Tension-Enhanced Hydrogen Evolution Reaction on Vanadium Disulfide Monolayer

NASA Astrophysics Data System (ADS)

Pan, Hui

2016-02-01

Water electrolysis is an efficient way for hydrogen production. Finding efficient, cheap, and eco-friendly electrocatalysts is essential to the development of this technology. In the work, we present a first-principles study on the effects of tension on the hydrogen evolution reaction of a novel electrocatalyst, vanadium disulfide (VS2) monolayer. Two electrocatalytic processes, individual and collective processes, are investigated. We show that the catalytic ability of VS2 monolayer at higher hydrogen coverage can be efficiently improved by escalating tension. We find that the individual process is easier to occur in a wide range of hydrogen coverage and the collective process is possible at a certain hydrogen coverage under the same tension. The best hydrogen evolution reaction with near-zero Gibbs free energy can be achieved by tuning tension. We further show that the change of catalytic activity with tension and hydrogen coverage is induced by the change of free carrier density around the Fermi level, that is, higher carrier density, better catalytic performance. It is expected that tension can be a simple way to improve the catalytic activity, leading to the design of novel electrocatalysts for efficient hydrogen production from water electrolysis.

Growth and structural evolution of Sn on Ag(001): Epitaxial monolayer to thick alloy film

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

Chakraborty, Suvankar; Menon, Krishnakumar S. R., E-mail: krishna.menon@saha.ac.in

The growth and structure of Sn on Ag(001), from submonolayer to thick film coverages at room temperature, are studied using low energy electron diffraction, x-ray photoemission spectroscopy and angle-resolved photoemission spectroscopy (ARPES) techniques. The authors observe different growth modes for submonolayer Sn coverages and for higher Sn coverages. Systematic surface structural evolution, consistent with the substitution of surface Ag atoms by Sn atoms, is observed for submonolayer Sn coverages while an ordered Ag-Sn bulk alloy film is formed for higher Sn coverages with an Ag overlayer. For monolayer coverage of Sn, a pseudomorphic growth of a Sn layer without alloyingmore » is determined. ARPES results also confirm the presence of an ordered Ag overlayer on the bulk Ag-Sn alloy film, suggesting the formation of an Ag/Ag{sub 3}Sn/Ag(001) sandwich structure at the surface for higher Sn coverages. The present results illustrate the complex interplay of atomic mobilities, surface free-energies, and alloy formation energies in determining the growth and structural properties of the system.« less

Thermal desorption study of physical forces at the PTFE surface

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Pepper, S. V.

1987-01-01

Thermal desorption spectroscopy (TDS) of the polytetrafluoroethylene (PTFE) surface was successfully employed to study the possible role of physical forces in the enhancement of metal-PTFE adhesion by radiation. The thermal desorption spectra were analyzed without assumptions to yield the activation energy for desorption over a range of xenon coverage from less than 0.1 monolayer to more than 100 monolayers. For multilayer coverage, the desorption is zero-order with an activation energy equal to the sublimation energy of xenon. For submonolayer coverages, the order for desorption from the unirradiated PTFE surface is 0.73 and the activation energy for desorption is between 3.32 and 3.36 kcal/mol; less than the xenon sublimation energy. The effect of irradiation is to increase the activation energy for desorption to as high as 4 kcal/mol at low coverage.

Thermal desorption study of physical forces at the PTFE surface

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Pepper, S. V.

1985-01-01

Thermal desorption spectroscopy (TDS) of the polytetrafluoroethylene (PTFE) surface was successfully employed to study the possibile role of physical forces in the enhancement of metal-PTFE adhesion by radiation. The thermal desorption spectra were analyzed without assumptions to yield the activation energy for desorption over a range of xenon coverage from less than 0.1 monolayer to more than 100 monolayers. For multilayer coverage, the desorption is zero-order with an activation energy equal to the sublimation energy of xenon. For submonolayer coverages, the order for desorption from the unirradiated PTFE surface is 0.73 and the activation energy for desorption is between 3.32 and 3.36 kcal/mol; less than the xenon sublimation energy. The effect of irradiation is to increase the activation energy for desorption to as high as 4 kcal/mol at low coverage.

Effect of Illumination Angle on the Performance of Dusted Thermal Control Surfaces in a Simulated Lunar Environment

NASA Technical Reports Server (NTRS)

Gaier, James R.

2009-01-01

JSC-1A lunar simulant has been applied to AZ93 and AgFEP thermal control surfaces on aluminum substrates in a simulated lunar environment. The temperature of these surfaces was monitored as they were heated with a solar simulator using varying angles of incidence and cooled in a 30 K coldbox. Thermal modeling was used to determine the solar absorptivity (a) and infrared emissivity (e) of the thermal control surfaces in both their clean and dusted states. It was found that even a sub-monolayer of dust can significantly raise the a of either type of surface. A full monolayer can increase the a/e ratio by a factor of 3 to 4 over a clean surface. Little angular dependence of the a of pristine thermal control surfaces for both AZ93 and AgFEP was observed, at least until 30 from the surface. The dusted surfaces showed the most angular dependence of a when the incidence angle was in the range of 25 to 35 . Samples with a full monolayer, like those with no dust, showed little angular dependence in a. The e of the dusted thermal control surfaces was within the spread of clean surfaces, with the exception of high dust coverage, where a small increase was observed at shallow angles.

Recombinant albumin monolayers on latex particles.

PubMed

Sofińska, Kamila; Adamczyk, Zbigniew; Kujda, Marta; Nattich-Rak, Małgorzata

2014-01-14

The adsorption of recombinant human serum albumin (rHSA) on negatively charged polystyrene latex micro-particles was studied at pH 3.5 and the NaCl concentration range of 10(-3) to 0.15 M. The electrophoretic mobility of latex monotonically increased with the albumin concentration in the suspension. The coverage of adsorbed albumin was quantitatively determined using the depletion method, where the residual protein concentration was determined by electrokinetic measurements and AFM imaging. It was shown that albumin adsorption was irreversible. Its maximum coverage on latex varied between 0.7 mg m(-2) for 10(-3) M NaCl to 1.3 mg m(-2) for 0.15 M NaCl. The latter value matches the maximum coverage previously determined for human serum albumin on mica using the streaming potential method. The increase in the maximum coverage was interpreted in terms of reduced electrostatic repulsion among adsorbed molecules. These facts confirm that albumin adsorption at pH 3.5 is governed by electrostatic interactions and proceeds analogously to colloid particle deposition. The stability of albumin monolayers was measured in additional experiments where changes in the latex electrophoretic mobility and the concentration of free albumin in solutions were monitored over prolonged time periods. Based on these experimental data, a robust procedure of preparing albumin monolayers on latex particles of well-controlled coverage and molecule distribution was proposed.

Predictions for partial and monolayer coverages of O2 on graphite

NASA Technical Reports Server (NTRS)

Pan, R. P.; Etters, R. D.; Kobashi, K.; Chandrasekharan, V.

1982-01-01

Monolayer properties of O2 on graphite are calculated using a pattern recognition, optimization scheme. Equilibrium monolayers are predicted at two different densities with properties in agreement with recent X-ray diffraction, specific heat, and neutron scattering data. Properties of the extremely low density regime are calculated using a model based upon a distribution of two-dimensional O2 clusters. The results are consistent with experimental evidence.

Characterization and reactivity of organic monolayers on gold and platinum surfaces

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

Wu, Chien-Ching

1995-12-06

Purpose is to understand how the mobilization, dielectric, orientation, composition, coverage, and structure of self-assembled organic monolayers on metal surfaces affects the surface reactivities and properties of these films in order to facilitate the construction of desired films. Two model systems were used: tiols at Au and aromatic acids at Pt. Surface analysis methods, including contact angle, electrochemistry, ellipsometry, infrared reflection absorption spectroscopy (IRRAS), and x-ray photospectroscopy, were used to study the self-assembled organic monolayers on Au and Pt. IRRAS, contact angle, and electrochemistry were used to determine the surface pK a of phenylcarboxylic acids and pyridylcarboxylic acids monolayers onmore » Pt. These techniques were also used to determine the orientation of polymethylene chain axis and the carboxylic follow the structural evolution of the chains and end group of the thiolate monolayers during formation. IRRAS was also used to assess the carboxylic acid group in terms of its possible existence as the non-hydrogen-bonded species, the hydrogen-bonded dimeric group, and the hydrogen-bonded polymeric group. These different forms of the end group were also followed vs coverage, as well as the reactivity vs solution pH. IRRAS and contact angle were used to calculate the rate constant of the esterification of carboxylic acid-terminated monolayers on Au.« less

Irreversible adsorption of particles on heterogeneous surfaces.

PubMed

Adamczyk, Zbigniew; Jaszczółt, Katarzyna; Michna, Aneta; Siwek, Barbara; Szyk-Warszyńska, Lilianna; Zembala, Maria

2005-12-30

Methods of theoretical and experimental evaluation of irreversible adsorption of particles, e.g., colloids and globular proteins at heterogeneous surfaces were reviewed. The theoretical models were based on the generalized random sequential adsorption (RSA) approach. Within the scope of these models, localized adsorption of particles occurring as a result of short-ranged attractive interactions with discrete adsorption sites was analyzed. Monte-Carlo type simulations performed according to this model enabled one to determine the initial flux, adsorption kinetics, jamming coverage and the structure of the particle monolayer as a function of the site coverage and the particle/site size ratio, denoted by lambda. It was revealed that the initial flux increased significantly with the site coverage theta(s) and the lambda parameter. This behavior was quantitatively interpreted in terms of the scaled particle theory. It also was demonstrated that particle adsorption kinetics and the jamming coverage increased significantly, at fixed site coverage, when the lambda parameter increased. Practically, for alpha = lambda2theta(s) > 1 the jamming coverage at the heterogeneous surfaces attained the value pertinent to continuous surfaces. The results obtained prove unequivocally that spherically shaped sites were more efficient in binding particles in comparison with disk-shaped sites. It also was predicted that for particle size ratio lambda < 4 the site multiplicity effect plays a dominant role, affecting significantly the structure of particle monolayers and the jamming coverage. Experimental results validating main aspects of these theoretical predictions also have been reviewed. These results were derived by using monodisperse latex particles adsorbing on substrates produced by covering uniform surface by adsorption sites of a desired size, coverage and surface charge. Particle deposition occurred under diffusion-controlled transport conditions and their coverage was evaluated by direct particle counting using the optical and electron microscopy. Adsorption kinetics was quantitatively interpreted in terms of numerical solutions of the governing diffusion equation with the non-linear boundary condition derived from Monte-Carlo simulations. It was proven that for site coverage as low as a few percent the initial flux at heterogeneous surfaces attained the maximum value pertinent to homogeneous surfaces. It also was demonstrated that the structure of larger particle monolayers, characterized in terms of the pair correlation function, showed much more short-range ordering than predicted for homogeneous surface monolayers at the same coverage. The last part of this review was devoted to detection of polyelectrolyte multilayers on various substrates via particle deposition experiments.

Simulation studies on structural and thermal properties of alkane thiol capped gold nanoparticles.

PubMed

Devi, J Meena

2017-06-01

The structural and thermal properties of the passivated gold nanoparticles were explored employing molecular dynamics simulation for the different surface coverage densities of the self-assembled monolayer (SAM) of alkane thiol. The structural properties of the monolayer protected gold nanoparticles such us overall shape, organization and conformation of the capping alkane thiol chains were found to be influenced by the capping density. The structural order of the thiol capped gold nanoparticles enhances with the increase in the surface coverage density. The specific heat capacity of the alkane thiol capped gold nanoparticles was found to increase linearly with the thiol coverage density. This may be attributed to the enhancement in the lattice vibrational energy. The present simulation results suggest, that the structural and thermal properties of the alkane thiol capped gold nanoparticles may be modified by the suitable selection of the SAM coverage density. Copyright © 2017 Elsevier Inc. All rights reserved.

A temperature-programmed X-ray photoelectron spectroscopy (TPXPS) study of chlorine adsorption and diffusion on Ag(1 1 1)

NASA Astrophysics Data System (ADS)

Piao, H.; Adib, K.; Barteau, Mark A.

2004-05-01

Synchrotron-based temperature programmed X-ray photoelectron spectroscopy (TPXPS) has been used to investigate the surface chloridation of Ag(1 1 1) to monolayer coverages. At 100 K both atomic and molecular chlorine species are present on the surface; adsorption at 300 K or annealing the adlayer at 100 K to this temperature generates adsorbed Cl atoms. As the surface is heated from 300 to 600 K, chlorine atoms diffuse below the surface, as demonstrated by attenuation of the Cl2p signals in TPXPS experiments. Quantitative analysis of the extent of attenuation is consistent with chlorine diffusion below the topmost silver layer. For coverages in the monolayer and sub-monolayer regime, chlorine diffusion to and from the bulk appears not to be significant, in contrast to previous results obtained at higher chlorine loadings. Chlorine is removed from the surface at 650-780 K by desorption as AgCl. These results demonstrate that chlorine diffusion beneath the surface does occur at coverages and temperatures relevant to olefin epoxidation processes carried out on silver catalysts with chlorine promoters. The surface sensitivity advantages of synchrotron-based XPS experiments were critical to observing Cl diffusion to the sub-surface at low coverages.

Single Crystalline Film of Hexagonal Boron Nitride Atomic Monolayer by Controlling Nucleation Seeds and Domains

PubMed Central

Wu, Qinke; Park, Ji-Hoon; Park, Sangwoo; Jung, Seong Jun; Suh, Hwansoo; Park, Noejung; Wongwiriyapan, Winadda; Lee, Sungjoo; Lee, Young Hee; Song, Young Jae

2015-01-01

A monolayer hexagonal boron nitride (h-BN) film with controllable domain morphology and domain size (varying from less than 1 μm to more than 100 μm) with uniform crystalline orientation was successfully synthesized by chemical vapor deposition (CVD). The key for this extremely large single crystalline domain size of a h-BN monolayer is a decrease in the density of nucleation seeds by increasing the hydrogen gas flow during the h-BN growth. Moreover, the well-defined shape of h-BN flakes can be selectively grown by controlling Cu-annealing time under argon atmosphere prior to h-BN growth, which provides the h-BN shape varies in triangular, trapezoidal, hexagonal and complex shapes. The uniform crystalline orientation of h-BN from different nucleation seeds can be easily confirmed by polarized optical microscopy (POM) with a liquid crystal coating. Furthermore, seamlessly merged h-BN flakes without structural domain boundaries were evidence by a selective hydrogen etching after a full coverage of a h-BN film was achieved. This seamless large-area and atomic monolayer of single crystalline h-BN film can offer as an ideal and practical template of graphene-based devices or alternative two-dimensional materials for industrial applications with scalability. PMID:26537788

Single Crystalline Film of Hexagonal Boron Nitride Atomic Monolayer by Controlling Nucleation Seeds and Domains

NASA Astrophysics Data System (ADS)

Wu, Qinke; Park, Ji-Hoon; Park, Sangwoo; Jung, Seong Jun; Suh, Hwansoo; Park, Noejung; Wongwiriyapan, Winadda; Lee, Sungjoo; Lee, Young Hee; Song, Young Jae

2015-11-01

A monolayer hexagonal boron nitride (h-BN) film with controllable domain morphology and domain size (varying from less than 1 μm to more than 100 μm) with uniform crystalline orientation was successfully synthesized by chemical vapor deposition (CVD). The key for this extremely large single crystalline domain size of a h-BN monolayer is a decrease in the density of nucleation seeds by increasing the hydrogen gas flow during the h-BN growth. Moreover, the well-defined shape of h-BN flakes can be selectively grown by controlling Cu-annealing time under argon atmosphere prior to h-BN growth, which provides the h-BN shape varies in triangular, trapezoidal, hexagonal and complex shapes. The uniform crystalline orientation of h-BN from different nucleation seeds can be easily confirmed by polarized optical microscopy (POM) with a liquid crystal coating. Furthermore, seamlessly merged h-BN flakes without structural domain boundaries were evidence by a selective hydrogen etching after a full coverage of a h-BN film was achieved. This seamless large-area and atomic monolayer of single crystalline h-BN film can offer as an ideal and practical template of graphene-based devices or alternative two-dimensional materials for industrial applications with scalability.

Fibrinogen adsorption mechanisms at the gold substrate revealed by QCM-D measurements and RSA modeling.

PubMed

Kubiak, Katarzyna; Adamczyk, Zbigniew; Cieśla, Michał

2016-03-01

Adsorption kinetics of fibrinogen at a gold substrate at various pHs was thoroughly studied using the QCM-D method. The experimental were interpreted in terms of theoretical calculations performed according to the random sequential adsorption model (RSA). In this way, the hydration functions and water factors of fibrinogen monolayers were quantitatively evaluated at various pHs. It was revealed that for the lower range of fibrinogen coverage the hydration function were considerably lower than previously obtained for the silica sensor [33]. The lower hydration of fibrinogen monolayers on the gold sensor was attributed to its higher roughness. However, for higher fibrinogen coverage the hydration functions for both sensors became identical exhibiting an universal behavior. By using the hydration functions, the fibrinogen adsorption/desorption runs derived from QCM-D measurements were converted to the Γd vs. the time relationships. This allowed to precisely determine the maximum coverage that varied between 1.6mgm(-2) at pH 3.5 and 4.5mgm(-2) at pH 7.4 (for ionic strength of 0.15M). These results agree with theoretical eRSA modeling and previous experimental data derived by using ellipsometry, OWLS and TIRF. Various fibrinogen adsorption mechanisms were revealed by exploiting the maximum coverage data. These results allow one to develop a method for preparing fibrinogen monolayers of well-controlled coverage and molecule orientation. Copyright © 2015 Elsevier B.V. All rights reserved.

Desorption Kinetics of Benzene and Cyclohexane from a Graphene Surface.

PubMed

Smith, R Scott; Kay, Bruce D

2018-01-18

The desorption kinetics for benzene and cyclohexane from a graphene covered Pt(111) surface were investigated using temperature-programmed desorption (TPD). The benzene desorption spectra show well-resolved monolayer and multilayer desorption peaks. The benzene monolayer and submonolayer TPD spectra for coverages greater than ∼0.1 ML have nearly the same desorption peak temperature and have line shapes which are consistent with first-order desorption kinetics. For benzene coverages greater than 1 ML, the TPD spectra align on a common leading edge which is consistent with zero-order desorption. An "inversion" procedure in which the prefactor is varied to find the value that best reproduces the entire set of experimental desorption spectra was used to analyze the benzene data. The inversion analysis of the benzene TPD spectra yielded a desorption activation energy of 54 ± 3 kJ/mol with a prefactor of 10 17±1 s -1 . The TPD spectra for cyclohexane also have well-resolved monolayer and multilayer desorption features. The desorption leading edges for the monolayer and the multilayer TPD spectra are aligned indicating zero-order desorption kinetics in both cases. An Arrhenius analysis of the monolayer cyclohexane TPD spectra yielded a desorption activation energy of 53.5 ± 2 kJ/mol with a prefactor of 10 16±1 ML s -1 .

Effect of functional end groups of silane self assembled monolayer surfaces on apatite formation, fibronectin adsorption and osteoblast cell function

PubMed Central

Toworfe, G.K.; Bhattacharyya, S.; Composto, R.J.; Adams, C.S.; Shapiro, I.M.; Ducheyne, P.

2008-01-01

Bioactive glass (BG) can directly bond to living bone without fibrous tissue encapsulation. Key mechanistic steps of BG’s activity are attributed to calcium phosphate formation, surface hydroxylation and fibronectin (FN) adsorption. In the present study, self-assembled monolayers (SAMs) of alkanesilanes with different surface chemistry (OH, NH2, and COOH) were used as a model system to mimic BG’s surface activity. Calcium phosphate (Ca-P) was formed on SAMs by immersion in a solution which simulates the electrolyte content of physiological fluids. FN adsorption kinetics and monolayer coverage was determined on SAMs with or without Ca-P coating. The surface roughness was also examined on these substrates before and after FN adsorption. The effects of FN-adsorbed, Ca-P coated SAMs on the function of MC3T3-E1 were evaluated by cell growth, expression of alkaline phosphatase activity, and actin cytoskeleton formation. We demonstrate that, although the FN monolayer coverage and the rms roughness are similar on −OH and −COOH terminated SAMs with or without Ca-P coating, higher levels of ALP activity, more actin cytoskeleton formation and more cell growth are obtained on −OH and −COOH terminated SAMs with Ca-P coating. In addition, although the FN monolayer coverage is higher on Ca-P coated −NH2 terminated SAMs and SiOx surfaces, higher levels of ALP activity and more cell growth are obtained on Ca-P coated −OH and −COOH terminated SAMs. Thus with same Ca-P coatings, different surface functional groups have different effects on the function of osteoblastic cells. These findings represent new insights into the mechanism of bioactivity of BG and, thereby, may lead to designing superior constructs for bone grafting. PMID:19012271

Density functional theory with van der waals corrections study of the adsorption of alkyl, alkylthiol, alkoxyl, and amino-alkyl chains on the H:Si(111) surface.

PubMed

Arefi, Hadi H; Nolan, Michael; Fagas, Giorgos

2014-11-11

Surface modification of silicon with organic monolayers tethered to the surface by different linkers is an important process in realizing future miniaturized electronic and sensor devices. Understanding the roles played by the nature of the linking group and the chain length on the adsorption structures and stabilities of these assemblies is vital to advance this technology. This paper presents a density functional theory (DFT) study of the hydrogen passivated Si(111) surface modified with alkyl chains of the general formula H:Si-(CH2)n-CH2 and H:Si-X-(CH2)n-CH3, where X = NH, O, S and n = (0, 1, 3, 5, 7, 9, 11), at half coverage. For (X)-hexane and (X)-dodecane functionalization, we also examined various coverages up to full monolayer grafting in order to validate the result of half covered surface and the linker effect on the coverage. We find that it is necessary to take into account the van der Waals interaction between the alkyl chains. The strongest binding is for the oxygen linker, followed by S, N, and C, irrespective of chain length. The result revealed that the sequence of the stability is independent of coverage; however, linkers other than carbon can shift the optimum coverage considerably and allow further packing density. For all linkers apart from sulfur, structural properties, in particular, surface-linker-chain angles, saturate to a single value once n > 3. For sulfur, we identify three regimes, namely, n = 0-3, n = 5-7, and n = 9-11, each with its own characteristic adsorption structures. Where possible, our computational results are shown to be consistent with the available experimental data and show how the fundamental structural properties of modified Si surfaces can be controlled by the choice of linking group and chain length.

Hematite/silica nanoparticle bilayers on mica: AFM and electrokinetic characterization.

PubMed

Morga, Maria; Adamczyk, Zbigniew; Kosior, Dominik; Oćwieja, Magdalena

2018-06-06

Quantitative studies on self-assembled hematite/silica nanoparticle (NP) bilayers on mica were performed by applying scanning electron microscopy (SEM), atomic force microscopy (AFM), and streaming potential measurements. The coverage of the supporting hematite layers was adjusted by changing the bulk concentration of the suspension and the deposition time. The coverage was determined by direct enumeration of deposited particles from AFM images and SEM micrographs. Afterward, silica nanoparticle monolayers were assembled under diffusion-controlled transport. A unique functional relationship was derived connecting the silica coverage with the hematite precursor layer coverage. The formation of the hematite monolayer and the hematite/silica bilayer was also monitored in situ by streaming potential measurements. It was confirmed that the zeta potential of the bilayers was independent of the supporting layer coverage, exceeding 0.15. These measurements were theoretically interpreted in terms of the general electrokinetic model that allowed for deriving a formula for calculating nanoparticle coverage in the bilayers. Additionally, from desorption experiments, the interactions among hematite/silica particles in the bilayers were determined using DLVO theory. These results facilitate the development of a robust method of preparing nanoparticle bilayers with controlled properties, with potential applications in catalytic processes.

Peierls instability as the insulating origin of the Na/Si(111)-(3 × 1) surface with a Na coverage of 2/3 monolayers

NASA Astrophysics Data System (ADS)

Kang, Myung Ho; Kwon, Se Gab; Jung, Sung Chul

2018-03-01

Density functional theory (DFT) calculations are used to investigate the insulating origin of the Na/Si(111)-(3 × 1) surface with a Na coverage of 2/3 monolayers. In the coverage definition, one monolayer refers to one Na atom per surface Si atom, so this surface contains an odd number of electrons (i.e., three Si dangling-bond electrons plus two Na electrons) per 3 × 1 unit cell. Interestingly, this odd-electron surface has been ascribed to a Mott-Hubbard insulator to account for the measured insulating band structure with a gap of about 0.8 eV. Here, we instead propose a Peierls instability as the origin of the experimental band gap. The concept of Peierls instability is fundamental in one-dimensional metal systems but has not been taken into account in previous studies of this surface. Our DFT calculations demonstrate that the linear chain structure of Si dangling bonds in this surface is energetically unstable with respect to a × 2 buckling modulation, and the buckling-induced band gap of 0.79 eV explains well the measured insulating nature.

A high-coverage nanoparticle monolayer for the fabrication of a subwavelength structure on InP substrates.

PubMed

Kim, Dae-Seon; Park, Min-Su; Jang, Jae-Hyung

2011-08-01

Subwavelength structures (SWSs) were fabricated on the Indium Phosphide (InP) substrate by utilizing the confined convective self-assembly (CCSA) method followed by reactive ion etching (RIE). The surface condition of the InP substrate was changed by depositing a 30-nm-thick SiO2 layer and subsequently treating the surface with O2 plasma to achieve better surface coverage. The surface coverage of nanoparticle monolayer reached 90% by using O2 plasma-treated SiO2/InP substrate among three kinds of starting substrates such as the bare InP, SiO2/InP and O2 plasma-treated SiO2/InP substrate. A nanoparticle monolayer consisting of polystyrene spheres with diameter of 300 nm was used as an etch mask for transferring a two-dimensional periodic pattern onto the InP substrate. The fabricated conical SWS with an aspect ratio of 1.25 on the O2 plasma-treated SiO2/InP substrate exhibited the lowest reflectance. The average reflectance of the conical SWS was 5.84% in a spectral range between 200 and 900 nm under the normal incident angle.

Electron solvation and localization at interfaces

NASA Astrophysics Data System (ADS)

Harris, Charles B.; Szymanski, Paul; Garrett-Roe, Sean; Miller, Andre D.; Gaffney, Kelly J.; Liu, Simon H.; Bezel, Ilya

2003-12-01

Two-photon photoemission of thiolate/Ag(111), nitrile/Ag(111), and alcohol/Ag(111) interfaces elucidates electron solvation and localization in two dimensions. For low coverages of thiolates on Ag(111), the occupied (HOMO) and unoccupied (LUMO) electronic states of the sulfer-silver bond are localized due to the lattice gas structure of the adsorbate. As the coverage saturates and the adsorbate-adsorbate nearest neighbor distance decreases, the HOMO and LUMO delocalize across many adsorbate molecules. Alcohol- and nitrile-covered Ag(111) surfaces solvate excess image potential state (IPS) electrons. In the case of alcohol-covered surfaces, this solvation is due to a shift in the local workfunction of the surface. For two-monolayer coverages of nitriles/Ag(111), localization accompanies solvation of the IPS. The size of the localized electron can be estimated by Fourier transformation of the wavefunction from momentum- to position-space. The IPS electron localizes to 15 +/- 4 angstroms full-width at half maximum in the plane of the surface, i.e., to a single lattice site.

I Situ Structural Study of Underpotential Deposition and Electrocatalysis on GOLD(111) Electrodes

NASA Astrophysics Data System (ADS)

Chen, Chun-Hsien

This thesis work has studied systems of Bi, Pb, Ag, and Hg underpotential deposition (UPD) on Au(111) electrodes. The application of the atomic force microscope (AFM), the scanning tunneling microscope (STM), and the surface x-ray scattering (SXS) to these UPD studies has provided in situ measurements from which we investigate factors that determine UPD surface structures and correlate these structures with surface reactivity. For all the UPD systems in this thesis work, atomic level features of the electrode surface have been revealed. In the case of Pb UPD, Pb starts to deposit by forming islands which exhibit a hexagonal close packed structure of Pb adatoms, while, in the other systems, the UPD adatoms form open lattices. In the Bi and Pb studies, we correlate the activities of the modified surface toward electroreduction of H_2O_2 with the adlattice structures. A heterobimetallic bridge model for H_2O_2 on the surface could explain the enhanced reactivity. The full monolayers of Bi and Hg, rhombohedral metals, form rectangular lattice structures on the hexagonal Au(111) surfaces. The partial charge retention on the Bi and Hg adatom opens the adlayer structure when the coverage is less than a full monolayer. The structure of the first submonolayers of Ag UPD is electrolyte-dependent. The electrode surface exhibits 3 x 3 and 4 x 4 overlayer structures in solutions containing sulfate and nitrate, respectively. In perchloric acid another open structure is observed and a close-packed monolayer is formed in acetic acid. The different monolayer structures give rise to packing densities which correlate with electrolyte size. This implies that the anions participate in reducing metal ions.

Surface Coverage and Structure of Mixed DNA/Alkylthiol Monolayers on Gold: Characterization by XPS, NEXAFS, and Fluorescence Intensity Measurements

PubMed Central

Lee, Chi-Ying; Gong, Ping; Harbers, Gregory M.; Grainger, David W.; Castner, David G.; Gamble, Lara J.

2006-01-01

Self-assembly of thiol-terminated single-stranded DNA (HS-ssDNA) on gold has served as an important model system for DNA immobilization at surfaces. Here, we report a detailed study of the surface composition and structure of mixed self-assembled DNA monolayers containing a short alkylthiol surface diluent [11-mercapto-1-undecanol (MCU)] on gold supports. These mixed DNA monolayers were studied with X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and fluorescence intensity measurements. XPS results on sequentially adsorbed DNA/MCU monolayers on gold indicated that adsorbed MCU molecules first incorporate into the HS-ssDNA monolayer and, upon longer MCU exposures, displace adsorbed HS-ssDNA molecules from the surface. Thus, HS-ssDNA surface coverage steadily decreased with MCU exposure time. Polarization-dependent NEXAFS and fluorescence results both show changes in signals consistent with changes in DNA orientation after only 30 min of MCU exposure. NEXAFS polarization dependence (followed by monitoring the N 1s → π* transition) of the mixed DNA monolayers indicated that the DNA nucleotide base ring structures are oriented more parallel to the gold surface compared to DNA bases in pure HS-ssDNA monolayers. This indicates that HS-ssDNA oligomers reorient toward a more-upright position upon MCU incorporation. Fluorescence intensity results using end-labeled DNA probes on gold show little observable fluorescence on pure HS-ssDNA monolayers, likely due to substrate quenching effects between the fluorophore and the gold. MCU diluent incorporation into HS-ssDNA monolayers initially increases DNA fluorescence signal by densifying the chemisorbed monolayer, prompting an upright orientation of the DNA, and moving the terminal fluorophore away from the substrate. Immobilized DNA probe density and DNA target hybridization in these mixed DNA monolayers, as well as effects of MCU diluent on DNA hybridization in complex milieu (i.e., serum) were characterized by surface plasmon resonance (SPR) and 32P-radiometric assays and reported in a related study PMID:16689533

The characterization of organic monolayers at gold surfaces using scanning tunneling microscopy and atomic force microscopy correlation with macrostructural properties

NASA Astrophysics Data System (ADS)

Alves, C. A.

1992-09-01

Monolayer films formed by self-assembly of organothiols at epitaxially grown Au(111) films at mica were examined in air using scanning tunneling (STM) and atomic force microscopies (AFM). n-Alkanethiolate monolayers exhibit a hexagonal packing arrangement with nearest-neighbor and next-nearest-neighbor spacings of 0.50 and 0.87 nm. This arrangement is consistent with (the square root of 3 x the square root of 3)R30 deg adlayer structure at Au(111). STM reveals the structure of the Au-bound sulfur, while AFM details the structure at the monolayer/air interface, revealing that the order at the Au-S interface is retained up to the monolayer/air interface. The investigation of the self-assembled (CF3CF2)7(CH2)2SH monolayer at Au(111) by AFM reveals a (2 x 2) adlayer structure, with nearest-neighbor and next-nearest-neighbor spacings of 0.58 plus or minus 0.02 nm and 1.0 plus or minus 0.02 nm, respectively. This is consistent with the larger van der Waals diameter of the fluorinated chain. Coverage of this fluorinated thiolate monolayer is (6.3 plus or minus 0.8) x 10(exp -10) mol/cm(sup 2), consistent with the expected 0.25 monolayer coverage of the (2 x 2) adlayer structure at Au(111). Infrared reflection spectroscopy also confirmed this. Upon prolonged exposure to air, the thiolate species is oxidized to elemental sulfur in the forms of cyclooctasulfur (cyclo-S8) and other allotropes. STM reveals square structures on aged thiolate monolayers. Dimensions of these squares (0.40-0.50 nm per side) are close to those of cyclo-S8. Electrochemical reductive desorption experiments also reveal a change in the surface species with time, with a second desorption wave.

Phase diagram of the CF{sub 4} monolayer and bilayer on graphite

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

Thomas, Petros; Hess, George B., E-mail: gbh@virginia.edu

2014-05-21

We report an experimental study of physisorbed monolayers and bilayers of CF{sub 4} on graphite using infrared reflection absorption spectroscopy supplemented by ellipsometry. The symmetric C–F stretch mode ν{sub 3} near 1283 cm{sup −1} in the gas is strongly blue shifted in the film by dynamic dipole coupling. This blue shift provides a very sensitive measure of the inter-molecular spacing in the monolayer and, less directly, in the bilayer. We find that important corrections are necessary to the volumetric coverage scales used in previous heat capacity and x-ray diffraction studies of this system. This requires quantitative and some qualitative changesmore » to the previously proposed phase diagram. We find evidence for a new phase transition in the middle of the hexagonal incommensurate region and construct new phase diagrams in both the variables coverage-temperature and chemical potential-temperature. We determine the compressibility and thermal expansion in the low-pressure hexagonal incommensurate phase and values for the entropy change in several phase transitions. Below about 55 K there is evidence of solution of up to 7% of an impurity, most likely CO, in our monolayer but not the bilayer film.« less

Solvent effects on the adsorption and self-organization of Mn12 on Au(111).

PubMed

Pineider, Francesco; Mannini, Matteo; Sessoli, Roberta; Caneschi, Andrea; Barreca, Davide; Armelao, Lidia; Cornia, Andrea; Tondello, Eugenio; Gatteschi, Dante

2007-11-06

A sulfur-containing single molecule magnet, [Mn12O12(O2CC6H4SCH3)16(H2O)4], was assembled from solution on a Au(111) surface affording both submonolayer and monolayer coverages. The adsorbate morphology and the degree of coverage were inspected by scanning tunneling microscopy (STM), while X-ray photoelectron spectroscopy (XPS) allowed the determination of the chemical nature of the adsorbate on a qualitative and quantitative basis. The properties of the adsorbates were found to be strongly dependent on the solvent used to dissolve the magnetic complex. In particular, systems prepared from tetrahydrofuran solutions gave arrays of isolated and partially ordered clusters on the gold substrate, while samples prepared from dichloromethane exhibited a homogeneous monolayer coverage of the whole Au(111) surface. These findings are relevant to the optimization of magnetic addressing of single molecule magnets on surfaces.

Opening and retraction of particulate soap films

NASA Astrophysics Data System (ADS)

Timounay, Yousra; Lorenceau, Elise; Rouyer, Florence

2015-07-01

We study for the first time the bursting dynamics of thin liquid films laden with hydrophobic micronic particles either with free or constrained edges. We highlight that the particles can arrange in bilayer or monolayer configurations and explore a range of particles coverage from zero to random close packing. When the particles bridge the two interfaces (monolayer configuration) of free-edge films, the hole opens intermittently. For the other cases, we observe constant retraction velocities, modeled by balancing liquid and particles inertia against surface tension as in Taylor-Culick theory. But, this approach is only valid up to a critical value of particles coverage due to the interplay between the interfaces and the friction between particles.

Network structure control of binary mixed langmuir monolayers of homo-PS and PS-b-P2VP.

PubMed

Wen, Gangyao

2010-03-25

Our recent work showed there existed a composition window for mixed Langmuir monolayers of homopolystyrene (h-PS) and a symmetric diblock copolymer polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) to form necklace-network structures at the air/water interface. In order to study further the possible mechanism and control the network structure (i.e., surface coverage and nanoaggregate diameter), effects of spreading solution concentration and volume, subphase temperature, and transfer pressure on the network structure were studied by the Langmuir monolayer technique and tapping mode atomic force microscopy. With the increase of transfer pressure, there existed a novel nonlinear behavior for the nanoaggregate diameter first to increase, then to decrease, and finally to increase again, while the surface coverage tended to increase step by step. Moreover, with the elevation of temperature, chain motion between the adjoining nanoaggregates tended to be improved and thus the nanoaggregate diameter tended to be more uniform.

Island morphology statistics and growth mechanism for oxidation of the Al(111) surface with thermal O2 and NO

NASA Astrophysics Data System (ADS)

Sexton, J. Z.; Kummel, A. C.

2004-10-01

Scanning tunneling microscopy (STM) was employed to study the mechanism for the oxidation of Al(111) with thermal O2 and NO in the 20%-40% monolayer coverage regime. Experiments show that the islands formed upon exposure to thermal O2 and NO have dramatically different shapes, which are ultimately dictated by the dynamics of the gas surface interaction. The circumference-to-area ratio and other island morphology statistics are used to quantify the average difference in the two island types. Ultrahigh-vacuum STM was employed to make the following observations: (1) Oxygen islands on the Al(111) surface, formed upon exposure to thermal oxygen, are elongated and noncompact. (2) Mixed O/N islands on the Al(111) surface, formed upon exposure to thermal nitric oxide (NO), are round and compact. (3) STM movies acquired during thermal O2 exposure indicate that a complex mechanism involving chemisorption initiated rearrangement of preexisting oxygen islands leads to the asymmetric and elongated island shapes. The overall mechanism for the oxidation of the Al(111) surface can be summarized in three regimes. Low coverage is dominated by widely isolated small oxygen features (<3 O atoms) where normal dissociative chemisorption and oxygen abstraction mechanisms are present. At 20%-40% monolayer coverage, additional oxygen chemisorption induces rearrangement of preexisting islands to form free-energy minimum island shapes. At greater than ˜40% monolayer coverage, the apparent surface oxygen coverage asymptotes corresponding to the conversion of the 2D islands to 3D Al2O3 surface crystallites. The rearrangement of oxygen islands on the surface to form the observed islands indicates that there is a short-range oxygen-oxygen attractive potential and a long-range oxygen-oxygen repulsive potential.

Molecular layer deposition of APTES on silicon nanowire biosensors: Surface characterization, stability and pH response

NASA Astrophysics Data System (ADS)

Liang, Yuchen; Huang, Jie; Zang, Pengyuan; Kim, Jiyoung; Hu, Walter

2014-12-01

We report the use of molecular layer deposition (MLD) for depositing 3-aminopropyltriethoxysilane (APTES) on a silicon dioxide surface. The APTES monolayer was characterized using spectroscopic ellipsometry, contact angle goniometry, and atomic force microscopy. Effects of reaction time of repeating pulses and simultaneous feeding of water vapor with APTES were tested. The results indicate that the synergistic effects of water vapor and reaction time are significant for the formation of a stable monolayer. Additionally, increasing the number of repeating pulses improved the APTES surface coverage but led to saturation after 10 pulses. In comparing MLD with solution-phase deposition, the APTES surface coverage and the surface quality were nearly equivalent. The hydrolytic stability of the resulting films was also studied. The results confirmed that the hydrolysis process was necessary for MLD to obtain stable surface chemistry. Furthermore, we compared the pH sensing results of Si nanowire field effect transistors (Si NWFETs) modified by both the MLD and solution methods. The highly repeatable pH sensing results reflected the stability of APTES monolayers. The results also showed an improved pH response of the sensor prepared by MLD compared to the one prepared by the solution treatment, which indicated higher surface coverage of APTES.

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.

Human fibrinogen adsorption on positively charged latex particles.

PubMed

Zeliszewska, Paulina; Bratek-Skicki, Anna; Adamczyk, Zbigniew; Cieśla, Michał

2014-09-23

Fibrinogen (Fb) adsorption on positively charged latex particles (average diameter of 800 nm) was studied using the microelectrophoretic and the concentration depletion methods based on AFM imaging. Monolayers on latex were adsorbed from diluted bulk solutions at pH 7.4 and an ionic strength in the range of 10(-3) to 0.15 M where fibrinogen molecules exhibited an average negative charge. The electrophoretic mobility of the latex after controlled fibrinogen adsorption was systematically measured. A monotonic decrease in the electrophoretic mobility of fibrinogen-covered latex was observed for all ionic strengths. The results of these experiments were interpreted according to the three-dimensional electrokinetic model. It was also determined using the concentration depletion method that fibrinogen adsorption was irreversible and the maximum coverage was equal to 0.6 mg m(-2) for ionic strength 10(-3) M and 1.3 mg m(-2) for ionic strength 0.15 M. The increase of the maximum coverage was confirmed by theoretical modeling based on the random sequential adsorption approach. Paradoxically, the maximum coverage of fibrinogen on positively charged latex particles was more than two times lower than the maximum coverage obtained for negative latex particles (3.2 mg m(-2)) at pH 7.4 and ionic strength of 0.15 M. This was interpreted as a result of the side-on adsorption of fibrinogen molecules with their negatively charged core attached to the positively charged latex surface. The stability and acid base properties of fibrinogen monolayers on latex were also determined in pH cycling experiments where it was observed that there were no irreversible conformational changes in the fibrinogen monolayers. Additionally, the zeta potential of monolayers was more positive than the zeta potential of fibrinogen in the bulk, which proves a heterogeneous charge distribution. These experimental data reveal a new, side-on adsorption mechanism of fibrinogen on positively charged surfaces and confirmed the decisive role of electrostatic interactions in this process.

Self-assembled monolayer structures of hexadecylamine on Cu surfaces: density-functional theory.

PubMed

Liu, Shih-Hsien; Balankura, Tonnam; Fichthorn, Kristen A

2016-12-07

We used dispersion-corrected density-functional theory to probe possible structures for adsorbed layers of hexadecylamine (HDA) on Cu(100) and Cu(111). HDA forms self-assembled layers on these surfaces, analogous to alkanethiols on various metal surfaces, and it binds by donating electrons in the amine group to the Cu surface atoms, consistent with experiment. van der Waals interactions between the alkyl tails of HDA molecules are stronger than the interaction between the amine group and the Cu surfaces. Strong HDA-tail interactions lead to coverage-dependent tilting of the HDA layers, such that the tilt angle is larger for lower coverages. At full monolayer coverage, the energetically preferred binding configuration for HDA on Cu(100) is a (5 × 3) pattern - although we cannot rule out incommensurate structures - while the pattern is preferred on Cu(111). A major motivation for this study is to understand the experimentally observed capability of HDA as a capping agent for producing {100}-faceted Cu nanocrystals. Consistent with experiment, we find that HDA binds more strongly to Cu(100) than to Cu(111). This strong binding stems from the capability of HDA to form more densely packed layers on Cu(100), which leads to stronger HDA-tail interactions, as well as the stronger binding of the amine group to Cu(100). We estimate the surface energies of HDA-covered Cu(100) and Cu(111) surfaces and find that these surfaces are nearly isoenergetic. By drawing analogies to previous theoretical work, it seems likely that HDA-covered Cu nanocrystals could have kinetic shapes that primarily express {100} facets, as is seen experimentally.

Interdye Hole Transport Accelerates Recombination in Dye Sensitized Mesoporous Films.

PubMed

Moia, Davide; Szumska, Anna; Vaissier, Valérie; Planells, Miquel; Robertson, Neil; O'Regan, Brian C; Nelson, Jenny; Barnes, Piers R F

2016-10-12

Charge recombination between oxidized dyes attached to mesoporous TiO 2 and electrons in the TiO 2 was studied in inert electrolytes using transient absorption spectroscopy. Simultaneously, hole transport within the dye monolayers was monitored by transient absorption anisotropy. The rate of recombination decreased when hole transport was inhibited selectively, either by decreasing the dye surface coverage or by changing the electrolyte environment. From Monte Carlo simulations of electron and hole diffusion in a particle, modeled as a cubic structure, we identify the conditions under which hole lifetime depends on the hole diffusion coefficient for the case of normal (disorder free) diffusion. From simulations of transient absorption and transient absorption anisotropy, we find that the rate and the dispersive character of hole transport in the dye monolayer observed spectroscopically can be explained by incomplete coverage and disorder in the monolayer. We show that dispersive transport in the dye monolayer combined with inhomogeneity in the TiO 2 surface reactivity can contribute to the observed stretched electron-hole recombination dynamics and electron density dependence of hole lifetimes. Our experimental and computational analysis of lateral processes at interfaces can be applied to investigate and optimize charge transport and recombination in solar energy conversion devices using electrodes functionalized with molecular light absorbers and catalysts.

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

Smith, R. Scott; Kay, Bruce D.

The desorption kinetics for benzene and cyclohexane from a graphene covered Pt(111) surface were investigated using temperature programmed desorption (TPD). The benzene desorption spectra show well-resolved monolayer and multilayer desorption peaks. The benzene monolayer TPD spectra have the same desorption peak temperature and have line shapes which are consistent with first-order desorption kinetics. For benzene coverages greater than 1 ML, the TPD spectra align on a common leading edge which is consistent with zero-order desorption. An inversion analysis of the monolayer benzene TPD spectra yielded a desorption activation energy of 54 ± 3 kJ/mol with a prefactor of 1017 ±more » 1 s-1. The TPD spectra for cyclohexane also have well-resolved monolayer and multilayer desorption features. The desorption leading edges for the monolayer and the multilayer TPD spectra are aligned indicating zero-order desorption kinetics in both cases. An Arrhenius analysis of the monolayer cyclohexane TPD spectra yielded a desorption activation energy of 53.5 ± 2 kJ/mol with a prefactor of 1016 ± 1 ML s-1.« less

Bidisperse silica nanoparticles close-packed monolayer on silicon substrate by three step spin method

NASA Astrophysics Data System (ADS)

Khanna, Sakshum; Marathey, Priyanka; Utsav, Chaliawala, Harsh; Mukhopadhyay, Indrajit

2018-05-01

We present the studies on the structural properties of monolayer Bidisperse silica (SiO2) nanoparticles (BDS) on Silicon (Si-100) substrate using spin coating technique. The Bidisperse silica nanoparticle was synthesised by the modified sol-gel process. Nanoparticles on the substrate are generally assembled in non-close/close-packed monolayer (CPM) form. The CPM form is obtained by depositing the colloidal suspension onto the silicon substrate using complex techniques. Here we report an effective method for forming a monolayer of bidisperse silica nanoparticle by three step spin coating technique. The samples were prepared by mixing the monodisperse solutions of different particles size 40 and 100 nm diameters. The bidisperse silica nanoparticles were self-assembled on the silicon substrate forming a close-packed monolayer film. The scanning electron microscope images of bidisperse films provided in-depth film structure of the film. The maximum surface coverage obtained was around 70-80%.

Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts

DOE PAGES

Hunt, Sean T.; Milina, Maria; Alba-Rubio, Ana C.; ...

2016-05-20

Here, we demonstrated the self-assembly of transition metal carbide nanoparticles coated with atomically thin noble metal monolayers by carburizing mixtures of noble metal salts and transition metal oxides encapsulated in removable silica templates. This approach allows for control of the final core-shell architecture, including particle size, monolayer coverage, and heterometallic composition. Carbon-supported Ti 0.1W 0.9C nanoparticles coated with Pt or bimetallic PtRu monolayers exhibited enhanced resistance to sintering and CO poisoning, achieving an order of magnitude increase in specific activity over commercial catalysts for methanol electrooxidation after 10,000 cycles. These core-shell materials provide a new direction to reduce the loading,more » enhance the activity, and increase the stability of noble metal catalysts.« less

Au Nanoparticle Sub-Monolayers Sandwiched between Sol-Gel Oxide Thin Films

PubMed Central

Della Gaspera, Enrico; Menin, Enrico; Sada, Cinzia

2018-01-01

Sub-monolayers of monodisperse Au colloids with different surface coverage have been embedded in between two different metal oxide thin films, combining sol-gel depositions and proper substrates functionalization processes. The synthetized films were TiO2, ZnO, and NiO. X-ray diffraction shows the crystallinity of all the oxides and verifies the nominal surface coverage of Au colloids. The surface plasmon resonance (SPR) of the metal nanoparticles is affected by both bottom and top oxides: in fact, the SPR peak of Au that is sandwiched between two different oxides is centered between the SPR frequencies of Au sub-monolayers covered with only one oxide, suggesting that Au colloids effectively lay in between the two oxide layers. The desired organization of Au nanoparticles and the morphological structure of the prepared multi-layered structures has been confirmed by Rutherford backscattering spectrometry (RBS), Secondary Ion Mass Spectrometry (SIMS), and Scanning Electron Microscopy (SEM) analyses that show a high quality sandwich structure. The multi-layered structures have been also tested as optical gas sensors. PMID:29538338

Quaterrylene molecules on Ag(111): self-assembly behavior and voltage pulse induced trimer formation.

PubMed

He, Yangyong; Cai, Zeying; Shao, Jian; Xu, Li; She, Limin; Zheng, Yue; Zhong, Dingyong

2018-05-03

The self-assembly behavior of quaterrylene (QR) molecules on Ag(111) surfaces has been investigated by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. It is found that the QR molecules are highly mobile on the Ag(111) surface at 78 K. No ordered assembled structure is formed on the surface with a sub-monolayer coverage up to 0.8 monolayer due to the intermolecular repulsive interactions, whereas ordered molecular structures are observed at one monolayer coverage. According to our DFT calculations, charge transfer occurs between the substrate and the adsorbed QR molecule. As a result, out-of-plane dipoles appear at the interface, which are ascribed to the repulsive dipole-dipole interactions between the QR molecules. Furthermore, due to the planar geometry, the QR molecules exhibit relatively low diffusion barriers on Ag(111). By applying a voltage pulse between the tunneling gap, immobilization and aggregation of QR molecules take place, resulting in the formation of a triangle-shaped trimer. Our work demonstrates the ability of manipulating intermolecular repulsive and attractive interactions at the single molecular level.

Theoretical aspects of studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.; Reed, J. A.

