Flow boundary conditions for chain-end adsorbing polymer blends.

PubMed

Zhou, Xin; Andrienko, Denis; Delle Site, Luigi; Kremer, Kurt

2005-09-08

Using the phenol-terminated polycarbonate blend as an example, we demonstrate that the hydrodynamic boundary conditions for a flow of an adsorbing polymer melt are extremely sensitive to the structure of the epitaxial layer. Under shear, the adsorbed parts (chain ends) of the polymer melt move along the equipotential lines of the surface potential whereas the adsorbed additives serve as the surface defects. In response to the increase of the number of the adsorbed additives the surface layer becomes thinner and solidifies. This results in a gradual transition from the slip to the no-slip boundary condition for the melt flow, with a nonmonotonic dependence of the slip length on the surface concentration of the adsorbed ends.

Electronic structure studies of adsorbate-induced surface reconstructions: oxygen on Rh(1 0 0)

NASA Astrophysics Data System (ADS)

Kirsch, Janet E.; Harris, Suzanne

2004-03-01

Solid-state Fenske-Hall band structure calculations have been used to study the electronic structure and bonding that occur on an "asymmetric" clock reconstructed Rh(1 0 0) surface with a half-monolayer of O atom adsorbates. The displacement of the top-layer Rh atoms on reconstructed O/Rh(1 0 0) is similar to that observed when a half-monolayer of C or N atoms adsorb onto clean Ni(1 0 0). Unlike the five-coordinate C or N adsorbates that adsorb into effectively coplanar sites on the Ni(1 0 0) surface, however, O atoms sit well above the Rh surface plane and occupy three-coordinate adsorption sites. The results of these calculations show that the asymmetric clock reconstruction of O/Rh(1 0 0) increases the negative charge localized on the highly electronegative O atoms and strengthens the O-Rh bonding relative to an unreconstructed surface. This suggests that, in contrast to the C(N)/Ni(1 0 0) clock, which appears to be driven primarily by the restoration of metal-metal bonding, the asymmetric O/Rh(1 0 0) clock reconstruction is driven by the optimization of the O atom bonding environment. Comparisons of the O/Rh(1 0 0) and C(N, O)/Ni(1 0 0) surfaces further indicate that the electronegativity and electron count of the adsorbed species, as well as the electron count and physical size of the metal, all play a role in determining the preferred atomic geometries of these adsorbate-covered transition metal surfaces.

Forces between Two Glass Surfaces with Adsorbed Hexadecyltrimethylammonium Salicylate.

PubMed

Imae, T; Kato, M; Rutland, M

2000-02-22

Forces have been measured for hexadecyltrimethylammonium salicylate (C(16)TASal) layers on glass beads. During the inward process, hydrophobic attraction occurred at lower adsorption of C(16)TASal and electrostatic repulsion interactions happened at higher adsorption. While the jump-in phenomenon was observed for solutions of concentrations below the critical micelle concentration (cmc = 0.15 mM), the step-in phenomenon was characteristic for solutions at the cmc and above the cmc, suggesting the push-out of adsorbed C(16)TASal layers and/or inserted micelles. The remarkable pull-off phenomenon on the outward process occurred for all solutions, indicating a strong interaction between C(16)TASal molecules. For aqueous 0.15 mM C(16)TASal solutions of various NaSal concentrations, on the inward process, the electrostatic repulsive interaction decreased with adding NaSal. This is due to the electrostatic shielding by salt excess. The height of the force wall on the inward process reached a maximum at 0.01 M NaSal, but the interlocking between molecules on two surfaces during the outward process was minimized at 0.1 M NaSal. These tendencies, which are different from that of the electrostatic repulsion interaction, imply the strong cohesion between adsorbed C(16)TASal layers.

Double-Layer Structured CO2 Adsorbent Functionalized with Modified Polyethyleneimine for High Physical and Chemical Stability.

PubMed

Jeon, Sunbin; Jung, Hyunchul; Kim, Sung Hyun; Lee, Ki Bong

2018-06-18

CO 2 capture using polyethyleneimine (PEI)-impregnated silica adsorbents has been receiving a lot of attention. However, the absence of physical stability (evaporation and leaching of amine) and chemical stability (urea formation) of the PEI-impregnated silica adsorbent has been generally established. Therefore, in this study, a double-layer impregnated structure, developed using modified PEI, is newly proposed to enhance the physical and chemical stabilities of the adsorbent. Epoxy-modified PEI and diepoxide-cross-linked PEI were impregnated via a dry impregnation method in the first and second layers, respectively. The physical stability of the double-layer structured adsorbent was noticeably enhanced when compared to the conventional adsorbents with a single layer. In addition to the enhanced physical stability, the result of simulated temperature swing adsorption cycles revealed that the double-layer structured adsorbent presented a high potential working capacity (3.5 mmol/g) and less urea formation under CO 2 -rich regeneration conditions. The enhanced physical and chemical stabilities as well as the high CO 2 working capacity of the double-layer structured adsorbent were mainly attributed to the second layer consisting of diepoxide-cross-linked PEI.

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.

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.

Influence of alkane and perfluorocarbon vapors on adsorbed surface layers and spread insoluble monolayers of surfactants, proteins and lipids.

PubMed

Fainerman, V B; Aksenenko, E V; Miller, R

2017-06-01

The influence of hexane vapor in the air atmosphere on the surface tension of water and solutions of C 10 EO 8 , C n TAB and proteins are presented. For dry air, a fast and strong decrease of surface tension of water was observed. In humid air, the process is slower and the surface tension higher. There are differences between the results obtained by the maximum bubble pressure, pendant drop and emerging bubble methods, which are discussed in terms of depletion and initial surface load. The surface tension of aqueous solutions of β-сasein (BCS), β-lactoglobulin (BLG) and human serum albumin (HSA) at the interfaces with air and air-saturated hexane vapor were measured. The results indicate that the equilibrium surface tension in the hexane vapor atmosphere is considerably lower (at 13-20mN/m) as compared to the values at the interface with pure air. A reorientation model is proposed assuming several states of adsorbed molecules with different molar area values. The newly developed theoretical model is used to describe the effect of alkane vapor in the gas phase on the surface tension. This model assumes that the first layer is composed of surfactant (or protein) molecules mixed with alkane, and the second layer is formed by alkane molecules only. The processing of the experimental data for the equilibrium surface tension for the C 10 EO 8 and BCS solutions results in a perfect agreement between the observed and calculated values. The co-adsorption mechanism of dipalmitoyl phosphatidyl choline (DPPC) and the fluorocarbon molecules leads to remarkable differences in the surface pressure term of cohesion Π coh . This in turn leads to a very efficient fluidization of the monolayer. It was found that the adsorption equilibrium constant for dioctanoyl phosphatidyl choline is increased in the presence of perfluorohexane, and the intermolecular interaction of the components is strong. Copyright © 2015 Elsevier B.V. All rights reserved.

Internal Reflection Spectra of Surface Compounds and Adsorbed Molecules

NASA Astrophysics Data System (ADS)

Zolotarev, V. M.; Lygin, V. I.; Tarasevich, B. N.

1981-01-01

The application of attenuated total reflection (ATR) spectroscopy in surface studies of inorganic adsorbents and catalysts, polymers, and optically transparent electrodes is discussed. The basic principles of ATR spectroscopy as applied to surface phenomena are considered, with special reference to thin films, industrial adsorbents and catalysts, and polymer degradation processes. 276 references.

Modifying protein adsorption by layers of glutathione pre-adsorbed on Au(111)

NASA Astrophysics Data System (ADS)

Vallée, Anne; Humblot, Vincent; Méthivier, Christophe; Dumas, Paul; Pradier, Claire-Marie

2011-12-01

Molecular interaction with metal surfaces raises fundamental questions regarding their binding tendency, their dispersion on the surface, as well as their conformation which may change their biological properties; addressing these questions, and being able to tune protein interactions, is of primary importance for the control of biointerfaces. In this study, one tripeptide, GSH (glu-cys-gly), was used to condition gold surfaces and thus influence the adsorption of bovine serum albumin (BSA). Depending on the pH value of the GSH solution, cationic, zwitterionic or anionic forms of the tripeptide could be stabilised on the surface, before interacting with BSA solutions. The amount of proteins was observed to depend both on the chemical state of the adsorbed underlying peptide and on the solvent of the protein solution, indicating an important role of electrostatic interactions upon protein adsorption. Moreover, atomic force microscopy (AFM), and synchrotron IR microscopy revealed a heterogeneous distribution of proteins on the GSH layer.

Electric-field-induced forces between two surfaces filled with an insulating liquid: the role of adsorbed water

NASA Astrophysics Data System (ADS)

Wang, Yong Jian; Xu, Zuli; Sheng, Ping; Tong, Penger

2014-06-01

A systematic study of the electric-field-induced forces between a solid glass sphere and a flat gold-plated substrate filled with an insulating liquid has been carried out. Using atomic force microscopy, we measure the electrostatic force f(s, V) between the sphere and substrate as a function of the surface separation s and applied voltage V. The measured f(s, V) is found to be well described by an equation for a conducting sphere. Further force measurements for the "wet" porous glass spheres filled with an aqueous solution of urea and the dried porous glass spheres filled with (dry) air suggest that there is a water layer of a few nanometers in thickness adsorbed on the hydrophilic glass surface under ambient conditions. This adsorbed water layer is more conductive than the dielectric core of the glass sphere, making the sphere surface to be at a potential close to that of the cantilever electrode. As a result, the electric field is strongly concentrated in the gap region between the glass sphere and gold-plate substrate and thus their electrostatic attraction is enhanced. This surface conductivity effect is further supported by the thermal gravimetric analysis (TGA) and force response measurements to a time-dependent electric field. The experiment clearly demonstrates that the adsorption of a conductive water layer on a hydrophilic surface plays a dominant role in determining the electrostatic interaction between the dielectric sphere and substrate.

Patterned layers of adsorbed extracellular matrix proteins: influence on mammalian cell adhesion.

PubMed

Dupont-Gillain, C C; Alaerts, J A; Dewez, J L; Rouxhet, P G

2004-01-01

Three patterned systems aiming at the control of mammalian cell behavior are presented. The determinant feature common to these systems is the spatial distribution of extracellular matrix (ECM) proteins (mainly collagen) on polymer substrates. This distribution differs from one system to another with respect to the scale at which it is affected, from the supracellular to the supramolecular scale, and with respect to the way it is produced. In the first system, the surface of polystyrene was oxidized selectively to form micrometer-scale patterns, using photolithography. Adsorption of ECM proteins in presence of a competitor was enhanced on the oxidized domains, allowing selective cell adhesion to be achieved. In the second system, electron beam lithography was used to engrave grooves (depth and width approximately 1 microm) on a poly(methyl methacrylate) (PMMA) substratum. No modification of the surface chemistry associated to the created topography could be detected. Cell orientation along the grooves was only observed when collagen was preadsorbed on the substratum. In the third system, collagen adsorbed on PMMA was dried in conditions ensuring the formation of a nanometer-scale pattern. Cell adhesion was enhanced on such patterned collagen layers compared to smooth collagen layers.

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

PubMed

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

2015-12-15

The objective of this work is to investigate the rate, extent, and structure of amphoteric proteins with charged solid surfaces over a range of applied potentials and surface charges. We use Electrochemical Quartz Crystal Microbalance with Dissipation Monitoring (E-QCM-D) to investigate the adsorption of amphoteric Bovine Serum Albumin (BSA) to a gold electrode while systematically varying the surface charge on the adsorbate and adsorbent by manipulating pH and applied potential, respectively. We also perform cyclic voltammetry-E-QCM-D on an adsorbed layer of BSA to elucidate conformational changes in response to varied applied potentials. We confirm previous results demonstrating that increasing magnitude of applied potential on the gold electrode is positively correlated with increasing mass adsorption when the protein and the surface are oppositely charged. On the other hand, we find that the rate of BSA adsorption is not governed by simple electrostatics, but instead depends on solution pH, an observation not well documented in the literature. Cyclic voltammetry with simultaneous E-QCM-D measurements suggest that BSA protein undergoes a conformational change as the surface potential varies. Copyright © 2015 Elsevier Inc. All rights reserved.

Quantum impurity models for magnetic adsorbates on superconductor surfaces

NASA Astrophysics Data System (ADS)

Žitko, Rok

2018-05-01

Magnetic atoms adsorbed on surfaces have a quenched orbital moment while their ground-state spin multiplet is partially split as a consequence of the spin-orbit coupling which, even if intrinsically weak, has a large effect due to the abrupt change of the potential at the surface. Such metal adsorbates should be modelled using quantum impurity models that include the relevant internal degrees of freedom and the interaction terms, in particular the magnetic anisotropy and the Kondo exchange coupling. When adsorbed on superconducting surfaces, these impurities have complex spectra of sub-gap excitations due to magnetic anisotropy splitting and Kondo screening. Both anisotropy splitting and Zeeman splitting due to the external magnetic field are significantly renormalized by the coupling to the substrate electrons. In this work I discuss the quantum-to-classical crossover and the applicability of classical static-local-spin picture for discussing magnetic nanostructures on superconductors.

Adsorbate-driven morphological changes on Cu(111) nano-pits

DOE PAGES

Mudiyanselage, K.; Xu, F.; Hoffmann, F. M.; ...

2014-12-09

Adsorbate-driven morphological changes of pitted-Cu(111) surfaces have been investigated following the adsorption and desorption of CO and H. The morphology of the pitted-Cu(111) surfaces, prepared by Ar + sputtering, exposed a few atomic layers deep nested hexagonal pits of diameters from 8 to 38 nm with steep step bundles. The roughness of pitted-Cu(111) surfaces can be healed by heating to 450-500 K in vacuum. Adsorption of CO on the pitted-Cu(111) surface leads to two infrared peaks at 2089-2090 and 2101-2105 cm -1 for CO adsorbed on under-coordinated sites in addition to the peak at 2071 cm -1 for CO adsorbedmore » on atop sites of the close-packed Cu(111) surface. CO adsorbed on under-coordinated sites is thermally more stable than that of atop Cu(111) sites. Annealing of the CO-covered surface from 100 to 300 K leads to minor changes of the surface morphology. In contrast, annealing of a H covered surface to 300 K creates a smooth Cu(111) surface as deduced from infrared data of adsorbed CO and scanning tunnelling microscopy (STM) imaging. The observation of significant adsorbate-driven morphological changes with H is attributed to its stronger modification of the Cu(111) surface by the formation of a sub-surface hydride with a hexagonal structure, which relaxes into the healed Cu(111) surface upon hydrogen desorption. These morphological changes occur ~150 K below the temperature required for healing of the pitted-Cu(111) surface by annealing in vacuum. In contrast, the adsorption of CO, which only interacts with the top-most Cu layer and desorbs by 160 K, does not significantly change the morphology of the pitted-Cu(111) surface.« less

Static and hydrodynamic studies of the conformation of adsorbed macromolecules at the solid/liquid interface

NASA Astrophysics Data System (ADS)

Yavorsky, D. P.

1981-08-01

The structure of an adsorbed macromolecular layer at the solid/liquid interface under both stationary and flow conditions is examined. The conformation of adsorbed bovine serum albumin (BSA) is deduced from the thickness of surface layers formed on the pore walls of track etched (mica) membranes. Changes in membrane permeability due to protein adsorption are related directly to a net reduction in pore size or an equivalent adsorbed layer thickness. Complementary permeability measurements using electrolyte conduction, tracer diffusion, and pressure driven flow have verified the unique structural qualities of the track etched membrane and collectively demonstrate an ability to determine bare pore size with an accuracy of + or - 2A. The average static thickness of an adsorbed BSA layer, as derived from electrolyte conduction and tracer diffusion, was 43 + or - 3A independent of pore size. In comparison with the known BSA solution dimensions, this measured thickness is consistent with a monolayer of structurally unperturbed protein molecules each oriented in a "side-on" position. Pronounced conformational changes in adsorbed BSA layers were observed under conditions of shear flow. Electrostatic interactions were also shown to significantly affect adsorbed protein conformation through changes in solution ionic strength and surface charge.

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

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

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

PubMed

Tachikawa, Hiroto

2016-09-22

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

Structural features of the adsorption layer of pentacene on the graphite surface and the PMMA/graphite hybrid surface

NASA Astrophysics Data System (ADS)

Fadeeva, A. I.; Gorbunov, V. A.; Litunenko, T. A.

2017-08-01

Using the molecular dynamics and the Monte Carlo methods, we have studied the structural features and growth mechanism of the pentacene film on graphite and polymethylmethacrylate /graphite surfaces. Monolayer capacity and molecular area, optimal angles between the pentacene molecules and graphite and PMMA/graphite surfaces as well as the characteristic angles between the neighboring pentacene molecules in the adsorption layer were estimated. It is shown that the orientation of the pentacene molecules in the film is determined by a number of factors, including the surface concentration of the molecules, relief of the surface, presence or absence of the polymer layer and its thickness. The pentacene molecules adsorbed on the graphite surface keep a horizontal position relative to the long axis at any surface coverage/thickness of the film. In the presence of the PMMA layer on the graphite, the increase of the number of pentacene molecules as well as the thickness of the PMMA layer induce the change of molecular orientation from predominantly horizontal to vertical one. The reason for such behavior is supposed to be the roughness of the PMMA surface.

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.

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.

Quantification of the Influence of Protein-Protein Interactions on Adsorbed Protein Structure and Bioactivity

PubMed Central

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

2013-01-01

While protein-surface interactions have been widely studied, relatively little is understood at this time regarding how protein-surface interaction effects are influenced by protein-protein interactions and how these effects combine with the internal stability of a protein to influence its adsorbed-state structure and bioactivity. The objectives of this study were to develop a method to study these combined effects under widely varying protein-protein interaction conditions using hen egg-white lysozyme (HEWL) adsorbed on silica glass, poly(methyl methacrylate), and polyethylene as our model systems. In order to vary protein-protein interaction effects over a wide range, HEWL was first adsorbed to each surface type under widely varying protein solution concentrations for 2 h to saturate the surface, followed by immersion in pure buffer solution for 15 h to equilibrate the adsorbed protein layers in the absence of additionally adsorbing protein. Periodic measurements were made at selected time points of the areal density of the adsorbed protein layer as an indicator of the level of protein-protein interaction effects within the layer, and these values were then correlated with measurements of the adsorbed protein’s secondary structure and bioactivity. The results from these studies indicate that protein-protein interaction effects help stabilize the structure of HEWL adsorbed on silica glass, have little influence on the structural behavior of HEWL on HDPE, and actually serve to destabilize HEWL’s structure on PMMA. The bioactivity of HEWL on silica glass and HDPE was found to decrease in direct proportion to the degree of adsorption-induce protein unfolding. A direct correlation between bioactivity and the conformational state of adsorbed HEWL was less apparent on PMMA, thus suggesting that other factors influenced HEWL’s bioactivity on this surface, such as the accessibility of HEWL’s bioactive site being blocked by neighboring proteins or the surface

Astrocytes Specifically Remove Surface-Adsorbed Fibrinogen and Locally Express Chondroitin Sulfate Proteoglycans

PubMed Central

Hsiao, Tony W.; Swarup, Vimal P.; Kuberan, Balagurunathan; Tresco, Patrick A.; Hlady, Vladimir

2013-01-01

Surface-adsorbed fibrinogen (FBG) was recognized by adhering astrocytes and removed from the substrates in vitro by a two-phase removal process. The cells removed adsorbed FBG from binary proteins surface patterns (FBG + laminin, or FBG + albumin) while leaving the other protein behind. Astrocytes preferentially expressed chondroitin sulfate proteoglycan (CSPG) at the loci of fibrinogen stimuli; however no differences in overall CSPG production as a function of FBG surface coverage were identified. Removal of FBG by astrocytes was also found to be independent of transforming growth factor type β (TGF-β) receptor based signaling as cells maintained CSPG production in the presence of TGF-β receptor kinase inhibitor, SB 431542. The inhibitor decreased CSPG expression, but did not abolicsh it entirely. Because blood contact and subsequent FBG adsorption are unavoidable in neural implantations, the results indicate that implant-adsorbed FBG may contribute to reactive astrogliosis around the implant as astrocytes specifically recognize adsorbed FBG. PMID:23499985

Tunable electronic structure and spin splitting in single and multiple Fe-adsorbed g-C2N with different layers: A first-principles study

NASA Astrophysics Data System (ADS)

Zheng, Z. D.; Wang, X. C.; Mi, W. B.

2018-04-01

The electronic structure of Fe adsorbed g-C2N with different layers is investigated by first-principles calculations. The Fe1 and Fe2 represent the Fe adsorptions at Csbnd C and Csbnd N rings, and Fe11 and Fe121 adsorption sites are also considered. The Fe1 adsorbed g-C2N is metallic with layer from n = 1 to 4, and the maximum spin splitting is 515, 428, 46 and 133 meV. The band gap of Fe2 adsorbed g-C2N with different layers is 0, 0, 117 and 6 meV, and the maximum spin splitting is 565, 369, 195 and 146 meV, respectively. All of the Fe11 adsorbed g-C2N are metallic with layer from n = 1 to 4, and the maximum spin splitting is 199, 0, 83 and 203 meV. An indirect band gap of 215 meV appears in Fe121 adsorbed g-C2N at layer n = 3, and the maximum spin splitting is 283, 211, 304 and 153 meV, respectively. Our results show that the electronic structures of Fe adsorbed novel two-dimensional semiconductor g-C2N can be tuned by different layers. Moreover, the spin splitting of Fe2 adsorbed g-C2N decreases monotonically as g-C2N layer increases from n = 1 to 4, which will provide more potential applications in spintronic devices.

Atomic force microscopy of adsorbed proteoglycan mimetic nanoparticles: Toward new glycocalyx-mimetic model surfaces.

PubMed

Hedayati, Mohammadhasan; Kipper, Matt J

2018-06-15

Blood vessels present a dense, non-uniform, polysaccharide-rich layer, called the endothelial glycocalyx. The polysaccharides in the glycocalyx include polyanionic glycosaminoglycans (GAGs). This polysaccharide-rich surface has excellent and unique blood compatibility. We report new methods for preparing and characterizing dense GAG surfaces that can serve as models of the vascular endothelial glycocalyx. The GAG-rich surfaces are prepared by adsorbing heparin or chondroitin sulfate-containing polyelectrolyte complex nanoparticles (PCNs) to chitosan-hyaluronan polyelectrolyte multilayers (PEMs). The surfaces are characterized by PeakForce tapping atomic force microscopy, both in air and in aqueous pH 7.4 buffer, and by PeakForce quantitative nanomechanics (PF-QNM) mode with high spatial resolution. These new surfaces provide access to heparin-rich or chondroitin sulfate-rich coatings that mimic both composition and nanoscale structural features of the vascular endothelial glycocalyx. Copyright © 2018. Published by Elsevier Ltd.

Effect of adsorbed/intercalated anionic dyes into the mechanical properties of PVA: layered zinc hydroxide nitrate nanocomposites.

PubMed

Marangoni, Rafael; Mikowski, Alexandre; Wypych, Fernando

2010-11-15

Zinc hydroxide nitrate (ZHN) was adsorbed with anions of blue dyes (Chicago sky blue, CSB; Evans blue, EB; and Niagara blue, NB) and intercalated with anions of orange dyes (Orange G, OG; Orange II, OII; methyl orange, MO). Transparent, homogeneous and colored nanocomposite films were obtained by casting after dispersing the pigments (dye-intercalated/adsorbed into LHSs) into commercial poly(vinyl alcohol) (PVA). The films were characterized by XRD, UV-Vis spectroscopy, and mechanical testing. The mechanical properties of the PVA compounded with the dye-intercalated/adsorbed ZHN were evaluated, and reasonable increases in Young's modulus and ultimate tensile strength were observed, depending on the amount and choice of layered filler. These results demonstrate the possibility of using a new class of layered hydroxide salts intercalated and adsorbed with anionic dyes to prepare multifunctional polymer nanocomposite materials. Copyright © 2010 Elsevier Inc. All rights reserved.

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.

Multiscale structure, interfacial cohesion, adsorbed layers, miscibility and properties in dense polymer-particle mixtures

NASA Astrophysics Data System (ADS)

Schweizer, Ken

2012-02-01

A major goal in polymer nanocomposite research is to understand and predict how the chemical and physical nature of individual polymers and nanoparticles, and thermodynamic state (temperature, composition, solvent dilution, filler loading), determine bulk assembly, miscibility and properties. Microscopic PRISM theory provides a route to this goal for equilibrium disordered mixtures. A major prediction is that by manipulating the net polymer-particle interfacial attraction, miscibility is realizable via the formation of thin thermodynamically stable adsorbed layers, which, however, are destroyed by entropic depletion and bridging attraction effects if interface cohesion is too weak or strong, respectively. This and related issues are quantitatively explored for miscible mixtures of hydrocarbon polymers, silica nanospheres, and solvent using x-ray scattering, neutron scattering and rheology. Under melt conditions, quantitative agreement between theory and silica scattering experiments is achieved under both steric stabilization and weak depletion conditions. Using contrast matching neutron scattering to characterize the collective structure factors of polymers, particles and their interface, the existence and size of adsorbed polymer layers, and their consequences on microstructure, is determined. Failure of the incompressible RPA, accuracy of PRISM theory, the nm thickness of adsorbed layers, and qualitative sensitivity of the bulk modulus to interfacial cohesion and particle size are demonstrated for concentrated PEO-silica-ethanol nanocomposites. Temperature-dependent complexity is discovered when water is the solvent, and nonequilibrium effects emerge for adsorbing entangled polymers that strongly impact structure. By varying polymer chemistry, the effect of polymer-particle attraction on the intrinsic viscosity is explored with striking non-classical effects observed. This work was performed in collaboration with S.Y.Kim, L.M.Hall, C.Zukoski and B.Anderson.

Model simulations of the adsorption of statherin to solid surfaces: Effects of surface charge and hydrophobicity

NASA Astrophysics Data System (ADS)

Skepö, M.

2008-11-01

The structural properties of the salivary protein statherin upon adsorption have been examined using a coarse-grained model and Monte Carlo simulation. A simple model system with focus on electrostatic interactions and short-ranged attractions among the uncharged amino acids has been used. To mimic hydrophobically modified surfaces, an extra short-ranged interaction was implemented between the amino acids and the surface. It has been shown that the adsorption and the thickness of the adsorbed layer are determined by (i) the affinity for the surface, i.e., denser layer with an extrashort-ranged potential, and (ii) the distribution of the charges along the chain. If all the amino acids have a high affinity for the surface, the protein adsorbs in a train conformation, if the surface is negatively charged the protein adsorbs in a tail-train conformation, whereas if the surface is positively charged the protein adsorbs in a loop conformation. The latter gives rise to a more confined adsorbed layer.

Interfacial layers from the protein HFBII hydrophobin: dynamic surface tension, dilatational elasticity and relaxation times.

PubMed

Alexandrov, Nikola A; Marinova, Krastanka G; Gurkov, Theodor D; Danov, Krassimir D; Kralchevsky, Peter A; Stoyanov, Simeon D; Blijdenstein, Theodorus B J; Arnaudov, Luben N; Pelan, Eddie G; Lips, Alex

2012-06-15

The pendant-drop method (with drop-shape analysis) and Langmuir trough are applied to investigate the characteristic relaxation times and elasticity of interfacial layers from the protein HFBII hydrophobin. Such layers undergo a transition from fluid to elastic solid films. The transition is detected as an increase in the error of the fit of the pendant-drop profile by means of the Laplace equation of capillarity. The relaxation of surface tension after interfacial expansion follows an exponential-decay law, which indicates adsorption kinetics under barrier control. The experimental data for the relaxation time suggest that the adsorption rate is determined by the balance of two opposing factors: (i) the barrier to detachment of protein molecules from bulk aggregates and (ii) the attraction of the detached molecules by the adsorption layer due to the hydrophobic surface force. The hydrophobic attraction can explain why a greater surface coverage leads to a faster adsorption. The relaxation of surface tension after interfacial compression follows a different, square-root law. Such behavior can be attributed to surface diffusion of adsorbed protein molecules that are condensing at the periphery of interfacial protein aggregates. The surface dilatational elasticity, E, is determined in experiments on quick expansion or compression of the interfacial protein layers. At lower surface pressures (<11 mN/m) the experiments on expansion, compression and oscillations give close values of E that are increasing with the rise of surface pressure. At higher surface pressures, E exhibits the opposite tendency and the data are scattered. The latter behavior can be explained with a two-dimensional condensation of adsorbed protein molecules at the higher surface pressures. The results could be important for the understanding and control of dynamic processes in foams and emulsions stabilized by hydrophobins, as well as for the modification of solid surfaces by adsorption of such

Physicochemical controls on adsorbed water film thickness in unsaturated geological media

NASA Astrophysics Data System (ADS)

Tokunaga, Tetsu K.

2011-08-01

Adsorbed water films commonly coat mineral surfaces in unsaturated soils and rocks, reducing flow and transport rates. Therefore, it is important to understand how adsorbed film thickness depends on matric potential, surface chemistry, and solution chemistry. Here the problem of adsorbed water film thickness is examined by combining capillary scaling with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Novel aspects of this analysis include determining capillary influences on film thicknesses and incorporating solution chemistry-dependent electrostatic potential at air-water interfaces. Capillary analysis of monodisperse packings of spherical grains provided estimated ranges of matric potentials where adsorbed films are stable and showed that pendular rings within drained porous media retain most of the "residual" water except under very low matric potentials. Within drained pores, capillary contributions to thinning of adsorbed films on spherical grains are shown to be small, such that DLVO calculations for flat surfaces are suitable approximations. Hamaker constants of common soil minerals were obtained to determine ranges of the dispersion component to matric potential-dependent film thickness. The pressure component associated with electrical double-layer forces was estimated using the compression and linear superposition approximations. The pH-dependent electrical double-layer pressure component is the dominant contribution to film thicknesses at intermediate values of matric potential, especially in lower ionic strength solutions (<10 mol m-3) on surfaces with higher-magnitude electrostatic potentials (more negative than ≈-50 mV). Adsorbed water films are predicted to usually range in thickness from ≈1 to 20 nm in drained pores and fractures of unsaturated environments.

Double layer mixed matrix membrane adsorbers improving capacity and safety hemodialysis

NASA Astrophysics Data System (ADS)

Saiful; Borneman, Z.; Wessling, M.

2018-05-01

Double layer mixed matrix membranes adsorbers have been developed for blood toxin removal by embedding activated carbon into cellulose acetate macroporous membranes. The membranes are prepared by phase inversion method via water vapor induced phase separation followed by an immersion precipitation step. Double layer MMM consisting of an active support and a separating layer. The active support layer consists of activated carbon particles embedded in macroporous cellulose acetate; the separating layer consists of particle free cellulose acetate. The double layer membrane possess an open and interconnected macroporous structure with a high loading of activated carbon available for blood toxins removal. The MMM AC has a swelling degree of 6.5 %, porosity of 53 % and clean water flux of 800 Lm-2h-1bar-1. The prepared membranes show a high dynamic Creatinine (Crt) removal during hemodilysis process. The Crt removal by adsorption contributes to amore than 83 % of the total removal. The double layer adsorptive membrane proves hemodialysis membrane can integrated with adsorption, in which blood toxins are removed in one step.

Conformational changes of the amyloid beta-peptide (1-40) adsorbed on solid surfaces.

PubMed

Giacomelli, Carla E; Norde, Willem

2005-05-23

The conformational change of the 39-43 residues of the amyloid beta-peptide (Abeta) toward a beta-sheet enriched state promotes self-aggregation of the peptide molecules and constitutes the major peptide component of the amyloid plaques in Alzheimer patients. The crucial question behind the self-aggregation of Abeta is related to the different pathways the peptide may take after cleavage from the amyloid precursor proteins at cellular membranes. This work is aiming at determining the conformation of the Abeta (1-40) adsorbed on hydrophobic Teflon and hydrophilic silica particles, as model sorbent surfaces mimicking the apolar transmembrane environment and the polar, charged membrane surface, respectively. The mechanism by which the Abeta interacts with solid surfaces strongly depends on the hydrophobic/hydrophilic character of the particles. Hydrophobic and electrostatic interactions contribute differently in each case, causing a completely different conformational change of the adsorbed molecules on the two surfaces. When hydrophobic interactions between the peptide and the sorbent prevail, the adsorbed Abeta (1-40) mainly adopts an alpha-helix conformation due to H-bonding in the apolar part of the peptide that is oriented towards the surface. On the other hand, when the peptide adsorbs by electrostatic interactions beta-sheet formation is promoted due to intermolecular association between the apolar parts of the adsorbed peptide. Irrespective of the characteristics of the solid sorbent, crowding the surface results in intermolecular association between adsorbed molecules leading to a strong aggregation tendency of the Abeta (1-40). [Diagram: see text] CD spectra of Abeta (1-40) at pH 7: A) in solution ([Abeta]=0.2 mg.ml(-1)) freshly prepared (line) and after overnight incubation (symbols);B) on Teflon (Gamma=0.5 mg.m(-2)).

In situ modification of chromatography adsorbents using cold atmospheric pressure plasmas

NASA Astrophysics Data System (ADS)

Olszewski, P.; Willett, T. C.; Theodosiou, E.; Thomas, O. R. T.; Walsh, J. L.

2013-05-01

Efficient manufacturing of increasingly sophisticated biopharmaceuticals requires the development of new breeds of chromatographic materials featuring two or more layers, with each layer affording different functions. This letter reports the in situ modification of a commercial beaded anion exchange adsorbent using atmospheric pressure plasma generated within gas bubbles. The results show that exposure to He-O2 plasma in this way yields significant reductions in the surface binding of plasmid DNA to the adsorbent exterior, with minimal loss of core protein binding capacity; thus, a bi-layered chromatography material exhibiting both size excluding and anion exchange functionalities within the same bead is produced.

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

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. Copyright © 2013 Elsevier Ltd. All rights reserved.

Nonadiabatic dynamics of electron scattering from adsorbates in surface bands

NASA Astrophysics Data System (ADS)

Gumhalter, Branko; Šiber, Antonio; Buljan, Hrvoje; Fauster, Thomas

2008-10-01

We present a comparative study of nonadiabatic dynamics of electron scattering in quasi-two-dimensional surface band which is induced by the long-range component of the interactions with a random array of adsorbates. Using three complementary model descriptions of intraband spatiotemporal propagation of quasiparticles that go beyond the single-adsorbate scattering approach we are able to identify distinct subsequent regimes of evolution of an electron following its promotion into an unoccupied band state: (i) early quadratic or ballistic decay of the initial-state survival probability within the Heisenberg uncertainty window, (ii) preasymptotic exponential decay governed by the self-consistent Fermi golden rule scattering rate, and (iii) asymptotic decay described by a combined inverse power-law and logarithmic behavior. The developed models are applied to discuss the dynamics of intraband adsorbate-induced scattering of hot electrons excited into the n=1 image-potential band on Cu(100) surface during the first stage of a two-photon photoemission process. Estimates of crossovers between the distinct evolution regimes enable assessments of the lifespan of a standard quasiparticle behavior and thereby of the range of applicability of the widely used Fermi golden rule and optical Bloch equations approach for description of adsorbate-induced quasiparticle decay and dephasing in ultrafast experiments.

The molecular mechanism of mediation of adsorbed serum proteins to endothelial cells adhesion and growth on biomaterials.

PubMed

Yang, Dayun; Lü, Xiaoying; Hong, Ying; Xi, Tingfei; Zhang, Deyuan

2013-07-01

To explore molecular mechanism of mediation of adsorbed proteins to cell adhesion and growth on biomaterials, this study examined endothelial cell adhesion, morphology and viability on bare and titanium nitride (TiN) coated nickel titanium (NiTi) alloys and chitosan film firstly, and then identified the type and amount of serum proteins adsorbed on the three surfaces by proteomic technology. Subsequently, the mediation role of the identified proteins to cell adhesion and growth was investigated with bioinformatics analyses, and further confirmed by a series of cellular and molecular biological experiments. Results showed that the type and amount of adsorbed serum proteins associated with cell adhesion and growth was obviously higher on the alloys than on the chitosan film, and these proteins mediated endothelial cell adhesion and growth on the alloys via four ways. First, proteins such as adiponectin in the adsorbed protein layer bound with cell surface receptors to generate signal transduction, which activated cell surface integrins through increasing intracellular calcium level. Another way, thrombospondin 1 in the adsorbed protein layer promoted TGF-β signaling pathway activation and enhanced integrins expression. The third, RGD sequence containing proteins such as fibronectin 1, vitronectin and thrombospondin 1 in the adsorbed protein layer bound with activated integrins to activate focal adhesion pathway, increased focal adhesion formation and actin cytoskeleton organization and mediated cell adhesion and spreading. In addition, the activated focal adhesion pathway promoted the expression of cell growth related genes and resulted in cell proliferation. The fourth route, coagulation factor II (F2) and fibronectin 1 in the adsorbed protein layer bound with cell surface F2 receptor and integrin, activated regulation of actin cytoskeleton pathway and regulated actin cytoskeleton organization. Copyright © 2013 Elsevier Ltd. All rights reserved.

Theory of raman scattering from molecules adsorbed at semiconductor surfaces

NASA Astrophysics Data System (ADS)

Ueba, H.

1983-09-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 ofmore » 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.« less

The effects of spatial inhomogeneities on flow through the endothelial surface layer.

PubMed

Leiderman, Karin M; Miller, Laura A; Fogelson, Aaron L

2008-05-21

Flow through the endothelial surface layer (the glycocalyx and adsorbed plasma proteins) plays an important but poorly understood role in cell signaling through a process known as mechanotransduction. Characterizing the flow rates and shear stresses throughout this layer is critical for understanding how flow-induced ionic currents, deformations of transmembrane proteins, and the convection of extracellular molecules signal biochemical events within the cell, including cytoskeletal rearrangements, gene activation, and the release of vasodilators. Previous mathematical models of flow through the endothelial surface layer are based upon the assumptions that the layer is of constant hydraulic permeability and constant height. These models also assume that the layer is continuous across the endothelium and that the layer extends into only a small portion of the vessel lumen. Results of these models predict that fluid shear stress is dissipated through the surface layer and is thus negligible near endothelial cell membranes. In this paper, such assumptions are removed, and the resultant flow rates and shear stresses through the layer are described. The endothelial surface layer is modeled as clumps of a Brinkman medium immersed in a Newtonian fluid. The width and spacing of each clump, hydraulic permeability, and fraction of the vessel lumen occupied by the layer are varied. The two-dimensional Navier-Stokes equations with an additional Brinkman resistance term are solved using a projection method. Several fluid shear stress transitions in which the stress at the membrane shifts from low to high values are described. These transitions could be significant to cell signaling since the endothelial surface layer is likely dynamic in its composition, density, and height.

Surface-enhanced Raman spectrum of Gly-Gly adsorbed on the silver colloidal surface

NASA Astrophysics Data System (ADS)

Xiaojuan, Yuan; Huaimin, Gu; Jiwei, Wu

2010-08-01

Raman and SERS spectra of homodipeptide Gly-Gly and Gly were recorded and compared in this paper, and band assignment for the functional groups contained in these molecules was analyzed in detail. Time-dependent and pH-dependent SERS spectra of Gly-Gly molecule adsorbed on nano-colloidal silver surface were also studied. The time-dependent SERS spectra of Gly-Gly are characterized by the increase in intensity of bands primarily representing the vibrational signatures emanating from the amino and amide moiety of Gly-Gly molecule. It is found that the adsorption style of Gly-Gly on the silver colloid changes as time goes on; at 5 min after adding the sample to the silver colloid, Gly-Gly adsorbs on silver surface firstly through the carboxylate, amino and amide groups, and then the carboxylate group is far away from the silver surface at 10 min to 3 days. The SERS variation of Gly-Gly with the change of pH suggests that the adsorption style is pH-dependent, the different adsorption behavior of the Gly-Gly occurs on silver surface at different pH values.

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 TiO 2 (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 TiO 2 (110) surface.

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.

Viscoelastic properties of cationic starch adsorbed on quartz studied by QCM-D.

PubMed

Tammelin, Tekla; Merta, Juha; Johansson, Leena-Sisko; Stenius, Per

2004-12-07

The adsorption and viscoelastic properties of layers of a cationic polyelectrolyte (cationic starch, CS, with 2-hydroxy-3-trimethylammoniumchloride as the substituent) adsorbed from aqueous solutions (pH 7.5, added NaCl 0, 1, 100, and 500 mM) on silica were studied with a quartz crystal microbalance with dissipation (QCM-D). Three different starches were investigated (weight-average molecular weights M(w) approximately 8.7 x 10(5) and 4.5 x 10(5) with degree of substitution DS = 0.75 and M(w) approximately 8.8 x 10(5) with DS = 0.2). At low ionic strength, the adsorbed layers are thin and rigid and the amount adsorbed can be calculated using the Sauerbrey equation. When the ionic strength is increased, significant changes take place in the amount of adsorbed CS and the viscoelasticity of the adsorbed layer. These changes were analyzed assuming that the layer can be described as a Voigt element on a rigid surface in contact with purely viscous solvent. It was found that CS with low charge density forms a thicker and more mobile layer with higher viscosity and elasticity than CS with high charge density. The polymers adsorbed on the silica even when the ionic strength was so high that electrostatic interactions were effectively screened. At this high ionic strength, it was possible to study the effect of molecular weight and molecular weight distribution of the CS on the properties of the adsorbed film. Increasing the molecular weight of CS resulted in a larger hydrodynamic thickness. CS with a narrow molecular weight distribution formed a more compact and rigid layer than broadly distributed CS, presumably due to the better packing of the molecules.

Structure of Irreversibly Adsorbed Star Polymers

NASA Astrophysics Data System (ADS)

Akgun, Bulent; Aykan, Meryem Seyma; Canavar, Seda; Satija, Sushil K.; Uhrig, David; Hong, Kunlun

Formation of irreversibly adsorbed polymer chains on solid substrates have a huge impact on the wetting, glass transition, aging and polymer chain mobility in thin films. In recent years there has been many reports on the formation, kinetics and dynamics of these layers formed by linear homopolymers. Recent studies showed that by varying the number of polymer arms and arm molecular weight one can tune the glass transition temperature of thin polymer films. Using polymer architecture as a tool, the behavior of thin films can be tuned between the behavior of linear chains and soft colloids. We have studied the effect of polymer chain architecture on the structure of dead layer using X-ray reflectivity (XR) and atomic force microscopy. Layer thicknesses and densities of flattened and loosely adsorbed chains has been measured for linear, 4-arm, and 8-arm star polymers with identical total molecular weight as a function of substrate surface energy, annealing temperature and annealing time. Star polymers have been synthesized using anionic polymerization. XR measurements showed that 8-arm star PS molecules form the densest and the thickest dead layers among these three molecules.

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2008-02-01

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

Modulating surface rheology by electrostatic protein/polysaccharide interactions.

