). Six independent variables used in the optimization experiments include pH (4-10), speed (0.27-9.66 rcf), contact time (2-24 h), particle size (1-4.35 mm), dilution factor (100-500) and adsorbent dosage (65-125 g/L). The chemical functional groups were determined using Fourier transform irradiation (FTIR). The elemental composition were detected using SEM-EDX, while thermal decomposition was investigated using thermo gravimetric analysis (TGA) in order to determine the effects of carbonization temperature on the adsorbent. The results revealed that the optimal reduction of COD and NH3N from raw POME was observed at pH 10, 50 rpm, within 2 h and 3 mm of particle size as well as at dilution factor of 500 and 125 g L(-1) of adsorbent dosage, the observed and predicted reduction were 89.60 vs. 85.01 and 75.61 vs. 74.04%, respectively for COD and NH3N. The main functional groups in the adsorbent were OH, NH, CO, CC, COC, COH, and CH. The SEM-EDX analysis revealed that the CBP-composite has a smooth surface with high contents of carbon. The activated CBP has very stable temperature profile with no significant weight loss (9.85%). In conclusion, the CBP-composite investigated here has characteristics high potential for the remediation of COD and NH3N from raw POME.

  11. The Lowest Atmosphere: Atmospheric Boundary Layer Including Atmospheric Surface Layer.

    DTIC Science & Technology

    1996-04-01

    troposphere" as a result of frictional forces. A good definition of the atmospheric boundary layer (ABL) (provided to me by the late Dr. Rudy...wind extends light flag. Raises dust and loose paper; small branches are moved. Small trees in leaf begin to sway; crested wavelets form on inland...Calm. Sea like a mirror. Light air Ripples like scales, no foam crest. Light breeze Small wavelets ; crests have glassy appearance, do not break

  12. 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

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

    PubMed

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

    2014-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  15. Angular dependence of the electron energy loss spectra from a clean and adsorbate covered W(001) surface

    NASA Astrophysics Data System (ADS)

    Avery, N. R.

    1981-11-01

    A dispersion analysis of the EELS from a W(001) surface in the range 1 < ΔE < 35 eV has been performed and compared with recent and complete optical data for tungsten. The non-dispersive ( k ˜ 0) EELS correlated well with a combination of the surface and bulk loss functions calculated from the optical data. Losses at 1-5 eV and a pair at 32 and 34.5 eV were assigned to interband and N 6,7 core ionization excitations respectively. The principal bulk and surface plasmon losses were identified at 24.0 and 20.3 eV respectively. Two further losses at 14.0 and 9.6 eV were also observed and assigned to subsidiary plasmon losses. All four plasmon losses showed only minimal energy dispersion, never exceeding 1.5 eV. A momentum selectivity for separating bulk and surface interband losses was demonstrated with the non-dispersive losses arising from excitations within the bulk even with incident energies as low as 88 eV, whereas their dispersive counterparts were extremely sensitive to the chemical state of the surface. New adsorbate derived losses which develop during adsorption were associated with excitations from the new deep lying adsorbate levels to final state levels at or near the Fermi level. It was concluded that this final state was also responsible for the N 6,7 ionization losses.

  16. Study of IR laser photoacoustic spectra of organic molecules adsorbed on metal surface

    NASA Astrophysics Data System (ADS)

    Lu, Huizong; Chen, Kaitai; Wang, Zhaoyong

    1987-06-01

    Using a branch-tuning CW CO2 laser in the range of 0.2 to 10.8 microns, the IR photoacoustic spectra of organic molecules absorbed on a silver surface were studied. The absorbed molecular spectra of four layers of arachidic acid and cellulose diacetate with different surface densities was studied. No peak shift was found in a comparison between IR photoacoustic spectra of solid arachidic acid near 944/cm and the corresponding IR Fourier spectra of solid archidic acid. The IR photoacoustic spectra of cellulose diacetate with sigma sub 1 = 14,000/sq cm and sigma sub 1 = 5.5 x 10 to the 15th/sq cm respectively was compared with the corresponding transmission spectra of solid cellulose diacetate. It was found that the peak of the former near 1054/cm had a red shift of about 5/cm while the peak of the latter had no obvious shift within the range of accuracy of the experiment.

  17. Surface Photochemistry: 3,3′-Dialkylthia and Selenocarbocyanine Dyes Adsorbed onto Microcrystalline Cellulose

    PubMed Central

    Vieira Ferreira, Luís F.; Ferreira, Diana P.; Duarte, Paulo; Oliveira, A. S.; Torres, E.; Machado, I. Ferreira; Almeida, P.; Reis, Lucinda V.; Santos, Paulo F.

    2012-01-01

    In this work, thia and selenocarbocyanines with n-alkyl chains of different length, namely with methyl, ethyl, propyl, hexyl and decyl substituents, were studied in homogeneous and heterogeneous media for comparison purposes. For both carbocyanine dyes adsorbed onto microcrystalline cellulose, a remarkable increase in the fluorescence quantum yields and lifetimes were detected, when compared with solution. Contrary to the solution behaviour, where the increase in the n-alkyl chains length increases to a certain extent the fluorescence emission ΦF and τF, on powdered solid samples a decrease of ΦF and τF was observed. The use of an integrating sphere enabled us to obtain absolute ΦF’s for all the powdered samples. The main difference for liquid homogeneous samples is that the increase of the alkyl chain strongly decreases the ΦF values, both for thiacarbocyanines and selenocarbocyanines. A lifetime distribution analysis for the fluorescence of these dyes adsorbed onto microcrystalline cellulose, evidenced location on the ordered and crystalline part of the substrate, as well as on the more disordered region where the lifetime is smaller. The increase of the n-alkyl chains length decreases the photoisomer emission for the dyes adsorbed onto microcrystalline cellulose, as detected for high fluences of the laser excitation, for most samples. PMID:22312274

  18. Surface photochemistry: 3,3'-dialkylthia and selenocarbocyanine dyes adsorbed onto microcrystalline cellulose.

    PubMed

    Vieira Ferreira, Luís F; Ferreira, Diana P; Duarte, Paulo; Oliveira, A S; Torres, E; Machado, I Ferreira; Almeida, P; Reis, Lucinda V; Santos, Paulo F

    2012-01-01

    In this work, thia and selenocarbocyanines with n-alkyl chains of different length, namely with methyl, ethyl, propyl, hexyl and decyl substituents, were studied in homogeneous and heterogeneous media for comparison purposes. For both carbocyanine dyes adsorbed onto microcrystalline cellulose, a remarkable increase in the fluorescence quantum yields and lifetimes were detected, when compared with solution. Contrary to the solution behaviour, where the increase in the n-alkyl chains length increases to a certain extent the fluorescence emission Φ(F) and τ(F), on powdered solid samples a decrease of Φ(F) and τ(F) was observed. The use of an integrating sphere enabled us to obtain absolute Φ(F)'s for all the powdered samples. The main difference for liquid homogeneous samples is that the increase of the alkyl chain strongly decreases the Φ(F) values, both for thiacarbocyanines and selenocarbocyanines. A lifetime distribution analysis for the fluorescence of these dyes adsorbed onto microcrystalline cellulose, evidenced location on the ordered and crystalline part of the substrate, as well as on the more disordered region where the lifetime is smaller. The increase of the n-alkyl chains length decreases the photoisomer emission for the dyes adsorbed onto microcrystalline cellulose, as detected for high fluences of the laser excitation, for most samples.

  19. 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.}

  20. NO2 interaction with Au atom adsorbed on perfect and defective MgO(100) surfaces: density functional theory calculations.

    PubMed

    Ammar, H Y; Eid, Kh M

    2013-10-01

    The interactions of nitrogen dioxide molecule (NO2) on Au atom adsorbed on the surfaces of metal oxide MgO (100) on both anionic (O2-) and defect (F(s) and F(s)(+)-centers) sites have been studied using the Density Functional Theory (DFT) in combination with embedded cluster model. The adsorption energies of NO2 molecule (N-down as well as O-down) on O(-2), F(s) and F(s)(+)-sites were considered. Full optimization for the additive materials and partial optimization for MgO substrate surfaces have been done. The formation energies were evaluated for F(s) and F(s)(+) of MgO substrate surfaces. Some parameters, the Ionization Potential (IP) and electron Affinity (eA), for defect free and defect containing surfaces have been calculated. The interaction properties of NO2 have been analyzed in terms of the adsorption energy, the electron donation (basicity), the elongation of N-O bond length and the charge distribution by using Natural Bond Orbital (NBO) analysis. The adsorption properties were examined by calculation of the Density of State (DOS). The presence of the Au atom increases the surface chemistry of the anionic O(2-)-site of MgO substrate surfaces. On the other hand, the presence of the Au atom decreases the surface chemistry of the F(s) and F(s)(+)-sites of MgO substrate surfaces. Generally, the NO2 molecule is strongly adsorbed (chemisorption) on the MgO substrate surfaces containing F(s) and F(s)(+)-centers.

  1. Ratio of the surface-enhanced anti-Stokes scattering to the surface-enhanced Stokes-Raman scattering for molecules adsorbed on a silver electrode

    NASA Astrophysics Data System (ADS)

    Brolo, A. G.; Sanderson, A. C.; Smith, A. P.

    2004-01-01

    Surface-enhanced Raman scattering (SERS) from oxazine 720 (oxa), rhodamine 6G (R6G), and pyridine (py) adsorbed on a rough silver surface was observed. The silver electrode was immersed in aqueous solutions permitting control of the potential bias applied to the surface. SERS spectra in the Stokes and anti-Stokes regions were obtained for several applied potentials and two laser excitation energies. Normalized ratios between the anti-Stokes and the Stokes intensities K were calculated from the SERS spectra. The K ratios differed from unity for all the systems investigated. A preferential enhancement of the (surface-enhanced) Stokes scattering was observed for oxa and py. In contrast, the K ratios were higher than unity for R6G, indicating an increase in the anti-Stokes signal. The K ratios measured in this work decreased with the excitation energy and showed a dependence on the energy of the vibrational modes. These results were satisfactorily explained using resonance models, based on the charge-transfer and electromagnetic theories for SERS. No evidence for a SERS-induced nonthermal population distribution among the vibrational states of the adsorbed molecules (vibrational optical pumping) was found. Therefore, we conclude that the main features of the preferential enhancement of the anti-Stokes scattering for an adsorbed molecule on rough silver can be fully understood in the context of current SERS theories.

  2. Tunable surface charge of ZnS:Cu nano-adsorbent induced the selective preconcentration of cationic dyes from wastewater.

    PubMed

    Wang, Yongjing; Chen, Dagui; Wang, Yandi; Huang, Feng; Hu, Qichang; Lin, Zhang

    2012-06-21

    A novel environmentally friendly nano-adsorbent is developed by doping Cu(+) cations into the lattice of ZnS microspheres. The adsorbent shows selective adsorbability for cationic dyes in low concentrations in wastewater. The adsorbed dye could be successfully eluted with alcohol, resulting in a 1000 fold enrichment of the dye solution.

  3. Novel adsorbent based on multi-walled carbon nanotubes bonding on the external surface of porous silica gel particulates for trapping volatile organic compounds.

    PubMed

    Wang, Li; Liu, Jiemin; Zhao, Peng; Ning, Zhanwu; Fan, Huili

    2010-09-10

    A novel adsorbent, 3-amino-propylsilica gel-multi-walled carbon nanotubes (APSG-MW), was prepared by chemical bonding multi-walled carbon nanotubes on silica gel. The surface area of APSG-MW was 98 m(2)/g, and the particle size was between 60 and 80 mesh with the average size of 215.0 microm. The adsorption capability of the new adsorbent to volatile organic compounds (VOCs) was measured. The effect of water to the adsorbent and its stability during storage were also investigated. Duplicate precision (DP) and distributed volume pair (DVP) on the basis of the EPA TO-17 criteria were estimated. The results showed that the sampling precision of the adsorbent was more superior compared to the MWCNTs because of the better air permeability. The new adsorbent was successfully applied in the determination of VOCs in ambient indoor air.

  4. Removal of adsorbed gases with CO2 snow

    NASA Astrophysics Data System (ADS)

    Zito, Richard R.

    1991-09-01

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

  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. Trilinear analysis of thin-layer chromatography retention of 35 model compounds chromatographed on nine adsorbents with 20 pure solvents.

    PubMed

    Komsta, Łukasz; Skibiński, Robert; Bezpalko, Natalia; Mielniczek, Aleksandra; Stępkowska, Barbara

    2016-11-01

    The RF value dataset of 35 model compounds, chromatographed with 20 pure solvents as the mobile phase each on nine adsorbents: RP2, RP8, RP18, alumina, cellulose, CN, DIOL, NH2 , and silica, was subjected to trilinear analysis with parallel factor analysis. The two-factor optimal model explained 87% of total information in this complex dataset. The first obtained score (trend) represents two features: the presence of hydrogen bonding and heteroatoms of solute and the mean elution force of the solvent. The second trend represents molecule size, aromaticity, and number of carbons, interconnected with presence of chlorine in mobile phase. The correlation between the scores and molecular descriptors were checked to interpret these trends quantitatively. The scores of adsorbents were slightly intercorrelated, showing NH2 , alumina, and cellulose as outliers from main adsorbents cloud. The obtained results suggest that molecular size and aromaticity, connected with chlorine atoms in mobile phase, is the second source of retention variability.

  7. Phase transition of 2×2 adsorbates on FCC(1 1 1) and HCP(0 0 0 1) surfaces

    NASA Astrophysics Data System (ADS)

    Sakamoto, Yoshifumi

    2003-04-01

    Order-disorder transition of adsorbates at metal surfaces is discussed based on Monte Carlo calculations for a lattice gas model on a triangular net. Repulsive interactions up to second neighbour sites and fixed concentration 1/4 of particles of lattice gas, are assumed for the 2×2 ordered structure. Calculated phase diagram and the critical exponent for susceptibility are presented. Stress is put on cases other than the second-order transition belonging to the four-state Potts universality class.

  8. A grazing incidence surface X-ray absorption fine structure (GIXAFS) study of alkanethiols adsorbed on Au, Ag, and Cu

    NASA Astrophysics Data System (ADS)

    Floriano, Pierre N.; Schlieben, Olaf; Doomes, Edward E.; Klein, Ingo; Janssen, J.; Hormes, Josef; Poliakoff, E. D.; McCarley, Robin L.

    2000-04-01

    Self-assembled monolayers of n-alkanethiols, CH 3-(CH 2) x-SH, on Au, Ag, and Cu have been studied with GIXAFS at the sulfur K-edge. For both pentanethiol and decanethiol monolayers on Ag and Cu, the three-fold hollow site is found to be the most probable sulfur binding site. However, observations for octadecanethiol indicate that the three-fold hollow site is not the exclusive binding site. In addition, the possible existence of disulfide bonds on the metal surface (adsorbed dialkyldisulfides) is not supported by the data. Preliminary results from monolayers on Au are also reported.

  9. 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.

  10. 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.

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

    PubMed

    Persson, B N J

    2012-03-07

    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.

  12. Preparation and characterization of polar polymeric adsorbents with high surface area for the removal of phenol from water.

    PubMed

    Zeng, Xiaowei; Yu, Tingjun; Wang, Peng; Yuan, Ronghua; Wen, Qing; Fan, Yunge; Wang, Chunhong; Shi, Rongfu

    2010-05-15

    Preparation of methyl methacrylate (MMA)/divinylbenzene (DVB) and ethylene glycol dimethacrylate (EGDMA)/DVB copolymers via suspension polymerization yielded precursors which possess residual vinyl groups. Post-crosslinking of appropriate dichloroethane swollen precursors without external crosslinking agent in the presence of anhydrous ferric chloride (FeCl(3)) yielded post-crosslinked resins with high surface area and suitable polarity. FT-IR spectrum indicated that increasing the proportion of MMA or EGDMA in monomer mixtures notably reduces the amount of the pendant vinyl groups onto the matrix of the precursors. Furthermore, the pendant vinyl groups of precursors were almost absent when the content of MMA and EGDMA increased to 40 mol% and 20 mol% in the monomers, respectively. The specific surface areas and pore volumes of copolymers showed a remarkable increase after post-crosslinking. Experimental results showed that isotherms of phenol adsorption onto these polymeric adsorbents could be represented by Freundlich model and Langmuir model reasonably. PDE-5 pc exhibited higher adsorption capacity of phenol than other adsorbents, which resulted from synergistic effect of larger specific surface area and polar groups onto the network. Column adsorption/desorption dynamic curves suggested that PDE-5 pc is a potential candidate for treatment of chemical effluent containing phenol and phenolic pollutants.

  13. Infrared spectral investigations of UV irradiated nucleobases adsorbed on mineral surfaces

    NASA Astrophysics Data System (ADS)

    Brucato, John Robert; Pace, Emanuele; Pucci, Amaranta; Branciamore, Sergio; Cestelli Guidi, Mariangela; Fornaro, Teresa

    The interaction between electromagnetic radiation and bio-molecules in heterogeneous environments is a prebiotically relevant process. Minerals may have a pivotal role in the prebiotic evolution of complex chemical systems, mediating the effects of electromagnetic radiation, influencing the photostability of bio-molecules, catalyzing important chemical reactions and/or protecting molecules against degradation. In particular, nucleobases are relevant bio-molecules to investigate both in the prebiotic context, because they are coding components of nucleic acids, and from the standpoint of the survival of biological systems in space conditions. In this talk, laboratory results on photostability of nucleobases adsorbed on minerals will be presented.

  14. 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

  15. 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.

  16. 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.

  17. Adsorption of globular proteins on locally planar surfaces. II. Models for the effect of multiple adsorbate conformations on adsorption equilibria and kinetics.

    PubMed Central

    Minton, A P

    1999-01-01

    Equilibrium and kinetic models for nonspecific adsorption of proteins to planar surfaces are presented. These models allow for the possibility of multiple interconvertible surface conformations of adsorbed protein. Steric repulsion resulting in area exclusion by adsorbed molecules is taken into account by treating the adsorbate as a thermodynamically nonideal two-dimensional fluid. In the equilibrium model, the possibility of attractive interactions between adsorbed molecules is taken into account in a limited fashion by permitting one of the adsorbed species to self-associate. Calculated equilibrium adsorption isotherms exhibit apparent high-affinity and low-affinity binding regions, corresponding respectively to adsorption of ligand at low fractional area occupancy in an energetically favorable side-on conformation and conversion at higher fractional area occupancy of the side-on conformation to an entropically favored end-on conformation. Adsorbate self-association may lead to considerable steepening of the adsorption isotherm, compensating to a variable extent for the broadening effect of steric repulsion. Kinetic calculations suggest that in the absence of attractive interactions between adsorbate molecules, the process of adsorption may be highly "stretched" along the time axis, rendering the attainment of adsorption equilibrium in the context of conventional experiments problematic. PMID:9876132

  18. Assessment of fibronectin conformation adsorbed to polytetrafluoroethylene surfaces from serum protein mixtures and correlation to support of cell attachment in culture.