2011-03-01

The study of adsorption of oxygen on transition metal surface is important for the understanding of oxidation, heterogeneous catalysis, and metal corrosion. The structures formed on transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which results from diffusion of oxygen into the sub-surface regions. In this work we present the results of an ab-initio investigation of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the Cu(100) missing row reconstructed surface under conditions of high oxygen coverage. Calculations are performed for various surface and subsurface oxygen coverages ranging from 0.50 to 1.50 monolayers. Calculations are also performed for the on-surface adsorption of oxygen on the unreconstructed Cu(001) surface for coverages up to one monolayer to use for comparison. Estimates of the positron binding energy, positron work function, and annihilation characteristics reveal their sensitivity to atomic structure of the topmost layers of the surface and charge transfer. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy.

Coverage Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-selected Ions

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

Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

2012-11-29

The ionic charge state of monodisperse cationic gold clusters on surfaces may be controlled by selecting the coverage of mass-selected ions soft landed onto a substrate. Polydisperse diphosphine-capped gold clusters were synthesized in solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine in the presence of 1,3-bis(diphenylphosphino)propane. The polydisperse gold clusters were introduced into the gas phase by electrospray ionization and mass selection was employed to select a multiply charged cationic cluster species (Au11L53+, m/z = 1409, L = 1,3-bis(diphenylphosphino)propane) which was delivered to the surfaces of four different self-assembled monolayers on gold (SAMs) at coverages of 1011 and 1012 clusters/mm2.more » Employing the spatial profiling capabilities of in-situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) it is shown that, in addition to the chemical functionality of the monolayer (as demonstrated previously: ACS Nano, 2012, 6, 573) the coverage of cationic gold clusters on the surface may be used to control the distribution of ionic charge states of the soft-landed multiply charged clusters. In the case of a 1H,1H,2H,2H-perfluorodecanethiol SAM (FSAM) almost complete retention of charge by the deposited Au11L53+ clusters was observed at a lower coverage of 1011 clusters/mm2. In contrast, at a higher coverage of 1012 clusters/mm2, pronounced reduction of charge to Au11L52+ and Au11L5+ was observed on the FSAM. When soft landed onto 16- and 11-mercaptohexadecanoic acid surfaces on gold (16,11-COOH-SAMs), the mass-selected Au11L53+ clusters exhibited partial reduction of charge to Au11L52+ at lower coverage and additional reduction of charge to both Au11L52+ and Au11L5+ at higher coverage. The reduction of charge was found to be more pronounced on the surface of the shorter (thinner) C11 than the longer (thicker) C16-COOH-SAM. On the surface of the 1-dodecanethiol (HSAM) monolayer, the most abundant charge state was found to be Au11L52+ at lower coverage and Au11L5+ at higher coverage, respectively. A coverage-dependent electron tunneling mechanism is proposed to account for the observed reduction of charge of mass-selected multiply charged gold clusters soft landed on SAMs. The results demonstrate that one of the critical parameters that influence the chemical and physical properties of supported metal clusters, ionic charge state, may be controlled by selecting the coverage of charged species soft landed onto surfaces.« less

The Kinetics and Dynamics of Elementary Gas-Phase Reactions

DTIC Science & Technology

2002-09-01

We report CRDS measurements of thin films of oxazine 1, oxazine 170 and malachite green dyes deposited on borosilicate substrates. The method...measure monolayer and sub-monolayer quantities of dye. The minimum observed concentration of malachite green in the present work was calculated to be...the dyes: at surface coverages of ~ 2.8 × 10-7 mol m-2, the ratio of malachite green dimers to monomers was estimated as Cd/Cm = 0.22. The Kinetics

Adsorbate-induced shifts of electronic surface states: Cs on the (100) faces of tungsten, molybdenum, and tantalum

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

Soukiassian, P.; Riwan, R.; Lecante, J.

1985-04-15

The adsorption of cesium on the (100) faces of W, Mo, and Ta for coverages between 0 and 1 monolayer is studied by angle-resolved ultraviolet photoemission spectroscopy with use of synchro- tron radiation, by electron-energy-loss spectroscopy, and by low-energy electron diffraction. With increasing cesiation, the W(100) surface state at Gamma-bar located 0.3 eV below the Fermi level is shifted by up to 1.0 eV to larger binding energies while remaining sharp and intense. A similar behavior is observed on Ta(100), whereas on Mo(100) the shift of 0.9 eV of this surface state is accompanied by a pronounced attenuation of itsmore » intensity. These experimental shifts are shown to be in excellent agreement with all-electron local-density-functional results obtained with the full-potential linearized augmented-plane-wave method for Cs monolayers on the W(100) and Mo(100) surfaces. Based on these ab initio results, the electronic origin of the shifts is understood by the formation of strongly polarized covalent bonds between the d-like surface states and the Cs 6s--derived valence states. It is argued that even at high Cs coverages, the main electron-energy-loss peaks, which are observed between 1 and 2 eV, could be interpreted as Cs 6s..-->..6p--like interband transitions rather than as surface-plasmon peaks.« less

Phospholipids as an alternative to direct covalent coupling: surface functionalization of nanoporous alumina for protein recognition and purification.

PubMed

Lazzara, Thomas D; Behn, Daniela; Kliesch, Torben-Tobias; Janshoff, Andreas; Steinem, Claudia

2012-01-15

Anodic aluminum oxide (AAO) substrates with aligned, cylindrical, non-intersecting pores with diameters of 75 nm and depths of 3.5 or 10 μm were functionalized with lipid monolayers harboring different receptor lipids. AAO was first functionalized with dodecyl-trichlorosilane, followed by fusion of small unilamellar vesicles (SUVs) forming a lipid monolayer. The SUVs' lipid composition was transferred onto the AAO surface, allowing us to control the surface receptor density. Owing to the optical transparency of the AAO, the overall vesicle spreading process and subsequent protein binding to the receptor-doped lipid monolayers could be investigated in situ by optical waveguide spectroscopy (OWS). SUV spreading occurred at the pore-rim interface, followed by lateral diffusion of lipids within the pore-interior surface until homogeneous coverage was achieved with a lipid monolayer. The functionality of the system was demonstrated through streptavidin binding onto a biotin-DOPE containing POPC membrane, showing maximum protein coverage at 10 mol% of biotin-DOPE. The system enabled us to monitor in real-time the selective extraction of two histidine-tagged proteins, PIGEA14 (14 kDa) and ezrin (70 kDa), directly from cell lysate solutions using a DOGS-NTA(Ni)/DOPC (1:9) membrane. The purification process including protein binding and elution was monitored by OWS and confirmed by SDS-PAGE. Copyright © 2011 Elsevier Inc. All rights reserved.

Temperature-dependent surface density of alkylthiol monolayers on gold nanocrystals

NASA Astrophysics Data System (ADS)

Liu, Xuepeng; Lu, Pin; Zhai, Hua; Wu, Yucheng

2018-03-01

Atomistic molecular dynamics (MD) simulations are performed to study the surface density of passivating monolayers of alkylthiol chains on gold nanocrystals at temperatures ranging from 1 to 800 K. The results show that the surface density of alkylthiol monolayer reaches a maximum value at near room temperature (200-300 K), while significantly decreases with increasing temperature in the higher temperature region (> 300 {{K}}), and slightly decreases with decreasing temperature at low temperature (< 200 {{K}}). We find that the temperature dependence of surface ligand density in the higher temperature region is attributed to the substantial ligand desorption induced by the thermal fluctuation, while that at low temperature results from the reduction in entropy caused by the change in the ordering of passivating monolayer. These results are expected helpful to understand the temperature-dependent surface coverage of gold nanocrystals.

Adsorption of acrolein, propanal, and allyl alcohol on Pd(111): a combined infrared reflection–absorption spectroscopy and temperature programmed desorption study

PubMed Central

Dostert, Karl-Heinz; O'Brien, Casey P.; Mirabella, Francesca; Ivars-Barceló, Francisco

2016-01-01

Atomistic-level understanding of the interaction of α,β-unsaturated aldehydes and their derivatives with late transition metals is of fundamental importance for the rational design of new catalytic materials with the desired selectivity towards C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C vs. CO bond partial hydrogenation. In this study, we investigate the interaction of acrolein, and its partial hydrogenation products propanal and allyl alcohol, with Pd(111) as a prototypical system. A combination of infrared reflection–absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) experiments was applied under well-defined ultrahigh vacuum (UHV) conditions to obtain detailed information on the adsorption geometries of acrolein, propanal, and allyl alcohol as a function of coverage. We compare the IR spectra obtained for multilayer coverages, reflecting the molecular structure of unperturbed molecules, with the spectra acquired for sub-monolayer coverages, at which the chemical bonds of the molecules are strongly distorted. Coverage-dependent IR spectra of acrolein on Pd(111) point to the strong changes in the adsorption geometry with increasing acrolein coverage. Acrolein adsorbs with the CC and CO bonds lying parallel to the surface in the low coverage regime and changes its geometry to a more upright orientation with increasing coverage. TPD studies indicate decomposition of the species adsorbed in the sub-monolayer regime upon heating. Similar strong coverage dependence of the IR spectra were found for propanal and allyl alcohol. For all investigated molecules a detailed assignment of vibrational bands is reported. PMID:27149902

Surface studies of thermionic cathodes and the mechanism of operation of an impregnated tungsten cathode

NASA Technical Reports Server (NTRS)

Forman, R.

1976-01-01

The surface properties of conventional impregnated cathodes were investigated by the use of Auger spectroscopy and work function measurements, and these were compared with a synthesized barium or barium oxide coated tungsten surface. The barium and barium oxide coated surfaces were prepared by evaporating barium onto a tungsten surface that can be heated to elevated temperatures. Multilayer or monolayer coverages can be investigated using this technique. The results of this study show that the surface of an impregnated tungsten cathode is identical to that observed for a synthesized monolayer or partial monolayer of barium on partially oxidized tungsten, using the criteria of identical Auger patterns and work functions. Desorption measurements of barium from a tungsten surface were also made. These results in conjunction with Auger and work function data were interpreted to show that throughout most of its life an impregnated cathode operating in the range of 1100 C has a partial monolayer rather than a monolayer of barium on its surface.

Adsorption behavior of Fe atoms on a naphthalocyanine monolayer on Ag(111) surface

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

Yan, Ling -Hao; Wu, Rong -Ting; Bao, De -Liang

2015-05-29

Adsorption behavior of Fe atoms on a metal-free naphthalocyanine (H 2Nc) monolayer on Ag(111) surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional theory (DFT) based calculations. We found that the Fe atoms adsorbed at the centers of H 2Nc molecules and formed Fe-H 2Nc complexes at low coverage. DFT calculations show that the configuration of Fe at the center of a molecule is the most stable site, in good agreement with the experimental observations. After an Fe-H 2Nc complex monolayer was formed, the extra Fe atoms self-assembled to Fe clusters of uniform sizemore » and adsorbed dispersively at the interstitial positions of Fe-H 2Nc complex monolayer. Furthermore, the H 2Nc monolayer grown on Ag(111) could be a good template to grow dispersed magnetic metal atoms and clusters at room temperature for further investigation of their magnetism-related properties.« less

Molecular nano-arches on silicon

NASA Astrophysics Data System (ADS)

Dobrin, S.

2007-08-01

The formation of molecular nano-arches on the Si(1 1 1)-7 × 7 surface was modeled using density functional theory (DFT). It has been suggested, based on the calculations, that the arches are formed by molecular dimers of chlorobenzene at near-monolayer coverages. Molecules of the dimer are covalently bound to two silicon adatoms and to each other thereby forming a molecular arch on the surface. The structure of the molecular dimer was calculated at the B3LYP/6-31G(d) level of theory. The dimers were found to be stable at room temperature, and to form a near-monolayer coverage, which has been observed in the experiment [X.H. Chen, Q. Kong, J.C. Polanyi, D. Rogers, S. So, Surf. Sci. 340 (1995) 224; Y. Cao, J.F. Deng, G.Q. Xu, J. Chem. Phys. 112 (2000) 4759].

Structural properties of oligonucleotide monolayers on gold surfaces probed by fluorescence investigations.

PubMed

Rant, Ulrich; Arinaga, Kenji; Fujita, Shozo; Yokoyama, Naoki; Abstreiter, Gerhard; Tornow, Marc

2004-11-09

We present optical investigations on the conformation of oligonucleotide layers on Au surfaces. Our studies concentrate on the effect of varying surface coverage densities on the structural properties of layers of 12- and 24mer single-stranded DNA, tethered to the Au surface at one end while being labeled with a fluorescent marker at the opposing end. The distance-dependent energy transfer from the marker dye to the metal surface, which causes quenching of the observed fluorescence, is used to provide information on the orientation of the DNA strands relative to the surface. Variations in the oligonucleotide coverage density, as determined from electrochemical quantification, over 2 orders of magnitude are achieved by employing different preparation conditions. The observed enhancement in fluorescence intensity with increasing DNA coverage can be related to a model involving mutual steric interactions of oligonucleotides on the surface, as well as fluorescence quenching theory. Finally, the applicability of the presented concepts for investigations of heterogeneous monolayers is demonstrated by means of studying the coadsorption of mercaptohexanol onto DNA-modified Au surfaces.

“Click” Immobilization on Alkylated Silicon Substrates: Model for the Study of Surface Bound Antimicrobial Peptides

PubMed Central

Li, Yan; Santos, Catherine M.; Kumar, Amit; Zhao, Meirong; Lopez, Analette I.; Qin, Guoting; McDermott, Alison M.

2011-01-01

We describe an effective approach for the covalent immobilization of antimicrobial peptides (AMPs) to bioinert substrates via CuI-catalyzed azide–alkyne cycloaddition (CuAAC). The bioinert substrates were prepared by surface hydrosilylation of oligo-(ethylene glycol) (OEG) terminated alkenes on hydrogen-terminated silicon surfaces. To render the OEG monolayers “clickable”, mixed monolayers were prepared using OEG-alkenes with and without a terminal alkyne protected by a trimethylgermanyl (TMG) group. The mixed monolayers were characterized by X-ray photoelectron spectroscopy (XPS), elliposometry and contact angle measurement. The TMG protecting group can be readily removed to yield a free terminal alkyne by catalytic amounts of CuI in an aqueous media. This step can then be combined with the subsequent CuAAC reaction. Thus, the immobilization of an azide modified AMP (N3-IG-25) was achieved in a one-pot de-protection/coupling reaction. Varying the ratio of the two alkenes in the deposition mixture allowed for control over the density of the alkynyl groups in the mixed monolayer, and subsequently the coverage of the AMPs on the monolayer. These samples allowed for study of the dependence of antimicrobial activities on the AMP density. The results show that a relative low coverage of AMPs (~1.6×1013 molecule per cm2) is sufficient to significantly suppress the viability of Pseudomonas aeruginosa, while the surface presenting the highest density of AMPs (~2.8×1013 molecule per cm2) is still cyto-compatible. The remarkable antibacterial activity is attributed to the long and flexible linker and the site-specific “click” immobilization, which may facilitate the covalently attached peptides to interact with and disrupt the bacterial membranes. PMID:21264959

Synthesis of Graphene Based Membranes: Effect of Substrate Surface Properties on Monolayer Graphene Transfer.

PubMed

Kafiah, Feras; Khan, Zafarullah; Ibrahim, Ahmed; Atieh, Muataz; Laoui, Tahar

2017-01-21

In this work, we report the transfer of graphene onto eight commercial microfiltration substrates having different pore sizes and surface characteristics. Monolayer graphene grown on copper by the chemical vapor deposition (CVD) process was transferred by the pressing method over the target substrates, followed by wet etching of copper to obtain monolayer graphene/polymer membranes. Scanning electron microscopy (SEM), atomic force microscopy (AFM), and contact angle (CA) measurements were carried out to explore the graphene layer transferability. Three factors, namely, the substrate roughness, its pore size, and its surface wetting (degree of hydrophobicity) are found to affect the conformality and coverage of the transferred graphene monolayer on the substrate surface. A good quality graphene transfer is achieved on the substrate with the following characteristics; being hydrophobic (CA > 90°), having small pore size, and low surface roughness, with a CA to RMS (root mean square) ratio higher than 2.7°/nm.

Formation of positively charged gold nanoparticle monolayers on silica sensors.

PubMed

Oćwieja, Magdalena; Maciejewska-Prończuk, Julia; Adamczyk, Zbigniew; Roman, Maciej

2017-09-01

Formation of positively charged gold nanoparticle monolayers on the Si/SiO 2 was studied under in situ conditions using quartz microbalance (QCM). The gold nanoparticles were synthesized in a chemical reduction method using sodium borohydride as reducing agent. Cysteamine hydrochloride was applied to generate a positive surface charge of nanoparticles. The micrographs obtained from transmission electron microscopy (TEM) revealed that the average size of nanoparticles was equal to 12±3nm. The stability of nanoparticle suspensions under controlled pH and ionic strength was determined by dynamic light scattering (DLS). The electrophoretic mobility measurements showed that the zeta potential of nanoparticles was positive, decreasing with ionic strength and pH from 56mV at pH 4.2 and I=10 -4 M to 22mV at pH 8.3 and I=3×10 -3 M. The surface enhanced Raman spectroscopy (SERS) confirmed chemisorption of cysteamine on nanoparticles and the contribution of amine moieties in the generation of nanoparticle charge. The influence of suspension concentration, ionic strength and flow rate on the kinetics of nanoparticle deposition on the sensors was quantitatively determined. It was confirmed that the deposition for the low coverage regime is governed by the bulk mass transfer that results in a linear increase of the coverage with time. The significant increase in the maximum coverage of gold monolayers with ionic strength was interpreted as due to the decreasing range of the electrostatic interactions among deposited particles. Moreover, the hydratation of formed monolayers, their structure and the stability were determined by the comparison of the QCM results with those obtained by AFM and SEM. The experimental data were adequately interpreted in terms of the extended random sequential adsorption (eRSA) model that considers the bulk and surface transfer steps in a rigorous way. The obtained results are useful for a facile fabrication of gold nanoparticle-based biosensors capable to bind target molecules via available amine moieties. Copyright © 2017 Elsevier Inc. All rights reserved.

Reactive Capture of Gold Nanoparticles by Strongly Physisorbed Monolayers on Graphite

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

Wei, Xiaoliang; Tong, Wenjun; Fidler, Vlastimil

2012-12-01

Anthracene Diels Alder adducts (DAa) bearing two long side chains (H-(CH2)22O(CH2)6OCH2-) at the 1- and 5-positions form self-assembled monolayers (SAMs) at the phenyloctane - highly oriented pyrolytic graphite (HOPG) interface. The long DAa side chains promote strong physisorption of the monolayer to HOPG and maintain the monolayer morphology upon rinsing or incubation in ethanol and air-drying of the substrate. Incorporating a carboxylic acid group on the DAa core enables capture of 1 - 4 nm diameter gold nanoparticles (AuNP) provided (i) the monolayer containing DAa-carboxylic acids is treated with Cu2+ ions and (ii) the organic coating on the AuNP containsmore » carboxylic acids (11-mercaptoundecanoic acid, MUA-AuNP). AuNP capture by the monolayer proceeds with formation of Cu2+ - carboxylate coordination complexes. The captured AuNP appear as mono- and multi-layered clusters at high coverage on HOPG. The surface density of the captured AuNPs can be adjusted from AuNP multi-layers to isolated AuNPs by varying incubation times, MUA-AuNP concentration, the number density of carboxylic acids in the monolayer, the number of MUA per AuNP, and the post-incubation treatments.« less

Real-time x-ray scattering study of the initial growth of organic crystals on polymer brushes

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

An, Sung Yup; Ahn, Kwangseok; Kim, Doris Yangsoo

2014-04-21

We studied the early-stage growth structures of pentacene organic crystals grown on polymer brushes using real-time x-ray scattering techniques. In situ x-ray reflectivity and atomic force microscopy analyses revealed that at temperatures close to the glass transition temperature of polymer brush, the pentacene overlayer on a polymer brush film showed incomplete condensation and 3D island structures from the first monolayer. A growth model based on these observations was used to quantitatively analyze the real-time anti-Bragg x-ray scattering intensities measured during pentacene growth to obtain the time-dependent layer coverage of the individual pentacene monolayers. The extracted total coverage confirmed significant desorptionmore » and incomplete condensation in the pentacene films deposited on the polymer brushes. These effects are ascribed to the change in the surface viscoelasticity of the polymer brushes around the glass transition temperature.« less

First-principles study of adsorption-induced magnetic properties of InSe monolayers

NASA Astrophysics Data System (ADS)

Fu, Zhaoming; Yang, Bowen; Zhang, Na; Ma, Dongwei; Yang, Zongxian

2018-04-01

In this work we studied the adsorption-induced magnetic behaviors on the two-dimensional InSe monolayer. Six kinds of adatoms (H, B, C, N, O and F) are taken into account. It is found that the InSe with adsorbing C and F have nonzero magnetic moments and good stability. Importantly, the magnetism of C and F modified InSe monolayers completely comes from p electrons of adatoms and substrates. The strength of magnetic exchange interaction can be controlled by changing the coverage of adsorbates. This p-electron magnetic material is thought to have obvious advantages compared to conventional d- or f-electron magnets. Our research is meaningful for practical applications in spintronic electronics and two dimensional magnetic semiconductors.

Transition from overlayer growth to alloying growth of Ga on Si(111)-alpha-(sqrt[3]xsqrt[3])-Au.

PubMed

Yamanaka, T; Ino, S

2002-11-04

Atomic depth distribution and growth modes of Ga on an Si(111)-alpha-(sqrt[3]xsqrt[3])-Au surface at room temperature were studied after each monolayer deposition of Ga via reflection high-energy electron diffraction and characteristic x-ray spectroscopy measurements as functions of glancing angle theta(g) of the incident electron beam. One monolayer of Ga grew on the Au layer, and the sqrt[3]xsqrt[3] periodicity was conserved below the Ga overlayer. Above a critical Ga coverage of about one monolayer, this growth mode drastically changed; i.e., Au atoms dissociated from the sqrt[3]xsqrt[3] structure and Ga grew into islands of Ga-Au alloy.

Zn2+ and Sr2+ Adsorption at the TiO2 (110)-Electrolyte Interface: Influence of Ionic Strength, Coverage, and Anions

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

Zhang,Z.; Fenter, P.; Cheng, L.

2006-01-01

The X-ray standing wave technique was used to probe the sensitivity of Zn{sup 2+} and Sr{sup 2+} ion adsorption to changes in both the adsorbed ion coverage and the background electrolyte species and concentrations at the rutile ({alpha}-TiO{sub 2}) (110)-aqueous interface. Measurements were made with various background electrolytes (NaCl, NaTr, RbCl, NaBr) at concentrations as high as 1 m. The results demonstrate that Zn{sub 2+} and Sr{sub 2+} reside primarily in the condensed layer and that the ion heights above the Ti-O surface plane are insensitive to ionic strength and the choice of background electrolyte (with <0.1 Angstroms changes overmore » the full compositional range). The lack of any specific anion coadsorption upon probing with Br{sup -}, coupled with the insensitivity of Zn{sup 2+} and Sr{sup 2+} cation heights to changes in the background electrolyte, implies that anions do not play a significant role in the adsorption of these divalent metal ions to the rutile (110) surface. Absolute ion coverage measurements for Zn{sup 2+} and Sr{sup 2+} show a maximum Stern-layer coverage of {approx}0.5 monolayer, with no significant variation in height as a function of Stern-layer coverage. These observations are discussed in the context of Gouy-Chapman-Stern models of the electrical double layer developed from macroscopic sorption and pH-titration studies of rutile powder suspensions. Direct comparison between these experimental observations and the MUltiSIte Complexation (MUSIC) model predictions of cation surface coverage as a function of ionic strength revealed good agreement between measured and predicted surface coverages with no adjustable parameters.« less

Molecular printboards: monolayers of beta-cyclodextrins on silicon oxide surfaces.

PubMed

Onclin, Steffen; Mulder, Alart; Huskens, Jurriaan; Ravoo, Bart Jan; Reinhoudt, David N

2004-06-22

Monolayers of beta-cyclodextrin host molecules have been prepared on SiO2 surfaces. An ordered and stable cyano-terminated monolayer was modified in three consecutive surface reactions. First, the cyanide groups were reduced to their corresponding free amines using Red Al as a reducing agent. Second, 1,4-phenylene diisothiocyanate was used to react with the amine monolayer where it acts as a linking molecule, exposing isothiocyanates that can be derivatized further. Finally, per-6-amino beta-cyclodextrin was reacted with these isothiocyanate functions to yield a monolayer exposing beta-cyclodextrin. All monolayers were characterized by contact angle measurements, ellipsometric thickness measurements, Brewster angle Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry, which indicate the formation of a densely packed cyclodextrin surface. It was demonstrated that the beta-cyclodextrin monolayer could bind suitable guest molecules in a reversible manner. A fluorescent molecule (1), equipped with two adamantyl groups for complexation, was adsorbed onto the host monolayer from solution to form a monolayer of guest molecules. Subsequently, the guest molecules were desorbed from the surface by competition with increasing beta-cyclodextrin concentration in solution. The data were fitted using a model. An intrinsic binding constant of 3.3 +/- 1 x 10(5) M(-1) was obtained, which corresponds well to previously obtained results with a divalent guest molecule on beta-cyclodextrin monolayers on gold. In addition, the number of guest molecules bound to the host surface was determined, and a surface coverage of ca. 30% was found.

Positron states on the Cs/Cu(100) surface

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

Koeymen, A.R.; Lee, K.H.; Mehl, D.

1991-02-01

The attenuation of the CuM{sub 23}VV Auger peak with Cs coverage on Cu(100) is measured using both positron-annihilation-induced Auger electron emission (PAES) and conventional (electron induced) Auger electron spectroscopy (EAES). The Cs coverage varies from 0 to 1 physical monolayer (ML). The data indicates that below 0.5 ML in agreement with first order theoretical calculations the positrons are trapped at the Cu/Cs interface. At higher Cs coverages the thermal desorption of the positrons as positronium drops the PAES intensity to zero whereas the EAES signal changes linearly as expected.

Aryl diazonium for biomolecules immobilization onto SPRi chips.

PubMed

Mandon, Céline A; Blum, Loïc J; Marquette, Christophe A

2009-12-21

A method for the immobilization of proteins at the surface of surface plasmon resonance imaging (SPRi) chips is presented. The technology, based on the electro-deposition of a 4-carboxymethyl aryl diazonium (CMA) monolayer is compared to a classical thioctic acid self-assembled monolayer. SPRi live recording experiments followed by the quantification of the diazonium surface coverage demonstrate the presence of a monolayer of electro-deposited molecules (11*10(12) molecules mm(-2)). This monolayer, when activated through a classical carbodiimide route, generates a surface suitable for the protein immobilization. In the present study, protein A and BSA are immobilized as specific and control spots (150 microm id), respectively. The AFM characterization of the spots deposited onto CMA or thioctic acid modified chips prove the presence of 4.7 nm protein monolayers. Finally, the SPRi detection capabilities of the two surface chemistries are compared according to specific signal, non-specific interaction and regeneration possibilities. Advantages are given to the CMA surface modification since no measurable non-specific signal is obtained while reaching a higher specific signal.

The Effects of Anchor Groups on (1) TiO2-Catalyzed Photooxidation and (2) Linker-Assisted Assembly on TiO2

NASA Astrophysics Data System (ADS)

Anderson, Ian Mark

Quantum dot-sensitized solar cells (QDSSCs) are a popular target for research due to their potential for highly efficient, easily tuned absorption. Typically, light is absorbed by quantum dots attached to a semiconductor substrate, such as TiO2, via bifunctional linker molecules. This research aims to create a patterned monolayer of linker molecules on a TiO2 film, which would in turn allow the attachment of a patterned layer of quantum dots. One method for the creation of a patterned monolayer is the functionalization of a TiO2 film with a linker molecule, followed by illumination with a laser at 355 nm. This initiates a TiO 2-catalyzed oxidation reaction, causing loss of surface coverage. A second linker molecule can then be adsorbed onto the TiO2 surface in the illuminated area. Towards that end, the behaviors of carboxylic and phosphonic acids adsorbed on TiO2 have been studied. TiO2 films were functionalized by immersion in solutions a single adsorbate and surface coverage was determined by IR spectroscopy. It is shown that phosphonic acids attain higher surface coverage than carboxylic acids, and will displace them from TiO2 when in a polar solvent. Alkyl chain lengths, which can influence stabilities of monolayers, are shown not to have an effect on this relationship. Equilibrium binding data for the adsorption of n-hexadecanoic acid to TiO2 from a THF solution are presented. It is shown that solvent polarity can affect monolayer stability; carboxylates and phosphonates undergo more desorption into polar solvents than nonpolar. Through illumination, it was possible to remove nearly all adsorbed linkers from TiO2. However, the illuminated areas were found not to be receptive to attachment by a second adsorbate. A possible reason for this behavior is presented. I also report on the synthesis and characterization of a straight-chain, thiol-terminated phosphonic acid. Initial experiments involving monolayer formation and quantum dot attachment are presented. Finally, it was found that quantum dots attach in high amounts to linker-functionalized TiO2 when suspended in pyridine. This increased surface attachment was present even when the linker molecule used lacked a functional group which would bind to the CdSe surface.

Formation and stability of dense arrays of Au nanoclusters on hexagonal boron nitride/Rh(111)

NASA Astrophysics Data System (ADS)

Patterson, Matthew C.; Habenicht, Bradley F.; Kurtz, Richard L.; Liu, Li; Xu, Ye; Sprunger, Phillip T.

2014-05-01

We have studied the nucleation and growth of Au clusters at submonolayer and greater coverages on the h-BN nanomesh grown on Rh(111) by means of scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). STM reveals that submonolayer Au deposited at 115 K nucleates within the nanomesh pores and remains confined to the pores even after warming to room temperature. Whereas there is a propensity of monoatomic high islands at low temperature, upon annealing, bi- and multilayer Au clusters emerge. Deposition of higher coverages of Au similarly results in Au clusters primarily confined to the nanomesh pores at room temperature. XPS analysis of core-level electronic states in the deposited Au shows strong final-state effects induced by restricted particle size dominating for low Au coverage, with indications that larger Au clusters are negatively charged by interaction through the h-BN monolayer. DFT calculations suggest that the structure of the Au clusters transitions from monolayer to bilayer at a size between 30 and 37 atoms per cluster, in line with our experiment. Bader charge analysis supports the negative charge state of deposited Au.

High coverage fluid-phase floating lipid bilayers supported by ω-thiolipid self-assembled monolayers

PubMed Central

Hughes, Arwel V.; Holt, Stephen A.; Daulton, Emma; Soliakov, Andrei; Charlton, Timothy R.; Roser, Steven J.; Lakey, Jeremy H.

2014-01-01

Large area lipid bilayers, on solid surfaces, are useful in physical studies of biological membranes. It is advantageous to minimize the interactions of these bilayers with the substrate and this can be achieved via the formation of a floating supported bilayer (FSB) upon either a surface bound phospholipid bilayer or monolayer. The FSB's independence is enabled by the continuous water layer (greater than 15 Å) that remains between the two. However, previous FSBs have had limited stability and low density. Here, we demonstrate by surface plasmon resonance and neutron reflectivity, the formation of a complete self-assembled monolayer (SAM) on gold surfaces by a synthetic phosphatidylcholine bearing a thiol group at the end of one fatty acyl chain. Furthermore, a very dense FSB (more than 96%) of saturated phosphatidylcholine can be formed on this SAM by sequential Langmuir–Blodgett and Langmuir–Schaefer procedures. Neutron reflectivity used both isotopic and magnetic contrast to enhance the accuracy of the data fits. This system offers the means to study transmembrane proteins, membrane potential effects (using the gold as an electrode) and even model bacterial outer membranes. Using unsaturated phosphatidylcholines, which have previously failed to form stable FSBs, we achieved a coverage of 73%. PMID:25030385

Growth patterns of self-assembled InAs quantum dots near the two-dimensional to three-dimensional transition

NASA Astrophysics Data System (ADS)

Colocci, M.; Bogani, F.; Carraresi, L.; Mattolini, R.; Bosacchi, A.; Franchi, S.; Frigeri, P.; Rosa-Clot, M.; Taddei, S.

1997-06-01

Self-assembled InAs quantum dots have been grown by molecular beam epitaxy in such a way as to obtain a continuous variation of InAs coverages across the wafer. Structured photoluminescence spectra are observed after excitation of a large number of dots; deconvolution into Gaussian components yields narrow emission bands (full width at half-maximum 20-30 meV) separated in energy by an average spacing of 30-40 meV. We ascribe the individual bands of the photoluminescence spectra after low excitation to families of dots with similar shapes and with heights differing by one monolayer, as strongly supported by numerical calculations of the fundamental electronic transitions in quantum dot structures.

Nanoparticle layer deposition for highly controlled multilayer formation based on high- coverage monolayers of nanoparticles

PubMed Central

Liu, Yue; Williams, Mackenzie G.; Miller, Timothy J.; Teplyakov, Andrew V.

2015-01-01

This paper establishes a strategy for chemical deposition of functionalized nanoparticles onto solid substrates in a layer-by-layer process based on self-limiting surface chemical reactions leading to complete monolayer formation within the multilayer system without any additional intermediate layers – nanoparticle layer deposition (NPLD). This approach is fundamentally different from previously established traditional layer-by-layer deposition techniques and is conceptually more similar to well-known atomic and molecular – layer deposition processes. The NPLD approach uses efficient chemical functionalization of the solid substrate material and complementary functionalization of nanoparticles to produce a nearly 100% coverage of these nanoparticles with the use of “click chemistry”. Following this initial deposition, a second complete monolayer of nanoparticles is deposited using a copper-catalyzed “click reaction” with the azide-terminated silica nanoparticles of a different size. This layer-by-layer growth is demonstrated to produce stable covalently-bound multilayers of nearly perfect structure over macroscopic solid substrates. The formation of stable covalent bonds is confirmed spectroscopically and the stability of the multilayers produced is tested by sonication in a variety of common solvents. The 1-, 2- and 3-layer structures are interrogated by electron microscopy and atomic force microscopy and the thickness of the multilayers formed is fully consistent with that expected for highly efficient monolayer formation with each cycle of growth. This approach can be extended to include a variety of materials deposited in a predesigned sequence on different substrates with a highly conformal filling. PMID:26726273

Wafer-scale synthesis of monolayer and few-layer MoS2 via thermal vapor sulfurization

NASA Astrophysics Data System (ADS)

Robertson, John; Liu, Xue; Yue, Chunlei; Escarra, Matthew; Wei, Jiang

2017-12-01

Monolayer molybdenum disulfide (MoS2) is an atomically thin, direct bandgap semiconductor crystal potentially capable of miniaturizing optoelectronic devices to an atomic scale. However, the development of 2D MoS2-based optoelectronic devices depends upon the existence of a high optical quality and large-area monolayer MoS2 synthesis technique. To address this need, we present a thermal vapor sulfurization (TVS) technique that uses powder MoS2 as a sulfur vapor source. The technique reduces and stabilizes the flow of sulfur vapor, enabling monolayer wafer-scale MoS2 growth. MoS2 thickness is also controlled with great precision; we demonstrate the ability to synthesize MoS2 sheets between 1 and 4 layers thick, while also showing the ability to create films with average thickness intermediate between integer layer numbers. The films exhibit wafer-scale coverage and uniformity, with electrical quality varying depending on the final thickness of the grown MoS2. The direct bandgap of grown monolayer MoS2 is analyzed using internal and external photoluminescence quantum efficiency. The photoluminescence quantum efficiency is shown to be competitive with untreated exfoliated MoS2 monolayer crystals. The ability to consistently grow wafer-scale monolayer MoS2 with high optical quality makes this technique a valuable tool for the development of 2D optoelectronic devices such as photovoltaics, detectors, and light emitters.

Phosphonic Acids on an Atomically Defined Oxide Surface: The Binding Motif Changes with Surface Coverage.

PubMed

Schuschke, Christian; Schwarz, Matthias; Hohner, Chantal; Silva, Thais N; Fromm, Lukas; Döpper, Tibor; Görling, Andreas; Libuda, Jörg

2018-04-19

We have studied the anchoring mechanism of a phosphonic acid on an atomically defined oxide surface. Using time-resolved infrared reflection absorption spectroscopy, we investigated the reaction of deuterated phenylphosphonic acid (DPPA, C 6 H 5 PO 3 D 2 ) with an atomically defined Co 3 O 4 (111) surface in situ during film growth by physical vapor deposition. We show that the binding motif of the phosphonate anchor group changes as a function of coverage. At low coverage, DPPA binds in the form of a chelating tridentate phosphonate, while a transition to a chelating bidentate occurs close to monolayer saturation coverage. However, the coverage-dependent change in the binding motif is not associated with a major change of the molecular orientation, suggesting that the rigid phosphonate linker always maintains the DPPA in a strongly tilted orientation irrespective of the surface coverage.

A systematic study of atmospheric pressure chemical vapor deposition growth of large-area monolayer graphene.

PubMed

Liu, Lixin; Zhou, Hailong; Cheng, Rui; Chen, Yu; Lin, Yung-Chen; Qu, Yongquan; Bai, Jingwei; Ivanov, Ivan A; Liu, Gang; Huang, Yu; Duan, Xiangfeng

2012-01-28

Graphene has attracted considerable interest as a potential material for future electronics. Although mechanical peel is known to produce high quality graphene flakes, practical applications require continuous graphene layers over a large area. The catalyst-assisted chemical vapor deposition (CVD) is a promising synthetic method to deliver wafer-sized graphene. Here we present a systematic study on the nucleation and growth of crystallized graphene domains in an atmospheric pressure chemical vapor deposition (APCVD) process. Parametric studies show that the mean size of the graphene domains increases with increasing growth temperature and CH 4 partial pressure, while the density of domains decreases with increasing growth temperature and is independent of the CH 4 partial pressure. Our studies show that nucleation of graphene domains on copper substrate is highly dependent on the initial annealing temperature. A two-step synthetic process with higher initial annealing temperature but lower growth temperature is developed to reduce domain density and achieve high quality full-surface coverage of monolayer graphene films. Electrical transport measurements demonstrate that the resulting graphene exhibits a high carrier mobility of up to 3000 cm 2 V -1 s -1 at room temperature.

IR spectroscopic study of the displacement of an SF6 monolayer on graphite by Xe

NASA Astrophysics Data System (ADS)

Hess, G. B.; Xia, Yu

2017-09-01

We report a study of displacement by xenon of a monolayer of sulphur hexafluoride initially condensed on a graphite surface. Earlier work showed that, below 112 K, Xe displaces SF6 almost completely in a first-order transition. Working at higher temperatures, we show that this system has a simple eutectic-like phase diagram, at least for SF6 not too dilute. In our experiment, both adsorbates are in equilibrium with their respective vapors in a cold cell. In our infrared reflection-absorption spectroscopy measurements, the SF6 coverage on the surface is monitored by the frequency shift due to dynamic dipole coupling of the collective mode of the strong SF6 ν3 vibrational resonance. Simulations relate this frequency shift to the SF6 areal density. Below T ≈ 134 K, with increasing Xe pressure, a small amount Xe dissolves in the solid SF6 monolayer preceding its displacement by a solid predominantly Xe monolayer in a first-order transition. Above 134 K, there is a weaker first-order transition to a mixed liquid monolayer, followed by continuous increase in Xe concentration. If the initial SF6 monolayer is near its melting line, the melting transition on adding Xe appears to become continuous.

IR spectroscopic study of the displacement of an SF6 monolayer on graphite by Xe.

PubMed

Hess, G B; Xia, Yu

2017-09-07

We report a study of displacement by xenon of a monolayer of sulphur hexafluoride initially condensed on a graphite surface. Earlier work showed that, below 112 K, Xe displaces SF 6 almost completely in a first-order transition. Working at higher temperatures, we show that this system has a simple eutectic-like phase diagram, at least for SF 6 not too dilute. In our experiment, both adsorbates are in equilibrium with their respective vapors in a cold cell. In our infrared reflection-absorption spectroscopy measurements, the SF 6 coverage on the surface is monitored by the frequency shift due to dynamic dipole coupling of the collective mode of the strong SF 6 ν 3 vibrational resonance. Simulations relate this frequency shift to the SF 6 areal density. Below T ≈ 134 K, with increasing Xe pressure, a small amount Xe dissolves in the solid SF 6 monolayer preceding its displacement by a solid predominantly Xe monolayer in a first-order transition. Above 134 K, there is a weaker first-order transition to a mixed liquid monolayer, followed by continuous increase in Xe concentration. If the initial SF 6 monolayer is near its melting line, the melting transition on adding Xe appears to become continuous.

A surprising way to control the charge transport in molecular electronics: the subtle impact of the coverage of self-assembled monolayers of floppy molecules adsorbed on metallic electrodes.

PubMed

Bâldea, Ioan

2017-10-26

Inspired by earlier attempts in organic electronics aiming at controlling charge injection from metals into organic materials by manipulating the Schottky energy barrier using self-assembled monolayers (SAMs), recent experimental and theoretical work in molecular electronics showed that metal-organic interfaces can be controlled via changes in the metal work function that are induced by SAMs. In this paper we indicate a different route to achieve interface-driven control over the charge transfer/transport at the molecular scale. It is based on the fact that, in floppy molecule based SAMs, the molecular conformation can be tuned by varying the coverage of the adsorbate. We demonstrate this effect with the aid of benchmark molecules that are often used to fabricate nanojunctions and consist of two rings that can easily rotate relative to each other. We show that, by varying the coverage of the SAM, the twisting angle φ of the considered molecular species can be modified by a factor of two. Given the fact that the low bias conductance G scales as cos 2  φ, this results in a change in G of over one order of magnitude for the considered molecular species. Tuning the twisting angle by controlling the SAM coverage may be significant, e.g., for current efforts to fabricate molecular switches. Conversely, the lack of control over the local SAM coverage may be problematic for the reproducibility and interpretation of the STM (scanning tunneling microscope) measurements on repeatedly forming single molecule break junctions.

Effect of the size of silver nanoparticles on SERS signal enhancement

NASA Astrophysics Data System (ADS)

He, Rui Xiu; Liang, Robert; Peng, Peng; Norman Zhou, Y.

2017-08-01

The localized surface plasmon resonance arising from plasmonic materials is beneficial in solution-based and thin-film sensing applications, which increase the sensitivity of the analyte being tested. Silver nanoparticles from 35 to 65 nm in diameter were synthesized using a low-temperature method and deposited in a monolayer on a (3-aminopropyl)triethoxysilane (APTES)-functionalized glass slide. The effect of particle size on monolayer structure, optical behavior, and surface-enhanced Raman scattering (SERS) is studied. While increasing particle size decreases particle coverage, it also changes the localized surface plasmon resonance and thus the SERS activity of individual nanoparticles. Using a laser excitation wavelength of 633 nm, the stronger localized surface plasmon resonance coupling to this excitation wavelength at larger particle sizes trumps the loss in surface coverage, and greater SERS signals are observed. The SERS signal enhancement accounts for the higher SERS signal, which was verified using a finite element model of a silver nanoparticle dimer with various nanoparticle sizes and separation distances.

Surface-interface exploration of Mg deposited on Si(100) and oxidation effect on interfacial layer

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

Sarpi, B.; Daineche, R.; Girardeaux, C.

Using scanning tunneling microscopy and spectroscopy, Auger electron spectroscopy, and low energy electron diffraction, we have studied the growth of Mg deposited on Si(100)-(2 × 1). Coverage from 0.05 monolayer (ML) to 3 ML was investigated at room temperature. The growth mode of the magnesium is a two steps process. At very low coverage, there is formation of an amorphous ultrathin silicide layer with a band gap of 0.74 eV, followed by a layer-by-layer growth of Mg on top of this silicide layer. Topographic images reveal that each metallic Mg layer is formed by 2D islands coalescence process on top of the silicidemore » interfacial layer. During oxidation of the Mg monolayer, the interfacial silicide layer acts as diffusion barrier for the oxygen atoms with a decomposition of the silicide film to a magnesium oxide as function of O{sub 2} exposure.« less

Tuning the structure of thermosensitive gold nanoparticle monolayers.

PubMed

Rezende, Camila A; Shan, Jun; Lee, Lay-Theng; Zalczer, Gilbert; Tenhu, Heikki

2009-07-23

Gold nanoparticles grafted with poly(N-isopropylacrylamide) (PNIPAM) are rendered amphiphilic and thermosensitive. When spread on the surface of water, they form stable Langmuir monolayers that exhibit surface plasmon resonance. Using Langmuir balance and contrast-matched neutron reflectivity, the detailed structural properties of these nanocomposite monolayers are revealed. At low surface coverage, the gold nanoparticles are anchored to the interface by an adsorbed PNIPAM layer that forms a thin and compact pancake structure. Upon isothermal compression (T=20 degrees C), the adsorbed layer thickens with partial desorption of polymer chains to form brush structures. Two distinct polymer conformations thus coexist: an adsorbed conformation that assures stability of the monolayer, and brush structures that dangle in the subphase. An increase in temperature to 30 degrees C results in contractions of both adsorbed and brush layers with a concomitant decrease in interparticle distance, indicating vertical as well as lateral contractions of the graft polymer layer. The reversibility of this thermal response is also shown by the contraction-expansion of the polymer layers in heating-cooling cycles. The structure of the monolayer can thus be tuned by compression and reversibly by temperature. These compression and thermally induced conformational changes are discussed in relation to optical properties.

Dispersion of nano-silicon carbide (SiC) powder in aqueous suspensions

NASA Astrophysics Data System (ADS)

Singh, Bimal P.; Jena, Jayadev; Besra, Laxmidhar; Bhattacharjee, Sarama

2007-10-01

The dispersion characteristics of nanosize silicon carbide (SiC) suspension were investigated in terms of surface charge, particle size, rheological measurement and adsorption study. Ammonium polycarboxylate has been used as dispersant to stabilize the suspension. It was found that the isoelectric point (iep) of SiC powder was pHiep (4.9). The surface charge of powder changed significantly in presence of the ammonium polycarboxylate dispersant and iep shifted significantly towards lower acidic pH (3.6). The shift in iep has been quantified in terms of Δ G 0 SP, the specific free energy of adsorption between the surface sites and the adsorbing polyelectrolyte (APC). The values of Δ G 0 SP (-10.85 RT unit) estimated by the electro kinetic data compare well with those obtained from adsorption isotherms (-9.521 RT unit). The experimentally determined optimum concentration of dispersant required for maximizing the dispersion was found to be 2.4 mg/g of SiC (corresponding to an adsorbed amount of 1.10 mg/g), at pH 7.5. This is much below the full monolayer coverage (corresponding to adsorbed amount of 1.75 mg/g) of the particles surface by the dispersant. The surface charge quantity, rheological, pH, electro kinetic and adsorption isotherm results were used to explain and correlate the stability of the nanosize silicon carbide in aqueous media. At pH 7.5, where both SiC surface and APC are negatively charged, the adsorption of APC was low because of limited availability of favourable adsorption sites. In addition, the brush-like configuration of the adsorbed polymer prevented close approach of any additional dispersant; hence stabilization of the slurry happens at a comparatively lower concentration than the monolayer coverage.

Pulmonary surfactant protein C containing lipid films at the air-water interface as a model for the surface of lung alveoli.

PubMed

Post, A; Nahmen, A V; Schmitt, M; Ruths, J; Riegler, H; Sieber, M; Galla, H J

1995-01-01

The pulmonary surfactant lines as a complex monolayer of lipids and proteins the alveolar epithelial surface. The monolayer dynamically adapts the surface tension of this interface to the varying surface areas during inhalation and exhalation. Its presence in the alveoli is thus a prerequisite for a proper lung function. The lipid moiety represents about 90% of the surfactant and contains mainly dipalmitoylphosphatidylcholine (DPPC) and phosphatidylglycerol (PG). The surfactant proteins involved in the surface tension adaption are called SP-A, SP-B and SP-C. The aim of the present investigation is to analyse the properties of monolayer films made from pure SP-C and from mixtures of DPPC, DPPG and SP-C in order to mimic the surfactant monolayer with minimal compositional requirement. Pressure-area diagrams were taken. Ellipsometric measurements at the air-water interface of a Langmuir film balance allowed measurement of the changes in monolayer thickness upon compression. Isotherms of pure SP-C monolayers exhibit a plateau between 22 and 25 mN/m. A further plateau is reached at higher compression. Structures of the monolayer formed during compression are reversible during expansion. Together with ellipsometric data which show a stepwise increase in film thickness (coverage) during compression, we conclude that pure SP-C films rearrange reversibly into multilayers of homogenous thickness. Lipid monolayers collapse locally and irreversibly if films are compressed to approximately 0.4 nm2/molecule. In contrast, mixed DPPG/SP-C monolayers with less than 5 mol% protein collapse in a controlled and reversible way. The pressure-area diagrams exhibit a plateau at 20 mN/m, indicating partial demixing of SP-C and DPPG.(ABSTRACT TRUNCATED AT 250 WORDS)

Interfacial and thermal energy driven growth and evolution of Langmuir-Schaefer monolayers of Au-nanoparticles.

PubMed

Mukhopadhyay, Mala; Hazra, S

2018-01-03

Structures of Langmuir-Schaefer (LS) monolayers of thiol-coated Au-nanoparticles (DT-AuNPs) deposited on H-terminated and OTS self-assembled Si substrates (of different hydrophobic strength and stability) and their evolution with time under ambient conditions, which plays an important role for their practical use as 2D-nanostructures over large areas, were investigated using the X-ray reflectivity technique. The strong effect of substrate surface energy (γ) on the initial structures and the competitive role of room temperature thermal energy (kT) and the change in interfacial energy (Δγ) at ambient conditions on the evolution and final structures of the DT-AuNP LS monolayers are evident. The strong-hydrophobic OTS-Si substrate, during transfer, seems to induce strong attraction towards hydrophobic DT-AuNPs on hydrophilic (repulsive) water to form vertically compact partially covered (with voids) monolayer structures (of perfect monolayer thickness) at low pressure and nearly covered buckled monolayer structures (of enhanced monolayer thickness) at high pressure. After transfer, the small kT-energy (in absence of repulsive water) probably fluctuates the DT-AuNPs to form vertically expanded monolayer structures, through systematic exponential growth with time. The effect is prominent for the film deposited at low pressure, where the initial film-coverage and film-thickness are low. On the other hand, the weak-hydrophobic H-Si substrate, during transfer, appears to induce optimum attraction towards DT-AuNPs to better mimic the Langmuir monolayer structures on it. After transfer, the change in the substrate surface nature, from weak-hydrophobic to weak-hydrophilic with time (i.e. Δγ-energy, apart from the kT-energy), enhances the size of the voids and weakens the monolayer/bilayer structure to form a similar expanded monolayer structure, the thickness of which is probably optimized by the available thermal energy.