PubMed

Ganzevles, Renate A; Zinoviadou, Kyriaki; van Vliet, Ton; Cohen, Martien A; de Jongh, Harmen H

2006-11-21

There is a large interest in mixed protein/polysaccharide layers at air-water and oil-water interfaces because of their ability to stabilize foams and emulsions. Mixed protein/polysaccharide adsorbed layers at air-water interfaces can be prepared either by adsorption of soluble protein/polysaccharide complexes or by sequential adsorption of complexes or polysaccharides to a previously formed protein layer. Even though the final protein and polysaccharide bulk concentrations are the same, the behavior of the adsorbed layers can be very different, depending on the method of preparation. The surface shear modulus of a sequentially formed beta-lactoglobulin/pectin layer can be up to a factor of 6 higher than that of a layer made by simultaneous adsorption. Furthermore, the surface dilatational modulus and surface shear modulus strongly (up to factors of 2 and 7, respectively) depend on the bulk -lactoglobulin/pectin mixing ratio. On the basis of the surface rheological behavior, a mechanistic understanding of how the structure of the adsorbed layers depends on the protein/polysaccharide interaction in bulk solution, mixing ratio, ionic strength, and order of adsorption to the interface (simultaneous or sequential) is derived. Insight into the effect of protein/polysaccharide interactions on the properties of adsorbed layers provides a solid basis to modulate surface rheological behavior.

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

NASA Astrophysics Data System (ADS)

Downer, Michael

2002-03-01

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

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.

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.

Molecular Structure and Equilibrium Forces of Bovine Submaxillary Mucin Adsorbed at a Solid-Liquid Interface.

PubMed

Zappone, Bruno; Patil, Navinkumar J; Madsen, Jan B; Pakkanen, Kirsi I; Lee, Seunghwan

2015-04-21

By combining dynamic light scattering, circular dichroism spectroscopy, atomic force microscopy, and surface force apparatus, the conformation of bovine submaxillary mucin in dilute solution and nanomechanical properties of mucin layers adsorbed on mica have been investigated. The samples were prepared by additional chromatographic purification of commercially available products. The mucin molecule was found to have a z-average hydrodynamic diameter of ca. 35 nm in phosphate buffered solution, without any particular secondary or tertiary structure. The contour length of the mucin is larger than, yet of the same order of magnitude as the diameter, indicating that the molecule can be modeled as a relatively rigid polymeric chain due to the large persistence length of the central glycosylated domain. Mucin molecules adsorbed abundantly onto mica from saline buffer, generating polymer-like, long-ranged, repulsive, and nonhysteretic forces upon compression of the adsorbed layers. Detailed analysis of such forces suggests that adsorbed mucins had an elongated conformation favored by the stiffness of the central domain. Acidification of aqueous media was chosen as means to reduce mucin-mucin and mucin-substrate electrostatic interactions. The hydrodynamic diameter in solution did not significantly change when the pH was lowered, showing that the large persistence length of the mucin molecule is due to steric hindrance between sugar chains, rather than electrostatic interactions. Remarkably, the force generated by an adsorbed layer with a fixed surface coverage also remained unaltered upon acidification. This observation can be linked to the surface-protective, pH-resistant role of bovine submaxillary mucin in the variable environmental conditions of the oral cavity.

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.

Tuning Surface Energy Landscapes in Metallic Quantum Films using Alkali Adsorbates

NASA Astrophysics Data System (ADS)

Khajetoorians, Alexander; Qin, Shengyong; Zhu, Wenguang; Eisele, Holger; Zhang, Zhenyu; Shih, Chih-Kang

2008-03-01

Quantum confinement shows a strong interplay with growth and kinetics in thin metal systems where the Fermi wavelength has a special relationship to the surface normal lattice constant. In the case of Pb/Si(111) systems, this relationship reveals an interesting thickness-dependent bilayer oscillation in the density of states and surface energy up to a phase. In this paper, we report on a novel effect: tuning of the energy landscape of a flat-top quantum Pb mesa using Cs adsorbates. Using STM/STS, we show that depositing Cs adsorbates on a thin Pb mesa promotes quantum stable Pb nanoislands on preferentially unstable thicknesses. Thickness-dependent nanoisland densities show a strong bilayer oscillation correlating with quantum stability. By modifying the Cs coverage on the mesa surface, we can tune the lateral size distribution of the nanoislands and the overall amplitude of the island density oscillation. Nanoisland formation is linked to a step decoration of Cs adatoms along the step edge of the nanoisland.

An in situ XPS study of L-cysteine co-adsorbed with water on polycrystalline copper and gold

NASA Astrophysics Data System (ADS)

Jürgensen, Astrid; Raschke, Hannes; Esser, Norbert; Hergenröder, Roland

2018-03-01

The interactions of biomolecules with metal surfaces are important because an adsorbed layer of such molecules introduces complex reactive functionality to the substrate. However, studying these interactions is challenging: they usually take place in an aqueous environment, and the structure of the first few monolayers on the surface is of particular interest, as these layers determine most interfacial properties. Ideally, this requires surface sensitive analysis methods that are operated under ambient conditions, for example ambient pressure x-ray photoelectron spectroscopy (AP-XPS). This paper focuses on an AP-XPS study of the interaction of water vapour and l-Cysteine on polycrystalline copper and gold surfaces. Thin films of l-Cysteine were characterized with XPS in UHV and in a water vapour atmosphere (P ≤ 1 mbar): the structure of the adsorbed l-Cysteine layer depended on substrate material and deposition method, and exposure of the surface to water vapour led to the formation of hydrogen bonds between H2O molecules and the COO- and NH2 groups of adsorbed l-Cysteine zwitterions and neutral molecules, respectively. This study also proved that it is possible to investigate monolayers of biomolecules in a gas atmosphere with AP-XPS using a conventional laboratory Al-Kα x-ray source.

Changes in the quaternary structure of amelogenin when adsorbed onto surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tarasevich, Barbara J.; Lea, Alan S.; Bernt, William

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 groupmore » 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.« less

Study of space charge layer in silver bromide microcrystals by means of ultraviolet photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Tani, Tadaaki; Inami, Yoshiyasu

2000-09-01

Ultraviolet photoelectron spectroscopy has been successfully used to measure the heights of the tops of the valence bands of the surfaces of AgBr layers on Ag substrates for the verification of the space charge layer model. According to this model, the positive space charge layer (composed of negative charges with excess negative kink sites on the surface and corresponding positive charges with interstitial silver ions in the interior) is formed in silver halides, causing the difference in the electronic energy levels between their surface and interior. The depression of the positive space charge layer of AgBr caused by such adsorbates as photographic stabilizers and antifoggants was estimated from the decrease in the ionic conductivity of cubic AgBr microcrystals by the adsorbates. It was confirmed by the decrease in the heights of the tops of the valence bands of the surfaces of AgBr layers caused by the adsorbates in the presence of thin gelatin membranes on their surfaces. This result provided the explanation for the fact that the adsorbates increased the number of the microcrystals which formed latent image centers on the surface and decreased the number of the microcrystals, which formed latent image centers in the interior.

Plasma protein adsorption to zwitterionic poly (carboxybetaine methacrylate) modified surfaces: chain chemistry and end-group effects on protein adsorption kinetics, adsorbed amounts and immunoblots.

PubMed

Abraham, Sinoj; Bahniuk, Markian S; Unsworth, Larry D

2012-12-01

Protein-surface interactions are crucial to the overall biocompatability of biomaterials, and are thought to be the impetus towards the adverse host responses such as blood coagulation and complement activation. Only a few studies hint at the ultra-low fouling potential of zwitterionic poly(carboxybetaine methacrylate) (PCBMA) grafted surfaces and, of those, very few systematically investigate their non-fouling behavior. In this work, single protein adsorption studies as well as protein adsorption from complex solutions (i.e. human plasma) were used to evaluate the non-fouling potential of PCBMA grafted silica wafers prepared by nitroxide-mediated free radical polymerization. PCBMAs used for surface grafting varied in charge separating spacer groups that influence the overall surface charges, and chain end-groups that influence the overall hydrophilicity, thereby, allows a better understanding of these effects towards the protein adsorption for these materials. In situ ellipsometry was used to quantify the adsorbed layer thickness and adsorption kinetics for the adsorption of four proteins from single protein buffer solutions, viz, lysozyme, α-lactalbumin, human serum albumin and fibrinogen. Total amount of protein adsorbed on surfaces differed as a function of surface properties and protein characteristics. Finally, immunoblots results showed that human plasma protein adsorption to these surfaces resulted, primarily, in the adsorption of human serum albumin, with total protein adsorbed amounts being the lowest for PCBMA-3 (TEMPO). It was apparent that surface charge and chain hydrophilicity directly influenced protein adsorption behavior of PCBMA systems and are promising materials for biomedical applications.

In-situ probing of coupled atomic restructuring and metallicity of oxide heterointerfaces induced by polar adsorbates

NASA Astrophysics Data System (ADS)

Ryu, S.; Zhou, H.; Paudel, T. R.; Irwin, J.; Podkaminer, J. P.; Bark, C. W.; Lee, D.; Kim, T. H.; Fong, D. D.; Rzchowski, M. S.; Tsymbal, E. Y.; Eom, C. B.

2017-10-01

Microscopic understanding of the surface-controlled conductivity of the two dimensional electron gas at complex oxide interfaces is crucial for developing functional interfaces. We observe conductivity and structural modification using in-situ synchrotron surface x-ray diffraction as the surface of a model LaAlO3/SrTiO3 (001) heterostructure is changed by polar adsorbates. We find that polar adsorbate-induced interfacial metallicity reduces polar distortions in the LaAlO3 layer. First-principles density functional theory calculations show that surface dipoles introduced by polar adsorbates lead to additional charge transfer and the reduction of polar displacements in the LaAlO3 layer, consistent with the experimental observations. Our study supports that internal structural deformations controlling functionalities can be driven without the application of direct electrical or thermal bias and offers a route to tuning interfacial properties. These results also highlight the important role of in-situ x-ray scattering with atomic resolution in capturing and exploring structural distortions and charge density changes caused by external perturbations such as chemical adsorption, redox reaction, and generation and/or annihilation of surface defects.

In-situ probing of coupled atomic restructuring and metallicity of oxide heterointerfaces induced by polar adsorbates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryu, S.; Zhou, H.; Paudel, T. R.

Microscopic understanding of the surface-controlled conductivity of the two dimensional electron gas at complex oxide interfaces is crucial for developing functional interfaces. We observe conductivity and structural modification using in-situ synchrotron surface x-ray diffraction as the surface of a model LaAlO3/SrTiO3 (001) heterostructure is changed by polar adsorbates. We find that polar adsorbate-induced interfacial metallicity reduces polar distortions in the LaAlO3 layer. First-principles density functional theory calculations show that surface dipoles introduced by polar adsorbates lead to additional charge transfer and the reduction of polar displacements in the LaAlO3 layer, consistent with the experimental observations. Our study supports that internalmore » structural deformations controlling functionalities can be driven without the application of direct electrical or thermal bias and offers a route to tuning interfacial properties. These results also highlight the important role of in-situ x-ray scattering with atomic resolution in capturing and exploring structural distortions and charge density changes caused by external perturbations such as chemical adsorption, redox reaction, and generation and/or annihilation of surface defects.« less

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

Polymeric ionic liquid based on magnetic materials fabricated through layer-by-layer assembly as adsorbents for extraction of pesticides.

PubMed

He, Lijun; Cui, Wenhang; Wang, Yali; Zhao, Wenjie; Xiang, Guoqiang; Jiang, Xiuming; Mao, Pu; He, Juan; Zhang, Shusheng

2017-11-03

In this study, layer-by-layer assembly of polyelectrolyte multilayer films on magnetic silica provided a convenient and controllable way to prepare polymeric ionic liquid-based magnetic adsorbents. The resulting particles were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, and magnetic measurements. The data showed that the magnetic particles had more homogeneous spherical shapes with higher saturation magnetization when compared to those obtained by free radical polymerization method. This facilitated the convenient collection of magnetic particles, with higher extraction repeatability. The extraction performance of the multilayer polymeric ionic liquid-based adsorbents was evaluated by magnetic solid-phase extraction of four pesticides including quinalphos, fenthion, phoxim, and chlorpropham. The data suggested that the extraction efficiency depended on the number of layers in the film. The parameters affecting the extraction efficiency were optimized, and good linearity ranging from 2 to 250μgL -1 was obtained with correlation coefficients of 0.9994-0.9998. Moreover, the proposed method presented low limit of detection (0.5μgL -1 , S/N=3) and limit of quantification (1.5μgL -1 , S/N=10), and good repeatability expressed by the relative standard deviation (2.0%-4.6%, n=5). The extraction recoveries of four pesticides were found to range from 58.9% to 85.8%. The reliability of the proposed method was demonstrated by analyzing environmental water samples, and the results revealed satisfactory spiked recovery, relative standard deviation, and selectivity. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrokinetic flow in a capillary with a charge-regulating surface polymer layer.

PubMed

Keh, Huan J; Ding, Jau M

2003-07-15

An analytical study of the steady electrokinetic flow in a long uniform capillary tube or slit is presented. The inside wall of the capillary is covered by a layer of adsorbed or covalently bound charge-regulating polymer in equilibrium with the ambient electrolyte solution. In this solvent-permeable and ion-penetrable surface polyelectrolyte layer, ionogenic functional groups and frictional segments are assumed to distribute at uniform densities. The electrical potential and space charge density distributions in the cross section of the capillary are obtained by solving the linearized Poisson-Boltzmann equation. The fluid velocity profile due to the application of an electric field and a pressure gradient through the capillary is obtained from the analytical solution of a modified Navier-Stokes/Brinkman equation. Explicit formulas for the electroosmotic velocity, the average fluid velocity and electric current density on the cross section, and the streaming potential in the capillary are also derived. The results demonstrate that the direction of the electroosmotic flow and the magnitudes of the fluid velocity and electric current density are dominated by the fixed charge density inside the surface polymer layer, which is determined by the regulation characteristics such as the dissociation equilibrium constants of the ionogenic functional groups in the surface layer and the concentration of the potential-determining ions in the bulk solution.

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).

Normal and frictional interactions of purified human statherin adsorbed on molecularly-smooth solid substrata.

PubMed

Harvey, Neale M; Carpenter, Guy H; Proctor, Gordon B; Klein, Jacob

2011-09-01

Human salivary statherin was purified from parotid saliva and adsorbed to bare hydrophilic (HP) mica and STAI-coated hydrophobic (HB) mica in a series of Surface Force Balance experiments that measured the normal (F(n)) and friction forces (F(s)*) between statherin-coated mica substrata. Readings were taken both in the presence of statherin solution (HP and HB mica) and after rinsing (HP mica). F(n) measurements showed, for both substrata, monotonic steric repulsion that set on at a surface separation D ~20 nm, indicating an adsorbed layer whose unperturbed thickness was ca 10 nm. An additional longer-ranged repulsion, probably of electrostatic double-layer origin, was observed for rinsed surfaces under pure water. Under applied pressures of ~1 MPa, each surface layer was compressed to a thickness of ca 2 nm on both types of substratum, comparable with earlier estimates of the size of the statherin molecule. Friction measurements, in contrast with F(n) observations, were markedly different on the two different substrata: friction coefficients, μ ≡ ∂F(s)*/∂F(n), on the HB substratum (μ ≈ 0.88) were almost an order of magnitude higher than on the HP substratum (μ ≈ 0.09 and 0.12 for unrinsed and rinsed, respectively), and on the HB mica there was a lower dependence of friction on sliding speed than on the HP mica. The observations were attributed to statherin adsorbing to the mica in multimer aggregates, with internal re-arrangement of the protein molecules within the aggregate dependent on the substratum to which the aggregate adsorbed. This internal re-arrangement permitted aggregates to be of similar size on HP and HB mica but to have different internal molecular orientations, thus exposing different moieties to the solution in each case and accounting for the very different friction behaviour.

TOPICAL REVIEW: Quasielastic He atom scattering from surfaces: a stochastic description of the dynamics of interacting adsorbates

NASA Astrophysics Data System (ADS)

Martínez-Casado, R.; Vega, J. L.; Sanz, A. S.; Miret-Artés, S.

2007-08-01

The study of diffusion and low-frequency vibrational motions of particles on metal surfaces is of paramount importance; it provides valuable information on the nature of the adsorbate-substrate and substrate-substrate interactions. In particular, the experimental broadening observed in the diffusive peak with increasing coverage is usually interpreted in terms of a dipole-dipole-like interaction among adsorbates via extensive molecular dynamics calculations within the Langevin framework. Here we present an alternative way to interpret this broadening by means of a purely stochastic description, namely the interacting single-adsorbate approximation, where two noise sources are considered: (1) a Gaussian white noise accounting for the surface friction and temperature, and (2) a white shot noise replacing the interaction potential between adsorbates. Standard Langevin numerical simulations for flat and corrugated surfaces (with a separable potential) illustrate the dynamics of Na atoms on a Cu(100) surface which fit fairly well to the analytical expressions issued from simple models (free particle and anharmonic oscillator) when the Gaussian approximation is assumed. A similar broadening is also expected for the frustrated translational mode peaks.

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

PubMed

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

2014-11-01

Layered double hydroxides (LDHs) are a class of anion clays consisting of brucite-like host layers and interlayer anions, which have attracted increasing interest in the fields of catalysis/adsorption. By virtue of the versatility in composition, morphology, and architecture of LDH materials, as well as their unique structural properties (intercalation, topological transformation, and self-assembly with other functional materials), LDHs display great potential in the design and fabrication of nanomaterials applied in photocatalysis, heterogeneous catalysis, and adsorption/separation processes. Taking advantage of the structural merits and various control synthesis strategies of LDHs, the active center structure (e.g., crystal facets, defects, geometric and electronic states, etc.) and macro-nano morphology can be facilely manipulated for specific catalytic/adsorbent processes with largely enhanced performances. In this review, the latest advancements in the design and preparation of LDH-based functional nanomaterials for sustainable development in catalysis and adsorption are summarized. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

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

Quantum confinement effects on electronic photomobilities at nanostructured semiconductor surfaces: Si(111) without and with adsorbed Ag clusters

NASA Astrophysics Data System (ADS)

Hembree, Robert H.; Vazhappilly, Tijo; Micha, David A.

2017-12-01

The conductivity of holes and electrons photoexcited in Si slabs is affected by the slab thickness and by adsorbates. The mobilities of those charged carriers depend on how many layers compose the slab, and this has important scientific and technical consequences for the understanding of photovoltaic materials. A previously developed general computational procedure combining density matrix and electronic band structure treatments has been applied to extensive calculations of mobilities of photoexcited electrons and holes at Si(111) nanostructured surfaces with varying slab thickness and for varying photon energies, to investigate the expected change in mobility magnitudes as the slab thickness is increased. Results have been obtained with and without adsorbed silver clusters for comparison of their optical and photovoltaic properties. Band states were generated using a modified ab initio density functional treatment with the PBE exchange and correlation density functionals and with periodic boundary conditions for large atomic supercells. An energy gap correction was applied to the unoccupied orbital energies of each band structure by running more accurate HSE hybrid functional calculations for a Si(111) slab. Photoexcited state populations for slabs with 6, 8, 10, and 12 layers were generated using a steady state reduced density matrix including dissipative effects due to energy exchange with excitons and phonons in the medium. Mobilities have been calculated from the derivatives of voltage-driven electronic energies with respect to electronic momentum, for each energy band and for the average over bands. Results show two clear trends: (a) adding Ag increases the hole photomobilities and (b) decreasing the slab thickness increases hole photomobilities. The increased hole populations in 6- and 8-layer systems and the large increase in hole mobility for these thinner slabs can be interpreted as a quantum confinement effect of hole orbitals. As the slab thickness

Controlled enzymatic cutting of DNA molecules adsorbed on surfaces using soft lithography

NASA Astrophysics Data System (ADS)

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

2013-03-01

The enzyme DNase I was applied to adsorbed and aligned DNA molecules (Lamda, 48.5 kilobase pairs (kbp), and T4, 165.6 kbp), stretched linearly on a surface, by stamping with a polydimethylsiloxane (PDMS) grating. The DNAs were cut by the enzyme into separated, micron-sized segments along the length of the molecules at positions determined by the grating dimensions (3-20 microns). Ozone-treated PDMS stamps were coated with DNase I solutions and placed in contact with surface-adsorbed DNA molecules deposited on a 750 polymethylmethacrylate (PMMA) film spun-cast onto a silicon substrate. The stamps were applied under pressure for times up to 15 minutes at 37 C. The cutting was observed by fluorescence microscopy imaging of DNA labeled with YOYO dye. Cutting was found to be efficient despite the steric hindrance due to surface attachment of the molecules. Methods for detaching and separating the cut segments for sequencing applications will be discussed. Supported by NSF-DMR program.

Electronic damping of anharmonic adsorbate vibrations at metallic surfaces

NASA Astrophysics Data System (ADS)

Tremblay, Jean Christophe; Monturet, Serge; Saalfrank, Peter

2010-03-01

The nonadiabatic coupling of an adsorbate close to a metallic surface leads to electronic damping of adsorbate vibrations and line broadening in vibrational spectroscopy. Here, a perturbative treatment of the electronic contribution to the lifetime broadening serves as a building block for a new approach, in which anharmonic vibrational transition rates are calculated from a position-dependent coupling function. Different models for the coupling function will be tested, all related to embedding theory. The first two are models based on a scattering approach with (i) a jellium-type and (ii) a density functional theory based embedding density, respectively. In a third variant a further refined model is used for the embedding density, and a semiempirical approach is taken in which a scaling factor is chosen to match harmonic, single-site, first-principles transition rates, obtained from periodic density functional theory. For the example of hydrogen atoms on (adsorption) and below (subsurface absorption) a Pd(111) surface, lifetimes of and transition rates between vibrational levels are computed. The transition rates emerging from different models serve as input for the selective subsurface adsorption of hydrogen in palladium starting from an adsorption site, by using sequences of infrared laser pulses in a laser distillation scheme.

Adsorbed Polymer Nanolayers on Solids: Mechanism, Structure and Applications

NASA Astrophysics Data System (ADS)

Sen, Mani Kuntal

In this thesis, by combining various advanced x-ray scattering, spectroscopic and other surface sensitive characterization techniques, I report the equilibrium polymer chain conformations, structures, dynamics and properties of polymeric materials at the solid-polymer melt interfaces. Following the introduction, in chapter 2, I highlight that the backbone chains (constituted of CH and CH2 groups) of the flattened polystyrene (PS) chains preferentially orient normal to the weakly interactive substrate surface via thermal annealing regardless of the initial chain conformations, while the orientation of the phenyl rings becomes randomized, thereby increasing the number of surface-segmental contacts (i.e., enthalpic gain) which is the driving force for the flattening process of the polymer chains even onto a weakly interactive solid. In chapter 3, I elucidate the flattened structures in block copolymer (BCP) thin films where both blocks lie flat on the substrate, forming a 2D randomly phase-separated structure irrespective of their microdomain structures and interfacial energetics. In chapter 4, I reveal the presence of an irreversibly adsorbed BCP layer which showed suppressed dynamics even at temperatures far above the individual glass transition temperatures of the blocks. Furthermore, this adsorbed BCP layer plays a crucial role in controlling the microdomain orientation in the entire film. In chapter 5, I report a radically new paradigm of designing a polymeric coating layer of a few nanometers thick ("polymer nanolayer") with anti-biofouling properties.

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.

Advanced wide-field surface plasmon microscopy of single adsorbing nanoparticles

NASA Astrophysics Data System (ADS)

Nizamov, Shavkat; Scherbahn, Vitali; Mirsky, Vladimir M.

2017-05-01

In-situ detection and characterization of nanoparticles in biological media as well as in food or other complex samples is still a big challenge for existing analytical methods. Here we describe a label-free and cost-effective analytical method for detection of nanoparticles in the concentration range 106 -1010 NPs/ml. The proposed method is based on the surface plasmon resonance microscopy (SPRM) with a large field of view ( 1.3mm2 ). It is able to detect and count adsorbing nanoparticles individually, totally up to the hundreds of thousands of NPs on the sensor surface. At constant diffusion conditions the detection rate is proportional to the number concentration of NPs, this provides an approach to determine the NPs concentration. The adsorption of nanoparticle can be manipulated by the surface functionalization, pH and electrolyte concentration of suspensions. Images of detected nanoparticles can be quantified in order to characterize them individually. The image intensity grows quasi-linearly with nanoparticle size for the given material. However, the size and material of nanoparticle cannot be resolved directly from the image. For determination of chemical composition, SPRM can be assisted by electrochemical analysis. In this case, the gold sensor surface is used both as a resonant media for plasmon microscopy and as a working electrode. Under potential sweep, the adsorbed NPs can be subjected to electrochemical dissolution, which is detected optically. The potential of this conversion characterizes the material of NPs.

Poly(L-lysine) Interfaces via Dual Click Reactions on Surface-Bound Custom-Designed Dithiol Adsorbates.

PubMed

Shakiba, Amin; Jamison, Andrew C; Lee, T Randall

2015-06-09

Surfaces modified with poly(L-lysine) can be used to immobilize selected biomolecules electrostatically. This report describes the preparation of a set of self-assembled monolayers (SAMs) from three different azide-terminated adsorbates as platforms for performing controlled surface attachments and as a means of determining the parameters that afford stable poly(L-lysine)-modified SAM surfaces having controlled packing densities. A maleimide-terminated alkyne linker was "clicked" to the azide-terminated surfaces via a copper-catalyzed cycloaddition reaction to produce the attachment sites for the polypeptides. A thiol-Michael addition was then used to immobilize cysteine-terminated poly(L-lysine) moieties on the gold surface, avoiding adsorbate self-reactions with this two-step procedure. Each step in this process was analyzed by ellipsometry, X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, and contact angle goniometry to determine which adsorbate structure most effectively produced the targeted polypeptide interface. Additionally, a series of mixed SAMs using an azidoalkanethiol in combination with a normal alkanethiol having an equivalent alkyl chain were prepared to provide data to determine how dilution of the azide reactive site on the SAM surface influences the initial click reaction. Overall, the collected data demonstrate the advantages of an appropriately designed bidentate absorbate and its potential to form effective platforms for biomolecule surface attachment via click reactions.

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

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.

Effect of the morphology of adsorbed oleate on the wettability of a collophane surface

NASA Astrophysics Data System (ADS)

Ye, Junjian; Zhang, Qin; Li, Xianbo; Wang, Xianchen; Ke, Baolin; Li, Xianhai; Shen, Zhihui

2018-06-01

The adsorption of surfactants on a solid surface could alter its wettability, which offers a wide range of relevant applications such as mineral flotation, hydrophobic material preparation and nanomaterial dispersion. The morphology of adsorbed oleate on a collophane surface was visualized using the peakforce tapping mode of atomic force microscopy (AFM), and its effect on the wettability of collophane was analysed by contact angle measurements, adsorption measurements and molecular dynamics (MD) simulations. The AFM images demonstrated that the adsorbed structure varied with different oleate concentrations. First, the small cylindrical micelles with concomitant monolayer and bilayer structures were observed above the hemimicelle concentration (hmc) of 1 × 10-5 mol/L, which enhanced the hydrophobicity of the collophane surface, and the collophane surface was not completely covered with the oleate monolayer due to surface heterogeneity. Then, large cylindrical micelles with a major bilayer were formed as the critical micelle concentration (cmc) of 1 × 10-3 mol/L was approached, which decreased its hydrophobicity, and finally the formation of large cylindrical micelles with multilayer at the cmc caused the hydrophilicity of the collophane surface. Therefore, there was a suitable equilibrium concentration between the hmc and cmc for oleate as a collector during mineral flotation, and oleate could also be used as a dispersant for colloidal stability when its equilibrium concentration reached the cmc. The effect of the adsorbed structure on the wettability of collophane was also confirmed by MD simulations. This study provides a good understanding of the surface modification of particles by surfactants for flotation and dispersion applications.

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.

Surface layer formation of LiCoO2 thin film electrodes in non-aqueous electrolyte containing lithium bis(oxalate)borate

NASA Astrophysics Data System (ADS)

Matsui, Masaki; Dokko, Kaoru; Akita, Yasuhiro; Munakata, Hirokazu; Kanamura, Kiyoshi

2012-07-01

Surface layer formation processes on a LiCoO2 thin film electrode in a non-aqueous electrolyte containing lithium bis(oxalate)borate (LiBOB) were investigated using in situ FTIR spectroscopy and X-ray photoelectron spectroscopy (XPS). The in situ FTIR spectra of the electrolyte solution containing LiBOB showed that the adsorption of BOB anions on the electrode surface occurred during the charge process of the LiCoO2 thin film electrode above 4.0 V. XPS analysis for the LiCoO2 thin film electrode charged in an electrolyte containing LiBOB suggested that the adsorbed BOB anions on the electrode surface prevent the continuous decomposition of hexafluorophosphate (PF6) anions resulting in the formation of a very thin surface layer containing organic species, while the LiCoO2 charged in a LiPF6 solution had a relatively thick surface layer containing organic species and inorganic species.

Adsorbed Molecules and Surface Treatment Effect on Optical Properties of ZnO Nanowires Grown by MOCVD

NASA Astrophysics Data System (ADS)

Jabri, S.; Souissi, H.; Sallet, V.; Lusson, A.; Meftah, A.; Galtier, P.; Oueslati, M.

2017-07-01

We have investigated the optical properties of ZnO nanowires grown by metalorganic chemical vapor deposition (MOCVD) with nitrous oxide (N2O) as oxygen precursor. Photoluminescence (PL) and Raman measurements showed the influence of adsorbed molecules on the optical properties. Low-temperature (4 K) PL studies on the surface exciton (SX) at 3.3660 eV elucidated the nature and origin of this emission. In particular, surface treatment by annealing at high temperature under inert gas reduced the emission intensity of SX. Raman vibrational spectra proved that presence of a considerable amount of adsorbed molecules on the surface of ZnO nanowires plays a key role in the occurrence of surface excitons.

Amine-pillared Nanosheet Adsorbents for CO2 Capture Applications

NASA Astrophysics Data System (ADS)

Jiang, Hui

Amine-functionalized solid adsorbents have gained attention within the last decade for their application in carbon dioxide capture, due to their many advantages such as low energy cost for regeneration, tunable structure, elimination of corrosion problems, and additional advantages. However, one of the challenges facing this technology is to accomplish both high CO 2 capture capacity along with high CO2 diffusion rates concurrently. Current amine-based solid sorbents such as porous materials similar to SBA-15 have large pores diffusion entering molecules; however, the pores become clogged upon amine inclusion. To meet this challenge, our group's solution involves the creation of a new type of material which we are calling-amino-pillared nanosheet (APN) adsorbents which are generated from layered nanosheet precursors. These materials are being proposed because of their unique lamellar structure which exhibits ability to be modified by organic or inorganic pillars through consecutive swelling and pillaring steps to form large mesoporous interlayer spaces. After the expansion of the layer space through swelling and pillaring, the large pore space can be functionalized with amine groups. This selective functionalization is possible by the choice of amine group introduced. Our choice, large amine molecules, do not access the micropore within each layer; however, either physically or chemically immobilized onto the surface of the mesoporous interlayer space between each layer. The final goal of the research is to investigate the ability to prepare APN adsorbents from a model nanoporous layered materials including nanosheets precursor material MCM-22(P) and nanoporous layered silicate material AMH-3. MCM-22(P) contains 2-dimensional porous channels, 6 membered rings (MB) openings perpendicular to the layers and 10 MB channels in the plane of the layers. However, the transport limiting openings (6 MB) to the layers is smaller than CO2 gas molecules. In contrast, AMH-3 has

Efficient surface enhanced Raman scattering on confeito-like gold nanoparticle-adsorbed self-assembled monolayers.

PubMed

Chang, Chia-Chi; Imae, Toyoko; Chen, Liang-Yih; Ujihara, Masaki

2015-12-28

Confeito-like gold nanoparticles (AuNPs; average diameter = 80 nm) exhibiting a plasmon absorption band at 590 nm were adsorbed through immersion-adsorption on two self-assembled monolayers (SAMs) of 3-aminopropyltriethoxysilane (APTES-SAM) and polystyrene spheres coated with amine-terminated poly(amido amine) dendrimers (DEN/PS-SAM). The surface enhanced Raman scattering (SERS) effect on the SAM substrates was examined using the molecules of a probe dye, rhodamine 6G (R6G). The Raman scattering was strongly intensified on both substrates, but the enhancement factor (>10,000) of the AuNP/DEN/PS-SAM hierarchy substrate was 5-10 times higher than that of the AuNP/APTES-SAM substrate. This strong enhancement is attributed to the large surface area of the substrate and the presence of hot spots. Furthermore, analyzing the R6G concentration dependence of SERS suggested that the enhancement mechanism effectively excited the R6G molecules in the first layer on the hot spots and invoked the strong SERS effect. These results indicate that the SERS activity of confeito-like AuNPs on SAM substrates has high potential in molecular electronic devices and ultrasensitive analyses.

The effect of adsorbates on the electrical stability of graphene studied by transient photocurrent spectroscopy

NASA Astrophysics Data System (ADS)

Kalkan, S. B.; Aydın, H.; Özkendir, D.; ćelebi, C.

2018-01-01

Adsorbate induced variations in the electrical conductivity of graphene layers with two different types of charge carriers are investigated by using the Transient Photocurrent Spectroscopy (TPS) measurement technique. In-vacuum TPS measurements taken for a duration of 5 ks revealed that the adsorption/desorption of atmospheric adsorbates leads to more than a 110% increment and a 45% decrement in the conductivity of epitaxial graphene (n-type) and chemical vapor deposition graphene (p-type) layers on semi-insulating silicon carbide (SiC) substrates, respectively. The graphene layers on SiC are encapsulated and passivated with a thin SiO2 film grown by the Pulsed Electron Deposition method. The measurements conducted for short periods and a few cycles showed that the encapsulation process completely suppresses the time dependent conductivity instability of graphene independent of its charge carrier type. The obtained results are used to construct an experimental model for identifying adsorbate related conductivity variations in graphene and also in other 2D materials with an inherently high surface-to-volume ratio.

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.

Differences between tethered polyelectrolyte chains adsorbed onto bare mica and hydrophobically modified mica, comparison with theory.

NASA Astrophysics Data System (ADS)

Balastre, Marc; Tamashiro, Mario N.; Hernandez, Ernesto; Pincus, Philip; Tirrell, Matthew

2001-03-01

End-grafted polymers generated from the adsorption of asymmetric diblock copolymers on solid surface play an important role in many areas of science and technology. While the small insoluble block acts as an anchor, the charged soluble block confers useful properties to the surface. This study looks at tethered layers of poly(styrene sulfonate)/poly(t-butyl styrene) (PtBS-PSS) adsorbed on both mica (hydrophilic) and octadecyltriethoxysilane (OTE) modified mica (hydrophobic). Normal compressing forces at two different constant grafting densities (bare and modified mica) were measured with the surface force apparatus and compared with theoretical prediction. The effect of salt concentration (Cs) upon the thickness of the self-assembled layers (Lo) was measured in each case. For adsorption of diblock copolymers onto OTE the resulting scaling relationship is much closer to the brush theory, Lo Cs-1/3. This result suggests that the adsorbed amount on mica is not high enough to form a brush.

Effects of surface imperfections on the binding of CH 3OH and H 2O on FeS 2(100): using adsorbed Xe as a probe of mineral surface structure

NASA Astrophysics Data System (ADS)

Guevremont, J. M.; Strongin, D. R.; Schoonen, M. A. A.

1997-11-01

Studies are presented that investigate the adsorption and binding of CH 3OH and H 2O on the atomically clean (100) crystallographic plane of pyrite, FeS 2. Temperature programmed desorption suggests that both reactants adsorb molecularly at 90 K and desorb thermally between 170 and 400 K depending on the surface coverage. Photoemission of adsorbed xenon (PAX) suggests that the surface of pyrite is heterogeneous and contains a significant fraction of defect sites that are believed to be, at least in part, anion vacancy or sulfur-deficient sites. An upper limit of 0.2 is proposed for the fraction of surface sites that are defects on FeS 2(100). PAX indicates that these defect sites at low adsorbate coverage serve as the exclusive binding sites for H 2O and CH 3OH adsorbate. We speculate, on the basis of our ability to interpret PAX data for pyrite, that PAX may be of use for understanding the effect of short range order on adsorbate binding on other complex mineral surfaces. On the basis of high resolution electron energy loss spectroscopy, it is found that some dissociation of the adsorbate occurs on the pyrite. Vibrational data obtained with this technique suggests that FeO species result from the adsorbate decomposition. After saturation of the defect sites, further molecular adsorption is accommodated on the less reactive surface that we postulate is largely disulfide, the characteristic structural group of pyrite.

Coarse-grained modeling of proline rich protein 1 (PRP-1) in bulk solution and adsorbed to a negatively charged surface.

PubMed

Skepö, Marie; Linse, Per; Arnebrant, Thomas

2006-06-22

Structural properties of the acidic proline rich protein PRP-1 of salivary origin in bulk solution and adsorbed onto a negatively charged surface have been studied by Monte Carlo simulations. A simple model system with focus on electrostatic interactions and short-ranged attractions among the uncharged amino acids has been used. In addition to PRP-1, some mutants were considered to assess the role of the interactions in the systems. Contrary to polyelectrolytes, the protein has a compact structure in salt-free bulk solutions, whereas at high salt concentration the protein becomes more extended. The protein adsorbs to a negatively charged surface, although its net charge is negative. The adsorbed protein displays an extended structure, which becomes more compact upon addition of salt. Hence, the conformational response upon salt addition in the adsorbed state is the opposite as compared to that in bulk solution. The conformational behavior of PRP-1 in bulk solution and at charged surfaces as well as its propensity to adsorb to surfaces with the same net charge are rationalized by the block polyampholytic character of the protein. The presence of a triad of positively charged amino acids in the C-terminal was found to be important for the adsorption of the protein.

Surface studies on scandate cathodes and synthesized scandates

NASA Technical Reports Server (NTRS)

Lesny, Gary; Forman, Ralph

1990-01-01

Auger, ESCA, electron emission, evaporation, and desorption measurements were made on three different types of scandate surfaces. They are: (1) an impregnated top layer scandate cathode, (2) an unimpregnated top layer scandate cathode with a deposited barium or barium oxide adsorbate surface layer, and (3) a synthesized scandate surface, which replicates a scandate cathode surface. The purpose of these experiments was to determine the role that Sc2O3 plays in making the scandate cathode a more copious electron emitter than the conventional impregnated-type cathode. The synthesized scandate surface experiments consisted of depositing multilayer scandium on a tungsten surface, oxidizing the scandium, and then depositing either Ba or BaO on the scandium oxide surface. The results of these measurements showed that the low work function portions of the thin-film scandate cathode are where the Sc2O3 is the substrate and BaO is the adsorbate.

Method of making dense, conformal, ultra-thin cap layers for nanoporous low-k ILD by plasma assisted atomic layer deposition

DOEpatents

Jiang, Ying-Bing [Albuquerque, NM; Cecchi, Joseph L [Albuquerque, NM; Brinker, C Jeffrey [Albuquerque, NM

2011-05-24

Barrier layers and methods for forming barrier layers on a porous layer are provided. The methods can include chemically adsorbing a plurality of first molecules on a surface of the porous layer in a chamber and forming a first layer of the first molecules on the surface of the porous layer. A plasma can then be used to react a plurality of second molecules with the first layer of first molecules to form a first layer of a barrier layer. The barrier layers can seal the pores of the porous material, function as a diffusion barrier, be conformal, and/or have a negligible impact on the overall ILD k value of the porous material.

Transverse thermal depinning and nonlinear sliding friction of an adsorbed monolayer.

PubMed

Granato, E; Ying, S C

2000-12-18

We study the response of an adsorbed monolayer under a driving force as a model of sliding friction phenomena between two crystalline surfaces with a boundary lubrication layer. Using Langevin-dynamics simulation, we determine the nonlinear response in the direction transverse to a high symmetry direction along which the layer is already sliding. We find that below a finite transition temperature there exist a critical depinning force and hysteresis effects in the transverse response in the dynamical state when the adlayer is sliding smoothly along the longitudinal direction.

Functional Layer-by-Layer Thin Films of Inducible Nitric Oxide (NO) Synthase Oxygenase and Polyethylenimine: Modulation of Enzyme Loading and NO-Release Activity.

PubMed

Gunasekera, Bhagya; Abou Diwan, Charbel; Altawallbeh, Ghaith; Kalil, Haitham; Maher, Shaimaa; Xu, Song; Bayachou, Mekki

2018-03-07

Nitric oxide (NO) release counteracts platelet aggregation and prevents the thrombosis cascade in the inner walls of blood vessels. NO-release coatings also prevent thrombus formation on the surface of blood-contacting medical devices. Our previous work has shown that inducible nitric oxide synthase (iNOS) films release NO fluxes upon enzymatic conversion of the substrate l-arginine. In this work, we report on the modulation of enzyme loading in layer-by-layer (LbL) thin films of inducible nitric oxide synthase oxygenase (iNOSoxy) on polyethylenimine (PEI). The layer of iNOSoxy is electrostatically adsorbed onto the PEI layer. The pH of the iNOSoxy solution affects the amount of enzyme adsorbed. The overall negative surface charge of iNOSoxy in solution depends on the pH and hence determines the density of adsorbed protein on the positively charged PEI layer. We used buffered iNOSoxy solutions adjusted to pHs 8.6 and 7.0, while saline PEI solution was used at pH 7.0. Atomic force microscopy imaging of the outermost layer shows higher protein adsorption with iNOSoxy at pH 8.6 than with a solution of iNOSoxy at pH 7.0. Graphite electrodes with PEI/iNOSoxy films show higher catalytic currents for nitric oxide reduction mediated by iNOSoxy. The higher enzyme loading translates into higher NO flux when the enzyme-modified surface is exposed to a solution containing the substrate and a source of electrons. Spectrophotometric assays showed higher NO fluxes with iNOSoxy/PEI films built at pH 8.6 than with films built at pH 7.0. Fourier transform infrared analysis of iNOSoxy adsorbed on PEI at pH 8.6 and 7.0 shows structural differences of iNOSoxy in films, which explains the observed changes in enzymatic activity. Our findings show that pH provides a strategy to optimize the NOS loading and enzyme activity in NOS-based LbL thin films, which enables improved NO release with minimum layers of PEI/NOS.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eisenhardt, A.; Reiß, S.; Krischok, S., E-mail: stefan.krischok@tu-ilmenau.de

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 disappearancemore » of surface states, which initially pin the Fermi level and induce downward band bending.« less

Electrospray surface-enhanced Raman spectroscopy (ES-SERS) for probing surface chemical compositions of atmospherically relevant particles

NASA Astrophysics Data System (ADS)

Gen, Masao; Chan, Chak K.

2017-11-01

We present electrospray surface-enhanced Raman spectroscopy (ES-SERS) as a new approach to measuring the surface chemical compositions of atmospherically relevant particles. The surface-sensitive SERS is realized by electrospraying Ag nanoparticle aerosols over analyte particles. Spectral features at v(SO42-), v(C-H) and v(O-H) modes were observed from the normal Raman and SERS measurements of laboratory-generated supermicron particles of ammonium sulfate (AS), AS mixed with succinic acid (AS / SA) and AS mixed with sucrose (AS / sucrose). SERS measurements showed strong interaction (or chemisorption) between Ag nanoparticles and surface aqueous sulfate [SO42-] with [SO42-]AS / sucrose > [SO42-]AS / SA > [SO42-]AS. Enhanced spectra of the solid AS and AS / SA particles revealed the formation of surface-adsorbed water on their surfaces at 60 % relative humidity. These observations of surface aqueous sulfate and adsorbed water demonstrate a possible role of surface-adsorbed water in facilitating the dissolution of sulfate from the bulk phase into its water layer(s). Submicron ambient aerosol particles collected in Hong Kong exhibited non-enhanced features of black carbon and enhanced features of sulfate and organic matter (carbonyl group), indicating an enrichment of sulfate and organic matter on the particle surface.