    PubMed

    Grainger, David W; Pavon-Djavid, Graciella; Migonney, Veronique; Josefowicz, Marcel

    2003-01-01

    Surfaces of polytetrafluoroethylene (PTFE) were exposed to buffered aqueous solutions containing radio-labeled human fibronectin ([125I]Fn), Fn/bovine serum albumin (BSA) binary mixtures of various ratios or whole human plasma dilutions for 1 h. Total adsorbed Fn and albumin adsorption following rinsing was quantified on this surface. 125I-labeled monoclonal antibodies against either the tenth type-III Fn repeat unit (containing the cell-binding RGDS integrin recognition motif) or the Fn amino-terminal domain were used to probe the accessibility of each of these respective Fn regions post-adsorption. Human umbilical vein endothelial cells (HUVECs) were cultured on PTFE surfaces pre-exposed to each of these protein adsorption conditions and compared to identical conditions on tissue culture polystyrene (TCPS). Fn adsorption to PTFE is dependent upon the concentration of albumin co-adsorbing from solution: albumin out-competes Fn for PTFE surface sites even at non-physiological Fn/HSA ratios 10-100-fold biased in Fn. Antibodies against Fn do not readily recognize Fn adsorbed on PTFE as the HSA co-adsorption concentration in either binary mixtures or in plasma increases, indicating albumin masking of adsorbed Fn. At Fn/HSA ratios rich in Fn (1:1, 1:100), albumin co-adsorption actually improves anti-Fn antibody recognition of adsorbed Fn. HUVEC attachment efficiency to PTFE after protein adsorption correlates with amounts of Fn adsorbed and levels of anti-Fn antibody recognition of Fn on PTFE, linking cell attachment to integrin recognition of both adsorbed Fn density and Fn adsorbed conformation on PTFE surfaces.

  19. Surface thermodynamic homeostasis of salivary conditioning films through polar-apolar layering.

    PubMed

    van der Mei, Henny C; White, Don J; Atema-Smit, Jelly; Geertsema-Doornbusch, Gésinda I; Busscher, Henk J

    2012-02-01

    Salivary conditioning films (SCFs) form on all surfaces exposed to the oral cavity and control diverse oral surface phenomena. Oral chemotherapeutics and dietary components present perturbations to SCFs. Here we determine the surface energetics of SCFs through contact angle measurements with various liquids on SCFs following perturbations with a variety of chemotherapeutics as well as after renewed SCF formation. Sixteen-hour SCFs on polished enamel surfaces were treated with a variety of chemotherapeutics, including toothpastes and mouthrinses. After treatment with chemotherapeutics, a SCF was applied again for 3 h. Contact angles with four different liquids on untreated and treated SCF-coated enamel surfaces were measured and surface free energies were calculated. Perturbations either caused the SCF to become more polar or more apolar, but in all cases, renewed SCF formation compensated these changes. Thus, a polar SCF attracts different salivary proteins or adsorbs proteins in a different conformation to create a more apolar SCF surface after renewed SCF formation and vice versa for apolar SCFs. This polar-apolar layering in SCF formation presents a powerful mechanism in the oral cavity to maintain surface thermodynamic homeostasis--defining oral surface properties within a narrow, biological range and influencing chemotherapeutic strategies. Surface chemical changes brought about by dietary or chemotherapeutic perturbations to SCFs make it more polar or apolar, but new SCFs are rapidly formed compensating for changes in surface energetics.

  20. Zipper and layer-by-layer assemblies of artificial photosystems analyzed by combining optical and piezoelectric surface techniques.

    PubMed

    Porus, Mariya; Maroni, Plinio; Bhosale, Rajesh; Sakai, Naomi; Matile, Stefan; Borkovec, Michal

    2011-06-07

    Quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) were used to study zipper and layer-by-layer multilayer assemblies of artificial photosystems based on naphthalenediimides (NDIs) attached to an oligophenylethynyl (OPE-NDI) or p-oligophenyl (POP-NDI) backbone in dry and wet state. For the most interesting OPE-NDI zipper, one obtains for the dry film a monolayer thickness of 1.85 nm and a density of 1.58 g/cm(3), while the wet film has a larger monolayer thickness of 3.6 nm with a water content of 36%. The dry thickness of a monolayer in OPE-NDI zippers corresponds to about one-half of the length of the OPE scaffold in agreement with the proposed structure of the zipper. The low water content of the OPE-NDI films confirms their compact structure. The dry monolayer thickness of the POP-NDI films of 1.45 nm is smaller than that for the OPE-NDI films, which is probably related to a tilt of the POP scaffolds within the adsorbed layer. The POP-NDI films swell in water much more substantially, suggesting a much more open structure. These features are in excellent agreement with the better photophysical performance of the OPE-NDI assemblies when compared to the POP-NDI films.

  1. 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.

  2. Tunable hybrid surface waves supported by a graphene layer

    NASA Astrophysics Data System (ADS)

    Iorsh, I. V.; Shadrivov, I. V.; Belov, P. A.; Kivshar, Yu. S.

    2013-05-01

    We study electromagnetic waves localized near the surface of a semi-infinite dielectric medium covered by a graphene layer in the presence of a strong external magnetic field. We demonstrate that a novel type of hybrid TE-TM polarized surface plasmons can propagate along the graphene layer. We analyze the effect of the Hall conductivity on the polarization properties of these hybrid surface waves and suggest a possibility to tune the graphene plasmons by the external magnetic field.

  3. 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

  4. Surface induced vibrational modes in the fluorescence spectra of PTCDA adsorbed on the KCl(100) and NaCl(100) surfaces.

    PubMed

    Paulheim, A; Marquardt, C; Sokolowski, M; Hochheim, M; Bredow, T; Aldahhak, H; Rauls, E; Schmidt, W G

    2016-12-07

    We report a combined experiment-theory study on low energy vibrational modes in fluorescence spectra of perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) molecules. Using very low coverages, isolated molecules were adsorbed on terrace sites or at sites located at residual steps on (100) oriented alkali halide films (KCl and NaCl). The low energy modes couple to the optical transition only because the PTCDA molecule is geometrically distorted (C2v) upon adsorption on the surface; they would be absent for the parent planar (D2h) PTCDA molecule. The modes differ in number and energy for molecules adsorbed on regular terrace sites and molecules adsorbed at step edge sites. Modes appearing for step edge sites have the character of frustrated rotations. Their coupling to the optical transition is a consequence of the further reduced symmetry of the step edge sites. We find a larger number of vibrational modes on NaCl than on KCl. We explain this by the stronger electrostatic bonding of the PTCDA on NaCl compared to KCl. It causes the optical transition to induce stronger changes in the molecular coordinates, thus leading to larger Franck-Condon factors and thus stronger coupling. Our results demonstrate how optical spectroscopy can be used to gain information on adsorption sites of molecules at low surface concentrations.

  5. Preservation of Archaeal Surface Layer Structure During Mineralization

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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.

  6. 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

  7. 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

  8. Crystalline structures of alkylamide monolayers adsorbed on the surface of graphite.

    PubMed

    Bhinde, Tej; Clarke, Stuart M; Phillips, Tamsin K; Arnold, Thomas; Parker, Julia E

    2010-06-01

    Synchrotron X-ray and neutron diffraction have been used to determine the two-dimensional crystalline structures of alkylamides adsorbed on graphite at submonolayer coverage. The calculated structures show that the plane of the carbon backbone of the amide molecules is parallel to the graphite substrate. The molecules form hydrogen-bonded dimers, and adjacent dimers form additional hydrogen bonds yielding extended chains. By presenting data from a number of members of the homologous series, we have identified that these chains pack in different arrangements depending on the number of carbons in the amide molecule. The amide monolayers are found to be very stable relative to other closely related alkyl species, a feature which is attributed to the extensive hydrogen bonding present in these systems. The characteristics of the hydrogen bonds have been determined and are found to be in close agreement with those present in the bulk materials.

  9. Surface-Enhanced Raman Scattering for Redox-Active Adsorbates: Pentaammineosmium(III)/(II) and Pentaammineruthenium(II) Containing Nitrogen Heterocycle Ligands.

    DTIC Science & Technology

    1984-04-01

    electrode reactions involving simple one- electron transfer for which both redox states are detectably adsorbed and structurally similar. Although... Taube at Stanford University. We also thank Henry Taube for his advice and encouragement. The research program of M.J.W. is supported in part by the...k AD-Ai42 418 SURFACE-ENHANCED RAMAN SCATTERING FOR REDOX -ACTIVE ii ADSORBATES: PENTRNIN..(U) PURDUE UNIV LAFAYETTE IN DEPT OF CHEMISTRY S

  10. Method of coating aluminum substrates with solid adsorbent

    SciTech Connect

    Dunn, S.R.; McKeon, M.J.; Cohen, A.P.; Behan, A.S.

    1992-06-09

    This patent describes a method of coating a surface of an aluminum substrate with a layer of solid adsorbent selected from the group consisting of crystalline molecular sieves, activated alumina, and mixtures thereof. It comprises heating the surface in an oxygen containing atmosphere to a temperature of at least about 200{degrees} C and sufficient to enable bonding of the solid adsorbent to the surface, contacting the heated surface with a slurry comprising the adsorbent and a binder selected from the group consisting of volclay, kaolin, sepiolite, attapulgite, silicates, aluminates, activated alumina, and mixtures thereof in a suspending liquid to form a slurry-coated surface, and removing sufficient liquid to form an adsorbent coating thereon.

  11. Discovery of Cellulose Surface Layer Conformation by Nonlinear Vibrational Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Libing; Fu, Li; Wang, Hong-Fei; Yang, Bin

    2017-03-01

    Significant questions remain in respect to cellulose’s structure and polymorphs, particularly the cellulose surface layers and the bulk crystalline core as well as the conformational differences. Total Internal Reflection Sum Frequency Generation Vibrational Spectroscopy (TIR-SFG-VS) combined with conventional SFG-VS (non-TIR) enables selectively characterizing the molecular structures of surface layers and the crystalline core of cellulose, revealing their differences for the first time. From the SFG spectra in the C-H and O-H regions, we found that the surface layers of Avicel are essentially amorphous while the surface layers of Iβ cellulose are crystalline but with different structural and spectroscopic signatures compared with its crystalline core. The differences between hydrogen bonding networks of cellulose surface and crystalline core were also shown by the SFG signal. The discovery here represents yet another instance of the importance of spectroscopic observations in transformative advances to understand the structure of the cellulosic biomass.

  12. Discovery of Cellulose Surface Layer Conformation by Nonlinear Vibrational Spectroscopy

    PubMed Central

    Zhang, Libing; Fu, Li; Wang, Hong-fei; Yang, Bin

    2017-01-01

    Significant questions remain in respect to cellulose’s structure and polymorphs, particularly the cellulose surface layers and the bulk crystalline core as well as the conformational differences. Total Internal Reflection Sum Frequency Generation Vibrational Spectroscopy (TIR-SFG-VS) combined with conventional SFG-VS (non-TIR) enables selectively characterizing the molecular structures of surface layers and the crystalline core of cellulose, revealing their differences for the first time. From the SFG spectra in the C-H and O-H regions, we found that the surface layers of Avicel are essentially amorphous while the surface layers of Iβ cellulose are crystalline but with different structural and spectroscopic signatures compared with its crystalline core. The differences between hydrogen bonding networks of cellulose surface and crystalline core were also shown by the SFG signal. The discovery here represents yet another instance of the importance of spectroscopic observations in transformative advances to understand the structure of the cellulosic biomass. PMID:28290542

  13. Acoustic Tomography of the Atmospheric Surface Layer

    DTIC Science & Technology

    2014-11-28

    resolution of an ultrasonic anemometer , it was suggested that one consider it is as a small acoustic tomography array and apply appropriate inverse...Fairall, D. Keith Wilson, Ludovic Bariteau. Sonic Anemometer as a Small Acoustic Tomography Array, Boundary-Layer Meteorology, (08 2013): 0. doi...Received Paper 3.00 S. N. Vecherin, V. E. Ostashev, D. K. Wilson, A. Grached. Utilization of an acoustic tomography array as a large sonic anemometer

  14. 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.

  15. 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.

  16. Improve oxidation resistance at high temperature by nanocrystalline surface layer

    NASA Astrophysics Data System (ADS)

    Xia, Z. X.; Zhang, C.; Huang, X. F.; Liu, W. B.; Yang, Z. G.

    2015-08-01

    An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surface layer, which causes the fast oxidation in the initial oxidation stage. The formation of (Fe,Cr)2O3 inner layer would inhabit fast diffusion of alloy elements in the nanocrystalline surface layer of P91 steel in the later oxidation stage, and it causes a decrease in the parabolic oxidation rate compared with conventional specimens. This study provides a novel approach to improve the oxidation resistance of heat resistant steel without changing its Cr content.

  17. 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

  18. 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.

  19. Characterization of polar molecular species adsorbed on LiNbO3 surfaces

    NASA Astrophysics Data System (ADS)

    Bharath, Satyaveda; Pearl, Thomas

    2008-10-01

    In order to explore the mechanisms of adsorption on ferroelectric surfaces, single crystalline lithium niobate (LiNbO3: LN), `Z-cut'; along the (0001) plane, has been prepared and characterized and subsequently exposed to a polar molecule. 4-n-octyl-4'-cyanobiphenyl (8CB) liquid crystal was chosen as our model system. Low-energy electron diffraction, atomic force microscopy, surface contact angle measurement, and X-ray photoelectron spectroscopy were used to characterize the surface of LN as well as the nature of the films grown on the surface. Atomically flat LN surfaces were prepared as a support for monolayer thick, 8CB molecular domains. Preferential attachment for positive domains was observed indicating an interaction between the polar end group of the molecule and the surface charge of the surface. Understanding anchoring mechanisms for polarizable molecules on uniformly poled surfaces allows for a fuller appreciation of how ferroelectric surfaces can be used for controlling molecular organization.

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

    DOEpatents

    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.

  1. Classical and Mixed Quantum-Classical Dynamics of Adsorbate-Surface Systems: Application to Non-Thermal Desorption

    NASA Astrophysics Data System (ADS)

    Dzegilenko, Fedor N.

    1995-01-01

    Both classical and mixed quantum-classical approaches have been used to study the non-thermal desorption of CO from a variety of model surfaces to which it is weakly adsorbed. In addition to three degrees of freedom for the CO adsorbate (bond stretching, physisorption, libration) which are treated quantum mechanically in the mixed method, a significant number of lattice degrees of freedom have been included using the generalized Langevin approximation. In the mixed method, two sets of equations for the quantum and classical subsystems (coupled via the Ehrenfest theorem) are solved self-consistently using the discrete variable representation method for the propagation of the quantum wave function. Non-thermal amounts of energy have been put into both the CO stretching and librational modes at t = 0. We find that for initial values of the stretching quantum number vstr = 0 -4 desorption does not take place at all within the simulation time unless there is also significant librational excitation. The detailed mechanism by which librational energy causes desorption is discussed. The role of the surface is also explored; we find that the probability of desorption is a non-monotonic function of the Debye frequency of the solid in the range 28-5000 cm^{-1}, and is larger for "non-rigid" lattices with low Debye frequencies in both of the methods. The classical results are explained in terms of resonances between low frequency libration and physisorption modes and high frequency phonon modes. For the combined method, two different mechanisms for desorption (due to lattice effects and due to symmetry properties of wave function) have been found and analyzed in detail. A comparative analysis of the two methods is presented and the limitations of the mixed scheme are discussed. An indirect mechanism for populating rapidly desorbing, highly excited levels of surface CO, based on intermolecular V to V,R energy exchange between the CO and vibrationally excited surface hydroxyl

  2. Effect of surface modifiers on the electrode reactions and conformation of cytochrome c3 adsorbed on a silver electrode.

    PubMed

    Hobara, D; Niki, K; Cotton, T M

    1998-01-01

    Surface-enhanced resonance Raman scattering and electroreflectance voltammetry were used to investigate the effect of electrode surface modification on the structure and redox properties of cytochrome c3 immobilized on Ag surfaces. It is shown that the redox reactions of cytochrome c3 are more reversible at an 11-mercaptoundecanoic acid modified Ag electrode as compared to a bare metal surface. The heme of cytochrome c3 is in a mixed low and high spin state when adsorbed at the bare electrode, whereas only the low spin form is present on the 11-mercaptoundecanoic acid modified electrode, suggesting that the native conformation is maintained in the latter case. The reduction potential is close to that of the most positive macroscopic potential as determined by electroreflectance spectroscopy. In contrast, the reduction potential as determined by SERRS undergoes a large positive shift in the presence of 4,4'-bipyridine, the magnitude of which is dependent upon the concentration of 4,4'-bipyridine. These results indicate that the effect of the cytochrome c3 interaction with the 4,4'-bipyridine-modified surface is significantly different as compared to its interaction with the 11-mercaptoundecaodoic acid modified surface. Moreover, the results emphasize that electrode modifiers can have dramatically different effects on the redox properties of different proteins. It is well known that 4,4'-bipyridine acts as a redox promoter in the case of cytochrome c, whereas no electrochemical or electroreflectance response was observed in the case of cytochrome c3.

  3. 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.

  4. THE EFFECT OF ADSORBED SULFUR ON THE SURFACE SELF-DIFFUSION OF COPPER.

    DTIC Science & Technology

    SULFUR), * DIFFUSION ), (*ADSORPTION, (*COPPER, SURFACES, HYDROGEN, SINGLE CRYSTALS, ANNEALING, HYDROGEN COMPOUNDS, SULFIDES, GRAIN BOUNDARIES, HIGH TEMPERATURE, IMPURITIES, ENTHALPY, CHEMISORPTION, MOBILITY.

  5. Bioactive macroporous titanium surface layer on titanium substrate.

    PubMed

    Kim, H M; Kokubo, T; Fujibayashi, S; Nishiguchi, S; Nakamura, T

    2000-12-05

    A macroporous titanium surface layer is often formed on titanium and titanium alloy implants for morphological fixation of the implants to bone via bony ingrowth into the porous structure. The surface of titanium metal was recently shown to become highly bioactive by being subjected to 5.0 M-NaOH treatment at 60 degrees C for 24 h and subsequent heat treatment at 600 degrees C for 1 h. In the present study, the NaOH and heat treatments were applied to a macroporous titanium surface layer formed on titanium substrate by a plasma spraying method. The NaOH and heat treatments produced an uniform amorphous sodium titanate layer on the surface of the porous titanium. The sodium titanate induced a bonelike apatite formation in simulated body fluid at an early soaking period, whereby the apatite layer grew uniformly along the surface and cross-sectional macrotextures of the porous titanium. This indicates that the NaOH and heat treatments lead to a bioactive macroporous titanium surface layer on titanium substrate. Such a bioactive macroporous layer on an implant is expected not only to enhance bony ingrowth into the porous structure, but also to provide a chemical integration with bone via apatite formation on its surface in the body.

  6. Comprehensive study of pore evolution, mesostructural stability, and simultaneous surface functionalization of ordered mesoporous carbon (FDU-15) by wet oxidation as a promising adsorbent.

    PubMed

    Wu, Zhangxiong; Webley, Paul A; Zhao, Dongyuan

    2010-06-15

    Fuctionalization of porous carbon materials through chemical methods orientates the development of new hybrid materials with specific functions. In this paper, a comprehensive study of pore evolution, mesostructural oxidation resistance, and simultaneous surface functionalization of ordered mesoporous carbon FDU-15 under various oxidation conditions is presented for the first time. The mesostructure and pore evolution with increasing oxidative strength are retrieved from XRD, TEM, and N(2) sorption techniques. The textural properties can be conveniently manipulated by changing the oxidation parameters, including different oxidative solution, temperature, and duration. It is revealed that the mesoporous carbon FDU-15 shows excellent structural stability under severe oxidation treatments by acidic (NH(4))(2)S(2)O(8), HNO(3), and H(2)O(2) solutions, much more stable than the mesostructural analogue CMK-3 carbon prepared by the nanocasting method. The surface area and porosity deteriorate to a large extent compared to the pristine carbon, with the micropores/small mesopores as the major contribution to the deterioration. The micropore/small mesopore can be blocked by the attached surface oxides under mild oxidation, while reopened with more carbon layer dissolution under more severe conditions. Simultaneously, high densities of surface oxygen complexes, especially carboxylic groups, can be generated. The contents and properties of the surface oxygen-containing groups are extensively studied by FTIR, TG, elemental analyses, and water and ammonia adsorption techniques. Such surface-functionalized mesoporous carbons can be used as a highly efficient adsorbent for immobilization of heavy metal ions as well as functional organic and biomolecules, with high capacities and excellent binding capabilities. Thus, we believe that the functionalized mesoporous carbon materials can be utilized as a promising solid and stable support for water treatment and organic

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

    PubMed Central

    Yazdani, Maryam; Bahrami, Hajir; Arami, Mokhtar

    2014-01-01

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

  8. Nanoscale Surface Modification of Layered Materials

    NASA Astrophysics Data System (ADS)

    O'Shea, Aaron

    2011-11-01

    A scanning electron microscope can magnify a sample many times greater than a standard microscope, down to nanoscale dimensions. It can also be used to form patterns on the surfaces of certain materials, a technique used to create microchips. We have developed a technique that simplifies and expedites this process using an unmodified scanning electron microscope. Using this technique, we are able to alter the surface chemistry in a controlled pattern on a special class of materials called transition metal dichalcogenides. These materials have many useful applications: industrial lubricants; high strength nanocomposites; advanced solar cells; and next generation electronics. Altering the surface chemistry of these materials at the nanoscale results in unusual quantum behavior, which is useful in nanotechnology.