Coverage Dependent Assembly of Anthraquinone on Au(111)

NASA Astrophysics Data System (ADS)

Conrad, Brad; Deloach, Andrew; Einstein, Theodore; Dougherty, Daniel

A study of adsorbate-adsorbate and surface state mediated interactions of anthraquinone (AnQ) on Au(111) is presented. We utilize scanning tunneling microscopy (STM) to characterize the coverage dependence of AnQ structure formation. Ordered structures are observed up to a single monolayer (ML) and are found to be strongly dependent on molecular surface density. While the complete ML forms a well-ordered close-packed layer, for a narrow range of sub-ML coverages irregular close-packed islands are observed to coexist with a disordered pore network linking neighboring islands. This network displays a characteristic pore size and at lower coverages, the soliton walls of the herringbone reconstruction are shown to promote formation of distinct pore nanostructures. We will discuss these nanostructure formations in the context of surface mediated and more direct adsorbate interactions.

Ice-like water supports hydration forces and eases sliding friction

PubMed Central

Dhopatkar, Nishad; Defante, Adrian P.; Dhinojwala, Ali

2016-01-01

The nature of interfacial water is critical in several natural processes, including the aggregation of lipids into the bilayer, protein folding, lubrication of synovial joints, and underwater gecko adhesion. The nanometer-thin water layer trapped between two surfaces has been identified to have properties that are very different from those of bulk water, but the molecular cause of such discrepancy is often undetermined. Using surface-sensitive sum frequency generation (SFG) spectroscopy, we discover a strongly coordinated water layer confined between two charged surfaces, formed by the adsorption of a cationic surfactant on the hydrophobic surfaces. By varying the adsorbed surfactant coverage and hence the surface charge density, we observe a progressively evolving water structure that minimizes the sliding friction only beyond the surfactant concentration needed for monolayer formation. At complete surfactant coverage, the strongly coordinated confined water results in hydration forces, sustains confinement and sliding pressures, and reduces dynamic friction. Observing SFG signals requires breakdown in centrosymmetry, and the SFG signal from two oppositely oriented surfactant monolayers cancels out due to symmetry. Surprisingly, we observe the SFG signal for the water confined between the two charged surfactant monolayers, suggesting that this interfacial water layer is noncentrosymmetric. The structure of molecules under confinement and its macroscopic manifestation on adhesion and friction have significance in many complicated interfacial processes prevalent in biology, chemistry, and engineering. PMID:27574706

Adsorption of alkali and alkaline earth metal atoms and dimers on monolayer germanium carbide

NASA Astrophysics Data System (ADS)

Gökçe, Aytaç Gürhan; Ersan, Fatih

2017-01-01

First-principles plane wave calculations have been performed to study the adsorption of alkali and alkaline earth metals on monolayer germanium carbide (GeC). We found that the favourable adsorption sites on GeC sheet for single alkali and alkaline earth adatoms are generally different from graphene or germanene. Among them, Mg, Na and their dimers have weakly bounded to GeC due to their closed valence electron shells, so they may have high mobility on GeC. Two different levels of adatom coverage (? and ?) have been investigated and we concluded that different electronic structures and magnetic moments for both coverages owing to alkali and alkaline earth atoms have long range electrostatic interactions. Lithium atom prefers to adsorbed on hollow site similar to other group-IV monolayers and the adsorption results in metallisation of GeC instead of semiconducting behaviour. Na and K adsorption can induce 1 ? total magnetic moment on GeC structures and they have shown semiconductor property which may have potential use in spintronic devices. We also showed that alkali or alkaline earth metal atoms can form dimer on GeC sheet. Calculated adsorption energies suggest that clustering of alkali and alkaline earth atoms is energetically favourable. All dimer adsorbed GeC systems have nonmagnetic semiconductor property with varying band gaps from 0.391 to 1.311 eV which are very suitable values for various device applications.

Thermodynamic balance of perylene self-assembly on Ag(110)

NASA Astrophysics Data System (ADS)

Bobrov, Kirill; Kalashnyk, Nataliya; Guillemot, Laurent

2016-10-01

We present a room temperature STM study of perylene adsorption on Ag(110) at the monolayer coverage regime. We found that structure and symmetry of the perylene monolayer are settled by thermodynamic balance of the three factors: (i) the ability of perylene molecules to recognize specific adsorption sites on the (110) lattice, (ii) the intermolecular interaction, and (iii) the accommodation of thermal motion of the molecules. The moderate strength of the site recognition and the intermolecular interaction, of the same order of magnitude as kT ˜ 25 meV, represents a key feature of the thermodynamic balance. It bestows to this system the unique quality to form the quasi-liquid monolayer of epitaxial as well as self-assembling character. The perylene monolayer accommodates the short-range motion of the molecules instead of quenching it. It precludes the formation of possible solid nuclei and maintains common registry of the included molecules. The surface registry of the quasi-liquid phase is provided by locking of a structure-related fraction of the perylene molecules into specific adsorption sites of the (110) lattice favorable in terms of intermolecular interaction.

Nanoparticle monolayers under stress: mechanically forced desorption from a fluid-fluid interface

NASA Astrophysics Data System (ADS)

Garbin, Valeria; Crocker, John C.; Stebe, Kathleen J.

2011-11-01

Nanoparticle-laden interfaces are studied for applications to materials with tunable electronic and optical properties, as emulsion stabilizers, and in catalysis. The mechanical response of nanoparticle monolayers under applied stress is of emerging interest since it impacts the success of these applications. Here we focus on the response of nanoparticle-laden interfaces to compression. A monolayer of nanoparticles is allowed to spontaneously form by adsorption from an aqueous suspension onto a pendant drop of oil. The effective surface pressure Π of the composite interface is monitored by pendant drop tensiometry. As the drop is compressed, the nanoparticles are mechanically forced out of the interface into the aqueous phase. A new optical method is developed to measure the nanoparticle area density in situ. We show that desorption occurs at a coverage that corresponds to close packing of the ligand-capped particles, suggesting that ligand-induced repulsion plays a crucial role in the desorption process.

Ordering of Air-Oxidized Decanethiols on Au(111).

PubMed

Sotthewes, Kai; Kap, Özlem; Wu, Hairong; Thompson, Damien; Huskens, Jurriaan; Zandvliet, Harold J W

2018-04-19

Self-assembled monolayers (SAMs) of alkanethiols on gold are a commonly used platform for nanotechnology owing to their ease of preparation and high surface coverage. Unfortunately, the gold-sulfur bond is oxidized at ambient conditions which alters the stability and structure of the monolayer. We show using scanning tunneling microscopy and X-ray photoelectron spectroscopy that decanethiolate molecules oxidize into decanesulfonates that organize into a hitherto unknown striped phase. Air-exposed SAMs oxidize, as can be determined by a shift of the S 2p peak and the appearance of O 1s photoelectrons as part of the decanethiol monolayer transforms into a lamellae-like decanesulfonate structure when exposed to air. The herringbone structure of the Au(111) surface is preserved, indicating that the interaction between the molecules and the surface is rather weak as these findings are substantiated by density functional theory calculations.

Passivation of InGaAs(001)-(2 × 4) by Self-Limiting Chemical Vapor Deposition of a Silicon Hydride Control Layer.

PubMed

Edmonds, Mary; Kent, Tyler; Chagarov, Evgueni; Sardashti, Kasra; Droopad, Ravi; Chang, Mei; Kachian, Jessica; Park, Jun Hong; Kummel, Andrew

2015-07-08

A saturated Si-Hx seed layer for gate oxide or contact conductor ALD has been deposited via two separate self-limiting and saturating CVD processes on InGaAs(001)-(2 × 4) at substrate temperatures of 250 and 350 °C. For the first self-limiting process, a single silicon precursor, Si3H8, was dosed at a substrate temperature of 250 °C, and XPS results show the deposited silicon hydride layer saturated at about 4 monolayers of silicon coverage with hydrogen termination. STS results show the surface Fermi level remains unpinned following the deposition of the saturated silicon hydride layer, indicating the InGaAs surface dangling bonds are electrically passivated by Si-Hx. For the second self-limiting process, Si2Cl6 was dosed at a substrate temperature of 350 °C, and XPS results show the deposited silicon chloride layer saturated at about 2.5 monolayers of silicon coverage with chlorine termination. Atomic hydrogen produced by a thermal gas cracker was subsequently dosed at 350 °C to remove the Si-Cl termination by replacing with Si-H termination as confirmed by XPS, and STS results confirm the saturated Si-Hx bilayer leaves the InGaAs(001)-(2 × 4) surface Fermi level unpinned. Density function theory modeling of silicon hydride surface passivation shows an Si-Hx monolayer can remove all the dangling bonds and leave a charge balanced surface on InGaAs.

Density-functional theory study of the initial oxygen incorporation in Pd(111)

NASA Astrophysics Data System (ADS)

Todorova, Mira; Reuter, Karsten; Scheffler, Matthias

2005-05-01

Pd(111) has recently been shown to exhibit a propensity to form a subnanometer thin surface oxide film already well before a full monolayer coverage of adsorbed O atoms is reached on the surface. Aiming at an atomic-scale understanding of this finding, we study the initial oxygen incorporation into the Pd(111) surface using density-functional theory. We find that oxygen incorporation into the sub-surface region starts at essentially the same coverage as formation of the surface oxide. This implies that the role of sub-surface oxygen should be considered as that of a metastable precursor in the oxidation process of the surface. The mechanisms found to play a role towards the ensuing stabilization of an ordered oxidic structure with a mixed on-surface/sub-surface site occupation follow a clear trend over the late 4d transition metal series, as seen by comparing our data to previously published studies concerned with oxide formation at the basal surface of Ru, Rh, and Ag. The formation of a linearly aligned O-TM-O trilayered structure (TM=Ru,Rh,Pd,Ag) , together with an efficient coupling to the underlying substrate seem to be key ingredients in this respect.

The First Layer of 4He, H2, and Ne Adsorbed on HiPco™ Carbon Nanotube Bundles

NASA Astrophysics Data System (ADS)

Vilches, O. E.; Ramachandran, S.; Wilson, T. A.; Dash, J. G.

2006-09-01

We summarize results from AC and DC heat capacity measurements of 4He, H2, and Ne adsorbed on HiPco™ purified, closed-end single-wall carbon nanotube bundles (SWNTB) for the first adsorbed layer. We find two regions in the coverage domain: below ≈1/3 monolayer the adsorbate occupies high binding energy sites, mostly the external grooves of the bundles, while above ≈1/3 monolayer the external graphene surface is covered. No phase transitions have been observed at any temperature for all the adsorbates, a range of T where two-dimensional phases and phase transitions are seen for the same adsorbates deposited on exfoliated graphite.

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

Wang, Nana; Cheng, Lu; Wang, Jianpu, E-mail: iamjpwang@njtech.edu.cn

Amino acid self-assembled monolayers are used in the fabrication of light-emitting diodes based on organic-inorganic halide perovskites. The monolayers of amino acids provide modified interfaces by anchoring to the surfaces of ZnO charge-transporting layers using carboxyl groups, leaving the amino groups to facilitate the nucleation of MAPbBr{sub 3} perovskite films. This surface-modification strategy, together with chlorobenzene-assisted fast crystallization method, results in good surface coverage and reduced defect density of the perovskite films. These efforts lead to green perovskite light emitting diodes with a low turn-on voltage of 2 V and an external quantum efficiency of 0.43% at a brightness of ∼5000 cdmore » m{sup −2}.« less

Adsorption behavior of Zn porphyrins on a (1 0 1) face of anatase TiO2

NASA Astrophysics Data System (ADS)

Zajac, Lukasz; Bodek, Lukasz; Such, Bartosz

2018-06-01

The adsorption behavior of porphyrin molecules on anatase TiO2(1 0 1) has been investigated with scanning tunneling microscopy (STM) in ultra-high vacuum (UHV) at room temperature. At low coverage, the ZnTPP molecules have a tendency to adsorb on the one type of step edges forming molecular chains. Due to relatively high mobility of molecules stable assemblies appear only close to a monolayer coverage. Zn porphyrins in self-assembled molecular domains form a commensurate structure. In-plane rotation of the molecules leads to formation of two domains of different chirality.

Dehydration and Dehydrogenation of Ethylene Glycol on Rutile TiO2(110)

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

Li, Zhenjun; Kay, Bruce D.; Dohnalek, Zdenek

2013-08-07

The interactions of ethylene glycol (EG) with partially reduced rutile TiO2(110) surface have been studied using temperature programmed desorption (TPD). The saturation coverage on the surface Ti rows is determined to be 0.43 monolayer (ML), slightly less than one EG per two Ti sites. Most of the adsorbed ethanol (~80%) undergoes further reactions to other products. Two major channels are observed, dehydration yielding ethylene and water and dehydrogenation yielding acetaldehyde and hydrogen. Hydrogen formation is rather surprising as it has not been observed previously on TiO2(110) from simple organic molecules. The coverage dependent yields of ethylene and acetaldehyde correlate wellmore » with that of water and hydrogen, respectively. Dehydration dominates at lower EG coverages (< 0.2 ML) and plateaus as the coverage is increased to saturation. Dehydrogenation is observed primarily at higher EG coverages (>0.2 ML). Our results suggest that the observed dehydration and dehydrogenation reactions proceed via different surface intermediates.« less

An efficient Monte Carlo algorithm for the fast equilibration and atomistic simulation of alkanethiol self-assembled monolayers on a Au(111) substrate.

PubMed

Alexiadis, Orestis; Daoulas, Kostas Ch; Mavrantzas, Vlasis G

2008-01-31

A new Monte Carlo algorithm is presented for the simulation of atomistically detailed alkanethiol self-assembled monolayers (R-SH) on a Au(111) surface. Built on a set of simpler but also more complex (sometimes nonphysical) moves, the new algorithm is capable of efficiently driving all alkanethiol molecules to the Au(111) surface, thereby leading to full surface coverage, irrespective of the initial setup of the system. This circumvents a significant limitation of previous methods in which the simulations typically started from optimally packed structures on the substrate close to thermal equilibrium. Further, by considering an extended ensemble of configurations each one of which corresponds to a different value of the sulfur-sulfur repulsive core potential, sigmass, and by allowing for configurations to swap between systems characterized by different sigmass values, the new algorithm can adequately simulate model R-SH/Au(111) systems for values of sigmass ranging from 4.25 A corresponding to the Hautman-Klein molecular model (J. Chem. Phys. 1989, 91, 4994; 1990, 93, 7483) to 4.97 A corresponding to the Siepmann-McDonald model (Langmuir 1993, 9, 2351), and practically any chain length. Detailed results are presented quantifying the efficiency and robustness of the new method. Representative simulation data for the dependence of the structural and conformational properties of the formed monolayer on the details of the employed molecular model are reported and discussed; an investigation of the variation of molecular organization and ordering on the Au(111) substrate for three CH3-(CH2)n-SH/Au(111) systems with n=9, 15, and 21 is also included.

Large-area synthesis of monolayered MoS(2(1-x))Se(2x) with a tunable band gap and its enhanced electrochemical catalytic activity.

PubMed

Yang, Lei; Fu, Qi; Wang, Wenhui; Huang, Jian; Huang, Jianliu; Zhang, Jingyu; Xiang, Bin

2015-06-21

"Band gap engineering" in two-dimensional (2D) materials plays an important role in tailoring their physical and chemical properties. The tuning of the band gap is typically achieved by controlling the composition of the semiconductor alloys. However, large-area preparation of 2D alloys remains a major challenge. Here, we report the large-area synthesis of high-quality monolayered MoS2(1-x)Se2x with a size coverage of hundreds of microns using a chemical vapor deposition method. The photoluminescence (PL) spectroscopy results confirm the tunable band gap in MoS2(1-x)Se2x, which is modulated by varying the Se content. Atomic-scale analysis was performed and the chemical composition was characterized using high-resolution scanning transmission electron microscopy and X-ray photoemission spectroscopy. With the introduction of Se into monolayered MoS2, it leads to enhanced catalytic activity in an electrochemical reaction for hydrogen generation, compared to monolayered MoS2 and MoSe2. It is promising as a potential alternative to expensive noble metals.

Covalent immobilization of native biomolecules onto Au(111) via N-hydroxysuccinimide ester functionalized self-assembled monolayers for scanning probe microscopy.

PubMed Central

Wagner, P; Hegner, M; Kernen, P; Zaugg, F; Semenza, G

1996-01-01

We have worked out a procedure for covalent binding of native biomacromolecules on flat gold surfaces for scanning probe microscopy in aqueous buffer solutions and for other nanotechnological applications, such as the direct measurement of interaction forces between immobilized macromolecules, of their elastomechanical properties, etc. It is based on the covalent immobilization of amino group-containing biomolecules (e.g., proteins, phospholipids) onto atomically flat gold surfaces via omega-functionalized self-assembled monolayers. We present the synthesis of the parent compound, dithio-bis(succinimidylundecanoate) (DSU), and a detailed study of the chemical and physical properties of the monolayer it forms spontaneously on Au(111). Scanning tunneling microscopy and atomic force microscopy (AFM) revealed a monolayer arrangement with the well-known depressions that are known to stem from an etch process during the self-assembly. The total density of the omega-N-hydroxysuccinimidyl groups on atomically flat gold was 585 pmol/cm(2), as determined by chemisorption of (14)C-labeled DSU. This corresponded to approximately 75% of the maximum density of the omega-unsubstituted alkanethiol. Measurements of the kinetics of monolayer formation showed a very fast initial phase, with total coverage within 30 S. A subsequent slower rearrangement of the chemisorbed molecules, as indicated by AFM, led to a decrease in the number of monolayer depressions in approximately 60 min. The rate of hydrolysis of the omega-N-hydroxysuccinimide groups at the monolayer/water interface was found to be very slow, even at moderately alkaline pH values. Furthermore, the binding of low-molecular-weight amines and of a model protein was investigated in detail. Images FIGURE 1 FIGURE 2 FIGURE 9 PMID:9172730

Part I: an x-ray scattering study of cholera toxin penetration and induced phase transformations in lipid membranes.

PubMed

Miller, C E; Majewski, J; Watkins, E B; Kuhl, T L

2008-07-01

Cholera toxin is a highly efficient biotoxin, which is frequently used as a tool to investigate protein-membrane interactions and as a reporter for membrane rafts. Cholera toxin binds selectively to gangliosides with highest affinity to GM(1). However, the mechanism by which cholera toxin crosses the membrane remains unresolved. Using x-ray reflectivity and grazing incidence diffraction, we have been able to monitor the binding and penetration of cholera toxin into a model lipid monolayer containing the receptor GM(1) at the air-water interface. Very high toxin coverage was obtained allowing precise measurements of how toxin binding alters lipid packing. Grazing incidence x-ray diffraction revealed the coexistence of two monolayer phases after toxin binding. The first was identical to the monolayer before toxin binding. In regions where toxin was bound, a second membrane phase exhibited a decrease in order as evidenced by a larger area per molecule and tilt angle with concomitant thinning of the monolayer. These results demonstrate that cholera toxin binding induces the formation of structurally distinct, less ordered domains in gel phases. Furthermore, the largest decrease in lateral order to the monolayer occurred at low pH, supporting a low endosomal pH in the infection pathway. Surprisingly, at pH = 8 toxin penetration by the binding portion of the toxin, the B(5) pentamer, was also observed.

Controllable Growth of Large-Size Crystalline MoS2 and Resist-Free Transfer Assisted with a Cu Thin Film.

PubMed

Lin, Ziyuan; Zhao, Yuda; Zhou, Changjian; Zhong, Ren; Wang, Xinsheng; Tsang, Yuen Hong; Chai, Yang

2015-12-21

Two-dimensional MoS2 is a promising material for future nanoelectronics and optoelectronics. It has remained a great challenge to grow large-size crystalline and high surface coverage monolayer MoS2. In this work, we investigate the controllable growth of monolayer MoS2 evolving from triangular flakes to continuous thin films by optimizing the concentration of gaseous MoS2, which has been shown a both thermodynamic and kinetic growth factor. A single-crystal monolayer MoS2 larger than 300 μm was successfully grown by suppressing the nuclei density and supplying sufficient source. Furthermore, we present a facile process of transferring the centimeter scale MoS2 assisted with a copper thin film. Our results show the absence of observable residues or wrinkles after we transfer MoS2 from the growth substrates onto flat substrates using this technique, which can be further extended to transfer other two-dimensional layered materials.

Controllable Growth of Large-Size Crystalline MoS2 and Resist-Free Transfer Assisted with a Cu Thin Film

NASA Astrophysics Data System (ADS)

Lin, Ziyuan; Zhao, Yuda; Zhou, Changjian; Zhong, Ren; Wang, Xinsheng; Tsang, Yuen Hong; Chai, Yang

2015-12-01

Two-dimensional MoS2 is a promising material for future nanoelectronics and optoelectronics. It has remained a great challenge to grow large-size crystalline and high surface coverage monolayer MoS2. In this work, we investigate the controllable growth of monolayer MoS2 evolving from triangular flakes to continuous thin films by optimizing the concentration of gaseous MoS2, which has been shown a both thermodynamic and kinetic growth factor. A single-crystal monolayer MoS2 larger than 300 μm was successfully grown by suppressing the nuclei density and supplying sufficient source. Furthermore, we present a facile process of transferring the centimeter scale MoS2 assisted with a copper thin film. Our results show the absence of observable residues or wrinkles after we transfer MoS2 from the growth substrates onto flat substrates using this technique, which can be further extended to transfer other two-dimensional layered materials.

Directed Assembly of Molecules on Graphene/Ru(0001)

NASA Astrophysics Data System (ADS)

Zhang, L. Z.; Zhang, H. G.; Sun, J. T.; Pan, Y.; Liu, Q.; Mao, J. H.; Zhou, H. T.; Low, T.; Guo, H. M.; Du, S. X.; Gao, H.-J.

2012-02-01

Recently, the graphene monolayers have been seen to adopt a superstructure - moir'e pattern - on Ru(0001). By using low temperature scanning tunneling spectroscopy, we identified the laterally localized electronic states on this system. The individual states are separated by 3 nm and comprise regions of about 90 carbon atoms. This constitutes a highly regular quantum dot-array with molecular precision. It is evidenced by quantum well resonances with energies that relate to the corrugation of the graphene layer. By using scanning tunneling microscopy/spectroscopy, we demonstrate the selective adsorption and formation of ordered molecular arrays of FePc and pentacene molecules on the graphene/Ru(0001) templates. With in-depth investigations of the molecular adsorption and assembly processes we reveal the existence lateral electric dipoles in the epitaxial graphene monolayers and the capability of the dipoles in directing and driving the molecular adsorption and assembly. When increasing the molecular coverage, we observed the formation of regular Kagome lattices that duplicate the lattice of the moir'e pattern of monolayer graphene.

Nanopatterning of Si(001) for bottom-up fabrication of nanostructures.

PubMed

Hu, Yanfang; Kalachahi, Hedieh Hosseinzadeh; Das, Amal K; Koch, Reinhold

2012-04-27

The epitaxial growth of Si on Si(001) under conditions at which the (2 × n) superstructure is forming has been investigated by scanning tunneling microscopy and Monte Carlo simulations. Our experiments reveal a periodic change of the surface morphology with the surface coverage of Si. A regular (2 × n) stripe pattern is observed at coverages of 0.7-0.9 monolayers that periodically alternates with less dense surface structures at lower Si surface coverages. The MC simulations show that the growth of Si is affected by step-edge barriers, which favors the formation of a rather uniform two-dimensional framework-like configuration. Subsequent deposition of Ge onto the (2 × n) stripe pattern yields a dense array of small Ge nanostructures.

An operando Raman study of molecular structure and reactivity of molybdenum(VI) oxide supported on anatase for the oxidative dehydrogenation of ethane.

PubMed

Tsilomelekis, George; Boghosian, Soghomon

2012-02-21

Supported molybdenum oxide catalysts on TiO(2) (anatase) with surface densities in the range of 1.8-17.0 Mo per nm(2) were studied at temperatures of 410-480 °C for unraveling the configuration and molecular structure of the deposited (MoO(x))(n) species and examining their behavior for the ethane oxidative dehydrogenation (ODH). In situ Raman and in situ FTIR spectra under oxidizing conditions combined with (18)O/(16)O isotope exchange studies provide the first sound evidence for mono-oxo configuration for the deposited (MoO(x))(n) species on anatase. Isolated O=Mo(-O-)(3) tetra-coordinated species in C(3v)-like symmetry prevail at all surface coverages with a low presence of associated (polymeric) species (probably penta-coordinated) evidenced at high coverages, below the approximate monolayer of 6 Mo per nm(2). A mechanistic scenario for (18)O/(16)O isotope exchange and next-nearest-neighbor vibrational isotope effect is proposed at the molecular level to account for the pertinent spectral observations. Catalytic measurements for ethane ODH with simultaneous monitoring of operando Raman spectra were performed. The selectivity to ethylene increases with increasing surface density up to the monolayer coverage, where primary steps of ethane activation follow selective reaction pathways leading to ∼100% C(2)H(4) selectivity. The operando Raman spectra and a quantitative exploitation of the relative normalized Mo=O band intensities for surface densities of 1.8-5.9 Mo per nm(2) and various residence times show that the terminal Mo=O sites are involved in non-selective reaction turnovers. Reaction routes follow primarily non-selective pathways at low coverage and selective pathways at high coverage. Trends in the initial rates of ethane consumption (apparent reactivity per Mo) as a function of Mo surface density are discussed on the basis of several factors.

Ordered Fe(II)Ti(IV)O3 Mixed Monolayer Oxide on Rutile TiO2(011).

PubMed

Halpegamage, Sandamali; Ding, Pan; Gong, Xue-Qing; Batzill, Matthias

2015-08-25

Oxide monolayers supported or intermixed with an oxide support are potential nanocatalysts whose properties are determined by the interplay with the support. For fundamental studies of monolayer oxides on metal oxide supports, well-defined systems are needed, but so far, the synthesis of monolayer oxides with long-range order on single-crystal oxide surfaces is rare. Here, we show by a combination of scanning tunneling microscopy, photoemission spectroscopy, and density functional theory (DFT)-based computational analysis that the rutile TiO2(011) surface supports the formation of an ordered mixed FeTiO3 monolayer. Deposition of iron in a slightly oxidizing atmosphere (10(-8) Torr O2) and annealing to 300 °C results in a well-ordered surface structure with Fe in a 2+ charge state and Ti in a 4+ charge states. Low-energy ion scattering suggests that the cation surface composition is close to half Fe and half Ti. This surface is stable in ultrahigh vacuum to annealing temperatures of 300 °C before the iron is reduced. DFT simulations confirm that a surface structure with coverage of 50% FeO units is stable and forms an ordered structure. Although distinct from known bulk phases of the iron-titanium oxide systems, the FeTiO3 monolayer exhibits some resemblance to the ilmenite structure, which may suggest that a variety of different mixed oxide phases (of systems that exist in a bulk ilmenite phase) may be synthesized in this way on the rutile TiO2(011) substrate.

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

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Effective elastic properties of a van der Waals molecular monolayer at a metal surface

NASA Astrophysics Data System (ADS)

Sun, Dezheng; Kim, Dae-Ho; Le, Duy; Borck, Øyvind; Berland, Kristian; Kim, Kwangmoo; Lu, Wenhao; Zhu, Yeming; Luo, Miaomiao; Wyrick, Jonathan; Cheng, Zhihai; Einstein, T. L.; Rahman, Talat S.; Hyldgaard, Per; Bartels, Ludwig

2010-11-01

Adsorbing anthracene on a Cu(111) surface results in a wide range of complex and intriguing superstructures spanning a coverage range from 1 per 17 to 1 per 15 substrate atoms. In accompanying first-principles density-functional theory calculations we show the essential role of van der Waals interactions in estimating the variation in anthracene adsorption energy and height across the sample. We can thereby evaluate the compression of the anthracene film in terms of continuum elastic properties, which results in an effective Young’s modulus of 1.5 GPa and a Poisson ratio ≈0.1 . These values suggest interpretation of the molecular monolayer as a porous material—in marked congruence with our microscopic observations.

Method for lubricating contacting surfaces

DOEpatents

Dugger, Michael T [Tijeras, NM; Ohlhausen, James A [Albuquerque, NM; Asay, David B [Boalsburg, PA; Kim, Seong H [State College, PA

2011-12-06

A method is provided for tribological lubrication of sliding contact surfaces, where two surfaces are in contact and in motion relative to each other, operating in a vapor-phase environment containing at least one alcohol compound at a concentration sufficiently high to provide one monolayer of coverage on at least one of the surfaces, where the alcohol compound continuously reacts at the surface to provide lubrication.

Navy Mobility Fuels Evaluation.

DTIC Science & Technology

1984-07-20

Test Results on di-Linoleic Acid in Isooctane ................................. 198 8.4.11 Comparison of Lucas and BOCM Test Results... acid ) required for monolayer coverage of the metal surfaces. TRW/Lucas Tester studies, applied to an investigation of corrosion inhibitors, demonstrate 1...not powerful lubricity enhancers. Compared to long chain organic acids they are about two orders of magnitude less effective. 12 ..... .. 39364-6006-UT

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

Jagannathan, Kaushik; Benson, David M.; Robinson, David B.

Nanofilms of Pd were grown using an electrochemical form of atomic layer deposition (E-ALD) on 100 nm evaporated Au films on glass. Multiple cycles of surface-limited redox replacement (SLRR) were used to grow deposits. Each SLRR involved the underpotential deposition (UPD) of a Cu atomic layer, followed by open circuit replacement via redox exchange with tetrachloropalladate, forming a Pd atomic layer: one E-ALD deposition cycle. That cycle was repeated in order to grow deposits of a desired thickness. 5 cycles of Pd deposition were performed on the Au on glass substrates, resulting in the formation of 2.5 monolayers of Pd.more » Those Pd films were then modified with varying coverages of Pt, also formed using SLRR. The amount of Pt was controlled by changing the potential for Cu UPD, and by increasing the number of Pt deposition cycles. Hydrogen absorption was studied using coulometry and cyclic voltammetry in 0.1 M H 2SO 4 as a function of Pt coverage. The presence of even a small fraction of a Pt monolayer dramatically increased the rate of hydrogen desorption. However, this did not reduce the films’ hydrogen storage capacity. The increase in desorption rate in the presence of Pt was over an order of magnitude.« less

Spectroscopic studies of model polar stratospheric cloud films

NASA Technical Reports Server (NTRS)

Tolbert, Margaret A.; Koehler, Birgit G.; Middlebrook, Ann M.

1993-01-01

Fourier transform infrared (FTIR) spectroscopy has been used to study nitric-acid/ice films representative of type I polar stratospheric clouds (PSCs). These studies reveal that in addition to amorphous nitric acid/ice mixtures, there are three stable stoichiometric hydrates of nitric acid: nitric-acid monohydrate (NAM), dihydrate (NAD), and trihydrate (NAT). We also observe two distinct crystalline forms of the trihydrate, which we denote alpha- and beta-NAT. These two forms appear to differ in their concentration of crystalline defects, but not in their chemical composition. In addition to probing the composition of type I PSCs, we have also used FTIR spectroscopy to study the interaction of HCl with model PSC films. In this work we find that for HCl pressures in the range 10 exp -5 to 10 exp -7 Torr, HCl is taken up by ice at 155 K to form a thin layer of HCl.6H2O. At 193 K, the uptake of HCl by ice was consistent with less than or equal to monolayer coverage. Uptake of HCl by alpha and beta-NAT at 175 K was also consistent with less than or equal to monolayer coverage.

Effect of Sulfuric Acid on the Uptake of Sulfur Dioxide on Soot

NASA Astrophysics Data System (ADS)

Slowik, J. G.; Koehler, B. G.

2001-05-01

The uptake of SO2 on soot may lead to the formation of sulfuric acid on the soot. The sulfuric acid then can affect the further uptake of SO2 on the soot. We are interested in the effect of submonolayer H2SO4 on the uptake of SO2. We measured the uptake of SO2 on n-hexane soot as a function SO2 pressure (10-7 to 10-4 Torr) and sulfuric acid coverage between -140\\deg and -120\\deg C. We generate sulfuric acid by adsorbing varying amounts of SO3 on soot, covering the SO3 with a thick layer of condensed H2O, and heating to 193 K to react the SO3 and H2O and to remove the excess H2O. The sulfuric acid coverage is in the range of monolayer or sub-monolayer. Adsorption of SO2 on soot with and without the sulfuric acid shows that the acid reduces the SO2 uptake by a factor of two or more. Varying the amount of acid has little effect on uptake. However, increasing the thickness of the soot substrate causes a significant increase in SO2 uptake.

Tunneling electron induced chemisorption of copper phthalocyanine molecules on the Cu(111) surface

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

Stock, T.; Nogami, J.

2014-02-17

The adsorption of up to one monolayer (ML) of copper phthalocyanine (CuPc) molecules on a room temperature Cu(111) surface has been studied using scanning tunneling microscopy (STM). Below 1 ML the molecules are in a fluid state and are highly mobile on the surface. At 1 ML coverage the molecules coalesce into a highly ordered 2D crystal phase. At sub-ML coverages, chemisorption of individual CuPc molecules can be induced through exposure to tunneling electrons at a tunneling bias voltage exceeding a threshold value. This tunneling electron induced effect has been exploited to perform molecular STM lithography.

Theoretical aspects of studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.

2010-10-01

The study of adsorption of oxygen on transition metal surface is important for the understanding of oxidation, heterogeneous catalysis, and metal corrosion. The structures formed on transition metal surfaces vary from simple adlayers of chemisorbed oxygen to oxygen diffusion into the sub-surface region and the formation of oxides. In this work we present the results of an ab-initio investigation of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. Calculations are also performed for the on-surface adsorption of oxygen on the unreconstructed Cu(001) surface for coverages up to one monolayer to use for comparison. The geometry of the surfaces with adsorbed oxygen is fully optimized. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy.

Coverage dependent molecular assembly of anthraquinone on Au(111)

NASA Astrophysics Data System (ADS)

DeLoach, Andrew S.; Conrad, Brad R.; Einstein, T. L.; Dougherty, Daniel B.

2017-11-01

A scanning tunneling microscopy study of anthraquinone (AQ) on the Au(111) surface shows that the molecules self-assemble into several structures depending on the local surface coverage. At high coverages, a close-packed saturated monolayer is observed, while at low coverages, mobile surface molecules coexist with stable chiral hexamer clusters. At intermediate coverages, a disordered 2D porous network interlinking close-packed islands is observed in contrast to the giant honeycomb networks observed for the same molecule on Cu(111). This difference verifies the predicted extreme sensitivity [J. Wyrick et al., Nano Lett. 11, 2944 (2011)] of the pore network to small changes in the surface electronic structure. Quantitative analysis of the 2D pore network reveals that the areas of the vacancy islands are distributed log-normally. Log-normal distributions are typically associated with the product of random variables (multiplicative noise), and we propose that the distribution of pore sizes for AQ on Au(111) originates from random linear rate constants for molecules to either desorb from the surface or detach from the region of a nucleated pore.

Coverage dependent molecular assembly of anthraquinone on Au(111).

PubMed

DeLoach, Andrew S; Conrad, Brad R; Einstein, T L; Dougherty, Daniel B

2017-11-14

A scanning tunneling microscopy study of anthraquinone (AQ) on the Au(111) surface shows that the molecules self-assemble into several structures depending on the local surface coverage. At high coverages, a close-packed saturated monolayer is observed, while at low coverages, mobile surface molecules coexist with stable chiral hexamer clusters. At intermediate coverages, a disordered 2D porous network interlinking close-packed islands is observed in contrast to the giant honeycomb networks observed for the same molecule on Cu(111). This difference verifies the predicted extreme sensitivity [J. Wyrick et al., Nano Lett. 11, 2944 (2011)] of the pore network to small changes in the surface electronic structure. Quantitative analysis of the 2D pore network reveals that the areas of the vacancy islands are distributed log-normally. Log-normal distributions are typically associated with the product of random variables (multiplicative noise), and we propose that the distribution of pore sizes for AQ on Au(111) originates from random linear rate constants for molecules to either desorb from the surface or detach from the region of a nucleated pore.

Desorption of oxygen from alloyed Ag/Pt(111)

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

Jankowski, Maciej; Wormeester, Herbert, E-mail: h.wormeester@utwente.nl; Zandvliet, Harold J. W.

2014-06-21

We have investigated the interaction of oxygen with the Ag/Pt(111) surface alloy by thermal desorption spectroscopy (TDS). The surface alloy was formed during the deposition of sub-monolayer amounts of silver on Pt(111) at 800 K and subsequent cooling to 300 K. The low-temperature phase of the surface alloy is composed of nanometer-sized silver rich stripes, embedded within platinum-rich domains, which were characterized with spot profile analysis low energy electron diffraction. The TDS measurements show that oxygen adsorption is blocked on Ag sites: the saturation coverage of oxygen decreases with increasing Ag coverage. Also, the activation energy for desorption (E{sub des})more » decreases with Ag coverage. The analysis of the desorption spectra from clean Pt(111) shows a linear decay of E{sub des} with oxygen coverage, which indicates repulsive interactions between the adsorbed oxygen atoms. In contrast, adsorption on alloyed Ag/Pt(111) leads to an attractive interaction between adsorbed oxygen atoms.« less

SFG and SPR Study of Sodium Dodecyl Sulfate Film Assembly on Positively Charged Surfaces

NASA Astrophysics Data System (ADS)

Song, Sanghun; Weidner, Tobias; Wagner, Matthew; Castner, David

2012-02-01

This study uses sum frequency generation (SFG) vibrational spectroscopy and surface plasmon resonance (SPR) sensing to investigate the structure of sodium dodecyl sulfate (SDS) films formed on positively charged and hydrophilic surfaces. The SPR signals show a good surface coverage suggesting that full monolayer coverage is reached at 1 mM. SFG spectra of SDS adsorbed exhibits well resolved CH3 peaks and OH peaks. At both 0.2 mM and 1 mM SDS concentration the intensity of both the CH3 and OH peaks decreased close to background levels. We found that the loss of SFG signal at 0.2 mM occurs at this concentration independent of surface charge density. It is more likely that the loss of signal is related to structural inhomogeneity induced by a striped phase - stand-up phase transition. This is supported by a distinct change of the relative SFG phase between CH3/OH near 0.2 mM. The second intensity minimum might be related to charge compensation effects. We observed a substrate dependence for the high concentration transition. We also observed distinct SFG signal phase changes for water molecules associated with SDS layers at different SDS solution concentrations indicating that the orientation of bound water changed with SDS surface structure.

Mediatorless solar energy conversion by covalently bonded thylakoid monolayer on the glassy carbon electrode.

PubMed

Lee, Jinhwan; Im, Jaekyun; Kim, Sunghyun

2016-04-01

Light reactions of photosynthesis that take place in thylakoid membranes found in plants or cyanobacteria are among the most effective ways of utilizing light. Unlike most researches that use photosystem I or photosystem II as conversion units for converting light to electricity, we have developed a simple method in which the thylakoid monolayer was covalently immobilized on the glassy carbon electrode surface. The activity of isolated thylakoid membrane was confirmed by measuring evolving oxygen under illumination. Glassy carbon surfaces were first modified with partial or full monolayers of carboxyphenyl groups by reductive C-C coupling using 4-aminobenzoic acid and aniline and then thylakoid membrane was bioconjugated through the peptide bond between amine residues of thylakoid and carboxyl groups on the surface. Surface properties of modified surfaces were characterized by cyclic voltammetry, contact angle measurements, and electrochemical impedance spectroscopy. Photocurrent of 230 nA cm(-2) was observed when the thylakoid monolayer was formed on the mixed monolayer of 4-carboxylpheny and benzene at applied potential of 0.4V vs. Ag/AgCl. A small photocurrent resulted when the 4-carboxyphenyl full monolayer was used. This work shows the possibility of solar energy conversion by directly employing the whole thylakoid membrane through simple surface modification. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation and characterization of carbon-supported sub-monolayer palladium decorated gold nanoparticles for the electro-oxidation of ethanol in alkaline media

NASA Astrophysics Data System (ADS)

Zhu, L. D.; Zhao, T. S.; Xu, J. B.; Liang, Z. X.

Carbon-supported gold nanoparticles (Au/C) are successfully decorated with mono- or sub-monolayer palladium atoms with different Pd/Au atomic ratios by a chemically epitaxial seeded growth method. TEM, UV-vis spectrometry and XRD techniques are used to characterize the particle size, dispersion, palladium coverage on gold seeds and crystal structures of the prepared catalysts. Cyclic voltammetric tests show that the Pd-decorated Au/C (denoted by Pd@Au/C) have higher specific activities than that of Pd/C for the oxidation of ethanol in alkaline media. This suggests that the Pd utilization is improved with such a surface-alloyed nanostructure. In addition, stable chronoamperometric responses are achieved with the so-prepared electrocatalysts during ethanol oxidation.

Fabrication of Calix[4]arene Derivative Monolayers to Control Orientation of Antibody Immobilization

PubMed Central

Chen, Hongxia; Liu, Feng; Qi, Fangjie; Koh, Kwangnak; Wang, Keming

2014-01-01

Three calix[4]arene (Cal-4) derivatives which separately contain ethylester (1), carboxylic acid (2), and crownether (3) at the lower rim with a common reactive thiol at the upper rim were synthesized and constructed to self-assembled monolayers (SAMs) on Au films. After spectroscopic characterization of the monolayers, surface coverage and orientation of antibody immobilized on the Cal-4 derivative SAMs were studied by surface plasmon resonance (SPR) technique. Experimental results revealed that the antibody could be immobilized on the Cal-4 derivatives spontaneously. The orientation of absorbed antibody on the Cal-4 derivative SAMs is related to the SAM’s dipole moment. The possible orientations of the antibody immobilized on the Cal-4 derivative 1 SAM are lying-on or side-on, while on the Cal-4 derivative 2 and Cal-4 derivative 3 head-on and end-on respectively. These experimental results demonstrate the surface dipole moment of Cal-4 derivative appears to be an important factor to antibody orientation. Cal-4 derivatives are useful in developing site direct protein chips. PMID:24690993

A novel fullerene lipoic acid derivative: Synthesis and preparation of self-assembled monolayers on gold

NASA Astrophysics Data System (ADS)

Viana, A. S.; Leupold, S.; Eberle, C.; Shokati, T.; Montforts, F.-P.; Abrantes, L. M.

2007-11-01

Synthesis and preparation of self-assembled monolayers of a novel fullerene lipoic acid derivative on gold are reported. The presence of densely packed SAMs was confirmed by ellipsometry and cyclic voltammetry. The electrochemical response of the modified electrode in organic media exhibits the first two redox peaks characteristic of the extended π-electron system of fullerene. C 60 surface coverage (1.4 × 10 -10 mol cm -2) has been electrochemically determined by the redox process of the adsorbed fullerene moiety and by reductive desorption of the SAM in strong alkaline solution. Electrochemical data indicate that all four sulphur atoms are involved in the self-assembly process, providing an increase of SAM stability in comparison to mono or di-thiolated appended molecules. Visualisation of discrete fullerene molecules by scanning tunnelling microscopy supplied further evidence for gold modification and molecular distribution on the surface. Mixed monolayers of hexanethiol and fullerene derivatives in a proportion of 1:2 have been also studied with the purpose of controlling the amount and distribution of fullerene units on the gold surface.

Fabrication of large area flexible nanoplasmonic templates with flow coating

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

Huang, Qian; Devetter, Brent M.; Roosendaal, Timothy

Here, we describe the development of a custom-built two-axis flow coater for the deposition of polymeric nanosphere monolayers used in the fabrication of large area nanoplasmonic films. The technique described here has the capability of depositing large areas (up to 7” x 10”) of self-assembled monolayers of polymeric nanospheres onto polyethylene terephthalate (PET) films. Here, three sets of film consisting of different diameter (ranging from 100 to 300 nm) polymeric nanospheres were used to demonstrate the capabilities of this instrument. To improve the surface wettability of the PET substrates during wet-deposition we enhanced the wettability by using a forced airmore » blown-arc plasma treatment system. Both the local microstructure, as confirmed by scanning electron microscopy, describing monolayer and multilayer coverage, and the overall macroscopic uniformity of the resultant nanostructured film were optimized by controlling the relative stage to blade speed and nanosphere concentration. As this is a scalable technique, large area films such as the ones described here, have a variety of crucial emerging applications in areas such as energy, catalysis, and chemical sensing.« less

Photoelectron spectroscopic studies of ultra-thin CuPc layers on a Si(111)-(√3 × √3)R30°-B surface

NASA Astrophysics Data System (ADS)

Menzli, S.; Laribi, A.; Mrezguia, H.; Arbi, I.; Akremi, A.; Chefi, C.; Chérioux, F.; Palmino, F.

2016-12-01

The adsorption of copper phthalocyanine (CuPc) molecules on Si(111)-(√3 × √3)R30°-B surface is investigated at room temperature under ultra-high vacuum. Crystallographic, chemical and electronic properties of the interface are investigated by low energy electron diffraction (LEED), ultraviolet and X-ray photoemission spectroscopies (UPS, XPS) and X-ray photoemission diffraction (XPD). LEED and XPD results shed light on the growth mechanism of CuPc on this substrate. At one monolayer coverage the growth mode was characterized by the formation of crystalline 3D nanoislands. The molecular packing deduced from this study appears very close to the one of the bulk CuPc α phase. The 3D islands are formed by molecules aligned in a standing manner. XPS core level spectra of the substrate reveal that there is no discernible chemical interaction between molecules and substrate. However there is charge transfer from molecules to the substrate. During the growth, the work function (WF) was found to decrease from 4.50 eV for the clean substrate to 3.70 eV for the highest coverage (30 monolayers). Within a thickness of two monolayers deposition, an interface dipole of 0.50 eV was found. A substrate band bending of 0.25 eV was deduced over all the range of exposure. UPS spectra indicate the existence of a band bending of the highest occupied molecular orbital (HOMO) of 0.30 eV. The changes in the work function, in the Fermi level position and in the onset of the molecular HOMO state have been used to determine the energy level alignment at the interface.

Multi-Ligand-Binding Flavoprotein Dodecin as a Key Element for Reversible Surface Modification in Nano-biotechnology.

PubMed

Gutiérrez Sánchez, Cristina; Su, Qiang; Schönherr, Holger; Grininger, Martin; Nöll, Gilbert

2015-01-01

In this paper the multiple (re)programming of protein-DNA nanostructures comprising generation, deletion, and reprogramming on the same flavin-DNA-modified surface is introduced. This work is based on a systematic study of the binding affinity of the multi-ligand-binding flavoprotein dodecin on flavin-terminated DNA monolayers by surface plasmon resonance and quartz crystal microbalance with dissipation (QCM-D) measurements, surface plasmon fluorescence spectroscopy (SPFS), and dynamic AFM force spectroscopy. Depending on the flavin surface coverage, a single apododecin is captured by one or more surface-immobilized flavins. The corresponding complex binding and unbinding rate constants kon(QCM) = 7.7 × 10(3) M(-1)·s(-1) and koff(QCM) = 4.5 × 10(-3) s(-1) (Kd(QCM) = 580 nM) were determined by QCM and were found to be in agreement with values for koff determined by SPFS and force spectroscopy. Even though a single apododecin-flavin bond is relatively weak, stable dodecin monolayers were formed on flavin-DNA-modified surfaces at high flavin surface coverage due to multivalent interactions between apododecin bearing six binding pockets and the surface-bound flavin-DNA ligands. If bi- or multivalent flavin ligands are adsorbed on dodecin monolayers, stable sandwich-type surface-DNA-flavin-apododecin-flavin ligand arrays are obtained. Nevertheless, the apododecin flavin complex is easily and quantitatively disassembled by flavin reduction. Binding and release of apododecin are reversible processes, which can be carried out alternatingly several times to release one type of ligand by an external redox trigger and subsequently replace it with a different ligand. Hence the versatile concept of reprogrammable functional biointerfaces with the multi-ligand-binding flavoprotein dodecin is demonstrated.

Controllable Growth of Monolayer MoS2 and MoSe2 Crystals Using Three-temperature-zone Furnace

NASA Astrophysics Data System (ADS)

Zheng, Binjie; Chen, Yuanfu

2017-12-01

Monolayer molybdenum disulfide (MoS2) and molybdenum diselenide (MoSe2) have attracted a great attention for their exceptional electronic and optoelectronic properties among the two dimensional family. However, controllable synthesis of monolayer crystals with high quality needs to be improved urgently. Here we demonstrate a chemical vapor deposition (CVD) growth of monolayer MoS2 and MoSe2 crystals using three-temperature-zone furnace. Systematical study of the effects of growth pressure, temperature and time on the thickness, morphology and grain size of crystals shows the good controllability. The photoluminescence (PL) characterizations indicate that the as-grown monolayer MoS2 and MoSe2 crystals possess excellent optical qualities with very small full-width-half-maximum (FWHM) of 96 me V and 57 me V, respectively. It is comparable to that of exfoliated monolayers and reveals their high crystal quality. It is promising that our strategy should be applicable for the growth of other transition metal dichalcogenides (TMDs) monolayer crystals.

Molecular beam studies of the growth and kinetics of self-assembled monolayers

NASA Astrophysics Data System (ADS)

Schwartz, Peter Vincent

Low energy helium diffraction, a quantitative structural characterization tool, has been used to measure the growth kinetics of self-assembled monolayers (SAMs). Special attention was given to the growth of decanethiol monolayers deposited from a molecular beam onto the (111) face of gold single crystals especially at the initial stages of growth. The influence of changing impingement rate, substrate temperature, and annealing treatments was investigated. We also studied the structure and dynamics of physisorbed adlayers on top of the monolayers and structural variations in monolayers caused by changes in chemical composition such as the addition of phenyl groups, and hydroxyl groups. Experimental work involved renovations to the existing diffractometer. The apparatus was improved with respect to its signal to noise ratio; efficiency in sample preparation and data collection; and the reproducibility of obtaining clean crystal surfaces. The renovations greatly extended the range of experiments of which the diffraction machine is capable. The growth of n-decanethiol SAMs by gas deposition was identified as a multi-stage process where the initial "lying down" layer grows on the bare gold surface with a near unity sticking coefficient, while the subsequent, "standing-up" phase grows with a sticking coefficient of about 10sp{-3}. The ordering and chemisorption of a single "lying down" layer of decanethiol was investigated by annealing a single layer physisorbed on a 130 K Au(111) surface to incrementally higher temperatures. The molecules first align themselves with the underlying gold substrate, then orient themselves in the "head to head" two molecule unit mesh, then chemisorb at still higher temperatures. Overlayers of long chain molecules grown on top of monolayers on Au(111) are found to be more ordered than the underlying monolayers themselves. The energy of adsorption to the organic surface is found to be very close to that of the bulk value, even for a gold-adlayer separation distance of about 4 A. Debye-Waller experiments were done to measure the stiffness of monolayers of different chain lengths, coverages and functional groups as well as overlayers.