Surface-enhanced Raman scattering (SERS) by molecules adsorbed at spherical particles: errata

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerker, M.; Wang, D.S.; Chew, H.

1980-12-15

A model for Raman scattering by a molecule adsorbed at the surface of a spherical particle is articulated by treating the molecule as a classical electric dipole. This follows Moskovits's suggestion (J. Chem. Phys. 69, 4159 (1978)) and the experiments by Creighton et al. (J. Chem. Soc. Faraday Trans. II, 75, 790(1979)) that such a system may exhibit SERS simlar to that at roughened electrode surfaces. The molecule is stimulated by a primary field comprised of the incident and near-scattered fields. Emission consists of the dipole field plus a scattered field, each at the shifted frequency. Addition of feedback termsmore » between the dipole and the particle makes only a negligible contribution to the fields. For pyridine adsorbed at the surface of a silver sphere, the 1010 cm/sup -1/ band is enhanced by approx.10/sup 6/ if the radius is much less than the wavelengths and the excitation wavelength is approx.382 nm, a wavelength for which the relative refractive index of silver is close to m = ..sqrt..2i. Detailed results are given for the effect upon the angular distribution and the polarization of the Raman emission of particle size, distance from the surface, excitation wavelength, and location of the molecule upon the surface. These results simulate those observed at roughened silver electrodes and suggest that the mechanism of SERS at those electrodes may resemble the electromagnetic mechanism elucidated here. The authors predict that comparable effects should be observed for fluorescent scattering. 53 references, 9 figures.« less

Mesoporous multi-shelled ZnO microspheres for the scattering layer of dye sensitized solar cell with a high efficiency

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia, Weiwei; Mei, Chao; Zeng, Xianghua, E-mail: xhzeng@yzu.edu.cn

2016-03-14

Both light scattering and dye adsorbing are important for the power conversion efficiency PCE performance of dye sensitized solar cell (DSSC). Nanostructured scattering layers with a large specific surface area are regarded as an efficient way to improve the PCE by increasing dye adsorbing, but excess adsorbed dye will hinder light scattering and light penetration. Thus, how to balance the dye adsorbing and light penetration is a key problem to improve the PCE performance. Here, multiple-shelled ZnO microspheres with a mesoporous surface are fabricated by a hydrothermal method and are used as scattering layers on the TiO{sub 2} photoanode ofmore » the DSSC in the presence of N719 dye and iodine–based electrolyte, and the results reveal that the DSSCs based on triple shelled ZnO microsphere with a mesoporous surface exhibit an enhanced PCE of 7.66%, which is 13.0% higher than those without the scattering layers (6.78%), indicating that multiple-shelled microspheres with a mesoporous surface can ensure enough light scattering between the shells, and a favorable concentration of the adsorbed dye can improve the light penetration. These results may provide a promising pathway to obtain the high efficient DSSCs.« less

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

PubMed

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

2015-05-20

A solid surface in contact with water or aqueous solution usually carries specific electric charges. These surface charges attract counter ions from the liquid side. Since the geometry of opposite charge distribution parallel to the solid-liquid interface is similar to that of a capacitor, it is called an electrical double layer capacitor (EDLC). Therefore, there is an electrical potential difference across an EDLC in equilibrium. When a liquid bridge is formed between two conducting plates, the system behaves as two serially connected EDLCs. In this work, we propose a new method for investigating the surface charge density on solid-liquid interfaces. By mechanically modulating the electrical double layers and simultaneously applying a dc bias voltage across the plates, an ac electric current can be generated. By measuring the voltage drop across a load resistor as a function of bias voltage, we can study the surface charge density on solid-liquid interfaces. Our experimental results agree very well with the simple equivalent electrical circuit model proposed here. Furthermore, using this method, one can determine the polarity of the adsorbed state on the solid surface depending on the material used. We expect this method to aid in the study of electrical phenomena on solid-liquid interfaces.

Surface-Induced Near-Field Scaling in the Knudsen Layer of a Rarefied Gas

NASA Astrophysics Data System (ADS)

Gazizulin, R. R.; Maillet, O.; Zhou, X.; Cid, A. Maldonado; Bourgeois, O.; Collin, E.

2018-01-01

We report on experiments performed within the Knudsen boundary layer of a low-pressure gas. The noninvasive probe we use is a suspended nanoelectromechanical string, which interacts with He 4 gas at cryogenic temperatures. When the pressure P is decreased, a reduction of the damping force below molecular friction ∝P had been first reported in Phys. Rev. Lett. 113, 136101 (2014), 10.1103/PhysRevLett.113.136101 and never reproduced since. We demonstrate that this effect is independent of geometry, but dependent on temperature. Within the framework of kinetic theory, this reduction is interpreted as a rarefaction phenomenon, carried through the boundary layer by a deviation from the usual Maxwell-Boltzmann equilibrium distribution induced by surface scattering. Adsorbed atoms are shown to play a key role in the process, which explains why room temperature data fail to reproduce it.

Quantum Chemical Study of Water Adsorption on the Surfaces of SrTiO3 Nanotubes.

PubMed

Bandura, Andrei V; Kuruch, Dmitry D; Evarestov, Robert A

2015-07-20

We have studied the adsorption of water molecules on the inner and outer surfaces of nanotubes generated by rolling (001) layers of SrTiO3 cubic crystals. The stability and the atomic and electronic structures of the adsorbed layers are determined by using hybrid density functional theory. The absorption energy and the preferred adsorbate structure are essentially governed by the nature of the surface of the nanotube. Dissociative adsorption prevails on the outer nanotube surfaces. The stability of the adsorbed layers on the inner surfaces is related to the possibility of the formation of hydrogen bonds between water molecules and surface oxygen atoms, and depends on the surface curvature. The presence of water molecules on the inner surface of the nanotubes leads to an increase of the electronic band gap. Externally TiO2 -terminated nanotubes could be used for the photocatalytic decomposition of water by ultraviolet radiation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Compliant layer chucking surface

DOEpatents

Blaedel, Kenneth L [Dublin, CA; Spence, Paul A [Pleasanton, CA; Thompson, Samuel L [Pleasanton, CA

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.

Surface stress induced by interactions of adsorbates and its effect on deformation and frequency of microcantilever sensors

NASA Astrophysics Data System (ADS)

Yi, X.; Duan, H. L.

2009-08-01

Surface stress is widely used to characterize the adsorption effect on the mechanical response of nanomaterials and nanodevices. However, quantitative relations between continuum-level descriptions of surface stress and molecular-level descriptions of adsorbate interactions are not well established. In this paper, we first obtain the relations between the adsorption-induced surface stress and the van der Waals and Coulomb interactions in terms of the physical and chemical interactions between adsorbates and solid surfaces. Then, we present a theoretical framework to predict the deflection and resonance frequencies of microcantilevers with the simultaneous effects of the eigenstrain, surface stress and adsorption mass. Finally, the adsorption-induced deflection and resonance frequency shift of microcantilevers are numerically analyzed for the van der Waals and Coulomb interactions. The present theoretical framework quantifies the mechanisms of the adsorption-induced surface stress, and thus provides guidelines to the analysis of the sensitivities, and the identification of the detected substance in the design and application of micro- and nanocantilever sensors.

Structural properties of atactic polystyrene adsorbed onto solid surfaces.

PubMed

Tatek, Yergou B; Tsige, Mesfin

2011-11-07

In the present work, we are studying the local conformation of chains in a thin film of polystyrene adsorbed on a solid substrate by using atomistically detailed simulations. The simulations are carried out by using the readily available and massively parallel molecular dynamics code known as LAMMPS. In particular, a special emphasis is given to the density and orientation of side chains (which consist of phenyl groups and methylene units) at solid/polymer and polymer/vacuum interfaces. Three types of substrates were used in our study: α-quartz, graphite, and amorphous silica. Our investigation was restricted to atactic polystyrene. Our results show that the density and structural properties of side chains depend on the type of surface. An excess of phenyl rings is observed near the α-quartz substrate while the film adsorbed on graphite is depleted in C(6)H(5). Moreover, the orientation of the rings and methylene units on the substrate/film interface show a strong dependence on the type of the substrate, while the rings at the film/vacuum interface show a marked tendency to point outward, away from the film. The results we obtained are in a large part in good agreement with previous experimental and simulation results.

Surface sodium lignosulphonate-immobilized sawdust particle as an efficient adsorbent for capturing Hg2+ from aqueous solution.

PubMed

Gao, Shan; Luo, Tiantian; Zhou, Qi; Luo, Wenjun; Li, Haifeng; Jing, Luru

2018-05-01

In this work, the soluble sodium lignosulphonate (LS Na ) molecules were successfully grafted onto the surface of pine sawdust (PSD) particles to obtain an efficient adsorbent (PSD-LS) for removing Hg 2+ from wastewater. In advance, the surface of sawdust particles were carboxymethylated by chloroacetic acid, the LS Na would be anchored on the surface by a heterogeneous esterification reaction occurred between the hydroxyl of LS Na and carboxyl on PSD surface. The resultant product (PSD-LS) exhibited a good adsorption performance for Hg 2+ with adsorption capacity up to 164.77 mg/g and it was characterized by scanning electron microscope (SEM), energy dispersive X-ray diffraction (EDX), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). The effects of pH, contact time, adsorption temperature and initial concentration on the adsorption of Hg 2+ were investigated. Results showed that the pseudo-second-order kinetics and Langmuir isotherm model could describe the adsorption process better. In addition, the composite adsorbent has outstanding reusability with high and stable desorption rates under several continuous cycle. These findings suggested that PSD-LS was a potential adsorbent to remove hazardous metal ions from wastewater. Copyright © 2018 Elsevier Inc. All rights reserved.

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

Treesearch

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

2004-01-01

Phosphorus from excess fertilizers and detergents ends up washing into lakes, creeks, and rivers. This overabundance of phosphorus causes excessive aquatic plant and algae growth and depletes the dissolved oxygen supply in the water. In this study, aluminum-impregnated mesoporous adsorbents were tested for their ability to remove phosphate from water. The surface...

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.

Adsorbed water and thin liquid films on Mars

NASA Astrophysics Data System (ADS)

Boxe, C. S.; Hand, K. P.; Nealson, K. H.; Yung, Y. L.; Yen, A. S.; Saiz-Lopez, A.

2012-07-01

At present, bulk liquid water on the surface and near-subsurface of Mars does not exist due to the scarcity of condensed- and gas-phase water, pressure and temperature constraints. Given that the nuclei of soil and ice, that is, the soil solid and ice lattice, respectively, are coated with adsorbed and/or thin liquid films of water well below 273 K and the availability of water limits biological activity, we quantify lower and upper limits for the thickness of such adsorbed/water films on the surface of the Martian regolith and for subsurface ice. These limits were calculated based on experimental and theoretical data for pure water ice and water ice containing impurities, where water ice containing impurities exhibit thin liquid film enhancements, ranging from 3 to 90. Close to the cold limit of water stability (i.e. 273 K), thin liquid film thicknesses at the surface of the Martian regolith is 0.06 nm (pure water ice) and ranges from 0.2 to 5 nm (water ice with impurities). An adsorbed water layer of 0.06 nm implies a dessicated surface as the thickness of one monolayer of water is 0.3 nm but represents 0.001-0.02% of the Martian atmospheric water vapour inventory. Taking into account the specific surface area (SSA) of surface-soil (i.e. top 1 mm of regolith and 0.06 nm adsorbed water layer), shows Martian surface-soil may contain interfacial water that represents 6-66% of the upper- and lower-limit atmospheric water vapour inventory and almost four times and 33%, the lower- and upper-limit Martian atmospheric water vapour inventory. Similarly, taking the SSA of Martian soil, the top 1 mm or regolith at 5 nm thin liquid water thickness, yields 1.10×1013 and 6.50×1013 litres of waters, respectively, 55-325 times larger than Mars' atmospheric water vapour inventory. Film thicknesses of 0.2 and 5 nm represent 2.3×104-1.5×106 litres of water, which is 6.0×10-7-4.0×10-4%, respectively, of a 10 pr μm water vapour column, and 3.0×10-6-4.0×10-4% and 6.0×10

Competitive Adsorption of Metals onto Magnetic Graphene Oxide: Comparison with Other Carbonaceous Adsorbents

PubMed Central

Hur, Jin; Shin, Jaewon; Yoo, Jeseung; Seo, Young-Soo

2015-01-01

Competitive adsorption isotherms of Cu(II), Pb(II), and Cd(II) were examined on a magnetic graphene oxide (GO), multiwalled carbon nanotubes (MWCNTs), and powered activated carbon (PAC). A series of analyses confirmed the successful synthesis of the magnetic GO based on a simple ultrasonification method. Irrespective of the adsorbents, the adsorption was highly dependent on pH, and the adsorption was well described by the Langmuir isotherm model. The maximum adsorption capacities of the adsorbents were generally higher in the order of Pb(II) > Cu(II) > Cd(II), which is the same as the degree of the electronegativity and the hydrated radius of the metals, suggesting that the metal adsorption may be governed by an ion exchange between positively charged metals and negatively charged surfaces, as well as diffusion of metals into the surface layer. The adsorption of each metal was mostly lower for multi- versus single-metal systems. The antagonistic effects were influenced by solution pH as well as the type of metals, and they were higher in the order of the magnetic GO > MWCNT > PAC. Dissolved HS played a greater role than HS adsorbed onto the adsorbents, competing with the adsorption sites for metal complexation. PMID:25861683

Bioactivity evolution of the surface functionalized bioactive glasses.

PubMed

Magyari, Klára; Baia, Lucian; Vulpoi, Adriana; Simon, Simion; Popescu, Octavian; Simon, Viorica

2015-02-01

The formation of a calcium phosphate layer on the surface of the SiO2 -CaO-P2 O5 glasses after immersion in simulated body fluid (SBF) generally demonstrates the bioactivity of these materials. Grafting of the surface by chemical bonding can minimize the structural changes in protein adsorbed on the surface. Therefore, in this study our interest was to evaluate the bioactivity and blood biocompatibility of the SiO2 -CaO-P2 O5 glasses after their surface modification by functionalization with aminopropyl-triethoxysilane and/or by fibrinogen. It is shown that the fibrinogen adsorbed on the glass surfaces induces a growing of the apatite-like layer. It is also evidenced that the protein content from SBF influences the growth of the apatite-like layer. Furthermore, the good blood compatibility of the materials after fibrinogen and bovine serum albumin adsorption is proved from the assessment of the β-sheet-β-turn ratio. © 2014 Wiley Periodicals, Inc.

Versatile Poly(Diallyl Dimethyl Ammonium Chloride)-Layered Nanocomposites for Removal of Cesium in Water Purification.

PubMed

Jang, Sung-Chan; Kang, Sung-Min; Kim, Gi Yong; Rethinasabapathy, Muruganantham; Haldorai, Yuvaraj; Lee, Ilsong; Han, Young-Kyu; Renshaw, Joanna C; Roh, Changhyun; Huh, Yun Suk

2018-06-12

In this work, we elucidate polymer-layered hollow Prussian blue-coated magnetic nanocomposites as an adsorbent to remove radioactive cesium from environmentally contaminated water. To do this, Fe₃O₄ nanoparticles prepared using a coprecipitation method were thickly covered with a layer of cationic polymer to attach hollow Prussian blue through a self-assembly process. The as-synthesized adsorbent was confirmed through various analytical techniques. The adsorbent showed a high surface area (166.16 m²/g) with an excellent cesium adsorbent capacity and removal efficiency of 32.8 mg/g and 99.69%, respectively. Moreover, the superparamagnetism allows effective recovery of the adsorbent using an external magnetic field after the adsorption process. Therefore, the magnetic adsorbent with a high adsorption efficiency and convenient recovery is expected to be effectively used for rapid remediation of radioactive contamination.

Commensurability and transformations of adsorbed phases on a heterogeneous solid with periodic distribution of surface energy

NASA Astrophysics Data System (ADS)

Cortés, Joaquin; Valencia, Eliana

1997-07-01

Monte Carlo experiments are used to investigate the adsorption of argon on a heterogeneous solid with a periodic distribution of surface energy. A study is made of the relation between the adsorbate molecule's diameter and the distance between the sites of maximum surface energy on the critical temperature, the observed phase changes, and the commensurability of the surface phase structure determined in the simulation.

How Does the Surface of Al-ITQ-HB 2D-MOF Condition the Intermolecular Interactions of an Adsorbed Organic Molecule?

PubMed

Caballero-Mancebo, Elena; Moreno, José María; Corma, Avelino; Díaz, Urbano; Cohen, Boiko; Douhal, Abderrazzak

2018-05-30

In this work, we unravel how the two-dimensional Al-ITQ-4-heptylbenzoic acid (HB) metal-organic framework (MOF) changes the interactions of Nile red (NR) adsorbed on its surface. Time-resolved emission experiments indicate the occurrence of energy transfer between adsorbed NR molecules, in abnormally long time constant of 2-2.5 ns, which gets shorter (∼0.25 ns) when the concentration of the surface-adsorbed NR increases. We identify the emission from local excited state of aggregates and charge transfer and energy transfer between adsorbed molecules. Femtosecond emission studies reveal an ultrafast process (∼425 fs) in the NR@Al-ITQ-HB composites, assigned to an intramolecular charge transfer in NR molecules. A comparison of the observed photobehavior with that of NR/SiO 2 and NR/Al 2 O 3 composites suggests that the occurrence of energy transfer in the NR@MOF complexes is a result of specific and nonspecific interactions, reflecting the different surface properties of Al-ITQ-HB that are of relevance to the reported high catalytic activity. Our results provide new knowledge for further researches on other composites with the aim to improve understanding of photocatalytic and photonic processes within MOFs.

Effect of adsorbate electrophilicity and spiky uneven surfaces on single gold nanourchin-based localized surface plasmon resonance sensors

NASA Astrophysics Data System (ADS)

Kim, Geun Wan; Ha, Ji Won

2018-04-01

We present single particle studies on gold nanourchins (AuNUs) for their use as localized surface plasmon resonance (LSPR) biosensors under dark-field (DF) microscopy. First, the LSPR wavelength of single AuNUs was red-shifted as thiol molecules were attached onto the surface. AuNUs with sharp tips showed higher sensitivity for detecting thiol molecules than gold nanospheres (AuNSs) of similar size. Second, the degree of red shift was affected by the electrophilicity of adsorbate molecules on the nanoparticle surface. Last, real-time monitoring of molecular binding events on single AuNUs was achieved with introducing 1 μM of 4-aminothiophenol.

Novel Shear-horizontal Surface Acoustic Wave Based Immunosensors Using SiO2Waveguiding Layers And Flow Injection Analysis.

PubMed

Guo, X S; Chen, Y Q; Yang, X L; Wang, L R

2005-01-01

Surface acoustic wave (SAW) devices based on shear-horizontal (SH) waves can be used as mass-sensitive immunosensors. This paper presents a novel SH-SAW sensor to detect anti-immunoglobulin (IgG) molecules by means of the antibody-antigen binding mechanism. The sensor system comprising dual delay lines was fabricated on 36° Y-X LiTaO3substrate. A SiO2layer was used as love mode waveguiding layers, well as insulating and chemically resistant protective layer. Moreover, flow injection analysis (FIA) method was used for continuous detection the protein molecules. The protein A was immobilized on the optional surface of the gold layer, then coupled with IgG to adsorb the antigens to be measured in the protein solution. The operational frequency of the system changed due to the interaction of antibody-antigen binding. The experimental result demonstrates the sensor has stable frequency response to the mass loading effect of the various anti-IgG concentrations with the sensitivity up to 3.3ng/ml/Hz.

Boundary layers of aqueous surfactant and block copolymer solutions against hydrophobic and hydrophilic solid surfaces

NASA Astrophysics Data System (ADS)

Steitz, Roland; Schemmel, Sebastian; Shi, Hongwei; Findenegg, Gerhard H.

2005-03-01

The boundary layer of aqueous surfactants and amphiphilic triblock copolymers against flat solid surfaces of different degrees of hydrophobicity was investigated by neutron reflectometry (NR), grazing incidence small angle neutron scattering (GISANS) and atomic force microscopy (AFM). Solid substrates of different hydrophobicities were prepared by appropriate surface treatment or by coating silicon wafers with polymer films of different chemical natures. For substrates coated with thin films (20-30 nm) of deuterated poly(styrene) (water contact angle \\theta_{\\mathrm {w}} \\approx 90^\\circ ), neutron reflectivity measurements on the polymer/water interface revealed a water depleted liquid boundary layer of 2-3 nm thickness and a density about 90% of the bulk water density. No pronounced depletion layer was found at the interface of water against a less hydrophobic polyelectrolyte coating (\\theta_{\\mathrm {w}} \\approx 63^\\circ ). It is believed that the observed depletion layer at the hydrophobic polymer/water interface is a precursor of the nanobubbles which have been observed by AFM at this interface. Decoration of the polymer coatings by adsorbed layers of nonionic CmEn surfactants improves their wettability by the aqueous phase at surfactant concentrations well below the critical micellar concentration (CMC) of the surfactant. Here, GISANS experiments conducted on the system SiO2/C8E4/D2O reveal that there is no preferred lateral organization of the C8E4 adsorption layers. For amphiphilic triblock copolymers (PEO-PPO-PEO) it is found that under equilibrium conditions they form solvent-swollen brushes both at the air/water and the solid/water interface. In the latter case, the brushes transform to uniform, dense layers after extensive rinsing with water and subsequent solvent evaporation. The primary adsorption layers maintain properties of the precursor brushes. In particular, their thickness scales with the number of ethylene oxide units (EO) of the block

Stern Layer Structure and Energetics at Mica-Water Interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bourg, Ian C.; Lee, Sang Soo; Fenter, Paul

2017-04-11

The screening of surface charge by dissolved ions at solid liquid interfaces in the region of interfacial fluid known as the electrical double layer (EDL)-plays a recurrent role in surface science, from ion adsorption to colloidal mechanics to the transport properties of nanoporous media. A persistent unknown in theories of EDL-related phenomena is the structure of the Stern layer, the near-surface portion of the EDL where water molecules and adsorbed ions form specific short-range interactions with surface atoms. Here, we describe a set of synchrotron X-ray reflectivity (XRR) experiments and molecular dynamics (MD) simulations carried out under identical conditions formore » a range of 0.1 M alkali chloride (Li-, Na-, K-, Rb-, or CsCl) solutions on the basal surface of muscovite mica, a mineral isostructural to phyllosilicate clay minerals and one of the most widely studied reference surfaces in interfacial science. Our XRR and MD simulation results provide a remarkably consistent view of the structure and energetics of the Stern layer, with some discrepancy on the fraction of the minor outer-sphere component of Rb and on the adsorption energetics of Li. The results of both techniques, along with surface complexation model calculations, provide insight into the sensitivity of water structure and ion adsorption to surface topography and the type of adsorbed counterion.« less

Surface enhanced Raman spectroscopy (SERS) from a molecule adsorbed on a nanoscale silver particle cluster in a holographic plate

NASA Astrophysics Data System (ADS)

Jusinski, Leonard E.; Bahuguna, Ramen; Das, Amrita; Arya, Karamjeet

2006-02-01

Surface enhanced Raman spectroscopy has become a viable technique for the detection of single molecules. This highly sensitive technique is due to the very large (up to 14 orders in magnitude) enhancement in the Raman cross section when the molecule is adsorbed on a metal nanoparticle cluster. We report here SERS (Surface Enhanced Raman Spectroscopy) experiments performed by adsorbing analyte molecules on nanoscale silver particle clusters within the gelatin layer of commercially available holographic plates which have been developed and fixed. The Ag particles range in size between 5 - 30 nanometers (nm). Sample preparation was performed by immersing the prepared holographic plate in an analyte solution for a few minutes. We report here the production of SERS signals from Rhodamine 6G (R6G) molecules of nanomolar concentration. These measurements demonstrate a fast, low cost, reproducible technique of producing SERS substrates in a matter of minutes compared to the conventional procedure of preparing Ag clusters from colloidal solutions. SERS active colloidal solutions require up to a full day to prepare. In addition, the preparations of colloidal aggregates are not consistent in shape, contain additional interfering chemicals, and do not generate consistent SERS enhancement. Colloidal solutions require the addition of KCl or NaCl to increase the ionic strength to allow aggregation and cluster formation. We find no need to add KCl or NaCl to create SERS active clusters in the holographic gelatin matrix. These holographic plates, prepared using simple, conventional procedures, can be stored in an inert environment and preserve SERS activity after several weeks subsequent to preparation.

Adsorption and conformational modification of fibronectin and fibrinogen adsorbed on hydroxyapatite. A QCM-D study.

PubMed

Fernández-Montes Moraleda, Belén; San Román, Julio; Rodríguez-Lorenzo, Luís M

2016-10-01

Hydroxyapatite is a bioactive ceramic frequently used for bone engineering/replacement. One of the parameters that influence the biological response to implanted materials is the conformation of the first adsorbed protein layer. In this work, the adsorption and conformational changes of two fibroid serum proteins; fibronectin and fibrinogen adsorbed onto four different hydroxyapatite powders are studied with a Quartz Crystal Microbalance with Dissipation (QCM-D). Each of the calcined apatites adsorbs less protein than their corresponding synthesized samples. Adsorption on synthesized samples yields always an extended conformation whereas a reorganization of the layer is observed for the calcined samples. Fg acquires a "Side on" conformation in all the samples at the beginning of the experiment except for one of the synthesized samples where an "End-on" conformation is obtained during the whole experiment. The Extended conformation is the active conformation for Fn. This conformation is favored by apatites with large specific surface area (SSA) and on highly concentrated media. Apatite surface features should be considered in the selection or design of materials for bone regeneration, since it is possible to control the conformation mode of attachment of Fn and Fg by an appropriate selection of them. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2585-2594, 2016. © 2016 Wiley Periodicals, Inc.

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 g U/kg ads, 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

Energy transfer and photochemistry on a metal surface: Mo(CO)/sub 6/ on Rh(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Germer, T.A.; Ho, W.

1989-05-01

The occurrence of photoinduced reactions on solid surfaces depends on the relative rates between the excited-state decomposition and the energy transfer to the surface. In this study, the photodecomposition of Mo(CO)/sub 6/ on Rh(100) at 90 K by 325-nm UV irradiation has been studied as a function of coverage and surface preparation using thermal desorption spectroscopy, electron energy-loss spectroscopy, and photoinduced desorption spectroscopy. It is found that Mo(CO)/sub 6/ adsorbs dissociatively on Rh(100) into carbonyl fragments and CO in the first monolayer and molecularly in multilayers. Photoinduced desorption of CO is observed for the multilayers adsorbed onto the dissociated firstmore » layer via a nonthermal electronic excitation of adsorbed metal carbonyls. The presence of the metal surface prevents complete decarbonylation as in the gas phase; deexcitation of electronically excited carbonyls is not sufficiently fast to quench all the observed photochemistry. It is also found that Mo(CO)/sub 6/ adsorbs molecularly on a presaturated CO ordered overlayer on Rh(100) and undergoes photodissociation to a greater degree than on the dissociated and disordered surface of carbonyl fragments. The ordered CO layer effectively screens the interaction between the molecular carbonyls and the Rh(100) layer surface.« less

Excited-state potential-energy surfaces of metal-adsorbed organic molecules from linear expansion Δ-self-consistent field density-functional theory (ΔSCF-DFT).

PubMed

Maurer, Reinhard J; Reuter, Karsten

2013-07-07

Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion Δ-self-consistent field method by Gavnholt et al. [Phys. Rev. B 78, 075441 (2008)] presents an efficient alternative to time consuming quasi-particle calculations. In this method, the standard Kohn-Sham equations of density-functional theory are solved with the constraint of a non-equilibrium occupation in a region of Hilbert-space resembling gas-phase orbitals of the adsorbate. In this work, we discuss the applicability of this method for the excited-state dynamics of metal-surface mounted organic adsorbates, specifically in the context of molecular switching. We present necessary advancements to allow for a consistent quality description of excited-state potential-energy surfaces (PESs), and illustrate the concept with the application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find that the explicit inclusion of substrate electronic states modifies the topologies of intra-molecular excited-state PESs of the molecule due to image charge and hybridization effects. While the molecule in gas phase shows a clear energetic separation of resonances that induce isomerization and backreaction, the surface-adsorbed molecule does not. The concomitant possibly simultaneous induction of both processes would lead to a significantly reduced switching efficiency of such a mechanism.

Adsorption-desorption mechanism of phosphate by immobilized nano-sized magnetite layer: interface and bulk interactions.

PubMed

Zach-Maor, Adva; Semiat, Raphael; Shemer, Hilla

2011-11-15

Phosphate adsorption mechanism by a homogenous porous layer of nano-sized magnetite particles immobilized onto granular activated carbon (nFe-GAC) was studied for both interface and bulk structures. X-ray Photoelectron Spectroscopy (XPS) analysis revealed phosphate bonding to the nFe-GAC predominantly through bidentate surface complexes. It was established that phosphate was adsorbed to the magnetite surface mainly via ligand exchange mechanism. Initially, phosphate was adsorbed by the active sites on the magnetite surface, after which it diffused into the interior of the nano-magnetite layer, as indicated by intraparticle diffusion model. This diffusion process continues regardless of interface interactions, revealing some of the outer magnetite binding sites for further phosphate uptake. Desorption, using NaOH solution, was found to be predominantly a surface reaction, at which hydroxyl ions replace the adsorbed phosphate ions only at the surface outer biding sites. Five successive fix-bed adsorption/regeneration cycles were successfully applied, without significant reduction in the nFe-GAC adsorption capacity and at high regeneration efficiency. Copyright © 2011 Elsevier Inc. All rights reserved.

Bioavailability of Carbon Nanomaterial-Adsorbed Polycyclic Aromatic Hydrocarbons to Pimphales promelas: Influence of Adsorbate Molecular Size and Configuration.

PubMed

Linard, Erica N; Apul, Onur G; Karanfil, Tanju; van den Hurk, Peter; Klaine, Stephen J

2017-08-15

Despite carbon nanomaterials' (CNMs) potential to alter the bioavailability of adsorbed contaminants, information characterizing the relationship between adsorption behavior and bioavailability of CNM-adsorbed contaminants is still limited. To investigate the influence of CNM morphology and organic contaminant (OC) physicochemical properties on this relationship, adsorption isotherms were generated for a suite of polycyclic aromatic hydrocarbons (PAHs) on multiwalled carbon nanotubes (MWCNTs) and exfoliated graphene (GN) in conjunction with determining the bioavailability of the adsorbed PAHs to Pimphales promelas using bile analysis via fluorescence spectroscopy. Although it appeared that GN adsorbed PAHs indiscriminately compared to MWCNTs, the subsequent bioavailability of GN-adsorbed PAHs was more sensitive to PAH morphology than MWCNTs. GN was effective at reducing bioavailability of linear PAHs by ∼70%, but had little impact on angular PAHs. MWCNTs were sensitive to molecular size, where bioavailability of two-ringed naphthalene was reduced by ∼80%, while bioavailability of the larger PAHs was reduced by less than 50%. Furthermore, the reduction in bioavailability of CNM-adsorbed PAHs was negatively correlated with the amount of CNM surface area covered by the adsorbed-PAHs. This study shows that the variability in bioavailability of CNM-adsorbed PAHs is largely driven by PAH size, configuration and surface area coverage.

Synthesis, performance, and modeling of immobilized nano-sized magnetite layer for phosphate removal.

PubMed

Zach-Maor, Adva; Semiat, Raphael; Shemer, Hilla

2011-05-15

A homogeneous layer of nano-sized magnetite particles (<4 nm) was synthesized by impregnation of modified granular activated carbon (GAC) with ferric chloride, for effective removal of phosphate. A proposed mechanism for the modification and formation of magnetite onto the GAC is specified. BET results showed a significant increase in the surface area of the matrix following iron loading, implying that a porous nanomagnetite layer was formed. Batch adsorption experiments revealed high efficiency of phosphate removal, by the newly developed adsorbent, attaining maximum adsorption capacity of 435 mg PO(4)/g Fe (corresponding to 1.1 mol PO(4)/mol Fe(3)O(4)). It was concluded that initially phosphate was adsorbed by the active sites on the magnetite surface, and then it diffused into the interior pores of the nanomagnetite layer. It was demonstrated that the latter is the rate-determining step for the process. Innovative correlation of the diffusion mechanism with the unique adsorption properties of the synthesized adsorbent is presented. Copyright © 2011 Elsevier Inc. All rights reserved.

Headgroup effects of template monolayers on the adsorption behavior and conformation of glucose oxidase adsorbed at air/liquid interfaces.

PubMed

Wang, Ke-Hsuan; Syu, Mei-Jywan; Chang, Chien-Hsiang; Lee, Yuh-Lang

2011-06-21

Stearic acid (SA) and octadecylamine (ODA) monolayers at the air/liquid interface were used as template layers to adsorb glucose oxidase (GOx) from aqueous solution. The effect of the template monolayers on the adsorption behavior of GOx was studied in terms of the variation of surface pressure, the evolution of surface morphology observed by BAM and AFM, and the conformation of adsorbed GOx. The results show that the presence of a template monolayer can enhance the adsorption rate of GOx; furthermore, ODA has a higher ability, compared to SA, to adsorb GOx, which is attributed to the electrostatic attractive interaction between ODA and GOx. For adsorption performed on a bare surface or on an SA monolayer, the surface pressure approaches an equilibrium value (ca. 8 mN/m) after 2 to 3 h of adsorption and remains nearly constant in the following adsorption process. For the adsorption on an ODA monolayer, the surface pressure will increase further 1 to 2 h after approaching the first equilibrium pressure, which is termed the second adsorption stage. The measurement of circular dichroism (CD) spectroscopy indicates that the Langmuir-Blodgett films of adsorbed GOx transferred at the first equilibrium state (π = 8 mN/m) have mainly a β-sheet conformation, which is independent of the type of template monolayers. However, the ODA/GOx LB film transferred at the second adsorption stage has mainly an α-helix conformation. It is concluded that the specific interaction between ODA and GOx not only leads to a higher adsorption rate and adsorbed amount of GOx but also induces a conformation change in adsorbed GOx from β-sheet to α-helix. The present results indicate that is possible to control the conformation of adsorbed protein by selecting the appropriate template monolayer. © 2011 American Chemical Society

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.

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

NASA Astrophysics Data System (ADS)

López-Moreno, S.; Romero, A. H.

2015-04-01

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

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

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

PubMed

López-Moreno, S; Romero, A H

2015-04-21

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

Fibrinogen adsorption on blocked surface of albumin.

PubMed

Holmberg, Maria; Hou, Xiaolin

2011-05-01

We have investigated the adsorption of albumin and fibrinogen onto PET (polyethylene terephthalate) and glass surfaces and how pre-adsorption of albumin onto these surfaces can affect the adsorption of later added fibrinogen. For materials and devices being exposed to blood, adsorption of fibrinogen is often a non-wanted event, since fibrinogen is part of the clotting cascade and unspecific adsorption of fibrinogen can have an influence on the activation of platelets. Albumin is often used as blocking agent for avoiding unspecific protein adsorption onto surfaces in devices designed to handle biological samples, including protein solutions. It is based on the assumption that proteins adsorbs as a monolayer on surfaces and that proteins do not adsorb on top of each other. By labelling albumin and fibrinogen with two different radioactive iodine isotopes that emit gamma radiation with different energies, the adsorption of both albumin and fibrinogen has been monitored simultaneously on the same sample. Information about topography and coverage of adsorbed protein layers has been obtained using AFM (Atomic Force Microscopy) analysis in liquid. Our studies show that albumin adsorbs in a multilayer fashion on PET and that fibrinogen adsorbs on top of albumin when albumin is pre-adsorbed on the surfaces. Copyright © 2010 Elsevier B.V. All rights reserved.

Analysis and comparison of inertinite-derived adsorbent with conventional adsorbents.

PubMed

Gangupomu, Roja Haritha; Kositkanawuth, Ketwalee; Sattler, Melanie L; Ramirez, David; Dennis, Brian H; MacDonnell, Frederick M; Billo, Richard; Priest, John W

2012-05-01

To increase U.S. petroleum energy-independence, the University of Texas at Arlington (UT Arlington) has developed a coal liquefaction process that uses a hydrogenated solvent and a proprietary catalyst to convert lignite coal to crude oil. This paper reports on part of the environmental evaluation of the liquefaction process: the evaluation of the solid residual from liquefying the coal, called inertinite, as a potential adsorbent for air and water purification. Inertinite samples derived from Arkansas and Texas lignite coals were used as test samples. In the activated carbon creation process, inertinite samples were heated in a tube furnace (Lindberg, Type 55035, Arlington, UT) at temperatures ranging between 300 and 850 degrees C for time spans of 60, 90, and 120 min, using steam and carbon dioxide as oxidizing gases. Activated inertinite samples were then characterized by ultra-high-purity nitrogen adsorption isotherms at 77 K using a high-speed surface area and pore size analyzer (Quantachrome, Nova 2200e, Kingsville, TX). Surface area and total pore volume were determined using the Brunauer Emmet, and Teller method, for the inertinite samples, as well as for four commercially available activated carbons (gas-phase adsorbents Calgon Fluepac-B and BPL 4 x 6; liquid-phase adsorbents Filtrasorb 200 and Carbsorb 30). In addition, adsorption isotherms were developed for inertinite and the two commercially available gas-phase carbons, using methyl ethyl ketone (MEK) as an example compound. Adsorption capacity was measured gravimetrically with a symmetric vapor sorption analyzer (VTI, Inc., Model SGA-100, Kingsville, TX). Also, liquid-phase adsorption experiments were conducted using methyl orange as an example organic compound. The study showed that using inertinite from coal can be beneficially reused as an adsorbent for air or water pollution control, although its surface area and adsorption capacity are not as high as those for commercially available activated

Acoustic Tomography of the Atmospheric Surface Layer

DTIC Science & Technology

2014-11-28

Report Title Acoustic tomography of the atmospheric surface layer (ASL) is based on the measurements of the travel times of sound propagation between...SECURITY CLASSIFICATION OF: Acoustic tomography of the atmospheric surface layer (ASL) is based on the measurements of the travel times of sound ...organ. In the case of acoustic tomography of the atmospheric surface layer (ASL), the travel times of sound propagation between speakers and

Influence of temperature and molecular structure on ionic liquid solvation layers.

PubMed

Wakeham, Deborah; Hayes, Robert; Warr, Gregory G; Atkin, Rob

2009-04-30

Atomic force microscopy (AFM) force profiling is used to investigate the structure of adsorbed and solvation layers formed on a mica surface by various room temperature ionic liquids (ILs) ethylammonium nitrate (EAN), ethanolammonium nitrate (EtAN), ethylammonium formate (EAF), propylammonium formate (PAF), ethylmethylammonium formate (EMAF), and dimethylethylammonium formate (DMEAF). At least seven layers are observed for EAN at 14 degrees C (melting point 13 degrees C), decreasing as the temperature is increased to 30 degrees C due to thermal energy disrupting solvophobic forces that lead to segregation of cation alkyl tails from the charged ammonium and nitrate moieties. The number and properties of the solvation layers can also be controlled by introducing an alcohol moiety to the cation's alkyl tail (EtAN), or by replacing the nitrate anion with formate (EAF and PAF), even leading to the detection of distinct cation and anion sublayers. Substitution of primary by secondary or tertiary ammonium cations reduces the number of solvation layers formed, and also weakens the cation layer adsorbed onto mica. The observed solvation and adsorbed layer structures are discussed in terms of the intermolecular cohesive forces within the ILs.

Mercury adsorption properties of sulfur-impregnated adsorbents

USGS Publications Warehouse

Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

2002-01-01

Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

Detection of creatinine enriched on a surface imprinted polystyrene film using FT-ATR-IR.

PubMed

Sreenivasan, K

2006-01-01

The surface of polystyrene (PS) was chemically modified by coating a thin layer of polyaniline (PANI) by oxidizing aniline using ammonium persulfate. Affinity sites for creatinine, a clinically relevant molecule, were created in the coated layer by adding creatinine as print molecules during the oxidation. The imprinted layer adsorbed creatinine was compared to non-imprinted surface reflecting the creation of creatinine-specific sites on the surface. The equilibrium was attained rapidly, indicating that a material of this kind is suitable for sensing applications. The adsorbed creatinine on the surface was detected using the technique of Fourier transform attenuated total internal reflection infra red spectroscopy (FT-ATR-IR). The results show that molecularly imprinted surface can enrich molecules of interest and the enriched molecules can be detected using FT-IR.

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. © 2015 Wiley Periodicals, Inc.

ELLIPSOMETRY OF ELECTROCHEMICAL SURFACE LAYERS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muller, R.H.

1977-06-01

Ellipsometry is concerned with the analysis and interpretation of changes in the state of polarization caused by reflection. The technique has found increasing interest in recent years for the measurement of thin films because it is unusually sensitive, disturbs the object minimally and can be applied to surfaces contained in any optically transparent medium. Film thicknesses amenable to measurement range from fractional monoatomic coverage to microscopic thicknesses. The measurement of changes in the state of polarization of light due to reflection provides an unusually sensitive tool for observing surface layers in any optically transparent environment. A fast, self-compensating ellipsometer hasmore » been used to observe the electrochemical formation of reacted surface layers. The optical effect of mass-transport boundary layers and component imperfections have been taken into account in the interpretation of results.« less

Optimization of implant/bone attachment: The effects of implant surface porosity, bioactive ceramic coatings, and delivery of adsorbed growth factors

NASA Astrophysics Data System (ADS)

Melican, Mora Carolynne

Various surface treatments and coating materials have been tested for use on metal alloy orthopaedic implants. Their purpose has been to enhance the bioactivity of the implant surfaces, and thus to increase the rate and degree of bony attachment in vivo in an attempt to hasten recovery time, increase implant service lifetime, and lessen pain associated with loosened orthopaedic implants. A series of in vivo and in vitro studies were performed to determine the influence of different implant surfaces including porous metal surfaces with varied porosity with depth, resorbable and non-resorbable plasma-sprayed hydroxyapatite (HA) coatings, and finally HA coatings with an adsorbed layer of human recombinant bone morphogenetic protein (rhBMP-2), an osteoinductive protein. Textured as-cast metal surfaces produced by investment casting in three dimensionally printed ceramic molds have exhibited superior bony ingrowth and attachment. Plasma-sprayed HA coatings have been shown to be appropriate substrates for osteoblast proliferation (particularly on highly crystalline HA) and stem cell proliferation (particularly on less crystalline HA). Less crystalline HA coatings have shown promise as delivery systems for different levels of rhBMP-2. The osteoinductive protein has been shown to remain active after delivery to the system, and was most effective when delivered in concentrations ranging from 30 to 50 ng/ml. Combinations of these surface treatments for metal implant surfaces warrant further investigation.

Retention of contaminants Cd and Hg adsorbed and intercalated in aluminosilicate clays: A first principles study

NASA Astrophysics Data System (ADS)

Crasto de Lima, F. D.; Miwa, R. H.; Miranda, Caetano R.