  9. 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.

  10. Process Conditions of Forming the Surface Layer of Aluminum Powder Product by Layer-by-layer Laser Sintering

    NASA Astrophysics Data System (ADS)

    Saprykina, N. A.; Saprykin, A. A.; Ibragimov, E. A.; Arkhipova, D. A.

    2016-07-01

    The paper presents data on state of the art in selective laser sintering of products. Layer-by-layer sintering is shown to be a future-oriented technology, making it possible to synthesize products of metal powder materials. Factors, influencing the quality of a sintered product, are revealed in the paper. It presents outcomes of experiments, focused on the dependence of surface layer thickness of sintered aluminum powder PA-4 on laser processing conditions. Basic factors, influencing the quality of a sintered surface layer include laser power, speeds of scanning and moving the laser beam on the layer of powder. Thickness of the sintered layer varies from 0.74 to 1.55 mm, as the result of changing the laser processing conditions.

  11. Amplification of nonlinear surface waves in an inhomogeneous transition layer

    NASA Astrophysics Data System (ADS)

    Brodin, G.; Gradov, O. M.

    1991-12-01

    A plasma with a boundary transition layer of variable depth in the presence of a powerful electromagnetic field is considered. It is shown that a displacement of the boundary will grow, and will propagate as a nonlinear surface wave in the direction in which the depth of the transition layer decreases.

  12. 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.

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

    PubMed

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

    2015-03-05

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

  14. Novel adhesive properties of poly(ethylene-oxide) adsorbed nanolayers

    NASA Astrophysics Data System (ADS)

    Zeng, Wenduo

    Solid-polymer interfaces play crucial roles in the multidisciplinary field of nanotechnology and are the confluence of physics, chemistry, biology, and engineering. There is now growing evidence that polymer chains irreversibly adsorb even onto weakly attractive solid surfaces, forming a nanometer-thick adsorbed polymer layer ("adsorbed polymer nanolayers"). It has also been reported that the adsorbed layers greatly impact on local structures and properties of supported polymer thin films. In this thesis, I aim to clarify adhesive and tribological properties of adsorbed poly(ethylene-oxide) (PEO) nanolayers onto silicon (Si) substrates, which remain unsolved so far. The adsorbed nanolayers were prepared by the established protocol: one has to equilibrate the melt or dense solution against a solid surface; the unadsorbed chains can be then removed by a good solvent, while the adsorbed chains are assumed to maintain the same conformation due to the irreversible freezing through many physical solid-segment contacts. I firstly characterized the formation process and the surface/film structures of the adsorbed nanolayers by using X-ray reflectivity, grazing incidence X-ray diffraction, and atomic force microscopy. Secondly, to compare the surface energy of the adsorbed layers with the bulk, static contact angle measurements with two liquids (water and glycerol) were carried out using a optical contact angle meter equipped with a video camera. Thirdly, I designed and constructed a custom-built adhesion-testing device to quantify the adhesive property. The experimental results provide new insight into the microscopic structure - macroscopic property relationship at the solid-polymer interface.

  15. 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.

  16. Turbulent Boundary Layer Flow over Superhydrophobic Surfaces

    DTIC Science & Technology

    2013-05-10

    determined by the user via variable -frequency drive units that control the pumps . The water tunnel is able to produce friction Reynolds numbers up to 4000 and...gradient flow. The test surface is affixed to the bottom wall. Water from the holding tank is pumped into the tunnel at a specific speed ...as a plane moving through the air, a car driving down the road (through air), and a ship traveling through water. Based on an object’s geometry and

  17. 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 (√3x√3)R30° 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(√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.

  18. 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.

  19. 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.

  20. 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.

  1. Observation of UV-induced Auger features in catechol adsorbed on anatase TiO2 (101) single crystal surface

    NASA Astrophysics Data System (ADS)

    Thomas, Andrew G.; Syres, Karen L.

    2012-04-01

    We have investigated the electronic structure of catechol adsorbed on the anatase TiO2 (101) surface under illumination with ultraviolet (UV) light (4.75 eV) using resonant photoemission spectroscopy. UV illumination results in the appearance of a strong Ti MVV (M refers to photoionization of 3p level and VV the Auger decay process via the valence levels) feature at a kinetic energy of 26.2 eV. This is attributed to the creation of localised states following catechol to Ti-3d excitation by the UV source. A sharp resonance attributed to excitation from Ti 3p states into these localised states is observed in constant final state spectra.

  2. On the possible mechanism of the W(001) surface reconstruction with adsorbed hydrogen

    NASA Astrophysics Data System (ADS)

    Egorushkin, V. E.; Savushkin, E. V.

    1990-12-01

    The reconstruction of the (001) face of tungsten is treated as a Jahn-Teller transition connected with two narrow surface electronic bands along the Γ M lines. The surface periodic lattice distortion is found to be accompanied by the occurence of the hydrogen ordering in an adlayer with the result that the reconstruction temperature raises.

  3. 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.

  4. 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.

  5. Turbulent swirling layer with free surface

    NASA Astrophysics Data System (ADS)

    Bardet, Philippe; Peterson, Per; Savas, Omer

    2007-11-01

    A turbulent annular liquid wall jet, or vortex tube, generated by helical injection inside a tube was characterized experimentally. The resulting hollow confined swirling layer is proposed for use in a thick liquid first-wall chamber concept for inertial fusion power plants. The velocity fields were measured with a single camera split-screen stereoscopic particle image velocimetry scheme. The flow was studied at 5 stations between 1.5 and 4.5 ``vortex tube'' diameters downstream of the injection nozzle in a horizontal plane that coincides with the tube axis. Up to 1024 independent realizations were recorded and analyzed for Reynolds numbers ranging from 3,200 to 14,000 at each station. The turbulent structures are non-isotropic and non-homogeneous. Gradients in average velocity and Reynolds stress result in turbulent kinetic energy production. Between 1.5 and 3.5 diameters, the average azimuthal velocity profile alone is non uniform away from the wall. Persistent large vortical structures are observed. The turbulent kinetic energy decreases slowly with distance while the dissipation decreases rapidly. At 4.5 diameters, the wall effect influences strongly the average velocity profiles. The vortical structures disappear and the turbulent kinetic energy increases.

  6. "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.

  7. Double Charged Surface Layers in Lead Halide Perovskite Crystals.

    PubMed

    Sarmah, Smritakshi P; Burlakov, Victor M; Yengel, Emre; Murali, Banavoth; Alarousu, Erkki; El-Zohry, Ahmed M; Yang, Chen; Alias, Mohd S; Zhumekenov, Ayan A; Saidaminov, Makhsud I; Cho, Namchul; Wehbe, Nimer; Mitra, Somak; Ajia, Idris; Dey, Sukumar; Mansour, Ahmed E; Abdelsamie, Maged; Amassian, Aram; Roqan, Iman S; Ooi, Boon S; Goriely, Alain; Bakr, Osman M; Mohammed, Omar F

    2017-03-08

    Understanding defect chemistry, particularly ion migration, and its significant effect on the surface's optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrated that the surface layers of the perovskite crystals may acquire a high concentration of positively charged vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near the surface generates an electric field that can induce an increase of optical band gap in the surface layers relative to the bulk. We found that the charge separation, electric field, and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskite crystals. Our findings reveal the peculiarity of surface effects that are currently limiting the applications of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them.

  8. In vitro surface reaction layer formation and dissolution of calcium phosphate cement-bioactive glass composites.

    PubMed

    Liu, Changsheng; Chen, Chien-Wen; Ducheyne, Paul

    2008-09-01

    Composites of hydrated calcium phosphate cement (CPC) and bioactive glass (BG) containing Si were immersed in vitro to study the effect of chemical composition on surface reaction layer formation and dissolution/precipitation behavior. The solutions used were 0.05 M tris hydroxymethyl aminomethane/HCl (tris buffer), tris buffer supplemented with plasma electrolyte (TE) with pH 7.4 at 37 degrees C, and this solution complemented with 10% newborn bovine serum (TES). The post-immersion solutions were analyzed for changes in Ca, PO(4) and Si concentrations. The reacted surfaces were analyzed using Fourier transform infrared (FTIR), and scanning electron microscopy with energy dispersive x-ray analysis. The sample weight variations after immersion were also determined. The results showed that the composition of the bioactive composite CPCs greatly affected their behavior in solution and the formation of apatite bioactive surface reaction layers. After immersion in the TE solution, Ca ions were taken up by all samples during the entire immersion duration. Initially, the P ion concentration increased sharply, and then decreased. This reaction pattern reveals the formation of an amorphous calcium phosphate layer on the surface of these composite CPCs. FTIR revealed that the layer was, in fact, poorly crystallized Ca-deficient carbonate apatite. The thickness of the layer was 12-14 microm and it was composed of rod-like apatite with directional arrangement. For immersion in the TES solution, the Ca and Si ion concentrations showed a similar behavior to that in TE, but the release rate of Si ions was higher. FTIR revealed that after TES immersion, not only did the typical, poorly crystallized, Ca-deficient carbonated apatite form, as it did in TE, but also the serum proteins co-adsorbed on the surface and thereby affected the surface reaction layer formation. A thinner apatite layer was formed and was composed of a micro-porous layer comprising rounded particles in a glue

  9. Hyperbolic Spirals as Surface Structures in Thin Layers.

    PubMed

    Weh, Lothar

    2001-03-15

    When thin layers of 4-chloro-3-methylphenol and a copolymer of methyl(methacrylate) and maleic acid dissolved in acetone are dried by solvent evaporation, various surface structures appear. Besides linear surface deformations that can ramify like fractals, spirals of the hyperbolic type have been found. The surface structures are due to crystallization processes and flows caused by surface tension differences. The spirals are surface elevations with grooves on both sides as shown by surface profile measurements by means of a microscope interferometer. The addition of surfactants reduces the structure formation. A large surfactant concentration prevents the structure formation. Copyright 2001 Academic Press.

  10. Modeling cross-hatch surface morphology in growing mismatched layers

    NASA Astrophysics Data System (ADS)

    Andrews, A. M.; Speck, J. S.; Romanov, A. E.; Bobeth, M.; Pompe, W.

    2002-02-01

    We propose and investigate a model for the development of cross-hatch surface morphology in growing mismatched layers. The model incorporates two important elements: (i) strain relaxation due to dislocation glide in the layer (film) interior that is also associated with misfit dislocation formation at the film/substrate interface and (ii) lateral surface transport that eliminates surface steps that originated from dislocation glide. A combination of dislocation-assisted strain relaxation and surface step flow leads to the appearance of surface height undulations during layer growth. A Monte Carlo simulation technique was applied to model dislocation nucleation events in the course of strain relaxation. The simulation was used to model the influence of dislocations on film surface height profiles. The surface height displacement was calculated from the analytic elasticity solutions for edge dislocations near a free surface. The results of the modeling predict that the average amplitude of the surface undulations and their apparent wavelength both increase with increasing film relaxation and film thickness. The developed cross-hatch pattern is characterized by an atomically smooth but mesoscopically (lateral dimensions ˜0.1-10 μm) rough surface morphology. The conclusions of the model are in agreement with atomic force microscopy observations of cross-hatch surface relief in In0.25Ga0.75As/GaAs samples grown well beyond the critical thickness for misfit dislocation formation.

  11. Ambient DESI and LESA-MS Analysis of Proteins Adsorbed to a Biomaterial Surface Using In-Situ Surface Tryptic Digestion

    NASA Astrophysics Data System (ADS)

    Rao, Wei; Celiz, Adam D.; Scurr, David J.; Alexander, Morgan R.; Barrett, David A.

    2013-12-01

    The detection and identification of proteins adsorbed onto biomaterial surfaces under ambient conditions has significant experimental advantages but has proven to be difficult to achieve with conventional measuring technologies. In this study, we present an adaptation of desorption electrospray ionization (DESI) and liquid extraction surface analysis (LESA) mass spectrometry (MS) coupled with in-situ surface tryptic digestion to identify protein species from a biomaterial surface. Cytochrome c, myoglobin, and BSA in a combination of single and mixture spots were printed in an array format onto Permanox slides, followed by in-situ surface digestion and detection via MS. Automated tandem MS performed on surface peptides was able to identify the proteins via MASCOT. Limits of detection were determined for DESI-MS and a comparison of DESI and LESA-MS peptide spectra characteristics and sensitivity was made. DESI-MS images of the arrays were produced and analyzed with imaging multivariate analysis to automatically separate peptide peaks for each of the proteins within a mixture into distinct components. This is the first time that DESI and LESA-MS have been used for the in-situ detection of surface digested proteins on biomaterial surfaces and presents a promising proof of concept for the use of ambient MS in the rapid and automated analysis of surface proteins.

  12. 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

  13. Electrostatic fluctuation interactions between neutral surfaces with adsorbed, mobile ions or dipoles

    NASA Astrophysics Data System (ADS)

    Attard, Phil; Kjellander, Roland; Mitchell, D. John; Jönsson, Bo

    1988-08-01

    The electrostatic fluctuation interactions between two surfaces which carry charged or dipolar, laterally mobile particles, are investigated using both a formally exact theory and approximate methods. Each surface constitutes the boundary between two dielectric continua and has no net charge. The exact analysis demonstrates the interdependence of the van der Waals interaction between the dielectric media and the electrostatic image interactions of the particles. General asymptotic laws for the pressure between the surfaces, valid at large separations, are extracted from the exact equations. Even at relatively small separations, the asymptotic expressions give surprisingly good estimates of the actual interactions, as calculated using the hypernetted chain equation and Monte Carlo techniques. A simple mean field perturbation approximation is also investigated and is shown to give good results, provided accurate pair distributions are known for the corresponding isolated, single surface.

  14. Kosterlitz-Thouless transition for 4He films adsorbed to rough surfaces.

    PubMed

    Luhman, D R; Hallock, R B

    2004-08-20

    We report the study of adsorption isotherms of 4He on several well characterized rough CaF2 surfaces using a quartz crystal microbalance technique at 1.672 K. The signature of decoupled mass observed on crossing the Kosterlitz-Thouless transition as a function of 4He film thickness decreases and becomes increasingly difficult to identify as the surface roughness is increased. A peak in the dissipation, indicative of the onset of superfluidity, changes little with roughness.

  15. 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.

  16. Certification of hardened surface layers by magnetic and electromagnetic methods

    NASA Astrophysics Data System (ADS)

    Mitropol'skaya, S. Yu.

    2013-07-01

    The possibilities of certification of hardened surface layers by measurement of coercive force, eddy current inspection and analysis of the field dependence of differential magnetic permeability μ d ( H) are considered. The advantages of analysis of the pattern of peaks on the μ d ( H) dependence for estimating the state of surface-hardened steels subjected to subsequent force loading are shown.

  17. Poly(ethylene oxide) Mushrooms Adsorbed at Silica-Ionic Liquid Interfaces Reduce Friction.

    PubMed

    Sweeney, James; Webber, Grant B; Atkin, Rob

    2016-03-01

    The adsorbed layer conformation and lubricity of 35, 100, and 300 kDa PEO adsorbed to ionic liquid (IL)-silica interfaces from 0.01 wt % solutions have been investigated using colloid probe atomic force microscopy. The ILs used were propylammonium nitrate (PAN) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), which are protic and aprotic ILs, respectively. Normal force curves reveal steric interactions consistent with adsorbed polymer layers which are best fit using the mushroom model. Friction measurements show that the adsorbed polymer layer markedly reduces friction compared to surfaces sliding in the pure ILs and that lubricity increases with polymer length. When polymer is adsorbed to the sliding surfaces, friction is controlled by the creation and disruption of intermolecular interactions between entangled chains and the dragging of polymer chains through the interpenetration region. These experiments show that added polymer can reduce friction while maintaining the useful properties of ILs as lubricants.

  18. Multi-layer enhancement to polysilicon surface-micromachining technology

    SciTech Connect

    Sniegowski, J.J.; Rodgers, M.S.

    1997-10-01

    A multi-level polysilicon surface-micromachining technology consisting of 5 layers of polysilicon is presented. Surface topography and film mechanical stress are the major impediments encountered in the development of a multilayer surface-micromachining process. However, excellent mechanical film characteristics have been obtained through the use of chemical-mechanical polishing for planarization of topography and by proper sequencing of film deposition with thermal anneals. Examples of operating microactuators, geared power-transfer mechanisms, and optical elements demonstrate the mechanical advantages of construction with 5 polysilicon layers.

  19. Surface-stabilized nonferromagnetic ordering of a layered ferromagnetic manganite.

    PubMed

    Nascimento, V B; Freeland, J W; Saniz, R; Moore, R G; Mazur, D; Liu, H; Pan, M H; Rundgren, J; Gray, K E; Rosenberg, R A; Zheng, H; Mitchell, J F; Freeman, A J; Veltruska, K; Plummer, E W

    2009-11-27

    An outstanding question regarding the probing or possible device applications of correlated electronic materials (CEMs) with layered structure is the extent to which their bulk and surface properties differ or not. The broken translational symmetry at the surface can lead to distinct functionality due to the charge, lattice, orbital, and spin coupling. Here we report on the case of bilayered manganites with hole doping levels corresponding to bulk ferromagnetic order. We find that, although the hole doping level is measured to be the same as in the bulk, the surface layer is not ferromagnetic. Further, our low-energy electron diffraction and x-ray measurements show that there is a c-axis collapse in the outermost layer. Bulk theoretical calculations reveal that, even at fixed doping level, the relaxation of the Jahn-Teller distortion at the surface is consistent with the stabilization of an A-type antiferromagnetic state.

  20. Surface hopping dynamics of direct trans --> cis photoswitching of an azobenzene derivative in constrained adsorbate geometries

    NASA Astrophysics Data System (ADS)

    Floß, Gereon; Granucci, Giovanni; Saalfrank, Peter

    2012-12-01

    With ongoing miniaturization of electronic devices, the need for individually addressable, switchable molecules arises. An example are azobenzenes on surfaces which have been shown to be switchable between trans and cis forms. Here, we examine the "direct" (rather than substrate-mediated) channel of the trans → cis photoisomerization after ππ* excitation of tetra-tert-butyl-azobenzene physisorbed on surfaces mimicking Au(111) and Bi(111), respectively. In spirit of the direct channel, the electronic structure of the surface is neglected, the latter merely acting as a rigid platform which weakly interacts with the molecule via Van-der-Waals forces. Starting from thermal ensembles which represent the trans-form, sudden excitations promote the molecules to ππ*-excited states which are non-adiabatically coupled among themselves and to a nπ*-excited and the ground state, respectively. After excitation, relaxation to the ground state by internal conversion takes place, possibly accompanied by isomerization. The process is described here by "on the fly" semiclassical surface hopping dynamics in conjunction with a semiempirical Hamiltonian (AM1) and configuration-interaction type methods. It is found that steric constraints imposed by the substrate lead to reduced but non-vanishing, trans → cis reaction yields and longer internal conversion times than for the isolated molecule. Implications for recent experiments for azobenzenes on surfaces are discussed.