Negative electron affinity from aluminium on the diamond (1 0 0) surface: a theoretical study

NASA Astrophysics Data System (ADS)

James, Michael C.; Croot, Alex; May, Paul W.; Allan, Neil L.

2018-06-01

Density functional theory calculations were performed to model the adsorption of up to 1 monolayer (ML) of aluminium on the bare and O-terminated (1 0 0) diamond surface. Large adsorption energies of up to  ‑6.36 eV per atom are observed for the Al-adsorbed O-terminated diamond surface. Most adsorption sites give a negative electron affinity (NEA), with the largest NEAs  ‑1.47 eV on the bare surface (1 ML coverage) and  ‑1.36 eV on the O-terminated surface (0.25 ML coverage). The associated adsorption energies per Al atom for these sites are  ‑4.11 eV and  ‑5.24 eV, respectively. Thus, with suitably controlled coverage, Al on diamond shows promise as a thermally-stable surface for electron emission applications.

Deposition of zeolite nanoparticles onto porous silica monolith

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

Gackowski, Mariusz; Bielanska, Elzbieta; Szczepanowicz, Krzysztof

2016-06-01

A facile and effective method of deposition of MFl zeolite nanoparticles (nanocrystals) onto macro-/mesoporous silica monolith was proposed. The electrostatic interaction between those two materials was induces by adsorption of cationic polyelectrolytes. That can be realized either by adsorption of polyelectrolyte onto silica monolith or on zeolite nanocrystals. The effect of time, concentration of zeolite nanocrystals, type of polyelectrolyte, and ultrasound treatment is scrutinized. Adsorption of polyelectrolyte onto silica monolith with subsequent deposition of nanocrystals resulted in a monolayer coverage assessed with SEM images. Infrared spectroscopy was applied as a useful method to determine the deposition effectiveness of zeolite nanocrystalsmore » onto silica. Modification of nanocrystals with polyelectrolyte resulted in a multilayer coverage due to agglomeration of particles. On the other hand, the excess of polyelectrolyte in the system resulted in a low coverage due to competition between polyelectrolyte and modified nanocrystals.« less

Characterization and kinetics of surface functionalization and binding of biologically and chemically significant molecules

NASA Astrophysics Data System (ADS)

Steiner, Rachel

The purpose of this project is to investigate intermolecular interactions of organic molecular assemblies. By understanding the structure and physical interactions in these assemblies, we gain insights into practical applications for nanoscale systems built upon these surface structures. It is possible for organic chemists to create many forms of modified organic molecules, functionalizing them with specific reactive end groups. Through surface functionalization, enabling covalent or highly associative binding, it is possible to create ordered molecular assemblies of these molecules. Scientists can study the nature of this structure and the intermolecular interactions through spectroscopic, optical, and scattering experiments. To understand the self-assembly process in molecular systems, we preliminarily created monolayer films on silica substrates with a variety of organic molecules. In particular, we functionalized silica substrates with hydroxyl groups and covalently bound acid chloride functionalized aromatic compounds, with and without an underlying adhesion layer of 3-aminopropyltriethoxysilane. We characterized the monolayer assemblies with ellipsometry, UV-vis absorption spectroscopy, FTIR spectroscopy, and fluorescence/photoemission spectroscopy, obtaining a quantitative measure of the molecular surface coverage. In order to understand the nature of these molecular assemblies, we also pursued an in-depth kinetic study to control and optimize the monolayer formation process. Through use of UV-vis spectroscopy, we determined that the monolayer formation can best be modeled with diffusion-limited Langmuir kinetics. Specifically, we concluded that for anthracene acid chloride in dichloromethane the average diffusion coefficient was 1.6x10-7 cm2/sec. Additionally, we find we are able to achieve surface coverages of approximately 2x1014 molecules/cm2. Having established the ability to create ordered molecular assemblies, through surface functionalization, enabling covalent or highly associative binding, we continued to explore the field of molecular assemblies by studying the binding and structure of molecules to carbon nanostructures. Previous studies have shown that alkyl side chains and aromatic compounds, such as pyrene, will bind non-covalently to the sidewalls of carbon nanotubes through pi-pi interactions. We explored functionalization of carbon nanotubes and graphene by using microscopy to examine the adsorption of biomolecules onto nanotube sidewalls and graphene.

Transmission X-ray scattering as a probe for complex liquid-surface structures

DOE PAGES

Fukuto, Masafumi; Yang, Lin; Nykypanchuk, Dmytro; ...

2016-01-28

The need for functional materials calls for increasing complexity in self-assembly systems. As a result, the ability to probe both local structure and heterogeneities, such as phase-coexistence and domain morphologies, has become increasingly important to controlling self-assembly processes, including those at liquid surfaces. The traditional X-ray scattering methods for liquid surfaces, such as specular reflectivity and grazing-incidence diffraction, are not well suited to spatially resolving lateral heterogeneities due to large illuminated footprint. A possible alternative approach is to use scanning transmission X-ray scattering to simultaneously probe local intermolecular structures and heterogeneous domain morphologies on liquid surfaces. To test the feasibilitymore » of this approach, transmission small- and wide-angle X-ray scattering (TSAXS/TWAXS) studies of Langmuir films formed on water meniscus against a vertically immersed hydrophilic Si substrate were recently carried out. First-order diffraction rings were observed in TSAXS patterns from a monolayer of hexagonally packed gold nanoparticles and in TWAXS patterns from a monolayer of fluorinated fatty acids, both as a Langmuir monolayer on water meniscus and as a Langmuir–Blodgett monolayer on the substrate. The patterns taken at multiple spots have been analyzed to extract the shape of the meniscus surface and the ordered-monolayer coverage as a function of spot position. These results, together with continual improvement in the brightness and spot size of X-ray beams available at synchrotron facilities, support the possibility of using scanning-probe TSAXS/TWAXS to characterize heterogeneous structures at liquid surfaces.« less

Fluorescence, polarized fluorescence, and Brewster angle microscopy of palmitic acid and lung surfactant protein B monolayers.

PubMed Central

Lipp, M M; Lee, K Y; Waring, A; Zasadzinski, J A

1997-01-01

Fluorescence, polarized fluorescence, and Brewster angle microscopy reveal that human lung surfactant protein SP-B and its amino terminus (SP-B[1-25]) alter the phase behavior of palmitic acid monolayers by inhibiting the formation of condensed phases and creating a new fluid protein-rich phase. This fluid phase forms a network that separates condensed phase domains at coexistence and persists to high surface pressures. The network changes the monolayer collapse mechanism from heterogeneous nucleation/growth and fracturing processes to a more homogeneous process through isolating individual condensed phase domains. This results in higher surface pressures at collapse, and monolayers easier to respread on expansion, factors essential to the in vivo function of lung surfactant. The network is stabilized by a low-line tension between the coexisting phases, as confirmed by the observation of extended linear domains, or "stripe" phases, and a Gouy-Chapman analysis of protein-containing monolayers. Comparison of isotherm data and observed morphologies of monolayers containing SP-B(1-25) with those containing the full SP-B sequence show that the shortened peptide retains most of the native activity of the full-length protein, which may lead to cheaper and more effective synthetic replacement formulations. Images FIGURE 1 FIGURE 3 FIGURE 4 FIGURE 6 FIGURE 7 FIGURE 8 FIGURE 9 FIGURE 10 PMID:9168053

Ternary Surface Monolayers for Ultrasensitive (Zeptomole) Amperometric Detection of Nucleic-Acid Hybridization without Signal Amplification

PubMed Central

Wu, Jie; Campuzano, Susana; Halford, Colin; Haake, David A.; Wang, Joseph

2010-01-01

A ternary surface monolayer, consisting of co-assembled thiolated capture probe (SHCP) mercaptohexanol (MCH) and dithiothreitol (DTT), is shown to offer dramatic improvements in the signal-to-noise characteristics of electrochemical DNA hybridization biosensors based on common self-assembled monolayers (SAMs). Remarkably low detection limits down to 40 zmole (in 4 μL samples) as well as only 1 CFU E. coli per sensor are thus obtained without any additional amplification step in connection to the commonly used horseradish peroxidase/3,3′,5,5′-tetramethylbenzidine (HRP/TMB) system. Such dramatic improvements in the detection limits (compared to common binary alkanethiol interfaces and to most electrochemical DNA sensing strategies without target or signal amplification) are attributed primarily to the remarkably higher resistance to non-specific adsorption. This reflects the highly compact layer (with lower pinhole density) produced by the coupling of the cyclic- and linear-configuration ‘backfillers’ that leads to a remarkably low background noise even in the presence of complex sample matrices. A wide range of surface compositions have been investigated and the ternary mixed monolayer has been systematically optimized. Detailed impedance spectroscopy and cyclic voltammetric studies shed useful insights into the surface coverage. The impressive sensitivity and high specificity of the simple developed methodology indicate great promise for a wide range of nucleic acid testing, including clinical diagnostics, biothreat detection, food safety and forensic analysis. PMID:20883023

Ternary surface monolayers for ultrasensitive (zeptomole) amperometric detection of nucleic acid hybridization without signal amplification.

PubMed

Wu, Jie; Campuzano, Susana; Halford, Colin; Haake, David A; Wang, Joseph

2010-11-01

A ternary surface monolayer, consisting of coassembled thiolated capture probe, mercaptohexanol and dithiothreitol, is shown to offer dramatic improvements in the signal-to-noise characteristics of electrochemical DNA hybridization biosensors based on common self-assembled monolayers. Remarkably low detection limits down to 40 zmol (in 4 μL samples) as well as only 1 CFU Escherichia coli per sensor are thus obtained without any additional amplification step in connection to the commonly used horseradish peroxidase/3,3',5,5'-tetramethylbenzidine system. Such dramatic improvements in the detection limits (compared to those of common binary alkanethiol interfaces and to those of most electrochemical DNA sensing strategies without target or signal amplification) are attributed primarily to the remarkably higher resistance to nonspecific adsorption. This reflects the highly compact layer (with lower pinhole density) produced by the coupling of the cyclic- and linear-configuration "backfillers" that leads to a remarkably low background noise even in the presence of complex sample matrixes. A wide range of surface compositions have been investigated, and the ternary mixed monolayer has been systematically optimized. Detailed impedance spectroscopy and cyclic voltammetric studies shed useful insights into the surface coverage. The impressive sensitivity and high specificity of the simple developed methodology indicate great promise for a wide range of nucleic acid testing, including clinical diagnostics, biothreat detection, food safety, and forensic analysis.

Superstructures at Te/Au(111) interface evolving upon increasing Te coverage

NASA Astrophysics Data System (ADS)

Guan, Jiaqi; Huang, Xiaochun; Xu, Xiaofeng; Zhang, Shuyuan; Jia, Xun; Zhu, Xuetao; Wang, Weihua; Guo, Jiandong

2018-03-01

By in-situ low temperature scanning tunneling microscopy, we systematically investigated the superstructure evolution at Te/Au(111) interface upon increasing Te coverage. Te atoms form one-dimensional √{ 3} R30∘ chains at ∼0.10 monolayer (ML) coverage. Two two-dimensional chiral superstructures, (√{ 111} ×√{ 111}) R 4 .7∘ and (3√{ 21} × 3√{ 21}) R 10 .9∘ , are selectively formed with the Te coverage below and above 1/3 ML, respectively. The two chiral superstructures can be converted to each other reversibly by adding Te atoms or moderately annealing. A honeycomb-like superstructure, decorated with adatoms that are distributed in quasi-one-dimensional chains, is observed by further increasing the Te coverage to 4/9 ML. At the Te/Au(111) interface, an interfacial state at -0.65 eV to -0.55 eV below the Fermi level is also resolved by scanning tunneling spectroscopy. The formation of these Te-induced high-order superstructures is accompanied by relaxation of gold atoms in the surface layer, indicating a strong Te-Au interaction. Our work demonstrates a reliable method to fabricate Te nanostructures on noble metals in a controlled way.

Monolayer nanoparticle-covered liquid marbles derived from a sol-gel coating

NASA Astrophysics Data System (ADS)

Li, Xiaoguang; Wang, Yiqi; Huang, Junchao; Yang, Yao; Wang, Renxian; Geng, Xingguo; Zang, Duyang

2017-12-01

A sol-gel coating consisting of hydrophobic SiO2 nanoparticles (NPs) was used to produce monolayer NP-covered (mNPc) liquid marbles. The simplest approach was rolling a droplet on this coating, and an identifiable signet allowed determination of the coverage ratio of the resulting liquid marble. Alternatively, the particles were squeezed onto a droplet surface with two such coatings, generating surface buckling from interfacial NP jamming, and then a liquid marble was produced via a jamming-relief process in which water was added into the buckled droplet. This process revealed an ˜7% reduction in particle distance after interfacial jamming. The mNPc liquid marbles obtained by the two methods were transparent with smooth profiles, as naked droplets, and could be advantageously used in fundamental and applied researches for their unique functions.

Direct visualization of atomically precise nitrogen-doped graphene nanoribbons

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

Zhang, Yi; Zhang, Yanfang; Li, Geng

2014-07-14

We have fabricated atomically precise nitrogen-doped chevron-type graphene nanoribbons by using the on-surface synthesis technique combined with the nitrogen substitution of the precursors. Scanning tunneling microscopy and spectroscopy indicate that the well-defined nanoribbons tend to align with the neighbors side-by-side with a band gap of 1.02 eV, which is in good agreement with the density functional theory calculation result. The influence of the high precursor coverage on the quality of the nanoribbons is also studied. We find that graphene nanoribbons with sufficient aspect ratios can only be fabricated at sub-monolayer precursor coverage. This work provides a way to construct atomically precisemore » nitrogen-doped graphene nanoribbons.« less

Phosphorus adlayers on Platinum (110)

NASA Astrophysics Data System (ADS)

Heikkinen, Olli; Riihimäki, Ari; Sainio, Jani; Lahtinen, Jouko

2017-10-01

Platinum is a metal utilized in many applications. Its catalytic activity can be decreased due to chemical poisoning caused e.g. by phosphorus. To gain more understanding of its poisoning, we present a study of phosphorus adsorption on a platinum (110) single crystal surface. Using X-ray photoelectron spectroscopy, we have found that the adsorbate coverage saturates at around 3 monolayers. Annealing the phosphorus-covered platinum surface at 750 °C gives rise to three different ordered adlayer structures, with symmetries of 2 × 3, 11 × 4 and √{ 2} × 1 , from the lowest to the highest coverage, detected with low-energy electron diffraction. We have studied the sample topography with scanning tunnelling microscopy. We also present a tentative model for the observed structures and their evolution.

Electronic structure and dynamics of thin Ge/GaAs(110) heterostructures

NASA Astrophysics Data System (ADS)

Haight, R.; Silberman, J. A.

1990-10-01

Using angle-resolved picosecond laser photoemission we have investigated both occupied and transiently excited empty states at the surface of Ge grown epitaxially on GaAs(110). We observe a normally unoccupied, Ge layer derived state whose separation from the valence-band maximum of the system is 700±50 meV at six monolayers Ge coverage. The evolution of the electronic structure is followed as a function of coverage and correlated with low-energy electron diffraction. The time dependence of the transiently occupied Ge signal is compared with that of the clean GaAs(110) surface and shows that electrons are prevented from diffusing into the GaAs bulk by the conduction-band offset of 330±40 meV.

Exploring the effect of oxygen coverage on the electronic, magnetic and chemical properties of Ni(111) supported h-BN sheet: A density functional study

NASA Astrophysics Data System (ADS)

Wasey, A. H. M. Abdul; Das, G. P.; Majumder, C.

2017-05-01

Traditionally, h-BN is used as coating material to prevent corrosion on the metal surface. In sharp contrast to this, here we show catalytic behavior of h-BN monolayer deposited on Ni(111) surface, clearly demonstrating the influence of the support in modulation of h-BN electronic structure. Using first principles density functional theory we have studied the interaction of O2 molecules with the h-BN/Ni(111) surface. The activation of Osbnd O bond, which is the most important step for oxidative catalysis, showed dependence on the O2 coverage. Thus this study is extremely important to predict the optimum O2 pressure in reaction chamber for efficient catalysis.

Surface-protein interactions on different stainless steel grades: effects of protein adsorption, surface changes and metal release.

PubMed

Hedberg, Y; Wang, X; Hedberg, J; Lundin, M; Blomberg, E; Wallinder, I Odnevall

2013-04-01

Implantation using stainless steels (SS) is an example where an understanding of protein-induced metal release from SS is important when assessing potential toxicological risks. Here, the protein-induced metal release was investigated for austenitic (AISI 304, 310, and 316L), ferritic (AISI 430), and duplex (AISI 2205) grades in a phosphate buffered saline (PBS, pH 7.4) solution containing either bovine serum albumin (BSA) or lysozyme (LSZ). The results show that both BSA and LSZ induce a significant enrichment of chromium in the surface oxide of all stainless steel grades. Both proteins induced an enhanced extent of released iron, chromium, nickel and manganese, very significant in the case of BSA (up to 40-fold increase), whereas both proteins reduced the corrosion resistance of SS, with the reverse situation for iron metal (reduced corrosion rates and reduced metal release in the presence of proteins). A full monolayer coverage is necessary to induce the effects observed.

Tunable Electronic and Topological Properties of Germanene by Functional Group Modification

PubMed Central

Ren, Ceng-Ceng; Zhang, Shu-Feng; Ji, Wei-Xiao; Zhang, Chang-Wen; Li, Ping; Wang, Pei-Ji

2018-01-01

Electronic and topological properties of two-dimensional germanene modified by functional group X (X = H, F, OH, CH3) at full coverage are studied with first-principles calculation. Without considering the effect of spin-orbit coupling (SOC), all functionalized configurations become semiconductors, removing the Dirac cone at K point in pristine germanene. We also find that their band gaps can be especially well tuned by an external strain. When the SOC is switched on, GeX (X = H, CH3) is a normal insulator and strain leads to a phase transition to a topological insulator (TI) phase. However, GeX (X = F, OH) becomes a TI with a large gap of 0.19 eV for X = F and 0.24 eV for X = OH, even without external strains. More interestingly, when all these functionalized monolayers form a bilayer structure, semiconductor-metal states are observed. All these results suggest a possible route of modulating the electronic properties of germanene and promote applications in nanoelectronics. PMID:29509699

Water and Carbon Dioxide Adsorption at Olivine Surfaces

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

Kerisit, Sebastien N.; Bylaska, Eric J.; Felmy, Andrew R.

2013-11-14

Plane-wave density functional theory (DFT) calculations were performed to simulate water and carbon dioxide adsorption at the (010) surface of five olivine minerals, namely, forsterite (Mg2SiO4), calcio-olivine (Ca2SiO4), tephroite (Mn2SiO4), fayalite (Fe2SiO4), and Co-olivine (Co2SiO4). Adsorption energies per water molecule obtained from energy minimizations varied from -78 kJ mol-1 for fayalite to -128 kJ mol-1 for calcio-olivine at sub-monolayer coverage and became less exothermic as coverage increased. In contrast, carbon dioxide adsorption energies at sub-monolayer coverage ranged from -20 kJ mol-1 for fayalite to -59 kJ mol-1 for calcio-olivine. Therefore, the DFT calculations show a strong driving force for carbonmore » dioxide displacement by water at the surface of all olivine minerals in a competitive adsorption scenario. Additionally, adsorption energies for both water and carbon dioxide were found to be more exothermic for the alkaline-earth (AE) olivines than for the transition-metal (TM) olivines and to not correlate with the solvation enthalpies of the corresponding divalent cations. However, a correlation was obtained with the charge of the surface divalent cation indicating that the more ionic character of the AE cations in the olivine structure relative to the TM cations leads to greater interactions with adsorbed water and carbon dioxide molecules at the surface and thus more exothermic adsorption energies for the AE olivines. For calcio-olivine, which exhibits the highest divalent cation charge of the five olivines, ab initio molecular dynamics simulations showed that this effect leads both water and carbon dioxide to react with the surface and form hydroxyl groups and a carbonate-like species, respectively.« less

Identification of the nitrogen-based blister agents bis(2-chloroethyl)methylamine (HN-2) and tris(2-chloroethyl)amine (HN-3) and their hydrolysis products on soil using ion trap secondary ion mass spectrometry.

PubMed

Gresham, G L; Groenewold, G S; Olson, J E

2000-12-01

The nitrogen blister agents HN-2 (bis(2-chloroethyl)methylamine) and HN-3 (tris(2-chloroethyl)amine) were directly analyzed on the surface of soil samples using ion trap secondary ion mass spectrometry (SIMS). In the presence of water, HN-1 (bis(2-choroethyl)ethylamine), HN-2 and HN-3 undergo hydrolysis to form N-ethyldiethanolamine, N-methyldiethanolamine and triethanolamine (TEA), respectively; these compounds can be readily detected as adsorbed species on soil particles. When soil samples spiked with HN-3 in alcohol were analyzed, 2-alkoxyethylamine derivatives were observed on the sample surfaces. This result shows that nitrogen blister agents will undergo condensation reactions with nucleophilic compounds and emphasizes the need for an analytical methodology capable of detecting a range of degradation and condensation products on environmental surfaces. The ability of ion trap SIMS to isolate and accumulate ions, and then perform tandem mass spectrometric analysis improves the detection of low-abundance surface contaminants and the selectivity of the technique. Utilizing these techniques, the limits of detection for HN-3 were studied as a function of surface coverage. It was found that HN-3 could be detected at a surface coverage of 0.01 monolayer, which corresponds to 20 ppm (mass/mass) for a soil having a surface area of 2.2 m(2) g(-1). TEA, the exhaustive hydrolysis product of HN-3, was detected at a surface coverage of 0.001 monolayer, which corresponds to 0.86 ppm. Copyright 2000 John Wiley & Sons, Ltd.

In vitro toxicity of photodynamic antimicrobial chemotherapy on human keratinocytes proliferation.

PubMed

Migliario, Mario; Rizzi, Manuela; Rocchetti, Vincenzo; Cannas, Mario; Renò, Filippo

2013-02-01

This in vitro experimental study has been designed to assess the effects of photodynamic antimicrobial chemotherapy (PACT) on human keratinocytes proliferation. Human keratinocytes (HaCaT) monolayers (∼0.5 cm(2)) have been irradiated with 635 nm red laser light with a fluence of 82.5 or 112.5 J/cm(2) in the absence or presence of toluidine (TB). Cell proliferation, monolayer area coverage, cytokeratin 5 (K5) and filaggrin (Fil) expression, and metalloproteinase (MMP)-2 and MMP-9 activity were measured after 72 h from laser irradiation. HaCaT proliferation was reduced by TB staining. Cell exposure to both low- and high-fluence laser irradiation in both presence and absence of TB staining reduced their proliferation and monolayer area extension. Moreover both laser treatments were able to reduce K5 and Fil expression and MMP-9 production in keratinocytes not treated with TB. These data indicate that PACT could exert toxic effects on normal proliferating keratinocytes present around parodontal pockets. The observed reduced cell proliferation along with a reduced production of enzymes involved in wound healing could alter the clinical outcome of the patients treated with PACT.

Influence of surface hydroxylation on 3-aminopropyltriethoxysilane growth mode during chemical functionalization of GaN Surfaces: an angle-resolved X-ray photoelectron spectroscopy Study.

PubMed

Arranz, A; Palacio, C; García-Fresnadillo, D; Orellana, G; Navarro, A; Muñoz, E

2008-08-19

A comparative study of the chemical functionalization of undoped, n- and p-type GaN layers grown on sapphire substrates by metal-organic chemical vapor deposition was carried out. Both types of samples were chemically functionalized with 3-aminopropyltriethoxysilane (APTES) using a well-established silane-based approach for functionalizing hydroxylated surfaces. The untreated surfaces as well as those modified by hydroxylation and APTES deposition were analyzed using angle-resolved X-ray photoelectron spectroscopy. Strong differences were found between the APTES growth modes on n- and p-GaN surfaces that can be associated with the number of available hydroxyl groups on the GaN surface of each sample. Depending on the density of surface hydroxyl groups, different mechanisms of APTES attachment to the GaN surface take place in such a way that the APTES growth mode changes from a monolayer to a multilayer growth mode when the number of surface hydroxyl groups is decreased. Specifically, a monolayer growth mode with a surface coverage of approximately 78% was found on p-GaN, whereas the formation of a dense film, approximately 3 monolayers thick, was observed on n-GaN.

Controlling Protein Surface Orientation by Strategic Placement of Oligo-Histidine Tags

PubMed Central

2017-01-01

We report oriented immobilization of proteins using the standard hexahistidine (His6)-Ni2+:NTA (nitrilotriacetic acid) methodology, which we systematically tuned to give control of surface coverage. Fluorescence microscopy and surface plasmon resonance measurements of self-assembled monolayers (SAMs) of red fluorescent proteins (TagRFP) showed that binding strength increased by 1 order of magnitude for each additional His6-tag on the TagRFP proteins. All TagRFP variants with His6-tags located on only one side of the barrel-shaped protein yielded a 1.5 times higher surface coverage compared to variants with His6-tags on opposite sides of the so-called β-barrel. Time-resolved fluorescence anisotropy measurements supported by polarized infrared spectroscopy verified that the orientation (and thus coverage and functionality) of proteins on surfaces can be controlled by strategic placement of a His6-tag on the protein. Molecular dynamics simulations show how the differently tagged proteins reside at the surface in “end-on” and “side-on” orientations with each His6-tag contributing to binding. Also, not every dihistidine subunit in a given His6-tag forms a full coordination bond with the Ni2+:NTA SAMs, which varied with the position of the His6-tag on the protein. At equal valency but different tag positions on the protein, differences in binding were caused by probing for Ni2+:NTA moieties and by additional electrostatic interactions between different fractions of the β-barrel structure and charged NTA moieties. Potential of mean force calculations indicate there is no specific single-protein interaction mode that provides a clear preferential surface orientation, suggesting that the experimentally measured preference for the end-on orientation is a supra-protein, not a single-protein, effect. PMID:28850777

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

PubMed

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

2015-04-07

In situ scanning tunneling microscopy combined with density functional theory molecular dynamics simulations reveal a complex structure for the self-assembled monolayer (SAM) of racemic 2-butanethiol on Au(111) in aqueous solution. Six adsorbate molecules occupy a (10×√3)R30° cell organized as two RSAuSR adatom-bound motifs plus two RS species bound directly to face-centered-cubic and hexagonally close-packed sites. This is the first time that these competing head-group arrangements have been observed in the same ordered SAM. Such unusual packing is favored as it facilitates SAMs with anomalously high coverage (30%), much larger than that for enantiomerically resolved 2-butanethiol or secondary-branched butanethiol (25%) and near that for linear-chain 1-butanethiol (33%). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanical properties of hydrogenated bilayer graphene

NASA Astrophysics Data System (ADS)

Andrew, R. C.; Mapasha, R. E.; Chetty, N.

2013-06-01

Using first principle methods, we study the mechanical properties of monolayer and bilayer graphene with 50% and 100% coverage of hydrogen. We employ the vdW-DF, vdW-DF-C09x, and vdW-DF2-C09x van der Waals functionals for the exchange correlation interactions that give significantly improved interlayer spacings and energies. We also use the PBE form for the generalized gradient corrected exchange correlation functional for comparison. We present a consistent theoretical framework for the in-plane layer modulus and the out-of-plane interlayer modulus and we calculate, for the first time, these properties for these systems. This gives a measure of the change of the strength properties when monolayer and bilayer graphene are hydrogenated. Moreover, comparing the relative performance of these functionals in describing hydrogenated bilayered graphenes, we also benchmark these functionals in how they calculate the properties of graphite.

Mechanical Properties of a vdW molecular monolayer at a metal surface: Structural Polymorphism leading to facile compression

NASA Astrophysics Data System (ADS)

Sun, Dezheng; Kim, Daeho; Le, Duy; Borck, Øyvind; Berland, Kristian; Kim, Kwangmoo; Lu, Wenhao; Zhu, Yeming; Luo, Miaomiao; Wyrick, Jon; Cheng, Zhihai; Einstein, T. L.; Rahman, Talat; Hyldgaard, Per; Bartels, Ludwig

2011-03-01

Intermolecular force plays an important role in self-assembly and surface pattern formation. Anthracene and similar unsubstituted arenes attach to a metallic substrate predominantly through van der Waals interaction leading. In this contribution we present images how anthracene on Cu(111) forms a large number of highly ordered patterns that feature a broad array of structural motifs. Density functional theory modeling including vdW interactions allows us to model the energetic of the pattern formation at high fidelity. Moreover, it allows us to deduce the strain energy associated with films of varying coverage. From this work, we obtain the Young's modulus and Poisson Ratio of a molecular monolayer, which resemble properties conventionally found for porous materials. These patterns are in marked contrast to those found after introduction of functional groups in the molecules, such as carbonyls or thiols.

Perfluoropentacene adsorption on Cu(110)

NASA Astrophysics Data System (ADS)

Gall, J.; Zhang, L.; Fu, X.; Zeppenfeld, P.; Sun, L. D.

2017-09-01

The adsorption of perfluoropentacene (PFP) on the Cu(110) surface has been investigated using reflectance difference spectroscopy (RDS), low-energy electron diffraction, and low-temperature scanning tunneling microscopy. The PFP molecules within the first monolayer align their long molecular axis exclusively oriented along the [001] azimuthal direction of the Cu substrate. In comparison with the adsorption behavior of pentacene on the same surface, a strong effect of the fluorination regarding the molecular orientation and the intermolecular and molecule-substrate interactions was identified. Furthermore, a two-dimensional gas-solid phase transition accompanied by a reversible azimuthal rotation of the PFP molecules was observed at the beginning of the second monolayer growth. The change of the optical anisotropy associated with this reorientation was used to explore the two-dimensional (2D) condensation as a function of coverage and temperature by RDS, and the 2D heat of condensation in the PFP bilayer on Cu(110) was determined to be 105 meV.

Full melting of a two-dimensional complex plasma crystal triggered by localized pulsed laser heating

NASA Astrophysics Data System (ADS)

Couëdel, L.; Nosenko, V.; Rubin-Zuzic, M.; Zhdanov, S.; Elskens, Y.; Hall, T.; Ivlev, A. V.

2018-04-01

The full melting of a two-dimensional plasma crystal was induced in a principally stable monolayer by localized laser stimulation. Two distinct behaviors of the crystal after laser stimulation were observed depending on the amount of injected energy: (i) below a well-defined threshold, the laser melted area recrystallized; (ii) above the threshold, it expanded outwards in a similar fashion to mode-coupling instability-induced melting, rapidly destroying the crystalline order of the whole complex plasma monolayer. The reported experimental observations are due to the fluid mode-coupling instability, which can pump energy into the particle monolayer at a rate surpassing the heat transport and damping rates in the energetic localized melted spot, resulting in its further growth. This behavior exhibits remarkable similarities with impulsive spot heating in ordinary reactive matter.

Two- and three-dimensional growth of Bi on i -Al-Pd-Mn studied using medium-energy ion scattering

NASA Astrophysics Data System (ADS)

Noakes, T. C. Q.; Bailey, P.; McConville, C. F.; Draxler, M.; Walker, M.; Brown, M. G.; Hentz, A.; Woodruff, D. P.; Lograsso, T. A.; Ross, A. R.; Smerdon, J. A.; Leung, L.; McGrath, R.

2010-11-01

Recent work on the growth of thin metal films on quasicrystalline substrates has indicated the formation of so-called “magic height” islands with multiples of 4 atomic layers (AL) arising as a result of quantum size effects, which lead to enhanced stability. Here the results of a study are reported of Bi deposition on i -Al-Pd-Mn using medium-energy ion scattering to characterize the island thickness and the structural arrangement of Bi atoms within the islands. In addition, data were taken from annealed surfaces after Bi cluster desorption to leave a single aperiodic monolayer of Bi at the surface. Scattered-ion energy spectra from the Bi islands are consistent with a single Bi monolayer covered with mainly 4 AL islands for both 1.8 and 3.2 monolayer equivalent coverages but with some occupation of 2 and 8 Al islands as well. The angular dependence of the scattered-ion intensity (“blocking curve”) from Bi has been compared with simulations for various models of both rhombohedral Bi and a distorted “black-phosphorus”-like structure. The data demonstrate bilayer formation within the Bi islands. In the case of the aperiodic Bi monolayer, the blocking curves from substrate scattering are found to be inconsistent with two high-symmetry sites on the quasicrystalline surface that theory indicates are energetically favorable but do not exclude the formation of pentagonal arrangements of Bi atoms as seen in other recent experimental work.

Simultaneous adsorption of CO2 and H2O under Mars-like conditions and application to the evolution of the Martian climate

NASA Technical Reports Server (NTRS)

Zent, Aaron, P.; Quinn, Richard C.

1995-01-01

The Martian regolith is the most substantial volatile reservoir on the planet; estimates of its adsorbed inventory have been based on simple measurements of the adsorption of either water or CO2 in isolation. Under some conditions, H2O can poison adsorbate surfaces, such that CO2 uptake is greatly reduced. We have made the first measurements of the simultaneous adsorption of CO2 and H2O under conditions appropriate to the Martian regolith and have found that at H2O monolayer coverage above about 0.5, CO2 begins to be displaced into the gas phase. We have developed an empirical expression that describes our co-adsorption data and have applied it to standard models of the Martian regolith. We find that currently, H2O does not substantially displace CO, implying that the adsorbate inventories previously derived may be accurate, not more than 3-4 kPa (30-40 mbar). No substantial increase in atmospheric pressure is predicted at higher obliquities because high-latitude ground ice buffers the partial pressure of H2O in the pores, preventing high monolayer coverages of H2O from displacing CO2. The peak atmospheric pressure at high obliquity does increase as the total inventory of exchangeable CO2 increases.

Simutaneous adsorption of CO2 and H2O under Mars-like conditions and application to the evolution of the Martian climate

NASA Technical Reports Server (NTRS)

Zent, Aaron P.; Quinn, Richard C.

1995-01-01

The Martian regolith is the most substantial volatile reservoir on the planet; estimates of its adsorbed inventory have been based on simple measurements of the adsorption of either water or CO2 in isolation. Under some conditions, H2O can poison adsorbate surfaces, such that CO2 uptake is greatly reduced. We have made the first measurements of the simultaneous adsorption of CO2 and H2O under conditions appropriate to the Martian regolith and have found that at H2O monolayer coverage above about 0.5, CO2 begins to be displaced into the gas phase. We have developed an empirical expression that describes our co-adsorption data and have applied it to standard models of the Martian regolith. We find that currently, H2O does not substantially displace CO2, implying that the adsorbate inventories previously derived may be accurate, not more than 3-4 kPa (30-40 mbar). No substantial increase in atmospheric pressure is predicted at higher obliquities because high-latitude ground ice buffers the partial pressure of H2O in the pores, preventing high monolayer coverages of H2O from displacing CO2. The peak atmospheric pressure at high obliquity does increase as the total inventory of exchangeable CO2 increases.

Surface morphology of vacuum-evaporated pentacene film on Si substrate studied by in situ grazing-incidence small-angle X-ray scattering: I. The initial stage of formation of pentacene film

NASA Astrophysics Data System (ADS)

Hirosawa, Ichiro; Watanabe, Takeshi; Koganezawa, Tomoyuki; Kikuchi, Mamoru; Yoshimoto, Noriyuki

2018-03-01

The progress of the surface morphology of a growing sub-monolayered pentacene film on a Si substrate was studied by in situ grazing-incidence small angle X-ray scattering (GISAXS). The observed GISAXS profiles did not show sizes of pentacene islands but mainly protuberances on the boundaries around pentacene film. Scattering of X-ray by residual pits in the pentacene film was also detected in the GISAXS profiles of an almost fully covered film. The average radius of pentacene protuberances increased from 13 to 24 nm as the coverage increased to 0.83 monolayer, and the most frequent radius was almost constant at approximately 9 nm. This result suggests that the population of larger protuberances increase with increasing lengths of boundaries of the pentacene film. It can also be considered that the detected protuberances were crystallites of pentacene, since the average size of protuberances was nearly equal to crystallite sizes of pentacene films. The almost constant characteristic distance of 610 nm and amplitudes of pair correlation functions at low coverages suggest that the growth of pentacene films obeyed the diffusion-limited aggregation (DLA) model, as previously reported. It is also considered that the sites of islands show a triangular distribution for small variations of estimated correlation distances.

Hydrogen Sorption Kinetics on Bare and Platinum-Modified Palladium Nanofilms, Grown by Electrochemical Atomic Layer Deposition (E-ALD)

DOE PAGES

Jagannathan, Kaushik; Benson, David M.; Robinson, David B.; ...

2016-01-01

Nanofilms of Pd were grown using an electrochemical form of atomic layer deposition (E-ALD) on 100 nm evaporated Au films on glass. Multiple cycles of surface-limited redox replacement (SLRR) were used to grow deposits. Each SLRR involved the underpotential deposition (UPD) of a Cu atomic layer, followed by open circuit replacement via redox exchange with tetrachloropalladate, forming a Pd atomic layer: one E-ALD deposition cycle. That cycle was repeated in order to grow deposits of a desired thickness. 5 cycles of Pd deposition were performed on the Au on glass substrates, resulting in the formation of 2.5 monolayers of Pd.more » Those Pd films were then modified with varying coverages of Pt, also formed using SLRR. The amount of Pt was controlled by changing the potential for Cu UPD, and by increasing the number of Pt deposition cycles. Hydrogen absorption was studied using coulometry and cyclic voltammetry in 0.1 M H 2SO 4 as a function of Pt coverage. The presence of even a small fraction of a Pt monolayer dramatically increased the rate of hydrogen desorption. However, this did not reduce the films’ hydrogen storage capacity. The increase in desorption rate in the presence of Pt was over an order of magnitude.« less

Characterization of protein immobilization on nanoporous gold using atomic force microscopy and scanning electron microscopy†

PubMed Central

Tan, Yih Horng; Schallom, John R.; Ganesh, N. Vijaya; Fujikawa, Kohki; Demchenko, Alexei V.

2011-01-01

Nanoporous gold (NPG), made by dealloying low carat gold alloys, is a relatively new nanomaterial finding application in catalysis, sensing, and as a support for biomolecules. NPG has attracted considerable interest due to its open bicontinuous structure, high surface-to-volume ratio, tunable porosity, chemical stability and biocompatibility. NPG also has the attractive feature of being able to be modified by self-assembled monolayers. Here we use scanning electron microscopy (SEM) and atomic force microscopy (AFM) to characterize a highly efficient approach for protein immobilization on NPG using N-hydroxysuccinimide (NHS) ester functionalized self-assembled monolayers on NPG with pore sizes in the range of tens of nanometres. Comparison of coupling under static versus flow conditions suggests that BSA (Bovine Serum Albumin) and IgG (Immunoglobulin G) can only be immobilized onto the interior surfaces of free standing NPG monoliths with good coverage under flow conditions. AFM is used to examine protein coverage on both the exterior and interior of protein modified NPG. Access to the interior surface of NPG for AFM imaging is achieved using a special procedure for cleaving NPG. AFM is also used to examine BSA immobilized on rough gold surfaces as a comparative study. In principle, the general approach described should be applicable to many enzymes, proteins and protein complexes since both pore sizes and functional groups present on the NPG surfaces are controllable. PMID:21750834

Desorption kinetics of methanol, ethanol, and water from graphene.

PubMed

Smith, R Scott; Matthiesen, Jesper; Kay, Bruce D

2014-09-18

The desorption kinetics of methanol, ethanol, and water from graphene covered Pt(111) are investigated. The temperature programmed desorption (TPD) spectra for both methanol and ethanol have well-resolved first, second, third, and multilayer layer desorption peaks. The alignment of the leading edges is consistent with zero-order desorption kinetics from all layers. In contrast, for water, the first and second layers are not resolved. At low water coverages (<1 monolayer (ML)) the initial desorption leading edges are aligned but then fall out of alignment at higher temperatures. For thicker water layers (10-100 ML), the desorption leading edges are in alignment throughout the desorption of the film. The coverage dependence of the desorption behavoir suggests that at low water coverages the nonalignment of the desorption leading edges is due to water dewetting from the graphene substrate. Kinetic simulations reveal that the experimental results are consistent with zero-order desorption. The simulations also show that fractional order desorption kinetics would be readily apparent in the experimental TPD spectra.

Hydrophilic Cucurbit[7]uril-Pseudorotaxane-Anchored-Monolayer-Protected Gold Nanorods

DTIC Science & Technology

2013-03-20

FULL PAPER DOI:10.1002/ejic.201300010 Hydrophilic Cucurbit[7]uril-Pseudorotaxane-Anchored- Monolayer-Protected Gold Nanorods Xiang Ma,[a] Yuhua Xue... Cao , Q. Wang, H. Tian, Chem. Commun. 2011, 47, 3559–3561. [8] a) I. Hwang, K. Baek, M. Jung, Y. Kim, K. M. Park, D. W. Lee, N. Selvapalam, K. Kim, J. Am

Coverage evolution of the unoccupied Density of States in sulfur superstructures on Ru(0001)

NASA Astrophysics Data System (ADS)

Pisarra, M.; Bernardo-Gavito, R.; Navarro, J. J.; Black, A.; Díaz, C.; Calleja, F.; Granados, D.; Miranda, R.; Martín, F.; Vázquez de Parga, A. L.

2018-03-01

Sulfur adsorbed on Ru(0001) presents a large number of ordered structures. This characteristic makes S/Ru(0001) the ideal system to investigate the effect of different periodicities on the electronic properties of interfaces. We have performed scanning tunneling microscopy/spectroscopy experiments and density functional theory calculations showing that a sulfur adlayer generates interface states inside the Γ directional gap of Ru(0001) and that the position of such states varies monotonically with sulfur coverage. This is the result of the interplay between band folding effects arising from the new periodicity of the system and electron localization on the sulfur monolayer. As a consequence, by varying the amount of sulfur in S/Ru(0001) one can control the electronic properties of these interfacial materials.

Arresting dissolution by interfacial rheology design

PubMed Central

Beltramo, Peter J.; Gupta, Manish; Alicke, Alexandra; Liascukiene, Irma; Gunes, Deniz Z.; Baroud, Charles N.

2017-01-01

A strategy to halt dissolution of particle-coated air bubbles in water based on interfacial rheology design is presented. Whereas previously a dense monolayer was believed to be required for such an “armored bubble” to resist dissolution, in fact engineering a 2D yield stress interface suffices to achieve such performance at submonolayer particle coverages. We use a suite of interfacial rheology techniques to characterize spherical and ellipsoidal particles at an air–water interface as a function of surface coverage. Bubbles with varying particle coverages are made and their resistance to dissolution evaluated using a microfluidic technique. Whereas a bare bubble only has a single pressure at which a given radius is stable, we find a range of pressures over which bubble dissolution is arrested for armored bubbles. The link between interfacial rheology and macroscopic dissolution of ∼ 100 μm bubbles coated with ∼ 1 μm particles is presented and discussed. The generic design rationale is confirmed by using nonspherical particles, which develop significant yield stress at even lower surface coverages. Hence, it can be applied to successfully inhibit Ostwald ripening in a multitude of foam and emulsion applications. PMID:28893993

Initial oxidation behavior of Ni3Al (210) surface induced by supersonic oxygen molecular beam at room temperature

NASA Astrophysics Data System (ADS)

Xu, Ya; Sakurai, Junya; Teraoka, Yuden; Yoshigoe, Akitaka; Demura, Masahiko; Hirano, Toshiyuki

2017-01-01

The initial oxidation behavior of a clean Ni3Al (210) surface was studied at 300 K using a supersonic O2 molecular beam (O2 SSMB) having an O2 translational energy of 2.3 eV, and real-time photoemission spectroscopy performed with high-brilliance synchrotron radiation. The evolution behaviors of the O 1s, Ni 2p, Al 2p, and Ni 3p spectra were examined during irradiation with the O2 SSMB. The spectral analysis revealed that both the Al atoms and the Ni atoms on the surface were oxidized; however, the oxidation of Al progressed much faster than that of Ni. The oxidation of Al began to occur and AlOx was formed at an oxygen coverage of 0.26 monolayer (ML) (1 ML was defined as the atomic density of the Ni3Al (210) surface) and saturated at an oxygen coverage of 2.5 ML. In contrast, the oxidation of Ni commenced a little late at an oxygen coverage of 1.6 ML and slowly progressed to saturation, which occurred at an oxygen coverage of 4.89 ML.

Origin of the instability of octadecylamine Langmuir monolayer at low pH

DOE PAGES

Avazbaeva, Zaure; Sung, Woongmo; Lee, Jonggwan; ...

2015-11-30

In this paper, it has been reported that an octadecylamine (ODA) Langmuir monolayer becomes unstable at low pH values with no measurable surface pressure at around pH 3.5, suggesting significant dissolution of the ODA molecule into the subphase solution (Albrecht, Colloids Surf. A 2006, 284–285, 166–174). However, by lowering the pH further, ODA molecules reoccupy the surface, and a full monolayer is recovered at pH 2.5. Using surface sum-frequency spectroscopy and pressure–area isotherms, it is found that the recovered monolayer at very low pH has a larger area per molecule with many gauche defects in the ODA molecules as comparedmore » to that at high pH values. This structural change suggests that the reappearance of the monolayer is due to the adsorbed Cl– counterions to the protonated amine groups, leading to partial charge neutralization. This proposition is confirmed by intentionally adding monovalent salts (i.e., NaCl, NaBr, or NaI) to the subphase to recover the monolayer at pH 3.5, in which the detailed structure of the monolayer is confirmed by sum frequency spectra and the adsorbed anions by X-ray reflectivity.« less

Vacancy-Rich Monolayer BiO 2-x as a Highly Efficient UV, Visible, and Near-Infrared Responsive Photocatalyst

DOE PAGES

Li, Jun; Wu, Xiaoyong; Pan, Wenfeng; ...

2017-09-08

Here in this paper, a full-spectrum responsive vacancy-rich monolayer BiO 2-x has been synthesized. The increased density of states at the conduction band (CB) minimum in the monolayer BiO 2-x is responsible for the enhanced photon response and photo-absorption, which were confirmed by UV/Vis-NIR diffuse reflectance spectra (DRS) and photocurrent measurements. Compared to bulk BiO 2-x, monolayer BiO 2-x has exhibited enhanced photocatalytic performance for rhodamine B and phenol removal under UV, visible, and near-infrared light (NIR) irradiation, which can be attributed to the vacancy VBi-O"' as confirmed by the positron annihilation spectra. The presence of V Bi-O"' defects inmore » monolayer BiO 2-x promoted the separation of electrons and holes. This finding provides an atomic level understanding for developing highly efficient UV, visible, and NIR light responsive photocatalysts.« less

Vacancy-Rich Monolayer BiO 2-x as a Highly Efficient UV, Visible, and Near-Infrared Responsive Photocatalyst

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

Li, Jun; Wu, Xiaoyong; Pan, Wenfeng

Here in this paper, a full-spectrum responsive vacancy-rich monolayer BiO 2-x has been synthesized. The increased density of states at the conduction band (CB) minimum in the monolayer BiO 2-x is responsible for the enhanced photon response and photo-absorption, which were confirmed by UV/Vis-NIR diffuse reflectance spectra (DRS) and photocurrent measurements. Compared to bulk BiO 2-x, monolayer BiO 2-x has exhibited enhanced photocatalytic performance for rhodamine B and phenol removal under UV, visible, and near-infrared light (NIR) irradiation, which can be attributed to the vacancy VBi-O"' as confirmed by the positron annihilation spectra. The presence of V Bi-O"' defects inmore » monolayer BiO 2-x promoted the separation of electrons and holes. This finding provides an atomic level understanding for developing highly efficient UV, visible, and NIR light responsive photocatalysts.« less

Platinum Monolayer Electrocatalysts for Oxygen Reduction

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

Vukmirovic, Miomir B.; Zhang, Junliang; Sasaki, Kotaro

2007-01-20

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. We have synthesized a new class of electrocatalysts for the oxygen reduction reaction, consisting of a monolayer of Pt or mixed monolayer of Pt and another late transition metal (Au, Pd, Ir, Ru, Rh, Re or Os) deposited on a Pd(1 1 1) single crystal or on carbon-supported Pd nanoparticles. Several of these electrocatalysts exhibited very high activity, amounting tomore » 20-fold increase in a Pt mass activity, compared with conventional all-Pt electrocatalysts. Their superior activity reflects a low OH coverage on Pt, caused by the lateral repulsion between the OH adsorbed on Pt and the OH or O adsorbed on neighboring, other than Pt, late transition metal atoms. The origin of this effect was identified through a combination of experimental and theoretical methods, employing electrochemical techniques, X-ray absorption spectroscopy, and periodic, self-consistent density functional theory calculations. This new class of electrocatalysts promises to alleviate some major problems of existing fuel cell technology by simultaneously decreasing materials cost and enhancing performance.« less

Epitaxial MoS2/GaN structures to enable vertical 2D/3D semiconductor heterostructure devices

NASA Astrophysics Data System (ADS)

Ruzmetov, D.; Zhang, K.; Stan, G.; Kalanyan, B.; Eichfeld, S.; Burke, R.; Shah, P.; O'Regan, T.; Crowne, F.; Birdwell, A. G.; Robinson, J.; Davydov, A.; Ivanov, T.

MoS2/GaN structures are investigated as a building block for vertical 2D/3D semiconductor heterostructure devices that utilize a 3D substrate (GaN) as an active component of the semiconductor device without the need of mechanical transfer of the 2D layer. Our CVD-grown monolayer MoS2 has been shown to be epitaxially aligned to the GaN lattice which is a pre-requisite for high quality 2D/3D interfaces desired for efficient vertical transport and large area growth. The MoS2 coverage is nearly 50 % including isolated triangles and monolayer islands. The GaN template is a double-layer grown by MOCVD on sapphire and allows for measurement of transport perpendicular to the 2D layer. Photoluminescence, Raman, XPS, Kelvin force probe microscopy, and SEM analysis identified high quality monolayer MoS2. The MoS2/GaN structures electrically conduct in the out-of-plane direction and across the van der Waals gap, as measured with conducting AFM (CAFM). The CAFM current maps and I-V characteristics are analyzed to estimate the MoS2/GaN contact resistivity to be less than 4 Ω-cm2 and current spreading in the MoS2 monolayer to be approx. 1 μm in diameter. Epitaxial MoS2/GaN heterostructures present a promising platform for the design of energy-efficient, high-speed vertical devices incorporating 2D layered materials with 3D semiconductors.