2017-11-01

Layered clay materials have been used to incorporate transition metal (TM) contaminants. Based on first-principles calculations, we have examined the energetic stability and the electronic properties due to the incorporation of Cd and Hg in layered clay materials, kaolinite (KAO) and pyrophyllite (PYR). The TM can be (i) adsorbed on the clay surface as well as (ii) intercalated between the clay layers. For the intercalated case, the contaminant incorporation rate can be optimized by controlling the interlayer spacing of the clay, namely, pillared clays. Our total energy results reveal that the incorporation of the TMs can be maximized through a suitable tuning of vertical distance between the clay layers. Based on the calculated TM/clay binding energies and the Langmuir absorption model, we estimate the concentrations of the TMs. Further kinetic properties have been examined by calculating the activation energies, where we found energy barriers of ˜20 and ˜130 meV for adsorbed and intercalated cases, respectively. The adsorption and intercalation of ionized TM adatoms were also considered within the deprotonated KAO surface. This also leads to an optimal interlayer distance which maximizes the TM incorporation rate. By mapping the total charge transfers at the TM/clay interface, we identify a net electronic charge transfer from the TM adatoms to the topmost clay surface layer. The effect of such a charge transfer on the electronic structure of the clay (host) has been examined through a set of X-ray absorption near edge structure (XANES) simulations, characterizing the changes of the XANES spectra upon the presence of the contaminants. Finally, for the pillared clays, we quantify the Cd and Hg K-edge energy shifts of the TMs as a function of the interlayer distance between the clay layers and the Al K-edge spectra for the pristine and pillared clays.

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

NASA Astrophysics Data System (ADS)

Swint, Amy Lynn

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

Organic light emitting diode with surface modification layer

DOEpatents

Basil, John D.; Bhandari, Abhinav; Buhay, Harry; Arbab, Mehran; Marietti, Gary J.

2017-09-12

An organic light emitting diode (10) includes a substrate (12) having a first surface (14) and a second surface (16), a first electrode (32), and a second electrode (38). An emissive layer (36) is located between the first electrode (32) and the second electrode (38). The organic light emitting diode (10) further includes a surface modification layer (18). The surface modification layer (18) includes a non-planar surface (30, 52).

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

DOE PAGES

Hiebel, Fanny; Shong, Bonggeun; Chen, Wei; ...

2016-10-12

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 CO 2 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 relativelymore » small molecule, weak intermolecular interaction provides the energy required for molecular self-assembly and reorganization of the metal surface.« less

Surface-Bound Casein Modulates the Adsorption and Activity of Kinesin on SiO2 Surfaces

PubMed Central

Ozeki, Tomomitsu; Verma, Vivek; Uppalapati, Maruti; Suzuki, Yukiko; Nakamura, Mikihiko; Catchmark, Jeffrey M.; Hancock, William O.

2009-01-01

Abstract Conventional kinesin is routinely adsorbed to hydrophilic surfaces such as SiO2. Pretreatment of surfaces with casein has become the standard protocol for achieving optimal kinesin activity, but the mechanism by which casein enhances kinesin surface adsorption and function is poorly understood. We used quartz crystal microbalance measurements and microtubule gliding assays to uncover the role that casein plays in enhancing the activity of surface-adsorbed kinesin. On SiO2 surfaces, casein adsorbs as both a tightly bound monolayer and a reversibly bound second layer that has a dissociation constant of 500 nM and can be desorbed by washing with casein-free buffer. Experiments using truncated kinesins demonstrate that in the presence of soluble casein, kinesin tails bind well to the surface, whereas kinesin head binding is blocked. Removing soluble casein reverses these binding profiles. Surprisingly, reversibly bound casein plays only a moderate role during kinesin adsorption, but it significantly enhances kinesin activity when surface-adsorbed motors are interacting with microtubules. These results point to a model in which a dynamic casein bilayer prevents reversible association of the heads with the surface and enhances association of the kinesin tail with the surface. Understanding protein-surface interactions in this model system should provide a framework for engineering surfaces for functional adsorption of other motor proteins and surface-active enzymes. PMID:19383474

Nano-sized Adsorbate Structure Formation in Anisotropic Multilayer System

NASA Astrophysics Data System (ADS)

Kharchenko, Vasyl O.; Kharchenko, Dmitrii O.; Yanovsky, Vladimir V.

2017-05-01

In this article, we study dynamics of adsorbate island formation in a model plasma-condensate system numerically. We derive the generalized reaction-diffusion model for adsorptive multilayer system by taking into account anisotropy in transfer of adatoms between neighbor layers induced by electric field. It will be found that with an increase in the electric field strength, a structural transformation from nano-holes inside adsorbate matrix toward separated nano-sized adsorbate islands on a substrate is realized. Dynamics of adsorbate island sizes and corresponding distributions are analyzed in detail. This study provides an insight into details of self-organization of adatoms into nano-sized adsorbate islands in anisotropic multilayer plasma-condensate systems.

Layer-selective synthesis of bilayer graphene via chemical vapor deposition

NASA Astrophysics Data System (ADS)

Yang, Ning; Choi, Kyoungjun; Robertson, John; Park, Hyung Gyu

2017-09-01

A controlled synthesis of high-quality AB-stacked bilayer graphene by chemical vapor deposition demands a detailed understanding of the mechanism and kinetics. By decoupling the growth of the two layers via a growth-and-regrowth scheme, we report the kinetics and termination mechanisms of the bilayer graphene growth on copper. We observe, for the first time, that the secondary layer growth follows Gompertzian kinetics. Our observations affirm the postulate of a time-variant transition from a mass-transport-limited to a reaction-limited regimes and identify the mechanistic disparity between the monolayer growth and the secondary-layer expansion underneath the monolayer cover. It is the continuous carbon supply that drives the expansion of the graphene secondary layer, rather than the initially captured carbon amount, suggesting an essential role of the surface diffusion of reactant adsorbates in the interspace between the top graphene layer and the underneath copper surface. We anticipate that the layer selectivity of the growth relies on the entrance energetics of the adsorbed reactants to the graphene-copper interspace across the primary-layer edge, which could be engineered by tailoring the edge termination state. The temperature-reliant saturation area of the secondary-layer expansion is understood as a result of competitive attachment of carbon and hydrogen adatoms to the secondary-layer graphene edge.

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.

Structural, electronic and optical properties of CO adsorbed on the defective anatase TiO2 (101) surface; a DFT study

NASA Astrophysics Data System (ADS)

Rafique, Muhammad; Shuai, Yong; Hassan, Muhammad

2017-08-01

This paper illustrates the study of stable structural, electronic and optical properties of carbon mono oxide (CO) molecule adsorbed on pure anatase TiO2 (101) surface and CO molecule adsorbed on defective anatase TiO2 (101) surface containing oxygen (O) atom subsurface vacancy using first-principles study calculations based on density functional theory (DFT) method. A foreign molecule CO was added in the interstitial space of anatase TiO2 (101) surface. It was observed that, adsorption of CO molecule is not favorable on pure anatase TiO2 (101) surface, however adsorption process is improved when subsurface contains O atom vacancy defect. In case of anatase TiO2 (101) surface containing subsurface vacancy, adsorption process is exothermic, resulting in stable structures. The adsorption energies calculated for CO molecules adsorbed at O2c site, at defect site and at Ti5c site of anatase surface containing subsurface O vacancy are 0.16 eV (at O2c), 0.32 eV (at defect site) and 0.43 eV (at Ti5c) site. DOS and PDOS plots are calculated for all the structures. Results indicated that CO molecule adsorption introduces surface states at the Fermi energy level (EF) as shown in partial density of states (PDOS) plots. The dielectric matrix and absorption coefficient (α) for defective anatase TiO2 (101) surface, CO adsorbed at O2c site, at defect site and at Ti5C site of anatase TiO2 (101) surface containing O atom subsurface vacancy has been calculated within the random phase approximation (RPA) using VASP (Vienna ab-initio simulation package) code. It was observed that upon CO adsorption at defective anatase surface, real and imaginary dielectric function peaks were shifted towards lower energy level and a small absorption peak was observed at 1.1 eV energy level which is not present in case of defective anatase (101) surface. CO adsorption produces a red shift in the absorption spectrum of anatase TiO2 (101) surface containing subsurface O atom vacancy.

Graphene nanosheets and graphite oxide as promising adsorbents for removal of organic contaminants from aqueous solution.

PubMed

Ji, Liangliang; Chen, Wei; Xu, Zhaoyi; Zheng, Shourong; Zhu, Dongqiang

2013-01-01

Graphenes are an emerging class of carbon nanomaterials whose adsorption properties toward organic compounds have not been well understood. In the present study, graphene nanosheets were prepared by reoxidation and abrupt heating of graphite oxide, which was prepared by sequential chemical oxidation of commercial nonporous graphite powder. Adsorption properties of three aromatic compounds (naphthalene, 2-naphthol, and 1-naphthylamine) and one pharmaceutical compound (tylosin) on graphene nanosheets and graphite oxide were examined to explore the potential of these two adsorbents for the removal of organic contaminants from aqueous solutions. Compared with the literature data of adsorption on carbon nanotubes, adsorption of bulky, flexible tylosin on graphene nanosheets exhibited markedly faster adsorption kinetics, which can be attributed to their opened-up layer structure. Graphene nanosheets and graphite oxide showed similar sequences of adsorption affinity: 1-naphthylamine > 2-naphthol > tylosin > naphthalene (with much larger differences observed on graphite oxide). It was proposed that the strong adsorption of the three aromatic compounds was mainly due to π-π electron donor-acceptor interactions with the graphitic surfaces of adsorbents. Additionally, Lewis acid-base interaction was likely an important factor contributing to the strong adsorption of 1-naphthylamine and tylosin, especially for the O-functionality-abundant graphite oxide. After being normalized on the basis of adsorbent surface area, adsorption affinities of all four tested adsorbates on graphene nanosheets were very close to those on nonporous graphite powder, reflecting complete accessibility of the adsorbent surface area in adsorption. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Surface modification of nanoporous alumina layers by deposition of Ag nanoparticles. Effect of alumina pore diameter on the morphology of silver deposit and its influence on SERS activity

NASA Astrophysics Data System (ADS)

Pisarek, Marcin; Nowakowski, Robert; Kudelski, Andrzej; Holdynski, Marcin; Roguska, Agata; Janik-Czachor, Maria; Kurowska-Tabor, Elżbieta; Sulka, Grzegorz D.

2015-12-01

Self-organized Al2O3 nanoporous/nanotubular (Al2O3-NP) oxide layers decorated with silver nanoparticles (Ag-NPs) exhibiting specific properties may serve as attractive SERS substrates for investigating the interactions between an adsorbate and adsorbent, or as stable platforms for detecting various organic compounds. This article presents the influence of the size of the alumina nanopores with a deposit of silver nanoparticles obtained by the magnetron sputtering technique on the morphology of silver film. Moreover, the effect of pore diameter on the intensity of SERS spectra in Ag-NPs/Al2O3-NP/Al composites has also been estimated. For such investigations we used pyridine as a probe molecule, since it has a large cross-section for Raman scattering. To characterize the morphology of the composite oxide layer Ag-NPs/Al2O3-NP/Al, before and after deposition of Ag-NPs by PVD methods (Physical Vapor Deposition), we used scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface analytical technique of surface-enhanced Raman spectroscopy (SERS) was used to investigate the surface activity of the composite. The results obtained show that, for a carefully controlled amount of Ag (0.020 mg/cm2 - deposited on the top of alumina nanopores whose average size varies from ∼86 nm up to ∼320 nm) in the composites investigated, pore size significantly affects SERS enhancement. We obtained distinctly higher intensities of SERS spectra for substrates with an Ag-NPs deposit having a larger diameter of the alumina nanopores. AFM results suggest that both the lateral and perpendicular distribution of Ag-NPs within and on the top of the largest pores is responsible for the highest SERS activity of the resulting Ag-NPs/Al2O3-NP/Al composite layer, since it produces a variety of cavities and slits which function as resonators for the adsorbed molecules. The Ag-NPs/MeOx-NP/Me composite layers obtained ensure a good reproducibility of the SERS measurements.

Improved Modeling of Surface Layer Parameters in a AGCM Using Refined Vertical Resolution in the Surface Layer

NASA Astrophysics Data System (ADS)

Shin, H. H.; Zhao, M.; Ming, Y.; Chen, X.; Lin, S. J.

2017-12-01

Surface layer (SL) parameters in atmospheric models - such as 2-m air temperature (T2), 10-m wind speed (U10), and surface turbulent fluxes - are computed by applying the Monin-Obukhov Similarity Theory (MOST) to the lowest model level height (LMH) in the models. The underlying assumption is that LMH is within surface layer height (SLH), but most AGCMs hardly meet the condition in stable boundary layers (SBLs) over land. To assess the errors in modeled SL parameters caused by this, offline computations of the MOST are performed with different LMHs from 1 to 100 m, for an idealized SBL case with prescribed surface parameters (surface temperature, roughness length and Obukhov length), and vertical profiles of temperature and winds. The results show that when LMH is higher than SLH, T2 and U10 are underestimated by O(1 K) and O(1 m/s), respectively, and the biases increase as LMH increases. Based on this, the refined vertical resolution with an additional layer in the SL is applied to the GFDL AGCM, and it reduces the systematic cold biases in T2 and the systematic underestimation of U10.

Tensiometry and dilational rheology of mixed β-lactoglobulin/ionic surfactant adsorption layers at water/air and water/hexane interfaces.

PubMed

Dan, Abhijit; Gochev, Georgi; Miller, Reinhard

2015-07-01

Oscillating drop tensiometry was applied to study adsorbed interfacial layers at water/air and water/hexane interfaces formed from mixed solutions of β-lactoglobulin (BLG, 1 μM in 10 mM buffer, pH 7 - negative net charge) and the anionic surfactant SDS or the cationic DoTAB. The interfacial pressure Π and the dilational viscoelasticity modulus |E| of the mixed layers were measured for mixtures of varying surfactant concentrations. The double capillary technique was employed which enables exchange of the protein solution in the drop bulk by surfactant solution (sequential adsorption) or by pure buffer (washing out). The first protocol allows probing the influence of the surfactant on a pre-adsorbed protein layer thus studying the protein/surfactant interactions at the interface. The second protocol gives access to the residual values of Π and |E| measured after the washing out procedure thus bringing information about the process of protein desorption. The DoTAB/BLG complexes exhibit higher surface activity and higher resistance to desorption in comparison with those for the SDS/BLG complexes due to hydrophobization via electrostatic binding of surfactant molecules. The neutral DoTAB/BLG complexes achieve maximum elastic response of the mixed layer. Mixed BLG/surfactant layers at the water/oil interface are found to reach higher surface pressure and lower maximum dilational elasticity than those at the water/air surface. The sequential adsorption mode experiments and the desorption study reveal that binding of DoTAB to pre-adsorbed BLG globules is somehow restricted at the water/air surface in comparison with the case of complex formation in the solution bulk and subsequently adsorbed at the water/air surface. Maximum elasticity is achieved with washed out layers obtained after simultaneous adsorption, i.e. isolation of the most surface active DoTAB/BLG complex. These specific effects are much less pronounced at the W/H interface. Copyright © 2015 Elsevier Inc

Antibody adsorption on the surface of water studied by neutron reflection

PubMed Central

Li, Zongyi; Holman, Robert; Pan, Fang; Campbell, Richard A.; Campana, Mario; Li, Peixun; Webster, John R. P.; Bishop, Steven; Narwal, Rojaramani; Uddin, Shahid

2017-01-01

ABSTRACT Surface and interfacial adsorption of antibody molecules could cause structural unfolding and desorbed molecules could trigger solution aggregation, resulting in the compromise of physical stability. Although antibody adsorption is important and its relevance to many mechanistic processes has been proposed, few techniques can offer direct structural information about antibody adsorption under different conditions. The main aim of this study was to demonstrate the power of neutron reflection to unravel the amount and structural conformation of the adsorbed antibody layers at the air/water interface with and without surfactant, using a monoclonal antibody ‘COE-3′ as the model. By selecting isotopic contrasts from different ratios of H2O and D2O, the adsorbed amount, thickness and extent of the immersion of the antibody layer could be determined unambiguously. Upon mixing with the commonly-used non-ionic surfactant Polysorbate 80 (Tween 80), the surfactant in the mixed layer could be distinguished from antibody by using both hydrogenated and deuterated surfactants. Neutron reflection measurements from the co-adsorbed layers in null reflecting water revealed that, although the surfactant started to remove antibody from the surface at 1/100 critical micelle concentration (CMC) of the surfactant, complete removal was not achieved until above 1/10 CMC. The neutron study also revealed that antibody molecules retained their globular structure when either adsorbed by themselves or co-adsorbed with the surfactant under the conditions studied. PMID:28353420

Molecular lego for the assembly of biosensing layers.

PubMed

Mano, N; Kuhn, A

2005-03-31

We propose a procedure to assemble monolayers of redox mediator, coenzyme, enzyme and stabilizing polyelectrolyte on an electrode surface using essentially electrostatic and complexing interactions. In a first step a monolayer of redox mediator, substituted nitrofluorenones, is adsorbed. In a second step, a layer of calcium cations is immobilized at the interface. It establishes a bridge between the redox mediator and the subsequently adsorbed coenzyme NAD(+). In the next step we use the intrinsic affinity of the NAD(+) monolayer for dehydrogenases to build up a multilayer composed of mediator/Ca(2+)/NAD(+)/dehydrogenase. The so obtained modified electrode can be used as a biosensor. Quartz crystal microbalance measurements allowed us to better understand the different parameters responsible for the adsorption. A more detailed investigation of the system made it possible to finally stabilize the assembly sufficiently by the adsorption of a polyelectrolyte layer in order to perform rotating disk electrode measurements with the whole supramolecular architecture on the electrode surface.

Atomic scale friction of molecular adsorbates during diffusion.

PubMed

Lechner, B A J; de Wijn, A S; Hedgeland, H; Jardine, A P; Hinch, B J; Allison, W; Ellis, J

2013-05-21

Experimental observations suggest that molecular adsorbates exhibit a larger friction coefficient than atomic species of comparable mass, yet the origin of this increased friction is not well understood. We present a study of the microscopic origins of friction experienced by molecular adsorbates during surface diffusion. Helium spin-echo measurements of a range of five-membered aromatic molecules, cyclopentadienyl, pyrrole, and thiophene, on a copper(111) surface are compared with molecular dynamics simulations of the respective systems. The adsorbates have different chemical interactions with the surface and differ in bonding geometry, yet the measurements show that the friction is greater than 2 ps(-1) for all these molecules. We demonstrate that the internal and external degrees of freedom of these adsorbate species are a key factor in the underlying microscopic processes and identify the rotation modes as the ones contributing most to the total measured friction coefficient.

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.

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

NASA Astrophysics Data System (ADS)

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

2015-01-01

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

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.

Adsorption behavior of a human monoclonal antibody at hydrophilic and hydrophobic surfaces

PubMed Central

Couston, Ruairidh G.; Skoda, Maximilian W.; Uddin, Shahid; van der Walle, Christopher F.

2013-01-01

One aspiration for the formulation of human monoclonal antibodies (mAb) is to reach high solution concentrations without compromising stability. Protein surface activity leading to instability is well known, but our understanding of mAb adsorption to the solid-liquid interface in relevant pH and surfactant conditions is incomplete. To investigate these conditions, we used total internal reflection fluorescence (TIRF) and neutron reflectometry (NR). The mAb tested (“mAb-1”) showed highest surface loading to silica at pH 7.4 (~12 mg/m2), with lower surface loading at pH 5.5 (~5.5 mg/m2, further from its pI of 8.99) and to hydrophobized silica (~2 mg/m2). The extent of desorption of mAb-1 from silica or hydrophobized silica was related to the relative affinity of polysorbate 20 or 80 for the same surface. mAb-1 adsorbed to silica on co-injection with polysorbate (above its critical micelle concentration) and also to silica pre-coated with polysorbate. A bilayer model was developed from NR data for mAb-1 at concentrations of 50–5000 mg/L, pH 5.5, and 50–2000 mg/L, pH 7.4. The inner mAb-1 layer was adsorbed to the SiO2 surface at near saturation with an end-on” orientation, while the outer mAb-1 layer was sparse and molecules had a “side-on” orientation. A non-uniform triple layer was observed at 5000 mg/L, pH 7.4, suggesting mAb-1 adsorbed to the SiO2 surface as oligomers at this concentration and pH. mAb-1 adsorbed as a sparse monolayer to hydrophobized silica, with a layer thickness increasing with bulk concentration - suggesting a near end-on orientation without observable relaxation-unfolding. PMID:23196810

Observation of surface layering in a nonmetallic liquid

NASA Astrophysics Data System (ADS)

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

2006-03-01

Non-monotonic density profiles (layers) have previously been observed at the free surfaces of many metallic liquids, but not in isotropic dielectric liquids. Whether the presence of an electron gas is necessary for surface layering has been the subject of debate. Until recently, MD simulations have suggested that layering at free liquid interface may be a generic phenomenon and is not limited to the metallic liquids^1. The theories predict that if normal liquids can be cooled down to temperatures low enough, layering structure should be observed experimentally. However, this is difficult for most molecular liquids because these liquids freeze well above the temperature necessary for observing the layering structure. By studying the surface structure of liquid TEHOS (tetrakis(2-ethylhexoxy)silane), which combines relatively low freezing point and high boiling point compared to that of most molecular liquids, we have observed the evidence of layering at the free interface of liquid TEHOS using x-ray reflectivity. When cooled to T/Tc 0.25 (well above the bulk freezing point, Tc is the critical temperature of TEHOS), the surface roughness drops sharply and density oscillations appear near the surface. Lateral ordering of the surface layers is liquid-like, just as at liquid metal surfaces. 1. E. Chac'on and P. Tarazona, Phys. Rev. Lett. 91 166103-1 (2003)

Lotus Dust Mitigation Coating and Molecular Adsorber Coating

NASA Technical Reports Server (NTRS)

O'Connor, Kenneth M.; Abraham, Nithin S.

2015-01-01

NASA Goddard Space Flight Center has developed two unique coating formulations that will keep surfaces clean and sanitary and contain contaminants.The Lotus Dust Mitigation Coating, modeled after the self-cleaning, water-repellant lotus leaf, disallows buildup of dust, dirt, water, and more on surfaces. This coating, has been successfully tested on painted, aluminum, glass, silica, and some composite surfaces, could aid in keeping medical assets clean.The Molecular Adsorber Coating is a zeolite-based, sprayable molecular adsorber coating, designed to prevent outgassing in materials in vacuums. The coating works well to adsorb volatiles and contaminates in manufacturing and processing, such as in pharmaceutical production. The addition of a biocide would also aid in controlling bacteria levels.

Adsorption and activity of Thermomyces lanuginosus lipase on hydrophobic and hydrophilic surfaces measured with dual polarization interferometry (DPI) and confocal microscopy.

PubMed

Sonesson, Andreas W; Callisen, Thomas H; Brismar, Hjalmar; Elofsson, Ulla M

2008-02-15

The adsorption and activity of Thermomyces lanuginosus lipase (TLL) was measured with dual polarization interferometry (DPI) and confocal microscopy at a hydrophilic and hydrophobic surface. In the adsorption isotherms, it was evident that TLL both had higher affinity for the hydrophobic surface and adsorbed to a higher adsorbed amount (1.90 mg/m(2)) compared to the hydrophilic surface (1.40-1.50mg/m(2)). The thickness of the adsorbed layer was constant (approximately 3.5 nm) on both surfaces at an adsorbed amount >1.0mg/m(2), but decreased on the hydrophilic surface at lower surface coverage, which might be explained by partially unfolding of the TLL structure. However, a linear dependence of the refractive index of the adsorbed layer on adsorbed amount of TLL on C18 surfaces indicated that the structure of TLL was similar at low and high surface coverage. The activity of adsorbed TLL was measured towards carboxyfluorescein diacetate (CFDA) in solution, which upon lipase activity formed a fluorescent product. The surface fluorescence intensity increase was measured in a confocal microscope as a function of time after lipase adsorption. It was evident that TLL was more active on the hydrophilic surface, which suggested that a larger fraction of adsorbed TLL molecules were oriented with the active site facing the solution compared to the hydrophobic surface. Moreover, most of the activity remained when the TLL surface coverage decreased. Earlier reports on TLL surface mobility on the same surfaces have found that the lateral diffusion was highest on hydrophilic surfaces and at low surface coverage of TLL. Hence, a high lateral mobility might lead to a longer exposure time of the active site towards solution, thereby increasing the activity against a water-soluble substrate.

Assessment of surface turbulent fluxes using geostationary satellite surface skin temperatures and a mixed layer planetary boundary layer scheme

NASA Technical Reports Server (NTRS)

Diak, George R.; Stewart, Tod R.

1989-01-01

A method is presented for evaluating the fluxes of sensible and latent heating at the land surface, using satellite-measured surface temperature changes in a composite surface layer-mixed layer representation of the planetary boundary layer. The basic prognostic model is tested by comparison with synoptic station information at sites where surface evaporation climatology is well known. The remote sensing version of the model, using satellite-measured surface temperature changes, is then used to quantify the sharp spatial gradient in surface heating/evaporation across the central United States. An error analysis indicates that perhaps five levels of evaporation are recognizable by these methods and that the chief cause of error is the interaction of errors in the measurement of surface temperature change with errors in the assigment of surface roughness character. Finally, two new potential methods for remote sensing of the land-surface energy balance are suggested which will relay on space-borne instrumentation planned for the 1990s.

Adsorption of β-galactosidase on silica and aluminosilicate adsorbents

NASA Astrophysics Data System (ADS)

Atyaksheva, L. F.; Dobryakova, I. V.; Pilipenko, O. S.

2015-03-01

It is shown that adsorption of β-galactosidase of Aspergillus oryzae fungi on mesoporous and biporous silica and aluminosilicate adsorbents and the rate of the process grow along with the diameter of the pores of the adsorbent. It is found that the shape of the adsorption isotherms changes as well, depending on the texture of the adsorbent: the Michaelis constant rises from 0.3 mM for the enzyme in solution to 0.4-0.5 mM for the enzyme on a surface in the hydrolysis of o-nitrophenyl-β-D-galactopyranoside. It is concluded that β-galactosidase displays its maximum activity on the surface of biporous adsorbents.

Surface-enhanced Raman scattering studies on bombesin, its selected fragments and related peptides adsorbed at the silver colloidal surface

NASA Astrophysics Data System (ADS)

Podstawka-Proniewicz, Edyta; Ozaki, Yukihiro; Kim, Younkyoo; Xu, Yizhuang; Proniewicz, Leonard M.

2011-07-01

SERS studies presented in this work on BN8-14, [ D-Phe 6,β-Ala11,Phe13,Nle14]BN6-14, [ D-Tyr 6, β-Ala11,Phe13,Nle14]BN6-14, BN and its modified analogues, as well as NMB, NMC, and PG-L show that these molecules at pH 8.3 bind to a colloidal silver surface mainly through Trp 8 and Met 14 residues. Trp 8 adsorbs at the surface almost perpendicularly. Met 14 appears on the surface mainly as a P C-G conformer. His 12, as is evident from the spectra, practically does not take part in the adsorption process. Substitution of L-leucine at the 13 position of amino acid sequence with L-phenylalanine does not change substantially the pattern of the adsorption mechanism; however, substitution of phenylalanine at the 12 position (instead of L-histidine) causes changes in the SERS spectra that show that Phe 12 takes parallel orientation to the surface upon adsorption of [ D-Phe 12]BN, while in the case of [Tyr4, D-Phe 12]BN this residue is perpendicular to the surface and influences the orientation of the bound Trp 8. On the other hand, substitution of Asn with Tyr in the 6 position in nonapeptide fragment causes changes in the adsorption mechanism. In this case, the discussed fragment binds to the silver colloidal surface by Tyr 6, Trp 8, and Met 14. The SERS spectrum of NMC is very similar to that of BN; although it differs by the binding orientation of the amide bond towards the surface. Appearance of Phe 13 in NMB and PG-L causes that this residue competes successfully with Trp 8 forcing it to take tilted orientation. As seen from the enhancement of the characteristic Phe vibrations this moiety in NMB and PG-L adsorbs on the silver surface in a tilted fashion. This arrangements cause that the 8-14 peptide chain in all these studied compounds takes almost a parallel orientation to the surface while the 1-5 fragment of the peptide chain is removed from the silver surface vicinity.

Synthesis of low-cost adsorbent from rice bran for the removal of reactive dye based on the response surface methodology

NASA Astrophysics Data System (ADS)

Hong, Gui-Bing; Wang, Yi-Kai

2017-11-01

Rice bran is a major by-product of the rice milling industry and is abundant in Taiwan. This study proposed a simple method for modifying rice bran to make it a low-cost adsorbent to remove reactive blue 4 (RB4) from aqueous solutions. The effects of independent variables such as dye concentration (100-500 ppm), adsorbent dosage (20-120 mg) and temperature (30-60 °C) on the dye adsorption capacity of the modified rice bran adsorbent were investigated by using the response surface methodology (RSM). The results showed that the dye maximum adsorption capacity of the modified rice bran adsorbent was 151.3 mg g-1 with respect to a dye concentration of 500 ppm, adsorbent dosage of 65.36 mg, and temperature of 60 °C. The adsorption kinetics data followed the pseudo-second-order kinetic model, and the isotherm data fit the Langmuir isotherm model well. The maximum monolayer adsorption capacity was 178.57-185.19 mg g-1, which was comparable to that of other agricultural waste adsorbents used to remove RB4 from aqueous solutions in the literature. The thermodynamics analysis results indicated that the adsorption of RB4 onto the modified rice bran adsorbent is an endothermic, spontaneous monolayer adsorption that occurs through a physical process.

Combining surface enhanced Raman scattering (SERS) and high-performance thin-layer chromatography (HPTLC)

NASA Astrophysics Data System (ADS)

Koglin, E.

A new method for preparing SERS active surfaces using silver colloidal spheres deposited on HPTLC plates, used for thin-layer chromatography, is discussed in detail. The sensitivity of these activated HPTLC plates is so high that in-situ vibrational investigations of chromatogram spots are possible at the nanogram level. The HPTLC/SERS spectra of purine, benzoic acid and 1-nitro-pyrene adsorbed on silver colloidal activated silica gel plates are measured in the nanogram region. In addition we also report in this paper on the results of a feasibility study performed to evaluate the analytical potential of micro-Raman spectroscopy (triple monochromator, multichannel detection system) in SERS/HPTLC spot characterization. It permits the acquisition of Raman spectra from HPTLC spots down to 1 μm in size or other forms of microsamples approaching the picogram level in mass.

Laser modification of macroscopic properties of metal surface layer

NASA Astrophysics Data System (ADS)

Kostrubiec, Franciszek

1995-03-01

Surface laser treatment of metals comprises a number of diversified technological operations out of which the following can be considered the most common: oxidation and rendering surfaces amorphous, surface hardening of steel, modification of selected physical properties of metal surface layers. In the paper basic results of laser treatment of a group of metals used as base materials for electric contacts have been presented. The aim of the study was to test the usability of laser treatment from the viewpoint of requirements imposed on materials for electric contacts. The results presented in the paper refer to two different surface treatment technologies: (1) modification of infusible metal surface layer: tungsten and molybdenum through laser fusing of their surface layer and its crystallization, and (2) modification of surface layer properties of other metals through laser doping of their surface layer with foreign elements. In the paper a number of results of experimental investigations obtained by the team under the author's supervision are presented.

A proposed physical model for the impregnated tungsten cathode based on Auger surface studies of the Ba-O-W system

NASA Technical Reports Server (NTRS)

Forman, R.

1979-01-01

Auger spectra and work function measurements are used to study the surface reactions between tungsten surface and adsorbed layers of barium, and barium and oxygen. The barium on an impregnated tungsten cathod seems to be an intermediate state, probably a coadsorbed barium-oxygen layer on tungsten. A slightly revised version of the previously suggested (1976) impregnated tungsten cathode model is proposed. This revised model assumes that the cathode surface during life has an adsorbed surface layer of a monolayer or less of both barium and oxygen on the surface. At end of life, steep drop in electron emission and resultant cathode failure occur. Recent NASA life test results on TWT type tubes are reported and explained by the proposed model.

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

PubMed

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

2016-03-07

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

Development and Testing of Molecular Adsorber Coatings

NASA Technical Reports Server (NTRS)

Abraham, Nithin; Hasegawa, Mark; Straka, Sharon

2012-01-01

The effect of on-orbit molecular contamination has the potential to degrade the performance of spaceflight hardware and diminish the lifetime of the spacecraft. For example, sensitive surfaces, such as optical surfaces, electronics, detectors, and thermal control surfaces, are vulnerable to the damaging effects of contamination from outgassed materials. The current solution to protect these surfaces is through the use of zeolite coated ceramic adsorber pucks. However, these pucks and its additional complex mounting hardware requirements result in several disadvantages, such as size, weight, and cost related concerns, that impact the spacecraft design and the integration and test schedule. As a result, a new innovative molecular adsorber coating was developed as a sprayable alternative to mitigate the risk of on-orbit molecular contamination. In this study, the formulation for molecular adsorber coatings was optimized using various binders, pigment treatment methods, binder to pigment ratios, thicknesses, and spray application techniques. The formulations that passed coating adhesion and vacuum thermal cycling tests were further tested for its adsorptive capacity. Accelerated molecular capacitance tests were performed in an innovatively designed multi-unit system containing idealized contaminant sources. This novel system significantly increased the productivity of the testing phase for the various formulations that were developed. Work performed during the development and testing phases has demonstrated successful application of molecular adsorber coatings onto metallic substrates, as well as, very promising results for the adhesion performance and the molecular capacitance of the coating. Continued testing will assist in the qualification of molecular adsorber coatings for use on future contamination sensitive spaceflight missions.

Surface Characterization of an Organized Titanium Dioxide Layer

NASA Astrophysics Data System (ADS)

Curtis, Travis

Soft lithographic printing techniques can be used to control the surface morphology of titanium dioxide layers on length scales of several hundred nanometers. Controlling surface morphology and volumetric organization of titanium dioxide electrodes can potentially be used in dye-sensitized solar cell devices. This thesis explores how layer-by-layer replication can lead to well defined, dimensionally controlled volumes and details how these control mechanisms influence surface characteristics of the semiconducting oxide.

Work function variation of MoS{sub 2} atomic layers grown with chemical vapor deposition: The effects of thickness and the adsorption of water/oxygen molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Jong Hun; Kim, Jae Hyeon; Park, Jeong Young, E-mail: peterlee@skku.edu, E-mail: jeongypark@kaist.ac.kr

2015-06-22

The electrical properties of two-dimensional atomic sheets exhibit remarkable dependences on layer thickness and surface chemistry. Here, we investigated the variation of the work function properties of MoS{sub 2} films prepared with chemical vapor deposition (CVD) on SiO{sub 2} substrates with the number of film layers. Wafer-scale CVD MoS{sub 2} films with 2, 4, and 12 layers were fabricated on SiO{sub 2}, and their properties were evaluated by using Raman and photoluminescence spectroscopies. In accordance with our X-ray photoelectron spectroscopy results, our Kelvin probe force microscopy investigation found that the surface potential of the MoS{sub 2} films increases by ∼0.15 eVmore » when the number of layers is increased from 2 to 12. Photoemission spectroscopy (PES) with in-situ annealing under ultra high vacuum conditions was used to directly demonstrate that this work function shift is associated with the screening effects of oxygen or water molecules adsorbed on the film surface. After annealing, it was found with PES that the surface potential decreases by ∼0.2 eV upon the removal of the adsorbed layers, which confirms that adsorbed species have a role in the variation in the work function.« less

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

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.

Detection of Nisin and Fibrinogen Adsorption on Poly(ethylene Oxide) Coated Polyurethane Surfaces by Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS)

PubMed Central

Schilke, Karl F.; McGuire, Joseph

2011-01-01

Stable, pendant polyethylene oxide (PEO) layers were formed on medical-grade Pellethane® and Tygon® polyurethane surfaces, by adsorption and gamma-irradiation of PEO-polybutadiene-PEO triblock surfactants. Coated and uncoated polyurethanes were challenged individually or sequentially with nisin (a small polypeptide with antimicrobial activity) and/or fibrinogen, and then analyzed with time-of-flight secondary ion mass spectrometry (TOF-SIMS). Data reduction by robust principal components analysis (PCA) allowed detection of outliers, and distinguished adsorbed nisin and fibrinogen. Fibrinogen-contacted surfaces, with or without nisin, were very similar on uncoated polymer surfaces, consistent with nearly complete displacement or coverage of previously-adsorbed nisin by fibrinogen. In contrast, nisin-loaded PEO layers remained essentially unchanged upon challenge with fibrinogen, suggesting that the adsorbed nisin is stabilized within the pendant PEO layer, while the peptide-loaded PEO layer retains its ability to repel large proteins. Coatings of PEO loaded with therapeutic polypeptides on medical polymers have the potential to be used to produce anti-fouling and biofunctional surfaces for implantable or blood-contacting devices. PMID:21440897

Soil and surface layer type affect non-rainfall water inputs

NASA Astrophysics Data System (ADS)

Agam, Nurit; Berliner, Pedro; Jiang, Anxia

2017-04-01

Non-rainfall water inputs (NRWIs), which include fog deposition, dew formation, and direct water vapor adsorption by the soil, play a vital role in arid and semiarid regions. Environmental conditions, namely radiation, air temperature, air humidity, and wind speed, largely affect the water cycle driven by NRWIs. The substrate type (soil type and the existence/absence of a crust layer) may as well play a major role. Our objective was to quantify the effects of soil type (loess vs. sand) and surface layer (bare vs. crusted) on the gain and posterior evaporation of NRWIs in the Negev Highlands throughout the dry summer season. Four undisturbed soil samples (20 cm diameter and 50 cm depth) were excavated and simultaneously introduced into a PVC tube. Two samples were obtained in the Negev's Boker plain (loess soil) and two in the Nizzana sand dunes in the Western Negev. On one sample from each site the crust was removed while on the remaining one the natural crust was left in place. The samples were brought to the research site at the Jacob Bluestein Institutes for Desert Research, Ben-Gurion University of the Negev, Israel (31˚08' N, 34˚53' E, 400 meter above the sea level) where they were exposed to the same environmental conditions. The four samples in their PVC tubes were placed on top of scales and the samples mass was continuously monitored. Soil temperatures were monitored at depths of 1, 2, 3, 5 and10 cm in each microlysimeter (ML) using Copper-Constantan thermocouples. The results of particle size distribution indicated that the crust of the loess soil is probably a physical crust, i.e., a crust that forms due to raindroplets impact; while the crust on the sand soil is biological. On most days, the loess soils adsorbed more water than their corresponding sand soil samples. For both soils, the samples for which the crust was removed adsorbed more water than the samples for which it was intact. The difference in daily water adsorption amount between crusted

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).

Nanofiber adsorbents for high productivity downstream processing.

PubMed

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

2013-04-01

Electrospun polymeric nanofiber adsorbents offer an alternative ligand support surface for bioseparations. Their non-woven fiber structure with diameters in the sub-micron range creates a remarkably high surface area. To improve the purification productivity of biological molecules by chromatography, cellulose nanofiber adsorbents were fabricated and assembled into a cartridge and filter holder format with a volume of 0.15 mL, a bed height of 0.3 mm and diameter of 25 mm. The present study investigated the performance of diethylaminoethyl (DEAE) derivatized regenerated cellulose nanofiber adsorbents based on criteria including mass transfer and flow properties, binding capacity, and fouling effects. Our results show that nanofibers offer higher flow and mass transfer properties. The non-optimized DEAE-nanofiber adsorbents indicate a binding capacity of 10% that of packed bed systems with BSA as a single component system. However, they operate reproducibly at flowrates of a hundred times that of packed beds, resulting in a potential productivity increase of 10-fold. Lifetime studies showed that this novel adsorbent material operated reproducibly with complex feed material (centrifuged and 0.45 µm filtered yeast homogenate) and harsh cleaning-in-place conditions over multiple cycles. DEAE nanofibers showed superior operating performance in permeability and fouling over conventional adsorbents indicating their potential for bioseparation applications. Copyright © 2012 Wiley Periodicals, Inc.

Enhanced detection of thiophenol adsorbed on gold nanoparticles by SFG and DFG nonlinear optical spectroscopy.

PubMed

Pluchery, Olivier; Humbert, Christophe; Valamanesh, Mehrnoush; Lacaze, Emmanuelle; Busson, Bertrand

2009-09-21

Sum frequency generation (SFG) and difference frequency generation (DFG) are applied to study vibrational resonance of the thiophenol molecule adsorbed on two different gold samples. One sample is made of 17 nm gold nanoparticles (AuNPs) fixed on a silicon substrate that has been previously functionalized with a silane monolayer (aminopropyltriethoxysilane, APTES). This sample is fully characterized through visible reflection spectroscopy and AFM. The second sample is a gold monocrystal also covered with thiophenol molecules. From their comparison, an enhancement factor of 21 is deduced for the SFG signal on AuNPs with respect to the Au(111), related to the surface plasmon resonance (SPR). From a combined analysis of the SFG and DFG spectra, we demonstrate that SFG/DFG spectroscopy is able to identify the nature of the substrate where the molecules are adsorbed. This opens new perspectives for this nonlinear spectroscopy by adding to its well-known intrinsic surface specificity, the ability to selectively probe the chemical layer capping the AuNPs.

Milestone Report - Complete New Adsorbent Materials for Marine Testing to Demonstrate 4.5 g-U/kg Adsorbent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Janke, Christopher James; Das, Sadananda; Oyola, Yatsandra

2014-08-01

This report describes work on the successful completion of Milestone M2FT-14OR03100115 (8/20/2014) entitled, “Complete new adsorbent materials for marine testing to demonstrate 4.5 g-U/kg adsorbent”. This effort is part of the Seawater Uranium Recovery Program, sponsored by the U.S. Department of Energy, Office of Nuclear Energy, and involved the development of new adsorbent materials at the Oak Ridge National Laboratory (ORNL) and marine testing at the Pacific Northwest National Laboratory (PNNL). ORNL has recently developed two new families of fiber adsorbents that have demonstrated uranium adsorption capacities greater than 4.5 g-U/kg adsorbent after marine testing at PNNL. One adsorbent wasmore » synthesized by radiation-induced graft polymerization of itaconic acid and acrylonitrile onto high surface area polyethylene fibers followed by amidoximation and base conditioning. This fiber showed a capacity of 4.6 g-U/kg adsorbent in marine testing at PNNL. The second adsorbent was prepared by atom-transfer radical polymerization of t-butyl acrylate and acrylonitrile onto halide-functionalized round fibers followed by amidoximation and base hydrolysis. This fiber demonstrated uranium adsorption capacity of 5.4 g-U/kg adsorbent in marine testing at PNNL.« less

Self-interacting polymer chains terminally anchored to adsorbing surfaces of three-dimensional fractal lattices

NASA Astrophysics Data System (ADS)

Živić, I.; Elezović-Hadžić, S.; Milošević, S.

2018-01-01

We have studied the adsorption problem of self-attracting linear polymers, modeled by self-avoiding walks (SAWs), situated on three-dimensional fractal structures, exemplified by 3d Sierpinski gasket (SG) family of fractals as containers of a poor solvent. Members of SG family are enumerated by an integer b (b ≥ 2), and it is assumed that one side of each SG fractal is an impenetrable adsorbing surface. We calculate the critical exponents γ1 ,γ11, and γs, which are related to the numbers of all possible SAWs with one, both, and no ends anchored to the adsorbing boundary, respectively. By applying the exact renormalization group (RG) method (for the first three members of the SG fractal family, b = 2 , 3, and 4), we have obtained specific values of these exponents, for θ-chain and globular polymer phase. We discuss their mutual relations and relations with corresponding values pertinent to extended polymer chain phase.