  1. The Role of Non-Bonded Interactions in the Conformational Dynamics of Organophosphorous Hydrolase Adsorbed onto Functionalized Mesoporous Silica Surfaces

    PubMed Central

    Gomes, Diego E.B.; Lins, Roberto D.; Pascutti, Pedro G.; Lei, Chenghong; Soares, Thereza A.

    2009-01-01

    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 (FMS) 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 FMS surfaces. Explicit solvent molecular dynamics simulations have been performed for OPH in bulk solution and adsorbed onto two distinct interaction potential models of the FMS 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 electrostatic interactions are responsible for the binding of OPH to the FMS surface. However, these results also show that van der Waals forces are detrimental for interfacial adhesion. In addition, it is found that OPH adsorption onto the FMS models favors a protein conformation whose active site is fully accessible to the substrate in contrast to the unconfined protein. PMID:19938866

  2. Surface activity of Janus particles adsorbed at fluid-fluid interfaces: Theoretical and experimental aspects.

    PubMed

    Fernandez-Rodriguez, Miguel Angel; Rodriguez-Valverde, Miguel Angel; Cabrerizo-Vilchez, Miguel Angel; Hidalgo-Alvarez, Roque

    2016-07-01

    Since de Gennes coined in 1992 the term Janus particle (JP), there has been a continued effort to develop this field. The purpose of this review is to present the most relevant theoretical and experimental results obtained so far on the surface activity of amphiphilic JPs at fluid interfaces. The surface activity of JPs at fluid-fluid interfaces can be experimentally determined using two different methods: the classical Langmuir balance or the pendant drop tensiometry. The second method requires much less amount of sample than the first one, but it has also some experimental limitations. In all cases collected here the JPs exhibited a higher surface or interfacial activity than the corresponding homogeneous particles. This reveals the significant advantage of JPs for the stabilization of emulsions and foams.

  3. 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.

  4. 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.

  5. Nonlinear Surface Transport in the Thin Double-Layer Limit

    NASA Astrophysics Data System (ADS)

    Chu, Kevin; Bazant, Martin

    2006-03-01

    At high applied electric fields, ionic transport within the double layer plays a significant role in the overall response of electrokinetic systems. It is well-known that surface transport processes, including surface electromigration, surface diffusion and surface advection, may impact the strength of electrokinetic phenomena by affecting both the zeta-potential and the magnitude of the tangential electric field. Therefore, it is important to include these effects when formulating the effective boundary conditions for the equations that govern electrokinetic flow outside of the double layer. In this talk, we discuss the application of a general formulation of ``surface conservation laws'' for diffuse boundary layers to derive effective boundary conditions that capture the physics of electrokinetic surface transport. Previous analyses (e.g. Deryagin & Dukhin 1969) are only valid for weak applied fields and are based on a linearization of the concentration and potential about a reference solution, but our results are fully nonlinear and hold at large applied fields as long as the double layer is sufficiently thin. We compare our nonlinear surface transport theory with existing linear analogues and apply it to the canonical problem of induced-charge electro-osmosis around a metal sphere or cylinder in a strong DC field.

  6. 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.

  7. Mitigating nutrient leaching with a sub-surface drainage layer of granulated tires.

    PubMed

    Lisi, R D; Park, J K; Stier, J C

    2004-01-01

    Markets for scrap tires have expanded since the early 1990s with the development of value-added applications such as tire-derived fuel and crumb-rubber-amended asphalt. Granulated tires have also displayed the ability to adsorb volatile organic compounds, indicating that the rubber material can be a useful filter media. Sand-based root zones, typically used for golf course putting green and athletic field construction, lack sufficient cation exchange capacity to restrict nitrogen and phosphorus migration through the root zone and into sub-surface drainage systems. Therefore, the adsorptive properties of tire rubber for retaining nitrogen and phosphorus were studied when applied as a distinct sub-surface drainage or intermediate layer in golf course putting greens. A statistically significant reduction in the concentration of nitrate in leachate was achieved by replacing traditional pea gravel with equally sized granulated tires for the drainage layer media, although the mechanism of nitrate mitigation remains unclear. The results indicate that using granulated tires as a drainage layer or fill material beneath sand-based root zones does not compromise the function of the profile or quality of the vegetation while creating an environmentally beneficial and value-added option for scrap tire reuse.

  8. Tunable surface charge of ZnS : Cu nano-adsorbent induced the selective preconcentration of cationic dyes from wastewater

    NASA Astrophysics Data System (ADS)

    Wang, Yongjing; Chen, Dagui; Wang, Yandi; Huang, Feng; Hu, Qichang; Lin, Zhang

    2012-05-01

    A novel environmentally friendly nano-adsorbent is developed by doping Cu+ cations into the lattice of ZnS microspheres. The adsorbent shows selective adsorbability for cationic dyes in low concentrations in wastewater. The adsorbed dye could be successfully eluted with alcohol, resulting in a 1000 fold enrichment of the dye solution.A novel environmentally friendly nano-adsorbent is developed by doping Cu+ cations into the lattice of ZnS microspheres. The adsorbent shows selective adsorbability for cationic dyes in low concentrations in wastewater. The adsorbed dye could be successfully eluted with alcohol, resulting in a 1000 fold enrichment of the dye solution. Electronic supplementary information (ESI) available: Synthesis, structural details of ZnS : Cu, adsorption isotherm of RhB on ZnS : Cu, control experiments for the adsorption measurements, pH effect on the adsorbability, and preliminary assessment of the adsorption efficiency for real industrial wastewater. See DOI: 10.1039/c2nr30689a

  9. 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.

  10. Multi-layer surface profiling using gated wavefront sensing

    NASA Astrophysics Data System (ADS)

    Wang, Xin; Nordin, Nur Dalilla; Tik, Eddy Chow Mun; Tan, ChingSeong; Chew, Kuew Wai; Menoni, Carmen

    2015-01-01

    Recently, multi-layer surface profiling and inspection has been considered an emerging topic that can be used to solve various manufacturing inspection problems, such as graded index lenses, TSV (Thru-Silicon Via), and optical coating. In our study, we proposed a gated wavefront sensing approach to estimate the multi-layer surface profile. In this paper, we set up an experimental platform to validate our theoretical models and methods. Our test bed consists of pulse laser, collimator, prism, well-defined focusing lens, testing specimen, and gated wavefront sensing assembly (e.g., lenslet and gated camera). Typical wavefront measurement steps are carried out for the gated system, except the reflectance is timed against its time of flight as well as its intensity profile. By synchronizing the laser pulses to the camera gate time, it is possible to discriminate a multi-layer wavefront from its neighbouring discrete layer reflections.

  11. 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

    2011-10-06

    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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study

    NASA Astrophysics Data System (ADS)

    Vaissier, Valerie; Sakai, Victoria Garcia; Li, Xiaoe; Cabral, João T.; Nelson, Jenny; Barnes, Piers R. F.

    2016-12-01

    Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results.

  17. How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study

    PubMed Central

    Vaissier, Valerie; Sakai, Victoria Garcia; Li, Xiaoe; Cabral, João T.; Nelson, Jenny; Barnes, Piers R. F.

    2016-01-01

    Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results. PMID:27991538

  18. Patterning and pattern selection in a surface layer: Feedback between point defects population and surface layer temperature variations

    NASA Astrophysics Data System (ADS)

    Kharchenko, Dmitrii O.; Kharchenko, Vasyl O.; Bashtova, Anna I.; Lysenko, Irina O.

    2016-12-01

    We study dynamics of pattern formation in a prototype system of nonequilibrium point defects in thin foils under sustained nonequilibrium conditions. A reaction-diffusion model describing spatio-temporal behaviour of both vacancy population and local temperature of a surface layer is used. It is shown that pattern selection processes caused by coupling between defect population and local temperature of a surface are realized. Associated oscillatory dynamics of main statistical moments of both vacancy concentration field and surface layer temperature is analysed in detail. It is found that during the system evolution spatial distribution of local temperature variations of the surface layer relates to vacancy population distribution. It is shown that the mean size of vacancy clusters (from 30 nm up to 300 nm) evolves in oscillatory manner due to pattern selection processes. Morphology of defect complexes can be controlled by defects generation rate.

  19. Annual Report 2013-2014: Theoretical Studies of Nerve Agents Adsorbed on Surfaces

    DTIC Science & Technology

    2014-07-08

    L Whitten Professor of Chemistry North Carolina State University Raleigh, NC 27695 Telephone Number: 919-515-7960 Email: whitten@ncsu.edu...electronic states accurately and to identify factors that affect desorption energies and kinetics, solvation of nerve agents by water and the spectral...to describe surface interactions and low energy electronic states at high aaccuracy using theory in order to understand the details of bonding to

  20. Surface modes in sheared boundary layers over impedance linings

    NASA Astrophysics Data System (ADS)

    Brambley, E. J.

    2013-08-01

    Surface modes, being duct modes localized close to the duct wall, are analysed within a lined cylindrical duct with uniform flow apart from a thin boundary layer. As well as full numerical solutions of the Pridmore-Brown equation, simplified mathematical models are given where the duct lining and boundary layer are lumped together and modelled using a single boundary condition (a modification of the Myers boundary condition previously proposed by the author), from which a surface mode dispersion relation is derived. For a given frequency, up to six surface modes are shown to exist, rather than the maximum of four for uniform slipping flow. Not only is the different number and behaviour of surface modes important for frequency-domain mode-matching techniques, which depend on having found all relevant modes during matching, but the thin boundary layer is also shown to lead to different convective and absolute stability than for uniform slipping flow. Numerical examples are given comparing the predictions of the surface mode dispersion relation to full solutions of the Pridmore-Brown equation, and the accuracy with which surface modes are predicted is shown to be significantly increased compared with the uniform slipping flow assumption. The importance of not only the boundary layer thickness but also its profile (tanh or linear) is demonstrated. A Briggs-Bers stability analysis is also performed under the assumption of a mass-spring-damper or Helmholtz resonator impedance model.

  1. 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

  2. Passive hypervelocity boundary layer control using an ultrasonically absorptive surface

    NASA Astrophysics Data System (ADS)

    Rasheed, Adam

    A series of exploratory boundary layer transition experiments was performed on a sharp 5.06 degree half-angle round cone at zero angle-of-attack in the T5 Hypervelocity Shock Tunnel in order to test a novel hypersonic boundary layer control scheme. Recently performed linear stability analyses suggested that transition could be delayed in hypersonic boundary layers by using an ultrasonically absorptive surface that would damp the second mode (Mack mode). The cone used in the experiments was constructed with a smooth surface on half the cone (to serve as a control) and an acoustically absorptive porous surface on the other half. It was instrumented with flush-mounted thermocouples to detect the transition location. Test gases investigated included nitrogen and carbon dioxide at Mach 5 with specific reservoir enthalpy ranging from 1.3 MJ/kg to 13.0 MJ/kg and reservoir pressure ranging from 9.0 MPa to 50.0 MPa. Detailed comparisons were performed to insure that previous results obtained in similar boundary layer transition experiments (on a regular smooth surface) were reproduced and the results were extended to examine the effects of the porous surface. These experiments indicated that the porous surface was highly effective in delaying transition provided that the hole size was significantly smaller than the viscous length scale.

  3. Passive hypervelocity boundary layer control using an acoustically absortive surface

    NASA Astrophysics Data System (ADS)

    Rasheed, Adam

    A series of exploratory boundary layer transition experiments was performed on a sharp 5.06 degree half-angle round cone at zero angle-of-attack in the T5 Hypervelocity Shock Tunnel in order to test a novel hypersonic boundary layer control scheme. Recently performed linear stability analyses suggested that transition could be delayed in hypersonic boundary layers by using an ultrasonically absorptive surface that would damp the second mode (Mack mode). The cone used in the experiments was constructed with a smooth surface on half the cone (to serve as a control) and an acoustically absorptive porous surface on the other half. It was instrumented with flush-mounted thermocouples to detect the transition location. Test gases investigated included nitrogen and carbon dioxide at M = 5 with specific reservoir enthalpy ranging from 1.3 MJ/kg to 13.0 MJ/kg and reservoir pressure ranging from 9.0 MPa to 50.0 MPa. Detailed comparisons were performed to insure that previous results obtained in similar boundary layer transition experiments (on a regular smooth surface) were reproduced and the results were extended to examine the effects of the porous surface. These experiments indicated that the porous surface was highly effective in delaying transition provided that the hole size was significantly smaller than the viscous length scale.

  4. Facing extremes: archaeal surface-layer (glyco)proteins.

    PubMed

    Eichler, Jerry

    2003-12-01

    Archaea are best known in their capacities as extremophiles, i.e. micro-organisms able to thrive in some of the most drastic environments on Earth. The protein-based surface layer that envelopes many archaeal strains must thus correctly assemble and maintain its structural integrity in the face of the physical challenges associated with, for instance, life in high salinity, at elevated temperatures or in acidic surroundings. Study of archaeal surface-layer (glyco)proteins has thus offered insight into the strategies employed by these proteins to survive direct contact with extreme environments, yet has also served to elucidate other aspects of archaeal protein biosynthesis, including glycosylation, lipid modification and protein export. In this mini-review, recent advances in the study of archaeal surface-layer (glyco)proteins are discussed.

  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. 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.

  7. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

    Nanostructured materials offer key advantages for third-generation photovoltaics, such as the ability to achieve high optical absorption together with enhanced charge carrier collection using low cost components. However, the extensive interfacial areas in nanostructured photovoltaic devices can cause high recombination rates and a high density of surface electronic states. In this feature article, we provide a brief review of some nanostructured photovoltaic technologies including dye-sensitized, quantum dot sensitized and colloidal quantum dot solar cells. We then introduce the technique of atomic layer deposition (ALD), which is a vapor phase deposition method using a sequence of self-limiting surface reaction steps to grow thin, uniform and conformal films. We discuss how ALD has established itself as a promising tool for addressing different aspects of nanostructured photovoltaics. Examples include the use of ALD to synthesize absorber materials for both quantum dot and plasmonic solar cells, to grow barrier layers for dye and quantum dot sensitized solar cells, and to infiltrate coatings into colloidal quantum dot solar cell to improve charge carrier mobilities as well as stability. We also provide an example of monolayer surface modification in which adsorbed ligand molecules on quantum dots are used to tune the band structure of colloidal quantum dot solar cells for improved charge collection. Finally, we comment on the present challenges and future outlook of the use of ALD for nanostructured photovoltaics.

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

    PubMed

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

    2015-08-07

    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.

  10. Order disorder phase transition on the Pb-adsorbed Si(1 1 0) surface

    NASA Astrophysics Data System (ADS)

    Kim, Y. K.; Ahn, J. R.; Cho, E. S.; An, K.-S.; Yeom, H. W.; Koh, H.; Rotenberg, E.; Park, C. Y.

    2005-12-01

    A new reversible temperature-dependent phase transition on Pb/Si(1 1 0) was found by photoemission spectroscopy and low energy electron diffraction. The room temperature 1 × 1 surface was found to transit into low temperature 4 × 2 with a transition temperature of roughly 200 K. The phase transition does not induce a temperature-dependent variation in both the energy bands and the Si 2p and Pb 5d spectra. This indicates that the phase transition is close to an order-disorder one.

  11. In Situ Surface X-Ray Scattering of Metal Monolayers Adsorbed at Solid-Liquid Interfaces

    DTIC Science & Technology

    1991-11-09

    2D spreading pressure, a is the atomic area (.JTa,.,,2/2 for a hexagonal monolayer such as TI), p is the monolayer chemical potential, Z is the number...supported by the U.S. l)epartment of lEnergy. D)ivision of Material Sciences and )ivision of Chemical Sciences. REFERENCES 1. P . Eiscnberger and W.C. Marra...Wicslcr, P ). Yecc, and 1,.B. Sorensen, I Angmuir 7, 796 (199 1). 10. M. F. Toncy, in The Application of Surface A nalysis Methods to Dw’ttiromtzital

  12. Incorporation of alkaline phosphatase into layer-by-layer polyelectrolyte films on the surface of affi-gel heparin beads: physicochemical characterization and evaluation of the enzyme stability.

    PubMed

    Derbal, Lylia; Lesot, Hervé; Voegel, Jean Claude; Ball, Vincent

    2003-01-01

    The preparation of functionalized beads in the micrometer size range that can be used to probe the action of immobilized biomolecules on cell cultures during controlled periods of time is of fundamental importance in cell biology. However, the preparation and characterization of such particles is tedious because of their fast sedimentation. It is hence difficult to prepare such beads in a reproducible manner. This highlights the need to prepare an important batch of functionnalized particles and to store them under conditions where the loss of biological activity is minimized. The aim of this paper was to immobilize alkaline phosphatase (AP) as a model enzyme on the surface of Affi-gel heparin beads functionnalized by means of a layer-by-layer (LBL) film made of poly-l-glutamic (PGA) acid and poly-l-lysine (PLL). The enzyme has been adsorbed either on the top of the LBL film or embedded under five polyelectrolyte layers. When embedded, the enzyme was not released in buffer and retained more than 30% of its initial activity after 3 months of storage at 4 degrees C. However, when the enzyme was adsorbed on top of the LBL film, about 80% of the adsorbed enzyme was released in the buffer after a few days of storage. Longer storage did not lead to any further desorption and the remaining enzyme displayed the same evolution of its activity with time as the embedded enzyme. The time evolution of the enzyme activity on the beads is compared with that in solution alone and in the presence of PGA and PLL separately.

  13. 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.

  14. Wetting layer of copper on the tantalum (001) surface

    NASA Astrophysics Data System (ADS)

    Dupraz, Maxime; Poloni, Roberta; Ratter, Kitti; Rodney, David; De Santis, Maurizio; Gilles, Bruno; Beutier, Guillaume; Verdier, Marc

    2016-12-01

    The heteroepitaxial interface formed by copper deposited onto the tantalum (001) surface is studied by surface x-ray diffraction and ab initio calculations. The analysis of the crystal truncation rods reveals the presence of a wetting layer of copper made of two atomic planes pseudomorphic to the tantalum substrate, with the upper most atomic planes significantly deformed. These findings are in total agreement with the results of density-functional-theory calculations. The presence of the wetting layer confirms a Stranski-Krastanov growth mode and is thought to explain the extremely fast atomic diffusion of copper during the dewetting process in the solid state at high temperature.

  15. Surface reactions on thin layers of silane coupling agents

    SciTech Connect

    Kurth, D.G.; Bein, T. )

    1993-11-01

    The reactivity of immobilized functional groups in thin layers of (3-aminopropyl)triethoxysilane (APS), (3-mercaptopropyl)trimethoxysilane, (3-bromopropyl)trimethoxysilane, and (8-bromooctyl)trimethoxysilane on oxidized aluminum substrates was studied with reflection-adsorption infrared spectroscopy (RAIR), optical ellipsometry and contact-angle measurements. Mass changes on the surface associated with the surface-confined reactions were measured with the quartz crystal microbalance (QCM). Single layers of (3-aminopropyl)triethoxysilane on oxidized aluminum react with chlorodimethylsilane to give [(-O)[sub 3]Si(CH[sub 2])[sub 3]NH[sub 2][sup +]SiMe[sub 2]H]Cl[sup [minus

  16. 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.

  17. 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.

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

    SciTech Connect

    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.

  19. Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations

    NASA Astrophysics Data System (ADS)

    Meng, Qingyong; Meyer, Hans-Dieter

    2015-10-01

    Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed.