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

Avazbaeva, Zaure; Sung, Woongmo; Lee, Jonggwan

In this paper, it has been reported that an octadecylamine (ODA) Langmuir monolayer becomes unstable at low pH values with no measurable surface pressure at around pH 3.5, suggesting significant dissolution of the ODA molecule into the subphase solution (Albrecht, Colloids Surf. A 2006, 284–285, 166–174). However, by lowering the pH further, ODA molecules reoccupy the surface, and a full monolayer is recovered at pH 2.5. Using surface sum-frequency spectroscopy and pressure–area isotherms, it is found that the recovered monolayer at very low pH has a larger area per molecule with many gauche defects in the ODA molecules as comparedmore » to that at high pH values. This structural change suggests that the reappearance of the monolayer is due to the adsorbed Cl– counterions to the protonated amine groups, leading to partial charge neutralization. This proposition is confirmed by intentionally adding monovalent salts (i.e., NaCl, NaBr, or NaI) to the subphase to recover the monolayer at pH 3.5, in which the detailed structure of the monolayer is confirmed by sum frequency spectra and the adsorbed anions by X-ray reflectivity.« less

Full superconducting dome of strong Ising protection in gated monolayer WS2.

PubMed

Lu, Jianming; Zheliuk, Oleksandr; Chen, Qihong; Leermakers, Inge; Hussey, Nigel E; Zeitler, Uli; Ye, Jianting

2018-04-03

Many recent studies show that superconductivity not only exists in atomically thin monolayers but can exhibit enhanced properties such as a higher transition temperature and a stronger critical field. Nevertheless, besides being unstable in air, the weak tunability in these intrinsically metallic monolayers has limited the exploration of monolayer superconductivity, hindering their potential in electronic applications (e.g., superconductor-semiconductor hybrid devices). Here we show that using field effect gating, we can induce superconductivity in monolayer WS 2 grown by chemical vapor deposition, a typical ambient-stable semiconducting transition metal dichalcogenide (TMD), and we are able to access a complete set of competing electronic phases over an unprecedented doping range from band insulator, superconductor, to a reentrant insulator at high doping. Throughout the superconducting dome, the Cooper pair spin is pinned by a strong internal spin-orbit interaction, making this material arguably the most resilient superconductor in the external magnetic field. The reentrant insulating state at positive high gating voltages is attributed to localization induced by the characteristically weak screening of the monolayer, providing insight into many dome-like superconducting phases observed in field-induced quasi-2D superconductors.

Contact pin-printing of albumin-fungicide conjugate for silicon nitride-based sensors biofunctionalization: Multi-technique surface analysis for optimum immunoassay performance

NASA Astrophysics Data System (ADS)

Gajos, Katarzyna; Budkowski, Andrzej; Tsialla, Zoi; Petrou, Panagiota; Awsiuk, Kamil; Dąbczyński, Paweł; Bernasik, Andrzej; Rysz, Jakub; Misiakos, Konstantinos; Raptis, Ioannis; Kakabakos, Sotirios

2017-07-01

Mass fabrication of integrated biosensors on silicon chips is facilitated by contact pin-printing, applied for biofunctionalization of individual Si3N4-based transducers at wafer-scale. To optimize the biofunctionalization for immunochemical (competitive) detection of fungicide thiabendazole (TBZ), Si3N4 surfaces are modified with (3-aminopropyl)triethoxysilane and examined after: immobilization of BSA-TBZ conjugate (probe) from solutions with different concentration, blocking with bovine serum albumin (BSA), and immunoreaction with a mouse monoclonal antibody against TBZ. Nanostructure, surface density, probe composition and coverage uniformity of protein layers are evaluated with Atomic Force Microscopy, Spectroscopic Ellipsometry, Time-of-Flight Secondary Ion Mass Spectrometry and X-ray Photoelectron Spectroscopy. Contact pin-printing of overlapping probe spots is compared with hand spotted areas. Contact pin-printing resulted in two-fold increase of immobilized probe surface density as compared to hand spotting. Regarding BSA-TBZ immobilization, an incomplete monolayer develops into a bilayer as the concentration of BSA-TBZ molecules in the printing solution increases from 25 to 100 μg/mL. Upon blocking, however, a complete protein monolayer is formed for all the BSA-TBZ concentrations used. Free surface sites are filled with BSA for low surface coverage with BSA-TBZ, whereas loosely bound BSA-TBZ molecules are removed from the BSA-TBZ bilayer. As a consequence immunoreaction efficiency increases with the printing probe concentration.

Influence of surface coverage on the chemical desorption process

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

Minissale, M.; Dulieu, F., E-mail: francois.dulieu@obspm.fr

2014-07-07

In cold astrophysical environments, some molecules are observed in the gas phase whereas they should have been depleted, frozen on dust grains. In order to solve this problem, astrochemists have proposed that a fraction of molecules synthesized on the surface of dust grains could desorb just after their formation. Recently the chemical desorption process has been demonstrated experimentally, but the key parameters at play have not yet been fully understood. In this article, we propose a new procedure to analyze the ratio of di-oxygen and ozone synthesized after O atoms adsorption on oxidized graphite. We demonstrate that the chemical desorptionmore » efficiency of the two reaction paths (O+O and O+O{sub 2}) is different by one order of magnitude. We show the importance of the surface coverage: for the O+O reaction, the chemical desorption efficiency is close to 80% at zero coverage and tends to zero at one monolayer coverage. The coverage dependence of O+O chemical desorption is proved by varying the amount of pre-adsorbed N{sub 2} on the substrate from 0 to 1.5 ML. Finally, we discuss the relevance of the different physical parameters that could play a role in the chemical desorption process: binding energy, enthalpy of formation, and energy transfer from the new molecule to the surface or to other adsorbates.« less

Interplay between Vacuum-Grown Monolayers of Alkylphosphonic Acids and the Performance of Organic Transistors Based on Dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene.

PubMed

Hannah, Stuart; Cardona, Javier; Lamprou, Dimitrios A; Šutta, Pavol; Baran, Peter; Al Ruzaiqi, Afra; Johnston, Karen; Gleskova, Helena

2016-09-28

Monolayers of six alkylphosphonic acids ranging from C8 to C18 were prepared by vacuum evaporation and incorporated into low-voltage organic field-effect transistors based on dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT). Similar to solution-assembled monolayers, the molecular order for vacuum-deposited monolayers improved with increasing length of the aliphatic tail. At the same time, Fourier transform infrared (FTIR) measurements suggested lower molecular coverage for longer phosphonic acids. The comparison of FTIR and vibration frequencies calculated by density functional theory indicated that monodentate bonding does not occur for any phosphonic acid. All monolayers exhibited low surface energy of ∼17.5 mJ/m(2) with a dominating Lifshitz-van der Waals component. Their surface roughness was comparable, while the nanomechanical properties were varied but not correlated to the length of the molecule. However, large improvement in transistor performance was observed with increasing length of the aliphatic tail. Upon going from C8 to C18, the mean threshold voltage decreased from -1.37 to -1.24 V, the field-effect mobility increased from 0.03 to 0.33 cm(2)/(V·s), the off-current decreased from ∼8 × 10(-13) to ∼3 × 10(-13) A, and for transistors with L = 30 μm the on-current increased from ∼3 × 10(-8) to ∼2 × 10(-6) A, and the on/off-current ratio increased from ∼3 × 10(4) to ∼4 × 10(6). Similarly, transistors with longer phosphonic acids exhibited much better air and bias-stress stability. The achieved transistor performance opens up a completely "dry" fabrication route for ultrathin dielectrics and low-voltage organic transistors.

Low-temperature adsorption of H2S on Ni(001) studied by near-edge- and surface-extended-x-ray-absorption fine structure

NASA Astrophysics Data System (ADS)

McGrath, R.; MacDowell, A. A.; Hashizume, T.; Sette, F.; Citrin, P. H.

1989-11-01

The adsorption of H2S on Ni(001) has been studied with surface-extended x-ray-absorption fine structure and near-edge x-ray-absorption fine structure (NEXAFS) using the AT&T Bell Laboratories X15B beamline at the National Synchrotron Light Source. At 95 K and full saturation coverage, ~0.45 monolayer (ML) of S atoms in fourfold-hollow sites are produced, characteristic of room-temperature adsorption, accompanied by ~0.05 ML of oriented molecular H2S. Both these atomic and molecular chemisorbed species are buried under ~0.9 ML of disordered physisorbed H2S. No evidence for HS is found. Above 190 K the two molecular H2S phases desorb, leaving only dissociated S. These findings differ from previously reported interpretations of data obtained with high-resolution electron-energy-loss spectroscopy. They also exemplify the utility of NEXAFS for identifying and quantifying atomic and molecular surface species even when their difference involves only H and the two species coexist.

NH3 adsorption on anatase-TiO2(101)

NASA Astrophysics Data System (ADS)

Koust, Stig; Adamsen, Kræn C.; Kolsbjerg, Esben Leonhard; Li, Zheshen; Hammer, Bjørk; Wendt, Stefan; Lauritsen, Jeppe V.

2018-03-01

The adsorption of ammonia on anatase TiO2 is of fundamental importance for several catalytic applications of TiO2 and for probing acid-base interactions. Utilizing high-resolution scanning tunneling microscopy (STM), synchrotron X-ray photoelectron spectroscopy, temperature-programmed desorption (TPD), and density functional theory (DFT), we identify the adsorption mode and quantify the adsorption strength on the anatase TiO2(101) surface. It was found that ammonia adsorbs non-dissociatively as NH3 on regular five-fold coordinated titanium surface sites (5f-Ti) with an estimated exothermic adsorption energy of 1.2 eV for an isolated ammonia molecule. For higher adsorbate coverages, the adsorption energy progressively shifts to smaller values, due to repulsive intermolecular interactions. The repulsive adsorbate-adsorbate interactions are quantified using DFT and autocorrelation analysis of STM images, which both showed a repulsive energy of ˜50 meV for nearest neighbor sites and a lowering in binding energy for an ammonia molecule in a full monolayer of 0.28 eV, which is in agreement with TPD spectra.

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.

Chemical waves in the O2 + H2 reaction on a Rh(111) surface alloyed with nickel. I. Photoelectron emission microscopy

NASA Astrophysics Data System (ADS)

Smolinsky, Tim; von Boehn, Bernhard; Imbihl, Ronald

2018-04-01

Chemical waves that arise in the H2 + O2 reaction on a bimetallic Rh(111)/Ni surface have been studied in the 10-6 and 10-5 mbar range at T = 773 K with photoelectron emission microscopy (PEEM), low-energy electron diffraction (LEED), and Auger electron spectroscopy (AES). Nickel coverages of 0.3, 0.6, and 1.0 monolayers were investigated. Coadsorbed with some oxygen, Ni starts to penetrate the Rh bulk region substantially only beyond 900 K. In the 10-5 mbar range, chemical waves are characterized by three distinct gray levels in PEEM. This number reduces to only two levels in the 10-6 mbar range. In situ LEED showed the periodic appearance of a (n × 1) (n = 8, 10) pattern during chemical waves which was assigned to a 2D-Ni oxide. With in situ AES, one observes that the bright phase in PEEM correlates with a high Ni coverage and the dark phase with a low Ni coverage.

Investigation of multilayer domains in large-scale CVD monolayer graphene by optical imaging

NASA Astrophysics Data System (ADS)

Yu, Yuanfang; Li, Zhenzhen; Wang, Wenhui; Guo, Xitao; Jiang, Jie; Nan, Haiyan; Ni, Zhenhua

2017-03-01

CVD graphene is a promising candidate for optoelectronic applications due to its high quality and high yield. However, multi-layer domains could inevitably form at the nucleation centers during the growth. Here, we propose an optical imaging technique to precisely identify the multilayer domains and also the ratio of their coverage in large-scale CVD monolayer graphene. We have also shown that the stacking disorder in twisted bilayer graphene as well as the impurities on the graphene surface could be distinguished by optical imaging. Finally, we investigated the effects of bilayer domains on the optical and electrical properties of CVD graphene, and found that the carrier mobility of CVD graphene is seriously limited by scattering from bilayer domains. Our results could be useful for guiding future optoelectronic applications of large-scale CVD graphene. Project supported by the National Natural Science Foundation of China (Nos. 61422503, 61376104), the Open Research Funds of Key Laboratory of MEMS of Ministry of Education (SEU, China), and the Fundamental Research Funds for the Central Universities.

Characterization of nanostructured surfaces generated by reconstitution of the porin MspA from Mycobacterium smegmatis.

PubMed

Wörner, Michael; Lioubashevski, Oleg; Basel, Matthew T; Niebler, Sandra; Gogritchiani, Eliso; Egner, Nicole; Heinz, Christian; Hoferer, Jürgen; Cipolloni, Michela; Janik, Katharine; Katz, Evgeny; Braun, Andre M; Willner, Itamar; Niederweis, Michael; Bossmann, Stefan H

2007-06-01

Nanostructures with long-term stability at the surface of gold electrodes are generated by reconstituting the porin MspA from Mycobacterium smegmatis into a specially designed monolayer of long-chain lipid surfactant on gold. Tailored surface coverage of gold electrodes with long-chain surfactants is achieved by electrochemically assisted deposition of organic thiosulfates (Bunte salts). The subsequent reconstitution of the octameric-pore MspA is guided by its extraordinary self-assembling properties. Importantly, electrochemical reduction of copper(II) yields copper nanoparticles within the MspA nanopores. Electrochemical impedance spectroscopy, reflection electron microscopy, and atomic force microscopy (AFM) show that: 1) the MspA pores within the self-assembled monolayer (SAM) are monodisperse and electrochemically active, 2) MspA reconstitutes in SAMs and with a 10-nm thickness, 3) AFM is a suitable method to detect pores within SAMs, and 4) the electrochemical reduction of Cu2+ to Cu0 under overpotential conditions starts within the MspA pores.

The Kinetics of the as Grown and Annealed Self-Assembled Monolayer Studied by Force Spectroscopy

NASA Astrophysics Data System (ADS)

Habib, Huma; Yasar, M.; Mehmood, S.; Rafique, Saima; Bhatti, A. S.; Naeem, Aisha

The growth of biological systems like DNA, peptides and proteins are accredited to the self-assembly processes from the molecular level to the nanoscale. The flawless immobilization of DNA on any surface is quite an important step to the development of DNA-based biosensors. The present paper reports the use of atomic force microscopy to determine the mechanical properties of the as grown and annealed self-assembled monolayer (SAM) as well as the mutated DNA immobilized on the SAM. The SAM of alkane thiol (16-mercapto-1-hexadecanol) was developed on Au surface, which was then annealed and analyzed for its structural and mechanical properties. The surface coverage, height and monolayer’s order was studied as a function of incubation time and annealing time. Excessive annealing led to the defragmentation and desorption of SAM structures due to breaking of hydrocarbon bonds. AFM was employed to determine the detach separation, pull-off and work of adhesion of the as grown and annealed SAM.

Structure, dynamics and stability of water/scCO2/mineral interfaces from ab initio molecular dynamics simulations.

PubMed

Lee, Mal-Soon; Peter McGrail, B; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

2015-10-12

The boundary layer at solid-liquid interfaces is a unique reaction environment that poses significant scientific challenges to characterize and understand by experimentation alone. Using ab initio molecular dynamics (AIMD) methods, we report on the structure and dynamics of boundary layer formation, cation mobilization and carbonation under geologic carbon sequestration scenarios (T = 323 K and P = 90 bar) on a prototypical anorthite (001) surface. At low coverage, water film formation is enthalpically favored, but entropically hindered. Simulated adsorption isotherms show that a water monolayer will form even at the low water concentrations of water-saturated scCO2. Carbonation reactions readily occur at electron-rich terminal Oxygen sites adjacent to cation vacancies that readily form in the presence of a water monolayer. These results point to a carbonation mechanism that does not require prior carbonic acid formation in the bulk liquid. This work also highlights the modern capabilities of theoretical methods to address structure and reactivity at interfaces of high chemical complexity.

Hydrogenation-controlled phase transition on two-dimensional transition metal dichalcogenides and their unique physical and catalytic properties.

PubMed

Qu, Yuanju; Pan, Hui; Kwok, Chi Tat

2016-09-30

Two-dimensional (2D) transition metal dichalcogenides (TMDs) have been widely used from nanodevices to energy harvesting/storage because of their tunable physical and chemical properties. In this work, we systematically investigate the effects of hydrogenation on the structural, electronic, magnetic, and catalytic properties of 33 TMDs based on first-principles calculations. We find that the stable phases of TMD monolayers can transit from 1T to 2H phase or vice versa upon the hydrogenation. We show that the hydrogenation can switch their magnetic and electronic states accompanying with the phase transition. The hydrogenation can tune the magnetic states of TMDs among non-, ferro, para-, and antiferro-magnetism and their electronic states among semiconductor, metal, and half-metal. We further show that, out of 33 TMD monolayers, 2H-TiS 2 has impressive catalytic ability comparable to Pt in hydrogen evolution reaction in a wide range of hydrogen coverages. Our findings would shed the light on the multi-functional applications of TMDs.

Attachment chemistry of aromatic compounds on a Silicon(100) surface

NASA Astrophysics Data System (ADS)

Henriksson, Anders; Nishiori, Daiki; Maeda, Hiroaki; Miyachi, Mariko; Yamanoi, Yoshinori; Nishihara, Hiroshi

2018-03-01

A mild method was developed for the chemical attachment of aromatic compounds directly onto a hydrogen-terminated Si(100) (H-Si(100)) surface. In the presence of palladium catalyst and base, 4-iodophenylferrocene and a π-conjugated iron complex were attached to H-Si(100) electrodes and hydrogen-terminated silicon nanowires (H-SiNWs), both of which have predominant dihydride species on their surfaces. The reactions were conducted in 1,4-dioxane at 100 °C and the immobilization of both 4-ferrocenylphenyl group and π-conjugated molecular wires were confirmed and quantified by XPS and electrochemical measurements. We reported densely packed monolayer whose surface coverage (Γ), estimated from the electrochemical measurements are in analogue to similar monolayers prepared via thermal or light induced hydrosilylation reactions with alkenes or alkynes. The increase in electrochemical response observed on nanostructured silicon surfaces corresponds well to the increase in surface area, those strongly indicating that this method may be applied for the functionalization of electrodes with a variety of surface topographies.

Surface Electrostatic Potential and Water Orientation in the presence of Sodium Octanoate Dilute Monolayers Studied by Means of Molecular Dynamics Simulations.

PubMed

Bernardino, Kalil; de Moura, André F

2015-10-13

A series of atomistic molecular dynamics simulations were performed in the present investigation to assess the spontaneous formation of surfactant monolayers of sodium octanoate at the water-vacuum interface. The surfactant surface coverage increased until a saturation threshold was achieved, after which any further surfactant addition led to the formation of micellar aggregates within the solution. The saturated films were not densely packed, as might be expected for short-chained surfactants, and all films regardless of the surface coverage presented surfactant molecules with the same ordering pattern, namely, with the ionic heads toward the aqueous solution and the tails lying nearly parallel to the interface. The major contributions to the electrostatic surface potential came from the charged heads and the counterion distribution, which nearly canceled out each other. The balance between the oppositely charged ions rendered the electrostatic contributions from water meaningful, amounting to ca. 10% of the contributions arising from the ionic species. And even the aliphatic tails, whose atoms bear relatively small partial atomic charges as compared to the polar molecules and molecular fragments, contributed with ca. 20% of the total electrostatic surface potential of the systems under investigation. Although the aliphatic tails were not so orderly arranged as in a compact film, the C-H bonds assumed a preferential orientation, leading to an increased contribution to the electrostatic properties of the interface. The most prominent feature arising from the partitioning of the electrostatic potential into individual contributions was the long-range ordering of the water molecules. This ordering of the water molecules produced a repulsive dipole-dipole interaction between the two interfaces, which increased with the surface coverage. Only for a water layer wider than 10 nm was true bulk behavior observed, and the repulsive dipole-dipole interaction faded away.

Reactions of NO2 with BaO/Pt(111) Model Catalysts: The Effects of BaO Film Thickness and NO2 Pressure on the Formation of Ba(NOx)2 Species

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

Mudiyanselage, Kumudu; Yi, Cheol-Woo; Szanyi, Janos

2011-05-31

The adsorption and reaction of NO2 on BaO (<1, ~3, and >20 monolayer equivalent (MLE))/Pt(111) model systems were studied with temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and infrared reflection absorption spectroscopy (IRAS) under ultra-high vacuum (UHV) as well as elevated pressure conditions. NO2 reacts with sub-monolayer BaO (<1 MLE) to form nitrites only, whereas the reaction of NO2 with BaO (~3 MLE)/Pt(111) produces mainly nitrites and a small amount of nitrates under UHV conditions (PNO2 ~ 1.0 × 10-9 Torr) at 300 K. In contrast, a thick BaO(>20 MLE) layer on Pt(111) reacts with NO2 to form nitrite-nitratemore » ion pairs under the same conditions. At elevated NO2 pressures (≥ 1.0 × 10-5 Torr), however, BaO layers at all these three coverages convert to amorphous barium nitrates at 300 K. Upon annealing to 500 K, these amorphous barium nitrate layers transform into crystalline phases. The thermal decomposition of the thus-formed Ba(NOx)2 species is also influenced by the coverage of BaO on the Pt(111) substrate: at low BaO coverages, these species decompose at significantly lower temperatures in comparison with those formed on thick BaO films due to the presence of Ba(NOx)2/Pt interface where the decomposition can proceed at lower temperatures. However, the thermal decomposition of the thick Ba(NO3)2 films follows that of bulk nitrates. Results obtained from these BaO/Pt(111) model systems under UHV and elevated pressure conditions clearly demonstrate that both the BaO film thickness and the applied NO2 pressure are critical in the Ba(NOx)2 formation and subsequent thermal decomposition processes.« less

48 CFR 9903.304 - Concurrent full and modified coverage.

Code of Federal Regulations, 2010 CFR

2010-10-01

... modified coverage. 9903.304 Section 9903.304 Federal Acquisition Regulations System COST ACCOUNTING... AND COST ACCOUNTING STANDARDS CONTRACT COVERAGE CAS Rules and Regulations 9903.304 Concurrent full and... may compel the use of cost accounting practices that are not required under modified coverage. Under...

Approaching the intrinsic photoluminescence linewidth in transition metal dichalcogenide monolayers

DOE PAGES

Ajayi, Obafunso A.; Ardelean, Jenny V.; Shepard, Gabriella D.; ...

2017-07-24

Excitonic states in monolayer transition metal dichalcogenides (TMDCs) have been the subject of extensive recent interest. Their intrinsic properties can, however, be obscured due to the influence of inhomogeneity in the external environment. Here we report methods for fabricating high quality TMDC monolayers with narrow photoluminescence (PL) linewidth approaching the intrinsic limit. We find that encapsulation in hexagonal boron nitride (h-BN) sharply reduces the PL linewidth, and that passivation of the oxide substrate by an alkyl monolayer further decreases the linewidth and also minimizes the charged exciton (trion) peak. The combination of these sample preparation methods results in much reducedmore » spatial variation in the PL emission, with a full-width-at-half-maximum as low as 1.7 meV. Furthermore, analysis of the PL line shape yields a homogeneous width of 1.43 ± 0.08 meV and inhomogeneous broadening of 1.1 ± 0.3 meV.« less

Vacancy-Rich Monolayer BiO2-x as a Highly Efficient UV, Visible, and Near-Infrared Responsive Photocatalyst.

PubMed

Li, Jun; Wu, Xiaoyong; Pan, Wenfeng; Zhang, Gaoke; Chen, Hong

2018-01-08

Vacancy-rich layered materials with good electron-transfer property are of great interest. Herein, a full-spectrum responsive vacancy-rich monolayer BiO 2-x has been synthesized. The increased density of states at the conduction band (CB) minimum in the monolayer BiO 2-x is responsible for the enhanced photon response and photo-absorption, which were confirmed by UV/Vis-NIR diffuse reflectance spectra (DRS) and photocurrent measurements. Compared to bulk BiO 2-x , monolayer BiO 2-x has exhibited enhanced photocatalytic performance for rhodamine B and phenol removal under UV, visible, and near-infrared light (NIR) irradiation, which can be attributed to the vacancy V Bi-O ''' as confirmed by the positron annihilation spectra. The presence of V Bi-O ''' defects in monolayer BiO 2-x promoted the separation of electrons and holes. This finding provides an atomic level understanding for developing highly efficient UV, visible, and NIR light responsive photocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced Ge/Si(001) island areal density and self-organization due to P predeposition

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

Cho, B.; Bareno, J.; Petrov, I.

The predeposition of P, with coverages {theta}{sub P} ranging from 0 to 1 ML, on Si(001) significantly increases both the areal density and spatial self-organization of Ge islands grown by gas-source molecular beam epitaxy from hydride precursors. The Ge island density {rho}{sub Ge} initially increases with {theta}{sub P}, reaching a maximum of 1.4 x 10{sup 10} cm{sup -2} at {theta}{sub P} = 0.7 ML, a factor of four times higher than on bare Si(001) under the same deposition conditions, before decreasing at higher P coverages. The increase in {rho}{sub Ge}({theta}{sub P}) is due to a corresponding decrease in Ge adatommore » mean free paths resulting from passivation of surface dangling bonds by adsorbed pentavalent P atoms which, in addition, leads to surface roughening and, therefore, higher Ge coverages at constant Ge{sub 2}H{sub 6} dose. As {theta}{sub P} (and hence, {rho}{sub Ge}) increases, so does the degree of Ge island ordering along <100> directions due to the anisotropic strain field surrounding individual islands. Similar results are obtained for Ge island growth on P-doped Si(001) layers where strong P surface segregation provides partial monolayer coverage prior to Ge deposition.« less

Self-assembly of organic monolayers as protective and conductive bridges for nanometric surface-mount applications.

PubMed

Platzman, Ilia; Haick, Hossam; Tannenbaum, Rina

2010-09-01

In this work, we present a novel surface-mount placement process that could potentially overcome the inadequacies of the currently used stencil-printing technology, when applied to devices in which either their lateral and/or their horizontal dimensions approach the nanometric scale. Our novel process is based on the "bottom-up" design of an adhesive layer, operative in the molecular/nanoscale level, through the use of self-assembled monolayers (SAMs) that could form protective and conductive bridges between pads and components. On the basis of previous results, 1,4-phenylene diisocyanide (PDI) and terephthalic acid (TPA) were chosen to serve as the best candidates for the achievement of this goal. The quality and stability of these SAMs on annealed Cu surfaces (Rrms=0.15-1.1 nm) were examined in detail. Measurements showed that the SAMs of TPA and PDI molecules formed on top of Cu substrates created thermally stable organic monolayers with high surface coverage (∼90%), in which the molecules were closely packed and well-ordered. Moreover, the molecules assumed a standing-up phase conformation, in which the molecules bonded to the Cu substrate through one terminal functional group, with the other terminal group residing away from the substrate. To examine the ability of these monolayers to serve as "molecular wires," i.e., the capability to provide electrical conductivity, we developed a novel fabrication method of a parallel plate junction (PPJ) in order to create symmetric Cu-SAM-Cu electrical junctions. The current-bias measurements of these junctions indicated high tunneling efficiency. These achievements imply that the SAMs used in this study can serve as conductive molecular bridges that can potentially bind circuital pads/components.

Titration of submonolayer Au growth on Si(111)

NASA Astrophysics Data System (ADS)

Kautz, J.; Copel, M. W.; Gordon, M. S.; Tromp, R. M.; van der Molen, S. J.

2014-01-01

We study and analyze the growth of submonolayers of Au on Si(111) by a complementary set of surface techniques. Specifically, we focus on the 5×2 and the α√3 ×√3 structures. We determine the gold coverage of these structures as a function of temperature by means of low energy electron diffraction (LEED) and low energy electron microscopy (LEEM). These results are independently calibrated by ex-situ ion scattering experiments. This allows us to present a phase diagram for this system. Remarkably, for all temperatures considered (820-1040 K), we find a coverage for the 5×2 phase that is significantly (≈10%) higher than the value of 0.6 monolayers which is assumed in the latest structural models. Therefore, a further refinement of the present picture of the quasi-one-dimensional 5×2 structure is required.

Physisorption and desorption of H2, HD and D2 on amorphous solid water ice. Effect on mixing isotopologue on statistical population of adsorption sites.

PubMed

Amiaud, Lionel; Fillion, Jean-Hugues; Dulieu, François; Momeni, Anouchah; Lemaire, Jean-Louis

2015-11-28

We study the adsorption and desorption of three isotopologues of molecular hydrogen mixed on 10 ML of porous amorphous water ice (ASW) deposited at 10 K. Thermally programmed desorption (TPD) of H2, D2 and HD adsorbed at 10 K have been performed with different mixings. Various coverages of H2, HD and D2 have been explored and a model taking into account all species adsorbed on the surface is presented in detail. The model we propose allows to extract the parameters required to fully reproduce the desorption of H2, HD and D2 for various coverages and mixtures in the sub-monolayer regime. The model is based on a statistical description of the process in a grand-canonical ensemble where adsorbed molecules are described following a Fermi-Dirac distribution.

Self-organization of S adatoms on Au(111): √3R30° rows at low coverage

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

Walen, Holly, E-mail: hwalen@iastate.edu; Liu, Da-Jiang; Oh, Junepyo

Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed clean surface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, derivedmore » using a limited cluster expansion based on density functional theory energetics. Models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.« less

Self-organization of S adatoms on Au(111): √3R30° rows at low coverage

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

Walen, Holly; Liu, Da -Jiang; Oh, Junepyo

Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed cleansurface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, we derivedmore » using a limited cluster expansion based on density functional theory energetics. Furthermore, models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.« less

Self-organization of S adatoms on Au(111): √3R30° rows at low coverage

DOE PAGES

Walen, Holly; Liu, Da -Jiang; Oh, Junepyo; ...

2015-07-06

Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed cleansurface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, we derivedmore » using a limited cluster expansion based on density functional theory energetics. Furthermore, models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.« less

Self-organization of S adatoms on Au(111): √3R30° rows at low coverage.

PubMed

Walen, Holly; Liu, Da-Jiang; Oh, Junepyo; Lim, Hyunseob; Evans, J W; Kim, Yousoo; Thiel, P A

2015-07-07

Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed clean surface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, derived using a limited cluster expansion based on density functional theory energetics. Models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.

Droplet manipulation by an external electric field for crystalline film growth.

PubMed

Komino, Takeshi; Kuwabara, Hirokazu; Ikeda, Masaaki; Yahiro, Masayuki; Takimiya, Kazuo; Adachi, Chihaya

2013-07-30

Combining droplet manipulation by the application of an electric field with inkjet printing is proposed as a unique technique to control the surface wettability of substrates for solution-processed organic field-effect transistors (FETs). With the use of this technique, uniform thin films of 2,7-dioctyl[1]benzothieno[2,3,-b][1]benzothiopene (C8-BTBT) could be fabricated on the channels of FET substrates without self-assembled monolayer treatment. High-speed camera observation revealed that the crystals formed at the solid/liquid interface. The coverage of the crystals on the channels depended on the ac frequency of the external electric field applied during film formation, leading to a wide variation in the carrier transport of the films. The highest hole mobility of 0.03 cm(2) V(-1) s(-1) was obtained when the coverage was maximized with an ac frequency of 1 kHz.

Influence of preadsorbed oxygen on the sign and magnitude of the chemisorption-induced resistance change for H2 adsorption onto Fe films

NASA Technical Reports Server (NTRS)

Shanabarger, M. R.

1986-01-01

Measurements have been made of the chemisorption-induced resistance change for H2 adsorbed onto Fe film substrates predosed with fixed coverages of chemisorbed oxygen. The measurements were made at temperatures from 295 to 340 K and for estimated oxygen coverages of less than 0.1 monolayers. Two distinct resistance change components were observed in both the adsorption kinetics and the equilibrium isotherms: a positive component which is associated with the adsorption of H2 onto a clean Fe surface, and a negative component which was correlated with the presence of the chemisorbed oxygen. The resistance change isotherms can be fit with a model which assumes that each of the resistance change components result from dissociative chemisorbed hydrogen. Possible mechanisms for the chemisorbed-oxygen-induced negative resistance change are discussed.

The glass-liquid transition of water on hydrophobic surfaces

NASA Astrophysics Data System (ADS)

Souda, Ryutaro

2008-09-01

Interactions of thin water films with surfaces of graphite and vitrified room-temperature ionic liquid [1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6])] were investigated using time-of-flight secondary ion mass spectrometry as a function of temperature and annealing time to elucidate the glass-liquid transition of water at the molecular level. Surface diffusion of water occurs at temperatures higher than 120K, thereby forming three-dimensional clusters (a two-dimensional layer) on the [bmim][PF6] (graphite) surface. The hydrophobic effect of the surface decreases with increasing coverage of water; the bulklike properties evolve up to 40 ML, as evidenced by the occurrence of film dewetting at around the conventional glass transition temperature (140K). Results also showed that aging is necessary for the water monolayer (a 40 ML water film) to dewet the graphite ([bmim][PF6]) surface. The occurrence of aging is explainable by the successive evolution of two distinct liquids during the glass-liquid transition: low density liquid is followed by supercooled liquid water. The water monolayer on graphite is characterized by the preferred orientation of unpaired OH groups toward the surface; this structure is arrested during the aging time despite the occurrence of surface diffusion. However, the water monolayer formed on the [bmim][PF6] surface agglomerates immediately after the commencement of surface diffusion. The structure of low density liquid tends to be arrested by the attractive interaction with the neighbors.

Impedance spectroscopy for the detection and identification of unknown toxins

NASA Astrophysics Data System (ADS)

Riggs, B. C.; Plopper, G. E.; Paluh, J. L.; Phamduy, T. B.; Corr, D. T.; Chrisey, D. B.

2012-06-01

Advancements in biological and chemical warfare has allowed for the creation of novel toxins necessitating a universal, real-time sensor. We have used a function-based biosensor employing impedance spectroscopy using a low current density AC signal over a range of frequencies (62.5 Hz-64 kHz) to measure the electrical impedance of a confluent epithelial cell monolayer at 120 sec intervals. Madin Darby canine kidney (MDCK) epithelial cells were grown to confluence on thin film interdigitated gold electrodes. A stable impedance measurement of 2200 Ω was found after 24 hrs of growth. After exposure to cytotoxins anthrax lethal toxin and etoposide, the impedance decreased in a linear fashion resulting in a 50% drop in impedance over 50hrs showing significant difference from the control sample (~20% decrease). Immunofluorescent imaging showed that apoptosis was induced through the addition of toxins. Similarities of the impedance signal shows that the mechanism of cellular death was the same between ALT and etoposide. A revised equivalent circuit model was employed in order to quantify morphological changes in the cell monolayer such as tight junction integrity and cell surface area coverage. This model showed a faster response to cytotoxin (2 hrs) compared to raw measurements (20 hrs). We demonstrate that herein that impedance spectroscopy of epithelial monolayers serves as a real-time non-destructive sensor for unknown pathogens.

Node Scheduling Strategies for Achieving Full-View Area Coverage in Camera Sensor Networks.

PubMed

Wu, Peng-Fei; Xiao, Fu; Sha, Chao; Huang, Hai-Ping; Wang, Ru-Chuan; Xiong, Nai-Xue

2017-06-06

Unlike conventional scalar sensors, camera sensors at different positions can capture a variety of views of an object. Based on this intrinsic property, a novel model called full-view coverage was proposed. We study the problem that how to select the minimum number of sensors to guarantee the full-view coverage for the given region of interest (ROI). To tackle this issue, we derive the constraint condition of the sensor positions for full-view neighborhood coverage with the minimum number of nodes around the point. Next, we prove that the full-view area coverage can be approximately guaranteed, as long as the regular hexagons decided by the virtual grid are seamlessly stitched. Then we present two solutions for camera sensor networks in two different deployment strategies. By computing the theoretically optimal length of the virtual grids, we put forward the deployment pattern algorithm (DPA) in the deterministic implementation. To reduce the redundancy in random deployment, we come up with a local neighboring-optimal selection algorithm (LNSA) for achieving the full-view coverage. Finally, extensive simulation results show the feasibility of our proposed solutions.

Node Scheduling Strategies for Achieving Full-View Area Coverage in Camera Sensor Networks

PubMed Central

Wu, Peng-Fei; Xiao, Fu; Sha, Chao; Huang, Hai-Ping; Wang, Ru-Chuan; Xiong, Nai-Xue

2017-01-01

Unlike conventional scalar sensors, camera sensors at different positions can capture a variety of views of an object. Based on this intrinsic property, a novel model called full-view coverage was proposed. We study the problem that how to select the minimum number of sensors to guarantee the full-view coverage for the given region of interest (ROI). To tackle this issue, we derive the constraint condition of the sensor positions for full-view neighborhood coverage with the minimum number of nodes around the point. Next, we prove that the full-view area coverage can be approximately guaranteed, as long as the regular hexagons decided by the virtual grid are seamlessly stitched. Then we present two solutions for camera sensor networks in two different deployment strategies. By computing the theoretically optimal length of the virtual grids, we put forward the deployment pattern algorithm (DPA) in the deterministic implementation. To reduce the redundancy in random deployment, we come up with a local neighboring-optimal selection algorithm (LNSA) for achieving the full-view coverage. Finally, extensive simulation results show the feasibility of our proposed solutions. PMID:28587304

Dithiothreitol-Regulated Coverage of Oligonucleotide-Modified Gold Nanoparticles To Achieve Optimized Biosensor Performance.

PubMed

Liang, Pingping; Canoura, Juan; Yu, Haixiang; Alkhamis, Obtin; Xiao, Yi

2018-01-31

DNA-modified gold nanoparticles (AuNPs) are useful signal-reporters for detecting diverse molecules through various hybridization- and enzyme-based assays. However, their performance is heavily dependent on the probe DNA surface coverage, which can influence both target binding and enzymatic processing of the bound probes. Current methods used to adjust the surface coverage of DNA-modified AuNPs require the production of multiple batches of AuNPs under different conditions, which is costly and laborious. We here develop a single-step assay utilizing dithiothreitol (DTT) to fine-tune the surface coverage of DNA-modified AuNPs. DTT is superior to the commonly used surface diluent, mercaptohexanol, as it is less volatile, allowing for the rapid and reproducible controlling of surface coverage on AuNPs with only micromolar concentrations of DTT. Upon adsorption, DTT forms a dense monolayer on gold surfaces, which provides antifouling capabilities. Furthermore, surface-bound DTT adopts a cyclic conformation, which reorients DNA probes into an upright position and provides ample space to promote DNA hybridization, aptamer assembly, and nuclease digestion. We demonstrate the effects of surface coverage on AuNP-based sensors using DTT-regulated DNA-modified AuNPs. We then use these AuNPs to visually detect DNA and cocaine in colorimetric assays based on enzyme-mediated AuNP aggregation. We determine that DTT-regulated AuNPs with lower surface coverage achieve shorter reaction times and lower detection limits relative to those for assays using untreated AuNPs or DTT-regulated AuNPs with high surface coverage. Additionally, we demonstrate that our DTT-regulated AuNPs can perform cocaine detection in 50% urine without any significant matrix effects. We believe that DTT regulation of surface coverage can be broadly employed for optimizing DNA-modified AuNP performance for use in biosensors as well as drug delivery and therapeutic applications.

Metal/silicon Interfaces and Their Oxidation Behavior - Photoemission Spectroscopy Analysis.

NASA Astrophysics Data System (ADS)

Yeh, Jyh-Jye

Synchrotron radiation photoemission spectroscopy was used to study Ni/Si and Au/Si interface properties on the atomic scale at room temperature, after high temperature annealing and after oxygen exposures. Room temperature studies of metal/Si interfaces provide background for an understanding of the interface structure after elevated temperature annealing. Oxidation studies of Si surfaces covered with metal overlayers yield insight about the effect of metal atoms in the Si oxidation mechanisms and are useful in the identification of subtle differences in bonding relations between atoms at the metal/Si interfaces. Core level and valence band spectra with variable surface sensitivities were used to study the interactions between metal, Si, and oxygen for metal coverages and oxide thickness in the monolayer region. Interface morphology at the initial stage of metal/Si interface formation and after oxidation was modeled on the basis of the evolutions of metal and Si signals at different probing depths in the photoemission experiment. Both Ni/Si and Au/Si interfaces formed at room temperature have a diffusive region at the interface. This is composed of a layer of metal-Si alloy, formed by Si outdiffusion into the metal overlayer, above a layer of interstitial metal atoms in the Si substrate. Different atomic structures of these two regions at Ni/Si interface can account for the two different growth orientations of epitaxial Ni disilicides on the Si(111) surface after thermal annealing. Annealing the Au/Si interface at high temperature depletes all the Au atoms except for one monolayer of Au on the Si(111) surface. These phenomena are attributed to differences in the metal-Si chemical bonding relations associated with specific atomic structures. After oxygen exposures, both the Ni disilicide surface and Au covered Si surfaces (with different coverages and surface orderings) show silicon in higher oxidation states, in comparison to oxidized silicon on a clean surface. Preferential Si dioxide growth on the Au/Si surface is related to the strong distortion of the Si lattice when Au-Si bonds are formed. In comparison, a monolayer of Ni on a Si surface, with its weaker Ni-Si bond, does not enhance oxide formation.

The impact of the 2007-2009 recession on workers' health coverage.

PubMed

Fronstin, Paul

2011-04-01

IMPACT OF THE RECESSION: The 2007-2009 recession has taken its toll on the percentage of the population with employment-based health coverage. While, since 2000, there has been a slow erosion in the percentage of individuals under age 65 with employment-based health coverage, 2009 was the first year in which the percentage fell below 60 percent, and marked the largest one-year decline in coverage. FEWER WORKERS WITH COVERAGE: The percentage of workers with coverage through their own job fell from 53.2 percent in 2008 to 52 percent in 2009, a 2.4 percent decline in the likelihood that a worker has coverage through his or her own job. The percentage of workers with coverage as a dependent fell from 17 percent in 2008 to 16.3 percent in 2009, a 4.5 percent drop in the likelihood that a worker has coverage as a dependent. These declines occurred as the unemployment rate increased from an average of 5.8 percent in 2008 to 9.3 percent in 2009 (and reached a high of 10.1 percent during 2009). FIRM SIZE/INDUSTRY: The decline in the percentage of workers with coverage from their own job affected workers in private-sector firms of all sizes. Among public-sector workers, the decline from 73.4 percent to 73 percent was not statistically significant. Workers in all private-sector industries experienced a statistically significant decline in coverage between 2008 and 2009. HOURS WORKED: Full-time workers experienced a decline in coverage that was statistically significant while part-time workers did not. Among full-time workers, those employed full year experienced a statistically significant decline in coverage from their own job. Those employed full time but for only part of the year did not experience a statistically significant change in coverage. Among part-time workers, those employed full year experienced a statistically significant increase in the likelihood of having coverage in their own name, as did part-time workers employed for only part of the year. ANNUAL EARNINGS: The decline in the percentage of workers with coverage through their own job was limited to workers with lower annual earnings. Statistically significant declines were not found among any group of workers with annual earnings of at least $40,000. Workers with a high school education or less experienced a statistically significant decline in the likelihood of having coverage. Neither workers with a college degree nor those with a graduate degree experienced a statistically significant decline in coverage through their own job. Workers of all races experienced statistically significant declines in coverage between 2008 and 2009. Both men and women experienced a statistically significant decline in the percentage with health coverage through their own job. IMPACT OF STRUCTURAL CHANGES TO THE WORK FORCE: The movement of workers from the manufacturing industry to the service sector continued between 2008 and 2009. The percentage of workers employed on a full-time basis decreased while the percentage working part time increased. While there was an overall decline in the percentage of full-time workers, that decline was limited to workers employed full year. The percentage of workers employed on a full-time, part-year basis increased between 2008 and 2009. The distribution of workers by annual earnings shifted from middle-income workers to lower-income workers between 2008 and 2009.

Inequalities in full immunization coverage: trends in low- and middle-income countries

PubMed Central

Barros, Aluísio JD; Wong, Kerry LM; Johnson, Hope L; Pariyo, George; França, Giovanny VA; Wehrmeister, Fernando C; Victora, Cesar G

2016-01-01

Abstract Objective To investigate disparities in full immunization coverage across and within 86 low- and middle-income countries. Methods In May 2015, using data from the most recent Demographic and Health Surveys and Multiple Indicator Cluster Surveys, we investigated inequalities in full immunization coverage – i.e. one dose of bacille Calmette-Guérin vaccine, one dose of measles vaccine, three doses of vaccine against diphtheria, pertussis and tetanus and three doses of polio vaccine – in 86 low- or middle-income countries. We then investigated temporal trends in the level and inequality of such coverage in eight of the countries. Findings In each of the World Health Organization’s regions, it appeared that about 56–69% of eligible children in the low- and middle-income countries had received full immunization. However, within each region, the mean recorded level of such coverage varied greatly. In the African Region, for example, it varied from 11.4% in Chad to 90.3% in Rwanda. We detected pro-rich inequality in such coverage in 45 of the 83 countries for which the relevant data were available and pro-urban inequality in 35 of the 86 study countries. Among the countries in which we investigated coverage trends, Madagascar and Mozambique appeared to have made the greatest progress in improving levels of full immunization coverage over the last two decades, particularly among the poorest quintiles of their populations. Conclusion Most low- and middle-income countries are affected by pro-rich and pro-urban inequalities in full immunization coverage that are not apparent when only national mean values of such coverage are reported. PMID:27821882

Reactive molecular dynamics simulations of switching processes of azobenzene-based monolayer on surface

NASA Astrophysics Data System (ADS)

Tian, Ziqi; Wen, Jin; Ma, Jing

2013-07-01

It is a challenge to simulate the switching process of functional self-assembled monolayers (SAMs) on metal surfaces, since the systems consist of thousands of atoms and the switching is triggered by quantum-mechanical events. Herein a molecular dynamics simulation with a reactive rotation potential of N=N bond is implemented to investigate the dynamic conformational changes and packing effects on the stimuli-responsive isomerization of the terminally thiol functionalized azobiphenyls (AZOs), which are bound on the Au(111) surface. To, respectively, distinguish the time evolutions that start from cis and trans initial configurations, two different functions are established to model the potential energy curves for cis-to-trans and trans-to-cis transitions, instead of the only one cosine function used in the conventional non-reactive force fields. In order to simulate the conformation transitions of the AZO film on surface, a random switching function, depending on the N=N twisting angle, is constructed to consider both forward and backward cis/trans isomerization events and to trigger the reaction by changing the N atom types automatically. The factors that will influence the isomerization process, including the choice of ensembles and thermostat algorithms, the time intervals separating each switching, and the forms of the switching function, are systematically tested. Most AZO molecules switch from the cis to trans configuration with a coverage of 5.76 × 10-6 mol/m2 on a picosecond time scale, and a low coverage might make the switching irreversible, which is in agreement with the experiments.

Nanopatterning of Group V Elements for Tailoring the Electronic Properties of Semiconductors by Monolayer Doping.

PubMed

Thissen, Peter; Cho, Kyeongjae; Longo, Roberto C

2017-01-18

Control of the electronic properties of semiconductors is primarily achieved through doping. While scaling down the device dimensions to the molecular regime presents an increasing number of difficulties, doping control at the nanoscale is still regarded as one of the major challenges of the electronic industry. Within this context, new techniques such as monolayer doping (MLD) represent a substantial improvement toward surface doping with atomic and specific doping dose control at the nanoscale. Our previous work has explained in detail the atomistic mechanism behind MLD by means of density-functional theory calculations (Chem. Mater. 2016, 28, 1975). Here, we address the key questions that will ultimately allow one to optimize the scalability of the MLD process. First, we show that dopant coverage control cannot be achieved by simultaneous reaction of several group V elements, but stepwise reactions make it possible. Second, using ab initio molecular dynamics, we investigate the thermal decomposition of the molecular precursors, together with the stability of the corresponding binary and ternary dopant oxides, prior to the dopant diffusion into the semiconductor surface. Finally, the effect of the coverage and type of dopant on the electronic properties of the semiconductor is also analyzed. Furthermore, the atomistic characterization of the MLD process raises unexpected questions regarding possible crystal damage effects by dopant exchange with the semiconductor ions or the final distribution of the doping impurities within the crystal structure. By combining all our results, optimization recipes to create ultrashallow doped junctions at the nanoscale are finally proposed.

Optimizing pentacene thin-film transistor performance: Temperature and surface condition induced layer growth modification.

PubMed

Lassnig, R; Hollerer, M; Striedinger, B; Fian, A; Stadlober, B; Winkler, A

2015-11-01

In this work we present in situ electrical and surface analytical, as well as ex situ atomic force microscopy (AFM) studies on temperature and surface condition induced pentacene layer growth modifications, leading to the selection of optimized deposition conditions and entailing performance improvements. We prepared p ++ -silicon/silicon dioxide bottom-gate, gold bottom-contact transistor samples and evaluated the pentacene layer growth for three different surface conditions (sputtered, sputtered + carbon and unsputtered + carbon) at sample temperatures during deposition of 200 K, 300 K and 350 K. The AFM investigations focused on the gold contacts, the silicon dioxide channel region and the highly critical transition area. Evaluations of coverage dependent saturation mobilities, threshold voltages and corresponding AFM analysis were able to confirm that the first 3-4 full monolayers contribute to the majority of charge transport within the channel region. At high temperatures and on sputtered surfaces uniform layer formation in the contact-channel transition area is limited by dewetting, leading to the formation of trenches and the partial development of double layer islands within the channel region instead of full wetting layers. By combining the advantages of an initial high temperature deposition (well-ordered islands in the channel) and a subsequent low temperature deposition (continuous film formation for low contact resistance) we were able to prepare very thin (8 ML) pentacene transistors of comparably high mobility.

Optimizing pentacene thin-film transistor performance: Temperature and surface condition induced layer growth modification

PubMed Central

Lassnig, R.; Hollerer, M.; Striedinger, B.; Fian, A.; Stadlober, B.; Winkler, A.