Generation and characterization of surface layers on acoustically levitated drops.

PubMed

Tuckermann, Rudolf; Bauerecker, Sigurd; Cammenga, Heiko K

2007-06-15

Surface layers of natural and technical amphiphiles, e.g., octadecanol, stearic acid and related compounds as well as perfluorinated fatty alcohols (PFA), have been investigated on the surface of acoustically levitated drops. In contrast to Langmuir troughs, traditionally used in the research of surface layers at the air-water interface, acoustic levitation offers the advantages of a minimized and contact-less technique. Although the film pressure cannot be directly adjusted on acoustically levitated drops, it runs through a wide pressure range due to the shrinking surface of an evaporating drop. During this process, different states of the generated surface layer have been identified, in particular the phase transition from the gaseous or liquid-expanded to the liquid-condensed state of surface layers of octadecanol and other related amphiphiles. Characteristic parameters, such as the relative permeation resistance and the area per molecule in a condensed surface layer, have been quantified and were found comparable to results obtained from surface layers generated on Langmuir troughs.

Bacterial desorption from food container and food processing surfaces.

PubMed

McEldowney, S; Fletcher, M

1988-03-01

The desorption ofStaphylococcus aureus, Acinetobacter calcoaceticus, and a coryneform from the surfaces of materials used for manufacturing food containers (glass, tin plate, and polypropylene) or postprocess canning factory conveyor belts (stainless steel and nylon) was investigated. The effect of time, pH, temperature, and adsorbed organic layers on desorption was studied.S. aureus did not detach from the substrata at any pH investigated (between pH 5 and 9).A. calcoaceticus and the coryneform in some cases detached, depending upon pH and substratum composition. The degree of bacterial detachment from the substrata was not related to bacterial respiration at experimental pH values. Bacterial desorption was not affected by temperature (4-30°C) nor by an adsorbed layer of peptone and yeast extract on the substrata. The results indicate that bacterial desorption, hence bacterial removal during cleaning or their transfer via liquids flowing over colonized surfaces, is likely to vary with the surface composition and the bacterial species colonizing the surfaces.

Different Conformations of Surface Cellulose Molecules in Native Cellulose Microfibrils Revealed by Layer-by-Layer Peeling.

PubMed

Funahashi, Ryunosuke; Okita, Yusuke; Hondo, Hiromasa; Zhao, Mengchen; Saito, Tsuguyuki; Isogai, Akira

2017-11-13

Layer-by-layer peeling of surface molecules of native cellulose microfibrils was performed using a repeated sequential process of 2,2,6,6-tetramethylpiperidine-1-oxyl radical-mediated oxidation followed by hot alkali extraction. Both highly crystalline algal and tunicate celluloses and low-crystalline cotton and wood celluloses were investigated. Initially, the C6-hydroxy groups of the outermost surface molecules of each algal cellulose microfibril facing the exterior had the gauche-gauche (gg) conformation, whereas those facing the interior had the gauche-trans (gt) conformation. All the other C6-hydroxy groups of the cellulose molecules inside the microfibrils contributing to crystalline cellulose I had the trans-gauche (tg) conformation. After surface peeling, the originally second-layer molecules from the microfibril surface became the outermost surface molecules, and the original tg conformation changed to gg and gt conformations. The plant cellulose microfibrils likely had disordered structures for both the outermost surface and second-layer molecules, as demonstrated using the same layer-by-layer peeling technique.

The environmental effect on the radial breathing mode of carbon nanotubes. II. Shell model approximation for internally and externally adsorbed fluids

NASA Astrophysics Data System (ADS)

Longhurst, M. J.; Quirke, N.

2006-11-01

We have previously shown that the upshift in the radial breathing mode (RBM) of closed (or infinite) carbon nanotubes in solution is almost entirely due to coupling of the RBM with an adsorbed layer of fluid on the nanotube surface. The upshift can be modeled analytically by considering the adsorbed fluid as an infinitesimally thin shell, which interacts with the nanotube via a continuum Lennard-Jones potential. Here we extend the model to include internally as well as externally adsorbed waterlike molecules, and find that filling the nanotubes leads to an additional upshift of two to six wave numbers. We show that using molecular dynamics, the RBM can be accurately reproduced by replacing the fluid molecules with a mean field harmonic shell potential, greatly reducing simulation times.

Stability of surface and subsurface hydrogen on and in Au/Ni near-surface alloys

NASA Astrophysics Data System (ADS)

Celik, Fuat E.; Mavrikakis, Manos

2015-10-01

Periodic, self-consistent DFT-GGA (PW91) calculations were used to study the interaction of hydrogen atoms with the (111) surfaces of substitutional near-surface alloys (NSAs) of Au and Ni with different surface layer compositions and different arrangements of Au atoms in the surface layer. The effect of hydrogen adsorption on the surface and in the first and second subsurface layers of the NSAs was studied. Increasing the Au content in the surface layer weakens hydrogen binding on the surface, but strengthens subsurface binding, suggesting that the distribution of surface and subsurface hydrogen will be different than that on pure Ni(111). While the metal composition of the surface layer has an effect on the binding energy of hydrogen on NSA surfaces, the local composition of the binding site has a stronger effect. For example, fcc hollow sites consisting of three Ni atoms bind H nearly as strongly as on Ni(111), and fcc sites consisting of three Au atoms bind H nearly as weakly as on Au(111). Sites with one or two Au atoms show intermediate binding energies. The preference of hydrogen for three-fold Ni hollow sites alters the relative stabilities of different surface metal atom arrangements, and may provide a driving force for adsorbate-induced surface rearrangement.

Deformability of adsorbents during adsorption and principles of the thermodynamics of solid-phase systems

NASA Astrophysics Data System (ADS)

Tovbin, Yu. K.

2017-09-01

A microscopic theory of adsorption, based on a discrete continuum lattice gas model for noninert (including deformable) adsorbents that change their lattice parameters during adsorption, is presented. Cases of the complete and partial equilibrium states of the adsorbent are considered. In the former, the adsorbent consists of coexisting solid and vapor phases of adsorbent components, and the adsorbate is a mobile component of the vapor phase with an arbitrary density (up to that of the liquid adsorbate phase). The adsorptive transitioning to the bound state changes the state of the near-surface region of the adsorbent. In the latter, there are no equilibrium components of the adsorbent between the solid and vapor phases. The adsorbent state is shown to be determined by its prehistory, rather than set by chemical potentials of vapor of its components. Relations between the microscopic theory and thermodynamic interpretations are discussed: (1) adsorption on an open surface, (2) two-dimensional stratification of the adsorbate mobile phase on an open homogeneous surface, (3) small microcrystals in vacuum and the gas phase, and (4) adsorption in porous systems.

Potential of polyaniline modified clay nanocomposite as a selective decontamination adsorbent for Pb(II) ions from contaminated waters; kinetics and thermodynamic study.

PubMed

Piri, Somayeh; Zanjani, Zahra Alikhani; Piri, Farideh; Zamani, Abbasali; Yaftian, Mohamadreza; Davari, Mehdi

2016-01-01

Nowadays significant attention is to nanocomposite compounds in water cleaning. In this article the synthesis and characterization of conductive polyaniline/clay (PANI/clay) as a hybrid nanocomposite with extended chain conformation and its application for water purification are presented. Clay samples were obtained from the central plain of Abhar region, Abhar, Zanjan Province, Iran. Clay was dried and sieved before used as adsorbent. The conductive polyaniline was inflicted into the layers of clay to fabricate a hybrid material. The structural properties of the fabricated nanocomposite are studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM). The elimination process of Pb(II) and Cd(II) ions from synthetics aqueous phase on the surface of PANI/clay as adsorbent were evaluated in batch experiments. Flame atomic absorption instrument spectrophotometer was used for determination of the studied ions concentration. Consequence change of the pH and initial metal amount in aqueous solution, the procedure time and the used adsorbent dose as the effective parameters on the removal efficiency was investigated. Surface characterization was exhibited that the clay layers were flaked in the hybrid nanocomposite. The results show that what happen when a nanocomposite polyaniline chain is inserted between the clay layers. The adsorption of ions confirmed a pH dependency procedure and a maximum removal value was seen at pH 5.0. The adsorption isotherm and the kinetics of the adsorption processes were described by Temkin model and pseudo-second-order equation. Time of procedure, pH and initial ion amount have a severe effect on adsorption efficiency of PANI/clay. By using suggested synthesise method, nano-composite as the adsorbent simply will be prepared. The prepared PANI/clay showed excellent adsorption capability for decontamination of Pb ions from contaminated water. Both of suggested synthesise and

Comparing dissolved reactive phosphorus measured by DGT with ferrihydrite and titanium dioxide adsorbents: anionic interferences, adsorbent capacity and deployment time.

PubMed

Panther, Jared G; Teasdale, Peter R; Bennett, William W; Welsh, David T; Zhao, Huijun

2011-07-18

Two adsorbents (Metsorb and ferrihydrite) used in binding layers with the diffusive gradients in a thin film technique were evaluated for the measurement of dissolved reactive phosphorous (DRP) in synthetic and natural waters. Possible interferences were investigated with Cl(-) (up to 1.35 mol L(-1)) and SO(4)(2-) (up to 0.056 mol L(-1)) having no affect on either DGT binding layer, and HCO(3)(-) (up to 5.7 mmol L(-1)) having no effect on Metsorb-DGT, over 4 days. However, HCO(3)(-) interfered with the ferrihydrite-DGT measurement at concentrations typical of many natural waters (≥0.7 mmol L(-1)) after a deployment period of 1-2 days. The capacity of the Metsorb binding phase for DGT response was ∼37,000 ng P, whereas the capacities of a low-mass (17.8 mg of adsorbent per DGT sampler) and high-mass (29.2mg of adsorbent per DGT sampler) ferrihydrite binding phase were substantially lower (∼15,000 ng P and ∼25,000 ng P, low-mass and high-mass, respectively). Increasing the capacity of the ferrihydrite adsorbent allowed the ferrihydrite-DGT to be utilized for up to 3 days before interference by HCO(3)(-) was observed. Seawater deployments demonstrated that even high-capacity ferrihydrite-DGT devices underestimated the DRP concentration by 37%, whereas Metsorb-DGT measurements were accurate. The Metsorb-DGT is superior to the ferrihydrite-DGT for determining DRP over deployment times greater than 1 day and in waters with ≥0.7 mmol L(-1) HCO(3)(-). Based on the experience obtained from this detailed validation process, the authors propose a number of key requirements that need to be considered when developing new DGT binding layers, with testing the performance over longer deployment times being critical. Copyright © 2011 Elsevier B.V. All rights reserved.

Spectroscopic studies of conformational changes of β-lactoglobulin adsorbed on gold nanoparticle surfaces.

PubMed

Winuprasith, Thunnalin; Suphantharika, Manop; McClements, David Julian; He, Lili

2014-02-15

In this work, we investigated the conformational changes of a globular protein (β-lactoglobulin, β-lg) coated on the surface of 200 nm gold nanoparticles (GNPs) using a number of analytical techniques: dynamic light scattering (DLS); particle electrophoresis (ζ-potential); localized surface plasmon resonance (LSPR) spectroscopy; transmission electron microscopy (TEM); and surface-enhanced Raman scattering (SERS). The β-lg (pH 3) concentration had a pronounced effect on the aggregation and surface charge of β-lg-coated GNPs. The surface charge of GNPs changed from negative to positive as increasing amounts of β-lg molecule were added, indicating that the globular protein molecules adsorbed to the surfaces of the particles. Extensive particle aggregation occurred when β-lg did not saturate the GNP surfaces, which was attributed to electrostatic bridging flocculation. Modifications in LSPR and SERS spectra after addition of β-lg to the GNP suspensions supported the adsorption of β-lg to the particle surfaces. Moreover, SERS highlighted the importance of a number of specific molecular groups in the binding interaction, and suggested conformational changes of the globular protein after adsorption. This research provides useful information for characterizing and understanding the interactions between globular proteins and colloidal particles. Copyright © 2013 Elsevier Inc. All rights reserved.

Preparation of weak-light-driven TiO2-based catalysts via adsorbed-layer nanoreactor synthesis and enhancement of their photo-degradation performance in seawater

NASA Astrophysics Data System (ADS)

Wang, Ting; Xu, Zhi-yong; Zhu, Yi-chen; Wu, Li-guang; Yuan, Hao-xuan; Li, Chang-chun; Liu, Ya-yu; Cai, Jing

2017-11-01

Graphene oxide (GO) was first employed as a support in preparing TiO2 nanoparticles by adsorbed-layer nanoreactor synthesis (ALNS). Both TiO2 crystallization and GO reduction simultaneously occurred during solvothermal treatment with alcohol as a solvent. By transmission electron microscopy, high resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and photoluminescence spectroscopy, the results showed that TiO2 nanoparticles with less than 10 nm of size distributed very homogeneously on the GO surface. Tight interaction between TiO2 particles and GO surface could effectively inhibit the aggregation of TiO2 particles, during solvothermal treatment for anatase TiO2 formation. Alcohol could also reduce oxygenated functional groups on GO surface after solvothermal treatment. TiO2 particles with small size and the decrease in oxygenated functional groups on the GO surface both caused high separation efficiency of photo-generated charge carriers, thus resulting in high photo-degradation performance of catalysts. Strong phenol adsorption on photocatalyst was key to enhancing photo-degradation efficiency for phenol in seawater. Moreover, the change in catalyst structure was minimal at different temperatures of solvothermal treatment. But, the degradation rate and efficiency for phenol in seawater were obviously enhanced because of the sensitive structure-activity relationship of catalysts under weak-light irradiation.

Carboxymethylcellulose adsorption on molybdenite: the effect of electrolyte composition on adsorption, bubble-surface collisions, and flotation.

PubMed

Kor, Mohammad; Korczyk, Piotr M; Addai-Mensah, Jonas; Krasowska, Marta; Beattie, David A

2014-10-14

The adsorption of carboxymethylcellulose polymers on molybdenite was studied using spectroscopic ellipsometry and atomic force microscopy imaging with two polymers of differing degrees of carboxyl group substitution and at three different electrolyte conditions: 1 × 10(-2) M KCl, 2.76 × 10(-2) M KCl, and simulated flotation process water of multicomponent electrolyte content, with an ionic strength close to 2.76 × 10(-2) M. A higher degree of carboxyl substitution in the adsorbing polymer resulted in adsorbed layers that were thinner and with more patchy coverage; increasing the ionic strength of the electrolyte resulted in increased polymer layer thickness and coverage. The use of simulated process water resulted in the largest layer thickness and coverage for both polymers. The effect of the adsorbed polymer layer on bubble-particle attachment was studied with single bubble-surface collision experiments recorded with high-speed video capture and image processing and also with single mineral molybdenite flotation tests. The carboxymethylcellulose polymer with a lower degree of substitution resulted in almost complete prevention of wetting film rupture at the molybdenite surface under all electrolyte conditions. The polymer with a higher degree of substitution prevented rupture only when adsorbed from simulated process water. Molecular kinetic theory was used to quantify the effect of the polymer on the dewetting dynamics for collisions that resulted in wetting film rupture. Flotation experiments confirmed that adsorbed polymer layer properties, through their effect on the dynamics of bubble-particle attachment, are critical to predicting the effectiveness of polymers used to prevent mineral recovery in flotation.

Atomic and molecular layer deposition for surface modification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vähä-Nissi, Mika, E-mail: mika.vaha-nissi@vtt.fi; Sievänen, Jenni; Salo, Erkki

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 inkjetmore » 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.« less

Bioavailability of organic and inorganic phosphates adsorbed on short-range ordered aluminum precipitate.

PubMed

Shang, C; Caldwell, D E; Stewart, J W; Tiessen, H; Huang, P M

1996-01-01

A nonreductive community-level study of P availability was conducted using various forms of adsorbed P. Orthophosphate (Pi), inositol hexaphosphate (IHP), and glucose 6-phosphate (G6P) were adsorbed to a short-range ordered Al precipitate. These bound phosphates provided a P source sufficient to support the growth of microbial communities from acidic Brazilian soils (oxisols). Adsorbed IHP, the most abundant form of organic phosphate in most soils, had the lowest bioavailability among the three phosphates studied. Adsorbed G6P and Pi were almost equally available. The amount of adsorbed Pi (1 cmol P kg(-1)) required to support microbial growth was at least 30 times less than that of IHP (30 cmol P kg(-1)). With increased surface coverage, adsorbed IHP became more bioavailable. This availability was attributed to a change in the structure of surface complexes and presumably resulted from the decreased number of high-affinity surface sites remaining at high levels of coverage. It thus appears that the bioavailability of various forms of adsorbed phosphate was determined primarily by the stability of the phosphate-surface complexes that they formed, rather than by the total amount of phosphate adsorbed. IHP, having the potential to form stable multiple-ring complexes, had the highest surface affinity and the lowest bioavailability. Bioaggregates consisting of bacteria and Al precipitate were observed and may be necessary for effective release of adsorbed P. Bacteria in the genera Enterobacter and Pseudomonas were the predominate organisms selected during these P-limited enrichments.

Application of advanced sampling and analysis methods to predict the structure of adsorbed protein on a material surface

PubMed Central

Abramyan, Tigran M.; Hyde-Volpe, David L.; Stuart, Steven J.; Latour, Robert A.

2017-01-01

The use of standard molecular dynamics simulation methods to predict the interactions of a protein with a material surface have the inherent limitations of lacking the ability to determine the most likely conformations and orientations of the adsorbed protein on the surface and to determine the level of convergence attained by the simulation. In addition, standard mixing rules are typically applied to combine the nonbonded force field parameters of the solution and solid phases the system to represent interfacial behavior without validation. As a means to circumvent these problems, the authors demonstrate the application of an efficient advanced sampling method (TIGER2A) for the simulation of the adsorption of hen egg-white lysozyme on a crystalline (110) high-density polyethylene surface plane. Simulations are conducted to generate a Boltzmann-weighted ensemble of sampled states using force field parameters that were validated to represent interfacial behavior for this system. The resulting ensembles of sampled states were then analyzed using an in-house-developed cluster analysis method to predict the most probable orientations and conformations of the protein on the surface based on the amount of sampling performed, from which free energy differences between the adsorbed states were able to be calculated. In addition, by conducting two independent sets of TIGER2A simulations combined with cluster analyses, the authors demonstrate a method to estimate the degree of convergence achieved for a given amount of sampling. The results from these simulations demonstrate that these methods enable the most probable orientations and conformations of an adsorbed protein to be predicted and that the use of our validated interfacial force field parameter set provides closer agreement to available experimental results compared to using standard CHARMM force field parameterization to represent molecular behavior at the interface. PMID:28514864

Enrichment and association of lead and bacteria at particulate surfaces in a salt-marsh surface layer

USGS Publications Warehouse

Harvey, R.W.; Lion, Leonard W.; Young, L.Y.; Leckie, J.O.

1982-01-01

The particle-laden surface layer (approx 150-370 mu m) and subsurface waters of a South San Francisco Bay salt marsh were sampled over 2 tidal cycles and analyzed for particle numbers and particulate-associated and total concentrations of Pb and bacteria. Laboratory studies examined the ability of a bacterial isolate from the surface layer and a bacterial 'film-former' to sorb Pb at environmentally significant concentrations in seawater. Degrees by which Pb concentrated in the surface layer relative to the subsurface strongly correlated with enrichments of surface layer bacteria (bacterioneuston). A significant fraction of the bacterioneuston and surface layer Pb were associated with particles. Particle-bound bacterioneuston may interact with Pb at particulate surfaces in this microenvironment.

Influence of surface contamination on the wettability of heat transfer surfaces

DOE PAGES

Forrest, Eric Christopher; Schulze, Roland; Liu, Cheng; ...

2015-08-08

In this study, the wettability of heat transfer surfaces plays an important role in liquid–vapor phase change phenomena, including boiling incipience, the critical heat flux, the Leidenfrost transition, and condensation. The influence of adsorbed surface contamination at the nanoscale, though seldom considered, can have a profound impact on wetting behavior. This study quantitatively investigates the impact of contaminant layer thickness on wettability. Various cleaning treatments are explored on zirconium and 6061 aluminum to determine the effect on contaminant and oxide layer thickness. Angle-resolved X-ray photoelectron spectroscopy can be used to measure the thickness of oxide and contaminant layers, which ismore » then correlated to wettability by measuring the equilibrium contact angle. Results indicate that even after solvent cleaning, the contact angle of water on practical heat transfer surfaces is dominated by a hydrocarbon contaminant overlayer around five nanometers thick.« less

Influence of surface contamination on the wettability of heat transfer surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Forrest, Eric Christopher; Schulze, Roland; Liu, Cheng

In this study, the wettability of heat transfer surfaces plays an important role in liquid–vapor phase change phenomena, including boiling incipience, the critical heat flux, the Leidenfrost transition, and condensation. The influence of adsorbed surface contamination at the nanoscale, though seldom considered, can have a profound impact on wetting behavior. This study quantitatively investigates the impact of contaminant layer thickness on wettability. Various cleaning treatments are explored on zirconium and 6061 aluminum to determine the effect on contaminant and oxide layer thickness. Angle-resolved X-ray photoelectron spectroscopy can be used to measure the thickness of oxide and contaminant layers, which ismore » then correlated to wettability by measuring the equilibrium contact angle. Results indicate that even after solvent cleaning, the contact angle of water on practical heat transfer surfaces is dominated by a hydrocarbon contaminant overlayer around five nanometers thick.« less

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.

The humidity dependence of ozone deposition onto a variety of building surfaces

NASA Astrophysics Data System (ADS)

Grøntoft, Terje; Henriksen, Jan F.; Seip, Hans M.

Measurements of the dry deposition velocity of O 3 to material samples of calcareous stone, concrete and wood at varying humidity of the air, were performed in a deposition chamber. Equilibrium surface deposition velocities were found for various humidity values by fitting a model to the time-dependent deposition data. A deposition velocity-humidity model was derived giving three separate rate constants for the surface deposition velocities, i.e. on the dry surface, on the first mono-layer of adsorbed water and on additional surface water. The variation in the dry air equilibrium surface deposition velocities among the samples correlated with variations in effective areas, with larger effective areas giving higher measured deposition velocities. A minimum for the equilibrium surface deposition velocity was generally measured at an intermediate humidity close to the humidity found to correspond to one mono-layer of water molecules on the surfaces. At low air humidity the equilibrium surface deposition velocity of O 3 was found to decrease as more adsorbed water prevented direct contact of the O 3 molecules with the surface. This was partly compensated by an increase as more adsorbed water became available for reaction with O 3. At high air humidity the equilibrium surface deposition velocity was found to increase as the mass of water on the surface increased. The deposition velocity on bulk de-ionised water at RH=90% was an order of magnitude lower than on the sample surfaces.

Neutron Reflection Study of Surface Adsorption of Fc, Fab, and the Whole mAb.

PubMed

Li, Zongyi; Li, Ruiheng; Smith, Charles; Pan, Fang; Campana, Mario; Webster, John R P; van der Walle, Christopher F; Uddin, Shahid; Bishop, Steve M; Narwal, Rojaramani; Warwicker, Jim; Lu, Jian Ren

2017-07-12

Characterizing the influence of fragment crystallization (Fc) and antigen-binding fragment (Fab) on monoclonal antibody (mAb) adsorption at the air/water interface is an important step to understanding liquid mAb drug product stability during manufacture, shipping, and storage. Here, neutron reflection is used to study the air/water adsorption of a mAb and its Fc and Fab fragments. By varying the isotopic contrast, the adsorbed amount, thickness, orientation, and immersion of the adsorbed layers could be determined unambiguously. While Fc adsorption reached saturation within the hour, its surface adsorbed amount showed little variation with bulk concentration. In contrast, Fab adsorption was slower and the adsorbed amount was concentration dependent. The much higher Fc adsorption, as compared to Fab, was linked to its lower surface charge. Time and concentration dependence of mAb adsorption was dominated by Fab behavior, although both Fab and Fc behaviors contributed to the amount of mAb adsorbed. Changing the pH from 5.5 to 8.8 did not much perturb the adsorbed amount of Fc, Fab, or mAb. However, a small decrease in adsorption was observed for the Fc over pH 8-8.8 and vice versa for the Fab and mAb, consistent with a dominant Fab behavior. As bulk concentration increased from 5 to 50 ppm, the thicknesses of the Fc layers were almost constant at 40 Å, while Fab and mAb layers increased from 45 to 50 Å. These results imply that the adsorbed mAb, Fc, and Fab all retained their globular structures and were oriented with their short axial lengths perpendicular to the interface.

Hydroxyapatite with Permanent Electrical Polarization: Preparation, Characterization, and Response against Inorganic Adsorbates.

PubMed

Rivas, Manuel; Del Valle, Luis J; Armelin, Elaine; Bertran, Oscar; Turon, Pau; Puiggalí, Jordi; Alemán, Carlos

2018-04-16

Permanently polarized hydroxyapatite (HAp) particles have been prepared by applying a constant DC of 500 V at 1000 °C for 1 h to the sintered mineral. This process causes important chemical changes, as the formation of OH - defects (vacancies), the disappearance of hydrogenophosphate ions at the mineral surface layer, and structural variations reflected by the increment of the crystallinity. As a consequence, the electrochemical properties and electrical conductivity of the polarized mineral increase noticeably compared with as-prepared and sintered samples. Moreover, these increments remain practically unaltered after several months. In addition, permanent polarization favours significantly the ability of HAp to adsorb inorganic bioadsorbates in comparison with as-prepared and sintered samples. The adsorbates cause a significant increment of the electrochemical stability and electrical conductivity with respect to bare polarized HAp, which may have many implications for biomedical applications of permanently polarized HAp. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanostructured diamond layers enhance the infrared spectroscopy of biomolecules.

PubMed

Kozak, Halyna; Babchenko, Oleg; Artemenko, Anna; Ukraintsev, Egor; Remes, Zdenek; Rezek, Bohuslav; Kromka, Alexander

2014-03-04

We report on the fabrication and practical use of high-quality optical elements based on Au mirrors coated with diamond layers with flat, nanocolumnar, and nanoporous morphologies. Diamond layers (100 nm thickness) are grown at low temperatures (about 300 °C) from a methane, carbon dioxide, and hydrogen gas mixture by a pulsed microwave plasma system with linear antennas. Using grazing angle reflectance (GAR) Fourier transform infrared spectroscopy with p-polarized light, we compare the IR spectra of fetal bovine serum proteins adsorbed on diamond layers with oxidized (hydrophilic) surfaces. We show that the nanoporous diamond layers provide IR spectra with a signal gain of about 600% and a significantly improved sensitivity limit. This is attributed to its enhanced internal surface area. The improved sensitivity enabled us to distinguish weak infrared absorption peaks of <10-nm-thick protein layers and thereby to analyze the intimate diamond-molecule interface.

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

PubMed

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

2016-06-16

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

Surface Reactivity Enhancement on a Pd/Bi2Te3 Heterostructure through Robust Topological Surface States

PubMed Central

He, Qing Lin; Lai, Ying Hoi; Lu, Yao; Law, Kam Tuen; Sou, Iam Keong

2013-01-01

We present a study of the surface reactivity of a Pd/Bi2Te3 thin film heterostructure. The topological surface states from Bi2Te3, being delocalized and robust owing to their topological natures, were found to act as an effective electron bath that significantly enhances the surface reactivity of palladium in the presence of two oxidizing agents, oxygen and tellurium respectively, which is consistent with a theoretical calculation. The surface reactivity of the adsorbed tellurium on this heterostructure is also intensified possibly benefitted from the effective transfer of the bath electrons. A partially inserted iron ferromagnetic layer at the interface of this heterostructure was found to play two competing roles arising from the higher-lying d-band center of the Pd/Fe bilayer and the interaction between the ferromagnetism and the surface spin texture of Bi2Te3 on the surface reactivity and their characteristics also demonstrate that the electron bath effect is long-lasting against accumulated thickness of adsorbates. PMID:23970163

Atomistics of Ge deposition on Si(100) by atomic layer epitaxy.

PubMed

Lin, D S; Wu, J L; Pan, S Y; Chiang, T C

2003-01-31

Chlorine termination of mixed Ge/Si(100) surfaces substantially enhances the contrast between Ge and Si sites in scanning tunneling microscopy observations. This finding enables a detailed investigation of the spatial distribution of Ge atoms deposited on Si(100) by atomic layer epitaxy. The results are corroborated by photoemission measurements aided by an unusually large chemical shift between Cl adsorbed on Si and Ge. Adsorbate-substrate atomic exchange during growth is shown to be important. The resulting interface is thus graded, but characterized by a very short length scale of about one monolayer.

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

PubMed

Sakata, Sho; Inoue, Yuuki; Ishihara, Kazuhiko

2016-10-01

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

Stability of surface and subsurface hydrogen on and in Au/Ni near-surface alloys

DOE PAGES

Celik, Fuat E.; Mavrikakis, Manos

2015-01-12

Periodic, self-consistent DFT-GGA (PW91) calculations were used to study the interaction of hydrogen atoms with the (111) surfaces of substitutional near-surface alloys (NSAs) of Au and Ni with different surface layer compositions and different arrangements of Au atoms in the surface layer. The effect of hydrogen adsorption on the surface and in the first and second subsurface layers of the NSAs was studied. Increasing the Au content in the surface layer weakens hydrogen binding on the surface, but strengthens subsurface binding, suggesting that the distribution of surface and subsurface hydrogen will be different than that on pure Ni(111). While themore » metal composition of the surface layer has an effect on the binding energy of hydrogen on NSA surfaces, the local composition of the binding site has a stronger effect. For example, fcc hollow sites consisting of three Ni atoms bind H nearly as strongly as on Ni(111), and fcc sites consisting of three Au atoms bind H nearly as weakly as on Au(111). Sites with one or two Au atoms show intermediate binding energies. The preference of hydrogen for three-fold Ni hollow sites alters the relative stabilities of different surface metal atom arrangements, and may provide a driving force for adsorbate-induced surface rearrangement.« less

Stability of Surface and Subsurface Hydrogen on and in Au/Ni Near-Surface Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Celik, Fuat E.; Mavrikakis, Manos

2015-10-01

Periodic, self-consistent DFT-GGA (PW91) calculations were used to study the interaction of hydrogen atoms with the (111) surfaces of substitutional near-surface alloys (NSAs) of Au and Ni with different surface layer compositions and different arrangements of Au atoms in the surface layer. The effect of hydrogen adsorption on the surface and in the first and second subsurface layers of the NSAs was studied. Increasing the Au content in the surface layer weakens hydrogen binding on the surface, but strengthens subsurface binding, suggesting that the distribution of surface and subsurface hydrogen will be different than that on pure Ni(111). While themore » metal composition of the surface layer has an effect on the binding energy of hydrogen on NSA surfaces, the local composition of the binding site has a stronger effect. For example, fcc hollow sites consisting of three Ni atoms bind H nearly as strongly as on Ni(111), and fcc sites consisting of three Au atoms bind H nearly as weakly as on Au(111). Sites with one or two Au atoms show intermediate binding energies. The preference of hydrogen for three-fold Ni hollow sites alters the relative stabilities of different surface metal atom arrangements, and may provide a driving force for adsorbate-induced surface rearrangement.« less

Effect of Water Vapor and Surface Morphology on the Low Temperature Response of Metal Oxide Semiconductor Gas Sensors

PubMed Central

Maier, Konrad; Helwig, Andreas; Müller, Gerhard; Hille, Pascal; Eickhoff, Martin

2015-01-01

In this work the low temperature response of metal oxide semiconductor gas sensors is analyzed. Important characteristics of this low-temperature response are a pronounced selectivity to acid- and base-forming gases and a large disparity of response and recovery time constants which often leads to an integrator-type of gas response. We show that this kind of sensor performance is related to the trend of semiconductor gas sensors to adsorb water vapor in multi-layer form and that this ability is sensitively influenced by the surface morphology. In particular we show that surface roughness in the nanometer range enhances desorption of water from multi-layer adsorbates, enabling them to respond more swiftly to changes in the ambient humidity. Further experiments reveal that reactive gases, such as NO2 and NH3, which are easily absorbed in the water adsorbate layers, are more easily exchanged across the liquid/air interface when the humidity in the ambient air is high. PMID:28793583

Ocean haline skin layer and turbulent surface convections

NASA Astrophysics Data System (ADS)

Zhang, Y.; Zhang, X.

2012-04-01

The ocean haline skin layer is of great interest to oceanographic applications, while its attribute is still subject to considerable uncertainty due to observational difficulties. By introducing Batchelor micro-scale, a turbulent surface convection model is developed to determine the depths of various ocean skin layers with same model parameters. These parameters are derived from matching cool skin layer observations. Global distributions of salinity difference across ocean haline layers are then simulated, using surface forcing data mainly from OAFlux project and ISCCP. It is found that, even though both thickness of the haline layer and salinity increment across are greater than the early global simulations, the microwave remote sensing error caused by the haline microlayer effect is still smaller than that from other geophysical error sources. It is shown that forced convections due to sea surface wind stress are dominant over free convections driven by surface cooling in most regions of oceans. The free convection instability is largely controlled by cool skin effect for the thermal microlayer is much thicker and becomes unstable much earlier than the haline microlayer. The similarity of the global distributions of temperature difference and salinity difference across cool and haline skin layers is investigated by comparing their forcing fields of heat fluxes. The turbulent convection model is also found applicable to formulating gas transfer velocity at low wind.

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.

Lateral interactions and non-equilibrium in surface kinetics

NASA Astrophysics Data System (ADS)

Menzel, Dietrich

2016-08-01

Work modelling reactions between surface species frequently use Langmuir kinetics, assuming that the layer is in internal equilibrium, and that the chemical potential of adsorbates corresponds to that of an ideal gas. Coverage dependences of reacting species and of site blocking are usually treated with simple power law coverage dependences (linear in the simplest case), neglecting that lateral interactions are strong in adsorbate and co-adsorbate layers which may influence kinetics considerably. My research group has in the past investigated many co-adsorbate systems and simple reactions in them. We have collected a number of examples where strong deviations from simple coverage dependences exist, in blocking, promoting, and selecting reactions. Interactions can range from those between next neighbors to larger distances, and can be quite complex. In addition, internal equilibrium in the layer as well as equilibrium distributions over product degrees of freedom can be violated. The latter effect leads to non-equipartition of energy over molecular degrees of freedom (for products) or non-equal response to those of reactants. While such behavior can usually be described by dynamic or kinetic models, the deeper reasons require detailed theoretical analysis. Here, a selection of such cases is reviewed to exemplify these points.

Framework for scalable adsorbate–adsorbate interaction models

DOE PAGES

Hoffmann, Max J.; Medford, Andrew J.; Bligaard, Thomas

2016-06-02

Here, we present a framework for physically motivated models of adsorbate–adsorbate interaction between small molecules on transition and coinage metals based on modifications to the substrate electronic structure due to adsorption. We use this framework to develop one model for transition and one for coinage metal surfaces. The models for transition metals are based on the d-band center position, and the models for coinage metals are based on partial charges. The models require no empirical parameters, only two first-principles calculations per adsorbate as input, and therefore scale linearly with the number of reaction intermediates. By theory to theory comparison withmore » explicit density functional theory calculations over a wide range of adsorbates and surfaces, we show that the root-mean-squared error for differential adsorption energies is less than 0.2 eV for up to 1 ML coverage.« less

Drastic reduction of adsorption of CO and H2 on (111)-type Pd layers

NASA Technical Reports Server (NTRS)

Poppa, H.; Soria, F.

1983-01-01

Clean surfaces of (111)-type Pd layers, grown from the vapor phase on Mo(110) at room temperature, were used to study the adsorption of CO and H2 by temperature-programmed desorption, Auger electron spectroscopy, and low-energy electron diffraction. Mild annealing of the as-grown layers during a single desorption cycle (to about 600 K) drastically reduces the adsorption for both adsorbates. Low-dose argon-ion bombardment introduces surface imperfections which restore a high adsorption probability. The results are interpreted in terms of particular (111)-type surface structures that persist tp layer thicknesses of about four monolayers; the results raise questions with respect to the surface structure of supported thin epitaxial islands and particles of Pd and possibly also with respect to conventional methods of preparing bulk surfaces of Pd for adsorption studies.

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.

Molecular orbital imaging of cobalt phthalocyanine on native oxidized copper layers using STM.

PubMed

Guo, Qinmin; Huang, Min; Qin, Zhihui; Cao, Gengyu

2012-07-01

To observe molecular orbitals using scanning tunneling microscopy, well-ordered oxidized layers on Cu(001) were fabricated to screen the individual adsorbed cobalt phthalocyanine (CoPc) molecules from the electronic influence of the metal surface. Scanning tunneling microscope images of the molecule on this oxidized layer show similarities to the orbital distribution of the free molecule. The good match between the differential conductance mapping images and the calculated charge distribution at energy levels corresponding to the frontier orbitals of CoPc provides more evidence of the screening of the oxidized layer from interactions between the metal surface and supported molecules. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

Pyridinium molten salts as co-adsorbents in dye-sensitized solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, Jui-Cheng; Sun, I-Wen; Yang, Cheng-Hsien

2011-01-15

The influence of using pyridinium molten salts as co-adsorbents to modify the monolayer of a TiO{sub 2} semiconductor on the performance of a dye-sensitized solar cell is studied. The current-voltage characteristics are measured under AM 1.5 (100 mW cm{sup -2}). The pyridinium molten salts significantly enhance the open-circuit photovoltage (V{sub oc}), the short circuit photocurrent density (J{sub sc}) as well as the solar energy conversion efficiency ({eta}). 1-Ethyl-3-carboxypyridinium iodide ([ECP][I]) is applied successfully to prepare an insulating molecular layer with N719, and achieve high energy conversion efficiency as high as 4.49% at 100 mW cm{sup -2} and AM 1.5. Themore » resulting efficiency is 20% higher than that of a non-additive device. This enhancement of conversion efficiency is attributed to the negative shift of the conduction band (CB) edge and the abundant concentration of I{sup -} on the surface of the electrode when using [ECP][I] as the co-adsorbent. (author)« less

Innovative nano-layered solid sorbents for CO2 capture.

PubMed

Li, Bingyun; Jiang, Bingbing; Fauth, Daniel J; Gray, McMahan L; Pennline, Henry W; Richards, George A

2011-02-14

Nano-layered sorbents for CO(2) capture, for the first time, were developed using layer-by-layer nanoassembly. A CO(2)-adsorbing polymer and a strong polyelectrolyte were alternately immobilized within porous particles. The developed sorbents had fast CO(2) adsorption and desorption properties and their CO(2) capture capacity increased with increasing nano-layers of the CO(2)-adsorbing polymer.

Layer-by-layer assembly surface modified microbial biomass for enhancing biorecovery of secondary gold.

PubMed

Zhou, Ying; Zhu, Nengwu; Kang, Naixin; Cao, Yanlan; Shi, Chaohong; Wu, Pingxiao; Dang, Zhi; Zhang, Xiaoping; Qin, Benqian

2017-02-01

Enhancement of the biosorption capacity for gold is highly desirable for the biorecovery of secondary gold resources. In this study, polyethylenimine (PEI) was grafted on Shewanella haliotis surface through layer-by-layer assembly approach so as to improve the biosorption capacity of Au(III). Results showed that the relative contribution of amino group to the biosorption of Au(III) was the largest one (about 44%). After successful grafting 1, 2 and 3-layer PEI on the surface of biomass, the biosorption capacity significantly enhanced from 143.8mg/g to 597.1, 559.1, and 536.8mg/g, respectively. Interestingly, the biomass modified with 1-layer PEI exhibited 4.2 times higher biosorption capacity than the untreated control. When 1-layer modified biomass was subjected to optimizing the various conditions by response surface methodology, the theoretical maximum adsorption capacity could reach up to 727.3mg/g. All findings demonstrated that PEI modified S. haliotis was effective for enhancing gold biorecovery. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

PubMed

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

2014-05-14

Tungsten and cobalt carbonyls adsorbed on a substrate are typical starting points for the electron beam induced deposition of tungsten or cobalt based metallic nanostructures. We employ first principles molecular dynamics simulations to investigate the dynamics and vibrational spectra of W(CO)6 and W(CO)5 as well as Co2(CO)8 and Co(CO)4 precursor molecules on fully and partially hydroxylated silica surfaces. Such surfaces resemble the initial conditions of electron beam induced growth processes. We find that both W(CO)6 and Co2(CO)8 are stable at room temperature and mobile on a silica surface saturated with hydroxyl groups (OH), moving up to half an Angström per picosecond. In contrast, chemisorbed W(CO)5 or Co(CO)4 ions at room temperature do not change their binding site. These results contribute to gaining fundamental insight into how the molecules behave in the simulated time window of 20 ps and our determined vibrational spectra of all species provide signatures for experimentally distinguishing the form in which precursors cover a substrate.

Cross-Sectional Imaging of Boundary Lubrication Layer Formed by Fatty Acid by Means of Frequency-Modulation Atomic Force Microscopy.

PubMed

Hirayama, Tomoko; Kawamura, Ryota; Fujino, Keita; Matsuoka, Takashi; Komiya, Hiroshi; Onishi, Hiroshi

2017-10-10

To observe in situ the adsorption of fatty acid onto metal surfaces, cross-sectional images of the adsorption layer were acquired by frequency-modulation atomic force microscopy (FM-AFM). Hexadecane and palmitic acid were used as the base oil and typical fatty acid, respectively. A Cu-coated silicon wafer was prepared as the target substrate. The solvation structure formed by hexadecane molecules at the interface between the Cu substrate and the hexadecane was observed, and the layer pitch was found to be about 0.6 nm, which corresponds to the height of hexadecane molecules. This demonstrates that hexadecane molecules physically adsorbed onto the surface due to van der Waals forces with lying orientation because hexadecane is a nonpolar hydrocarbon. When hexadecane with palmitic acid was put on the Cu substrate instead of pure hexadecane, an adsorption layer of palmitic acid was observed at the interface. The layer pitch was about 2.5-2.8 nm, which matches the chain length of palmitic acid molecules well. This indicates that the original adsorption layer was monolayer or single bilayer in the local area. In addition, a cross-sectional image captured 1 h after observation started to reveal that the adsorbed additive layer gradually grew up to be thicker than about 20 nm due to an external stimulus, such as cantilever oscillation. This is the first report of in situ observation of an adsorbed layer by FM-AFM in the tribology field and demonstrates that FM-AFM is useful for clarifying the actual boundary lubrication mechanism.

Turbulent Boundary Layer Flow over Superhydrophobic Surfaces

DTIC Science & Technology

2013-05-10

DATES COVERED (From - To) 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Turbulent Boundary Layer Flow over Superhydrophobic ...modified surfaces. This study encompassed the testing of four different surfaces: 1) Teflon SLIP, 2) Aluminum SLIP, 3) Honeycomb Superhydrophobic and 4...Polydimethylsiloxane elastomer (PDMSe) Superhydrophobic . Each of these surfaces uses specific geometrical surface features to modify the original

Extracting Uranium from Seawater: Promising AF Series Adsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, S.; Oyola, Y.; Mayes, Richard T.