  20. 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.

  1. Surface X-Ray Scattering Measurements of the Substrate Induced Spatial Modulation of an Incommensurate Adsorbed Monolayer

    DTIC Science & Technology

    1991-01-29

    oa=0) mode. 24 IV. Results Before describing our x-ray measurements, we first discuss the underpotential electrochemical deposition of TI on Ag(l I...thus termed underpotential deposition (UPD). On single crystals, these initial deposits are believed to be well defined, ordered layers. 27 The UPI...necessary and irantify by block number) We report in-situ surface X-ray scattering measurements of electrochemically deposited TI monolayers on Ag(III). We

  2. Photon-exposure-dependent photon-stimulated desorption for obtaining photolysis cross section of molecules adsorbed on surface by monochromatic soft x-ray photons.

    PubMed

    Chou, L-C; Jang, C-Y; Wu, Y-H; Tsai, W-C; Wang, S-K; Chen, J; Chang, S-C; Liu, C-C; Shai, Y; Wen, C-R

    2008-12-07

    Photon-exposure-dependent positive- and negative-ion photon-stimulated desorption (PSD) was proposed to study the photoreactions and obtain the photolysis cross sections of molecules adsorbed on a single-crystal surface by monochromatic soft x-ray photons with energy near the core level of adsorbate. The changes in the F(+) and F(-) PSD ion yields were measured from CF(3)Cl molecules adsorbed on Si(111)-7x7 at 30 K (CF(3)Cl dose=0.3x10(15) molecules/cm(2), approximately 0.75 monolayer) during irradiation of monochromatic soft x-ray photons near the F(1s) edge. The PSD ion yield data show the following characteristics: (a) The dissociation of adsorbed CF(3)Cl molecules is due to a combination of direct photodissociation via excitation of F(1s) core level and substrate-mediated dissociation [dissociative attachment and dipolar dissociation induced by the photoelectrons emitting from the silicon substrate]. (b) the F(+) ion desorption is associated with the bond breaking of the surface CF(3)Cl, CF(2)Cl, CFCl, and SiF species. (c) the F(-) yield is mainly due to DA and DD of the adsorbed CF(3)Cl molecules. (d) The surface SiF is formed by reaction of the surface Si atom with the neutral fluorine atom, F(+), or F(-) ion produced by scission of C-F bond of CF(3)Cl, CF(2)Cl, or CFCl species. A kinetic model was proposed for the explanation of the photolysis of this submonolayer CF(3)Cl-covered surface. Based on this model and the variation rates of the F(+)F(-) signals during fixed-energy monochromatic photon bombardment at 690.2 and 692.6 eV [near the F(1s) edge], the photolysis cross section was deduced as a function of energy.

  3. Stabilization of aqueous nanoscale zerovalent iron dispersions by anionic polyelectrolytes: adsorbed anionic polyelectrolyte layer properties and their effect on aggregation and sedimentation

    NASA Astrophysics Data System (ADS)

    Phenrat, Tanapon; Saleh, Navid; Sirk, Kevin; Kim, Hye-Jin; Tilton, Robert D.; Lowry, Gregory V.

    2008-05-01

    Nanoscale zerovalent iron (NZVI) particles are 5-40 nm sized Fe0/Fe-oxide particles that rapidly transform many environmental contaminants to benign products and are a promising in situ remediation agent. Rapid aggregation and limited mobility in water-saturated porous media limits the ability to deliver NZVI dispersions in the subsurface. This study prepares stable NZVI dispersions through physisorption of commercially available anionic polyelectrolytes, characterizes the adsorbed polymer layer, and correlates the polymer coating properties with the ability to prevent rapid aggregation and sedimentation of NZVI dispersions. Poly(styrene sulfonate) with molecular weights of 70 k and 1,000 k g/mol (PSS70K and PSS1M), carboxymethyl cellulose with molecular weights of 90 k and 700 k g/mol (CMC90K and CMC700K), and polyaspartate with molecular weights of 2.5 k and 10 k g/mol (PAP2.5K and 10K) were compared. Particle size distributions were determined by dynamic light scattering during aggregation. The order of effectiveness to prevent rapid aggregation and stabilize the dispersions was PSS70K(83%) > ≈PAP10K(82%) > PAP2.5K(72%) > CMC700K(52%), where stability is defined operationally as the volume percent of particles that do not aggregate after 1 h. CMC90K and PSS1M could not stabilize RNIP relative to bare RNIP. A similar trend was observed for their ability to prevent sedimentation, with 40, 34, 32, 20, and 5 wt%, of the PSS70K, PAP10K, PAP2.5K, CMC700K, and CMC90K modified NZVI remaining suspended after 7 h of quiescent settling, respectively. The stable fractions with respect to both aggregation and sedimentation correlate well with the adsorbed polyelectrolyte mass and thickness of the adsorbed polyelectrolyte layers as determined by Oshima's soft particle theory. A fraction of the particles cannot be stabilized by any modifier and rapidly agglomerates to micron sized aggregates, as is also observed for unmodified NZVI. This non-dispersible fraction is

  4. Abstraction of Si and SiH x ( x=1, 2, 3) adsorbed on Cu(1 0 0) surfaces with gaseous H(D) towards silane

    NASA Astrophysics Data System (ADS)

    Kolovos-Vellianitis, D.; Kammler, Th.; Zecho, Th.; Küppers, J.

    2001-09-01

    The interaction of silane and disilane with Cu(1 0 0) surfaces was studied in the temperature range 77-650 K with thermal desorption and Auger electron spectroscopies. Silane admission to Cu(1 0 0) at low temperatures initially leads to a complete decomposition of the silanes into adsorbed Si and H. Close to saturation of the surface with H, SiH x species remain intact on the surface. They were identified as SiH 3 and to a smaller extent SiH 2 by monitoring the silane abstraction products and their kinetics during admitting gaseous D to the surface between 77 and 200 K. Silane desorption through recombination of SiH 3 and SiH 2 with adsorbed H occurs around 157 and 224 K, respectively. After hydrogen desorption around 300 K a Si covered surface remains, which can be converted to a clean Cu(1 0 0) surface by activating Si bulk diffusion around 700 K. Adsorbed Si is abstracted from the surface below 200 K by gaseous H via formation of silane through a sequence of four hydrogenation steps. The first hydrogenation reaction is rate determining and is significantly accelerated by increasing the temperature between 77 and 200 K. Above 200 K a thermally unstable SiH x species blocks the abstraction reaction. The reaction kinetics phenomenology is in accordance with an Eley-Rideal scenario.

  5. 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.

  6. 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.

  7. Surface chemistry of the atomic layer deposition of metals and group III oxides

    NASA Astrophysics Data System (ADS)

    Goldstein, David Nathan

    low impurities and a good growth rate. The second section of this thesis focuses on two metal ALD systems. One major drawback of metal ALD systems is their inability to nucleate on many oxide surfaces. This greatly limits the applications of metal ALD for interconnects and flexible electrodes. The first emphasis is an on a new palladium ALD system using palladium (II) hexafluoroacetylaceonate (Pd(hfac)2) and formalin. FT-IR studies show that the Pd(hfac)2 dissociatively adsorbs, releasing free hfacH molecules that bind to Lewis acid sites on the alumina. The observed nucleation period of Pd is linked to surface poisoning by hfacH. In a related experiment, I use trimethylaluminum exposures to remove excess hfacH from the surface. Trimethylaluminum is able to ligand exchange an easier to remove methyl group with the surface hfacH, This treatment causes palladium to nucleate much more rapidly and deposit at lower temperatures. Finally, I examine ToRuS, a new precursor solution for Ru ALD. ToRuS, a solution of RuO4 in perfluoroethers, deposits ruthenium faster and at lower temperatures than all other Ru precursors. The mechanism for deposition and role of the perfluoroethers, however, is poorly understood. In the first study, I couple FT-IR spectroscopy with ab-initio calculations to identify the surface species formed when the perfluoroether solvent adsorbs on alumina. These surface species bind strongly to the alumina surface, creating a nonpolar, fluorinated layer. I then use these results to understand how ToRuS deposits Ru films. The fluorinated layer solvates RuO4, stabilizing it near the surface until it can be reduced by H2 gas. FT-IR and XPS analysis shows that the fluorinated layer does not leave carbonaceous impurities on the ruthenium surface or impedes metal deposition.

  8. 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°.

  9. Surface modification of layered zirconium phosphate with PNIPAM.

    PubMed

    Wang, Xuezhen; Zhao, Di; Medina, Ilse B Nava; Diaz, Agustin; Wang, Huiliang; Clearfield, Abraham; Mannan, M Sam; Cheng, Zhengdong

    2016-04-04

    A new method was reported to modify layered zirconium phosphate (ZrP) with thermoresponsive polymer PNIPAM (poly N-isopropylacrylamide). PNIPAM was proved to be covalently grafted onto ZrP. (60)Co γ-rays irradiation produced peroxide groups on the surface which, upon heating, initiated free radical polymerization and subsequent attachment of PNIPAM.

  10. Laminarization of Turbulent Boundary Layer on Flexible and Rigid Surfaces

    NASA Technical Reports Server (NTRS)

    Maestrello, Lucio

    2001-01-01

    An investigation of the control of turbulent boundary layer flow over flexible and rigid surfaces downstream of a concave-convex geometry has been made. The concave-convex curvature induces centrifugal forces and a pressure gradient on the growth of the turbulent boundary layer. The favorable gradient is not sufficient to overcome the unfavorable; thus, the net effect is a destabilizing, of the flow into Gortler instabilities. This study shows that control of the turbulent boundary layer and structural loading can be successfully achieved by using localized surface heating because the subsequent cooling and geometrical shaping downstream over a favorable pressure gradient is effective in laminarization of the turbulence. Wires embedded in a thermally insulated substrate provide surface heating. The laminarized velocity profile adjusts to a lower Reynolds number, and the structure responds to a lower loading. In the laminarization, the turbulent energy is dissipated by molecular transport by both viscous and conductivity mechanisms. Laminarization reduces spanwise vorticity because of the longitudinal cooling gradient of the sublayer profile. The results demonstrate that the curvature-induced mean pressure gradient enhances the receptivity of the flow to localized surface heating, a potentially viable mechanism to laminarize turbulent boundary layer flow; thus, the flow reduces the response of the flexible structure and the resultant sound radiation.

  11. INTERACTION OF LASER RADIATION WITH MATTER. LASER PLASMA: Collective migration of adsorbed atoms on a solid surface in the laser radiation field

    NASA Astrophysics Data System (ADS)

    Andreev, V. V.; Ignat'ev, D. V.; Telegin, Gennadii G.

    2004-02-01

    The lateral (in the substrate plane) interaction between dipoles induced in particles adsorbed on a solid surface is studied in a comparatively weak laser radiation field with a Gaussian transverse distribution. It is shown that the particles migrate over the surface in the radial direction either outside an illuminated spot with the formation of a 'crater' or inside the spot with the formation of a 'mound'.

  12. 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.

  13. 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.

  14. Surface-enhanced Raman spectroscopy for detection of toxic amyloid β oligomers adsorbed on self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Voiciuk, Vladislava; Valincius, Gintaras; Budvytytė, Rima; Matijoška, Algirdas; Matulaitienė, Ieva; Niaura, Gediminas

    Surface-enhanced Raman spectroscopy (SERS) was used to detect different spectral features of small (1-2 nm) and large (5-10 nm) synthetic amyloid Aβ-42 oligomers, exhibiting high and no detectable neurotoxicities, respectively. Adsorption of peptides at self-assembled monolayers (SAM) terminated by methyl and pyridinium groups was employed to differentiate toxic and non-toxic oligomers. Three SAMs were analyzed: hydrophobic heptanethiol (HT) and octadecanethiol (ODT) as well as positively charged N-(6-mercapto)hexylpyridinium (MHP) chloride. SERS study revealed twofold adsorption effect, changes in the monolayer structure and appearance of new bands associated with the adsorbed peptides. A band at 1387 cm-1, observed as a result of the SAM and Aβ-42 interaction, is tentatively assigned to the peptide symmetric stretching vibration of carboxylate groups, and appears to be the most prominent spectral feature distinguishing toxic oligomers from the non-toxic Aβ-42 forms. This band was identified in the spectra of Aβ-42 adsorption on heptanethiol and MHP monolayers, while no clear perturbations were observed in the case of ODT monolayer.

  15. 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.

  16. Development of an enzymatic reactor applying spontaneously adsorbed trypsin on the surface of a PDMS microfluidic device.

    PubMed

    Kecskemeti, Adam; Bako, Jozsef; Csarnovics, Istvan; Csosz, Eva; Gaspar, Attila

    2017-03-15

    Herein, a microfluidic device (MD) containing immobilized trypsin for rapid and efficient proteolysis was described. Trypsin was immobilized via non-specific protein adsorption onto the hydrophobic poly(dimethylsiloxane) (PDMS) channel wall of the MD. Peptide mapping of bovine serum albumin (BSA) samples was carried out to estimate the stability of trypsin adsorbed on PDMS surface. Peptide maps of BSA samples were obtained by capillary zone electrophoresis (CZE), the RSD% for migration times were under 1%. Several proteins (hemoglobin, myoglobin, lysozyme, and BSA) in a wide molecular size range (15-70 kDa) were digested efficiently with ∼50 s contact time. The number of separated peaks correlated well with the expected number of peptides formed in the complete tryptic digestion of the proteins. Peptide mass fingerprinting of BSA and human serum was carried out. Trypsin retained its activity for 2 h; within this period, the MD can be used for multiple digestions. The main properties of this device are simple channel pattern, simple immobilization procedure, regenerability, and disposability; all these features make this MD one of the simplest yet applicable enzymatic microreactors. Graphical abstract Development of microfluidic device including a serpentine channel as an enzyme reactor for protein digestion.

  17. Effects of electronic relaxation processes on vibrational linewidths of adsorbates on surfaces: The case of CO/Cu(100)

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

    We investigate nonadiabatic effects for the vibrational stretch mode of the CO molecule adsorbed on the top site of the Cu(100) surface. By studying the long-wavelength (q ≈0 ) imaginary and real parts of the density functional theory based phonon self-energy due to the electron-phonon coupling Πλ we obtain the phonon linewidth and the frequency renormalization of the CO stretch mode, respectively. To simulate electronic scattering processes that lead to further damping of the phonon modes we include a phenomenological damping in the phonon self-energy, as well as in the single-electron spectral function that enters Πλ, through the momentum distribution function. For the specific case of electron-impurity scattering we explicitly show how this process opens the indirect intraband channel and broadens the linewidth of the CO stretch mode. To emphasize the importance of accounting for electronic scattering processes we compare the phonon linewidths in the clean noninteracting limit (infinite electron lifetime) and when electronic scattering processes are phenomenologically included (finite electron lifetime) with available experimental data. We find that the agreement with experiments is improved in the latter case.

  18. Surface boundary layer turbulence in the Southern ocean

    NASA Astrophysics Data System (ADS)

    Merrifield, Sophia; St. Laurent, Louis; Owens, Breck; Naveira Garabato, Alberto

    2015-04-01

    Due to the remote location and harsh conditions, few direct measurements of turbulence have been collected in the Southern Ocean. This region experiences some of the strongest wind forcing of the global ocean, leading to large inertial energy input. While mixed layers are known to have a strong seasonality and reach 500m depth, the depth structure of near-surface turbulent dissipation and diffusivity have not been examined using direct measurements. We present data collected during the Diapycnal and Isopycnal Mixing Experiment in the Southern Ocean (DIMES) field program. In a range of wind conditions, the wave affected surface layer (WASL), where surface wave physics are actively forcing turbulence, is contained to the upper 15-20m. The lag-correlation between wind stress and turbulence shows a strong relationship up to 6 hours (˜1/2 inertial period), with the winds leading the oceanic turbulent response, in the depth range between 20-50m. We find the following characterize the data: i) Profiles that have a well-defined hydrographic mixed layer show that dissipation decays in the mixed layer inversely with depth, ii) WASLs are typically 15 meters deep and 30% of mixed layer depth, iii) Subject to strong winds, the value of dissipation as a function of depth is significantly lower than predicted by theory. Many dynamical processes are known to be missing from upper-ocean parameterizations of mixing in global models. These include surface-wave driven processes such as Langmuir turbulence, submesocale frontal processes, and nonlocal representations of mixing. Using velocity, hydrographic, and turbulence measurements, the existence of coherent structures in the boundary layer are investigated.

  19. C70 self-assembly on In- and Tl-adsorbed Si(111)√{ 3 } ×√{ 3 } -Au surfaces

    NASA Astrophysics Data System (ADS)

    Olyanich, D. A.; Mararov, V. V.; Utas, T. V.; Zotov, A. V.; Saranin, A. A.

    2017-02-01

    Behavior of C70 fullerenes adsorbed onto the In- and Tl-modified Si(111)√{ 3 } ×√{ 3 } -Au surfaces at room temperature (RT) and 112 K has been studied using scanning tunneling microscopy observations and compared with the known results for the C60s on the same surfaces. During island growth at 112 K, both C70 and C60 are characterized by the same critical island size i=1. The difference is in an island shape as C70s tend to form chain-like islands built of double or triple molecular rows along the [ 1 bar 10 ] Si(111) substrate directions. At RT, C70s have a lower mobility as compared to C60s. In contrast to the C60 magic islands, the C70 islands do not demonstrate any strong preference for specific shapes or sizes. Extended C70 arrays exhibit a stripe-like 3×1 reconstruction where a single row of bright fullerenes mediated by a double row of dim fullerenes. The reconstruction is due to the different orientations of C70s within the layer which does not relate to the structure of the underlying Au/Si(111) substrate. This is in contrast to the hexagonal reconstructions of C60s where the bright fullerenes occupy the specific adsorption site atop Au trimers. The difference in the behavior of C70 and C60 is plausibly affected by the non-spherical shape of C70 molecule and a greater intermolecular C70-C70 interaction.

  20. Dehydrochlorination of adsorbed 1,1,2,2-tetrachloroethane on graphene oxide-based materials' surface: Comparison with dissolved form in aqueous environment.

    PubMed

    Chen, Weifeng; Ni, Jinzhi

    2017-02-15

    Dehydrochlorination of 1,1,2,2-tetrachloroethane (TeCA) in graphene oxide (GO)-based materials-water two-phase system can be enhanced strongly. However, the dehydrochlorination kinetic of adsorbed TeCA on GO-based materials' surface is still unclear. Thus, in this study the dehydrochlorination kinetics of adsorbed TeCA on GO based-materials' surface was compared to the kinetics of dissolved TeCA in aqueous solution. The results showed that the dehydrochlorination kinetic constants of adsorbed TeCA on GO-based materials' surface (ks_F) were much greater than those of dissolved TeCA in aqueous solution (ka) due to the deprotonated surface oxygen-containing functional groups (e.g. COO(-), and O(-)) served as conjugated bases to catalyze the reaction. In particular, at pH 8.0 and 9.0, the ks_F values for GO (20mg/L) were approximately 3 orders magnitude greater than ka values. Furthermore, the ks_F values of adsorbed TeCA for the low concentration of GO (20mg/L) were always greater than that for the high concentration of GO (100mg/L). The primary mechanism was that GO was apt to aggregate at high concentration, which enhanced the steric hindrance between O-containing functional groups and TeCA molecular. Consequently, the interfacial effects of GO-based materials at their low concentration could strongly enhance the transformation of adsorbed TeCA in aqueous environment.

  1. Progress in our understanding of structure bonding and reactivity of metal surfaces and adsorbed monolayers at the molecular level: A 25 year perspective

    NASA Astrophysics Data System (ADS)

    Somorjai, G. A.