2015-01-01

In this work we present in situ electrical and surface analytical, as well as ex situ atomic force microscopy (AFM) studies on temperature and surface condition induced pentacene layer growth modifications, leading to the selection of optimized deposition conditions and entailing performance improvements. We prepared p++-silicon/silicon dioxide bottom-gate, gold bottom-contact transistor samples and evaluated the pentacene layer growth for three different surface conditions (sputtered, sputtered + carbon and unsputtered + carbon) at sample temperatures during deposition of 200 K, 300 K and 350 K. The AFM investigations focused on the gold contacts, the silicon dioxide channel region and the highly critical transition area. Evaluations of coverage dependent saturation mobilities, threshold voltages and corresponding AFM analysis were able to confirm that the first 3–4 full monolayers contribute to the majority of charge transport within the channel region. At high temperatures and on sputtered surfaces uniform layer formation in the contact–channel transition area is limited by dewetting, leading to the formation of trenches and the partial development of double layer islands within the channel region instead of full wetting layers. By combining the advantages of an initial high temperature deposition (well-ordered islands in the channel) and a subsequent low temperature deposition (continuous film formation for low contact resistance) we were able to prepare very thin (8 ML) pentacene transistors of comparably high mobility. PMID:26543442

Conditioned medium of adipose-derived stromal cell culture in three-dimensional bioreactors for enhanced wound healing.

PubMed

Kwon, Sun Hyun; Bhang, Suk Ho; Jang, Hyeon-Ki; Rhim, Taiyoun; Kim, Byung-Soo

2015-03-01

It was previously shown that human adipose-derived stromal cell (hADSC)-conditioned medium (CM) promotes wound healing. An essential part of the wound healing process is neovascularization in the wound bed. We hypothesized that CM prepared from hADSCs cultured as spheroids in three-dimensional suspension bioreactors (spheroid CM) would contain much higher concentrations of angiogenic growth factors secreted by hADSCs, induce a higher extent of neovascularization in the wound bed, and improve wound healing as compared with CM prepared by conventional monolayer culture (monolayer CM). The concentrations of angiogenic growth factors (i.e., vascular endothelial growth factor, basic fibroblast growth factor, and hepatocyte growth factor) in spheroid CM were 20- to 145-fold higher than those in monolayer CM. Either fresh medium, monolayer CM, or spheroid CM was administered to full-thickness wounds created on the dorsal aspects of athymic mice. The monolayer CM promoted wound healing as compared with fresh medium or no treatment. Importantly, wound closure was faster, and dermal and epidermal regeneration was improved in the spheroid CM-treated mice compared with that in the monolayer CM-treated mice. The improved wound healing by spheroid CM may be attributed, at least in part, to enhanced neovascularization in the wound beds. The spheroid-based CM approach showed potential as a therapy for skin wound repair. Copyright © 2015 Elsevier Inc. All rights reserved.

Condensation of monovalent and divalent metal ions on a Langmuir monolayer

NASA Astrophysics Data System (ADS)

Bloch, J. Mati; Yun, Wenbing

1990-01-01

A system that consists of a monolayer spread on a solution containing a monovalent and a divalent ion is investigated. The solution of the Poisson-Boltzmann-Stern equation for this system indicates that the metal ions segregating to the surface can be found in two distinct states. Divalent ions are chemically condensed on the monolayer, while monovalent ions are electrically attracted to it. We derive simple expressions for the charge left on the surfactant monolayer and the amount of metal ions condensed on the monolayer. These formulas reproduce very accurately (to within pro milles) the values obtained using the nonlinear Grahame equation and eliminate the need to solve that equation. That permits a simple identification of the state of the surfactant monolayer and we propose a universal condensation chart that characterizes the state of the surfactant. We further derive a chemical equilibrium equation for the surface components that has considerable range of validity. This equation requires a knowledge of the bulk concentrations only, and thus allows in many cases the identification of the state of the monolayer, avoiding the need to solve the full nonlinear Poisson-Boltzmann equation. All existing experimental results on Langmuir systems are in good agreement with the one-dimensional Poisson-Boltzmann-Stern model with no adjustable parameters. Several of these fits are presented in this work and are also mapped on the condensation chart. Our calculations point to some characteristic differences between the monovalent and the divalent ions that explain why it is possible to build Langmuir-Blodgett multilayers from divalent compensated surfactants but not from monovalent ones.

A Hybrid Memetic Framework for Coverage Optimization in Wireless Sensor Networks.

PubMed

Chen, Chia-Pang; Mukhopadhyay, Subhas Chandra; Chuang, Cheng-Long; Lin, Tzu-Shiang; Liao, Min-Sheng; Wang, Yung-Chung; Jiang, Joe-Air

2015-10-01

One of the critical concerns in wireless sensor networks (WSNs) is the continuous maintenance of sensing coverage. Many particular applications, such as battlefield intrusion detection and object tracking, require a full-coverage at any time, which is typically resolved by adding redundant sensor nodes. With abundant energy, previous studies suggested that the network lifetime can be maximized while maintaining full coverage through organizing sensor nodes into a maximum number of disjoint sets and alternately turning them on. Since the power of sensor nodes is unevenly consumed over time, and early failure of sensor nodes leads to coverage loss, WSNs require dynamic coverage maintenance. Thus, the task of permanently sustaining full coverage is particularly formulated as a hybrid of disjoint set covers and dynamic-coverage-maintenance problems, and both have been proven to be nondeterministic polynomial-complete. In this paper, a hybrid memetic framework for coverage optimization (Hy-MFCO) is presented to cope with the hybrid problem using two major components: 1) a memetic algorithm (MA)-based scheduling strategy and 2) a heuristic recursive algorithm (HRA). First, the MA-based scheduling strategy adopts a dynamic chromosome structure to create disjoint sets, and then the HRA is utilized to compensate the loss of coverage by awaking some of the hibernated nodes in local regions when a disjoint set fails to maintain full coverage. The results obtained from real-world experiments using a WSN test-bed and computer simulations indicate that the proposed Hy-MFCO is able to maximize sensing coverage while achieving energy efficiency at the same time. Moreover, the results also show that the Hy-MFCO significantly outperforms the existing methods with respect to coverage preservation and energy efficiency.

Surface segregation in HAYNES 230 alloy

NASA Astrophysics Data System (ADS)

Pop, D.; Wolski, K.

2006-12-01

The surface segregation in the Ni-based alloy HAYNES 230 was studied by Auger Electron Spectroscopy and X-ray Photoelectron Spectroscopy between 400 and 1100 °C. The qualitative variations of the surface contents of S, P, W, Mo, N, Si, and Mn were determined as a function of annealing temperature and time. It was found that at 925 °C the maximum coverage of sulphur at the alloy surface is in the range 0.06-0.15 monolayers. Chromium evaporation from the HAYNES 230 surface under UHV conditions is clearly evidenced for annealing at 1100 °C.

Temperature dependence of photon-enhanced thermionic emission from GaAs surface with nonequilibrium Cs overlayers

NASA Astrophysics Data System (ADS)

Zhuravlev, A. G.; Alperovich, V. L.

2017-02-01

The temperature influence on the Cs/GaAs surface electronic properties, which determine the photon-enhanced thermionic emission (PETE), is studied. It was found that heating to moderate temperatures of about 100 °С leads to substantial changes in the magnitude and shape of Cs coverage dependences of photoemission current and surface band bending, along with the changes of relaxation kinetics after Cs deposition. A spectral proof of the PETE process is obtained under thermal cycling of the Cs/GaAs surface with 0.45 monolayer (ML) of Cs.

GIXAFS study of Fe3+ sorption and precipitation on natural quartz surfaces

USGS Publications Warehouse

Waychunas, G.; Davis, J.; Reitmeyer, R.

1999-01-01

Grazing-incidence EXAFS has been used to characterize the structure of Fe3+ sorbed onto natural single crystal quartz surfaces. Fe3+ sorption at ca. 5% monolayer coverage on a natural crystal allowed to equilibrate in air resulted in formation of hematite nuclei with strong texturing on r-and m-planes. EXAFS calculations suggests that both O and Fe backscattering is necessary to yield acceptable structural models, that about 50% of the sorbed iron resides in nuclei, and that the approximate dimensions of the nuclei can be estimated via Feff 7.0 calculations of various nuclei sizes and shapes.

Theoretical studies of positron states and annihilation characteristics at the oxidized Cu(100) surface

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Weiss, A. H.

2013-04-01

In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. An ab-initio study of the electronic properties of the Cu(100) missing row reconstructed surface at various on surface and sub-surface oxygen coverages has been performed on the basis of the density functional theory (DFT) using the Dmol3 code and the generalized gradient approximation (GGA). Surface structures in calculations have been constructed by adding oxygen atoms to various surface hollow and sub-surface octahedral sites of the 0.5 monolayer (ML) missing row reconstructed phase of the Cu(100) surface with oxygen coverages ranging from 0.5 to 1.5 ML. The charge redistribution at the surface and variations in atomic structure and chemical composition of the topmost layers associated with oxidation and surface reconstruction have been found to affect the spatial extent and localization of the positron surface state wave function and annihilation probabilities of surface trapped positrons with relevant core electrons. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). It has been shown that positron annihilation probabilities with Cu 3s and 3p core electrons decrease when total (on-surface and sub-surface) oxygen coverage of the Cu(100) surface increases up to 1 ML. The calculations show that for high oxygen coverage when total oxygen coverage is 1. 5 ML the positron is not bound to the surface.

Theoretical studies of positron states and annihilation characteristics at the oxidized Cu(100) surface

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

Fazleev, N. G.; Weiss, A. H.

2013-04-19

In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. An ab-initio study of the electronic properties of the Cu(100) missing row reconstructed surface at various on surface and sub-surface oxygen coverages has been performed on the basis of the density functional theory (DFT) using the Dmol3 code and the generalized gradient approximation (GGA). Surface structures in calculations have been constructed by adding oxygen atoms to various surface hollow and sub-surface octahedral sitesmore » of the 0.5 monolayer (ML) missing row reconstructed phase of the Cu(100) surface with oxygen coverages ranging from 0.5 to 1.5 ML. The charge redistribution at the surface and variations in atomic structure and chemical composition of the topmost layers associated with oxidation and surface reconstruction have been found to affect the spatial extent and localization of the positron surface state wave function and annihilation probabilities of surface trapped positrons with relevant core electrons. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). It has been shown that positron annihilation probabilities with Cu 3s and 3p core electrons decrease when total (on-surface and sub-surface) oxygen coverage of the Cu(100) surface increases up to 1 ML. The calculations show that for high oxygen coverage when total oxygen coverage is 1. 5 ML the positron is not bound to the surface.« less

Isotherm and thermodynamic studies of Zn (II) adsorption on lignite and coconut shell-based activated carbon fiber.

PubMed

Shrestha, Sohan; Son, Guntae; Lee, Seung Hwan; Lee, Tae Gwan

2013-08-01

The Zn (II) adsorption capacity of lignite and coconut shell-based activated carbon fiber (ACF) was evaluated as a function of initial Zn (II) concentration, temperature and contact time in batch adsorption process in this study. Adsorption uptake increased with initial Zn (II) concentration and temperature. Optimal contact time for the adsorption of Zn (II) ions onto lignite and coconut shell-based ACF was found to be 50 min. Removal percentage decreased from 88.0% to 78.54% with the increment in initial Zn (II) concentration from 5 to 50 mg L(-1). Equilibrium data fit well with Langmuir-I isotherm indicating homogeneous monolayer coverage of Zn (II) ions on the adsorbent surface. Maximum monolayer adsorption capacity of Zn (II) ions on ACF was found to be 9.43 mg g(-1). Surface morphology and functionality of ACF prior to and after adsorption were characterized by electron microscopy and infrared spectroscopy. Various thermodynamic parameters such as standard Gibbs free energy (ΔG°), standard enthalpy (ΔH°), and standard entropy (ΔS°) were evaluated. Copyright © 2013 Elsevier Ltd. All rights reserved.

Sharp organic interface of molecular C60 chains and a pentacene derivative SAM on Au(788): A combined STM & DFT study

NASA Astrophysics Data System (ADS)

Wang, Jun; Tang, Jian-Ming; Larson, Amanda M.; Miller, Glen P.; Pohl, Karsten

2013-12-01

Controlling the molecular structure of the donor-acceptor interface is essential to overcoming the efficiency bottleneck in organic photovoltaics. We present a study of self-assembled fullerene (C60) molecular chains on perfectly ordered 6,13-dichloropentacene (DCP) monolayers forming on a vicinal Au(788) surface using scanning tunneling microscopy in conjunction with density functional theory calculations. DCP is a novel pentacene derivative optimized for photovoltaic applications. The molecules form a brick-wall patterned centered rectangular lattice with the long axis parallel to the monatomic steps that separate the 3.9 nm wide Au(111) terraces. The strong interaction between the C60 molecules and the gold substrate is well screened by the DCP monolayer. At submonolayer C60 coverage, the fullerene molecules form long parallel chains, 1.1 nm apart, with a rectangular arrangement instead of the expected close-packed configuration along the upper step edges. The perfectly ordered DCP structure is unaffected by the C60 chain formation. The controlled sharp highly-ordered organic interface has the potential to improve the conversion efficiency in organic photovoltaics.

Molecular layers of ZnPc and FePc on Au(111) surface: Charge transfer and chemical interaction

NASA Astrophysics Data System (ADS)

Ahmadi, Sareh; Shariati, M. Nina; Yu, Shun; Göthelid, Mats

2012-08-01

We have studied zinc phthalocyanine (ZnPc) and iron phthalocyanine (FePc) thick films and monolayers on Au(111) using photoelectron spectroscopy and x-ray absorption spectroscopy. Both molecules are adsorbed flat on the surface at monolayer. ZnPc keeps this orientation in all investigated coverages, whereas FePc molecules stand up in the thick film. The stronger inter-molecular interaction of FePc molecules leads to change of orientation, as well as higher conductivity in FePc layer in comparison with ZnPc, which is reflected in thickness-dependent differences in core-level shifts. Work function changes indicate that both molecules donate charge to Au; through the π-system. However, the Fe3d derived lowest unoccupied molecular orbital receives charge from the substrate when forming an interface state at the Fermi level. Thus, the central atom plays an important role in mediating the charge, but the charge transfer as a whole is a balance between the two different charge transfer channels; π-system and the central atom.

Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on Forsterite, Mg2SiO4(011)

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

Smith, R. Scott; Li, Zhenjun; Dohnalek, Zdenek

We have examined the adsorbate-substrate interaction kinetics of CO2 and H2O on a natural forsterite crystal surface, Mg2SiO4(011), with 10-15% of substitutional Fe2+. We use temperature programmed desorption (TPD) and molecular beam techniques to determine the adsorption, desorption, and displacement kinetics for H2O and CO2. Neither CO2 nor H2O has distinct sub-monolayer desorption peaks but instead both have a broad continuous desorption feature that evolve smoothly into multilayer desorption. Inversion of the monolayer coverage spectra for both molecules reveals that the corresponding binding energies for H2O are greater than that for CO2 on all sites. The relative strength of thesemore » interactions is the dominant factor in the competitive adsorption/displacement kinetics. In experiments where the two adsorbates are co-dosed, H2O always binds to the highest energy binding sites available and displaces CO2. The onset of CO2 displacement by H2O occurs between 65 and 75 K.« less

Self-assembly and nanosphere lithography for large-area plasmonic patterns on graphene.

PubMed

Lotito, Valeria; Zambelli, Tomaso

2015-06-01

Plasmonic structures on graphene can tailor its optical properties, which is essential for sensing and optoelectronic applications, e.g. for the enhancement of photoresponsivity of graphene photodetectors. Control over their structural and, hence, spectral properties can be attained by using electron beam lithography, which is not a viable solution for the definition of patterns over large areas. For the fabrication of large-area plasmonic nanostructures, we propose to use self-assembled monolayers of nanospheres as a mask for metal evaporation and etching processes. An optimized approach based on self-assembly at air/water interface with a properly designed apparatus allows the attainment of monolayers of hexagonally closely packed patterns with high long-range order and large area coverage; special strategies are devised in order to protect graphene against damage resulting from surface treatment and further processing steps such as reactive ion etching, which could potentially impair graphene properties. Therefore we demonstrate that nanosphere lithography is a cost-effective solution to create plasmonic patterns on graphene. Copyright © 2014 Elsevier Inc. All rights reserved.

Full prescription coverage versus usual prescription coverage after coronary artery bypass graft surgery: analysis from the post-myocardial infarction free Rx event and economic evaluation (FREEE) randomized trial.

PubMed

Kulik, Alexander; Desai, Nihar R; Shrank, William H; Antman, Elliott M; Glynn, Robert J; Levin, Raisa; Reisman, Lonny; Brennan, Troyen; Choudhry, Niteesh K

2013-09-10

Eliminating out-of-pocket costs for patients after myocardial infarction (MI) improves adherence to preventive therapies and reduces clinical events. Because adherence to medical therapy is low among patients treated with coronary artery bypass graft surgery (CABG), we evaluated the impact of providing full prescription coverage to this patient subgroup. The MI Free Rx Event and Economic Evaluation (FREEE) trial randomly assigned 5855 patients with MI to full prescription coverage or usual formulary coverage for all statins, β-blockers, angiotensin-converting enzyme inhibitors, or angiotensin receptor blockers. We assessed the impact of full prescription coverage on adherence, clinical outcomes, and healthcare costs using adjusted models among the 1052 patients who underwent CABG at the index hospitalization and 4803 who did not. CABG patients were older and had more comorbid illness (P<0.01). After MI, CABG patients were significantly more likely to receive β-blockers and statins but were less likely to receive angiotensin-converting enzyme inhibitor/angiotensin receptor blocker therapy (P<0.01). Receiving full drug coverage increased rates of adherence to all preventative medications after CABG (all P<0.05). Full coverage was also associated with nonsignificant reductions in the rate of major vascular events or revascularization for patients treated with CABG (hazard ratio, 0.91; 95% confidence interval, 0.66-1.25) or without CABG (hazard ratio, 0.93; 95% confidence interval, 0.82-1.06), with no interaction noted (Pint=NS). After CABG, full prescription coverage significantly reduced patient out-of-pocket spending for drugs (P=0.001) without increasing overall health expenditures (P=NS). Eliminating drug copayments after MI provides consistent benefits to patients treated with or without CABG, leading to increased medication adherence, trends toward improved clinical outcomes, and reduced patient out-of-pocket expenses.

Cost-Effectiveness of Providing Full Drug Coverage to Increase Medication Adherence in Post–Myocardial Infarction Medicare Beneficiaries

PubMed Central

Choudhry, Niteesh K.; Patrick, Amanda R.; Antman, Elliott M.; Avorn, Jerry; Shrank, William H.

2009-01-01

Background Effective therapies for the secondary prevention of coronary heart disease–related events are significantly underused, and attempts to improve adherence have often yielded disappointing results. Elimination of patient out-of-pocket costs may be an effective strategy to enhance medication use. We sought to estimate the incremental cost-effectiveness of providing full coverage for aspirin, β-blockers, angiotensin-converting enzyme inhibitors or angiotensin receptor blockers, and statins (combination pharmacotherapy) to individuals enrolled in the Medicare drug benefit program after acute myocardial infarction. Methods and Results We created a Markov cost-effectiveness model to estimate the incremental cost-effectiveness of providing Medicare beneficiaries with full coverage for combination pharmacotherapy compared with current coverage under the Medicare Part D program. Our analysis was conducted from the societal perspective and considered a lifetime time horizon. In a sensitivity analysis, we repeated our analysis from the perspective of Medicare. In the model, post–myocardial infarction Medicare beneficiaries who received usual prescription drug coverage under the Part D program lived an average of 8.21 quality-adjusted life-years after their initial event, incurring coronary heart disease–related medical costs of $114 000. Those who received prescription drug coverage without deductibles or copayments lived an average of 8.56 quality-adjusted life-years and incurred $111 600 in coronary heart disease–related costs. Compared with current prescription drug coverage, full coverage for post–myocardial infarction secondary prevention therapies would result in greater functional life expectancy (0.35 quality-adjusted life-year) and less resource use ($2500). From the perspective of Medicare, full drug coverage was highly cost-effective ($7182/quality-adjusted life-year) but not cost saving. Conclusions Our analysis suggests that providing full coverage for combination therapy to post–myocardial infarction Medicare beneficiaries would save both lives and money from the societal perspective. PMID:18285564

Irreversible particle motion in surfactant-laden interfaces due to pressure-dependent surface viscosity

NASA Astrophysics Data System (ADS)

Manikantan, Harishankar; Squires, Todd M.

2017-09-01

The surface shear viscosity of an insoluble surfactant monolayer often depends strongly on its surface pressure. Here, we show that a particle moving within a bounded monolayer breaks the kinematic reversibility of low-Reynolds-number flows. The Lorentz reciprocal theorem allows such irreversibilities to be computed without solving the full nonlinear equations, giving the leading-order contribution of surface pressure-dependent surface viscosity. In particular, we show that a disc translating or rotating near an interfacial boundary experiences a force in the direction perpendicular to that boundary. In unbounded monolayers, coupled modes of motion can also lead to non-intuitive trajectories, which we illustrate using an interfacial analogue of the Magnus effect. This perturbative approach can be extended to more complex geometries, and to two-dimensional suspensions more generally.

Adsorption study of copper phthalocyanine on Si(111)(√3 × √3)R30°Ag surface

NASA Astrophysics Data System (ADS)

Menzli, S.; Ben Hamada, B.; Arbi, I.; Souissi, A.; Laribi, A.; Akremi, A.; Chefi, C.

2016-04-01

The adsorption of copper phthalocyanine (CuPc) molecules on Si(111)(√3 × √3)R30°Ag surface is studied at room temperature under ultra high vacuum. Crystallographic, chemical and electronic properties of the interface are investigated by low energy electron diffraction (LEED), ultraviolet and X-ray photoemission spectroscopies (UPS, XPS) and X-ray photoemission diffraction (XPD). LEED and XPD results indicate that after one monolayer deposition the molecular layer is highly ordered with a flat lying adsorption configuration. The corresponding pattern reveals the coexistence of three symmetrically equivalent orientations of molecules with respect to the substrate. XPS core level spectra of the substrate reveal that there is no discernible chemical interaction between molecules and substrate; however there is evidence of Fermi level movement. During the growth, the work function was found to decrease from 4.90 eV for the clean substrate to 4.35 eV for the highest coverage (60 monolayers). Within a thickness of two monolayer deposition an interface dipole of 0.35 eV and a band bending of 0.2 eV have been found. UPS spectra indicate the existence of a band bending of the highest occupied molecular orbital (HOMO) of 0.55 eV. The changes in the work function, in the Fermi level position and in the HOMO state have been used to determine the energy level alignment at the interface.

Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

PubMed Central

Wu, Di; Navrotsky, Alexandra

2015-01-01

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. Herein, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. These thermochemical observations directly support a structure where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. These differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces. PMID:25870281

Self assembled monolayers on silicon for molecular electronics.

PubMed

Aswal, D K; Lenfant, S; Guerin, D; Yakhmi, J V; Vuillaume, D

2006-05-24

We present an overview of various aspects of the self-assembly of organic monolayers on silicon substrates for molecular electronics applications. Different chemical strategies employed for grafting the self-assembled monolayers (SAMs) of alkanes having different chain lengths on native oxide of Si or on bare Si have been reviewed. The utility of different characterization techniques in determination of the thickness, molecular ordering and orientation, surface coverage, growth kinetics and chemical composition of the SAMs has been discussed by choosing appropriate examples. The metal counterelectrodes are an integral part of SAMs for measuring their electrical properties as well as using them for molecular electronic devices. A brief discussion on the variety of options available for the deposition of metal counterelectrodes, that is, soft metal contacts, vapor deposition and soft lithography, has been presented. Various theoretical models, namely, tunneling (direct and Fowler-Nordheim), thermionic emission, Poole-Frenkel emission and hopping conduction, used for explaining the electronic transport in dielectric SAMs have been outlined and, some experimental data on alkane SAMs have been analyzed using these models. It has been found that short alkyl chains show excellent agreement with tunneling models; while more experimental data on long alkyl chains are required to understand their transport mechanism(s). Finally, the concepts and realization of various molecular electronic components, that is, diodes, resonant tunnel diodes, memories and transistors, based on appropriate architecture of SAMs comprising of alkyl chains (sigma- molecule) and conjugated molecules (pi-molecule) have been presented.

Systematic study on dynamic atomic layer epitaxy of InN on/in +c-GaN matrix and fabrication of fine-structure InN/GaN quantum wells: Role of high growth temperature

NASA Astrophysics Data System (ADS)

Yoshikawa, Akihiko; Kusakabe, Kazuhide; Hashimoto, Naoki; Hwang, Eun-Sook; Imai, Daichi; Itoi, Takaomi

2016-12-01

The growth kinetics and properties of nominally 1-ML (monolayer)-thick InN wells on/in +c-GaN matrix fabricated using dynamic atomic layer epitaxy (D-ALEp) by plasma-assisted molecular beam epitaxy were systematically studied, with particular attention given to the effects of growth temperature. Attention was also given to how and where the ˜1-ML-thick InN layers were frozen or embedded on/in the +c-GaN matrix. The D-ALEp of InN on GaN was a two-stage process; in the 1st stage, an "In+N" bilayer/monolayer was formed on the GaN surface, while in the 2nd, this was capped by a GaN barrier layer. Each process was monitored in-situ using spectroscopic ellipsometry. The target growth temperature was above 620 °C and much higher than the upper critical epitaxy temperature of InN (˜500 °C). The "In+N" bilayer/monolayer tended to be an incommensurate phase, and the growth of InN layers was possible only when they were capped with a GaN layer. The InN layers could be coherently inserted into the GaN matrix under self-organizing and self-limiting epitaxy modes. The growth temperature was the most dominant growth parameter on both the growth process and the structure of the InN layers. Reflecting the inherent growth behavior of D-ALEp grown InN on/in +c-GaN at high growth temperature, the embedded InN layers in the GaN matrix were basically not full-ML in coverage, and the thickness of sheet-island-like InN layers was essentially either 1-ML or 2-ML. It was found that these InN layers tended to be frozen at the step edges on the GaN and around screw-type threading dislocations. The InN wells formed type-I band line-up heterostructures with GaN barriers, with exciton localization energies of about 300 and 500 meV at 15 K for the 1-ML and 2-ML InN wells, respectively.

Interfacial engineering of microstructured materials

NASA Astrophysics Data System (ADS)

Poda, Aimee

The tribological behavior of octadecyltrichlorosilane self assembled monolayers (OTS-SAMs) has been successfully exploited to reduce energy losses and to produce adequate adhesion barrier properties on many MEMS surfaces. Unfortunately, performance discrepancies are reported in the literature between films produced on smooth surfaces as compared to typical MEMS surfaces maintaining topographical roughness. Rational explanations in terms of reproducibility issues, production considerations, and the scale of measurement technique have been introduced to account for some of the variation. The tribological phenomena at the micro-scale are complicated by the fact that rather than inertial effects, the forces associated with the surface become dominant factors influencing the mechanical behavior of contacting components. In MEMS, real mechanical contacts typically consist of a few nanometer scale asperities. Furthermore, various surface topographies exist for MEMS device fabrication and their corresponding asperity profiles can vary drastically based on the production process. This dissertation presents research focusing on the influence of topographical asperities on OTS film properties of relevance for efficient tribological improvement. A fundamental approach has been taken to carefully examine the factors that contribute to high quality film formation, specifically formation temperature and the role of interfacial water layer associated with the sample surface. As evidenced on smooth surfaces, the characteristics for successful tribological performance of OTS films are strongly dependent on the lateral packing density and molecular orientation of the monolayer. Limited information is available on how monolayers associate on topographical asperities and whether these topographical asperities influence the interfacial reactivity of MEMS surfaces. A silica film produced from a low temperature, vapor-phase hydrolysis of tetrachlorosilane with a tunable topography is introduced and leveraged as a novel investigative platform for advanced analytical investigations often restricted to use on smooth surfaces. This tunable surface allows intellectual insight into the nature of surface properties associated with silica surfaces, the uptake of interfacial water and the subsequent influence of surface morphology on OTS film formation. FTIR analysis was utilized for an examination of interfacial properties on both smooth Si(100) surfaces and on the tunable MVD topography in combination with an investigation of OTS film formation mechanism. A dilute etchant technique is developed to provide topographic contrast for AFM imaging to allow direct examination of film packing characteristics in relation to surface asperities. A relationship between monolayer adsorption characteristics and topographical asperities with observed variations in monolayer order resultant from surface roughness has been elucidated. Results show that the packing structure of OTS monolayers is dependent on the local asperity curvature which is qualitatively different from that observed on flat surfaces. In addition, a difference in surface reactivity is observed as a result of different surface topographies with thicker silica layers maintaining a thicker interfacial water layer resulting in a higher coverage of OTS monolayers at similar reaction times and conditions. This work shows changes in surface reactivity as a consequence of different morphological surface characteristics and preparation procedures. Additional research is presented on a new class of SAM, namely octadecylphoshonic acid and its monolayer formation mechanism and properties are compared to conventional OTS monolayers. This monolayer is translated to investigative probes based on Aluminum oxide specifically tailored for a tribological comparison across multi-scale friction regimes.

Adsorption of xenon on vicinal copper and platinum surfaces

NASA Astrophysics Data System (ADS)

Baker, Layton

The adsorption of xenon was studied on Cu(111), Cu(221), Cu(643) and on Pt(111), Pt(221), and Pt(531) using low energy electron diffraction (LEED), temperature programmed desorption (TPD) of xenon, and ultraviolet photoemission of adsorbed xenon (PAX). These experiments were performed to study the atomic and electronic structure of stepped and step-kinked, chiral metal surfaces. Xenon TPD and PAX were performed on each surface in an attempt to titrate terrace, step edge, and kink adsorption sites by adsorption energetics (TPD) and local work function differences (PAX). Due to the complex behavior of xenon on the vicinal copper and platinum metal surfaces, adsorption sites on these surfaces could not be adequately titrated by xenon TPD. On Cu(221) and Cu(643), xenon desorption from step adsorption sites was not apparent leading to the conclusion that the energy difference between terrace and step adsorption is minuscule. On Pt(221) and Pt(531), xenon TPD indicated that xenon prefers to bond at step edges and that the xenon-xenon interaction at step edges in repulsive but no further indication of step-kink adsorption was observed. The Pt(221) and Pt(531) TPD spectra indicated that the xenon overlayer undergoes strong compression near monolayer coverage on these surfaces due to repulsion between step-edge adsorbed xenon and other encroaching xenon atoms. The PAX experiments on the copper and platinum surfaces demonstrated that the step adsorption sites have lower local work functions than terrace adsorption sites and that higher step density leads to a larger separation in the local work function of terrace and step adsorption sites. The PAX spectra also indicated that, for all surfaces studied at 50--70 K, step adsorption is favored at low coverage but the step sites are not saturated until monolayer coverage is reached; this observation is due to the large entropy difference between terrace and step adsorption states and to repulsive interactions between xenon atoms adsorbed at step edges (on the platinum surfaces). The results herein provide several novel observations regarding the adsorptive behavior of xenon on vicinal copper and platinum surfaces.

Overlayer growth and electronic properties of the Bi/GaSb(110) interface

NASA Astrophysics Data System (ADS)

Gavioli, Luca; Betti, Maria Grazia; Casarini, Paolo; Mariani, Carlo

1995-06-01

The overlayer growth and electronic properties of the Bi/GaSb(110) interface and of the two-dimensional ordered (1×1)- and (1×2)-Bi layers have been investigated by complementary spectroscopic techniques (high-resolution electron-energy-loss, photoemission, and Auger spectroscopy). Bismuth forms an epitaxial monolayer, followed by island formation (Stranski-Krastanov growth mode) covering an average surface area of 40% at a nominal coverage of 4 ML. The (1×2)-symmetry stable structural phase, obtained after annealing at ~220 °C, corresponds to an average nominal Bi coverage of about 0.7 ML, suggesting an atomic geometry different from the epitaxial-continued layer structure. The disposal of Bi atoms in the (1×2) structure should build up an ``open'' layer, as the Ga-related surface exciton quenched in the (1×1) epitaxial monolayer is present in the (1×2) stable phase. The two symmetry phases are characterized by strong absorption features at 1 eV [(1×1)-Bi] and 0.54 eV [(1×2)-Bi], related to interband electronic transitions between Bi-induced electronic states. The major Bi-related occupied electronic levels, present in the valence band of the (1×1)- and (1×2)-Bi layer, have been detected by angle-integrated ultraviolet photoemission spectroscopy. Both the (1×1) and (1×2) phases show a metallic nature, with a low density of electronic states at the Fermi level. Schottky barrier heights of 0.20 and 0.14 eV are estimated for the epitaxial (1×1)- and (1×2)-symmetry stage, respectively, by analyzing the space-charge layer conditions through the study of the dopant-induced free-carrier plasmon in the GaSb substrate.

The role of place-exchange, dislocations and substrate symmetry in nickel/gold(111) heteroepitaxy

NASA Astrophysics Data System (ADS)

Cullen, William Grady

1999-12-01

The epitaxial growth of Ni on Au(111) in ultrahigh vacuum was investigated using scanning tunneling microscopy (STM) and Auger electron spectroscopy (AES). Films in the coverage range 0--2 monolayers were studied. The goals were to investigate the influence of the substrate reconstruction on the morphology of the growing film and also the possibility of intermixing between Ni and Au. Deposition of Ni at room temperature led to the growth of two-dimensional islands which nucleate at the point dislocations of the Au(111) herringbone reconstruction, as found in previous studies. Anisotropic growth features were identified and shown to result from basic symmetry properties of the Au(111) reconstruction. In addition, significant internal structure was observed within the islands, indicating that the islands are of mixed composition, and that the overlayer is not pseudomorphic. Two-dimensional island ripening was observed after deposition of Ni at room temperature, followed by moderate annealing. Results of STM and AES experiments indicate that the mass transport during ripening is due to mobile Au atoms which have detached from the original islands. Deposition at high temperature was shown to result in the formation of large epitaxial Au islands due to Ni-Au place exchange and subsequent collision-mediated nucleation of Au atoms. Island size distributions were analyzed for comparison with scaling theories, and data collapse onto a common curve was observed at different coverages and temperatures. Based on the scaling analysis, a critical nucleus of i = 2 was inferred. The annealing and high-temperature deposition experiments demonstrated that a Ni monolayer is metastable at the Au(111) surface, i.e. Au tends to segregate and cover the Ni.

Spontaneous desorption and phase transitions of self-assembled alkanethiol and alicyclic thiol monolayers chemisorbed on Au(111) in ultrahigh vacuum at room temperature.

PubMed

Ito, Eisuke; Kang, Hungu; Lee, Dongjin; Park, Joon B; Hara, Masahiko; Noh, Jaegeun

2013-03-15

Scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) were used to examine the surface structure and adsorption conditions of hexanethiol (HT) and cyclohexanethiol (CHT) self-assembled monolayers (SAMs) on Au(111) as a function of storage period in ultrahigh vacuum (UHV) conditions of 3×10(-7) Pa at room temperature (RT). STM imaging revealed that after storage for 7 days, HT SAMs underwent phase transitions from c(4×2) phase to low coverage 4×√3 phase. This transition is due to a structural rearrangement of hexanethiolates that results from the spontaneous desorption of chemisorbed HT molecules on Au(111) surface. XPS measurements showed approximately 28% reduction in sulfur coverage, which indicates desorption of hexanethiolates from the surfaces. Contrary to HT SAMs, the structural order of CHT SAMs with (5×2√3)R35° phase completely disappeared after storage for 3 or 7 days. XPS results show desorption of more than 80% of the cyclohexanethiolates, even after storage for 3 days. We found that spontaneous desorption of CHT molecules on Au(111) in UHV at RT occurred quickly, whereas spontaneous desorption of HT molecules was much slower. Thermal desorption spectroscopy (TDS) results suggest CHT SAMs in UHV at RT can desorb more efficiently than HT SAMs due to formation of thiol desorption fragments that result from chemical reactions between surface hydrogen atoms and thiolates on Au(111) surfaces. This study clearly demonstrated that organic thiols chemisorbed on gold surfaces are desorbed spontaneously in UHV at RT and van der Waals interactions play an important role in determining the structural stability of thiolate SAMs in UHV. Copyright © 2012 Elsevier Inc. 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).

Boosting surface charge-transfer doping efficiency and robustness of diamond with WO3 and ReO3

NASA Astrophysics Data System (ADS)

Tordjman, Moshe; Weinfeld, Kamira; Kalish, Rafi

2017-09-01

An advanced charge-transfer yield is demonstrated by employing single monolayers of transition-metal oxides—tungsten trioxide (WO3) and rhenium trioxide (ReO3)—deposited on the hydrogenated diamond surface, resulting in improved p-type sheet conductivity and thermal stability. Surface conductivities, as determined by Hall effect measurements as a function of temperature for WO3, yield a record sheet hole carrier concentration value of up to 2.52 × 1014 cm-2 at room temperature for only a few monolayers of coverage. Transfer doping with ReO3 exhibits a consistent narrow sheet carrier concentration value of around 3 × 1013 cm-2, exhibiting a thermal stability of up to 450 °C. This enhanced conductivity and temperature robustness exceed those reported for previously exposed surface electron acceptor materials used so far on a diamond surface. X-ray photoelectron spectroscopy measurements of the C1s core level shift as a function of WO3 and ReO3 layer thicknesses are used to determine the respective increase in surface band bending of the accumulation layers, leading to a different sub-surface two-dimensional hole gas formation efficiency in both cases. This substantial difference in charge-exchange efficiency is unexpected since both surface acceptors have very close work functions. Consequently, these results lead us to consider additional factors influencing the transfer doping mechanism. Transfer doping with WO3 reveals the highest yet reported transfer doping efficiency per minimal surface acceptor coverage. This improved surface conductivity performance and thermal stability will promote the realization of 2D diamond-based electronic devices facing process fabrication challenges.

Thermodynamic Control of Two-Dimensional Molecular Ionic Nanostructures on Metal Surfaces

DOE PAGES

Jeon, Seokmin; Doak, Peter W.; Sumpter, Bobby G.; ...

2016-07-26

Bulk molecular ionic solids exhibit fascinating electronic properties, including electron correlations, phase transitions and superconducting ground states. In contrast, few of these phenomena have so far been observed in low-dimensional molecular structures, including thin films, nanoparticles and molecular blends, not in the least because most of such structures have so far been composed of nearly closed-shell molecules. It is therefore desirable to develop low-dimensional molecular structures of ionic molecules toward fundamental studies and potential applications. Here we present detailed analysis of monolayer-thick structures of the canonical TTF-TCNQ (tetrathiafulvalene 7,7,8,8-tetracyanoquinodimethane) system grown on low-index gold and silver surfaces. The most distinctivemore » property of the epitaxial growth is the wide abundance of stable TTF/TCNQ ratios, in sharp contrast to the predominance of 1:1 ratio in the bulk. We propose the existence of the surface phase-diagram that controls the structures of TTF-TCNQ on the surfaces, and demonstrate phase-transitions that occur upon progressively increasing the density of TCNQ while keeping the surface coverage of TTF fixed. Based on direct observations, we propose the binding motif behind the stable phases and infer the dominant interactions that enable the existence of the rich spectrum of surface structures. Finally, we also show that the surface phase diagram will control the epitaxy beyond monolayer coverage. Multiplicity of stable surface structures, the corollary rich phase diagram and the corresponding phase-transitions present an interesting opportunity for low-dimensional molecular systems, particularly if some of the electronic properties of the bulk can be preserved or modified in the surface phases.« less

First-Principles Study of Mo Segregation in MoNi(111): Effects of Chemisorbed Atomic Oxygen

PubMed Central

Yu, Yanlin; Xiao, Wei; Wang, Jianwei; Wang, Ligen

2015-01-01

Segregation at metal alloy surfaces is an important issue because many electrochemical and catalytic properties are directly correlated to the surface composition. We have performed density functional theory calculations for Mo segregation in MoNi(111) in the presence of chemisorbed atomic oxygen. In particular, the coverage dependence and possible adsorption-induced segregation phenomena are addressed by investigating segregation energies of the Mo atom in MoNi(111). The theoretical calculated results show that the Mo atom prefers to be embedded in the bulk for the clean MoNi(111), while it segregates to the top-most layer when the oxygen coverage is thicker than 1/9 monolayer (ML). Furthermore, we analyze the densities of states for the clean and oxygen-chemisorbed MoNi(111), and see a strong covalent bonding between Mo d-band states and O p-states. The present study provides valuable insight for exploring practical applications of Ni-based alloys as hydrogen evolution electrodes. PMID:28787811

Controlling the Nanoscale Patterning of AuNPs on Silicon Surfaces

PubMed Central

Williams, Sophie E.; Davies, Philip R.; Bowen, Jenna L.; Allender, Chris J.

2013-01-01

This study evaluates the effectiveness of vapour-phase deposition for creating sub-monolayer coverage of aminopropyl triethoxysilane (APTES) on silicon in order to exert control over subsequent gold nanoparticle deposition. Surface coverage was evaluated indirectly by observing the extent to which gold nanoparticles (AuNPs) deposited onto the modified silicon surface. By varying the distance of the silicon wafer from the APTES source and concentration of APTES in the evaporating media, control over subsequent gold nanoparticle deposition was achievable to an extent. Fine control over AuNP deposition (AuNPs/μm2) however, was best achieved by adjusting the ionic concentration of the AuNP-depositing solution. Furthermore it was demonstrated that although APTES was fully removed from the silicon surface following four hours incubation in water, the gold nanoparticle-amino surface complex was stable under the same conditions. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) were used to study these affects. PMID:28348330

Ru sub 3 (CO) sub 12 and Mo(CO) sub 6 adsorbed on Ru(001) and Au/Ru: An infrared reflection-absorption study

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

Malik, I.J.; Hrbek, J.

1990-01-01

The authors obtained infrared reflection absorption (IRAS) and thermal desorption spectroscopy (TDS) data for Ru{sub 3}(CO){sub 12}/Ru(001) and Mo(CO){sub 6}/Au/Ru systems for metal carbonyl coverages between submonolayer and approximately 20 monolayers. They characterized the C-O stretching mode of both systems (4cm{sup {minus}1}FWHM) and a deformation mode of Mo(CO){sub 6} at 608cm{sup {minus}1} (1 cm{sup {minus}1}FWHM). Both IRAS and TDS data suggest adsorption and desorption of metal carbonyls as molecular species with a preferential orientation in the overlayers. The IR intensity of the C-O stretch per a C-O bond projected onto the surface normal is approximately twice (five times) larger formore » Ru{sub 3}(CO){sub 12} (Mo(CO){sub 6}) at submonolayer coverages than for CO/Ru(001) at {theta}{sub CO}=0.68.« less

Ru sub 3 (CO) sub 12 and Mo(CO) sub 6 adsorbed on Ru(001) and Au/Ru: An infrared reflection-absorption study

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

Malik, I.J.; Hrbek, J.

1990-01-01

We obtained IRAS and TDS data for Ru{sub 3}(CO){sub 12}/Ru(001) and Mo(CO){sub 6}/Au/Ru systems for metal carbonyl coverages between submonolayer and approximately 20 monolayers. We characterized the C-O stretching mode of both systems (4 cm{sup {minus}1} FWHM) and a deformation mode of Mo(CO){sub 6} at 608 cm{sup {minus}1} (1 cm{sup {minus}1} FWHM). Both IRAS and TDS data suggest adsorption and desorption of metal carbonyls as molecular species with a preferential orientation in the overlayers. The IR intensity of the C-O stretch per a C-O bond projected onto the surface normal is approximately twice (five times) larger for Ru{sub 3}(CO){sub 12}more » (Mo(CO){sub 6}) at submonolayer coverages than for CO/Ru(001) at {theta}{sub CO}=0.68. 31 refs., 4 figs.« less

Unusual island formations of Ir on Ge (111) studied by STM

NASA Astrophysics Data System (ADS)

van Zijll, M.; Huffman, E.; Lovinger, D. J.; Chiang, S.

2017-12-01

Island formation on the Ir/Ge(111) surface is studied using ultrahigh vacuum scanning tunneling microscopy. Ir was deposited at room temperature onto a Ge (111) substrate with coverages between 0.5 and 2.0 monolayers (ML). The samples were annealed to temperatures between 550 and 800 K, and then cooled prior to imaging. With 1.0 ML Ir coverage, at annealing temperatures 650-750 K, round islands form at locations where domain boundaries of the substrate reconstruction intersect. Both the substrate and the islands display a (√{ 3} x√{ 3}) R30∘ reconstruction. Additionally, a novel surface formation is observed where the Ir gathers along the antiphase domain boundaries between competing surface domains of the Ge surface reconstruction. This gives the appearance of the Ir in the domain boundaries forming pathways between different islands. The islands formed at higher annealing temperatures resulted in larger island sizes, which is evidence of Ostwald ripening. We present a model for the islands and the pathways which is consistent with our observations.

Water interaction with laboratory-simulated fossil fuel combustion particles.

PubMed

Popovicheva, O B; Kireeva, E D; Shonija, N K; Khokhlova, T D

2009-10-01

To clarify the impact of fossil fuel combustion particles' composition on their capacity to take up water, we apply a laboratory approach in which the method of deposition of compounds, identified in the particulate coverage of diesel and aircraft engine soot particles, is developed. It is found that near-monolayer organic/inorganic coverage of the soot particles may be represented by three groups of fossil fuel combustion-derived particulate matter with respect to their Hansh's coefficients related to hydrophilic properties. Water adsorption measurements show that nonpolar organics (aliphatic and aromatic hydrocarbons) lead to hydrophobization of the soot surface. Acidic properties of organic compounds such as those of oxidized PAHs, ethers, ketones, aromatic, and aliphatic acids are related to higher water uptake, whereas inorganic acids and ionic compounds such as salts of organic acids are shown to be responsible for soot hydrophilization. This finding allows us to quantify the role of the chemical identity of soot surface compounds in water uptake and the water interaction with fossil fuel combustion particles in the humid atmosphere.

Effects of external magnetic field and out-of-plane strain on magneto-optical Kerr spectra in CrI3 monolayer.

PubMed

Guo, Guanxing; Bi, Gang; Cai, Chunfeng; Wu, Huizhen

2018-07-18

Magnetic semiconductors based on two-dimensional (2D) crystals have attracted attention owing to their intrinsic ferromagnetism and have potential for spintronic devices. Here, full-potential linearized augmented plane wave plus local orbitals method is used to explore the structural, electronic, magnetic, and magneto-optical properties of CrI 3 monolayer. Our first-principles calculations show that CrI 3 monolayer is a ferromagnetic indirect semiconductor with spin-up and spin-down band gaps of 1.23 and 1.90 eV, respectively, and a magnetic moment of 2.93 [Formula: see text] per Cr atom. Based on the macroscopic linear response theory, we systematically study the influences of external magnetic field and out-of-plane strain on the magneto-optical Kerr effect spectra in CrI 3 monolayer. The Kerr rotation of CrI 3 monolayer at 1.96 eV photon energy is [Formula: see text], which is consistent with the recent experiments. We find that the Kerr rotation reaches its maximum when the external magnetic field is perpendicular to CrI 3 plane, while it is almost zero on turning the magnetic field in the plane. This result as well as the sizable magnetocrystalline anisotropy energy (MAE) of 0.79 meV verifies that CrI 3 monolayer has a strong magnetic anisotropy with an out-of-plane easy axis. Further, applying out-of-plane compressive and tensile strain upon CrI 3 monolayer, we observe a redshift of the Kerr rotation spectra with the increase of the strain and the peak values of the Kerr rotation increase correspondingly. The rich electronic and magnetic properties, especially the magneto-optical spectra, render CrI 3 monolayer a promising 2D magnetic material for applications from sensing to data storage.

Fabrication and characterization of graphene/molecule/graphene vertical junctions with aryl alkane monolayers

NASA Astrophysics Data System (ADS)

Jeong, Inho; Song, Hyunwook

2017-11-01

In this study, we fabricated and characterized graphene/molecule/graphene (GMG) vertical junctions with aryl alkane monolayers. The constituent molecules were chemically self-assembled via electrophilic diazonium reactions into a monolayer on the graphene bottom electrode, while the other end physically contacted the graphene top electrode. A full understanding of the transport properties of molecular junctions is a key step in the realization of molecular-scale electronic devices and requires detailed microscopic characterization of the junction's active region. Using a multiprobe approach combining a variety of transport techniques, we elucidated the transport mechanisms and electronic structure of the GMG junctions, including temperature- and length-variable transport measurements, and transition voltage spectroscopy. These results provide criteria to establish a valid molecular junction and to determine the most probable transport characteristics of the GMG junctions.

Ab Initio Surface Phase Diagrams for Coadsorption of Aromatics and Hydrogen on the Pt(111) Surface

DOE PAGES

Ferguson, Glen Allen; Vorotnikov, Vassili; Wunder, Nicholas; ...

2016-11-02

Supported metal catalysts are commonly used for the hydrogenation and deoxygenation of biomass-derived aromatic compounds in catalytic fast pyrolysis. To date, the substrate-adsorbate interactions under reaction conditions crucial to these processes remain poorly understood, yet understanding this is critical to constructing detailed mechanistic models of the reactions important to catalytic fast pyrolysis. Density functional theory (DFT) has been used in identifying mechanistic details, but many of these works assume surface models that are not representative of realistic conditions, for example, under which the surface is covered with some concentration of hydrogen and aromatic compounds. In this study, we investigate hydrogen-guaiacolmore » coadsorption on Pt(111) using van der Waals-corrected DFT and ab initio thermodynamics over a range of temperatures and pressures relevant to bio-oil upgrading. We find that relative coverage of hydrogen and guaiacol is strongly dependent on the temperature and pressure of the system. Under conditions relevant to ex situ catalytic fast pyrolysis (CFP; 620-730 K, 1-10 bar), guaiacol and hydrogen chemisorb to the surface with a submonolayer hydrogen (~0.44 ML H), while under conditions relevant to hydrotreating (470-580 K, 10-200 bar), the surface exhibits a full-monolayer hydrogen coverage with guaiacol physisorbed to the surface. These results correlate with experimentally observed selectivities, which show ring saturation to methoxycyclohexanol at hydrotreating conditions and deoxygenation to phenol at CFP-relevant conditions. Additionally, the vibrational energy of the adsorbates on the surface significantly contributes to surface energy at higher coverage. Ignoring this contribution results in not only quantitatively, but also qualitatively incorrect interpretation of coadsorption, shifting the phase boundaries by more than 200 K and ~10-20 bar and predicting no guaiacol adsorption under CFP and hydrotreating conditions. We discuss the implications of this work in the context of modeling hydrogenation and deoxygenation reactions on Pt(111), and we find that only the models representative of equilibrium surface coverage can capture the hydrogenation kinetics correctly. Lastly, as a major outcome of this work, we introduce a freely available web-based tool, dubbed the Surface Phase Explorer (SPE), which allows researchers to conveniently determine surface composition for any one- or two-component system at thermodynamic equilibrium over a wide range of temperatures and pressures on any crystalline surface using standard DFT output.« less

From atoms to layers: in situ gold cluster growth kinetics during sputter deposition

NASA Astrophysics Data System (ADS)

Schwartzkopf, Matthias; Buffet, Adeline; Körstgens, Volker; Metwalli, Ezzeldin; Schlage, Kai; Benecke, Gunthard; Perlich, Jan; Rawolle, Monika; Rothkirch, André; Heidmann, Berit; Herzog, Gerd; Müller-Buschbaum, Peter; Röhlsberger, Ralf; Gehrke, Rainer; Stribeck, Norbert; Roth, Stephan V.