A new family of high-surface-area polyethylene fiber adsorbents named the AF series was recently developed at the Oak Ridge National Laboratory (ORNL). The AF series adsorbents were synthesized by radiation-induced graft polymerization of acrylonitrile and itaconic acid (at different monomer/comonomer mol ratios) onto high surface area polyethylene fibers. The degree of grafting (%DOG) of AF series adsorbents was found to be 154-354%. The grafted nitrile groups were converted to amidoxime groups by treating with hydroxylamine. The amidoximated adsorbents were then conditioned with 0.44 M KOH at 80 °C followed by screening at ORNL with sodium-based synthetic aqueous solution, spiked withmore » 8 ppm uranium. The uranium adsorption capacity in simulated seawater screening ranged from 170 to 200 g-U/kg-ads irrespective of %DOG. A monomer/comonomer molar ratio in the range of 7.57-10.14 seemed to be optimum for highest uranium loading capacity. Subsequently, the adsorbents were also tested with natural seawater at Pacific Northwest National Laboratory (PNNL) using flow-through column experiments to determine uranium loading capacity with varying KOH conditioning times at 80 °C. The highest adsorption capacity of AF1 measured after 56 days of marine testing was demonstrated as 3.9 g-U/kg-adsorbent and 3.2 g-U/kg-adsorbent for 1 and 3 h of KOH conditioning at 80 °C, respectively. Based on capacity values of several AF1 samples, it was observed that changing KOH conditioning from 1 to 3 h at 80 °C resulted in a 22-27% decrease in uranium adsorption capacity in seawater.« less

Modelling hazardous surface hoar layers in the mountain snowpack over space and time

NASA Astrophysics Data System (ADS)

Horton, Simon Earl

Surface hoar layers are a common failure layer in hazardous snow slab avalanches. Surface hoar crystals (frost) initially form on the surface of the snow, and once buried can remain a persistent weak layer for weeks or months. Avalanche forecasters have difficulty tracking the spatial distribution and mechanical properties of these layers in mountainous terrain. This thesis presents numerical models and remote sensing methods to track the distribution and properties of surface hoar layers over space and time. The formation of surface hoar was modelled with meteorological data by calculating the downward flux of water vapour from the atmospheric boundary layer. The timing of surface hoar formation and the modelled crystal size was verified at snow study sites throughout western Canada. The major surface hoar layers over several winters were predicted with fair success. Surface hoar formation was modelled over various spatial scales using meteorological data from weather forecast models. The largest surface hoar crystals formed in regions and elevation bands with clear skies, warm and humid air, cold snow surfaces, and light winds. Field surveys measured similar regional-scale patterns in surface hoar distribution. Surface hoar formation patterns on different slope aspects were observed, but were not modelled reliably. Mechanical field tests on buried surface hoar layers found layers increased in shear strength over time, but had persistent high propensity for fracture propagation. Layers with large crystals and layers overlying hard melt-freeze crusts showed greater signs of instability. Buried surface hoar layers were simulated with the snow cover model SNOWPACK and verified with avalanche observations, finding most hazardous surface hoar layers were identified with a structural stability index. Finally, the optical properties of surface hoar crystals were measured in the field with spectral instruments. Large plate-shaped crystals were less reflective at shortwave

Suppression of single-wall carbon nanotube redox reaction by adsorbed proteins

NASA Astrophysics Data System (ADS)

Nakayama, Tomohito; Tanaka, Takeshi; Shiraki, Kentaro; Hase, Muneaki; Hirano, Atsushi

2018-07-01

Single-wall carbon nanotubes (SWCNTs) are widely used in biological applications. In biological systems, proteins readily adsorb to SWCNTs. However, little is known about the effects of proteins on the physicochemical properties of SWCNTs, such as their redox reaction. In this study, we measured the absorption and Raman spectra of SWCNTs dispersed in the presence of proteins such as bovine serum albumin to observe the redox reaction of the protein-adsorbed SWCNTs. The adsorbed proteins suppressed the redox reaction by forming thick and dense layers around the SWCNTs. Our findings are useful for understanding the behaviors of SWCNTs in biological systems.

Durable superhydrophobic surfaces made by intensely connecting a bipolar top layer to the substrate with a middle connecting layer.

PubMed

Zhi, Jinghui; Zhang, Li-Zhi

2017-08-30

This study reported a simple fabrication method for a durable superhydrophobic surface. The superhydrophobic top layer of the durable superhydrophobic surface was connected intensely to the substrate through a middle connecting layer. Glycidoxypropyltrimethoxysilane (KH-560) after hydrolysis was used to obtain a hydrophilic middle connecting layer. It could be adhered to the hydrophilic substrate by covalent bonds. Ring-open reaction with octadecylamine let the KH-560 middle layer form a net-like structure. The net-like sturcture would then encompass and station the silica particles that were used to form the coarse micro structures, intensely to increase the durability. The top hydrophobic layer with nano-structures was formed on the KH-560 middle layer. It was obtained by a bipolar nano-silica solution modified by hexamethyldisilazane (HMDS). This layer was connected to the middle layer intensely by the polar Si hydroxy groups, while the non-polar methyl groups on the surface, accompanied by the micro and nano structures, made the surface rather hydrophobic. The covalently interfacial interactions between the substrate and the middle layer, and between the middle layer and the top layer, strengthened the durability of the superhydrophobic surface. The abrasion test results showed that the superhydrophobic surface could bear 180 abrasion cycles on 1200 CW sandpaper under 2 kPa applied pressure.

Effect of the endcapping of reversed-phase high-performance liquid chromatography adsorbents on the adsorption isotherm

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gritti, Fabrice; Guiochon, Georges A

2005-09-01

The retention mechanisms of n-propylbenzoate, 4-t ert-butylphenol, and caffeine on the endcapped Symmetry-C{sub 18} and the non-endcapped Resolve-C{sub 18} are compared. The adsorption isotherms were measured by frontal analysis (FA), using as the mobile phase mixtures of methanol or acetonitrile and water of various compositions. The isotherm data were modeled and the adsorption energy distributions calculated. The surface heterogeneity increases faster with decreasing methanol concentration on the non-endcapped than on the endcapped adsorbent. For instance, for methanol concentrations exceeding 30% (v/v), the adsorption of caffeine is accounted for by assuming three and two different types of adsorption sites on Resolve-C{submore » 18} and Symmetry-C{sub 18}, respectively. This is explained by the effect of the mobile phase composition on the structure of the C{sub 18}-bonded layer. The bare surface of bonded silica appears more accessible to solute molecules at high water contents in the mobile phase. On the other hand, replacing methanol by a stronger organic modifier like acetonitrile dampens the differences between non-endcapped and endcapped stationary phase and decreases the degree of surface heterogeneity of the adsorbent. For instance, at acetonitrile concentrations exceeding 20%, the surface appears nearly homogeneous for the adsorption of caffeine.« less

Application of low energy ion blocking for adsorption site determination of Na Atoms on a Cu(111) surface

NASA Astrophysics Data System (ADS)

Zhang, R.; Makarenko, B.; Bahrim, B.; Rabalais, J. W.

2010-07-01

Ion blocking in the low keV energy range is demonstrated to be a sensitive method for probing surface adsorption sites by means of the technique of time-of-flight scattering and recoiling spectroscopy (TOF-SARS). Adsorbed atoms can block the nearly isotropic backscattering of primary ions from surface atoms in the outmost layers of a crystal. The relative adsorption site position can be derived unambiguously by simple geometrical constructs between the adsorbed atom site and the surface atom sites. Classical ion trajectory simulations using the scattering and recoiling imaging code (SARIC) and molecular dynamics (MD) simulations provide the detailed ion trajectories. Herein we present a quantitative analysis of the blocking effects produced by sub-monolayer Na adsorbed on a Cu(111) surface at room temperature. The results show that the Na adsorption site preferences are different at different Na coverages. At a coverage θ = 0.25 monolayer, Na atoms preferentially populate the fcc threefold surface sites with a height of 2.7 ± 0.1 Å above the 1st layer Cu atoms. At a lower coverage of θ = 0.10 monolayer, there is no adsorption site preference for the Na atoms on the Cu(111) surface.

Characteristics of the Martian atmosphere surface layer

NASA Technical Reports Server (NTRS)

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

1990-01-01

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

Adsorption and Exchange Dynamics in Aging Hydroxyethylcellulose Layers on Silica.

PubMed

Mubarekyan; Santore

2000-07-15

The adsorption kinetics of hydroxyethylcellulose (HEC) on silica and relaxations in adsorbed HEC layers were probed using total internal reflectance fluorescence and near-Brewster reflectivity. Like many random-coil polymers, HEC was found to adsorb at the transport-limited rate. Relaxations occurred at nearly constant interfacial mass when HEC layers were exposed to aqueous solvent, causing the subsequent exchange of chains between the layer and the free solution to become increasingly hindered. Eventually, on the time scale of a day, layers became immobilized and unable to accommodate chains from free solution. A continued fluorescence decay, beyond time scales that could be probed with self exchange, suggested further relaxations of the adsorbed HEC. The polydisperse HEC system (with an average molecular weight near 450,000) behaved qualitatively similar to molecular weight standard polyethylene oxide (PEO) layers on silica. For instance, relaxations in PEO layers occurred on a time scale of 10-20 h, like the HEC layers. Young layers of the latter, however, exhibited self-exchange kinetics that were an order of magnitude slower than PEO layers of similar age. This difference in adsorbed layer dynamics was attributed to HEC's stiffer backbone, compared with flexible PEO. Copyright 2000 Academic Press.

Factors influencing antibiotics adsorption onto engineered adsorbents.

PubMed

Xia, Mingfang; Li, Aimin; Zhu, Zhaolian; Zhou, Qin; Yang, Weiben

2013-07-01

The study evaluated the adsorption of two antibiotics by four engineered adsorbents (hypercrosslinked resin MN-202, macroporous resin XAD-4, activated carbon F-400, and multi-walled carbon nanotubes (MWCNT)) from aqueous solutions. The dynamic results demonstrated the dominant influence of pore size in adsorption. The adsorption amounts of antibiotics on XAD-4 were attributed to the hydrophobic effect, whereas steric hindrance or micropore-filling played a main role in the adsorption of antibiotics by F-400 because of its high microporosity. Aside from F-400, similar patterns of pH-dependent adsorption were observed, implying the importance of antibiotic molecular forms to the adsorption process for adsorbents. Increasing the ionic concentration with CaC12 produced particular adsorption characteristics on MWCNT at pH 2.0 and F-400 at pH 8.0, which were attributed to the highly available contact surfaces and molecular sieving, respectively. Its hybrid characteristics incorporating a considerable portion of mesopores and micropores made hypercross linked MN-202 a superior antibiotic adsorbent with high adsorption capacity. Furthermore, the adsorption capacity of MWCNT on the basis of surface area was more advantageous than that of the other adsorbents because MWCNT has a much more compact molecular arrangement.

Effect of surface ionization on wetting layers

NASA Technical Reports Server (NTRS)

Kayser, R. F.

1986-01-01

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

Overview on the Surface Functionalization Mechanism and Determination of Surface Functional Groups of Plasma Treated Carbon Nanotubes.

PubMed

Saka, Cafer

2018-01-02

The use of carbon materials for many applications is due to the unique diversity of structures and properties ranging from chemical bonds between the carbon atoms of the materials to nanostructures, crystallite alignment, and microstructures. Carbon nanotubes and other nanoscale carbonaceous materials draw much attention due to their physical and chemical properties, such as high strength, high resistance to corrosion, electrical and thermal conductivity, stability and a qualified adsorbent. Carbon-based nanomaterials, which have a relatively large specific area and layered structure, can be used as an adsorbent for efficient removal of organic and inorganic contaminants. However, one of the biggest obstacles to the development of carbon-based nanomaterials adsorbents is insolubility and the lack of functional groups on the surface. There are several approaches to introduce functional groups on carbon nanotubes. One of these approaches, plasma applications, now has an important place in the creation of surface functional groups as a flexible, fast, and environmentally friendly method. This review focuses on recent information concerning the surface functionalization and modification of plasma treated carbon nanotube. This review considers the surface properties, advantages, and disadvantages of plasma-applied carbon nanotubes. It also examines the reaction mechanisms involved in the functional groups on the surface.

Development of the Molecular Adsorber Coating for Spacecraft and Instrument Interiors

NASA Technical Reports Server (NTRS)

Abraham, Nithin

2011-01-01

On-orbit Molecular Contamination occurs when materials outgas and deposit onto very sensitive interior surfaces of the spacecraft and instruments. The current solution, Molecular Adsorber Pucks, has disadvantages, which are reviewed. A new innovative solution, Molecular Adsorber Coating (MAC), is currently being formulated, optimized, and tested. It is a sprayable alternative composed of Zeolite-based coating with adsorbing properties.

Adsorbed radioactivity and radiographic imaging of surfaces of stainless steel and titanium

NASA Astrophysics Data System (ADS)

Jung, Haijo

1997-11-01

Type 304 stainless steel used for typical surface materials of spent fuel shipping casks and titanium were exposed in the spent fuel storage pool of a typical PWR power plant. Adsorption characteristics, effectiveness of decontamination by water cleaning and by electrocleaning, and swipe effectiveness on the metal surfaces were studied. A variety of environmental conditions had been manipulated to stimulate the potential 'weeping' phenomenon that often occurs with spent fuel shipping casks during transit. In a previous study, few heterogeneous effects of adsorbed contamination onto metal surfaces were observed. Radiographic images of cask surfaces were made in this study and showed clearly heterogeneous activity distributions. Acquired radiographic images were digitized and further analyzed with an image analysis computer package and compared to calibrated images by using standard sources. The measurements of activity distribution by using the radiographic image method were consistent with that using a HPGe detector. This radiographic image method was used to study the effects of electrocleaning for total and specified areas. The Modulation Transfer Function (MTF) of a film-screen system in contact with a radioactive metal surface was studied with neutron activated gold foils and showed more broad resolution properties than general diagnostic x-ray film-screen systems. Microstructure between normal areas and hot spots showed significant differences, and one hot spot appearing as a dot on the film image consisted of several small hot spots (about 10 μm in diameter). These hot spots were observed as structural defects of the metal surfaces.

Antiferromagnetic MnN layer on the MnGa(001) surface

NASA Astrophysics Data System (ADS)

Guerrero-Sánchez, J.; Takeuchi, Noboru

2016-12-01

Spin polarized first principles total energy calculations have been applied to study the stability and magnetic properties of the MnGa(001) surface and the formation of a topmost MnN layer with the deposit of nitrogen. Before nitrogen adsorption, surface formation energies show a stable gallium terminated ferromagnetic surface. After incorporation of nitrogen atoms, the antiferromagnetic manganese terminated surface becomes stable due to the formation of a MnN layer (Mn-N bonding at the surface). Spin density distribution shows a ferromagnetic/antiferromagnetic arrangement in the first surface layers. This thermodynamically stable structure may be exploited to growth MnGa/MnN magnetic heterostructures as well as to look for exchange biased systems.

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.

Expansible apparatus for removing the surface layer from a concrete object

DOEpatents

Allen, Charles H.

1979-01-01

A method and apparatus for removing the surface layer from a concrete object. The method consists of providing a hole having a circular wall in the surface layer of the object, the hole being at least as deep as the thickness of the surface layer to be removed, and applying an outward wedging pressure on the wall of the hole sufficient to spall the surface layer around the hole. By the proper spacing of an appropriate number of holes, it is possible to remove the entire surface layer from an object. The apparatus consists of an elongated tubular-shaped body having a relatively short handle with a solid wall at one end, the wall of the remainder of the body containing a plurality of evenly spaced longitudinal cuts to form a relatively long expandable section, the outer end of the expandable section having an expandable, wedge-shaped spalling edge extending from the outer surface of the wall, perpendicular to the longitudinal axis of the body, and expanding means in the body for outwardly expanding the expandable section and forcing the spalling edge into the wall of a hole with sufficient outward pressure to spall away the surface layer of concrete. The method and apparatus are particularly suitable for removing surface layers of concrete which are radioactively contaminated.

Electrografted diazonium salt layers for antifouling on the surface of surface plasmon resonance biosensors.

PubMed

Zou, Qiongjing; Kegel, Laurel L; Booksh, Karl S

2015-02-17

Electrografted diazonium salt layers on the surface of surface plasmon resonance (SPR) sensors present potential for a significant improvement in antifouling coatings. A pulsed potential deposition profile was used in order to circumvent mass-transport limitations for layer deposition rate. The influence of number of pulses with respect to antifouling efficacy was evaluated by nonspecific adsorption surface coverage of crude bovine serum proteins. Instead of using empirical and rough estimated values, the penetration depth and sensitivity of the SPR instrument were experimentally determined for the calculation of nonspecific adsorption surface coverage. This provides a method to better examine antifouling surface coatings and compare crossing different coatings and experimental systems. Direct comparison of antifouling performance of different diazonium salts was facilitated by a tripad SPR sensor design. The electrografted 4-phenylalanine diazonium chloride (4-APhe) layers with zwitterionic characteristic demonstrate ultralow fouling.

A Solid-State Deuterium NMR and SFG Study of the Side Chain Dynamics of Peptides Adsorbed onto Surfaces

PubMed Central

Breen, Nicholas F.; Weidner, Tobias; Li, Kun; Castner, David G.; Drobny, Gary P.

2011-01-01

The artificial amphiphilic peptide LKα14 adopts a helical structure at interfaces, with opposite orientation of its leucine (L, hydrophobic) and lysine (K, hydrophilic) side chains. When adsorbed onto surfaces, different residue side chains necessarily have different proximities to the surface, depending on both their position in the helix and the composition of the surface itself. Deuterating the individual leucine residues (isopropyl-d7) permits the use of solid-state deuterium NMR as a site-specific probe of side chain dynamics. In conjunction with SFG as a probe of the peptide binding face, we demonstrate that the mobility of specific leucine side chains at the interface is quantifiable in terms of their surface proximity. PMID:19764755

Evolution of carboxymethyl cellulose layer morphology on hydrophobic mineral surfaces: variation of polymer concentration and ionic strength.

PubMed

Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka; Beattie, David A

2010-06-15

The adsorption of carboxymethyl cellulose (CMC) on the basal planes of talc and molybdenite has been studied using in situ atomic force microscope (AFM) imaging. These experiments were partnered with quantitative adsorption isotherm determinations on particulate samples. The isotherms revealed a clear increase of the CMC adsorbed amount upon increasing the solution ionic strength for adsorption on both minerals. In addition, the shapes of the isotherms changed in response to the change in the electrolyte concentration, with CMC on talc displaying stepped (10(-3) M KCl), Langmuir (10(-2) M KCl), then Freundlich isotherm shapes (10(-1) M KCl), and CMC on molybdenite displaying stepped (10(-3) M KCl), Freundlich (10(-2) M KCl), then Langmuir isotherm shapes (10(-1) M KCl). AFM imaging of the polymer layer on the mineral surfaces with varying solution conditions mirrored and confirmed the conclusions from the isotherms: as the polymer solution concentration increased, coverage on the basal plane increased; as the ionic strength increased, coverage on the basal plane increased and the morphology of the layer changed from isolated well-distributed polymer domains to extensive adsorption and formation of dense, uneven polymer domains/features. In addition, comparison of the talc and molybdenite datasets points toward the presence of different binding mechanisms for CMC adsorption on the talc and molybdenite basal plane surfaces. 2010 Elsevier Inc. All rights reserved.

Casein Aggregates Built Step-by-Step on Charged Polyelectrolyte Film Surfaces Are Calcium Phosphate-cemented*

PubMed Central

Nagy, Krisztina; Pilbat, Ana-Maria; Groma, Géza; Szalontai, Balázs; Cuisinier, Frédéric J. G.

2010-01-01

The possible mechanism of casein aggregation and micelle buildup was studied in a new approach by letting α-casein adsorb from low concentration (0.1 mg·ml−1) solutions onto the charged surfaces of polyelectrolyte films. It was found that α-casein could adsorb onto both positively and negatively charged surfaces. However, only when its negative phosphoseryl clusters remained free, i.e. when it adsorbed onto a negative surface, could calcium phosphate (CaP) nanoclusters bind to the casein molecules. Once the CaP clusters were in place, step-by-step building of multilayered casein architectures became possible. The presence of CaP was essential; neither Ca2+ nor phosphate could alone facilitate casein aggregation. Thus, it seems that CaP is the organizing motive in the casein micelle formation. Atomic force microscopy revealed that even a single adsorbed casein layer was composed of very small (in the range of tens of nanometers) spherical forms. The stiffness of the adsorbed casein layer largely increased in the presence of CaP. On this basis, we can imagine that casein micelles emerge according to the following scheme. The amphipathic casein monomers aggregate into oligomers via hydrophobic interactions even in the absence of CaP. Full scale, CaP-carrying micelles could materialize by interlocking these casein oligomers with CaP nanoclusters. Such a mechanism would not contradict former experimental results and could offer a synthesis between the submicelle and the block copolymer models of casein micelles. PMID:20921229

Black Molecular Adsorber Coatings for Spaceflight Applications

NASA Technical Reports Server (NTRS)

Abraham, Nithin Susan; Hasegawa, Mark Makoto; Straka, Sharon A.

2014-01-01

The molecular adsorber coating is a new technology that was developed to mitigate the risk of on-orbit molecular contamination on spaceflight missions. The application of this coating would be ideal near highly sensitive, interior surfaces and instruments that are negatively impacted by outgassed molecules from materials, such as plastics, adhesives, lubricants, epoxies, and other similar compounds. This current, sprayable paint technology is comprised of inorganic white materials made from highly porous zeolite. In addition to good adhesion performance, thermal stability, and adsorptive capability, the molecular adsorber coating offers favorable thermal control characteristics. However, low reflectivity properties, which are typically offered by black thermal control coatings, are desired for some spaceflight applications. For example, black coatings are used on interior surfaces, in particular, on instrument baffles for optical stray light control. Similarly, they are also used within light paths between optical systems, such as telescopes, to absorb light. Recent efforts have been made to transform the white molecular adsorber coating into a black coating with similar adsorptive properties. This result is achieved by optimizing the current formulation with black pigments, while still maintaining its adsorption capability for outgassing control. Different binder to pigment ratios, coating thicknesses, and spray application techniques were explored to develop a black version of the molecular adsorber coating. During the development process, coating performance and adsorption characteristics were studied. The preliminary work performed on black molecular adsorber coatings thus far is very promising. Continued development and testing is necessary for its use on future contamination sensitive spaceflight missions.

Black molecular adsorber coatings for spaceflight applications

NASA Astrophysics Data System (ADS)

Abraham, Nithin S.; Hasegawa, Mark M.; Straka, Sharon A.

2014-09-01

The molecular adsorber coating is a new technology that was developed to mitigate the risk of on-orbit molecular contamination on spaceflight missions. The application of this coating would be ideal near highly sensitive, interior surfaces and instruments that are negatively impacted by outgassed molecules from materials, such as plastics, adhesives, lubricants, epoxies, and other similar compounds. This current, sprayable paint technology is comprised of inorganic white materials made from highly porous zeolite. In addition to good adhesion performance, thermal stability, and adsorptive capability, the molecular adsorber coating offers favorable thermal control characteristics. However, low reflectivity properties, which are typically offered by black thermal control coatings, are desired for some spaceflight applications. For example, black coatings are used on interior surfaces, in particular, on instrument baffles for optical stray light control. Similarly, they are also used within light paths between optical systems, such as telescopes, to absorb light. Recent efforts have been made to transform the white molecular adsorber coating into a black coating with similar adsorptive properties. This result is achieved by optimizing the current formulation with black pigments, while still maintaining its adsorption capability for outgassing control. Different binder to pigment ratios, coating thicknesses, and spray application techniques were explored to develop a black version of the molecular adsorber coating. During the development process, coating performance and adsorption characteristics were studied. The preliminary work performed on black molecular adsorber coatings thus far is very promising. Continued development and testing is necessary for its use on future contamination sensitive spaceflight missions.

State-specific enhancement of Cl+ and Cl- desorption for SiCl4 adsorbed on a Si(100) surface following Cl 2 p and Si 2 p core-level excitations.

PubMed

Chen, J M; Lu, K T

2001-04-02

State-specific desorption for SiCl4 adsorbed on a Si(100) surface at approximately 90 K with variable coverage following the Cl 2p and Si 2p core-level excitations has been investigated using synchrotron radiation. The Cl+ yields show a significant enhancement following the Cl 2p-->8a*1 excitation. The Cl- yields are notably enhanced at the 8a*1 resonance at both Cl 2p and Si 2p edges. The enhancement of the Cl- yield occurs through the formation of highly excited states of the adsorbed molecules. These results provide some new dissociation processes from adsorbates on surfaces via core-level excitation.

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.

Application of atomic force microscopy to microbial surfaces: from reconstituted cell surface layers to living cells.

PubMed

Dufrêne, Y F

2001-02-01

The application of atomic force microscopy (AFM) to probe the ultrastructure and physical properties of microbial cell surfaces is reviewed. The unique capabilities of AFM can be summarized as follows: imaging surface topography with (sub)nanometer lateral resolution; examining biological specimens under physiological conditions; measuring local properties and interaction forces. AFM is being used increasingly for: (i) visualizing the surface ultrastructure of microbial cell surface layers, including bacterial S-layers, purple membranes, porin OmpF crystals and fungal rodlet layers; (ii) monitoring conformational changes of individual membrane proteins; (iii) examining the morphology of bacterial biofilms, (iv) revealing the nanoscale structure of living microbial cells, including fungi, yeasts and bacteria, (v) mapping interaction forces at microbial surfaces, such as van der Waals and electrostatic forces, solvation forces, and steric/bridging forces; and (vi) probing the local mechanical properties of cell surface layers and of single cells.

A scheme for computing surface layer turbulent fluxes from mean flow surface observations

NASA Technical Reports Server (NTRS)

Hoffert, M. I.; Storch, J.

1978-01-01

A physical model and computational scheme are developed for generating turbulent surface stress, sensible heat flux and humidity flux from mean velocity, temperature and humidity at some fixed height in the atmospheric surface layer, where conditions at this reference level are presumed known from observations or the evolving state of a numerical atmospheric circulation model. The method is based on coupling the Monin-Obukov surface layer similarity profiles which include buoyant stability effects on mean velocity, temperature and humidity to a force-restore formulation for the evolution of surface soil temperature to yield the local values of shear stress, heat flux and surface temperature. A self-contained formulation is presented including parameterizations for solar and infrared radiant fluxes at the surface. Additional parameters needed to implement the scheme are the thermal heat capacity of the soil per unit surface area, surface aerodynamic roughness, latitude, solar declination, surface albedo, surface emissivity and atmospheric transmissivity to solar radiation.

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

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

Unusual Entropy of Adsorbed Methane on Zeolite-Templated Carbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stadie, Nicholas P.; Murialdo, Maxwell; Ahn, Channing C.

2015-11-25

Methane adsorption at high pressures and across a wide range of temperatures was investigated on the surface of three porous carbon adsorbents with complementary structural properties. The measured adsorption equilibria were analyzed using a method that can accurately account for nonideal fluid properties and distinguish between absolute and excess quantities of adsorption, and that also allows the direct calculation of the thermodynamic potentials relevant to adsorption. On zeolite-templated carbon (ZTC), a material that exhibits extremely high surface area with optimal pore size and homogeneous structure, methane adsorption occurs with unusual thermodynamic properties that are greatly beneficial for deliverable gas storage:more » an enthalpy of adsorption that increases with site occupancy, and an unusually low entropy of the adsorbed phase. The origin of these properties is elucidated by comparison of the experimental results with a statistical mechanical model. The results indicate that temperature-dependent clustering (i.e., reduced configurations) of the adsorbed phase due to enhanced lateral interactions can account for the peculiarities of methane adsorbed on ZTC.« less

Analysis of the electrodeposition and surface chemistry of CdTe, CdSe, and CdS thin films through substrate-overlayer surface-enhanced Raman spectroscopy.

PubMed

Gu, Junsi; Fahrenkrug, Eli; Maldonado, Stephen

2014-09-02

The substrate-overlayer approach has been used to acquire surface enhanced Raman spectra (SERS) during and after electrochemical atomic layer deposition (ECALD) of CdSe, CdTe, and CdS thin films. The collected data suggest that SERS measurements performed with off-resonance (i.e. far from the surface plasmonic wavelength of the underlying SERS substrate) laser excitation do not introduce perturbations to the ECALD processes. Spectra acquired in this way afford rapid insight on the quality of the semiconductor film during the course of an ECALD process. For example, SERS data are used to highlight ECALD conditions that yield crystalline CdSe and CdS films. In contrast, SERS measurements with short wavelength laser excitation show evidence of photoelectrochemical effects that were not germane to the intended ECALD process. Using the semiconductor films prepared by ECALD, the substrate-overlayer SERS approach also affords analysis of semiconductor surface adsorbates. Specifically, Raman spectra of benzenethiol adsorbed onto CdSe, CdTe, and CdS films are detailed. Spectral shifts in the vibronic features of adsorbate bonding suggest subtle differences in substrate-adsorbate interactions, highlighting the sensitivity of this methodology.

Surface reflectance anisotropy of indium-terminated GaAs(100) surfaces

NASA Astrophysics Data System (ADS)

Springer, C.; Resch-Esser, U.; Goletti, C.; Richter, W.; Fimland, B. O.

1997-04-01

The growth of thin indium-layers on the GaAs(100) As-rich {(2 × 4)}/{c(2 × 8) } surface has been investigated by reflectance anisotropy spectroscopy (RAS), LEED and AES. Clean surfaces of the {(2 × 4)}/{c(2 × 8) } reconstruction were prepared in UHV by thermal desorption of a protective arsenic layer deposited on homoepitaxially grown MBE layers. Room temperature deposition of indium on the {(2 × 4)}/{c(2 × 8) } surface and subsequent annealing at 450°C leads to a 90° rotation of symmetry in the LEED pattern at a threshold coverage of 0.5 monolayers, i.e. a change from the {(2 × 4)}/{c(2 × 8) } to the {(4 × 2)}/{c(8 × 2) } reconstruction. The RAS spectra show the evolution of a distinct negative feature at 1.8 eV, that shifts to 2.1 eV after annealing, corresponding to optical transitions attributed to In-dimers orientated along the [011]-direction. AES analysis shows a change in growth mode beyond 0.5 ML indicating saturation of all available adsorption sites at this coverage and RAS spectra show a contribution from additional disordered In. The AES spectra display no evidence of a surface exchange reaction between gallium and arsenic atoms, thus indicating a surface termination by In-dimers adsorbed on a layer of As.

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.

Intercalated layered clay composites and their applications

NASA Astrophysics Data System (ADS)

Phukan, Anjali

Supported inorganic reagents are rapidly emerging as new and environmentally acceptable reagents and catalysts. The smectite group of layered clay minerals, such as, Montmorillonite, provides promising character for adsorption, catalytic activity, supports etc. for their large surface area, swelling behavior and ion exchange properties. Aromatic compounds intercalated in layered clays are useful in optical molecular devices. Clay is a unique material for adsorption of heavy metals and various toxic substances. Clay surfaces are known to be catalytically active due to their surface acidity. Acid activated clays possess much improved surface areas and acidities and have higher pore volumes so that can absorb large molecules in the pores. The exchangeable cations in clay minerals play a key role in controlling surface acidity and catalytic activity. Recently, optically active metal-complex-Montmorillonite composites are reported to be active in antiracemization purposes. In view of the above, a research work, relating to the preparation of different modified clay composites and their catalytic applications were carried out. The different aspects and results of the present work have been reported in four major chapters. Chapter I: This is an introductory chapter, which contains a review of the literature regarding clay-based materials. Clay minerals are phyllosilicates with layer structure. Montmorillonite, a member of smectite group of clay, is 2:1 phyllosilicate, where a layer is composed of an octahedral sheet sandwiched by two tetrahedral sheets. Such clay shows cation exchange capacity (CEC) and is expressed in milli-equivalents per 100 gm of dry clay. Clays can be modified by interaction with metal ion, metal complexes, metal cluster and organic cations for various applications. Clays are also modified by treating with acid followed by impregnation with metal salts or ions. Montmorillonite can intercalate suitable metal complexes in excess of CEC to form double

Untangleing the effects of chain rigidity on the structure and dynamics of strongly adsorbed polymer melts

DOE PAGES

Carrillo, Jan-Michael Y.; Cheng, Shiwang; Kumar, Rajeev; ...

2015-06-11

Here, we present a detailed analysis of coarse-grained molecular dynamics simulations of semiflexible polymer melts in contact with a strongly adsorbing substrate. We have characterized the segments in the interfacial layer by counting the number of trains, loops, tails and unadsorbed segments. For more rigid chains, a tail and an adsorbed segment (a train) dominate while loops are more prevalent in more flexible chains. The tails exhibit a non-uniformly stretched conformation akin to the polydispersed pseudobrush envisioned by Guiselin. To probe the dynamics of the segments we computed the layer z-resolved intermediate coherent collective dynamics structure factor, S(q, t, z),more » mean-square displacement of segments, and the 2nd Legendre polynomial of the time-autocorrelation of unit bond vectors, 2[n i(t,z)•n i(0,z)]>. Our results show that segmental dynamics is slower for stiffer chains and there is a strong correlation between the structure and dynamics in the interfacial layer. There is no glassy layer, and the slowing down in dynamics of stiffer chains in the adsorbed region can be attributed to the densification and the more persistent layering of segments.« less

Linking Dynamics of the Near-surface Flow to Deeper Boundary Layer Forcing in the Nocturnal Boundary Layer

DTIC Science & Technology

2012-06-01

Kaimal and Finnigan (1994), modified) Figure 2.2 illustrates the evolution from unstable CBL to a nocturnal Stable Bound- ary Layer ( SBL ) in the absence...mixed layer acts as a cap for the SBL . The SBL persists through the night until sunrise when surface heating resumes and a new unstable layer begins...to form at the surface, gradually returning to a CBL. 7 2.2.1 Dynamics of the stable boundary layer Because the SBL is stably stratified, buoyancy

Investigation of the surface sensitivity of positron-annihilation-induced Auger-electron spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mehl, D.R.

1990-01-01

The first surface sensitivity studies of positron-annihilation-induced Auger-electron spectroscopy (PAES) are presented. Preliminary measurements on polycrystalline Al with adsorbates indicate that PAES is more selective of the surface than conventional electron-induced Auger electron spectroscopy (EAES). PAES and EAES studies of well-defined overlayer-metal systems of Cu(110)+S and Cu(110)+Cs verify that PAES is selective of the top atomic layer. This surface selectivity is accounted for by theoretical calculations which indicate that the positron surface state is displaced away from the substrate by the over-layer, decreasing the annihilation rate of positrons with substrate core electrons.

Extracting uranium from seawater: Promising AF series adsorbents

DOE PAGES

Das, Sadananda; Oyola, Y.; Mayes, Richard T.; ...

2015-11-02

Here, a new family of high surface area polyethylene fiber adsorbents (AF series) was recently developed at the Oak Ridge National Laboratory (ORNL). The AF series of were synthesized by radiation-induced graft polymerization of acrylonitrile and itaconic acid (at different monomer/co-monomer mol ratios) onto high surface area polyethylene fibers. The degree of grafting (%DOG) of AF series adsorbents was found to be 154 354%. The grafted nitrile groups were converted to amidoxime groups by treating with hydroxylamine. The amidoximated adsorbents were then conditioned with 0.44M KOH at 80 C followed by screening at ORNL with simulated seawater spiked with 8more » ppm uranium. Uranium adsorption capacity in simulated seawater screening ranged from 170-200 g-U/kg-ads irrespective of %DOG. A monomer/co-monomer mol ratio in the range of 7.57-10.14 seemed to be optimum for highest uranium loading capacity. Subsequently, the adsorbents were also tested with natural seawater at Pacific Northwest National Laboratory (PNNL) using flow-through exposure uptake experiments to determine uranium loading capacity with varying KOH conditioning time at 80 C. The highest adsorption capacity of AF1 measured after 56 days of marine testing was demonstrated as 3.9 g-U/kg-adsorbent and 3.2 g-U/kg-adsorbent for 1hr and 3hrs of KOH conditioning at 80 C, respectively. Based on capacity values of several AF1 samples, it was observed that changing KOH conditioning from 3hrs to 1hr at 80 C resulted in 22-27% increase in uranium loading capacity in seawater.« less

Extracting uranium from seawater: Promising AF series adsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Sadananda; Oyola, Y.; Mayes, Richard T.

Here, a new family of high surface area polyethylene fiber adsorbents (AF series) was recently developed at the Oak Ridge National Laboratory (ORNL). The AF series of were synthesized by radiation-induced graft polymerization of acrylonitrile and itaconic acid (at different monomer/co-monomer mol ratios) onto high surface area polyethylene fibers. The degree of grafting (%DOG) of AF series adsorbents was found to be 154 354%. The grafted nitrile groups were converted to amidoxime groups by treating with hydroxylamine. The amidoximated adsorbents were then conditioned with 0.44M KOH at 80 C followed by screening at ORNL with simulated seawater spiked with 8more » ppm uranium. Uranium adsorption capacity in simulated seawater screening ranged from 170-200 g-U/kg-ads irrespective of %DOG. A monomer/co-monomer mol ratio in the range of 7.57-10.14 seemed to be optimum for highest uranium loading capacity. Subsequently, the adsorbents were also tested with natural seawater at Pacific Northwest National Laboratory (PNNL) using flow-through exposure uptake experiments to determine uranium loading capacity with varying KOH conditioning time at 80 C. The highest adsorption capacity of AF1 measured after 56 days of marine testing was demonstrated as 3.9 g-U/kg-adsorbent and 3.2 g-U/kg-adsorbent for 1hr and 3hrs of KOH conditioning at 80 C, respectively. Based on capacity values of several AF1 samples, it was observed that changing KOH conditioning from 3hrs to 1hr at 80 C resulted in 22-27% increase in uranium loading capacity in seawater.« less

Exchange of adsorbed H2O and CO2 between the regolith and atmosphere of Mars caused by changes in surface insolation

NASA Technical Reports Server (NTRS)

Fanale, F. P.; Cannon, W. A.

1974-01-01

Estimates have been made of the capacity of the Martian regolith to exchange adsorbed H2O and CO2 with the atmosphere-plus-cap system (APCS). These estimates are based upon measured isotherms for H2O and CO2 adsorption on pulverized basalt at low temperatures and on theoretical considerations. A unit column (1 sq cm) of regolith with a deep subsurface temperature of -77 C, considered average for the disk, will contain about 0.4 g of adsorbed CO2 and about 1 g of adsorbed H2O per meter of depth. Under favorable circumstances the top 3 cm can exchange much more H2O with the lower atmosphere each day than is necessary to produce the diurnal brightening. The process appears to be seasonally reversible. The total regolith may contain, in the adsorbed phase alone, as much as 1% of the H2O and 5% of the CO2 surface inventories expected for a hypothetical Mars that has experienced degassing as intensive as that of earth.

Water Density in the Electric Double Layer at the Insulator/Electrolyte Solution Interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tikhonov,A.

I studied the spatial structure of the thick transition region between n-hexane and a colloidal solution of 7-nm silica particles by X-ray reflectivity and grazing incidence small-angle scattering. The interfacial structure is discussed in terms of a semiquantitative interface model wherein the potential gradient at the n-hexane/sol interface reflects the difference in the potentials of 'image forces' between the cationic Na{sup +} and anions (nanoparticles) and the specific adsorption of surface charge at the interface between the adsorbed layer and the solution, as well as at the interface between the adsorbed layer and n-hexane. The X-ray scattering data revealed thatmore » the average density of water in the field {approx}10{sup 9}-10{sup 10} V/m of the electrical double layer at the hexane/silica sol interface is the same as, or only few percent higher (1-7%) than, its density under normal conditions.« less

Modeling the surface of Campylobacter fetus: protein surface layer stability and resistance to cationic antimicrobial peptides.

PubMed

Roberts, James M D; Graham, Lori L; Quinn, Bonnie; Pink, David A

2013-03-01

Campylobacter fetus is a Gram negative bacterium recognized for its virulence in animals and humans. This bacterium possesses a paracrystalline array of high molecular weight proteins known as surface-layer proteins covering its cell surface. A mathematical model has been made of the outer membrane of this bacterium, both with its surface-layer proteins (S+) and without (S-). Monte Carlo computer simulation was used to understand the stability of the surface-layer protein structure as a function of ionic concentration. The interactions of an electrically-charged antimicrobial agent, the cationic antimicrobial peptide protamine, with surface-layer proteins and with the lipopolysaccharides of the outer membrane were modeled and analyzed. We found that (1) divalent ions stabilize the surface-layer protein array by reducing the fluctuations perpendicular and parallel to the membrane plane thereby promoting adhesion to the LPS region. This was achieved via (2) divalent ions bridging the negatively-charged LPS Core. The effect of this bridging is to bring individual Core regions closer together so that the O-antigens can (3) increase their attractive van der Waals interactions and "collapse" to form a surface with reduced perpendicular fluctuations. These findings provide support for the proposal of Yang et al. [1]. (4) No evidence for a significant increase in Ca(2+) concentration in the region of the surface-layer protein subunits was observed in S+ simulations compared to S- simulations. (5) We predicted the trends of protamine MIC tests performed on C. fetus and these were in good agreement with our experimental results. Copyright © 2012 Elsevier B.V. All rights reserved.

A quantum mechanical study of water adsorption on the (110) surfaces of rutile SnO₂ and TiO₂: investigating the effects of intermolecular interactions using hybrid-exchange density functional theory.

PubMed

Patel, M; Sanches, F F; Mallia, G; Harrison, N M

2014-10-21

Periodic hybrid-exchange density functional theory calculations are used to explore the first layer of water at model oxide surfaces, which is an important step for understanding the photocatalytic reactions involved in solar water splitting. By comparing the structure and properties of SnO2(110) and TiO2(110) surfaces in contact with water, the effects of structural and electronic differences on the water chemistry are examined. The dissociative adsorption mode at low coverage (1/7 ML) up to monolayer coverage (1 ML) on both SnO2 and TiO2(110) surfaces is analysed. To investigate further the intermolecular interactions between adjacent adsorbates, monolayer adsorption on each surface is explored in terms of binding energies and bond lengths. Analysis of the water adsorption geometry and energetics shows that the relative stability of water adsorption on SnO2(110) is governed largely by the strength of the chemisorption and hydrogen bonds at the surface of the adsorbate-substrate system. However on TiO2(110), a more complicated scenario of the first layer of water on its surface arises in which there is an interplay between chemisorption, hydrogen bonding and adsorbate-induced atomic displacements in the surface. Furthermore the projected density of states of each surface in contact with a mixture of adsorbed water molecules and adsorbed hydroxyls is presented and sheds some light on the nature of the crystalline chemical bonds as well as on why adsorbed water has often been reported to be unstable on rutile SnO2(110).

Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

DOEpatents

Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

2016-09-06

A fiber-based adsorbent and a related method of manufacture are provided. The fiber-based adsorbent includes polymer fibers with grafted side chains and an increased surface area per unit weight over known fibers to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. The polymer fibers include a circular morphology in some embodiments, having a mean diameter of less than 15 microns, optionally less than about 1 micron. In other embodiments, the polymer fibers include a non-circular morphology, optionally defining multiple gear-shaped, winged-shaped or lobe-shaped projections along the length of the polymer fibers. A method for forming the fiber-based adsorbents includes irradiating high surface area polymer fibers, grafting with polymerizable reactive monomers, reacting the grafted fibers with hydroxylamine, and conditioning with an alkaline solution. High surface area fiber-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

DOEpatents

Janke, Christopher J; Dai, Sheng; Oyola, Yatsandra

2014-05-13

A fiber-based adsorbent and a related method of manufacture are provided. The fiber-based adsorbent includes polymer fibers with grafted side chains and an increased surface area per unit weight over known fibers to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. The polymer fibers include a circular morphology in some embodiments, having a mean diameter of less than 15 microns, optionally less than about 1 micron. In other embodiments, the polymer fibers include a non-circular morphology, optionally defining multiple gear-shaped, winged-shaped or lobe-shaped projections along the length of the polymer fibers. A method for forming the fiber-based adsorbents includes irradiating high surface area polymer fibers, grafting with polymerizable reactive monomers, reacting the grafted fibers with hydroxylamine, and conditioning with an alkaline solution. High surface area fiber-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

Simulations of noble gases adsorbed on graphene

NASA Astrophysics Data System (ADS)

Maiga, Sidi; Gatica, Silvina

2014-03-01

We present results of Grand Canonical Monte Carlo simulations of adsorption of Kr, Ar and Xe on a suspended graphene sheet. We compute the adsorbate-adsorbate interaction by a Lennard-Jones potential. We adopt a hybrid model for the graphene-adsorbate force; in the hybrid model, the potential interaction with the nearest carbon atoms (within a distance rnn) is computed with an atomistic pair potential Ua; for the atoms at r>rnn, we compute the interaction energy as a continuous integration over a carbon uniform sheet with the density of graphene. For the atomistic potential Ua, we assume the anisotropic LJ potential adapted from the graphite-He interaction proposed by Cole et.al. This interaction includes the anisotropy of the C atoms on graphene, which originates in the anisotropic π-bonds. The adsorption isotherms, energy and structure of the layer are obtained and compared with experimental results. We also compare with the adsorption on graphite and carbon nanotubes. This research was supported by NSF/PRDM (Howard University) and NSF (DMR 1006010).

Layer Control of WSe2 via Selective Surface Layer Oxidation.

PubMed

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

2016-07-26

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

Glucose Oxidase Adsorption on Sequential Adsorbed Polyelectrolyte Films Studied by Spectroscopic Techniques

NASA Astrophysics Data System (ADS)

Tristán, Ferdinando; Solís, Araceli; Palestino, Gabriela; Gergely, Csilla; Cuisinier, Frédéric; Pérez, Elías

2005-04-01

The adsorption of Glucose Oxidase (GOX) on layers of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) deposited on Sequentially Adsorbed Polyelectrolyte Films (SAPFs) were studied by three different spectroscopic techniques. These techniques are: Optical Wave Light Spectroscopy (OWLS) to measure surface density; Fluorescence Resonance Energy Transfer (FRET) to verify the adsorption of GOX on the surface; and Fourier Transform Infrared Spectroscopy in Attenuated Total Reflection mode (FTIR-HATR) to inspect local structure of polyelectrolytes and GOX. Two positive and two negative polyelectrolytes are used: Cationic poly(ethyleneimine) (PEI) and poly(allylamine hydrochloride) (PAH) and anionic poly(sodium 4-styrene sulfonate) (PSS) and poly(acrylic acid) (PAA). These spectroscopic techniques do not require any labeling for GOX or SAPFs, specifically GOX and PSS are naturally fluorescent and are used as a couple donor-acceptor for the FRET technique. The SAPFs are formed by a (PEI)-(PSS/PAH)2 film followed by (PAA/PAH)n bilayers. GOX is finally deposited on top of SAPFs at different values of n (n=1..5). Our results show that GOX is adsorbed on positive ended SAPFs forming a monolayer. Contrary, GOX adsorption is not observed on negative ended film polyelectrolyte. GOX stability was tested adding a positive and a negative polyelectrolyte after GOX adsorption. Protein is partially removed by PAH and PAA, with lesser force by PAA.

Marine Atmospheric Surface Layer and Its Application to Electromagnetic Wave Propagation

NASA Astrophysics Data System (ADS)

Wang, Q.

2015-12-01

An important application of the atmospheric surface layer research is to characterize the near surface vertical gradients in temperature and humidity in order to predict radar and radio communication conditions in the environment. In this presentation, we will give an overview of a new research initiative funded under the Office of Naval Research (ONR) Multi-University Research Initiative (MURI): the Coupled Air-Sea Processes and EM Ducting Research (CASPER). The objective is to fully characterize the marine atmospheric boundary layer (MABL) as an electromagnetic (EM) propagation environment with the emphasis of spatial and temporal heterogeneities and surface wave/swell effects, both of which contravene the underlying assumptions of Monin-Obukhov Similarity Theory (MOST) used in coupled environmental forecast models. Furthermore, coastal variability in the inversion atop the MABL presents a challenge to forecast models and also causes practical issues in EM prediction models. These issues are the target of investigation of CASPER. CASPER measurement component includes two major field campaigns: CASPER-East (2015 Duck, NC) and CASPER-West (2018 southern California). This presentation will show the extensive measurements to be made during the CASPER -East field campaign with the focus on the marine atmospheric surface layer measurements with two research vessels, two research aircraft, surface flux buoy, wave gliders, ocean gliders, tethered balloons, and rawinsondes. Unlike previous research on the marine surface layer with the focus on surface fluxes and surface flux parameterization, CASPER field campaigns also emphasize of the surface layer profiles and the validation of the surface layer flux-profile relationship originally derived over land surfaces. Results from CASPER pilot experiment and preliminary results from CASPER-East field campaign will be discussed.

Free Energy Landscape of Cellulose as a Driving Factor in the Mobility of Adsorbed Water.

PubMed

Kulasinski, Karol

2017-06-06

The diffusion coefficient of water adsorbed in hydrophilic porous materials, such as noncrystalline cellulose, depends on water activity. Faster diffusion at higher water concentrations is observed in experimental and modeling studies. In this paper, two asymptotic water concentrations, near-vacuum and fully saturated, are investigated at the surface of crystalline cellulose with molecular dynamics simulations. An increasing water concentration leads to significant changes in the free energy landscape due to perturbation of local electrostatic potential. Smoothening of strong energy minima, corresponding to sorption sites, and formation of layered structure facilitates water transport in the vicinity of cellulose. The determined transition probabilities and hydrogen bond stability reflect the changes in the energy landscape. As a result of a concentration increase, the emerging basins of attraction and spreading out of those existing in the diluted state lead to an increase in water entropy. Thermal fluctuations of cellulose are demonstrated to rearrange the landscape in the diluted limit, increase adsorbed water entropy, and decrease the water-cellulose H-bond lifetime.

Surface Layering Near Room Temperature in a Nonmetallic Liquid

NASA Astrophysics Data System (ADS)

Chattopadhyay, Sudeshna; Stripe, Benjamin; Shively, Patrick; Evmenenko, Geunnadi; Dutta, Pulak; Ehrlich, Steven; Mo, Haiding

2009-03-01

Oscillatory density profiles (layers) have been observed at the free surfaces of many liquid metals at and above room temperature [1]. A surface-layered state has been previously reported only in one dielectric liquid, tetrakis(2-ethylhexoxy)silane (TEHOS), and only at lower temperatures [2]. We have used x-ray reflectivity to study a molecular liquid, pentaphenyl trimethyl trisiloxane. Below T˜ 267K (well above the freezing point for this liquid), density oscillations appear at the surface. This liquid has a higher Tc (˜1200K) than TEHOS (˜950K), so that layers appear at T/Tc 0.2 in both cases. Our results indicate that surface order is a universal phenomenon in both metallic and dielectric liquids, and that the underlying physics is likely to be the same since layers always appear at T<˜0.2Tc as theoretically predicted [3] [3pt] REFERENCES: [0pt] [1]. e.g. O. M. Magnussen et al., Phys. Rev. Lett. 74, 4444 (1995) [0pt] [2]. H. Mo et al. Phys. Rev. Lett. 96, 096107 (2006); Phys. Rev. B 76, 024206 (2007) [0pt] [3]. e.g. E. Chac'on et al., Phys. Rev. Lett. 87, 166101 (2001)

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

Quantitative analysis of desorption and decomposition kinetics of formic acid on Cu(111): The importance of hydrogen bonding between adsorbed species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo

2015-12-21

Quantitative analysis of desorption and decomposition kinetics of formic acid (HCOOH) on Cu(111) was performed by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy, and time-resolved infrared reflection absorption spectroscopy. The activation energy for desorption is estimated to be 53–75 kJ/mol by the threshold TPD method as a function of coverage. Vibrational spectra of the first layer HCOOH at 155.3 K show that adsorbed molecules form a polymeric structure via the hydrogen bonding network. Adsorbed HCOOH molecules are dissociated gradually into monodentate formate species. The activation energy for the dissociation into monodentate formate species is estimated to be 65.0 kJ/mol atmore » a submonolayer coverage (0.26 molecules/surface Cu atom). The hydrogen bonding between adsorbed HCOOH species plays an important role in the stabilization of HCOOH on Cu(111). The monodentate formate species are stabilized at higher coverages, because of the lack of vacant sites for the bidentate formation.« less

Surface Brillouin scattering study of the surface excitations in amorphous silicon layers produced by ion bombardment

NASA Astrophysics Data System (ADS)

Zhang, X.; Comins, J. D.; Every, A. G.; Stoddart, P. R.; Pang, W.; Derry, T. E.

1998-11-01

Thin amorphous silicon layers on crystalline silicon substrates have been produced by argon-ion bombardment of (001) silicon surfaces. Thermally induced surface excitations characteristic of this example of a soft-on-hard system have been investigated by surface Brillouin scattering (SBS) as a function of scattering-angle and amorphous-layer thickness. At large scattering angles or for sufficiently large layer thickness, a second peak is present in the SBS spectrum near the low-energy threshold for the continuum of bulk excitations of the system. The measured spectra are analyzed on the basis of surface elastodynamic Green's functions, which successfully simulate their detailed appearance and identify the second peak as either a Sezawa wave (true surface wave) or a pseudo-Sezawa wave (attenuated surface wave) depending on the scattering parameters. The attributes of the pseudo-Sezawa wave are described; these include its asymmetrical line shape and variation in intensity with k∥d (the product of the surface excitation wave vector and the layer thickness), and its emergence as the Sezawa wave from the low-energy side of the Lamb shoulder at a critical value of k∥d. Furthermore, the behavior of a pronounced minimum in the Lamb shoulder near the longitudinal wave threshold observed in the experiments is reported and is found to be in good agreement with the calculated spectra. The elastic constants of the amorphous silicon layer are determined from the velocity dispersion of the Rayleigh surface acoustic wave and the minimum in the Lamb shoulder.

Uniform surface modification of diatomaceous earth with amorphous manganese oxide and its adsorption characteristics for lead ions

NASA Astrophysics Data System (ADS)

Li, Song; Li, Duanyang; Su, Fei; Ren, Yuping; Qin, Gaowu

2014-10-01

A novel method to produce composite sorbent material compromising porous diatomaceous earth (DE) and surface functionalized amorphous MnO2 is reported. Via a simple in situ redox reaction over the carbonized DE powders, a uniform layer of amorphous MnO2 was anchored onto the DE surface. The hybrid adsorbent was characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. The batch method has been employed to investigate the effects of surface coating on adsorption performance of DE. According to the equilibrium studies, the adsorption capacity of DE for adsorbing lead ions after MnO2 modification increased more than six times. And the adsorption of Pb2+ on the MnO2 surface is based on ion-exchange mechanism. The developed strategy presents a novel opportunity to prepare composite adsorbent materials by integrating nanocrystals with porous matrix.

Ozonation of isoproturon adsorbed on silica particles under atmospheric conditions

NASA Astrophysics Data System (ADS)

Pflieger, Maryline; Grgić, Irena; Kitanovski, Zoran

2012-12-01

The results on heterogeneous ozonation of a phenylurea pesticide, isoproturon, under atmospheric conditions are presented for the first time in the present study. The study was carried out using an experimental device previously adopted and validated for the heterogeneous reactivity of organics toward ozone (Pflieger et al., 2011). Isoproturon was adsorbed on silica particles via a liquid-to-solid equilibrium with a load far below a monolayer (0.02% by weight/surface coverage of 0.5%). The rate constants were estimated by measuring the consumption of the organic (dark, T = 26 °C, RH < 1%). The experimental data were fitted by both the modified Langmuir-Hinshelwood and the Eley-Rideal patterns, resulting in atmospheric lifetimes of heterogeneous ozonation of 4 and 6 days, respectively (for 40 ppb of O3). Parameters, such as the number and the quantity of pesticides adsorbed on the solid support, which can significantly influence the heterogeneous kinetics, were investigated as well. The results obtained suggest that the organic compound is adsorbed in multilayer aggregates on the aerosol even though submonolayer coverage is assumed. The presence of a second herbicide, trifluralin, together with isoproturon on the aerosol surface does not affect the kinetics of ozonation, indicating that both compounds are adsorbed on different surface sites of silica particles.

Positional ordering of hard adsorbate particles in tubular nanopores

NASA Astrophysics Data System (ADS)

Gurin, Péter; Varga, Szabolcs; Martínez-Ratón, Yuri; Velasco, Enrique

2018-05-01

The phase behavior and structural properties of a monolayer of hard particles is examined in such a confinement where the adsorbed particles are constrained to the surface of a narrow hard cylindrical pore. The diameter of the pore is chosen such that only first- and second-neighbor interactions occur between the hard particles. The transfer operator method of [Percus and Zhang, Mol. Phys. 69, 347 (1990), 10.1080/00268979000100241] is reformulated to obtain information about the structure of the monolayer. We have found that a true phase transition is not possible in the examined range of pore diameters. The monolayer of hard spheres undergoes a structural change from fluidlike order to a zigzaglike solid one with increasing surface density. The case of hard cylinders is different in the sense that a layering takes place continuously between a low-density one-row and a high-density two-row monolayer. Our results reveal a clear discrepancy with classical density functional theories, which do not distinguish smecticlike ordering in bulk from that in narrow periodic pores.

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.

Discovery of Cellulose Surface Layer Conformation by Nonlinear Vibrational Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2017-03-14

Significant questions remain with respect to the structure and polymorphs of cellulose. These include the cellulose surface layers and the bulk crystalline core as well as the conformational differences. The Total Internal Reflection Sum Frequency Generation Vibrational Spectroscopy (TIR-SFG-VS) combined with the conventional SFG-VS (non-TIR) can help to resolve these questions by selectively characterizing the molecular structures of surface layers and the crystalline core of cellulose. 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 structuralmore » and spectroscopic signatures than that of its crystalline core. This work demonstrates the capacity of TIR and Non-TIR SFG-VS tools in selectively studying the structures and polymorphs of cellulose. In addition, these results also suggest that the assignments of major vibrational peaks for cellulose need to be further determined.« less

A model of the planetary boundary layer over a snow surface

NASA Technical Reports Server (NTRS)

Halberstam, I.; Melendez, R.

1979-01-01

A model of the planetary boundary layer over a snow surface has been developed. It contains the vertical heat exchange processes due to radiation, conduction, and atmospheric turbulence. Parametrization of the boundary layer is based on similarity functions developed by Hoffert and Sud (1976), which involve a dimensionless variable, dependent on boundary-layer height and a localized Monin-Obukhov length. The model also contains the atmospheric surface layer and the snowpack itself, where snowmelt and snow evaporation are calculated. The results indicate a strong dependence of surface temperatures, especially at night, on the bursts of turbulence which result from the frictional damping of surface-layer winds during periods of high stability, as described by Businger (1973). The model also shows the cooling and drying effect of the snow on the atmosphere, which may be the mechanism for air mass transformation in sub-Arctic regions.

Surface Modification Enhanced Reflection Intensity of Quartz Crystal Microbalance Sensors upon Molecular Adsorption.

PubMed

Kojima, Taisuke

2018-01-01

Molecular adsorption on a sensing surface involves molecule-substrate and molecule-molecule interactions. Combining optical systems and a quartz crystal microbalance (QCM) on the same sensing surface allows the quantification of such interactions and reveals the physicochemical properties of the adsorbed molecules. However, low sensitivity of the current reflection-based techniques compared to the QCM technique hinders the quantitative analysis of the adsorption events. Here, a layer-by-layer surface modification of a QCM sensor is studied to increase the optical sensitivity. The intermediate layers of organic-inorganic molecules and metal-metal oxide were explored on a gold (Au) surface of a QCM sensor. First, polyhedral oligomeric silsesquioxane-derivatives that served as the organic-inorganic intermediate layer were synthesized and modified on the Au-QCM surface. Meanwhile, titanium oxide, fabricated by anodic oxidation of titanium, was used as a metal-metal oxide intermediate layer on a titanium-coated QCM surface. The developed technique enabled interrogation of the molecular adsorption owing to the enhanced optical sensitivity.

Evaluation of Adsorption Characteristics of a Fibrous Adsorbent Containing Zwitter-Ionic Functional Group, Targeting Organic Acids.

PubMed

Nakazawa, Akira; Tang, Ning; Inoue, Yoshinori; Kamichatani, Waka; Katoh, Toshifumi; Saito, Mitsuru; Obara, Kenji; Toriba, Akira; Hayakawa, Kazuichi

2017-01-01

Diallylamine-maleic acid copolymer (DAM)-nonwoven fabric (DAM-f), a fibrous adsorbent, contains DAM with zwitter-ionic functional groups and forms a hydration layer on the surface. The aim of this report was to evaluate the adsorption selectivity of DAM-f to semi-volatile organic acid (C1-C5). In the aqueous phase, formic acid dissolved in the hydration layer bound to the imino group of DAM-f due to anion exchange interaction. In the gas phase, the adsorption amounts of organic acids increased with the exposure time. Moreover, the adsorption rate constants correlated with the air/water partition coefficients (log K aw ) for formic acid, propionic acid, butyric acid, valeric acid and isovaleric acid, except for acetic acid. These results indicate that DAM-f is highly selective to hydrophilic compounds which easily move from the air to the hydration layer of DAM-f.

A diffuse reflectance infrared Fourier transform spectroscopic study of adsorbed hydrazines

NASA Technical Reports Server (NTRS)

Davis, Dennis D.; Kilduff, Jan E.; Koontz, Steven L.

1988-01-01

Diffuse reflectance spectroscopy of fuel hydrazines adsorbed on silica, silica-alumina and alimina surfaces indicates that the primary surface-hydrazine interaction is hydrogen bonding. Hydrazine, on adsorption to a deuterated silica surface, undergoes a rapid H/D exchange with deuterated surface silanol (Si-OD) groups. Adsorption equilibria are rapidly established at room temperature. Monomethylhydrazine and unsymmetrical dimethylhydrazine are similarly adsorbed. On adsorption, the C-H stretching and methyl deformation modes of the methylhydrazines are shifted to higher frequencies by 10 to 20 cm(-1). These shifts are postulated to be due to changes in the lone-pair electro-density on the adjacent nitrogen atom and an electronegativity effect.

Phase properties of elastic waves in systems constituted of adsorbed diatomic molecules on the (001) surface of a simple cubic crystal

NASA Astrophysics Data System (ADS)

Deymier, P. A.; Runge, K.

2018-03-01

A Green's function-based numerical method is developed to calculate the phase of scattered elastic waves in a harmonic model of diatomic molecules adsorbed on the (001) surface of a simple cubic crystal. The phase properties of scattered waves depend on the configuration of the molecules. The configurations of adsorbed molecules on the crystal surface such as parallel chain-like arrays coupled via kinks are used to demonstrate not only linear but also non-linear dependency of the phase on the number of kinks along the chains. Non-linear behavior arises for scattered waves with frequencies in the vicinity of a diatomic molecule resonance. In the non-linear regime, the variation in phase with the number of kinks is formulated mathematically as unitary matrix operations leading to an analogy between phase-based elastic unitary operations and quantum gates. The advantage of elastic based unitary operations is that they are easily realizable physically and measurable.

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

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.

Characteristics of the Martian atmosphere surface layer

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

The structural and electronic properties of metal atoms adsorbed on graphene

NASA Astrophysics Data System (ADS)

Liu, Wenjiang; Zhang, Cheng; Deng, Mingsen; Cai, Shaohong

2017-09-01

Based on density functional theory (DFT), we studied the structural and electronic properties of seven different metal atoms adsorbed on graphene (M + graphene). The geometries, adsorption energies, density of states (DOS), band structures, electronic dipole moment, magnetic moment and work function (WF) of M + graphene were calculated. The adsorption energies ΔE indicated that Li, Na, K, Ca and Fe adsorbed on graphene were tending to form stable structures. However, diffusion would occur on Cu and Ag adsorbed on graphene. In addition, the electronic structure near the Fermi level of graphene was significantly affected by Fe (Cu and Ag), compared with Li (Na, K and Ca). The electronic dipole moment and magnetic moment of M + graphene were sensitive to the adsorbed metal atoms. Moreover, we found electropositive (electronegative) adsorption can decrease (increase) the WF of the surface. Specially, the WF of Ag + graphene and Fe + graphene would increase because surface dipole moment make a contribution to electron.

[A surface reacted layer study of titanium-zirconium alloy after dental casting].

PubMed

Zhang, Y; Guo, T; Li, Z; Li, C

2000-10-01

To investigate the influence of the mold temperature on the surface reacted layer of Ti-Zr alloy castings. Ti-Zr alloy was casted into a mold which was made of a zircon (ZrO2.SiO2) for inner coating and a phosphate-bonded material for outer investing with a casting machine (China) designed as vacuum, pressure and centrifuge. At three mold temperatures (room temperature, 300 degrees C, 600 degrees C) the Ti-Zr alloy was casted separately. The surface roughness of the castings was calculated by instrument of smooth finish (China). From the surface to the inner part the Knoop hardness and thickness in reacted layer of Ti-Zr alloy casting was measured. The structure of the surface reacted layer was analysed by SEM. Elemental analyses of the interfacial zone of the casting was made by element line scanning observation. The surface roughness of the castings was increased significantly with the mold temperature increasing. At a higher mold temperature the Knoop hardness of the reactive layer was increased. At the three mold temperature the outmost surface was very hard, and microhardness data decreased rapidly where they reached constant values. The thickness was about 85 microns for castings at room temperature and 300 degrees C, 105 microns for castings at 600 degrees C. From the SEM micrograph of the Ti-Zr alloy casting, the surface reacted layer could be divided into three different layers. The first layer was called non-structure layer, which thickness was about 10 microns for room temperature group, 20 microns for 300 degrees C and 25 microns for 600 degrees C. The second layer was characterized by coarse-grained acicular crystal, which thickness was about 50 microns for three mold temperatures. The third layer was Ti-Zr alloy. The element line scanning showed non-structure layer with higher level of element of O, Al, Si and Zr, The higher the mold temperature during casting, the deeper the Si permeating and in the second layer the element Si could also be found

`Surface-Layer' momentum fluxes in nocturnal slope flows over steep terrain

NASA Astrophysics Data System (ADS)

Oldroyd, H. J.; Pardyjak, E.; Higgins, C. W.; Parlange, M. B.

2017-12-01

A common working definition for the `surface layer' is the lowest 10% of the atmospheric boundary layer (ABL) where the turbulent fluxes are essentially constant. The latter part of this definition is a critical assumption that must hold for accurate flux estimations from land-surface models, wall models, similarity theory, flux-gradient relations and bulk transfer methods. We present cases from observed momentum fluxes in nocturnal slope flows over steep (35.5 degree), alpine terrain in Val Ferret, Switzerland that satisfy the classical definitions of the surface layer and other cases where no traditional surface layer is observed. These cases broadly fall into two distinct flow regimes occurring under clear-sky conditions: (1) buoyancy-driven, `katabatic flow', characterized by an elevated velocity maximum (katabatic jet peak) and (2) `downslope winds', for which larger-scale forcing prevents formation of a katabatic jet. Velocity profiles in downslope wind cases are quite similar to logarithmic profiles typically observed over horizontal and homogeneous terrain, and the corresponding momentum fluxes roughly resemble a constant-flux surface-layer. Contrastingly, velocity profiles in the katabatic regime exhibit a jet-like shape. This jet strongly modulates the corresponding momentum fluxes, which exhibit strong gradients over the shallow katabatic layer and usually change sign near the jet peak, where the velocity gradients also change sign. However, a counter-gradient momentum flux is frequently observed near the jet peak (and sometimes at higher levels), suggesting strong non-local turbulent transport within the katabatic jet layer. We compare our observations with katabatic flow theories and observational studies over shallow-angle slopes and use co-spectral analyses to better identify and understand the non-local transport dynamics. Finally, we show that because of the counter-gradient momentum fluxes, surface layer stability and even local stability can be

Adsorption and association of a symmetric PEO-PPO-PEO triblock copolymer on polypropylene, polyethylene, and cellulose surfaces.

PubMed

Li, Yan; Liu, Hongyi; Song, Junlong; Rojas, Orlando J; Hinestroza, Juan P

2011-07-01

The association of a symmetric polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO(19)-PPO(29)-PEO(19)) triblock copolymer adsorbed from aqueous solutions onto polypropylene (PP), polyethylene (PE), and cellulose surfaces was probed using Atomic Force Microscopy (AFM). Significant morphological differences between the polyolefin substrates (PP and PE) and the cellulose surfaces were observed after immersion of the films in the PEO(19)-PPO(29)-PEO(19) solutions. When the samples were scanned, while immersed in solutions of the triblock copolymer, it was revealed that the structures adsorbed on the polyolefin surfaces were smoothed by the adsorbed PEO(19)-PPO(29)-PEO(19). In contrast, those structures on the hydrophilic cellulose surfaces were sharpened. These observations were related to the roughness of the substrate and the energy of interaction between the surfaces and the PEO and PPO polymer segments. The interaction energy between each of the blocks and the surface was calculated using molecular dynamics simulations. It is speculated that the associative structures amply reported in aqueous solution at concentrations above the critical micelle concentration, CMC, are not necessarily preserved upon adsorption; instead, it appears that molecular arrangements of the anchor-buoy type and hemimicelles prevail. The reported data suggests that the roughness of the surface, as well as its degree of hydrophobicity, have a large influence on the nature of the resulting adsorbed layer. The reported observations are valuable in explaining the behavior of finishing additives and lubricants commonly used in textile and fiber processing, as well as the effect of the morphology of the boundary layers on friction and wear, especially in the case of symmetric triblock copolymers, which are commonly used as antifriction, antiwear additives.

Fullerene/layered antiferromagnetic reconstructed spinterface: Subsurface layer dominates molecular orbitals' spin-split and large induced magnetic moment

NASA Astrophysics Data System (ADS)

Shao, Yangfan; Pang, Rui; Pan, Hui; Shi, Xingqiang

2018-03-01

The interfaces between organic molecules and magnetic metals have gained increasing interest for both fundamental reasons and applications. Among them, the C60/layered antiferromagnetic (AFM) interfaces have been studied only for C60 bonded to the outermost ferromagnetic layer [S. L. Kawahara et al., Nano Lett. 12, 4558 (2012) and D. Li et al., Phys. Rev. B 93, 085425 (2016)]. Here, via density functional theory calculations combined with evidence from the literature, we demonstrate that C60 adsorption can reconstruct the layered-AFM Cr(001) surface at elevated annealing temperatures so that C60 bonds to both the outermost and the subsurface Cr layers in opposite spin directions. Surface reconstruction drastically changes the adsorbed molecule spintronic properties: (1) the spin-split p-d hybridization involves multi-orbitals of C60 and top two layers of Cr with opposite spin-polarization, (2) the subsurface Cr atom dominates the C60 electronic properties, and (3) the reconstruction induces a large magnetic moment of 0.58 μB in C60 as a synergistic effect of the top two Cr layers. The induced magnetic moment in C60 can be explained by the magnetic direct-exchange mechanism, which can be generalized to other C60/magnetic metal systems. Understanding these complex hybridization behaviors is a crucial step for molecular spintronic applications.

A Novel Surface Structure Consisting of Contact-active Antibacterial Upper-layer and Antifouling Sub-layer Derived from Gemini Quaternary Ammonium Salt Polyurethanes.

PubMed

He, Wei; Zhang, Yi; Li, Jiehua; Gao, Yunlong; Luo, Feng; Tan, Hong; Wang, Kunjie; Fu, Qiang

2016-08-26

Contact-active antibacterial surfaces play a vital role in preventing bacterial contamination of artificial surfaces. In the past, numerous researches have been focused on antibacterial surfaces comprising of antifouling upper-layer and antibacterial sub-layer. In this work, we demonstrate a reversed surface structure which integrate antibacterial upper-layer and antifouling sub-layer. These surfaces are prepared by simply casting gemini quaternary ammonium salt waterborne polyurethanes (GWPU) and their blends. Due to the high interfacial energy of gemini quaternary ammonium salt (GQAS), chain segments containing GQAS can accumulate at polymer/air interface to form an antibacterial upper-layer spontaneously during the film formation. Meanwhile, the soft segments composed of polyethylene glycol (PEG) formed the antifouling sub-layer. Our findings indicate that the combination of antibacterial upper-layer and antifouling sub-layer endow these surfaces strong, long-lasting antifouling and contact-active antibacterial properties, with a more than 99.99% killing efficiency against both gram-positive and gram-negative bacteria attached to them.

A Novel Surface Structure Consisting of Contact-active Antibacterial Upper-layer and Antifouling Sub-layer Derived from Gemini Quaternary Ammonium Salt Polyurethanes

PubMed Central

He, Wei; Zhang, Yi; Li, Jiehua; Gao, Yunlong; Luo, Feng; Tan, Hong; Wang, Kunjie; Fu, Qiang

2016-01-01

Contact-active antibacterial surfaces play a vital role in preventing bacterial contamination of artificial surfaces. In the past, numerous researches have been focused on antibacterial surfaces comprising of antifouling upper-layer and antibacterial sub-layer. In this work, we demonstrate a reversed surface structure which integrate antibacterial upper-layer and antifouling sub-layer. These surfaces are prepared by simply casting gemini quaternary ammonium salt waterborne polyurethanes (GWPU) and their blends. Due to the high interfacial energy of gemini quaternary ammonium salt (GQAS), chain segments containing GQAS can accumulate at polymer/air interface to form an antibacterial upper-layer spontaneously during the film formation. Meanwhile, the soft segments composed of polyethylene glycol (PEG) formed the antifouling sub-layer. Our findings indicate that the combination of antibacterial upper-layer and antifouling sub-layer endow these surfaces strong, long-lasting antifouling and contact-active antibacterial properties, with a more than 99.99% killing efficiency against both gram-positive and gram-negative bacteria attached to them. PMID:27561546

Amorphous surface layers in Ti-implanted Fe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knapp, J.A.; Follstaedt, D.M.; Picraux, S.T.

1979-01-01

Implanting Ti into high-purity Fe results in an amorphous surface layer which is composed of not only Fe and Ti, but also C. Implantations were carried out at room temperature over the energy range 90 to 190 keV and fluence range 1 to 2 x 10/sup 16/ at/cm/sup 2/. The Ti-implanted Fe system has been characterized using transmission electron microscopy (TEM), ion backscattering and channeling analysis, and (d,p) nuclear reaction analysis. The amorphous layer was observed to form at the surface and grow inward with increasing Ti fluence. For an implant of 1 x 10/sup 17/ Ti/cm/sup 2/ at 180more » keV the layer thickness was 150 A, while the measured range of the implanted Ti was approx. 550 A. This difference is due to the incorporation of C into the amorphous alloy by C being deposited on the surface during implantation and subsequently diffusing into the solid. Our results indicate that C is an essential constituent of the amorphous phase for Ti concentrations less than or equal to 10 at. %. For the 1 x 10/sup 17/ Ti/cm/sup 2/ implant, the concentration of C in the amorphous phase was approx. 25 at. %, while that of Ti was only approx. 3 at. %. A higher fluence implant of 2 x 10/sup 17/ Ti/cm/sup 2/ produced an amorphous layer with a lower C concentration of approx. 10 at. % and a Ti concentration of approx. 20 at. %.« less

One-pot preparation of silica-supported hybrid immobilized metal affinity adsorbent with macroporous surface based on surface imprinting coating technique combined with polysaccharide incorporated sol--gel process.

PubMed

Li, Feng; Li, Xue-Mei; Zhang, Shu-Sheng

2006-10-06

A simple and reliable one-pot approach using surface imprinting coating technique combined with polysaccharide incorporated sol-gel process was established to synthesize a new organic-inorganic hybrid matrix possessing macroporous surface and functional ligand. Using mesoporous silica gel being a support, immobilized metal affinity adsorbent with a macroporous shell/mesoporous core structure was obtained after metal ion loading. In the prepared matrix, covalently bonded coating and morphology manipulation on silica gel was achieved by using one-pot sol-gel process starting from an inorganic precursor, -glycidoxypropyltrimethoxysiloxane (GPTMS), and a functional biopolymer, chitosan (CS) at the atmosphere of imprinting polyethylene glycol (PEG). Self-hydrolysis of GPTMS, self-condensation, and co-condensation of silanol groups (Si-OH) from siloxane and silica gel surface, and in situ covalent cross-linking of CS created an orderly coating on silica gel surface. PEG extraction using hot ammonium hydroxide solution gave a chemically and mechanically stabilized pore structure and deactivated residual epoxy groups. The prepared matrix was characterized by using X-ray energy dispersion spectroscopy (EDX), scanning electron microscopy (SEM) and mercury intrusion porosimetry. The matrix possessed a high capacity for copper ion loading. Protein adsorption performance of the new immobilized metal affinity adsorbent was evaluated by batch adsorption and column chromatographic experiment using bovine serum albumin (BSA) as a simple model protein. Under the optimized coating conditions, the obtained macroporous surface resulted in a fast kinetics and high capability for protein adsorption, while the matrix non-charged with metal ions offered a low non-specific adsorption.

Steady Boundary Layer Disturbances Created By Two-Dimensional Surface Ripples

NASA Astrophysics Data System (ADS)

Kuester, Matthew

2017-11-01

Multiple experiments have shown that surface roughness can enhance the growth of Tollmien-Schlichting (T-S) waves in a laminar boundary layer. One of the common observations from these studies is a ``wall displacement'' effect, where the boundary layer profile shape remains relatively unchanged, but the origin of the profile pushes away from the wall. The objective of this work is to calculate the steady velocity field (including this wall displacement) of a laminar boundary layer over a surface with small, 2D surface ripples. The velocity field is a combination of a Blasius boundary layer and multiple disturbance modes, calculated using the linearized Navier-Stokes equations. The method of multiple scales is used to include non-parallel boundary layer effects of O (Rδ- 1) ; the non-parallel terms are necessary, because a wall displacement is mathematically inconsistent with a parallel boundary layer assumption. This technique is used to calculate the steady velocity field over ripples of varying height and wavelength, including cases where a separation bubble forms on the leeward side of the ripple. In future work, the steady velocity field will be the input for stability calculations, which will quantify the growth of T-S waves over rough surfaces. The author would like to acknowledge the support of the Kevin T. Crofton Aerospace & Ocean Engineering Department at Virginia Tech.

Surface morphological evolution of epitaxial CrN(001) layers

NASA Astrophysics Data System (ADS)

Frederick, J. R.; Gall, D.

2005-09-01

CrN layers, 57 and 230 nm thick, were grown on MgO(001) at Ts=600-800 °C by ultrahigh-vacuum magnetron sputter deposition in pure N2 discharges from an oblique deposition angle α=80°. Layers grown at 600 °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 °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 °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 Ts is raised from 600 to 700 to 800 °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 °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 β>0.5. In contrast, kinetic roughening controls the surface morphology for Ts=800 °C, as well as the epitaxial fraction of the layers grown at 600 and 700 °C, yielding relatively smooth surfaces and β<=0.27.

Polyethylenimine-impregnated mesoporous silica: effect of amine loading and surface alkyl chains on CO2 adsorption.

PubMed

Heydari-Gorji, Aliakbar; Belmabkhout, Youssef; Sayari, Abdelhamid

2011-10-18

Poly(ethyleneimine) (PEI) supported on pore-expanded MCM-41 whose surface is covered with a layer of long-alkyl chains was found to be a more efficient CO(2) adsorbent than PEI supported on the corresponding calcined silica and all PEI-impregnated materials reported in the literature. The layer of surface alkyl chains plays an important role in enhancing the dispersion of PEI, thus decreasing the diffusion resistance. It was also found that at low temperature, adsorbents with relatively low PEI contents are more efficient than their highly loaded counterparts because of the increased adsorption rate. Extensive CO(2) adsorption-desorption cycling showed that the use of humidified feed and purge gases affords materials with enhanced stability, despite limited loss due to amine evaporation. © 2011 American Chemical Society

Adsorption of virus-like particles on ion exchange surface: Conformational changes at different pH detected by dual polarization interferometry.

PubMed

Yang, Yanli; Mengran Yu; Zhang, Songping; Ma, Guanghui; Su, Zhiguo

2015-08-21

Disassembling of virus-like particles (VLPs) like hepatitis B virus surface antigen (HB-VLPs) during chromatographic process has been identified as a major cause of loss of antigen activity. In this study, dual polarization interferometry (DPI) measurement, together with chromatography experiments, were performed to study the adsorption and conformational change of HB-VLPs on ion exchange surface at three different pHs. Changes in pH values of buffer solution showed only minimal effect on the HB-VLPs assembly and antigen activity, while significantly different degree of HB-VLPs disassembling was observed after ion exchange chromatography (IEC) at different pHs, indicating the conformational change of HB-VLPs caused mainly by its interactions with the adsorbent surface. By creating an ion exchange surface on chip surface, the conformational changes of HB-VLPs during adsorption to the surface were monitored in real time by DPI for the first time. As pH increased from 7.0 to 9.0, strong electrostatic interactions between oppositely charged HB-VLPs and the ion exchange surface make the HB-VLPs spread thinly or even adsorbed in disassembled formation on the surface as revealed by significant decrease in thickness of the adsorbed layer measured by DPI. Such findings were consistent with the results of IEC experiments operated at different pHs, that more disassembled HB-VLPs were detected in the eluted proteins at pH 9.0. At low pH like pH 5.0, however, possible bi-layer adsorption was involved as evidenced by an adsorbed layer thickness higher than average diameter of the HB-VLPs. The "lateral" protein-protein interactions might be unfavorable and would make additional contribution to the disassembling of HB-VLPs besides the primary mechanism related to the protein-surface interactions; therefore, the lowest antigen activity was observed after IEC at pH 5.0. Such real-time information on conformational change of VLPs is helpful for better understanding the real mechanism

Surface structure and chemistry of Pt/Cu/Pt(1 1 1) near surface alloy model catalyst in CO

NASA Astrophysics Data System (ADS)

Zeng, Shibi; Nguyen, Luan; Cheng, Fang; Liu, Lacheng; Yu, Ying; Tao, Franklin (Feng)

2014-11-01

Near surface alloy (NSA) model catalyst Pt/Cu/Pt(1 1 1) was prepared on Pt(1 1 1) through a controlled vapor deposition of Cu atoms. Different coordination environments of Pt atoms of the topmost Pt layer with the underneath Cu atoms in the subsurface result in different local electronic structures of surface Pt atoms. Surface structure and chemistry of the NAS model catalyst in Torr pressure of CO were studied with high pressure scanning tunneling microscopy (HP-STM) and ambient pressure X-ray photoelectron spectroscopy (AP-XPS). In Torr pressure of CO, the topmost Pt layer of Pt/Cu/Pt(1 1 1) is restructured to thin nanoclusters with size of about 1 nm. Photoemission feature of O 1s of CO on Pt/Cu/Pt(1 1 1) suggests CO adsorbed on both edge and surface of these formed nanoclusters. This surface is active for CO oxidation. Atomic layers of carbon are formed on Pt/Cu/Pt(1 1 1) at 573 K in 2 Torr of CO.

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.

Enhanced magneto-optical imaging of internal stresses in the removed surface layer

NASA Astrophysics Data System (ADS)

Agalidi, Yuriy; Kozhukhar, Pavlo; Levyi, Sergii; Turbin, Dmitriy

2015-10-01

The paper describes a software method of reconstructing the state of the removed surface layer by visualising internal stresses in the underlying layers of the sample. Such a problem typically needs to be solved as part of forensic investigation that aims to reveal original marking of a sample with removed surface layer. For example, one may be interested in serial numbers of weapons or vehicles that had the surface layer of metal removed from the number plate. Experimental results of studying gradient internal stress fields in ferromagnetic sample using the NDI method of magneto-optical imaging (MOI) are presented. Numerical modelling results of internal stresses enclosed in the surface marking region are analysed and compared to the experimental results of magneto-optical imaging (MOI). MOI correction algorithm intended for reconstructing internal stress fields in the removed surface layer by extracting stresses retained by the underlying layers is described. Limiting ratios between parameters of a marking font are defined for the considered correction algorithm. Enhanced recognition properties for hidden stresses left by marking symbols are experimentally verified and confirmed.

Development of porous structured polyvinyl alcohol/zeolite/carbon composites as adsorbent

NASA Astrophysics Data System (ADS)

Laksmono, J. A.; Sudibandriyo, M.; Saputra, A. H.; Haryono, A.

2017-05-01

Adsorption is a separation process that has higher energy efficiency than others. Analyzing the nature of the adsorbate and the selection of suitable adsorbent are key success in adsorption. The performance of the adsorbent can be modified either physically or chemically to obtain the efficiency and effectiveness of the adsorption, this can be facilitated by using a composite adsorbent. In this study, we have conducted the preparation process of a polyvinyl alcohol (PVA)/zeolite/carbon composites. The resulting adsorbent composites are dedicated for ethanol - water dehydration proposes. The composites were prepared using cross-linked polymerization method followed by supercritical fluid extraction (SFE) to obtain the porous structured upon drying process. The characterization of the functional groups and morphology were performed by using Fourier Transform Infra-Red (FTIR) and Scanning Electron Microscopy (SEM), respectively. The FTIR analysis showed that composite prepared by SFE method formed hydrogen bonding confirmed by the appearance of peaks at 2950 - 3000 cm-1 compared to composite without SFE method, whereas, the results of SEM study showed the formation of three layered structures. On basis of the obtained results, it can be shown that PVA/zeolite/carbon has high potential to be develop further as an adsorbent composite.

Computer graphic visualization of orbiter lower surface boundary-layer transition

NASA Technical Reports Server (NTRS)

Throckmorton, D. A.; Hartung, L. C.

1984-01-01

Computer graphic techniques are applied to the processing of Shuttle Orbiter flight data in order to create a visual presentation of the extent and movement of the boundary-layer transition front over the orbiter lower surface during entry. Flight-measured surface temperature-time histories define the onset and completion of the boundary-layer transition process at any measurement location. The locus of points which define the spatial position of the boundary-layer transition front on the orbiter planform is plotted at each discrete time for which flight data are available. Displaying these images sequentially in real-time results in an animated simulation of the in-flight boundary-layer transition process.

Generation Mechanism of Work Hardened Surface Layer in Metal Cutting

NASA Astrophysics Data System (ADS)

Hikiji, Rikio; Kondo, Eiji; Kawagoishi, Norio; Arai, Minoru

Finish machining used to be carried out in grinding, but it is being replaced by cutting with very small undeformed chip thickness. In ultra precision process, the effects of the cutting conditions and the complicated factors on the machined surface integrity are the serious problems. In this research, work hardened surface layer was dealt with as an evaluation of the machined surface integrity and the effect of the mechanical factors on work hardening was investigated experimentally in orthogonal cutting. As a result, it was found that work hardened surface layer was affected not only by the shear angle varied under the cutting conditions and the thrust force of cutting resistance, but also by the thrust force acting point, the coefficient of the thrust force and the compressive stress equivalent to the bulk hardness. Furthermore, these mechanical factors acting on the depth of the work hardened surface layer were investigated with the calculation model.