    1995-12-01

    Over fifty techniques have been developed during the past 25 years that permit molecular level investigation of structure and bonding of the surface monolayer. Among them, low-energy electron diffraction surface crystallography and vibrational spectroscopies using photons and electrons have contributed the lion's share of quantitative experimental data. (Most of these investigations have utilized small area (~1 cm 2) external surfaces, although microporous large internal surface area samples were also scrutinized.) From these studies, the physical picture of the surface which emerges is one of a separate phase with distinct structure, composition, and bonding that is distinguishable from the solid bulk. The new surface phenomena which were discovered include clean surface reconstruction, adsorbate-induced restructuring, ordering and reactivity of surface defects (steps and kinks), cluster-like bonding, the large mobility of adsorbates, and the coadsorption bond. Techniques were also developed that permit in situ molecular level study of surfaces during reactions at high pressures and temperatures with good time resolution (10 -12-10 -3 sec). Molecular surface science has had a great impact in major applications involving surface phenomena-selective adsorption, heterogeneous catalysis, coatings, microelectronics, electrochemistry, and tribology-and spawned new surface technologies. The demands of these applications focus attention on the behavior of the buried interface, both solid-liquid and solid-solid.

  2. Stabilization of Leidenfrost vapour layer by textured superhydrophobic surfaces.

    PubMed

    Vakarelski, Ivan U; Patankar, Neelesh A; Marston, Jeremy O; Chan, Derek Y C; Thoroddsen, Sigurdur T

    2012-09-13

    In 1756, Leidenfrost observed that water drops skittered on a sufficiently hot skillet, owing to levitation by an evaporative vapour film. Such films are stable only when the hot surface is above a critical temperature, and are a central phenomenon in boiling. In this so-called Leidenfrost regime, the low thermal conductivity of the vapour layer inhibits heat transfer between the hot surface and the liquid. When the temperature of the cooling surface drops below the critical temperature, the vapour film collapses and the system enters a nucleate-boiling regime, which can result in vapour explosions that are particularly detrimental in certain contexts, such as in nuclear power plants. The presence of these vapour films can also reduce liquid-solid drag. Here we show how vapour film collapse can be completely suppressed at textured superhydrophobic surfaces. At a smooth hydrophobic surface, the vapour film still collapses on cooling, albeit at a reduced critical temperature, and the system switches explosively to nucleate boiling. In contrast, at textured, superhydrophobic surfaces, the vapour layer gradually relaxes until the surface is completely cooled, without exhibiting a nucleate-boiling phase. This result demonstrates that topological texture on superhydrophobic materials is critical in stabilizing the vapour layer and thus in controlling--by heat transfer--the liquid-gas phase transition at hot surfaces. This concept can potentially be applied to control other phase transitions, such as ice or frost formation, and to the design of low-drag surfaces at which the vapour phase is stabilized in the grooves of textures without heating.

  3. First-Principles Study of the Electric Field Effect on the Water-Adsorbed Rutile Titanium Dioxide Surface

    NASA Astrophysics Data System (ADS)

    Hmiel, Abraham L.

    TiO2 is a semiconducting material that has been used extensively in many industrial applications, and recently has become a candidate for photocatalytic water splitting, fuel cell anode support materials, sensors, and other novel nanodevices. The interface of TiO2 with water, historically well-studied but still poorly understood, presents a ubiquitous environmental challenge towards the ultimate practical usefulness of these technologies. Ground-state density functional theory (DFT) calculations studying the characteristics of molecular adsorption on model surfaces have been studied for decades, showing constant improvement in the description of the energetics and electronic structure at interfaces. These simulations are invaluable in the materials science innovation pipeline because they can interpret the results of experiments and investigate properties at the nanoscale that traditional methods cannot reach. In this work, spin-polarized DFT calculations within the generalized gradient approximation and with the recent self-consistent opt-B88 van der Waals functional have been applied to investigate the problem of molecularly adsorbed water on the rutile (110) TiO2 surface under the influence of an applied electric field. The effective screening medium theory is used to break the symmetry of the simulation in the slab normal direction and implement a metal-like boundary condition at the edges of the simulation cell to model the charged capacitor in a real electrochemical device. This study begins with an investigation of bulk and surface properties of TiO2 to obtain a sound theoretical baseline. Following that, an attempt to obtain simple and meaningful structure-property relationships of rectangular TiO 2 nanowires with (110) facets resulting from quantum confinement. Finally, a systematic study of energetics, geometrical configuration, charge partitioning, and electronic structure of water in monomer coverage up to monolayer coverage provides insight into the

  4. Tuning surface plasmons in graphene ribbons with liquid crystal layer

    NASA Astrophysics Data System (ADS)

    Reshetnyak, Viktor Yu.; Bunning, Timothy J.; Evans, Dean R.

    2016-09-01

    Surface plasmons in graphene possess stronger mode confinement and lower propagation loss. One way to excite the surface plasmons is placing a periodic array of graphene nano-ribbons on top of a dielectric substrate. However once the system is fabricated it is not possible to change its optical properties. Liquid crystals (LC) are a uniaxial medium with an optical axis easily controlled by external stimuli. We suggest tuning the surface plasmons in an array of graphene ribbons by placing a LC slab on top of the ribbons. A voltage applied to the LC layer shifts the graphene ribbons plasmonic notch and changes its depth.

  5. 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

    2015-05-07

    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.

  6. 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.

  7. All-nanoparticle layer-by-layer surface modification of micro- and ultrafiltration membranes.

    PubMed

    Escobar-Ferrand, Luis; Li, Diya; Lee, Daeyeon; Durning, Christopher J

    2014-05-20

    Layer-by-layer (LbL) deposition using primarily inorganic silica nanoparticles is employed for surface modification of polymeric micro- and ultrafiltration (MF/UF) membranes to produce novel thin film composite (TFC) membranes intended for nanofiltration (NF) and reverse osmosis (RO) applications. A wide variety of porous substrate membranes with different surface characteristics are successfully employed. This report gives detailed results for polycarbonate track etched (PCTE), polyethersulfone (PES), and sulfonated PES (SPEES) MF/UF substrates. Both spherical (cationic/anionic) and eccentric elongated (anionic) silica nanoparticles are deposited using conditions similar to those in prior works for solid substrates (e.g., Lee et al.). Appropriate selection of the pH for anionic and cationic particle deposition enables construction of nanoparticle-only layers 100-1200 nm in thickness atop the original porous membrane substrates. The surface layer thickness appears to vary linearly with the number of bilayers deposited, i.e., with the number of anionic/cationic deposition cycles. The deposition process is optimized to eliminate drying-induced cracking and improve mechanical durability via thickness control and postdeposition hydrothermal treatment. "Dead-end" permeation tests using dextran standards reveal the hydraulic characteristics and separations capability for the PCTE-based TFC membranes. The results show that nanoparticle-based LbL surface modification of MF and UF rated media can produce TFC membranes with NF capabilities.

  8. The Role of Surface Layer Processes in Solid Propellant Combustion.

    NASA Astrophysics Data System (ADS)

    Chakravarthy, Satyanarayanan R.

    The qualitative multidimensional theory of composite solid propellant combustion based on the sandwich burning methodology was applied to certain specific problems: (a) burning rate enhancement by ferric oxide, (b) plateau burning behavior caused by binder melt flow effects, and (c) characterization of the combustion of new energetic oxidizers--ADN and HNIW. Exothermic reactions at the interfacial contact lines between AP particles and the binder in the surface layer of the burning propellant assume significance in the presence of ferric oxide, and control the burning rate. Binder melt flow covers adjacent AP particle surfaces increasingly at higher pressures, and disperses the O/F leading edge flames attached to coarse particles. It also causes fine AP/binder matrix areas on the surface not to support a steady premixed flame at intermediate pressures, resulting in an overall decrease in the burning rate with increasing pressure, which implies plateau or mesa effects. ADN self -deflagration rate is significantly higher than that of AP, and controls the sandwich burning rate to a great extent. The O/F flame of ADN and binder still behaves as rate limiting, although strongly supported by ADN self-deflagration. ADN melts and vaporizes substantially before the binder, allowing for the possibility of complex physical processes in the surface layer. The strong exothermic decomposition of HNIW at moderate temperatures causes the oxidizer particles in the surface layer to be the sites of burning rate control. The problems addressed in this study combinedly point to the significance of crucial surface layer processes under the situations of interest, and signal a need to characterize such processes directly and in greater detail.

  9. Experimental study of shear layer instability below a free surface

    NASA Astrophysics Data System (ADS)

    André, Matthieu A.; Bardet, Philippe M.

    2015-11-01

    Relaxation of a laminar boundary layer at a free surface is an inviscidly unstable process and can lead to millimeter-scale surface waves, influencing interfacial processes. Due to the small time- and length-scales involved, previous experimental studies have been limited to visual observations and point-wise measurements of the surface profile to determine instability onset and frequency. However, effects of viscosity, surface tension, and non-linearity of the wave profile have not been systematically studied. In fact, no data have been reported on the velocity fields associated with this instability. In the present study, planar laser induced fluorescence and particle image velocimetry provide surface profiles coupled with liquid phase velocity fields for this instability in a time resolved manner. Wave steepness (ak, with a the amplitude and k the wave number) and Reynolds and Weber numbers based on momentum thickness range from 0 to 1.2, 143 to 177, and 4.79 to 6.61, respectively. Large datasets are analyzed to gain statistical information on the surface behavior. Discrete vortices are resolved, showing that the shear layer becomes unstable and rolls up above a Reynolds number of 140. The detection onset and steepness of the subsequent surface deformation by the vortices depend upon the Weber number. Non-linear behavior such as vortex motion and wave profile asymmetry are observed at steepness larger than 0.5.

  10. Structure and Redox Properties of 5-Amino-3-nitro-1H-1,2,4-triazole (ANTA) Adsorbed on a Silica Surface: A DFT M05 Computational Study.

    PubMed

    Sviatenko, Liudmyla K; Gorb, Leonid; Hill, Frances C; Leszczynska, Danuta; Leszczynski, Jerzy

    2015-07-23

    A cluster approximation was applied at the M05/tzvp level to model an adsorption of 5-amino-3-nitro-1H-1,2,4-triazole (ANTA) on the (001) surface of α-quartz. Structures of the obtained ANTA-silica complexes confirm a nearly parallel orientation of the nitro compound toward the surface. The atoms in molecules (AIM) method was applied to analyze binding between ANTA and the silica surface. Attachment or loss of an electron was found to lead to a significant deviation from coplanarity in the complexes and to a strengthening of a hydrogen bonding. Redox properties of the adsorbed ANTA were compared with those of gas-phase and hydrated species by calculation of the ionization potential, electron affinity, oxidation and reduction Gibbs free energies, and oxidation and reduction potentials. It was shown that the adsorbed ANTA has a lower ability to undergo redox transformations as compared to that of the hydrated one.

  11. 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.

  12. 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.; ...

    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.

  13. 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.

  14. Entropy-Driven Conformational Control of α,ω-Difunctional Bidentate-Dithiol Azo-Based Adsorbates Enables the Fabrication of Thermally Stable Surface-Grafted Polymer Films.

    PubMed

    Lee, Han Ju; Jamison, Andrew C; Lee, T Randall

    2016-06-22

    Thermally stable radical initiator monolayers were prepared from uniquely designed α,ω-difunctional adsorbates with bidentate headgroups for the growth of nanoscale polymer films on metal surfaces. The length of the spacer separating the bidentate headgroups was varied to afford 4,4'-(diazene-1,2-diyl)bis(N-(16-(3,5-bis(mercaptomethyl)phenoxy)hexadecyl)-4-cyanopentanamide) (B16), 4,4'-(diazene-1,2-diyl)bis(N-(16-(3,5-bis(mercapto-methyl)phenoxy)decyl)-4-cyanopentanamide) (B10), and 4,4'-(diazene-1,2-diyl)bis(N-(4-(3,5-bis(mercaptomethyl)phenoxy)butyl)-4-cyanopentanamide) (B4). The structural features of the self-assembled monolayers (SAMs) derived from B16, B10, and B4 were characterized by X-ray photoelectron spectroscopy (XPS), ellipsometry, and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and compared to those derived from an analogous α,ω-difunctional adsorbate with monodentate headgroups, 4,4'-(diazene-1,2-diyl)bis(4-cyano-N-(16-mercaptohexadecyl)pentanamide (M). These studies demonstrate that the conformation (i.e., hairpin vs standing up) of the bidentate initiator adsorbates on gold surfaces was easily controlled by adjusting the concentration of the adsorbates in solution. The results of solution-phase thermal desorption tests revealed that the radical initiator monolayers generated from B16, B10, and B4 exhibit an enhanced thermal stability when compared to those generated from M. Furthermore, a study of the growth of polymer films was performed to evaluate the utility of these new bidentate adsorbate SAMs as film-development platforms for new functional materials and devices. Specifically, surface-grafted polystyrene films were successfully generated from SAMs derived from B16. In contrast, attempts to grow polystyrene films from SAMs derived from M under a variety of analogous conditions were unsuccessful.

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

    SciTech Connect

    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) 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.

  16. 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

  17. The measurement of boundary layers on a compressor blade in cascade. II - Suction surface boundary layers

    NASA Technical Reports Server (NTRS)

    Deutsch, Steven; Zierke, William C.

    1987-01-01

    A one-component laser Doppler velocimeter (LDV) has been used to measure the two-dimensional, periodic flow field about a double circular arc, compressor blade in cascade. Eleven boundary layer profiles were taken on both the pressure and suction surfaces of the blade, and two were taken in the near wake. In this part of the study, the LDV system is described and the suction surface flow field is documented. The suction surface profiles appear to separate both at the leading edge and again somewhat beyond midchord; the leading edge separation apparently reattaches by 2.6 percent chord.

  18. 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.

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

    PubMed Central

    Dell'Angela, M.; Anniyev, T.; Beye, M.; Coffee, R.; Föhlisch, A.; Gladh, J.; Kaya, S.; Katayama, T.; Krupin, O.; Nilsson, A.; Nordlund, D.; Schlotter, W. F.; Sellberg, J. A.; Sorgenfrei, F.; Turner, J. J.; Öström, H.; Ogasawara, H.; Wolf, M.; Wurth, W.

    2015-01-01

    Vacuum space charge induced kinetic energy shifts of O 1s and Ru 3d core levels in femtosecond soft X-ray photoemission spectra (PES) have been studied at a free electron laser (FEL) for an oxygen layer on Ru(0001). We fully reproduced the measurements by simulating the in-vacuum expansion of the photoelectrons and demonstrate the space charge contribution of the high-order harmonics in the FEL beam. Employing the same analysis for 400 nm pump-X-ray probe PES, we can disentangle the delay dependent Ru 3d energy shifts into effects induced by space charge and by lattice heating from the femtosecond pump pulse. PMID:26798795

  20. Layer-by-layer rose petal mimic surface with oleophilicity and underwater oleophobicity.

    PubMed

    Huang, Hsiu-chin; Zacharia, Nicole S

    2015-01-20

    Surfaces designed with specific wetting properties are still a key challenge in materials science. We present here a facile preparation of a surface assembled by the layer-by-layer technique, using a colloidal dispersion of ionomer particles and linear polyethylene imine. The colloidal ethylene-co-methacrylic acid (EMAA) particles are on the order of half a micron in size with surface features from 40 to 100 nm in width. The resultant surface has roughness on two length scales, one on the micron scale due to the packing of particles and one on the nanoscale due to these surface features on the EMAA particles. This hierarchical structure results in a hydrophobic surface with good water pinning properties (∼550 μN). We show that there is a balance between maximizing contact angle and water pinning force. Furthermore, this surface is oleophilic with regard to many organic solvents, also demonstrating underwater oleophobicity, and given the difference in wetting between aqueous and organic phases, this material may be a candidate material for oil/water separations.

  1. Lag model for turbulent boundary layers over rough bleed surfaces

    NASA Astrophysics Data System (ADS)

    Lee, J.; Sloan, M. L.; Paynter, G. C.

    1994-07-01

    Boundary-layer mass removal (bleed) through spanwise bands of holes on a surface is used to prevent or control separation and to stabilize the normal shock in supersonic inlets. The addition of a transport equation lag relationship for eddy viscosity to the rough wall algebraic turbulence model of Cebeci and Chang was found to improve agreement between predicted and measured mean velocity distributions downstream of a bleed band. The model was demonstrated for a range of bleed configurations, bleed rates, and local freestream Mach numbers. In addition, the model was applied to the boundary-layer development over acoustic lining materials for the inlets and nozzles of commercial aircraft. The model was found to yield accurate results for integral boundary-layer properties unless there was a strong adverse pressure gradient.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Arctic Cloud-driven Mixed Layers and Surface Coupling State

    NASA Astrophysics Data System (ADS)

    Shupe, M.; Persson, O. P.; Solomon, A.; de Boer, G.

    2013-12-01

    Arctic low-level clouds interact with the atmosphere and underlying surface via many inter-related processes. The balance of cloud radiative warming and cooling effects imparts a strong control on the net surface energy budget. Cloud-driven atmospheric circulations can impact surface turbulent heat fluxes and influence the vertical mixing of atmospheric state parameters and aerosols. Large-scale advection of heat and moisture provides the background context within which these local interactions unfold. Importantly, these radiative, dynamical, and advective processes also contribute to a complex web of self-sustaining cloud processes that can promote cloud maintenance over long periods of time. We examine many of these processes, with a specific focus on the dynamical linkages between Arctic clouds and the surface that influence low-level atmospheric structure and mixing. Comprehensive, ground-based observations from meteorological towers, remote-sensors, and radiosondes are used to simultaneously characterize surface fluxes, atmospheric structure, cloud properties, in-cloud motions, and the depth of the cloud-driven mixed layer in multiple Arctic environments. Relationships among these parameters are explored to elucidate the properties of the system that determine the degree of vertical atmospheric mixing and the coupling state between cloud and surface. The influence of temperature and moisture inversions on this system is also explored. Transitions in the coupling state are utilized to illustrate the relative roles of different processes. Cases from a coastal Arctic site at Barrow, Alaska and a station embedded in the Arctic sea-ice pack are used to contrast conditional influences related to season and surface type. It is found that over sea-ice, where surface turbulent fluxes are weak, the coupling of cloud-level processes to the surface layer is largely due to proximity of the cloud-driven mixed layer to the surface, which appears to be primarily influenced by

  7. Leaching of cement: Study of the surface layer

    SciTech Connect

    Faucon, P.; Le Bescop, P.; Adenot, F.; Bonville, P.; Jacquinot, J.F.; Pineau, F.; Felix, B.

    1996-11-01

    Short-lived, and possibly long-lived, radioactive waste is, or will be, stored in concrete containers (casks, disposal structures, etc.). To predict the safety of these containers, the composition and structure of the material when degraded must be known. Leaching of cement pastes shows that the properties of the surface layer are similar whether or not the cement paste contains slag. Substantial amounts of calcium, and smaller amounts of silicon, are leached out. Iron and magnesium are not released, but their content in the surface layer increases, with respect to an internal reference. Magnesium precipitates in the form of hydrotalcite, whereas the calcium of calcium silicate hydrates (CSH) is replaced by iron and dissolves out. Hydrogarnets undergo little, or no, leaching.

  8. 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.

  9. 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.

  10. 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.

  11. Effects of adsorbed pyridine derivatives and ultrathin atomic-layer-deposited alumina coatings on the conduction band-edge energy of TiO2 and on redox-shuttle-derived dark currents.