2013-05-01

The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction of morphological real space parameters, such as cluster size and shape, correlation distance, layer porosity and surface coverage, directly from reciprocal space scattering data. This approach enables a large variety of future investigations of the influence of different process parameters on the thin metal film morphology. Furthermore, our study allows for deducing the wetting behavior of gold cluster films on solid substrates and provides a better understanding of the growth kinetics in general, which is essential for optimization of manufacturing parameters, saving energy and resources.The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction of morphological real space parameters, such as cluster size and shape, correlation distance, layer porosity and surface coverage, directly from reciprocal space scattering data. This approach enables a large variety of future investigations of the influence of different process parameters on the thin metal film morphology. Furthermore, our study allows for deducing the wetting behavior of gold cluster films on solid substrates and provides a better understanding of the growth kinetics in general, which is essential for optimization of manufacturing parameters, saving energy and resources. Electronic supplementary information (ESI) available: The full GISAXS image sequence of the experiment, the model-based IsGISAXS-simulation sequence as movie files for comparison and detailed information about sample cleaning, XRR, FESEM, IsGISAXS, comparison μGIWAXS/μGISAXS, and sampling statistics. See DOI: 10.1039/c3nr34216f

Investigating the interfacial dynamics of thin films

NASA Astrophysics Data System (ADS)

Rosenbaum, Aaron W.

This thesis probes the interfacial dynamics and associated phenomena of thin films. Surface specific tools were used to study the self-assembly of alkanethiols, the mono- and bilayer dynamics of SF6, and the surface motion of poly(methyl methacrylate). Non-pertubative helium atom scattering was the principal technique used to investigate these systems. A variety of other complementary tools, including scanning tunneling microscopy, electron diffraction, Auger spectroscopy, atomic force microscopy, and ellipsometry were used in tandem with the neutral atom scattering studies. Controlling the spontaneous assembly of alkanethiols on Au(111) requires a better fundamental understanding of the adsorbate-adsorbate and substrate-adsorbate interactions. Our characterization focused on two key components, the surface structure and adsorbate vibrations. The study indicates that the Au(111) reconstruction plays a larger role than anticipated in the low-density phase of alkanethiol monolayers. A new structure is proposed for the 1-decanethiol monolayer that impacts the low-energy vibrational mode. Varying the alkane chain lengths imparts insight into the assembly process via characterization of a dispersionless phonon mode. Studies of SF6 physisorbed on Au(111) bridge surface research on rare gas adsorbates with complicated dynamical organic thin films. Mono- and bilayer coverages of SF6/Au(111) were studied at cryogenic temperatures. Our experiments probed the surface properties of SF6 yielding insights into substrate and coverage effects. The study discovered a dispersionless Einstein oscillation with multiple harmonic overtones. A second layer of SF6 softened the mode, but did not show any indications of bulk or cooperative interactions. The vibrational properties of SF 6 showed both striking similarities and differences when compared with physisorbed rare gases. Lastly, this thesis will discuss studies of thin film poly(methyl methacrylate) on Si. The non-pertubative and surface specific nature of helium atom scattering allows for a deft study of the relationship between surface motion and the glass transition temperature. An added parameter in this complex organic system is the film thickness. The confinement effects and enhanced surface displacement were examined as a function of the thermal attenuation of both inelastic and elastic helium atom scattering. The Debye-Waller factor for these thin films of PMMA is similar to the low-density alkanethiol self-assembled monolayers discussed earlier.

A pragmatic, randomized, controlled study evaluating the impact of access to smoking cessation pharmacotherapy coverage on the proportion of successful quitters in a Canadian population of smokers motivated to quit (ACCESSATION).

PubMed

Selby, Peter; Brosky, Gerald; Oh, Paul; Raymond, Vincent; Arteaga, Carmen; Ranger, Suzanne

2014-05-07

Many smokers find the cost of smoking cessation medications a barrier. Financial coverage for these medications increases utilization of pharmacotherapies. This study assesses whether financial coverage increases the proportion of successful quitters. A pragmatic, open-label, randomized, controlled trial was conducted in 58 Canadian sites between March 2009 and September 2010. Smokers (≥10 cigarettes/day) without insurance coverage who were motivated to quit within 14 days were randomized (1:1) in a blinded manner to receive either full coverage eligibility for 26 weeks or no coverage. Pharmacotherapies covered were varenicline, bupropion, or nicotine patches/gum. Investigators/subjects were unblinded to study group assignment after randomization and prior to choosing a smoking cessation method(s). All subjects received brief smoking cessation counseling. The primary outcome measure was self-reported 7-day point prevalence of abstinence (PPA) at week 26. Of the 1380 randomized subjects (coverage, 696; no coverage, 684), 682 (98.0%) and 435 (63.6%), respectively, were dispensed at least one smoking cessation medication dose. The 7-day PPA at week 26 was higher in the full coverage versus no coverage group: 20.8% (n = 145) and 13.9% (n = 95), respectively; odds ratio (OR) = 1.64, 95% confidence interval (CI) 1.23-2.18; p = 0.001. Urine cotinine-confirmed 7-day PPA at week 26 was 15.7% (n = 109) and 10.1% (n = 69), respectively; OR = 1.68, 95% CI 1.21-2.33; p = 0.002. After pharmacotherapy, coverage eligibility was withdrawn from the full coverage group, continuous abstinence between weeks 26 and 52 was 6.6% (n = 46) and 5.6% (n = 38), in the full coverage and no coverage groups, respectively; OR = 1.19, 95% CI 0.76-1.87; p = 0.439. In this study, the adoption of a smoking cessation medication coverage drug policy was an effective intervention to improve 26-week quit rates in Canada. The advantages were lost once coverage was discontinued. Further study is required on the duration of coverage to prevent relapse to smoking. (clinicaltrials.gov identifier: NCT00818207; the study was sponsored by Pfizer Inc.).

Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces

DOE PAGES

Kaghazchi, Payam; Jacob, Timo; Chen, Wenhua; ...

2013-06-03

Here, we report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H 2 peak is seen from planar Ir(210) at all coverages whereas a single H 2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H 2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity inmore » recombination and desorption of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H 2 from faceted Ir(210): F1 from desorption of H 2 on {311} facets while F2 from desorption of H 2 on (110) facets.« less

Barrier Coverage for 3D Camera Sensor Networks

PubMed Central

Wu, Chengdong; Zhang, Yunzhou; Jia, Zixi; Ji, Peng; Chu, Hao

2017-01-01

Barrier coverage, an important research area with respect to camera sensor networks, consists of a number of camera sensors to detect intruders that pass through the barrier area. Existing works on barrier coverage such as local face-view barrier coverage and full-view barrier coverage typically assume that each intruder is considered as a point. However, the crucial feature (e.g., size) of the intruder should be taken into account in the real-world applications. In this paper, we propose a realistic resolution criterion based on a three-dimensional (3D) sensing model of a camera sensor for capturing the intruder’s face. Based on the new resolution criterion, we study the barrier coverage of a feasible deployment strategy in camera sensor networks. Performance results demonstrate that our barrier coverage with more practical considerations is capable of providing a desirable surveillance level. Moreover, compared with local face-view barrier coverage and full-view barrier coverage, our barrier coverage is more reasonable and closer to reality. To the best of our knowledge, our work is the first to propose barrier coverage for 3D camera sensor networks. PMID:28771167

Barrier Coverage for 3D Camera Sensor Networks.

PubMed

Si, Pengju; Wu, Chengdong; Zhang, Yunzhou; Jia, Zixi; Ji, Peng; Chu, Hao

2017-08-03

Barrier coverage, an important research area with respect to camera sensor networks, consists of a number of camera sensors to detect intruders that pass through the barrier area. Existing works on barrier coverage such as local face-view barrier coverage and full-view barrier coverage typically assume that each intruder is considered as a point. However, the crucial feature (e.g., size) of the intruder should be taken into account in the real-world applications. In this paper, we propose a realistic resolution criterion based on a three-dimensional (3D) sensing model of a camera sensor for capturing the intruder's face. Based on the new resolution criterion, we study the barrier coverage of a feasible deployment strategy in camera sensor networks. Performance results demonstrate that our barrier coverage with more practical considerations is capable of providing a desirable surveillance level. Moreover, compared with local face-view barrier coverage and full-view barrier coverage, our barrier coverage is more reasonable and closer to reality. To the best of our knowledge, our work is the first to propose barrier coverage for 3D camera sensor networks.

The Sapphire (0001) Surface, Clean and with d-metal Overlayers: Density Functional - LDA Results

NASA Astrophysics Data System (ADS)

Verdozzi, C.; Jennison, D. R.; Schultz, P. A.; Sears, M. P.

1998-03-01

Previous theoretical work for the a-Al2O3(0001) surface mostly used very thin slabs, and limited theoretical information is available on the binding of metal overlayers. Also, no systematic information is available about the dependence of the metal-ceramic interaction on metal coverage. We present here results using the local density approximation for the structural and electronic properties of the a-Al2O3(0001) surface, with and without d-metal overlayers Pt, Ag, Cu, and with sufficiently thick slabs to find the bottom of the unusually large and deep surface relaxation in this material. Our thick slab site-optimized calculations are performed for 1, 2/3 and 1/3 monolayer (ML) coverage. The adhesion energy and the nature of the interfacial bond vary greatly with metal coverage and can be understood in terms of the relative roles of the surface Madelung potential and the strength of the lateral metal-metal bond. Our study should in principle succeed in bracketing the phenomenology of adhesion and wetting at least for the right-most part of the d-metal periodic table. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under Contract DE-AC04-94AL85000. Corresponding author: claudio@sandia.gov.

The role of high oxygen vacancy concentration on modification of surface properties and H2S adsorption on the rutile TiO2 (110)

NASA Astrophysics Data System (ADS)

Wei, Shiqian; Wang, Fang; Dan, Meng; Zeng, Kaiyue; Zhou, Ying

2017-11-01

In this work, spin-polarized DFT + U method has been employed to investigate adsorption properties of H2S on the rutile TiO2 (110) surface with a high coverage of bridging oxygen vacancies (BOVs). The influence of different BOV coverage (θ-BOVs) on the surface electronic structure is examined. Defected states increase within the band gap with θ-BOVs increasing from 1/8 to 4/8 monolayer (ML). The high defected surface with θ-BOVs = 4/8 ML is determined to have a desired band structure and noticeable visible light response. In addition, H2S adsorption behaviors are noticeably affected by different H2S coverage (θ-H2S). Particularly, it is found molecular adsorption at θ-H2S ≤ 1/8 ML and dissociative adsorption at the higher θ-H2S. The maximization of spontaneous dissociation of H2S can be realized when the BOVs are all covered by H2S molecules. This work gains mechanistic insights into BOVs in tuning the surface properties and provides a guide for the effective utilization of the active surface sites on the rutile TiO2 (110) in the field of H2S splitting.

In situ Observation of Direct Electron Transfer Reaction of Cytochrome c Immobilized on ITO Electrode Modified with 11-{2-[2-(2-Methoxyethoxy)ethoxy]ethoxy}undecylphosphonic Acid Self-assembled Monolayer Film by Electrochemical Slab Optical Waveguide Spectroscopy.

PubMed

Matsuda, Naoki; Okabe, Hirotaka; Omura, Ayako; Nakano, Miki; Miyake, Koji

2017-01-01

To immobilize cytochrome c (cyt.c) on an ITO electrode while keeping its direct electron transfer (DET) functionality, the ITO electrode surface was modified with 11-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}undecylphosphonic acid (CH 3 O (CH 2 CH 2 O) 3 C 11 H 22 PO(OH) 2 , M-EG 3 -UPA) self-assembled monolayer (SAM) film. After a 100-times washing process to exchange a phosphate buffer saline solution surrounding cyt.c and ITO electrode to a fresh one, an in situ observation of visible absorption spectral change with slab optical waveguide (SOWG) spectroscopy showed that 87.7% of the cyt.c adsorbed on the M-EG 3 -UPA modified ITO electrode remained on the ITO electrode. The SOWG absorption spectra corresponding to oxidized and reduced cyt.c were observed with setting the ITO electrode potential at 0.3 and -0.3 V vs. Ag/AgCl, respectively, while probing the DET reaction between cyt.c and ITO electrode occurred. The amount of cyt.c was evaluated to be about 19.4% of a monolayer coverage based on the coulomb amount in oxidation and reduction peaks on cyclic voltammetry (CV) data. The CV peak current maintained to be 83.4% compared with the initial value for a M-EG 3 -UPA modified ITO electrode after 60 min continuous scan with 0.1 V/s between 0.3 and -0.3 V vs. Ag/AgCl.

Solid-State Densification of Spun-Cast Self-Assembled Monolayers for Use in Ultra-Thin Hybrid Dielectrics.

PubMed

Hutchins, Daniel O; Acton, Orb; Weidner, Tobias; Cernetic, Nathan; Baio, Joe E; Castner, David G; Ma, Hong; Jen, Alex K-Y

2012-11-15

Ultra-thin self-assembled monolayer (SAM)-oxide hybrid dielectrics have gained significant interest for their application in low-voltage organic thin film transistors (OTFTs). A [8-(11-phenoxy-undecyloxy)-octyl]phosphonic acid (PhO-19-PA) SAM on ultrathin AlO x (2.5 nm) has been developed to significantly enhance the dielectric performance of inorganic oxides through reduction of leakage current while maintaining similar capacitance to the underlying oxide structure. Rapid processing of this SAM in ambient conditions is achieved by spin coating, however, as-cast monolayer density is not sufficient for dielectric applications. Thermal annealing of a bulk spun-cast PhO-19-PA molecular film is explored as a mechanism for SAM densification. SAM density, or surface coverage, and order are examined as a function of annealing temperature. These SAM characteristics are probed through atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure spectroscopy (NEXAFS). It is found that at temperatures sufficient to melt the as-cast bulk molecular film, SAM densification is achieved; leading to a rapid processing technique for high performance SAM-oxide hybrid dielectric systems utilizing a single wet processing step. To demonstrate low-voltage devices based on this hybrid dielectric (with leakage current density of 7.7×10 -8 A cm -2 and capacitance density of 0.62 µF cm -2 at 3 V), pentacene thin-film transistors (OTFTs) are fabricated and yield sub 2 V operation and charge carrier mobilites of up to 1.1 cm 2 V -1 s -1 .

Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

DOE PAGES

Wu, Di; Navrotsky, Alexandra

2015-04-13

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. In this paper, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. Furthermore, these thermochemical observations directly support a structuremore » where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. Finally, these differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces.« less

Solid-State Densification of Spun-Cast Self-Assembled Monolayers for Use in Ultra-Thin Hybrid Dielectrics

PubMed Central

Hutchins, Daniel O.; Acton, Orb; Weidner, Tobias; Cernetic, Nathan; Baio, Joe E.; Castner, David G.; Ma, Hong; Jen, Alex K.-Y.

2013-01-01

Ultra-thin self-assembled monolayer (SAM)-oxide hybrid dielectrics have gained significant interest for their application in low-voltage organic thin film transistors (OTFTs). A [8-(11-phenoxy-undecyloxy)-octyl]phosphonic acid (PhO-19-PA) SAM on ultrathin AlOx (2.5 nm) has been developed to significantly enhance the dielectric performance of inorganic oxides through reduction of leakage current while maintaining similar capacitance to the underlying oxide structure. Rapid processing of this SAM in ambient conditions is achieved by spin coating, however, as-cast monolayer density is not sufficient for dielectric applications. Thermal annealing of a bulk spun-cast PhO-19-PA molecular film is explored as a mechanism for SAM densification. SAM density, or surface coverage, and order are examined as a function of annealing temperature. These SAM characteristics are probed through atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure spectroscopy (NEXAFS). It is found that at temperatures sufficient to melt the as-cast bulk molecular film, SAM densification is achieved; leading to a rapid processing technique for high performance SAM-oxide hybrid dielectric systems utilizing a single wet processing step. To demonstrate low-voltage devices based on this hybrid dielectric (with leakage current density of 7.7×10−8 A cm−2 and capacitance density of 0.62 µF cm−2 at 3 V), pentacene thin-film transistors (OTFTs) are fabricated and yield sub 2 V operation and charge carrier mobilites of up to 1.1 cm2 V−1 s−1. PMID:24288423

Thermal effects on electronic properties of CO/Pt(111) in water.

PubMed

Duan, Sai; Xu, Xin; Luo, Yi; Hermansson, Kersti; Tian, Zhong-Qun

2013-08-28

Structure and adsorption energy of carbon monoxide molecules adsorbed on the Pt(111) surfaces with various CO coverages in water as well as work function of the whole systems at room temperature of 298 K were studied by means of a hybrid method that combines classical molecular dynamics and density functional theory. We found that when the coverage of CO is around half monolayer, i.e. 50%, there is no obvious peak of the oxygen density profile appearing in the first water layer. This result reveals that, in this case, the external force applied to water molecules from the CO/Pt(111) surface almost vanishes as a result of the competitive adsorption between CO and water molecules on the Pt(111) surface. This coverage is also the critical point of the wetting/non-wetting conditions for the CO/Pt(111) surface. Averaged work function and adsorption energy from current simulations are consistent with those of previous studies, which show that thermal average is required for direct comparisons between theoretical predictions and experimental measurements. Meanwhile, the statistical behaviors of work function and adsorption energy at room temperature have also been calculated. The standard errors of the calculated work function for the water-CO/Pt(111) interfaces are around 0.6 eV at all CO coverages, while the standard error decreases from 1.29 to 0.05 eV as the CO coverage increases from 4% to 100% for the calculated adsorption energy. Moreover, the critical points for these electronic properties are the same as those for the wetting/non-wetting conditions. These findings provide a better understanding about the interfacial structure under specific adsorption conditions, which can have important applications on the structure of electric double layers and therefore offer a useful perspective for the design of the electrochemical catalysts.

Functional nicotinic acetylcholine receptor reconstitution in Au(111)-supported thiolipid monolayers

NASA Astrophysics Data System (ADS)

Pissinis, Diego E.; Diaz, Carolina; Maza, Eliana; Bonini, Ida C.; Barrantes, Francisco J.; Salvarezza, Roberto C.; Schilardi, Patricia L.

2015-09-01

The insertion and function of the muscle-type nicotinic acetylcholine receptor (nAChR) in Au(111)-supported thiolipid self-assembled monolayers have been studied by atomic force microscopy (AFM), surface plasmon resonance (SPR), and electrochemical techniques. It was possible for the first time to resolve the supramolecular arrangement of the protein spontaneously inserted in a thiolipid monolayer in an aqueous solution. Geometric supramolecular arrays of nAChRs were observed, most commonly in a triangular form compatible with three nAChR dimers of ~20 nm each. Addition of the full agonist carbamoylcholine activated and opened the nAChR ion channel, as revealed by the increase in capacitance relative to that of the nAChR-thiolipid system under basal conditions. Thus, the self-assembled system appears to be a viable biomimetic model to measure ionic conductance mediated by ion-gated ion channels under different experimental conditions, with potential applications in biotechnology and pharmacology.

Confinement effects on the miscibility of block copolymer blends.

PubMed

Spencer, Russell K W; Matsen, Mark W

2016-04-01

Thin films of long and short symmetric AB diblock copolymers are examined using self-consistent field theory (SCFT). We focus on hard confining walls with a preference for the A component, such that the lamellar domains orient parallel to the film with an even number ν of monolayers. For neat melts, confinement causes the lamellar period, D, to deviate from its bulk value, Db, in order to be commensurate with the film thickness, i.e., L = νD/2. For blends, however, the melt also has the option of macrophase separating into ν(l) large and ν((s)) small monolayers so as to provide a better fit, where L = ν(l)D(l)/2 + ν(s)D((s))/2. In addition to performing full SCFT calculations of the entire film, we develop a semi-analytical calculation for the coexistence of thick and thin monolayers that helps explain the complicated interplay between miscibility and commensurability.

Watching Electrons Transfer from Metals to Insulators using Two Photon Photoemission

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

Johns, James E.

2010-05-01

Ultrafast angle-resolved two photon photoemission was used to study the dynamics and interfacial band structure of ultrathin films adsorbed onto Ag(111). Studies focused on the image potential state (IPS) in each system as a probe for measuring changes in electronic behavior in differing environments. The energetics and dynamics of the IPS at the toluene/Ag(111) interface are strongly dependent upon coverage. For a single monolayer, the first IPS is bound by 0.81 eV below the vacuum level and has a lifetime of 50 femtoseconds (fs). Further adsorption of toluene creates islands of toluene with an exposed wetting layer underneath. The IPSmore » is then split into two peaks, one corresponding to the islands and one corresponding to the monolayer. The wetting layer IPS shows the same dynamics as the monolayer, while the lifetime of the islands increases exponentially with increasing thickness. Furthermore, the island IPS transitions from delocalized to localized within 500 fs, and electrons with larger parallel momenta decay much faster. Attempts were made using a stochastic model to extract the rates of localization and intraband cooling at differing momenta. In sexithiophene (6T) and dihexyl-sexithiophene (DH6T), the IPS was used as a probe to see if the nuclear motion of spectating side chains can interfere with molecular conduction. The energy and band mass of the IPS was measured for 6T and two geometries of DH6T on Ag(111). Electrons injected into the thicker coverages of DH6T grew exponentially heavier until they were completely localized by 230 fs, while those injected into 6T remained nearly free electron like. Based off of lifetime arguments and the density of defects, the most likely cause for the mass enhancement of the IPS in this system is small polaron formation caused by coupling of the electron to vibrations of the alkyl substituents. The energetic relaxation of the molecular adsorbate was also measured to be 20 meV/100 fs for the DH6T, and 0 meV/100 fs for the 6T. This relaxation is consistent with the localization of the charge creating a barrier for it moving from one lattice site to a neighboring one. Finally, the IPS was used to study the evolution of the surface band gap at the Mg/Ag(111) interface. The Mg(0001) surface band gap lies 1.6 eV below the Fermi level, and consequently shows no peak in the projected density of states for the IPS. A method for creating layer by layer growth of Mg on Ag(111) was determined using Auger Spectroscopy and low energy electron diffraction. By monitoring the decay of the intensity of the IPS versus coverage, it was determined that four layers of magnesium on Ag(111) is sufficient to completely eliminate the surface band gap« less

Spin-resolved band structure of a densely packed Pb monolayer on Si(111)

NASA Astrophysics Data System (ADS)

Brand, C.; Muff, S.; Fanciulli, M.; Pfnür, H.; Tringides, M. C.; Dil, J. H.; Tegenkamp, C.

2017-07-01

Monolayer structures of Pb on Si(111) attracted recently considerable interest as superconductivity was found in these truly two-dimensional (2D) structures. In this study, we analyzed the electronic surface band structure of the so-called striped incommensurate Pb phase with 4/3 ML coverage by means of spin-resolved photoemission spectroscopy. Our results fully agree with density functional theory calculations done by Ren et al. [Phys. Rev. B 94, 075436 (2016), 10.1103/PhysRevB.94.075436]. We observe a local Zeeman-type splitting of a fully occupied and spin-polarized surface band at the K¯√{3} points. The growth of this densely packed Pb structure results in the formation of imbalanced rotational domains, which triggered the detection of C3 v symmetry forbidden spin components for surface states around the Fermi energy. Moreover, the Fermi surface of the metallic surface state of this phase is Rashba spin split and revealed a pronounced warping. However, the 2D nesting vectors are incommensurate with the atomic structure, thus keeping this system rather immune against charge density wave formation and possibly enabling a superconducting behavior.

Resonance-mode electrochemical impedance measurements of silicon dioxide supported lipid bilayer formation and ion channel mediated charge transport.

PubMed

Lundgren, Anders; Hedlund, Julia; Andersson, Olof; Brändén, Magnus; Kunze, Angelika; Elwing, Hans; Höök, Fredrik

2011-10-15

A single-chip electrochemical method based on impedance measurements in resonance mode has been employed to study lipid monolayer and bilayer formation on hydrophobic alkanethiolate and SiO(2) substrates, respectively. The processes were monitored by temporally resolving changes in interfacial capacitance and resistance, revealing information about the rate of formation, coverage, and defect density (quality) of the layers at saturation. The resonance-based impedance measurements were shown to reveal significant differences in the layer formation process of bilayers made from (i) positively charged lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-ethylphosphocholine (POEPC), (ii) neutral lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) on SiO(2), and (iii) monolayers made from POEPC on hydrophobic alkanethiolate substrates. The observed responses were represented with an equivalent circuit, suggesting that the differences primarily originate from the presence of a conductive aqueous layer between the lipid bilayers and the SiO(2). In addition, by adding the ion channel gramicidin D to bilayers supported on SiO(2), channel-mediated charge transport could be measured with high sensitivity (resolution around 1 pA). © 2011 American Chemical Society

Reaction of hydrogen with Ag(111): binding states, minimum energy paths, and kinetics.

PubMed

Montoya, Alejandro; Schlunke, Anna; Haynes, Brian S

2006-08-31

The interaction of atomic and molecular hydrogen with the Ag(111) surface is studied using periodic density functional total-energy calculations. This paper focuses on the site preference for adsorption, ordered structures, and energy barriers for H diffusion and H recombination. Chemisorbed H atoms are unstable with respect to the H(2) molecule in all adsorption sites below monolayer coverage. The three-hollow sites are energetically the most favorable for H chemisorption. The binding energy of H to the surface decreases slightly up to one monolayer, suggesting a small repulsive H-H interaction on nonadjacent sites. Subsurface and vacancy sites are energetically less favorable for H adsorption than on-top sites. Recombination of chemisorbed H atoms leads to the formation of gas-phase H(2) with no molecular chemisorbed state. Recombination is an exothermic process and occurs on the bridge site with a pronounced energy barrier. This energy barrier is significantly higher than that inferred from experimental temperature-programmed desorption (TPD) studies. However, there is significant permeability of H atoms through the recombination energy barrier at low temperatures, thus increasing the rate constant for H(2) desorption due to quantum tunneling effects, and improving the agreement between experiment and theory.

Cost effectiveness of full coverage of the medical management of smoking cessation in France.

PubMed

Chevreul, Karine; Cadier, Benjamin; Durand-Zaleski, Isabelle; Chan, Elis; Thomas, Daniel

2014-05-01

To estimate the incremental cost effectiveness of full coverage of the medical management of smoking cessation from the perspective of statutory health insurance (SHI) in France. Cost-effectiveness analysis based on a Markov state-transition decision analytic model was used to compare full SHI coverage of smoking cessation and actual coverage based on an annual €50 lump sum per insured person among current French smokers aged 15-75 years. We used a scenario approach to take into account the many different behaviours of smokers and the likely variability of SHI policy choices in terms of participation rate and number and frequency of attempts covered. Drug treatments for smoking cessation combined with six medical consultations including individual counselling. The cost effectiveness of full coverage was expressed by the incremental cost-effectiveness ratio (ICER) in 2009 euros per life-year gained (LYG) at the lifetime horizon. The cost effectiveness per LYG for smokers ranged from €1786 to €2012, with an average value of €1911. The minimum value was very close to the maximum value with a difference of only €226. The cost-effectiveness ratio was only minimally sensitive to the participation rate, the number of attempts covered and the cessation rate. Compared to other health measures in primary and secondary prevention of cardiovascular disease already covered by SHI, full coverage of smoking cessation is the most cost-effective approach.

29 CFR 801.3 - Coverage.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 29 Labor 3 2013-07-01 2013-07-01 false Coverage. 801.3 Section 801.3 Labor Regulations Relating to... POLYGRAPH PROTECTION ACT OF 1988 General § 801.3 Coverage. (a) The coverage of the Act extends to “any... coverage to be coextensive with the full scope of the Congressional power to regulate commerce. See, for...

29 CFR 801.3 - Coverage.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 29 Labor 3 2014-07-01 2014-07-01 false Coverage. 801.3 Section 801.3 Labor Regulations Relating to... POLYGRAPH PROTECTION ACT OF 1988 General § 801.3 Coverage. (a) The coverage of the Act extends to “any... coverage to be coextensive with the full scope of the Congressional power to regulate commerce. See, for...

29 CFR 801.3 - Coverage.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 29 Labor 3 2011-07-01 2011-07-01 false Coverage. 801.3 Section 801.3 Labor Regulations Relating to... POLYGRAPH PROTECTION ACT OF 1988 General § 801.3 Coverage. (a) The coverage of the Act extends to “any... coverage to be coextensive with the full scope of the Congressional power to regulate commerce. See, for...

Improving catalytic selectivity through control of adsorption orientation

NASA Astrophysics Data System (ADS)

Pang, Simon H.

In this thesis, we present an investigation, starting from surface science experiments, leading to design of supported catalysts, of how adsorption orientation can be used to affect reaction selectivity of highly functional molecules. The surface chemistry of furfuryl alcohol and benzyl alcohol and their respective aldehydes was studied on a Pd(111) single-crystal surface under ultra-high vacuum conditions. Temperature-programmed desorption experiments showed that synergistic chemistry existed between the aromatic ring and the oxygen-containing functional group, each allowing the other to participate in reaction pathways that a monofunctional molecule could not. Most important of these was a deoxygenation reaction that occurred more readily when the surface was crowded by the highest exposures. High-resolution electron energy loss spectroscopy revealed that at these high exposures, molecules were oriented upright on the surface, with the aromatic function extending into vacuum. In contrast, at low exposures, molecules were oriented flat on the surface. The upright adsorption geometry was correlated with deoxygenation, whereas the flat-lying geometry was correlated with decarbonylation. The insight gained from surface science experiments was utilized in catalyst design. Self-assembled monolayers of alkanethiolates were used to systematically reduce the average surface ensemble size, and the reaction selectivity was tracked. When a sparsely-packed monolayer was used, such as one formed by 1-adamantanethiol, the reactant furfural was still able to lie flat on the surface and the reaction selectivity was similar to that of the uncoated catalyst. However, when a densely-packed monolayer, formed by 1-octadecanethiol, was used, furfural was not able to adsorb flat on the surface and instead adopted an upright conformation, leading to a drastic increase in aldehyde hydrogenation and hydrodeoxygenation reaction selectivity. Using an even higher sulfur coverage from a monolayer formed by 1,2-benzenedithiol, we determined that hydrodeoxygenation selectively occurred on catalyst particle steps and edges from an upright structure, whereas decarbonylation occurred on particle terraces from a flat-lying structure. Control of furfural adsorption orientation was also achieved through the use of NiCu bimetallic catalysts. The aromatic furan ring was repelled from surface Cu, leading to an upright structure. However, under hydrogenation conditions, Ni tended to be near the surface of thin films and catalysts, leading to less dramatic selectivity enhancement. The presence of a 1-octadecanethiol monolayer kinetically stabilized the surface termination, allowing Cu to remain at the surface.

Synchrotron X-Ray Diffraction Study of Structure and Growth of Adsorbed Layers

NASA Astrophysics Data System (ADS)

Dai, Pengcheng

Synchrotron x-ray diffraction and scanning-tunneling -microscopy (STM) experiments reveal a new commensurate monolayer structure of 10CB (decylcyanobiphenyl) molecules adsorbed on the (0001) graphite surface. Our results are consistent with two generic structures for nCB monolayers on surfaces of hexagonal symmetry. The monolayer d spacing of the new phase inferred by STM is 10% layer than that obtained by x-ray diffraction on the same sample. We suggest that part of this discrepancy results from a systematic error introduced in calibration of the STM length scale against the graphite substrate. For multilayer nCB films, we find that a polycrystalline structure is formed and most of the adsorbed molecules are aligned with their long axis perpendicular to the graphite surface. Synchrotron x-ray scattering has been used to investigate the structure and growth of xenon physisorbed on the Ag(111) surface using a specially designed ultra -high vacuum (UHV) chamber. For growth under quasi-equilibrium conditions, the bulk Xe-Xe spacing is reached at monolayer completion and solid films of thickness >= 220 A are observed in which an 'ABC' stacking sequence predominates. Under kinetic growth conditions, intensity oscillations at the Xe anti-Bragg position of the specular rod are observed as a function of time, indicating layer -by-layer growth. Analysis of the specular reflectivity at different coverages yields the fractional layer occupancies and the spacing between the Ag(111) surface and first Xe layer. We have conducted a series of low-energy electron diffraction (LEED) 'kinetic isotherm' experiments on both xenon and hexane rm(C_6H_{14 }) films adsorbed on the Ag(111) surface. Our preliminary results show that under the pressure and temperature range accessible to the experiments, all of the Xe kinetic isotherms fall on a universal curve which is concave upward. However, the hexane kinetic isotherms have a qualitatively different shape (S-like) at the higher temperatures while being similar to Xe at low temperatures. From these experiments, we determine that the growth of xenon from submonolayer to 0.9 monolayer is 'zero-order'. However, the growth of hexane is more complicated. It follows the 'first-order' at low temperatures, and changes to S-like shape at high temperatures which we do not yet understand.

Effects of the Affordable Care Act's Dependent Coverage Mandate on Private Health Insurance Coverage in Urban and Rural Areas.

PubMed

Look, Kevin A; Kim, Nam Hyo; Arora, Prachi

2017-01-01

To evaluate the impact of the Affordable Care Act's (ACA) dependent coverage mandate on insurance coverage among young adults in metropolitan and nonmetropolitan areas. A cross-sectional analysis was conducted using data from 2006-2009 and 2011 waves of the Medical Expenditure Panel Survey. A difference-in-difference analysis was used to compare changes in full-year private health insurance coverage among young adults aged 19-25 years with an older cohort aged 27-34 years. Separate regressions were estimated for individuals in metropolitan and nonmetropolitan areas and were tested for a differential impact by area of residence. Full-year private health insurance coverage significantly increased by 9.2 percentage points for young adults compared to the older cohort after the ACA mandate (P = .00). When stratifying the regression model by residence area, insurance coverage among young adults significantly increased by 9.0 percentage points in metropolitan areas (P = .00) and 10.1 percentage points in nonmetropolitan areas (P = .03). These changes were not significantly different from each other (P = .82), which suggests the ACA mandate's effects were not statistically different by area of residence. Although young adults in metropolitan and nonmetropolitan areas experienced increased access to private health insurance following the ACA's dependent coverage mandate, it did not appear to directly impact rural-urban disparities in health insurance coverage. Despite residents in both areas gaining insurance coverage, over one-third of young adults still lacked access to full-year health insurance coverage. © 2016 National Rural Health Association.

Effects of strain and thickness on the electronic and optical behaviors of two-dimensional hexagonal gallium nitride

NASA Astrophysics Data System (ADS)

Behzad, Somayeh

2017-06-01

The full potential linearized augmented plane wave (FP-LAPW) method within the framework of density functional theory has been used to study effects of strain and thickness on the electronic and optical properties of two-dimensional GaN. The band gap of monolayer and bilayer GaN under compressive in-plane strain change from indirect to direct with bond length shortening. Also, the semiconductor to semimetal transition occurs for monolayer and bilayer GaN under in-plane tensile strain with bond length elongation. It is found that the tensile and compressive strains cause the red and blue shifts in the optical spectra, respectively, for both monolayer and bilayer GaN. Applying the perpendicular strain on the bilayer GaN by decreasing the inter layer distance leads to the shift of valence band maximum towards the Γ point in the band structure and shift of peak positions and variation of peak intensities in ε2(ω) spectrum. The results show that the n-layer GaN has an indirect band gap for n < 16. The results suggest that monolayer and multilayer GaN are good candidates for application in optoelectronics and flexible electronics.

Peptide interfaces with graphene: an emerging intersection of analytical chemistry, theory, and materials.

PubMed

Russell, Shane R; Claridge, Shelley A

2016-04-01

Because noncovalent interface functionalization is frequently required in graphene-based devices, biomolecular self-assembly has begun to emerge as a route for controlling substrate electronic structure or binding specificity for soluble analytes. The remarkable diversity of structures that arise in biological self-assembly hints at the possibility of equally diverse and well-controlled surface chemistry at graphene interfaces. However, predicting and analyzing adsorbed monolayer structures at such interfaces raises substantial experimental and theoretical challenges. In contrast with the relatively well-developed monolayer chemistry and characterization methods applied at coinage metal surfaces, monolayers on graphene are both less robust and more structurally complex, levying more stringent requirements on characterization techniques. Theory presents opportunities to understand early binding events that lay the groundwork for full monolayer structure. However, predicting interactions between complex biomolecules, solvent, and substrate is necessitating a suite of new force fields and algorithms to assess likely binding configurations, solvent effects, and modulations to substrate electronic properties. This article briefly discusses emerging analytical and theoretical methods used to develop a rigorous chemical understanding of the self-assembly of peptide-graphene interfaces and prospects for future advances in the field.

Factors influencing full immunization coverage among 12-23 months of age children in Ethiopia: evidence from the national demographic and health survey in 2011.

PubMed

Lakew, Yihunie; Bekele, Alemayhu; Biadgilign, Sibhatu

2015-07-30

Immunization remains one of the most important public health interventions to reduce child morbidity and mortality. The 2011 national demographic and health survey (DHS) indicated low full immunization coverage among children aged 12-23 months in Ethiopia. Factors contributing to the low coverage of immunization have been poorly understood. The aim of this study was to identify factors associated with full immunization coverage among children aged 12-23 months in Ethiopia. This study used the 2011 Ethiopian demographic and health survey data. The survey was cross sectional by design and used a multistage cluster sampling procedure. A total of 1,927 mothers with children of 12-23 months of age were extracted from the children's dataset. Mothers' self-reported data and observations of vaccination cards were used to determine vaccine coverage. An adjusted odds ratio (AOR) with 95% confidence intervals (CI) was used to outline the independent predictors. The prevalence of fully immunized children was 24.3%. Specific vaccination coverage for three doses of DPT, three doses of polio, measles and BCG were 36.5%, 44.3%, 55.7% and 66.3%, respectively. The multivariable analysis showed that sources of information from vaccination card [AOR 95% CI; 7.7 (5.95-10.06)], received postnatal check-up within two months after birth [AOR 95% CI; 1.8 (1.28-2.56)], women's awareness of community conversation program [AOR 95% CI; 1.9 (1.44-2.49)] and women in the rich wealth index [AOR 95% CI; 1.4 (1.06-1.94)] were the predictors of full immunization coverage. Women from Afar [AOR 95% CI; 0.07 (0.01-0.68)], Amhara [AOR 95% CI; 0.33 (0.13-0.81)], Oromiya [AOR 95% CI; 0.15 (0.06-0.37)], Somali [AOR 95% CI; 0.15 (0.04-0.55)] and Southern Nation and Nationalities People administrative regions [AOR 95% CI; 0.35 (0.14-0.87)] were less likely to fully vaccinate their children. The overall full immunization coverage in Ethiopia was considerably low as compared to the national target set (66%). Health service use and access to information on maternal and child health were found to predict full immunization coverage. Appropriate strategies should be devised to enhance health information and accessibility for full immunization coverage by addressing the variations among regions.

Structural and electronic properties of AlN(0001) surface under partial N coverage as determined by ab initio approach

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

Strak, Pawel; Sakowski, Konrad; Kempisty, Pawel

2015-09-07

Properties of bare and nitrogen-covered Al-terminated AlN(0001) surface were determined using density functional theory (DFT) calculations. At a low nitrogen coverage, the Fermi level is pinned by Al broken bond states located below conduction band minimum. Adsorption of nitrogen is dissociative with an energy gain of 6.05 eV/molecule at a H3 site creating an overlap with states of three neighboring Al surface atoms. During this adsorption, electrons are transferred from Al broken bond to topmost N adatom states. Accompanying charge transfer depends on the Fermi level. In accordance with electron counting rule (ECR), the DFT results confirm the Fermi levelmore » is not pinned at the critical value of nitrogen coverage θ{sub N}(1) = 1/4 monolayer (ML), but it is shifted from an Al-broken bond state to Np{sub z} state. The equilibrium thermodynamic potential of nitrogen in vapor depends drastically on the Fermi level pinning being shifted by about 4 eV for an ECR state at 1/4 ML coverage. For coverage above 1/4 ML, adsorption is molecular with an energy gain of 1.5 eV at a skewed on-top position above an Al surface atom. Electronic states of the admolecule are occupied as in the free molecule, no electron transfer occurs and adsorption of a N{sub 2} molecule does not depend on the Fermi level. The equilibrium pressure of molecular nitrogen above an AlN(0001) surface depends critically on the Fermi level position, being very low and very high for low and high coverage, respectively. From this fact, one can conclude that at typical growth conditions, the Fermi level is not pinned, and the adsorption and incorporation of impurities depend on the position of Fermi level in the bulk.« less

Rheology and microrheology of materials at the air-water interface

NASA Astrophysics Data System (ADS)

Walder, Robert Benjamin

2008-10-01

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

48 CFR 9903.201-2 - Types of CAS coverage.

Code of Federal Regulations, 2010 CFR

2010-10-01

.... 9903.201-2 Section 9903.201-2 Federal Acquisition Regulations System COST ACCOUNTING STANDARDS BOARD... ACCOUNTING STANDARDS CONTRACT COVERAGE CAS Program Requirements 9903.201-2 Types of CAS coverage. (a) Full... net CAS-covered awards during its preceding cost accounting period. (b) Modified coverage. (1...

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

PubMed Central

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

2002-01-01

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

Fabrication of Supramolecular Chirality from Achiral Molecules at the Liquid/Liquid Interface Studied by Second Harmonic Generation.

PubMed

Lin, Lu; Zhang, Zhen; Guo, Yuan; Liu, Minghua

2018-01-09

We present the investigation into the supramolecular chirality of 5-octadecyloxy-2-(2-pyridylazo)phenol (PARC18) at water/1,2-dichloroethane interface by second harmonic generation (SHG). We observe that PARC18 molecules form supramolecular chirality through self-assembly at the liquid/liquid interface although they are achiral molecules. The bulk concentration of PARC18 in the organic phase has profound effects on the supramolecular chirality. By increasing bulk concentration, the enantiomeric excess at the interface first grows and then decreases until it eventually vanishes. Further analysis reveals that the enantiomeric excess is determined by the twist angle of PARC18 molecules at the interface rather than their orientational angle. At lower and higher bulk concentrations, the average twist angle of PARC18 molecules approaches zero, and the assemblies are achiral; whereas at medium bulk concentrations, the average twist angle is nonzero, so that the assemblies show supramolecular chirality. We also estimate the coverage of PARC18 molecules at the interface versus the bulk concentration and fit it to Langmuir adsorption model. The result indicates that PARC18 assemblies show strongest supramolecular chirality in a half-full monolayer. These findings highlight the opportunities for precise control of supramolecular chirality at liquid/liquid interfaces by manipulating the bulk concentration.

Molecular adsorption and multilayer growth of pentacene on Cu(100):Layer structure and energetics

NASA Astrophysics Data System (ADS)

Satta, M.; Iacobucci, S.; Larciprete, R.

2007-04-01

We used the partial charge tight binding method to perform a full structure optimization to determine equilibrium adsorption geometries, energetics, and local charge redistribution for molecular adsorption and multilayer growth of pentacene on Cu(100). We found that single molecule adsorption induces only a localized perturbation of the metal lattice which is limited to the topmost layers. At saturation coverage four stable topologies (Brick, Wave, Lines and Zigzag) were identified, all based on pentacene molecules lying flat on the metal surface and with the central phenyl ring adsorbed in top position. Only two (Brick and Wave) out of the four structures are able to sustain multilayer growth. In both cases, assembling beyond the second layer corresponds to a transition from the flat to a tilted geometry, in which the pentacenes adopt a face-plane-face arrangement leading to a herringbone structure. The energetics of the different structure are reported as a function of the molecular number density of the pentacene multilayer by calculating cohesive, stress, and electrostatic energies. The dominant tilted molecular orientation in the pentacene multilayer is in agreement with the average tilt angle of 65° between the molecular plane and the Cu surface derived by near edge x-ray absorption spectroscopy of a four monolayer pentacene film deposited on Cu(100).

In situ preparation, electrical and surface analytical characterization of pentacene thin film transistors

PubMed Central

Lassnig, R.; Striedinger, B.; Hollerer, M.; Fian, A.; Stadlober, B.; Winkler, A.

2015-01-01

The fabrication of organic thin film transistors with highly reproducible characteristics presents a very challenging task. We have prepared and analyzed model pentacene thin film transistors under ultra-high vacuum conditions, employing surface analytical tools and methods. Intentionally contaminating the gold contacts and SiO2 channel area with carbon through repeated adsorption, dissociation, and desorption of pentacene proved to be very advantageous in the creation of devices with stable and reproducible parameters. We mainly focused on the device properties, such as mobility and threshold voltage, as a function of film morphology and preparation temperature. At 300 K, pentacene displays Stranski-Krastanov growth, whereas at 200 K fine-grained, layer-like film growth takes place, which predominantly influences the threshold voltage. Temperature dependent mobility measurements demonstrate good agreement with the established multiple trapping and release model, which in turn indicates a predominant concentration of shallow traps in the crystal grains and at the oxide-semiconductor interface. Mobility and threshold voltage measurements as a function of coverage reveal that up to four full monolayers contribute to the overall charge transport. A significant influence on the effective mobility also stems from the access resistance at the gold contact-semiconductor interface, which is again strongly influenced by the temperature dependent, characteristic film growth mode. PMID:25814770

In situ preparation, electrical and surface analytical characterization of pentacene thin film transistors

NASA Astrophysics Data System (ADS)

Lassnig, R.; Striedinger, B.; Hollerer, M.; Fian, A.; Stadlober, B.; Winkler, A.

2014-09-01

The fabrication of organic thin film transistors with highly reproducible characteristics presents a very challenging task. We have prepared and analyzed model pentacene thin film transistors under ultra-high vacuum conditions, employing surface analytical tools and methods. Intentionally contaminating the gold contacts and SiO2 channel area with carbon through repeated adsorption, dissociation, and desorption of pentacene proved to be very advantageous in the creation of devices with stable and reproducible parameters. We mainly focused on the device properties, such as mobility and threshold voltage, as a function of film morphology and preparation temperature. At 300 K, pentacene displays Stranski-Krastanov growth, whereas at 200 K fine-grained, layer-like film growth takes place, which predominantly influences the threshold voltage. Temperature dependent mobility measurements demonstrate good agreement with the established multiple trapping and release model, which in turn indicates a predominant concentration of shallow traps in the crystal grains and at the oxide-semiconductor interface. Mobility and threshold voltage measurements as a function of coverage reveal that up to four full monolayers contribute to the overall charge transport. A significant influence on the effective mobility also stems from the access resistance at the gold contact-semiconductor interface, which is again strongly influenced by the temperature dependent, characteristic film growth mode.

A transparent projection screen based on plasmonic Ag nanocubes

NASA Astrophysics Data System (ADS)

Saito, Koichiro; Tatsuma, Tetsu

2015-12-01

A transparent and colourless projection screen is fabricated by depositing a silver nanocube sub-monolayer on a titania thin film. Backward scattering of the silver nanocubes is enhanced by titania in the blue and red regions, to which human eyes are less sensitive. As a result, this screen, which is cost-effective even for large areas, allows projection of full colour images.A transparent and colourless projection screen is fabricated by depositing a silver nanocube sub-monolayer on a titania thin film. Backward scattering of the silver nanocubes is enhanced by titania in the blue and red regions, to which human eyes are less sensitive. As a result, this screen, which is cost-effective even for large areas, allows projection of full colour images. Electronic supplementary information (ESI) available: Preparation of Ag nanocubes, calculated values for a Ag nanocube on TiO2 (Tables S1 and S2). See DOI: 10.1039/c5nr06766a

Changes in health insurance for US children and their parents: comparing 2003 to 2008.

PubMed

Angier, Heather; DeVoe, Jennifer E; Tillotson, Carrie; Wallace, Lorraine

2013-01-01

Recent policy changes have affected access to health insurance for families in the United States. Private health insurance premiums have increased, and state Medicaid programs have cut back coverage for adults. Concurrently, the Children's Health Insurance Program has made public insurance available to more children. We aimed to better understand how child and parent health insurance coverage patterns may have changed as a result of these policies. We analyzed data from the nationally representative Medical Expenditure Panel Survey, comparing cohorts from 2003 and 2008. We assessed cross-sectional and full-year coverage patterns for child/parent pairs, stratified by income. We conducted chi-square tests to assess significant differences in coverage over time. Middle-income child/parent pairs had the most significant changes in their coverage patterns. For example, those with full-year health insurance coverage significantly decreased from 85.4% in 2003 to 80.6% in 2008. There was also an increase in uninsured middle-income child/parent pairs for the full year (5.6% in 2003 to 8.3% in 2008) and an increase in pairs who had a gap in coverage (9.7% in 2003 to 13.0% in 2008). The percentage of middle-income child/parent pairs who were lacking insurance, for part or all of the year, has risen, suggesting that these families may be caught between affording private coverage and being eligible for public coverage. Unless private coverage becomes more affordable, insurance instability among middle-income families may persist despite the passage of the Patient Protection and Affordable Care Act.

Molecule signatures in photoluminescence spectra of transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Feierabend, Maja; Berghäuser, Gunnar; Selig, Malte; Brem, Samuel; Shegai, Timur; Eigler, Siegfried; Malic, Ermin

2018-01-01

Monolayer transition metal dichalcogenides (TMDs) show an optimal surface-to-volume ratio and are thus promising candidates for novel molecule sensor devices. It was recently predicted that a certain class of molecules exhibiting a large dipole moment can be detected through the activation of optically inaccessible (dark) excitonic states in absorption spectra of tungsten-based TMDs. In this paper, we investigate the molecule signatures in photoluminescence spectra in dependence of a number of different experimentally accessible quantities, such as excitation density, temperature, as well as molecular characteristics including the dipole moment and its orientation, molecule-TMD distance, molecular coverage, and distribution. We show that under certain optimal conditions even room-temperature detection of molecules can be achieved.