Surface rheology of saponin adsorption layers.

PubMed

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

2011-10-18

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

Orientation-dependent hydration structures at yttria-stabilized cubic zirconia surfaces

DOE PAGES

Hou, Binyang; Kim, Seunghyun; Kim, Taeho; ...

2016-11-30

Water interaction with surfaces is very important and plays key roles in many natural and technological processes. Because the experimental challenges that arise when studying the interaction water with specific crystalline surfaces, most studies on metal oxides have focused on powder samples, which averaged the interaction over different crystalline surfaces. As a result, studies on the crystal orientation-dependent interaction of water with metal oxides are rarely available in the literature. In this work, water adsorption at 8 mol % yttria-stabilized cubic single crystal zirconia (100) and (111) surfaces was studied in terms of interfacial hydration structures using high resolution X-raymore » reflectivity measurements. The interfacial electron density profiles derived from the structure factor analysis of the measured data show the existence of multiple layers of adsorbed water with additional peculiar metal adsorption near the oxide surfaces.Surface relaxation, depletion, and interaction between the adsorbed layers and bulk water are found to vary greatly between the two surfaces and are also different when compared to the previously studied (110) surface. The fractional ratio between chemisorbed and physisorbed water species were also quantitatively estimated, which turned out to vary dramatically from surface to surface. Finally, the result gives us a unique opportunity to reconsider the simplified 2:1 relation between chemisorption and physisorption, originally proposed by Morimoto et al. based on the adsorption isotherms of water on powder metal oxide samples.« less

Adsorbed molecules in external fields: Effect of confining potential

NASA Astrophysics Data System (ADS)

Tyagi, Ashish; Silotia, Poonam; Maan, Anjali; Prasad, Vinod

2016-12-01

We study the rotational excitation of a molecule adsorbed on a surface. As is well known the interaction potential between the surface and the molecule can be modeled in number of ways, depending on the molecular structure and the geometry under which the molecule is being adsorbed by the surface. We explore the effect of change of confining potential on the excitation, which is largely controlled by the static electric fields and continuous wave laser fields. We focus on dipolar molecules and hence we restrict ourselves to the first order interaction in field-molecule interaction potential either through permanent dipole moment or/and the molecular polarizability parameter. It is shown that confining potential shapes, strength of the confinement, strongly affect the excitation. We compare our results for different confining potentials.

Layer-by-Layer Heparinization of the Cell Surface by Using Heparin-Binding Peptide Functionalized Human Serum Albumin.

PubMed

Song, Guowei; Hu, Yaning; Liu, Yusheng; Jiang, Rui

2018-05-20

Layer-by-layer heparinization of therapeutic cells prior to transplantation is an effective way to inhibit the instant blood-mediated inflammatory reactions (IBMIRs), which are the major cause of early cell graft loss during post-transplantation. Here, a conjugate of heparin-binding peptide (HBP) and human serum albumin (HSA), HBP-HSA, was synthesized by using heterobifunctional crosslinker. After the first heparin layer was coated on human umbilical vein endothelial cells (HUVECs) by means of the HBP-polyethylene glycol-phospholipid conjugate, HBP-HSA and heparin were then applied to the cell surface sequentially to form multiple layers. The immobilization and retention of heparin were analyzed by confocal microscopy and flow cytometry, respectively, and the cytotoxity of HBP-HSA was further evaluated by cell viability assay. Results indicated that heparin was successfully introduced to the cell surface in a layer-by-layer way and retained for at least 24 h, while the cytotoxity of HBP-HSA was negligible at the working concentration. Accordingly, this conjugate provides a promising method for co-immobilization of heparin and HSA to the cell surface under physiological conditions with improved biocompatibility.

Non-linear boundary-layer receptivity due to distributed surface roughness

NASA Technical Reports Server (NTRS)

Amer, Tahani Reffet

1995-01-01

The process by which a laminar boundary layer internalizes the external disturbances in the form of instability waves is known as boundary-layer receptivity. The objective of the present research was to determine the effect of acoustic excitation on boundary-layer receptivity for a flat plate with distributed variable-amplitude surface roughness through measurements with a hot-wire probe. Tollmien-Schlichting mode shapes due to surface roughness receptivity have also been determined, analyzed, and shown to be in agreement with theory and other experimental work. It has been shown that there is a linear relationship between the surface roughness and receptivity for certain roughness configurations with constant roughness wavelength. In addition, strong non-linear receptivity effects exist for certain surface roughness configurations over a band where the surface roughness and T-S wavelength are matched. The results from the present experiment follow the trends predicted by theory and other experimental work for linear receptivity. In addition, the results show the existence of non-linear receptivity effects for certain combinations of surface roughness elements.

Trapping gases in metal-organic frameworks with a selective surface molecular barrier layer

DOE PAGES

Tan, Kui; Zuluaga, Sebastian; Fuentes, Erika; ...

2016-12-13

The main challenge for gas storage and separation in nanoporous materials is that many molecules of interest adsorb too weakly to be effectively retained. Instead of synthetically modifying the internal surface structure of the entire bulk—as is typically done to enhance adsorption—here we show that post exposure of a prototypical porous metal-organic framework to ethylenediamine can effectively retain a variety of weakly adsorbing molecules (for example, CO, CO 2, SO 2, C 2H 4, NO) inside the materials by forming a monolayer-thick cap at the external surface of microcrystals. Furthermore, this capping mechanism, based on hydrogen bonding as explained bymore » ab initio modelling, opens the door for potential selectivity. For example, water molecules are shown to disrupt the hydrogen-bonded amine network and diffuse through the cap without hindrance and fully displace/release the retained small molecules out of the metal-organic framework at room temperature. Lastly, these findings may provide alternative strategies for gas storage, delivery and separation.« less

Virtual ellipsometry on layered micro-facet surfaces.

PubMed

Wang, Chi; Wilkie, Alexander; Harcuba, Petr; Novosad, Lukas

2017-09-18

Microfacet-based BRDF models are a common tool to describe light scattering from glossy surfaces. Apart from their wide-ranging applications in optics, such models also play a significant role in computer graphics for photorealistic rendering purposes. In this paper, we mainly investigate the computer graphics aspect of this technology, and present a polarisation-aware brute force simulation of light interaction with both single and multiple layered micro-facet surfaces. Such surface models are commonly used in computer graphics, but the resulting BRDF is ultimately often only approximated. Recently, there has been work to try to make these approximations more accurate, and to better understand the behaviour of existing analytical models. However, these brute force verification attempts still emitted the polarisation state of light and, as we found out, this renders them prone to mis-estimating the shape of the resulting BRDF lobe for some particular material types, such as smooth layered dielectric surfaces. For these materials, non-polarising computations can mis-estimate some areas of the resulting BRDF shape by up to 23%. But we also identified some other material types, such as dielectric layers over rough conductors, for which the difference turned out to be almost negligible. The main contribution of our work is to clearly demonstrate that the effect of polarisation is important for accurate simulation of certain material types, and that there are also other common materials for which it can apparently be ignored. As this required a BRDF simulator that we could rely on, a secondary contribution is that we went to considerable lengths to validate our software. We compare it against a state-of-art model from graphics, a library from optics, and also against ellipsometric measurements of real surface samples.

Streaming current for particle-covered surfaces: simulations and experiments

NASA Astrophysics Data System (ADS)

Blawzdziewicz, Jerzy; Adamczyk, Zbigniew; Ekiel-Jezewska, Maria L.

2017-11-01

Developing in situ methods for assessment of surface coverage by adsorbed nanoparticles is crucial for numerous technological processes, including controlling protein deposition and fabricating diverse microstructured materials (e.g., antibacterial coatings, catalytic surfaces, and particle-based optical systems). For charged surfaces and particles, promising techniques for evaluating surface coverage are based on measurements of the electrokinetic streaming current associated with ion convection in the double-layer region. We have investigated the dependence of the streaming current on the area fraction of adsorbed particles for equilibrium and random-sequential-adsorption (RSA) distributions of spherical particles, and for periodic square and hexagonal sphere arrays. The RSA results have been verified experimentally. Our numerical results indicate that the streaming current weakly depends on the microstructure of the particle monolayer. Combining simulations with the virial expansion, we provide convenient fitting formulas for the particle and surface contributions to the streaming current as functions of area fractions. For particles that have the same ζ-potential as the surface, we find that surface roughness reduces the streaming current. Supported by NSF Award No. 1603627.

Limiting diffusion current at rotating disk electrode with dense particle layer.

PubMed

Weroński, P; Nosek, M; Batys, P

2013-09-28

Exploiting the concept of diffusion permeability of multilayer gel membrane and porous multilayer we have derived a simple analytical equation for the limiting diffusion current at rotating disk electrode (RDE) covered by a thin layer with variable tortuosity and porosity, under the assumption of negligible convection in the porous film. The variation of limiting diffusion current with the porosity and tortuosity of the film can be described in terms of the equivalent thickness of stagnant solution layer, i.e., the average ratio of squared tortuosity to porosity. In case of monolayer of monodisperse spherical particles, the equivalent layer thickness is an algebraic function of the surface coverage. Thus, by means of cyclic voltammetry of RDE with a deposited particle monolayer we can determine the monolayer surface coverage. The effect of particle layer adsorbed on the surface of RDE increases non-linearly with surface coverage. We have tested our theoretical results experimentally by means of cyclic voltammetry measurements of limiting diffusion current at the glassy carbon RDE covered with a monolayer of 3 μm silica particles. The theoretical and experimental results are in a good agreement at the surface coverage higher than 0.7. This result suggests that convection in a monolayer of 3 μm monodisperse spherical particles is negligibly small, in the context of the coverage determination, in the range of very dense particle layers.

Stormwater infiltration and surface runoff pollution reduction performance of permeable pavement layers.

PubMed

Niu, Zhi-Guang; Lv, Zhi-Wei; Zhang, Ying; Cui, Zhen-Zhen

2016-02-01

In this paper, the laboratory-scale permeable pavement layers, including a surface permeable brick layer, coarse sand bedding layers (thicknesses = 2, 3.5, and 5 cm), and single-graded gravel sub-base layers (thicknesses = 15, 20, 25, and 30 cm), were built to evaluate stormwater infiltration and surface runoff pollution reduction performance. And, the infiltration rate (I) and concentrations of suspended solids (SS), total phosphorus (TP), chemical oxygen demand (COD), ammonia nitrogen, and total nitrogen (TN) were measured under the simulated rainfall intensity of 72.4 mm/h over duration of 60 min. The results indicate that the thickness factor primarily influences the infiltration rate and pollutant removal rate. The highest steady infiltration rate was for surface brick layer 51.0 mm/h, for 5-cm sand bedding layer 32.3 mm/h, and for 30-cm gravel sub-base layer 42.3 mm/h, respectively. The SS average removal rate was relative higher (79.8 ∼ 98.6 %) for all layers due to the interception and filtration. The average removal rates of TP and COD were for surface layer 71.2 and 24.1 %, for 5-cm bedding layer 54.8 and 9.0 %, and for 20-cm sub-base layer 72.2 and 26.1 %. Ammonia nitrogen and TN cannot steadily be removed by layers according to the experiment results. The optimal thickness of bedding sands was 5 cm, and that of sub-base gravels was 20 ∼ 30 cm.

Magnetomechanical effect in silicon (Cz-Si) surface layers

NASA Astrophysics Data System (ADS)

Koplak, O. V.; Dmitriev, A. I.; Morgunov, R. B.

2012-07-01

The mechanical properties of near-surface layers of Czochralski-grown silicon crystals Cz- n-Si(111) have been found to undergo changes in response to an external constant magnetic field ( B ˜ 0.1 T). A magnetically induced variation in the microhardness, Young's modulus, and coefficient of plasticity of silicon crystals correlates with the change in the lattice parameter and internal stresses of the sample. The growth of an oxide film under exposure to a magnetic field plays the principal role in the magnetomechanical effect due to a decrease in the concentration of oxygen complexes in the near-surface layers of the sample. In microstructured silicon, where the surface is considerably more developed, the magnetic field induces more profound changes in the internal stresses as compared to single crystals.

Displacement energy of the surface layers of tungsten

NASA Astrophysics Data System (ADS)

Han, Longtao; Krstic, Predrag

2015-11-01

A molecular dynamics study with BOP potential is used to calculate the threshold displacement energy (ED) of primary knock-on atoms in the surface layers of the tungsten bcc crystal lattice at 300 K and at various crystallographic directions. Depending on the direction, ED is 10% to 75% smaller from the bulk value at the first layer, interfacing vacuum, while it reaches close to the bulk value already at the third tungsten layer. Supported by IACS of SBU and LDRD of PPPL.

Powder-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

DOEpatents

Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

2016-05-03

A powder-based adsorbent and a related method of manufacture are provided. The powder-based adsorbent includes polymer powder with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the powder-based adsorbent includes irradiating polymer powder, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Powder-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

Foam-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

DOEpatents

Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

2015-06-02

Foam-based adsorbents and a related method of manufacture are provided. The foam-based adsorbents include polymer foam with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the foam-based adsorbents includes irradiating polymer foam, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Foam-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

First principles study of the atomic layer deposition of alumina by TMA-H2O-process.

PubMed

Weckman, Timo; Laasonen, Kari

2015-07-14

Atomic layer deposition (ALD) is a coating technology used to produce highly uniform thin films. Aluminiumoxide, Al2O3, is mainly deposited using trimethylaluminium (TMA) and water as precursors and is the most studied ALD-process to date. However, only few theoretical studies have been reported in the literature. The surface reaction mechanisms and energetics previously reported focus on a gibbsite-like surface model but a more realistic description of the surface can be achieved when the hydroxylation of the surface is taken into account using dissociatively adsorbed water molecules. The adsorbed water changes the structure of the surface and reaction energetics change considerably when compared to previously studied surface model. Here we have studied the TMA-H2O process using density functional theory on a hydroxylated alumina surface and reproduced the previous results for comparison. Mechanisms and energetics during both the TMA and the subsequent water pulse are presented. TMA is found to adsorb exothermically onto the surface. The reaction barriers for the ligand-exchange reactions between the TMA and the surface hydroxyl groups were found to be much lower compared to previously presented results. TMA dissociation on the surface is predicted to saturate at monomethylaluminium. Barriers for proton diffusion between surface sites are observed to be low. TMA adsorption was also found to be cooperative with the formation of methyl bridges between the adsorbants. The water pulse was studied using single water molecules reacting with the DMA and MMA surface species. Barriers for these reactions were found to reasonable in the process conditions. However, stabilizing interactions amongst water molecules were found to lower the reaction barriers and the dynamical nature of water is predicted to be of importance. It is expected that these calculations can only set an upper limit for the barriers during the water pulse.

Near Surface Vapor Bubble Layers in Buoyant Low Stretch Burning of Polymethylmethacrylate

NASA Technical Reports Server (NTRS)

Olson, Sandra L.; Tien, J. S.

1999-01-01

Large-scale buoyant low stretch stagnation point diffusion flames over solid fuel (polymethylmethacrylate) were studied for a range of aerodynamic stretch rates of 2-12/ sec which are of the same order as spacecraft ventilation-induced stretch in a microgravity environment. An extensive layer of polymer material above the glass transition temperature is observed. Unique phenomena associated with this extensive glass layer included substantial swelling of the burning surface, in-depth bubble formation, and migration and/or elongation of the bubbles normal to the hot surface. The bubble layer acted to insulate the polymer surface by reducing the effective conductivity of the solid. The reduced in-depth conduction stabilized the flame for longer than expected from theory neglecting the bubble layer. While buoyancy acts to move the bubbles deeper into the molten polymer, thermocapillary forces and surface regression both act to bring the bubbles to the burning surface. Bubble layers may thus be very important in low gravity (low stretch) burning of materials. As bubbles reached the burning surface, monomer fuel vapors jetted from the surface, enhancing burning by entraining ambient air flow. Popping of these bubbles at the surface can expel burning droplets of the molten material, which may increase the fire propagation hazards at low stretch rates.

Redox Transformations of As and Se at the Surfaces of Natural and Synthetic Ferric Nontronites: Role of Structural and Adsorbed Fe(II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ilgen, Anastasia G.; Kruichak, Jessica N.; Artyushkova, Kateryna

Adsorption and redox transformations on clay mineral surfaces are prevalent in surface environments. We examined the redox reactivity of iron Fe(II)/Fe(III) associated with natural and synthetic ferric nontronites. Specifically, we assessed how Fe(II) residing in the octahedral sheets, or Fe(II) adsorbed at the edge sites alters redox activity of nontronites. To probe the redox activity we used arsenic (As) and selenium (Se). Activation of both synthetic and natural ferric nontronites was. observed following the introduction of Fe(II) into predominantly-Fe(III) octahedral sheets or through the adsorption of Fe(II) onto the mineral surface. The oxidation of As(III) to As(V) was observed viamore » catalytic (oxic conditions) and, to a lesser degree, via direct (anoxic conditions) pathways. We provide experimental evidence for electron transfer from As(III) to Fe(111) at the natural and synthetic nontronite surfaces, and illustrate that only a fraction of structural Fe(III) is accessible for redox transformations. We show that As adsorbed onto natural and synthetic nontronites forms identical adsorption complexes, namely inner-sphere binuclear bidentate. In conclusion, we show that the formation of an inner-sphere adsorption complex may be a necessary step for the redox transformation via catalytic or direct oxidation pathways.« less

Redox Transformations of As and Se at the Surfaces of Natural and Synthetic Ferric Nontronites: Role of Structural and Adsorbed Fe(II)

DOE PAGES

Ilgen, Anastasia G.; Kruichak, Jessica N.; Artyushkova, Kateryna; ...

2017-08-29

Adsorption and redox transformations on clay mineral surfaces are prevalent in surface environments. We examined the redox reactivity of iron Fe(II)/Fe(III) associated with natural and synthetic ferric nontronites. Specifically, we assessed how Fe(II) residing in the octahedral sheets, or Fe(II) adsorbed at the edge sites alters redox activity of nontronites. To probe the redox activity we used arsenic (As) and selenium (Se). Activation of both synthetic and natural ferric nontronites was. observed following the introduction of Fe(II) into predominantly-Fe(III) octahedral sheets or through the adsorption of Fe(II) onto the mineral surface. The oxidation of As(III) to As(V) was observed viamore » catalytic (oxic conditions) and, to a lesser degree, via direct (anoxic conditions) pathways. We provide experimental evidence for electron transfer from As(III) to Fe(111) at the natural and synthetic nontronite surfaces, and illustrate that only a fraction of structural Fe(III) is accessible for redox transformations. We show that As adsorbed onto natural and synthetic nontronites forms identical adsorption complexes, namely inner-sphere binuclear bidentate. In conclusion, we show that the formation of an inner-sphere adsorption complex may be a necessary step for the redox transformation via catalytic or direct oxidation pathways.« less

Optical Imaging and Spectroscopic Characterization of Self-Assembled Environmental Adsorbates on Graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gallagher, Patrick; Li, Yilei; Watanabe, Kenji

Topographic studies using scanning probes have found that graphene surfaces are often covered by micron-scale domains of periodic stripes with a 4 nm pitch. These stripes have been variously interpreted as structural ripples or as self-assembled adsorbates. We show that the stripe domains are optically anisotropic by imaging them using a polarization-contrast technique. Optical spectra between 1.1 and 2.8 eV reveal that the anisotropy in the in-plane dielectric function is predominantly real, reaching 0.6 for an assumed layer thickness of 0.3 nm. Furthermore, the spectra are incompatible with a rippled graphene sheet but would be quantitatively explained by the self-assemblymore » of chainlike organic molecules into nanoscale stripes.« less

Optical Imaging and Spectroscopic Characterization of Self-Assembled Environmental Adsorbates on Graphene

DOE PAGES

Gallagher, Patrick; Li, Yilei; Watanabe, Kenji; ...

2018-03-28

Topographic studies using scanning probes have found that graphene surfaces are often covered by micron-scale domains of periodic stripes with a 4 nm pitch. These stripes have been variously interpreted as structural ripples or as self-assembled adsorbates. We show that the stripe domains are optically anisotropic by imaging them using a polarization-contrast technique. Optical spectra between 1.1 and 2.8 eV reveal that the anisotropy in the in-plane dielectric function is predominantly real, reaching 0.6 for an assumed layer thickness of 0.3 nm. Furthermore, the spectra are incompatible with a rippled graphene sheet but would be quantitatively explained by the self-assemblymore » of chainlike organic molecules into nanoscale stripes.« less

The influence of adsorbent microstructure upon adsorption equilibria: Investigations of a model system

NASA Astrophysics Data System (ADS)

Kaminsky, R. D.; Monson, P. A.

1991-08-01

We present a theoretical study of the influence of the microstructure of a porous adsorbent upon associated adsorption behavior. A model is developed which describes the interactions of adsorbed molecules with an adsorbent treated as a matrix of particles each of which is a continuum of interaction centers. The model leads to an analytic expression for the adsorbate-adsorbent particle potential which is an analog of the 9-3 potential model for adsorption on planar solid surfaces. To illustrate the utility of the approach, an application to methane adsorbed in a microporous silica gel is presented. Several adsorbent microstructures are investigated, including a variety of crystal lattices as well as structures derived from equilibrium configurations of hard spheres. Adsorption in these structures is studied through calculation of Henry's law constants and by using grand canonical Monte Carlo simulation to determine adsorption isotherms and the structure of adsorbed fluids. The results obtained are related to details of the adsorbent microstructure.

Adsorption of water at the SrO surface of ruthenates

NASA Astrophysics Data System (ADS)

Halwidl, Daniel; Stöger, Bernhard; Mayr-Schmölzer, Wernfried; Pavelec, Jiri; Fobes, David; Peng, Jin; Mao, Zhiqiang; Parkinson, Gareth S.; Schmid, Michael; Mittendorfer, Florian; Redinger, Josef; Diebold, Ulrike

2016-04-01

Although perovskite oxides hold promise in applications ranging from solid oxide fuel cells to catalysts, their surface chemistry is poorly understood at the molecular level. Here we follow the formation of the first monolayer of water at the (001) surfaces of Srn+1RunO3n+1 (n = 1, 2) using low-temperature scanning tunnelling microscopy, X-ray photoelectron spectroscopy, and density functional theory. These layered perovskites cleave between neighbouring SrO planes, yielding almost ideal, rocksalt-like surfaces. An adsorbed monomer dissociates and forms a pair of hydroxide ions. The OH stemming from the original molecule stays trapped at Sr-Sr bridge positions, circling the surface OH with a measured activation energy of 187 +/- 10 meV. At higher coverage, dimers of dissociated water assemble into one-dimensional chains and form a percolating network where water adsorbs molecularly in the gaps. Our work shows the limitations of applying surface chemistry concepts derived for binary rocksalt oxides to perovskites.

Characteristics of Microactive Carbon from Bamboo Var. Petung as Adsorbent

NASA Astrophysics Data System (ADS)

Wirawan, I. P. S.; Sutrisno; Seminar, K. B.; Nelwan, L. O.

2018-05-01

Bamboo has unique characteristics, such as in the carbonization process at a temperature of 500°C, the carbon characteristics is homogeneous. The characteristics of bamboo have great potential as a future bio-energy resource. Apart from being a bio-energy source of bamboo can also be used as an adsorbent material in the form of activated carbon. Activated carbon is the most inexpensive and easy to produce adsorbent material. One of the activated carbons of bamboo materials used is the micro-active carbon from bamboo. Microactivated carbon bamboo has a pore structure which is good for adsorption because of its surface area being much better than the other adsorbent, mainly on mesopore and micropore pore size. The purpose of this research is to make micro-activated carbon adsorbent bamboo var. petungand to analyze their characteristics. The characteristic of microactivecarbon was analyzed by SEM EDS and Iod number. The result showed a variation in pore size from 1μm to 11.157μm. The surface area of micro-active carbon of 200 mesh and 80 mesh is 1954.95 m2g-1 and 1516.34 m2g-1.

Removal of acutely hazardous pharmaceuticals from water using multi-template imprinted polymer adsorbent.

PubMed

Venkatesh, Avinash; Chopra, Nikita; Krupadam, Reddithota J

2014-05-01

Molecularly imprinted polymer adsorbent has been prepared to remove a group of recalcitrant and acutely hazardous (p-type) chemicals from water and wastewaters. The polymer adsorbent exhibited twofold higher adsorption capacity than the commercially used polystyrene divinylbenzene resin (XAD) and powdered activated carbon adsorbents. Higher adsorption capacity of the polymer adsorbent was explained on the basis of high specific surface area formed during molecular imprinting process. Freundlich isotherms drawn showed that the adsorption of p-type chemicals onto polymer adsorbent was kinetically faster than the other reference adsorbents. Matrix effect on adsorption of p-type chemicals was minimal, and also polymer adsorbent was amenable to regeneration by washing with water/methanol (3:1, v/v) solution. The polymer adsorbent was unaltered in its adsorption capacity up to 10 cycles of adsorption and desorption, which will be more desirable in cost reduction of treatment compared with single-time-use activated carbon.

Aggregation, adsorption, and surface properties of multiply end-functionalized polystyrenes.

PubMed

Ansari, Imtiyaz A; Clarke, Nigel; Hutchings, Lian R; Pillay-Narrainen, Amilcar; Terry, Ann E; Thompson, Richard L; Webster, John R P

2007-04-10

The properties of polystyrene blends containing deuteriopolystyrene, multiply end-functionalized with C8F17 fluorocarbon groups, are strikingly analogous to those of surfactants in solution. These materials, denoted FxdPSy, where x is the number of fluorocarbon groups and y is the molecular weight of the dPS chain in kg/mol, were blended with unfunctionalized polystyrene, hPS. Nuclear reaction analysis experiments show that FxdPSy polymers adsorb spontaneously to solution and blend surfaces, resulting in a reduction in surface energy inferred from contact angle analysis. Aggregation of functionalized polymers in the bulk was found to be sensitive to FxdPSy structure and closely related to surface properties. At low concentrations, the functionalized polymers are freely dispersed in the hPS matrix, and in this range, the surface excess concentration grows sharply with increasing bulk concentration. At higher concentrations, surface excess concentrations and contact angles reach a plateau, small-angle neutron scattering data indicate small micellar aggregates of six to seven F2dPS10 polymer chains and much larger aggregates of F4dPS10. Whereas F2dPS10 aggregates are miscible with the hPS matrix, F4dPS10 forms a separate phase of multilamellar vesicles. Using neutron reflectometry (NR), we found that the extent of the adsorbed layer was approximately half the lamellar spacing of the multilamellar vesicles. NR data were fitted using an error function profile to describe the concentration profile of the adsorbed layer, and reasonable agreement was found with concentration profiles predicted by the SCFT model. The thermodynamic sticking energy of the fluorocarbon-functionalized polymer chains to the blend surface increases from 5.3kBT for x = 2 to 6.6kBT for x = 4 but appears to be somewhat dependent upon the blend concentration.

Molecular Adsorber Coating

NASA Technical Reports Server (NTRS)

Straka, Sharon; Peters, Wanda; Hasegawa, Mark; Hedgeland, Randy; Petro, John; Novo-Gradac, Kevin; Wong, Alfred; Triolo, Jack; Miller, Cory

2011-01-01

A document discusses a zeolite-based sprayable molecular adsorber coating that has been developed to alleviate the size and weight issues of current ceramic puck-based technology, while providing a configuration that more projects can use to protect against degradation from outgassed materials within a spacecraft, particularly contamination-sensitive instruments. This coating system demonstrates five times the adsorption capacity of previously developed adsorber coating slurries. The molecular adsorber formulation was developed and refined, and a procedure for spray application was developed. Samples were spray-coated and tested for capacity, thermal optical/radiative properties, coating adhesion, and thermal cycling. Work performed during this study indicates that the molecular adsorber formulation can be applied to aluminum, stainless steel, or other metal substrates that can accept silicate-based coatings. The coating can also function as a thermal- control coating. This adsorber will dramatically reduce the mass and volume restrictions, and is less expensive than the currently used molecular adsorber puck design.

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

PubMed

Etemadi, Omid; Yen, Teh Fu

2007-09-01

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

Elastic layer under axisymmetric indentation and surface energy effects

NASA Astrophysics Data System (ADS)

Intarit, Pong-in; Senjuntichai, Teerapong; Rungamornrat, Jaroon

2018-04-01

In this paper, a continuum-based approach is adopted to investigate the contact problem of an elastic layer with finite thickness and rigid base subjected to axisymmetric indentation with the consideration of surface energy effects. A complete Gurtin-Murdoch surface elasticity is employed to consider the influence of surface stresses. The indentation problem of a rigid frictionless punch with arbitrary axisymmetric profiles is formulated by employing the displacement Green's functions, derived with the aid of Hankel integral transform technique. The problem is solved by assuming the contact pressure distribution in terms of a linear combination of admissible functions and undetermined coefficients. Those coefficients are then obtained by employing a collocation technique and an efficient numerical quadrature scheme. The accuracy of proposed solution technique is verified by comparing with existing solutions for rigid indentation on an elastic half-space. Selected numerical results for the indenters with flat-ended cylindrical and paraboloidal punch profiles are presented to portray the influence of surface energy effects on elastic fields of the finite layer. It is found that the presence of surface stresses renders the layer stiffer, and the size-dependent behavior of elastic fields is observed in the present solutions. In addition, the surface energy effects become more pronounced with smaller contact area; thus, the influence of surface energy cannot be ignored in the analysis of indentation problem especially when the indenter size is very small such as in the case of nanoindentation.

Compositions of surface layers formed on amalgams in air, water, and saline.

PubMed

Hanawa, T; Gnade, B E; Ferracane, J L; Okabe, T; Watari, F

1993-12-01

The surface layers formed on both a zinc-free and a zinc-containing dental amalgam after polishing and aging in air, water, or saline, were characterized using x-ray photoelectron spectroscopy (XPS) to determine the compositions of the surface layers which might govern the release of mercury from amalgam. The XPS data revealed that the formation of the surface layer on the zinc-containing amalgam was affected by the environment in which the amalgam was polished and aged, whereas that on the zinc-free amalgam was not affected. In addition, among the elements contained in amalgam, zinc was the most reactive with the environment, and was preferentially dissolved from amalgam into water or saline. Mercury atoms existed in the metallic state in the surface layer.

Polymer-based adsorbent for heavy metals removal from aqueous solution

NASA Astrophysics Data System (ADS)

Mahmud, H. N. M. E.; Huq, A. K. O.; Yahya, R.

2017-06-01

A novel conducting polymer-based adsorbent, polypyrrole (PPy) fine powder has successfully been prepared as a new adsorbent and utilized in the adsorption of heavy metal ions like arsenic, zinc and cadmium ions from aqueous solution. PPy was chemically synthesized by using FeCl3.6H2O as an oxidant. The prepared PPy adsorbent was characterized by Brunauer-Emmet-Teller (BET) surface analysis, field emission scanning electron microscopy (FESEM) and attenuated total reflectance fourier transform infrared ATR-(FTIR) spectroscopy. The adsorption was conducted by varying different parameters such as, contact time, pH and adsorbent dosage. The concentrations of metal ions were measured by inductively coupled plasma mass spectroscopy (ICP-MS). The results show that PPy acts as an effective sorbent for the removal of arsenic, zinc and cadmium ions from aqueous solution. The as-prepared PPy fine powder is easy to prepare and appeared as an effective adsorbent for heavy metal ions particularly arsenic in wastewater treatment.

Thermocapillary convection in two immiscible liquid layers with free surface

NASA Technical Reports Server (NTRS)

Doi, Takao; Koster, Jean N.

1993-01-01

Thermocapillary convection is studied in two immiscible liquid layers with one free surface, one liquid/liquid interface, and differential heating applied parallel to the interfaces. An analytical solution is introduced for infinite horizontal layers. The defining parameter for the flow pattern is lambda, the ratio of the temperature coefficient of the interfacial tension to that of the surface tension. Four different flow patterns exist under zero gravity conditions. 'Halt' conditions which halt the fluid motion in the lower encapsulated liquid layer have been found. A numerical experiment is carried out to study effects of vertical end walls on the double layer convection in a 2D cavity. The halt condition obtained from the analytical study is found to be valid in the limit of small Reynolds numbers. The flow in the encapsulated liquid layer can be suppressed substantially.

[MoS4]2- Cluster Bridges in Co-Fe Layered Double Hydroxides for Mercury Uptake from S-Hg Mixed Flue Gas.

PubMed

Xu, Haomiao; Yuan, Yong; Liao, Yong; Xie, Jiangkun; Qu, Zan; Shangguan, Wenfeng; Yan, Naiqiang

2017-09-05

[MoS 4 ] 2- clusters were bridged between CoFe layered double hydroxide (LDH) layers using the ion-exchange method. [MoS 4 ] 2- /CoFe-LDH showed excellent Hg 0 removal performance under low and high concentrations of SO 2 , highlighting the potential for such material in S-Hg mixed flue gas purification. The maximum mercury capacity was as high as 16.39 mg/g. The structure and physical-chemical properties of [MoS 4 ] 2- /CoFe-LDH composites were characterized with FT-IR, XRD, TEM&SEM, XPS, and H 2 -TPR. [MoS 4 ] 2- clusters intercalated into the CoFe-LDH layered sheets; then, we enlarged the layer-to-layer spacing (from 0.622 to 0.880 nm) and enlarged the surface area (from 41.4 m 2 /g to 112.1 m 2 /g) of the composite. During the adsorption process, the interlayer [MoS 4 ] 2- cluster was the primary active site for mercury uptake. The adsorbed mercury existed as HgS on the material surface. The absence of active oxygen results in a composite with high sulfur resistance. Due to its high efficiency and SO 2 resistance, [MoS 4 ] 2- /CoFe-LDH is a promising adsorbent for mercury uptake from S-Hg mixed flue gas.

Synthesis of adsorbent from Tamarix hispida and modified by lanthanum metal for fluoride ions removal from wastewater: Adsorbent characteristics and real wastewater treatment data.

PubMed

Habibi, Nasim; Rouhi, Parham; Ramavandi, Bahman

2017-08-01

This data article describes a facile method for production of an adsorbent from Tamarix hispida wasted wood and modified by lanthanum metal for fluoride ions removal from wastewater. The main characteristics of the adsorbent consist of BET surface area, functional groups, and elemental analysis is presented. The data for attenuating the pollutants from a real wastewater treatment which was provided from a glass factory is also represented. More than 90% of fluoride content of the real wastewater was treated by the adsorbent. Generally, these data would be informative for extend research aim to industrial wastewater treatment and those who work in the wastewater treatment plants.

Adsorbed poly(aspartate) coating limits the adverse effects of dissolved groundwater solutes on Fe0 nanoparticle reactivity with trichloroethylene.

PubMed

Phenrat, Tanapon; Schoenfelder, Daniel; Kirschling, Teresa L; Tilton, Robert D; Lowry, Gregory V

2018-03-01

For in situ groundwater remediation, polyelectrolyte-modified nanoscale zerovalent iron particles (NZVIs) have to be delivered into the subsurface, where they degrade pollutants such as trichloroethylene (TCE). The effect of groundwater organic and ionic solutes on TCE dechlorination using polyelectrolyte-modified NZVIs is unexplored, but is required for an effective remediation design. This study evaluates the TCE dechlorination rate and reaction by-products using poly(aspartate) (PAP)-modified and bare NZVIs in groundwater samples from actual TCE-contaminated sites in Florida, South Carolina, and Michigan. The effects of groundwater solutes on short- and intermediate-term dechlorination rates were evaluated. An adsorbed PAP layer on the NZVIs appeared to limit the adverse effect of groundwater solutes on the TCE dechlorination rate in the first TCE dechlorination cycle (short-term effect). Presumably, the pre-adsorption of PAP "trains" and the Donnan potential in the adsorbed PAP layer prevented groundwater solutes from further blocking NZVI reactive sites, which appeared to substantially decrease the TCE dechlorination rate of bare NZVIs. In the second and third TCE dechlorination cycles (intermediate-term effect), TCE dechlorination rates using PAP-modified NZVIs increased substantially (~100 and 200%, respectively, from the rate of the first spike). The desorption of PAP from the surface of NZVIs over time due to salt-induced desorption is hypothesized to restore NZVI reactivity with TCE. This study suggests that NZVI surface modification with small, charged macromolecules, such as PAP, helps to restore NZVI reactivity due to gradual PAP desorption in groundwater.

Surface passivation investigation on ultra-thin atomic layer deposited aluminum oxide layers for their potential application to form tunnel layer passivated contacts

NASA Astrophysics Data System (ADS)

Xin, Zheng; Ling, Zhi Peng; Nandakumar, Naomi; Kaur, Gurleen; Ke, Cangming; Liao, Baochen; Aberle, Armin G.; Stangl, Rolf

2017-08-01

The surface passivation performance of atomic layer deposited ultra-thin aluminium oxide layers with different thickness in the tunnel layer regime, i.e., ranging from one atomic cycle (∼0.13 nm) to 11 atomic cycles (∼1.5 nm) on n-type silicon wafers is studied. The effect of thickness and thermal activation on passivation performance is investigated with corona-voltage metrology to measure the interface defect density D it(E) and the total interface charge Q tot. Furthermore, the bonding configuration variation of the AlO x films under various post-deposition thermal activation conditions is analyzed by Fourier transform infrared spectroscopy. Additionally, poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) is used as capping layer on ultra-thin AlO x tunneling layers to further reduce the surface recombination current density to values as low as 42 fA/cm2. This work is a useful reference for using ultra-thin ALD AlO x layers as tunnel layers in order to form hole selective passivated contacts for silicon solar cells.

The rapid alveolar absorption of diesel soot-adsorbed benzo[a]pyrene: bioavailability, metabolism and dosimetry of an inhaled particle-borne carcinogen.

PubMed

Gerde, P; Muggenburg, B A; Lundborg, M; Dahl, A R

2001-05-01

Exposure to diesel exhaust may contribute to lung cancer in humans. It remains unclear whether the carbonaceous core of the soot particle or its coat of adsorbed/condensed organics contributes most to cancer risk. Equally unclear are the extent and rate at which organic procarcinogens desorb from soot particles in the lungs following inhalation exposure and the extent of their metabolic activation in the lungs. To explore the basic relationship between a model polycyclic aromatic hydrocarbon (PAH) and a typical carrier particle, we investigated the rate and extent of release and metabolic fate of benzo[a]pyrene (BaP) adsorbed on the carbonaceous core of diesel soot. The native organic content of the soot had been denuded by toluene extraction. Exogenous BaP was adsorbed onto the denuded soot as a surface coating corresponding to 25% of a monomolecular layer. Dogs were exposed by inhalation to an aerosol bolus of the soot-adsorbed BAP: Following deposition in the alveolar region a fraction of BaP was rapidly desorbed from the soot and quickly absorbed into the circulation. Release rates then decreased drastically. When coatings reached approximately 16% of a monolayer the remaining BaP was not bioavailable and was retained on the particles after 5.6 months in the lung. However, the bioavailability of particles transported to the lymph nodes was markedly higher; after 5.6 months the surface coating of BaP was reduced to 10%. BaP that remained adsorbed on the soot surface after this period was approximately 30% parent compound. In contrast, the rapidly released pulse of BaP, which was quickly absorbed through the alveolar epithelium after inhalation, appeared mostly unmetabolized in the circulation, along with low concentrations of phase I and phase II BaP metabolites. However, within approximately 1 h this rapidly absorbed fraction of BaP was systemically metabolized into mostly conjugated phase II metabolites. The results indicate that absorption through the

Adsorbed molecules in external fields: Effect of confining potential.

PubMed

Tyagi, Ashish; Silotia, Poonam; Maan, Anjali; Prasad, Vinod

2016-12-05

We study the rotational excitation of a molecule adsorbed on a surface. As is well known the interaction potential between the surface and the molecule can be modeled in number of ways, depending on the molecular structure and the geometry under which the molecule is being adsorbed by the surface. We explore the effect of change of confining potential on the excitation, which is largely controlled by the static electric fields and continuous wave laser fields. We focus on dipolar molecules and hence we restrict ourselves to the first order interaction in field-molecule interaction potential either through permanent dipole moment or/and the molecular polarizability parameter. It is shown that confining potential shapes, strength of the confinement, strongly affect the excitation. We compare our results for different confining potentials. Copyright © 2016 Elsevier B.V. All rights reserved.

Formic Acid Dissociative Adsorption on NiO(111): Energetics and Structure of Adsorbed Formate

DOE PAGES

Zhao, Wei; Doyle, Andrew D.; Morgan, Sawyer E.; ...

2017-11-21

Here, the dissociative adsorption of carboxylic acids on oxide surfaces is important for understanding adsorbed carboxylates, which are important as intermediates in catalytic reactions, for the organo-functionalization of oxide surfaces, and in many other aspects of oxide surface chemistry. We present here the first direct experimental measurement of the heat of dissociative adsorption of any carboxylic acid on any single-crystal oxide surface. The enthalpy of the dissociative adsorption of formic acid, the simplest carboxylic acid, to produce adsorbed formate and hydrogen (as a surface hydroxyl) on a (2 × 2)-NiO(111) surface is measured by single crystal adsorption calorimetry. The differentialmore » heat of adsorption decreases with formic acid coverage from 202 to 99 kJ/mol at saturation (0.25 ML). The structure of the adsorbed products is clarified by density functional theory (DFT) calculations, which provide energies in reasonable agreement with the calorimetry. These calculations show that formic acid readily dissociates on both the oxygen and Ni terminations of the octapolar NiO(111) surfaces, donating its acid H to a surface lattice oxygen, while HCOO adsorbs preferentially with bridging-type geometry near the M-O 3/O-M 3 sites. The calculated energetics at low coverages agrees well with experimental data, while larger differences are observed at high coverage (0.25 ML). The large decrease in experimental heat of adsorption with coverage can be brought into agreement with the DFT energies if we assume that both types of octapolar surface terminations (O- and Ni-) are present on the starting surface.« less

Formic Acid Dissociative Adsorption on NiO(111): Energetics and Structure of Adsorbed Formate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Wei; Doyle, Andrew D.; Morgan, Sawyer E.

Here, the dissociative adsorption of carboxylic acids on oxide surfaces is important for understanding adsorbed carboxylates, which are important as intermediates in catalytic reactions, for the organo-functionalization of oxide surfaces, and in many other aspects of oxide surface chemistry. We present here the first direct experimental measurement of the heat of dissociative adsorption of any carboxylic acid on any single-crystal oxide surface. The enthalpy of the dissociative adsorption of formic acid, the simplest carboxylic acid, to produce adsorbed formate and hydrogen (as a surface hydroxyl) on a (2 × 2)-NiO(111) surface is measured by single crystal adsorption calorimetry. The differentialmore » heat of adsorption decreases with formic acid coverage from 202 to 99 kJ/mol at saturation (0.25 ML). The structure of the adsorbed products is clarified by density functional theory (DFT) calculations, which provide energies in reasonable agreement with the calorimetry. These calculations show that formic acid readily dissociates on both the oxygen and Ni terminations of the octapolar NiO(111) surfaces, donating its acid H to a surface lattice oxygen, while HCOO adsorbs preferentially with bridging-type geometry near the M-O 3/O-M 3 sites. The calculated energetics at low coverages agrees well with experimental data, while larger differences are observed at high coverage (0.25 ML). The large decrease in experimental heat of adsorption with coverage can be brought into agreement with the DFT energies if we assume that both types of octapolar surface terminations (O- and Ni-) are present on the starting surface.« less