    PubMed

    Katz, Michael J; Vermeer, Michael J D; Farha, Omar K; Pellin, Michael J; Hupp, Joseph T

    2013-01-15

    Both the adsorption of t-butylpyridine and the atomic-layer deposition of ultrathin conformal coatings of insulators (such as alumina) are known to boost open-circuit photovoltages substantially for dye-sensitized solar cells. One attractive interpretation is that these modifiers significantly shift the conduction-edge energy of the electrode, thereby shifting the onset potential for dark current arising from the interception of injected electrons by solution-phase redox shuttle components such as Co(phenanthroline)(3)(3+) and triiodide. For standard, high-area, nanoporous photoelectrodes, band-edge energies are difficult to measure directly. In contrast, for flat electrodes they are readily accessible from Mott-Schottky analyses of impedance data. Using such electrodes (specifically TiO(2)), we find that neither organic nor inorganic electrode-surface modifiers shift the conduction-band-edge energy sufficiently to account fully for the beneficial effects on electrode behavior (i.e., the suppression of dark current). Additional experiments reveal that the efficacy of ultrathin coatings of Al(2)O(3) arises chiefly from the passivation of redox-catalytic surface states. In contrast, adsorbed t-butylpyridine appears to suppress dark currents mainly by physically blocking access of shuttle molecules to the electrode surface. Studies with other derivatives of pyridine, including sterically and/or electronically diverse derivatives, show that heterocycle adsorption and the concomitant suppression of dark current does not require the coordination of surface Ti(IV) or Al(III) atoms. Notably, the favorable (i.e., negative) shifts in onset potential for the flow of dark current engendered by organic and inorganic surface modifiers are additive. Furthermore, they appear to be largely insensitive to the identity of shuttle molecules.

  12. 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.

  13. 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)

  14. Two-dimensional thin-layer chromatography with adsorbent gradient as a method of chromatographic fingerprinting of furanocoumarins for distinguishing selected varieties and forms of Heracleum spp.

    PubMed

    Cieśla, Lukasz; Bogucka-Kocka, Anna; Hajnos, Michał; Petruczynik, Anna; Waksmundzka-Hajnos, Monika

    2008-10-17

    There are a lot of taxonomic classifications of the genus Heracleum, and many authors indicate they need revision. Morphological identification is difficult to perform, as there are only few characteristic differences between each Heracleum species, varieties and forms. Furanocoumarins are characteristic compounds for the Apiaceae family, and they can be found in the whole genus in large quantities. Despite this fact, it is difficult to use the furanocoumarin profiles of plants, for their discrimination, as furanocoumarins are difficult to separate, due to their similar chemical structures and physicochemical properties. In this paper, a new, simple method is proposed for the discrimination of selected species, varieties and forms of the genus Heracleum. Thin-layer chromatography (TLC) with an adsorbent gradient (unmodified silica gel+octadecylsilica wettable with water) enables complete separation of the structural analogues. The proposed method gives the possibility to distinguish selected species, varieties and forms of the Heracleum genus, as they produce distinctive furanocoumarin fingerprints. The method is characterised by high specificity, precision, reproducibility and stability values. It is for the first time that graft TLC is used for constructing fingerprints of herbs. The complete separation of ten structural analogues, by combining gradient TLC with the unidimensional multiple development technique, has not been reported yet.

  15. Study on tribological properties of multi-layer surface texture on Babbitt alloys surface

    NASA Astrophysics Data System (ADS)

    Zhang, Dongya; Zhao, Feifei; Li, Yan; Li, Pengyang; Zeng, Qunfeng; Dong, Guangneng

    2016-12-01

    To improve tribological properties of Babbitt alloys, multi-layer surface texture consisted of the main grooves and secondary micro-dimples are fabricated on the Babbitt substrate through laser pulse ablation. The tribological behaviors of multi-layer surface texture are investigated using a rotating type pin-on-disc tribo-meter under variation sliding speeds, and the film pressure distributions on the textured surfaces are simulated using computational fluid dynamics (CFD) method for elucidating the possible mechanisms. The results suggest that: (i) the multi-layer surface texture can reduce friction coefficient of Babbitt alloy, which has lowest friction coefficient of 0.03, in case of the groove parameter of 300 μm width and 15% of area density; (ii) the improvement effect may be more sensitive to the groove area density and the siding speed, and the textured surface with lower area density has lower friction coefficient under high sliding speed. Based on the reasons of (i) the secondary micro-dimples on Babbitt alloy possesses a hydrophobicity surface and (ii) the CFD analysis indicates that main grooves enhancing hydrodynamic effect, thus the multi-layer surface texture is regarded as dramatically improve the lubricating properties of the Babbitt alloy.

  16. Turbulence effects on concentration statistics in the atmospheric surface layer

    SciTech Connect

    Biltoft, C.; Bowers, J.; Yee, E.; Klewicki, J.; Metzger, M.

    1996-12-31

    The dispersion of windborne material released near the earth`s surface is strongly influenced by this impenetrable boundary, which inhibits downward mixing and creates sharp vertical gradients in wind, temperature, turbulence. These strong gradients and the continuous creation of turbulence at the surface cause a rapid evolution of the vertical concentration structure for material released into the atmospheric surface layer (ASL). Recent developments in fast-response instrumentation and an increased realization of potential hazards from the release of common industrial chemicals into the ASL have led to a series of tripartite (US, UK, Canada) field experiments at the US Army Dugway Proving Ground, Utah. This paper contains a preliminary analysis of the data from the most recent follow-on experiments, which included measurements of the vertical profiles of mean and peak concentrations.

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

    PubMed

    Sobel, Nicolas; Hess, Christian

    2015-12-07

    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.

  18. Turbulent boundary layer measurements over high-porosity surfaces

    NASA Astrophysics Data System (ADS)

    Efstathiou, Christoph; Luhar, Mitul

    2016-11-01

    Porous surfaces are ubiquitous across a variety of turbulent boundary layer flows of scientific and engineering interest. While turbulent flows over smooth and rough walls have been studied extensively, experimental measurements over porous walls have thus far focused on packed beds, which are limited in porosity (Φ = 0 . 3 - 0 . 5) by their geometry. The current project seeks to address this limitation. A two-component laser doppler velocimeter (LDV) is used to generate velocity measurements in turbulent boundary layer flows over commercially available reticulated foams and 3D-printed porous media at Reynolds number Reθ 3000 - 4000 . Smooth wall profiles for mean and turbulent quantities are compared to data over substrates with porosity Φ > 0 . 8 and average pore sizes in the range 0.4-2.5mm (corresponding to 8 - 50 viscous units). Previous analytical and simulation efforts indicate that the effects of porous substrates on boundary layer flows depend on a modified Reynolds number defined using the length scale √{ κ}, where κ is substrate permeability. A custom permeameter is currently being developed to estimate κ for the substrates tested in the boundary layer experiments.

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

    PubMed Central

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

    2016-01-01

    Spoof surface plasmon polaritons (SPPs) in microwave frequency provide a high field confinement in subwavelength scale and low-loss and flexible transmissions, which have been widely used in novel transmission waveguides and functional devices. To play more important roles in modern integrated circuits and systems, it is necessary and helpful for the SPP modes to propagate among different layers of devices and chips. Owing to the highly confined property and organized near-field distribution, we show that the spoof SPPs could be easily transmitted from one layer into another layer via metallic holes and arc-shaped transitions. Such designs are suitable for both the ultrathin and flexible single-strip SPP waveguide and double-strip SPP waveguide for active SPP devices. Numerical simulations and experimental results demonstrate the broadband and high-efficiency multi-layer topological transmissions with controllable absorption that is related to the superposition area of corrugated metallic strips. The transmission coefficient of single-strip SPP waveguide is no worse than −0.8 dB within frequency band from 2.67 GHz to 10.2 GHz while the transmission of double-strip SPP waveguide keeps above −1 dB within frequency band from 2.26 GHz to 11.8 GHz. The proposed method will enhance the realizations of highly complicated plasmonic integrated circuits. PMID:26939995

  20. Cooperative Jahn-Teller effect in a 2D mesoscopic C{60/n-} system with D5d symmetry adsorbed on buffer layers using Ising EFT model

    NASA Astrophysics Data System (ADS)

    Abou Ghantous, M.; Moujaes, E. A.; Dunn, J. L.; Khater, A.

    2012-06-01

    Fullerene molecules adsorbed on surfaces often show macroscopic average distortions. As charged ions C60n- are known to be Jahn-Teller (JT) active, it is suggested that these distortions could be a manifestation of cooperative JT effects (CJTE) due to interactions between neighbouring fullerene ions. In order to understand the distortion properties it is necessary to take correlations between different distortions into account. However, this can't easily be done in the mean field approximation usually used to describe the CJTE. We therefore propose an alternative procedure to describe 2D mesoscopic islands of C60 ions in which a pseudo vector spin overrightarrow{S} is evoked to represent degenerate JT-distorted states when the quadratic JT coupling is considered. This approach is analogous to methods used for 2D magnetic systems. We then use the differential operator technique in effective field theory within the Ising approach. We include the effects of weak surface interactions and dynamic motion between equivalent distortions via terms equivalent to anisotropy and a transverse field in magnetism respectively. For distortions to D5d symmetry, we determine single site correlations as a function of temperature, the macroscopic average distortion describing a structural phase transition, and the isothermal response function. Phase diagrams are presented for relevant cases of the system parameters.

  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. 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

  3. 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

  4. 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.

  5. Effect of surface corrugation on low temperature phases of adsorbed (p-H2)7: A quantum path integral Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Cruz, Anthony; López, Gustavo E.

    2014-04-01

    By using path integral Monte Carlo simulations coupled to Replica Exchange algorithms, various phases of (p-H2)7 physically adsorbed on a model graphite surface were identified at low temperatures. At T=0.5 K, the expected superfluid phase was observed for flat and slightly corrugated surfaces. At intermediate and high corrugations, a "supersolid" phase in C7/16 registry and a solid phase in C1/3 registry were observed, respectively. At higher temperatures, the superfluid is converted to a fluid and the "supersolid" to a solid.

  6. Chemical reactivity of polycyclic organic compounds adsorbed on coal fly ash and related solid surfaces. Progress report, May 1985-April 1986

    SciTech Connect

    Mamantov, G.; Wehry, E.L.

    1986-04-01

    The fundamental objectives of this research are to characterize and understand the photochemical and nonphotochemical reactivity of polycyclic aromatic hydrocarbons (PAHs) and their derivatives as adsorbates on the surface of coal fly ash and related particulate solids. Specific efforts undertaken and results obtained during this period are summarized with detailed discussions presented in the form of Appendices. Results are tabulated from a thorough examination of the photochemistry of pyrene, benzo(a)pyrene (BaP), anthracene, phenanthrene, and benz(a)anthracene (BaA) as adsorbates on eight coal stack ashes. A procedure was developed to separate coal ashes into carbon and iron contents. Attempts to measure heats of absorption of PAHs on various coal ashes were made. Pyrene nitration occurred only when NO/sub 2/ was contaminated with nitric acid.

  7. Corrosion of Metal Films with Defective Surface Protection Layers.

    DTIC Science & Technology

    1980-07-01

    Evaporation 5 x I0- 100-150 25-35 S-Gun Sputtering 2 x 10-3 (argon) 6 35 was applied and patterned. Aqua regia was used to remove the platinum down to...Dielectric Layers Electrochemical Measurements Aluminum Thin Films Surface pH Measurements Gold Thin Films TRACT (Contfne o- reverse aide Hf nec.eary...between lines and line resis- tance were monitored at intervals. In one case, the potential was reversed after a certain time. Cathodic corrosion was

  8. Development of the camshaft with surface remelted chilled layer

    SciTech Connect

    Nonoyama, H.; Morita, A.; Fukuizumi, T.; Nakakobara, T.

    1986-01-01

    A camshaft for an automobile engine is generally made of chilled case iron. But, because of increased demand for higher performance engines, a camshaft with many cam-faces has been expected. The cam intervals were necessarily narrow. So it was difficult to manufacture the conventional chilled cast iron camshaft at a moderate price. In the case of a rocker-arm type valve mechanism, higher wear resistance was necessary. After due consideration to solve these problems, development of surface remelted chilled layer camshafts by Toyota's unique manufacturing method has been accomplished. In this paper, the excellent wear resistance, the low manufacturing cost and the characteristic manufacturing method are described.

  9. Force measurements on myelin basic protein adsorbed to mica and lipid bilayer surfaces done with the atomic force microscope.

    PubMed Central

    Mueller, H; Butt, H J; Bamberg, E

    1999-01-01

    The mechanical and adhesion properties of myelin basic protein (MBP) are important for its function, namely the compaction of the myelin sheath. To get more information about these properties we used atomic force microscopy to study tip-sample interaction of mica and mixed dioleoylphosphatidylserine (DOPS) (20%)/egg phosphatidylcholine (EPC) (80%) lipid bilayer surfaces in the absence and presence of bovine MBP. On mica or DOPS/EPC bilayers a short-range repulsive force (decay length 1.0-1.3 nm) was observed during the approach. The presence of MBP always led to an attractive force between tip and sample. When retracting the tip again, force curves on mica and on lipid layers were different. While attached to the mica surface, the MBP molecules exhibited elastic stretching behavior that agreed with the worm-like chain model, yielding a persistence length of 0.5 +/- 0.25 nm and an average contour length of 53 +/- 19 nm. MBP attached to a lipid bilayer did not show elastic stretching behavior. This shows that the protein adopts a different conformation when in contact with lipids. The lipid bilayer is strongly modified by MBP attachment, indicating formation of MBP-lipid complexes and possibly disruption of the original bilayer structure. PMID:9916039

  10. 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.

  11. Surface potentials and layer charge distributions in few-layer graphene films.

    PubMed

    Datta, Sujit S; Strachan, Douglas R; Mele, E J; Johnson, A T Charlie

    2009-01-01

    Graphene-derived nanomaterials are emerging as ideal candidates for postsilicon electronics. Elucidating the electronic interaction between an insulating substrate and few-layer graphene (FLG) films is crucial for device applications. Here, we report electrostatic force microscopy (EFM) measurements revealing that the FLG surface potential increases with film thickness, approaching a "bulk" value for samples with five or more graphene layers. This behavior is in sharp contrast with that expected for conventional conducting or semiconducting films, and derives from unique aspects of charge screening by graphene's relativistic low energy carriers. EFM measurements resolve previously unseen electronic perturbations extended along crystallographic directions of structurally disordered FLGs, likely resulting from long-range atomic defects. These results have important implications for graphene nanoelectronics and provide a powerful framework by which key properties can be further investigated.

  12. Adsorption of fluids on solid surfaces: A route toward very dense layers

    NASA Astrophysics Data System (ADS)

    Sartarelli, S. A.; Szybisz, L.

    2012-08-01

    Adsorption of Xe on single planar walls is investigated in the frame of a density functional theory. The strength of the adsorbate-substrate attraction is changed by considering surfaces of Cs, Na, Li, and Mg. The behavior is analyzed by varying the temperature T (between the triple point Tt and the critical Tc) and the coverage Γℓ. The obtained adsorption isotherms exhibit a variety of wetting situations. Density profiles are reported. It is shown that for strongly attractive surfaces the adsorbed liquid becomes very dense reaching densities characteristic of solids.

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

    PubMed

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

    2016-02-25

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

  14. Adsorbate-induced demagnetization and restructuring of ultrathin magnetic films: CO chemisorbed on γ-Fe/Cu(100)

    NASA Astrophysics Data System (ADS)

    Spišák, D.; Hafner, J.

    2001-09-01

    First-principles local-spin-density (LSD) investigations of the structural, magnetic, and electronic properties of clean and CO-adsorbed ultrathin γ-iron films epitaxially grown on Cu(100) surfaces demonstrate that both the geometrical and the magnetic structures of the films are profoundly modified by the adsorption of CO. The enhanced magnetic moments of the top-layer atoms are strongly quenched by the presence of the adsorbate. Due to the pronounced magnetovolume effect, this leads also to a correlated change in the interlayer relaxations. Strikingly, the adsorbate-induced demagnetization is primarily limited to those surface atoms directly bonded to the adsorbate. This leads to the formation of an in-plane magnetic pattern in a partially adsorbate-covered film. The comparison of the calculated vibrational eigenfrequencies of the CO adsorbate with experiment confirms the picture based on the LSD calculations.

  15. Multi-layer relaxations of Li surfaces from First Principles

    NASA Astrophysics Data System (ADS)

    Fei, Weiben; Staikov, Pavlin; Kara, Abdelkader; Rahman, Talat. S.

    1996-03-01

    We have undertaken a systematic study of the multi-layer relaxations of low Miller indices Li surfaces for both bcc and fcc structures. These calculations are done using ab initio, norm-conserving, non-local and soft pseudopotentials with partial core correction, and a plane wave basis. A preconditioned steepest descent method (N. Chetty, M. Weinert, T. S. Rahman, and J. W. Davenport, Phys. Rev. B 52) (1995) 6313. is used to solve iteratively Kohn-Sham equations for a given set of atomic positions. The different relaxation patterns are interpreted in terms of the surface electronic environments. The charge density profiles for these fully relaxed systems are examined and contrasted with the unrelaxed counterparts.

  16. Thermodynamics of elastic strength of the metal surface layer

    NASA Astrophysics Data System (ADS)

    Andreev, Yu. Ya.; Kiselev, D. A.

    2013-07-01

    This paper presents a physicochemical model that establishes a connection between the elastic strength of the surface layer (SL) of metal and its surface Gibbs energy. The elastic limit of SL along the low-index face of the metal single crystal under stress during the transition from elastic to plastic deformation was calculated. Calculation shows that the elastic limit of metal SL with fcc and bcc structures is approximately three orders of magnitude higher than the yield strength of these metals in bulk and close to nanohardness of the metals, in particular; for Cu(111) и Al(111), it is 5.3 and 2.8 GPa, respectively. In the light of the proposed model, the effect of lowering the elastic strength of metal SL due to adsorption of surfactant is formulated.

  17. Enhancing surface coverage and growth in layer-by-layer assembly of protein nanoparticles.

    PubMed

    Mohanta, Vaishakhi; Patil, Satish

    2013-10-29

    Thin films of bovine serum albumin (BSA) nanoparticles are fabricated via layer-by-layer assembly. The surface of BSA nanoparticles have two oppositely acting functional groups on the surface: amine (NH2) and carboxylate (COO(-)). The protonation and deprotonation of these functional groups at different pH vary the charge density on the particle surface, and entirely different growth can be observed by varying the nature of the complementary polymer and the pH of the particles. The complementary polymers used in this study are poly(dimethyldiallylammonium chloride) (PDDAC) and poly(acrylic acid) (PAA). The assembly of BSA nanoparticles based on electrostatic interaction with PDDAC suffers from the poor loading of the nanoparticles. The assembly with PAA aided by a hydrogen bonding interaction shows tremendous improvement in the growth of the assembly over PDDAC. Moreover, the pH of the BSA nanoparticles was observed to affect the loading of nanoparticles in the LbL assembly with PAA significantly.

  18. 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

  19. 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.

  20. Water-soluble sacrificial layers for surface micromachining.

    PubMed

    Linder, Vincent; Gates, Byron D; Ryan, Declan; Parviz, Babak A; Whitesides, George M

    2005-07-01

    This manuscript describes the use of water-soluble polymers for use as sacrificial layers in surface micromachining. Water-soluble polymers have two attractive characteristics for this application: 1) They can be deposited conveniently by spin-coating, and the solvent removed at a low temperature (95-150 degrees C), and 2) the resulting layer can be dissolved in water; no corrosive reagents or organic solvents are required. This technique is therefore compatible with a number of fragile materials, such as organic polymers, metal oxides and metals-materials that might be damaged during typical surface micromachining processes. The carboxylic acid groups of one polymer-poly(acrylic acid) (PAA)-can be transformed by reversible ion-exchange from water-soluble (Na+ counterion) to water-insoluble (Ca2+ counterion) forms. The use of PAA and dextran polymers as sacrificial materials is a useful technique for the fabrication of microstructures: Examples include metallic structures formed by the electrodeposition of nickel, and freestanding, polymeric structures formed by photolithography.

  1. Imaging Layers Based on Surface-Initiated Polymers

    NASA Astrophysics Data System (ADS)

    Montague, Martha; Edwards, Erik; Nealey, Paul

    2002-03-01

    Photoresist structures at the 70 nm and 50 nm technology nodes are of molecular dimensions, and allowable tolerances and margins are of atomic dimensions. It is unclear whether current resist processing based on preferential solubility of protected or deprotected polymer molecules in aqueous base will afford the necessary process latitude at this scale. We are developing thin film imaging materials (100 to 200 nm thick) composed of polymer chains that are grafted (polymerized) directly on the surface of the substrate. These brushes have been grown from silicon wafers using "living" free radical initiators that are tethered to the surface of the wafer. We pattern this system by taking advantage of chemical amplification. An acid-labile linkage was incorporated into the tether of the polymer brush, and by using a photo acid generator we can create acid in exposed regions of our imaging layer. This strategy allows us to decouple the imaging process from the chemistry of the polymer. The resist then can be designed to optimize properties such as transparency and etch resistance. We will evaluate the imaging layers for process latitude and resolution.

  2. 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.

  3. 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

  4. 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.

  5. Evolution of vortex-surface fields in transitional boundary layers

    NASA Astrophysics Data System (ADS)

    Yang, Yue; Zhao, Yaomin; Xiong, Shiying

    2016-11-01

    We apply the vortex-surface field (VSF), a Lagrangian-based structure-identification method, to the DNS database of transitional boundary layers. The VSFs are constructed from the vorticity fields within a sliding window at different times and locations using a recently developed boundary-constraint method. The isosurfaces of VSF, representing vortex surfaces consisting of vortex lines with different wall distances in the laminar stage, show different evolutionary geometries in transition. We observe that the vortex surfaces with significant deformation evolve from wall-parallel planar sheets through hairpin-like structures and packets into a turbulent spot with regeneration of small-scale hairpins. From quantitative analysis, we show that a small number of representative or influential vortex surfaces can contribute significantly to the increase of the drag coefficient in transition, which implies a reduced-order model based on VSF. This work has been supported in part by the National Natural Science Foundation of China (Grant Nos. 11472015, 11522215 and 11521091), and the Thousand Young Talents Program of China.

  6. Effects of surface barrier layer in AlGaAs/GaAs solar cells

    NASA Astrophysics Data System (ADS)

    Urabe, Hiroyuki; Kuramoto, Makoto; Nakano, Tomohiro; Kawaharazuka, Atsushi; Makimoto, Toshiki; Horikoshi, Yoshiji

    2015-09-01

    In this paper, we report the effects of surface barrier layers on the characteristics of AlGaAs/GaAs solar cells. The external quantum efficiency (EQE) spectra for AlGaAs barrier samples with different barrier layer AlAs fractions and thickness of the surface barrier layer were measured to increase the solar cell efficiency. The results show that the surface barrier layer is effective to block diffusing photoexcited electrons to the surface while the thicker barrier layer absorbs higher energy photons to generate carriers which recombine at the surface. The optimal surface barrier structure is a 50 nm thick Al0.7Ga0.3As.

  7. Real-time assessment of surface interactions with titanium passivation layer by surface plasmon resonance

    PubMed Central

    Hirata, Isao; Yoshida, Yasuhiro; Nagaoka, Noriyuki; Hiasa, Kyou; Abe, Yasuhiko; Maekawa, Kenji; Kuboki, Takuo; Akagawa, Yasumasa; Suzuki, Kazuomi; Van Meerbeek, Bart; Messersmith, Phillip B.; Okazaki, Masayuki

    2011-01-01

    The high corrosion resistance and strength-to-density ratio makes titanium widely used in major industry, but also in a gamut of medical applications. Here we report for the first time on our development of a titanium passivation layer sensor that makes use of surface plasmon resonance (SPR). The deposited titanium metal layer on the sensor was passivated in air, like titanium medical devices. Our ‘Ti-SPR sensor’ enables analysis of biomolecules interactions with the passivated surface of titanium in real time. As a proof of concept, corrosion of titanium passivation layer exposed to acid was monitored in real time. Also, the Ti-SPR sensor can accurately measure the time-dependence of protein adsorption onto titanium passivation layer with a sub-nanogram per square millimeter accuracy. Besides such SPR analyses, an SPR-imaging (SPRI) enables real-time assessment of chemical surface processes that occur simultaneously at ‘multiple independent spots’ on the Ti-SPR sensor, such as acid-corrosion or adhesion of cells. Our Ti-SPR sensor will therefore be very useful to study titanium-corrosion phenomena and biomolecular titanium-surface interactions with application in a broad range of industrial and biomedical fields. PMID:22154862

  8. Carbon 1s photoemission line analysis of C-based adsorbate on (111)In2O3 surface: The influence of reducing and oxidizing conditions

    NASA Astrophysics Data System (ADS)

    Brinzari, V.; Cho, B. K.; Korotcenkov, G.

    2016-12-01

    Synchrotron radiation photoemission study of C 1s line of (111) In2O3 surface was carried out under HV (high vacuum) doses of oxygen, carbon monoxide and water. Gas interaction with the surface was activated by heating of In2O3 monocrystalline film at temperatures of 160 or 250 °C. The study of complex structure of C 1 s line and evolution of its fine components allowed to establish their nature and to propose possible surface adsorbed species and reactions, including a direct chemisorption and dissociation of CO molecules. Reduction or oxidation of the surface determines whether the first (chemisorption) or the second (dissociation) process takes place. The latter is responsible for additional formation of ionosorbed oxygen. Both processes have not been previously reported for In2O3 and for conductive metal oxides.

  9. 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.

  10. 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.

  11. 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.

  12. Role of the endothelial surface layer in neutrophil recruitment.

    PubMed

    Marki, Alex; Esko, Jeffrey D; Pries, Axel R; Ley, Klaus

    2015-10-01

    Neutrophil recruitment in most tissues is limited to postcapillary venules, where E- and P-selectins are inducibly expressed by venular endothelial cells. These molecules support neutrophil rolling via binding of PSGL-1 and other ligands on neutrophils. Selectins extend ≤ 38 nm above the endothelial plasma membrane, and PSGL-1 extends to 50 nm above the neutrophil plasma membrane. However, endothelial cells are covered with an ESL composed of glycosaminoglycans that is ≥ 500 nm thick and has measurable resistance against compression. The neutrophil surface is also covered with a surface layer. These surface layers would be expected to completely shield adhesion molecules; thus, neutrophils should not be able to roll and adhere. However, in the cremaster muscle and in many other models investigated using intravital microscopy, neutrophils clearly roll, and their rolling is easily and quickly induced. This conundrum was thought to be resolved by the observation that the induction of selectins is accompanied by ESL shedding; however, ESL shedding only partially reduces the ESL thickness (to 200 nm) and thus is insufficient to expose adhesion molecules. In addition to its antiadhesive functions, the ESL also presents neutrophil arrest-inducing chemokines. ESL heparan sulfate can also bind L-selectin expressed by the neutrophils, which contributes to rolling and arrest. We conclude that ESL has both proadhesive and antiadhesive functions. However, most previous studies considered either only the proadhesive or only the antiadhesive effects of the ESL. An integrated model for the role of the ESL in neutrophil rolling, arrest, and transmigration is needed.

  13. 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.

  14. Generic nitric oxide (NO) generating surface by immobilizing organoselenium species via layer-by-layer assembly.

    PubMed

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

    2008-09-16

    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 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. In situ Fourier transform-infrared internal reflection spectroscopic analysis of hydrocarbon chain ordering of surfactants adsorbed at mineral oxide surfaces

    NASA Astrophysics Data System (ADS)

    Cross, William Murray

    The adsorption of surfactants at mineral oxide surfaces was investigated by in situ Fourier transform infrared internal reflection spectroscopy (FT-IR/IRS), and contact angle goniometry. FT-IR/IRS was used to determine both adsorption isotherms and the enthalpy of adsorption. Furthermore, the conformation and orientation of the hydrocarbon chain of SDS adsorbed at a sapphire internal reflection element (IRE) were determined. Contact angle goniometry was used to measure the effect of the surface phase of the surfactant on the hydrophobic character of sapphire surfaces in aqueous solutions. For SDS adsorbed by sapphire, in situ FT-IR/IRS experiments indicate that a surface phase transition occurs at an adsorption density of 2 to 3 x 10-10 mol/cm2 for both pD 2.9 and 6.9. This transition is characterized by a two to four wavenumber shift in the position of the asymmetric -CH2 stretching band. Based on solution spectroscopy studies, the surface phase was found to be similar to solution phase micelles and liquid crystals for adsorption densities less than the adsorption density of the surface phase transition. Whereas for adsorption densities in excess of the adsorption density of the surface phase transition, the surface phase resembled a solution phase coagel species. It was also found that the contact angle of an air bubble at the sapphire surface exhibited a sharp decrease at the adsorption density corresponding to the surface phase transition The effect of temperature on adsorption and phase behavior of SDS at the sapphire IRE surface was also determined. It was shown that a surface phase transition similar to that discussed occurred at approximately 298 K. The adsorption reaction was found to be exothermic, with a heat of adsorption of --1.3 kcal/mole for adsorption densities less than the adsorption density of the surface phase transition at 298 K and --4.1 kcal/mole for adsorption densities greater than the adsorption density of the surface phase transition

  1. Interaction of compliant surfaces with transitional and turbulent boundary layers

    NASA Astrophysics Data System (ADS)

    Gad-El-Hak, M.; Riley, J. J.; Blackwelder, R. F.

    The interaction of plastisol gel coatings of different thicknesses and shear moduli with transitional and turbulent boundary layers was investigated over a range of velocities. Whenever the free-stream velocity within the fluid was comparable to the transverse wave speed within the solid, large-amplitude static-divergence waves appeared on the surface of the solid. The amplitude of the waves was always of the order of the coating thickness. As the free-stream velocity increased, the waves became less two-dimensional and developed larger variations in their amplitude along the crests. This disturbance led to the formation of additional waves downstream having a shorter span. Ways of reducing or eliminating the static-divergence waves are briefly discussed.

  2. Measurement of atmospheric surface layer turbulence using unmanned aerial vehicles

    NASA Astrophysics Data System (ADS)

    Witte, Brandon; Smith, Lorli; Schlagenhauf, Cornelia; Bailey, Sean

    2016-11-01

    We describe measurements of the turbulence within the atmospheric surface layer using highly instrumented and autonomous unmanned aerial vehicles (UAVs). Results from the CLOUDMAP measurement campaign in Stillwater Oklahoma are presented including turbulence statistics measured during the transition from stably stratified to convective conditions. The measurements were made using pre-fabricated fixed-wing remote-control aircraft adapted to fly autonomously and carry multi-hole pressure probes, pressure, temperature and humidity sensors. Two aircraft were flown simultaneously, with one flying a flight path intended to profile the boundary layer up to 100 m and the other flying at a constant fixed altitude of 50 m. The evolution of various turbulent statistics was determined from these flights, including Reynolds stresses, correlations, spectra and structure functions. These results were compared to those measured by a sonic anemometer located on a 7.5 m tower. This work was supported by the National Science Foundation through Grant #CBET-1351411 and by National Science Foundation award #1539070, Collaboration Leading Operational UAS Development for Meteorology and Atmospheric Physics (CLOUDMAP).

  3. 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.

  4. Density functional theory study of SO2-adsorbed Ni(1 1 1) and hydroxylated NiO(1 1 1) surface

    NASA Astrophysics Data System (ADS)

    Wei, Xin; Dong, Chaofang; Chen, Zhanghua; Xiao, Kui; Li, Xiaogang

    2015-11-01

    Spin polarized, DFT + U periodic calculation is used as an effective way to model the adsorption process of SO2 on hydroxylated NiO(1 1 1) surface. The adsorption of atomic O and O2 on the clean Ni(1 1 1) surface is calculated to investigate the forming process of passive film. The molecular and dissociated adsorptions of H2O on NiO(1 1 1) surface are evaluated to construct defect-free hydroxylated NiO(1 1 1) surface. The adsorption of SO2 and atomic O on clean Ni(1 1 1) surface is also investigated to compare with the adsorption capacity between passive film and substrate. With respect to the single adsorption process of SO2 on defect-free hydroxylated NiO(1 1 1) surface, the effects of O vacancy of surface and atomic O closed to the surface are investigated. The calculation results show that there is no chemical adsorption of SO2 on the defect-free hydroxylated NiO(1 1 1) surface with or without atomic O. Either single SO2 or SO2 with atomic O prefer adsorbing on the hydroxylated NiO(1 1 1) surface with O vacancies. The adsorption behavior is strengthened with the increase of percentage of surface O vacancy. The existence of atomic O leads to the production of SO3 on the hydroxylated NiO(1 1 1) surface and strengthens the adsorption capacity of SO2. Furthermore, the results also reveal the relationship between the charge transfer and the adsorption energy of SO2 and atomic O on the hydroxylated NiO(1 1 1) surface and clean Ni(1 1 1) surface. We inferred that broken passive film susceptibility to corrosion compare with substrate when surface O vacancies aggregate and its concentration large enough.

  5. Surface Layer Turbulence Measurements during a Frontal Passage.

    NASA Astrophysics Data System (ADS)

    Piper, M.; Lundquist, Julie K.

    2004-07-01

    Very little is known about the nature of turbulence in the transition zone of a synoptic-scale cold front, especially at the dissipative scales. Lacking this knowledge, accurate models of surface frontogenesis are compromised. To address this problem, high-frequency measurements from sonic and hot-wire anemometers are used to analyze the finescale turbulence in the atmospheric surface layer (ASL) within a cold front observed in the MICROFRONTS field experiment. To quantify the turbulence in the front, velocity spectra and dissipation rates are calculated as functions of time and stability in the ASL. The normalized first and second moments of the one-dimensional velocity spectrum conform to the scaling suggested by Kolmogorov's equilibrium hypotheses, even during the intense turbulence associated with the frontal passage. The spectra compare well with other data collected at high Reλ in the ASL, but not as well with a recent model of the dissipative range of turbulence. Dissipation rate is calculated with one direct and two indirect techniques. The calculations from the different techniques compare well with one another and, when nondimensionalized, with a historical expression for dissipation rate as a function of ASL stability. The magnitude of the dissipation rate increases by an order of magnitude to a maximum value of 1.2 m2 s-3 during the frontal passage compared to prefrontal values of 0.05 m2 s-3; the latter is typical for a slightly stable nighttime boundary layer over land. These results can be used in assessing the effects of turbulence in traditional semigeostrophic models of frontal collapse. The dissipation rate calculations may be of particular use to modelers.


  6. Modification of Turbulent Boundary Layer Flows by Superhydrophobic Surfaces

    NASA Astrophysics Data System (ADS)

    Gose, James W.; Golovin, Kevin; Barros, Julio; Schultz, Michael P.; Tuteja, Anish; Perlin, Marc; Ceccio, Steven L.

    2016-11-01

    Measurements of near zero pressure gradient turbulent boundary layer (TBL) flow over several superhydrophobic surfaces (SHSs) are presented and compared to those for a hydraulically smooth baseline. The surfaces were developed at the University of Michigan as part of an ongoing research thrust to investigate the feasibility of SHSs for skin-friction drag reduction in turbulent flow. The SHSs were previously evaluated in fully-developed turbulent channel flow and have been shown to provide meaningful drag reduction. The TBL experiments were conducted at the USNA in a water tunnel with a test section 2.0 m (L) x 0.2 m (W) x 0.2 m (H). The free-stream speed was set to 1.26 m/s which corresponded to a friction Reynolds number of 1,500. The TBL was tripped at the test section inlet with a 0.8 mm diameter wire. The upper and side walls provided optical access, while the lower wall was either the smooth baseline or a spray coated SHS. The velocity measurements were obtained with a TSI FSA3500 two-component Laser-Doppler Velocimeter (LDV) and custom-designed beam displacer operated in coincidence mode. The LDV probe volume diameter was 45 μm (approx. one wall-unit). The measurements were recorded 1.5 m downstream of the trip. When the measured quantities were normalized using the inner variables, the results indicated a significant reduction in the near wall viscous and total stresses with little effect on the flow outside the inner layer.

  7. Metal-free phthalocyanine (H2Pc) molecule adsorbed on the Au(111) surface: formation of a wide domain along a single lattice direction

    PubMed Central

    Komeda, Tadahiro; Isshiki, Hironari; Liu, Jie

    2010-01-01

    Using low-temperature scanning tunneling microscopy (STM), we observed the bonding configuration of the metal-free phthalocyanine (H2Pc) molecule adsorbed on the Au(111) surface. A local lattice formation started from a quasi-square lattice aligned to the close-packed directions of the Au(111) surface. Although we expected the lattice alignment to be equally distributed along the three crystallographically equivalent directions, the domain aligned normal to the ridge of the herringbone structure was missing in the STM images. We attribute this effect to the uniaxial contraction of the reconstructed Au(111) surface that can account for the formation of a large lattice domain along a single crystallographical direction. PMID:27877365

  8. Application of response surface methodology to optimize the adsorption performance of a magnetic graphene oxide nanocomposite adsorbent for removal of methadone from the environment.

    PubMed

    Kumar Gupta, Vinod; Agarwal, Shilpi; Asif, Mohammad; Fakhri, Ali; Sadeghi, Nima

    2017-03-03

    Magnetic graphene oxide (MGO) nanocomposites have been synthesized by the co-precipitation route. The surface structure of MGO nanocomposites were analyzed by XRD, TEM, SEM, VSM and nitrogen adsorption-desorption instrumental technique. Response surface methodology was used to optimize the removal of methadone by MGO nanocomposites in aqueous solution. Experiments were conducted based on Box-Behnken design (BBD). The influence of three parameters on the removal of methadone was examined using the response surface methodological approach. The significance of independent variables and their interactions were tested by analysis of variance (ANOVA). The optimum pH, adsorbent dose and temperature were found to be 6.2, 0.0098g and 295.7K, respectively. Under these conditions, removal efficiency of methadone was found to be 87.20mg/g.

  9. Molecularly imprinted polydopamine nano-layer on the pore surface of porous particles for protein capture in HPLC column.

    PubMed

    Nematollahzadeh, Ali; Shojaei, Akbar; Abdekhodaie, Mohammad J; Sellergren, Börje

    2013-08-15

    Bio-inspired Human Serum Albumin (HSA) imprinted polydopamine nano-layer was produced through oxidative polymerization of dopamine on the pore surface of HSA modified porous silica particles. The coating thickness was controlled by the reaction time and thereby varied within 0-12 nm. The samples were characterized by elemental analysis, FT-IR, DSC, SEM, TEM, TGA, physisorption and thermoporometry. The characterization confirmed the success of evolution and deposition of polydopamine layer on the silica pore surface. Batch rebinding experiment showed that the molecularly imprinted polymer (MIP) with 8.7 nm coating thickness, in comparison with the thinner and thicker coatings, displays the highest uptake of the target protein. The chromatographic evaluation of the materials packed in HPLC columns showed that the HSA imprinted polydopamine offers good mechanical stability and retains practically all the target protein from an HSA solution or human plasma. Affinity of the imprinting column was examined by using Bovine Serum Albumin (BSA) and Immunoglobulin G (IgG) as competitive proteins. The results showed that the template, HSA, was the most adsorbed protein by the imprinted polydopamine layer.

  10. 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.

  11. Fabricating electrospun cellulose nanofibre adsorbents for ion-exchange chromatography.

    PubMed

    Dods, Stewart R; Hardick, Oliver; Stevens, Bob; Bracewell, Daniel G

    2015-01-09

    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