Size quantization patterns in self-assembled InAs/GaAs quantum dots

NASA Astrophysics Data System (ADS)

Colocci, M.; Bogani, F.; Carraresi, L.; Mattolini, R.; Bosacchi, A.; Franchi, S.; Frigeri, P.; Taddei, S.; Rosa-Clot, M.

1997-07-01

Molecular beam epitaxy has been used for growing self-assembled InAs quantum dots. A continuous variation of the InAs average coverage across the sample has been obtained by properly aligning the (001) GaAs substrate with respect to the molecular beam. Excitation of a large number of dots (laser spot diameter ≈ 100 μm) results in structured photoluminescence spectra; a clear quantization of the dot sizes is deduced from the distinct luminescence bands separated in energy by an average spacing of 20-30 meV. We ascribe the individual bands of the photoluminescence spectrum after low excitation to families of dots with roughly the same diameter and heights differing by one monolayer.

Formation mechanism of human serum albumin monolayers on positively charged polymer microparticles.

PubMed

Nattich-Rak, Małgorzata; Sadowska, Marta; Adamczyk, Zbigniew; Cieśla, Michał; Kąkol, Małgorzata

2017-11-01

Human serum albumin (HSA) adsorption on positively and negatively charged polystyrene microparticles was studied at various pHs and NaCl concentrations. Thorough electrophoretic mobility measurements were carried out that enabled to monitor in situ the progress of protein adsorption. The maximum coverage of irreversibly adsorbed HSA on microparticles was determined by different concentration depletion methods, one of them involving AFM imaging of residual molecules. An anomalous adsorption of HSA on the positive microparticles was observed at pH 3.5 where the maximum coverage attained 1.0mgm -2 for NaCl concentrations of 0.05M despite that the molecules were on average positively charged. For comparison, the maximum coverage of HSA on negatively charged microparticles was equal to 1.3mgm -2 at this pH and NaCl concentration. At pH 7.4 the maximum coverage on positive microparticles was equal to 2.1mgm -2 for 0.05M NaCl concentration. On the other hand, for negative microparticles, negligible adsorption of HSA was observed at pH 7.4 and 9.7. These experimental data were adequately interpreted in terms of the random sequential adsorption approach exploiting the bead model of the HSA molecule. Different orientations of adsorbed molecules, inert alia, the edge-on orientation prevailing for positively charged microparticles at pH 7.4, were confirmed. This was explained in terms of a heterogeneous charge distribution over the HSA molecule prevailing for a wide range of pHs. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Silicon incorporation in GaAs: From delta-doping to monolayer insertion

NASA Astrophysics Data System (ADS)

Wagner, J.; Newman, R. C.; Roberts, C.

1995-08-01

Raman spectroscopy was used to study the incorporation of Si into doping layers in GaAs, grown by molecular beam epitaxy at a temperature of 400 °C, for Si concentrations ranging from the δ-doping level to a ML coverage. The strength of the scattering by local vibrational modes of substitutional Si was almost constant for Si areal concentration [Si]A in the range 5×1012<[Si]A<5×1013 cm-2 but then decreased, dropping below the detection limit for [Si]A≳3×1014 cm-2. At these concentrations a new vibrational band emerged at a frequency close to 470 cm-1 and developed into the optic zone center phonon of a coherently strained epitaxial layer of Si embedded in GaAs when a coverage of ≊1.5 ML (9.3×1014 cm-2) was reached. These findings strongly indicate that the observed saturation and the eventual decrease of the concentration of substitutional silicon is caused by an increasing incorporation of deposited Si into two-dimensional islands of covalently bonded Si.

The effect of the surface composition of Ru-Pt bimetallic catalysts for methanol oxidation

DOE PAGES

Garrick, Taylor R.; Diao, Weijian; Tengco, John M.; ...

2016-02-23

Here, a series of Ru-Pt bimetallic catalysts prepared by the electroless deposition of controlled and variable amounts of Ru on the Pt surface of a commercially-available 20 wt% Pt/C catalyst has been characterized and evaluated for the oxidation of methanol. The activity of each Ru-Pt catalyst was determined as a function of surface composition via cyclic voltammetry. For the Ru-Pt bimetallic catalysts, activity passed through a maximum at approximately 50% monodisperse Ru surface coverage. However, due to the monolayer coverage of Ru on Pt, the amount of metal in the catalyst is minimized compared to a bulk 1:1 atomic ratiomore » of Ru:Pt seen in commercial bimetallic catalysts. Chemisorption and temperature programmed reduction experiments confirmed that the surface had characteristics of a true bimetallic catalyst. On a mass of Pt basis, the activity of this composition for methanol oxidation was 7 times higher than pure Pt and 3.5 times higher than a commercial catalyst with a 1:1 Pt:Ru bulk atomic ratio.« less

Magneto-optic superlattice thin films: Fabrication, structural and magnetic characterization

NASA Technical Reports Server (NTRS)

Falco, C. M.; Engel, B. N.; Vanleeuwen, R. A.; Yu, J.

1993-01-01

During this quarter studies were extended to determine the electronic contribution to the perpendicular interface anisotropy in Co-based multilayers. Using in situ Kerr effect measurements, the influences of different transition metals (TM = Ag, Au, Cu, and Pd) on the magnetic properties of single-crystal Co films grown on Pd (111) and Au (111) surfaces are investigated. Last quarter the discovery of a large peak in the perpendicular anisotropy when approximately one monolayer of Cu or Ag is deposited on the Co surface was reported. We now have added a computer-controlled stepper-motor drive to our MBE sample transfer mechanism. The motor allows us to move the sample at a constant velocity from behind a shutter during deposition. The film, therefore, is deposited as a wedge with a linear variation of thickness across the substrate. In this way, a continuous range of coverage on a single sample is studied. The stepper motor also provides the necessary control for precisely positioning the sample in the laser beam for Kerr effect measurements at the different coverages.

Dynamic in-plane potential gradients for actively controlling electrochemical reactions: Part I. Characterization of 1- and 2-component alkanethiol monolayer gradients on thin gold films. Part II. Applications of in-plane potential gradients

NASA Astrophysics Data System (ADS)

Balss, Karin Maria

The research contained in this thesis is focused on the formation and characterization of surface composition gradients on thin gold films that are formed by applications of in-plane potential gradients. Injecting milliamp currents into thin Au films yields significant in-plane voltage drops so that, rather than assuming a single value of potential, an in-plane potential gradient is imposed on the film which depends on the resistivity of the film, the cross sectional area and the magnitude of the potential drop. Furthermore, the in-plane electric potential gradient means that, relative to a solution reference couple, electrochemical reactions occurs at defined spatial positions corresponding to the local potential, V(x) ˜ E0. The spatial gradient in electrochemical potential can then produce spatially dependent electrochemistry. Surface-chemical potential gradients can be prepared by arranging the spread of potentials to span an electrochemical wave mediating redox-associated adsorption or desorption. Examples of reactions that can be spatially patterned include the electrosorption of alkanethiols and over-potential metal deposition. The unique advantage of this method for patterning spatial compositions is the control of surface coverage in both space and time. The thesis is organized into two parts. In Part I, formation and characterization of 1- and 2-component alkanethiol monolayer gradients is investigated. Numerous surface science tools are employed to examine the distribution in coverage obtained by application of in-plane potential gradients. Macroscopic characterization was obtained by sessile water drop contact angle measurements and surface plasmon resonance imaging. Gradients were also imaged on micron length scales with pulsed-force mode atomic force microscopy. Direct chemical evidence of surface compositions in aromatic thiol surface coverage was obtained by surface-enhanced Raman spectroscopy. In Part II, the applications of in-plane potential gradients is discussed. Electrochemical reactions other than electrosorption of alkanethiols were demonstrated with over-potential deposition of copper onto gold films. One application of these patterns is to control the movement of supermolecular objects. As a first step towards this goal, biological cells were seeded onto gradient patterns containing adhesion promoters and inhibitors. The morphology and adhesion was investigated as a function of concentration along the gradient.

The structural and electronic properties of cleaved silicon (111) surfaces following adsorption of silver

NASA Astrophysics Data System (ADS)

Le Lay, G.; Chauvet, A.; Manneville, M.; Kern, R.

Silver overlayers for coverages ranging from zero to several monolayers are evaporated on vacuum-cleaved (111) silicon surfaces and carefully examined using low-energy electron diffraction (diffraction patterns and I(v) curves), and Auger electron spectroscopy (condensation/desorption curves), with the aim of establishing a closer correlation between the adsorption process, the different superlattices observed (i.e. 7 × 7-R(±19°1), 3 × 3-R(30° ), 3 × 1 and 6 × 1), the growth mechanism of the deposit on the one hand and the electronic properties of the system recently probed using photoemission yield spectroscopy on the other hand. These new results basically confirm the direct relations we had previously shown between the growth mode as monitored with electron diffraction LEED, RHEED, TED and Auger spectroscopy, and the electronic structures as investigated by low energy electron spectroscopy, but permit a deeper insight into the adsorption process at low coverage. At room temperature on the 2 × 1 cleavage structure where the silver-silicon interaction is weak, the adsorbed phase is completed at about 6/7 of a monolayer (θ ≃ 6/7) and a local arrangement of vacancies in the adlayer yields the 7 superstructure, while little effect on the silicon dangling bonds is noticed, but when silver two-dimensional islands (θ > 6/7) growing in a quasi layer fashion have covered the substrate surface. At higher temperatures three-dimensional growth of crystallites occurs after completion of the 3 phase whose saturation coverage increases with condensation temperatures, maxima ranging from θ ˜ 0.7 to θ ˜ 1.0 ( T ˜ 500°C) for different cleaves. This Si(111) 3-Ag surface exhibits again the same dangling bond peak as a clean 2 × 1 Si surface, despite the fact that the interaction between Ag and Si is now rather strong, as is confirmed by desorption experiments ( T ˜ 600°C). We thus critically discuss the geometrical models of this 3 phase previously devised and tentatively propose a new one which accounts better for these recent results, along with models of the 3 × 1 and 6 × 1 structures observed in the course of the desorption process.

Evaluation of a vaccine passport to improve vaccine coverage in people living with HIV.

PubMed

Chadwick, D R; Corbett, K; Mann, S; Teruzzi, B; Horner, S

2018-01-01

An increased risk of vaccine-preventable infections (VPIs) is seen in people living with HIV (PLWH), and current vaccine coverage and immunity is variable. Vaccine passports have the potential to improve vaccine coverage. The objective was to assess how successful a vaccine passport was in improving vaccine coverage in PLWH. Baseline immunity to VPIs was established in PLWH attending a single HIV clinic and vaccinations required were determined based on the BHIVA Vaccination Guidelines (2015). The passport was completed and the PLWH informed about additional vaccines they should obtain from primary care. After 6-9 months the passport was reviewed including confirmation if vaccines were given. PLWH satisfaction with the system was evaluated by a survey. Seventy-three PLWH provided sufficient data for analysis. At baseline significant proportions of PLWH were not immune/unvaccinated to the main VPIs, especially human papillomavirus, pneumococcus and measles. After the passport was applied immunity improved significantly (56% overall, p < 0.01) for most VPIs; however, full coverage was not achieved. The system was popular with PLWH. The passport was successful in increasing vaccination coverage although full or near-full coverage was not achieved. A more successful service would probably be achieved by commissioning English HIV clinics to provide all vaccines.

A kinetic model of the formation of organic monolayers on hydrogen-terminated silicon by hydrosilation of alkenes.

PubMed

Woods, M; Carlsson, S; Hong, Q; Patole, S N; Lie, L H; Houlton, A; Horrocks, B R

2005-12-22

We have analyzed a kinetic model for the formation of organic monolayers based on a previously suggested free radical chain mechanism for the reaction of unsaturated molecules with hydrogen-terminated silicon surfaces (Linford, M. R.; Fenter, P. M.; Chidsey, C. E. D. J. Am. Chem. Soc 1995, 117, 3145). A direct consequence of this mechanism is the nonexponential growth of the monolayer, and this has been observed spectroscopically. In the model, the initiation of silyl radicals on the surface is pseudo first order with rate constant, ki, and the rate of propagation is determined by the concentration of radicals and unreacted Si-H nearest neighbor sites with a rate constant, kp. This propagation step determines the rate at which the monolayer forms by addition of alkene molecules to form a track of molecules that constitute a self-avoiding random walk on the surface. The initiation step describes how frequently new random walks commence. A termination step by which the radicals are destroyed is also included. The solution of the kinetic equations yields the fraction of alkylated surface sites and the mean length of the random walks as a function of time. In mean-field approximation we show that (1) the average length of the random walk is proportional to (kp/ki)1/2, (2) the monolayer surface coverage grows exponentially only after an induction period, (3) the effective first-order rate constant describing the growth of the monolayer and the induction period (kt) is k = (2ki kp)1/2, (4) at long times the effective first-order rate constant drops to ki, and (5) the overall activation energy for the growth kinetics is the mean of the activation energies for the initiation and propagation steps. Monte Carlo simulations of the mechanism produce qualitatively similar kinetic plots, but the mean random walk length (and effective rate constant) is overestimated by the mean field approximation and when kp > ki, we find k approximately ki0.7kp0.3 and Ea = (0.7Ei+ 0.3Ep). However the most striking prediction of the Monte Carlo simulations is that at long times, t > 1/k, the effective first-order rate constant decreases to ki even in the absence of a chemical termination step. Experimental kinetic data for the reaction of undec-1-ene with hydrogen-terminated porous silicon under thermal reflux in toluene and ethylbenzene gave a value of k = 0.06 min(-1) and an activation energy of 107 kJ mol(-1). The activation energy is in reasonable agreement with density functional calculations of the transition state energies for the initiation and propagation steps.

Structure and Dynamics of Forsterite-scCO2/H2O Interfaces as a Function of Water Content

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

Kerisit, Sebastien N.; Weare, John H.; Felmy, Andrew R.

Molecular dynamics (MD) simulations of forsterite surfaces in contact with supercritical carbon dioxide (scCO2) fluids of varying water content were performed to determine the partition of water between the scCO2 fluid and the mineral surface, the nature of CO2 and H2O bonding at the interface, and the regions of the interface that may be conducive to HxCO3(2-x)- formation. Calculations of the free energy of the associative adsorption of water onto the (010) forsterite surface from the scCO2 phase indicated that the formation of a water film up to three-monolayer thick can be exothermic even for water contents below the watermore » saturation concentration of the scCO2 fluid. In MD simulations of scCO2/H2O mixtures in contact with the (010) forsterite surface, H2O was found to readily displace CO2 at the surface and, therefore, CO2 directly contacted the surface only for water coverages below two monolayers. For thicker water films, a two-monolayer hydration layer formed that CO2 could not penetrate. Simulations of the hydroxylated (010) surface and of the (011) surface suggested that this conclusion can be extended to forsterite surfaces with different surface structures and/or compositions. The density, diffusion, and degree of hydration of CO2 as well as the extent of CO2/H2O mixing at the interface were all predicted to depend strongly on the thickness of the water-rich film, i.e., on the water content of the scCO2 fluid.« less

Method of making maximally dispersed heterogeneous catalysts

DOEpatents

Jennison, Dwight R [Albuquerque, NM

2005-11-15

A method of making a catalyst with monolayer or sub-monolayer metal by controlling the wetting characteristics on the support surface and increasing the adhesion between the catalytic metal and an oxide layer. There are two methods that have been demonstrated by experiment and supported by theory. In the first method, which is useful for noble metals as well as others, a negatively-charged species is introduced to the surface of a support in sub-ML coverage. The layer-by-layer growth of metal deposited onto the oxide surface is promoted because the adhesion strength of the metal-oxide interface is increased. This method can also be used to achieve nanoislands of metal upon sub-ML deposition. The negatively-charged species can either be deposited onto the oxide surface or a compound can be deposited that dissociates on, or reacts with, the surface to form the negatively-charged species. The deposited metal adatoms can thereby bond laterally to the negatively-charged species as well as vertically to the oxide surface. Thus the negatively-charged species serve as anchors for the metal. In the second method, a chemical reaction that occurs when most metals are deposited on a fully hydroxylated oxide surface is used to create cationic metal species that bind strongly both to the substrate and to metallic metal atoms. These are incorporated into the top layer of the substrate and bind strongly both to the substrate and to metallic metal atoms. In this case, these oxidized metal atoms serve as the anchors. Here, as in the previous method, nanoislands of catalytic metal can be achieved to increase catalytic activity, or monolayers or bilayers of reactive metal can also be made.

Film growth, adsorption and desorption kinetics of indigo on SiO2

PubMed Central

Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

2015-01-01

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer des orption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption. PMID:24832297

Film growth, adsorption and desorption kinetics of indigo on SiO{sub 2}

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

Scherwitzl, Boris, E-mail: b.scherwitzl@tugraz.at; Resel, Roland; Winkler, Adolf

2014-05-14

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation ofmore » dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.« less

Film growth, adsorption and desorption kinetics of indigo on SiO2.

PubMed

Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

2014-05-14

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.

Marangoni Effects of a Drop in an Extensional Flow: The Role of Surfactant Physical Chemistry

NASA Technical Reports Server (NTRS)

Stebe, Kathleen J.; Balasubramaniam, R. (Technical Monitor)

2002-01-01

While the changes in stresses caused by surfactant adsorption on non-deforming interfaces have been fairly well established, prior to this work, there were few studies addressing how surfactants alter stresses on strongly deforming interfaces. We chose the model problem of a drop in a uniaxial extensional flow to study these stress conditions To model surfactant effects at fluid interfaces, a proper description of the dependence of the surface tension on surface concentration, the surface equation of state, is required. We have adopted a surface equation of state that accounts for the maximum coverage limit; that is, because surfactants have a finite cross sectional area, there is an upper bound to the amount of surfactant that can adsorb in a monolayer. The surface tension reduces strongly only when this maximum coverage is approached. Since the Marangoni stresses go as the derivative of the surface equation of state times the surface concentration gradient, the non-linear equation of state determines both the effect of surfactants in the normal stress jump, (which is balanced by the product of the mean curvature of the interface times the surface tension), and the tangential stress jump, which is balanced by Marangoni stresses. First, the effects of surface coverage and intermolecular interactions among surfactants which drive aggregation of surfactants in the interface were studied. (see Pawar and Stebe, Physics of Fluids).

Adsorption of small hydrocarbons on rutile TiO2(110)

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

Chen, Long; Smith, R. Scott; Kay, Bruce D.

2016-08-01

Temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes with 1 - 4 carbon atoms of C1-C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of an additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar tomore » previous studies on the adsorption of n-alkanes on metal and metal oxide surfaces, we find the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2-C4 hydrocarbons are found nearly independent of the chain length with values of ~1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.« less

Adsorption of small hydrocarbons on rutile TiO 2(110)

DOE PAGES

Chen, Long; Smith, R. Scott; Kay, Bruce D.; ...

2015-11-21

Here, temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes of C 1–C 4) on rutile TiO 2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti 5c sites. Similar to previous studiesmore » on the adsorption of n-alkanes on metal and metal oxide surfaces, we find that the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti 5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti 5c sites were also determined. The saturation coverage of CH 4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C 2–C 4 hydrocarbons are found nearly independent of the chain length with values of ~ 1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.« less

Atom-Dependent Edge-Enhanced Second-Harmonic Generation on MoS2 Monolayers.

PubMed

Lin, Kuang-I; Ho, Yen-Hung; Liu, Shu-Bai; Ciou, Jian-Jhih; Huang, Bo-Ting; Chen, Christopher; Chang, Han-Ching; Tu, Chien-Liang; Chen, Chang-Hsiao

2018-02-14

Edge morphology and lattice orientation of single-crystal molybdenum disulfide (MoS 2 ) monolayers, a transition metal dichalcogenide (TMD), possessing a triangular shape with different edges grown by chemical vapor deposition are characterized by atomic force microscopy and transmission electron microscopy. Multiphoton laser scanning microscopy is utilized to study one-dimensional atomic edges of MoS 2 monolayers with localized midgap electronic states, which result in greatly enhanced optical second-harmonic generation (SHG). Microscopic S-zigzag edge and S-Mo Klein edge (bare Mo atoms protruding from a S-zigzag edge) terminations and the edge-atom dependent resonance energies can therefore be deduced based on SHG images. Theoretical calculations based on density functional theory clearly explain the lower energy of the S-zigzag edge states compared to the corresponding S-Mo Klein edge states. Characterization of the atomic-scale variation of edge-enhanced SHG is a step forward in this full-optical and high-yield technique of atomic-layer TMDs.

Silver nanocube aggregation gradient materials in search for total internal reflection with high phase sensitivity

NASA Astrophysics Data System (ADS)

König, Tobias A. F.; Ledin, Petr A.; Russell, Michael; Geldmeier, Jeffrey A.; Mahmoud, Mahmoud. A.; El-Sayed, Mostafa A.; Tsukruk, Vladimir V.

2015-03-01

We fabricated monolayer coatings of a silver nanocube aggregation to create a step-wise optical strip by applying different surface pressures during slow Langmuir-Blodgett deposition. The varying amount of randomly distributed nanocube aggregates with different surface coverages in gradient manner due to changes in surface pressure allows for continuous control of the polarization sensitive absorption of the incoming light over a broad optical spectrum. Optical characterization under total internal reflection conditions combined with electromagnetic simulations reveal that the broadband light absorption depends on the relative orientation of the nanoparticles to the polarization of the incoming light. By using computer simulations, we found that the electric field vector of the s-polarized light interacts with the different types of silver nanocube aggregations to excite different plasmonic resonances. The s-polarization shows dramatic changes of the plasmonic resonances at different angles of incidence (shift of 64 nm per 10° angle of incidence). With a low surface nanocube coverage (from 5% to 20%), we observed a polarization-selective high absorption of 80% (with an average 75%) of the incoming light over a broad optical range in the visible region from 400 nm to 700 nm. This large-area gradient material with location-dependent optical properties can be of particular interest for broadband light absorption, phase-sensitive sensors, and imaging.We fabricated monolayer coatings of a silver nanocube aggregation to create a step-wise optical strip by applying different surface pressures during slow Langmuir-Blodgett deposition. The varying amount of randomly distributed nanocube aggregates with different surface coverages in gradient manner due to changes in surface pressure allows for continuous control of the polarization sensitive absorption of the incoming light over a broad optical spectrum. Optical characterization under total internal reflection conditions combined with electromagnetic simulations reveal that the broadband light absorption depends on the relative orientation of the nanoparticles to the polarization of the incoming light. By using computer simulations, we found that the electric field vector of the s-polarized light interacts with the different types of silver nanocube aggregations to excite different plasmonic resonances. The s-polarization shows dramatic changes of the plasmonic resonances at different angles of incidence (shift of 64 nm per 10° angle of incidence). With a low surface nanocube coverage (from 5% to 20%), we observed a polarization-selective high absorption of 80% (with an average 75%) of the incoming light over a broad optical range in the visible region from 400 nm to 700 nm. This large-area gradient material with location-dependent optical properties can be of particular interest for broadband light absorption, phase-sensitive sensors, and imaging. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr06430e

New developments using carbon dioxide as a solvent: Monolayers and nanocomposites. 1. Reactions of organosilanes with oxidized silicon surfaces in carbon dioxide. 2. Polymer/polymer nanocomposites synthesized in carbon dioxide

NASA Astrophysics Data System (ADS)

Cao, Chuntao

The aim of this research was to explore new directions for carbon dioxide. The first project emphasized silyl monolayer synthesis. Silylation reactions were performed in both liquid and supercritical carbon dioxide. Different monofunctional organosilanes reacted with silica surfaces, forming covalently attached monolayers. These monolayers were characterized using contact angle measurements, X-ray photoelectron spectroscopy, and ellipsometry. Reaction kinetics were established, and compared with silylations in organic solvents. The reaction rate in CO2 is higher than that in conventional solvents while the final coverage is slightly lower than the optimized conditions for conventional solvents. Other multi-functional silanes were also studied. The silylation of nanoporous silica surfaces showed bonding densities almost as high as the maximum value reported in literature for small-pore substrates. Overall, CO2 is a good solvent for silylations on silica surfaces. The second project was to synthesize polymer/polymer nanocomposites using a CO2-assisted templating method. Semicrystalline polymers are composed of tens-of-nanometer thick crystalline lamellae and an amorphous matrix. CO2 normally swells only the amorphous and interlamellar regions. The goal of this research was to selectively bring monomers to the amorphous and interlamellar regions with the help of CO2. In situ polymerization and precipitation fixes the structure, replicating the nano-structure of the semicrystalline polymer substrate. Ring-opening metathesis polymerization was performed inside of CO2-swollen poly(4-methyl-1-pentene) (PMP) of high crystallinity. Several polymer/polymer nanocomposites were successfully produced using this method. They were characterized by a variety of techniques, such as transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and wide angle X-ray diffraction (WAXD). Infrared studies and TEM indicated that one type of composite, polynorbomene/PMP, had a gradient distribution of polynorbornene inside of the PMP matrix. Another composite, polyoctenamer/PMP prepared by cis-cyclooctene polymerization, exhibited very interesting mechanical properties. The poly(dicyclopentadiene)/PMP composites are unique nanometer-scale blends of a highly crosslinked thermoset with a thermoplastic polymer.

How to stabilize highly active Cu + cations in a mixed-oxide catalyst

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

Mudiyanselage, Kumudu; Luo, Si; Kim, Hyun You

Mixed-metal oxides exhibit novel properties that are not present in their isolated constituent metal oxides and play a significant role in heterogeneous catalysis. In this study, a titanium-copper mixed-oxide (TiCuO x) film has been synthesized on Cu(111) and characterized by complementary experimental and theoretical methods. At sub-monolayer coverages of titanium, a Cu 2O-like phase coexists with TiCuO x and TiO x domains. When the mixed-oxide surface is exposed at elevated temperatures (600–650 K) to oxygen, the formation of a well-ordered TiCuO x film occurs. Stepwise oxidation of TiCuO x shows that the formation of the mixed-oxide is faster than thatmore » of pure Cu 2O. As the Ti coverage increases, Ti-rich islands (TiO x) form. The adsorption of CO has been used to probe the exposed surface sites on the TiO x–CuO x system, indicating the existence of a new Cu + adsorption site that is not present on Cu 2O/Cu(111). Adsorption of CO on Cu + sites of TiCuO x is thermally more stable than on Cu(111), Cu 2O/Cu(111) or TiO 2(110). The Cu + sites in TiCuO x domains are stable under both reducing and oxidizing conditions whereas the Cu 2O domains present on sub-monolayer loads of Ti can be reduced or oxidized under mild conditions. Furthermore, the results presented here demonstrate novel properties of TiCuO x films, which are not present on Cu(111), Cu 2O/Cu(111), or TiO 2(110), and highlight the importance of the preparation and characterization of well-defined mixed-metal oxides in order to understand fundamental processes that could guide the design of new materials.« less

How to stabilize highly active Cu + cations in a mixed-oxide catalyst

DOE PAGES

Mudiyanselage, Kumudu; Luo, Si; Kim, Hyun You; ...

2015-09-12

Mixed-metal oxides exhibit novel properties that are not present in their isolated constituent metal oxides and play a significant role in heterogeneous catalysis. In this study, a titanium-copper mixed-oxide (TiCuO x) film has been synthesized on Cu(111) and characterized by complementary experimental and theoretical methods. At sub-monolayer coverages of titanium, a Cu 2O-like phase coexists with TiCuO x and TiO x domains. When the mixed-oxide surface is exposed at elevated temperatures (600–650 K) to oxygen, the formation of a well-ordered TiCuO x film occurs. Stepwise oxidation of TiCuO x shows that the formation of the mixed-oxide is faster than thatmore » of pure Cu 2O. As the Ti coverage increases, Ti-rich islands (TiO x) form. The adsorption of CO has been used to probe the exposed surface sites on the TiO x–CuO x system, indicating the existence of a new Cu + adsorption site that is not present on Cu 2O/Cu(111). Adsorption of CO on Cu + sites of TiCuO x is thermally more stable than on Cu(111), Cu 2O/Cu(111) or TiO 2(110). The Cu + sites in TiCuO x domains are stable under both reducing and oxidizing conditions whereas the Cu 2O domains present on sub-monolayer loads of Ti can be reduced or oxidized under mild conditions. Furthermore, the results presented here demonstrate novel properties of TiCuO x films, which are not present on Cu(111), Cu 2O/Cu(111), or TiO 2(110), and highlight the importance of the preparation and characterization of well-defined mixed-metal oxides in order to understand fundamental processes that could guide the design of new materials.« less

Quantized Advantages to a Proposed Satellite at L5 from Simulated Synoptic Magnetograms

NASA Astrophysics Data System (ADS)

Schwarz, A. M.; Petrie, G. J. D.

2017-12-01

The dependency the Earth and its inhabitants have on the Sun is delicate and complex and sometimes dangerous. At the NSO, we provide 24/7 coverage of the full-disk solar magnetic field used in solar forecasting, however this only includes data from the Sun's Earth facing side. Ideally we would like to have constant coverage of the entire solar surface, however we are limited in our solar viewing angle. Our project attempts to quantify the advantages of full-disk magnetograms from a proposed satellite at L5. With instrumentation at L5 we would have an additional 60 degrees of solar surface coverage not seen from Earth. These 60 degrees crucially contain the solar longitudes that are about to rotate towards Earth. Using a full-surface flux-transport model of the evolving solar photospheric field, I created a simulation of full-disk observations from Earth and L5. Using standard solar forecasting tools we quantify the relative accuracy of the Earth-Only and Earth plus L5 forecasts relative to the "ground truth" of the full surface field model, the ideal case. My results gauge exactly how much polar coverage is improved, contrast the spherical multipoles of each model, and use a Potential-Field Source-Surface (PFSS) magnetic field analysis model to find comparisons in the neutral lines and open field coverage.

Controlled deposition of size-selected MnO nanoparticle thin films for water splitting applications: reduction of onset potential with particle size

NASA Astrophysics Data System (ADS)

Khojasteh, Malak; Haghighat, Shima; Dawlaty, Jahan M.; Kresin, Vitaly V.

2018-05-01

Emulating water oxidation catalyzed by the oxomanganese clusters in the photosynthetic apparatus of plants has been a long-standing scientific challenge. The use of manganese oxide films has been explored, but while they may be catalytically active on the surface, their poor conductivity hinders their overall performance. We have approached this problem by using manganese oxide nanoparticles with sizes of 4, 6 and 8 nm, produced in a sputter-gas-aggregation source and soft-landed onto conducting electrodes. The mass loading of these catalytic particles was kept constant and corresponded to 45%–80% of a monolayer coverage. Measurements of the water oxidation threshold revealed that the onset potential decreases significantly with decreasing particle size. The final stoichiometry of the catalytically active nanoparticles, after exposure to air, was identified as predominantly MnO. The ability of such a sub-monolayer film to lower the reaction threshold implies that the key role is played by intrinsic size effects, i.e., by changes in the electronic properties and surface fields of the nanoparticles with decreasing size. We anticipate that this work will serve to bridge the knowledge gap between bulk thick film electrocatalysts and natural photosynthetic molecular-cluster complexes.

Activated carbon derived from carbon residue from biomass gasification and its application for dye adsorption: Kinetics, isotherms and thermodynamic studies.

PubMed

Maneerung, Thawatchai; Liew, Johan; Dai, Yanjun; Kawi, Sibudjing; Chong, Clive; Wang, Chi-Hwa

2016-01-01

In this work, activated carbon (AC) as an effective and low-cost adsorbent was successfully prepared from carbon residue (or char, one of the by-products from woody biomass gasification) via physical activation. The surface area of char was significantly increased from 172.24 to 776.46m(2)/g after steam activation at 900°C. The obtained activated carbons were then employed for the adsorption of dye (Rhodamine B) and it was found that activated carbon obtained from steam activation exhibited the highest adsorption capability, which is mainly attributed to the higher surface area and the abundance of hydroxyl (-OH) and carboxyl (-COOH) groups on the activated carbon surface. Moreover, it was also found that the adsorption capability significantly increased under the basic condition, which can be attributed to the increased electrostatic interaction between the deprotonated (negatively charged) activated carbon and dye molecules. Furthermore, the equilibrium data were fitted into different adsorption isotherms and found to fit well with Langmuir model (indicating that dye molecules form monolayer coverage on activated carbon) with a maximum monolayer adsorption capability of 189.83mg/g, whereas the adsorption kinetics followed the pseudo-second-order kinetics. Copyright © 2015 Elsevier Ltd. All rights reserved.

Argon and Krypton Adsorption Isotherms on Single Carbon Nanotube Devices

NASA Astrophysics Data System (ADS)

Wang, Zenghui; Morse, Peter; Wei, Jiang; Vilches, Oscar; Cobden, David

2009-03-01

We have fabricated mass balances each consisting of an individual single-walled carbon nanotube suspended across a micron-sized trench in an oxidized Si wafer. The vibrational resonance frequency of a nanotube, which is in the range 50-500 MHz, is determined by monitoring the current through it while applying an electrostatic driving signal. By tracking changes in the resonance frequency we have measured isotherms of adsorbed mass vs vapor pressure for Ar ot Kr at liquid nitrogen temperatures. The sensitivity of the balances corresponds to just a few atoms. We have compared the monolayer mass shifts due to Ar and Kr, and measured a family of isotherms of Ar below 77 K. From the latter we calculated the isosteric heat of adsorption on the nanotube surface, which is found to be lower than that of Ar on basal plane graphite and only slightly larger than the latent heat of sublimation of bulk Ar at these temperatures. In one device we observed a phase transition in the adsorbed Ar near monolayer completion. In another device, which probably consists of two nanotubes joined in parallel, we observed enhanced adsorption at lower coverages which may be in the groove between the two nanotubes. This work is supported by the NSF, grant number 0606078.

Electrochemical growth of CoNi and Pt-CoNi soft magnetic composites on an alkanethiol monolayer-modified ITO substrate.

PubMed

Escalera-López, D; Gómez, E; Vallés, E

2015-07-07

CoNi and Pt-CoNi magnetic layers on indium-tin oxide (ITO) substrates modified by an alkanethiol self-assembled monolayer (SAM) have been electrochemically obtained as an initial stage to prepare semiconducting layer-SAM-magnetic layer hybrid structures. The best conditions to obtain the maximum compactness of adsorbed layers of dodecanethiol (C12-SH) on ITO substrate have been studied using contact angle, AFM, XPS and electrochemical tests. The electrochemical characterization (electrochemical probe or voltammetric response in blank solutions) is fundamental to ensure the maximum blocking of the substrate. Although the electrodeposition process on the SAM-modified ITO substrate is very slow if the blocking of the surface is significant, non-cracked metallic layers of CoNi, with or without a previously electrodeposited seed-layer of platinum, have been obtained by optimizing the deposition potentials. Initial nucleation is expected to take place at the pinhole defects of the C12-SH SAM, followed by a mushroom-like growth regime through the SAM interface that allows the formation of a continuous metallic layer electrically connected to the ITO surface. Due to the potential of the methodology, the preparation of patterned metallic deposits on ITO substrate using SAMs with different coverage as templates is feasible.

Low capping group surface density on zinc oxide nanocrystals.

PubMed

Valdez, Carolyn N; Schimpf, Alina M; Gamelin, Daniel R; Mayer, James M

2014-09-23

The ligand shell of colloidal nanocrystals can dramatically affect their stability and reaction chemistry. We present a methodology to quantify the dodecylamine (DDA) capping shell of colloidal zinc oxide nanocrystals in a nonpolar solvent. Using NMR spectroscopy, three different binding regimes are observed: strongly bound, weakly associated, and free in solution. The surface density of bound DDA is constant over a range of nanocrystal sizes, and is low compared to both predictions of the number of surface cations and maximum coverages of self-assembled monolayers. The density of strongly bound DDA ligands on the as-prepared ZnO NCs is 25% of the most conservative estimate of the maximum surface DDA density. Thus, these NCs do not resemble the common picture of a densely capped surface ligand layer. Annealing the ZnO NCs in molten DDA for 12 h at 160 °C, which is thought to remove surface hydroxide groups, resulted in a decrease of the weakly associated DDA and an increase in the density of strongly bound DDA, to ca. 80% of the estimated density of a self-assembled monolayer on a flat ZnO surface. These findings suggest that as-prepared nanocrystal surfaces contain hydroxide groups (protons on the ZnO surfaces) that inhibit strong binding of DDA.

Shared responsibility for employers regarding health coverage. Final regulations.

PubMed

2014-02-12

This document contains final regulations providing guidance to employers that are subject to the shared responsibility provisions regarding employee health coverage under section 4980H of the Internal Revenue Code (Code), enacted by the Affordable Care Act. These regulations affect employers referred to as applicable large employers (generally meaning, for each year, employers that had 50 or more full-time employees, including full-time equivalent employees, during the prior year). Generally, under section 4980H an applicable large employer that, for a calendar month, fails to offer to its full-time employees health coverage that is affordable and provides minimum value may be subject to an assessable payment if a full-time employee enrolls for that month in a qualified health plan for which the employee receives a premium tax credit.

Dystrophin Hot-Spot Mutants Leading to Becker Muscular Dystrophy Insert More Deeply into Membrane Models than the Native Protein.

PubMed

Ameziane-Le Hir, Sarah; Paboeuf, Gilles; Tascon, Christophe; Hubert, Jean-François; Le Rumeur, Elisabeth; Vié, Véronique; Raguénès-Nicol, Céline

2016-07-26

Dystrophin (DYS) is a membrane skeleton protein whose mutations lead to lethal Duchenne muscular dystrophy or to the milder Becker muscular dystrophy (BMD). One third of BMD "in-frame" exon deletions are located in the region that codes for spectrin-like repeats R16 to R21. We focused on four prevalent mutated proteins deleted in this area (called RΔ45-47, RΔ45-48, RΔ45-49, and RΔ45-51 according to the deleted exon numbers), analyzing protein/membrane interactions. Two of the mutants, RΔ45-48 and RΔ45-51, led to mild pathologies and displayed a similar triple coiled-coil structure as the full-length DYS R16-21, whereas the two others, RΔ45-47 and RΔ45-49, induced more severe pathologies and showed "fractional" structures unrelated to the normal one. To explore lipid packing, small unilamellar liposomes (SUVs) and planar monolayers were used at various initial surface pressures. The dissociation constants determined by microscale thermophoresis (MST) were much higher for the full-length DYS R161-21 than for the mutants; thus the wild type protein has weaker SUV binding. Comparing surface pressures after protein adsorption and analysis of atomic force microscopy images of mixed protein/lipid monolayers revealed that the mutants insert more into the lipid monolayer than the wild type does. In fact, in both models every deletion mutant showed more interactions with membranes than the full-length protein did. This means that mutations in the R16-21 part of dystrophin disturb the protein's molecular behavior as it relates to membranes, regardless of whether the accompanying pathology is mild or severe.

Picosecond Dynamics Of The GaAs (110) Surface Studied With Laser Photoemission

NASA Astrophysics Data System (ADS)

Haight, R.; Silberman, J. A.; Lilie, M. I.

1988-08-01

A novel laser system and detection scheme is described which has been developed to investigate the transient dynamics of photoexcited electrons at material surfaces and interfaces with photoemission. The excited carrier population on the surface of GaAs (110) and the related Cr/GaAs (110) surface has been studied with 1-2 picosecond time resolution. Studies reveal a rapid rise and fall of the photexcited carrier population at the clean semiconductor surface within 15 picoseconds of excitation. For times greater than 15 picoseconds the carrier density decays slowly. Studies of the photoexcited surface after deposition of small numbers of Cr atoms reveal a remarkable decrease in the carrier density observed at the surface for a coverage as low as .006 monolayer.

Coadsorption of H2O and CO2 on the Martian surface

NASA Technical Reports Server (NTRS)

Zent, A. P.

1987-01-01

The adsorption of both CO2 and H2O was measured, under conditions of temperature and partial pressure similar to Mars, for a variety of absorbents. Both adsorb at coverages that exceed a monolayer at their respective Martian abundances. Clearly, their simultaneous presence in the Martian atmosphere will result in coadsorption of both at concentrations that may differ greatly from those measured during separate measurements. To the best of our knowledge, no data exists on the coadsorption of both gases. Co-adsorption experiments were begun and pertinent results will be reported. In the meantime the predicted behavior of such a system was mathematically explored as a compliment to the data, and to aid in its eventual interpretation.

Covalent Coupling of Nanoparticles with Low-Density Functional Ligands to Surfaces via Click Chemistry

PubMed Central

Rianasari, Ina; de Jong, Michel P.; Huskens, Jurriaan; van der Wiel, Wilfred G.

2013-01-01

We demonstrate the application of the 1,3-dipolar cycloaddition (“click” reaction) to couple gold nanoparticles (Au NPs) functionalized with low densities of functional ligands. The ligand coverage on the citrate-stabilized Au NPs was adjusted by the ligand:Au surface atom ratio, while maintaining the colloidal stability of the Au NPs in aqueous solution. A procedure was developed to determine the driving forces governing the selectivity and reactivity of citrate-stabilized and ligand-functionalized Au NPs on patterned self-assembled monolayers. We observed selective and remarkably stable chemical bonding of the Au NPs to the complimentarily functionalized substrate areas, even when estimating that only 1–2 chemical bonds are formed between the particles and the substrate. PMID:23434666

Surface alloy engineering in 2D trigonal lattice: giant Rashba spin splitting and two large topological gaps

NASA Astrophysics Data System (ADS)

Liu, Zhao; Jin, Yingdi; Yang, Yuchen; Wang, Z. F.; Yang, Jinlong

2018-02-01

We demonstrate that sp 2 based trigonal lattice can exhibit giant Rashba splitting and two large topological gaps simultaneously. First, an effective tight binding model is developed to describe the Rashba spin-orbit coupling (SOC) on a real surface and give a topological phase diagram based on two independent SOC parameters. Second, based on density functional theory calculations, it is proposed that Au/Si(111)-\\sqrt{3}× \\sqrt{3} surface with 1/3 monolayer Bi coverage is a good material candidate to realize both giant Rashba splitting and two large topological gaps. These results would inspire great research interests for searching two-dimensional topological insulator and manipulating Rashba spin splitting through surface alloy engineering.

Interaction of diamond (111)-(1 × 1) and (2 × 1) surfaces with OH: a first principles study.

PubMed

Stampfl, C; Derry, T E; Makau, N W

2010-12-01

The properties of hydroxyl groups on C(111)-(1 × 1) and reconstructed (2 × 1) surfaces at different sites and for various coverages are investigated using density functional theory. Out of the adsorption sites considered, i.e. face centred cubic, hexagonal close packed, on-top and bridge sites, the on-top site is the most stable for OH on the C(111)-(1 × 1) surface for all coverages. On the reconstructed (2 × 1) surface the on-top site is the preferred configuration. Adsorption of OH was not stable however at any site on the reconstructed C(111)-(2 × 1) relative to the (1 × 1) surface; thus adsorption of OH leads to the de-reconstruction of the former surface. Both the 0.5 and 1 monolayer (ML) coverages were able to lift the (2 × 1) surface reconstruction. Repulsion between the OH adsorbates on the (1 × 1) surface sets in for coverages greater than 0.5 ML. A general decrease in the work function with increasing OH coverage was observed on both the (1 × 1) and (2 × 1) surfaces relative to the values of their respective clean surfaces. Regarding the electronic structure, O 2p states on the reconstructed (2 × 1) surface are observed at around - 21, - 8.75 , - 5 and - 2.5 eV, while O 2s states are present at - 22.5 eV. On the (1 × 1) surface (for 0.33 ML in the on-top site), O 2p states occurred between - 8 and - 9 eV, - 5 and - 4 eV and at around - 2.5 eV. O 2s states are established between - 22.5 and - 21 eV. The valence band width is 21 eV, and a hybrid 2s/2p state that is characteristic of diamond is located at about 12.5 eV below the valence band minimum.

Cost variability of suggested generic treatment alternatives under the Medicare Part D benefit.

PubMed

Patel, Rajul A; Walberg, Mark P; Tong, Emily; Tan, Florence; Rummel, Ashley E; Woelfel, Joseph A; Carr-Lopez, Sian M; Galal, Suzanne M

2014-03-01

The substitution of generic treatment alternatives for brand-name drugs is a strategy that can help lower Medicare beneficiary out-of-pocket costs. Beginning in 2011, Medicare beneficiaries reaching the coverage gap received a 50% discount on the full drug cost of brand-name medications and a 7% discount on generic medications filled during the gap. This discount will increase until 2020, when beneficiaries will be responsible for 25% of total drug costs during the coverage gap. To examine the cost variability of brand and generic drugs within 4 therapeutic classes before and during the coverage gap for each 2011 California stand-alone prescription drug plan (PDP) and prospective coverage gap costs in 2020 to determine the effects on beneficiary out-of-pocket drug costs. Equivalent doses of brand and generic drugs in the following 4 pharmacological classes were examined: angiotensin II receptor blockers (ARBs), bisphosphonates, HMG-CoA reductase inhibitors (statins), and proton pump inhibitors (PPIs). The full drug cost and patient copay/coinsurance amounts during initial coverage and the coverage gap of each drug was recorded based on information retrieved from the Medicare website. These drug cost data were recorded for 28 California PDPs. The highest cost difference between a brand medication and a Centers for Medicare Medicaid Services (CMS)-suggested generic treatment alternative varied between $110.53 and $195.49 at full cost and between $51.37 and $82.35 in the coverage gap. The lowest cost difference varied between $38.45 and $76.93 at full cost and between -$4.11 and $18.52 during the gap. Medicare beneficiaries can realize significant out-of-pocket cost savings for their drugs by taking CMS-suggested generic treatment alternatives. However, due to larger discounts on brand medications made available through recent changes reducing the coverage gap, the potential dollar savings by taking suggested generic treatment alternatives during the gap is less compelling and will decrease as subsidies increase.

Synthesis, Characterization, and Properties of the Two-Dimensional Chalcogenides: Monolayers, Alloys, and Heterostructures

NASA Astrophysics Data System (ADS)

Cain, Jeffrey D.

Inspired by the triumphs of graphene, and motivated by its limitations, the science and engineering community is rapidly exploring the landscape of other layered materials in their atomically-thin forms. Dominating this landscape are the layered chalcogenides; diverse in chemistry, crystal structure, and properties, there are well over 100 primary members of this material family. Driven by quantum confinement, single layers (or few, in some cases) of these materials exhibit electronic, optical, and mechanical properties that diverge dramatically from their bulk counterparts. While initially isolated in monolayer form via mechanical exfoliation, the field of two-dimensional (2D) materials is being forced evolve to more scalable and reliable methods. Focusing on the chalcogenides (e.g. MoS2, Bi 2Se3, etc.), this dissertation introduces and mechanistically examines multiple novel synthetic approaches for the direct growth of monolayers, heterostructures, and alloys with the desired quality, reproducibility and generality. The first methods described in this thesis are physical vapor transport (PVT) and evaporative thinning (ET): a facile, top-down synthesis approach for creating ultrathin specimens of layered materials down to the two-dimensional limit. Evaporative thinning, applied in this study to the fabrication of A2X3 (Bi2Se3 and Sb2Te3) monolayers, is based on the controlled evaporation of material from initially thick specimens until the 2D limit is reached. The resultant flakes are characterized with a suite of imaging and spectroscopic techniques and the mechanism of ET is investigated via in-situ heating within a transmission electron microscope. Additionally, the basic transport properties of the resultant flakes are probed. The growth of ultrathin GeSe flakes is explored using PVT and the material's basic structure, properties, and stability are addressed. Second, oxide precursor based chemical vapor deposition (CVD) is presented for the direct growth of monolayer transition metal dichalcogenides materials (TMDs), MX2. Specifically, synthetic protocols for monolayers of the semiconducting TMDs, MoS2, WS2, and MoSe2, are presented and the layers are completely characterized with a full suite of techniques including scanning/transmission electron microscopy, scanning probe microscopy, and photo-spectroscopy (photoluminescence, Raman scattering) among others. Furthermore, the nucleation and growth processes in CVD grown TMD monolayers is investigated using aberration-corrected scanning transmission electron microscopy and a step-by-step nucleation and growth mechanism for monolayer TMDs is elucidated. Third, the use of monolayers as building blocks for more complex structures is explored and a predictive approach for the synthesis of van der Waals heterostructures and monolayer alloys is designed. This is accomplished using an intellectual framework analogous to the Time-Temperature-Transformation (TTT) diagrams that are ubiquitous in traditional materials science and metallurgy. These are called Time-Temperature-Architecture (TTA) diagrams, wherein the term "architecture" defines the specific conformation of the 2D components. These diagrams provide process guidance to synthesize a library of heterostructures with a range of morphologies and monolayer alloys within both the transition metal sulfide and selenide systems. Lastly, some next steps for future research are outlined. An appendix of summaries of collaborative studies of the optical and electronic properties of CVD grown monolayers TMDs is appended.

Molecular chirality and domain shapes in lipid monolayers on aqueous surfaces

NASA Astrophysics Data System (ADS)

Krüger, Peter; Lösche, Mathias

2000-11-01

The shapes of domain boundaries in the mesoscopic phase separation of phospholipids in aqueous surface monolayers are analyzed with particular attention to the influence of molecular chirality. We have calculated equilibrium shapes of such boundaries, and show that the concept of spontaneous curvature-derived from an effective pair potential between the chiral molecules-yields an adequate description of the contribution of chirality to the total energy of the system. For enantiomeric dipalmitoylphosphatidylcholine in pure monolayers, and in mixtures with impurities that adsorb preferentially at the (one-dimensional) boundary line between the isotropic and anisotropic fluid phases, such as cyanobiphenyl (5CB), a total energy term that includes line tension, electrostatic dipole-dipole interaction, and spontaneous curvature is sufficient to describe the shapes of well-separated domain boundaries in full detail. As soon as interdomain distances fall below the domain sizes upon compression of a monolayer, fluctuations take over in determining its detailed structural morphology. Using Minkowski measures for the well-studied dimyristoyl phosphatidic acid (DMPA)/cholesterol system, we show that calculations accounting for line tension, electrostatic repulsion, and molecular chirality yield boundary shapes that are of the same topology as the experimentally observed structures. At a fixed molecular area in the phase coexistence region, the DMPA/cholesterol system undergoes an exponential decay of the line tension λ with decreasing subphase temperature T.

48 CFR 9903.201-2 - Types of CAS coverage.

Code of Federal Regulations, 2012 CFR

2012-10-01

... later award of a CAS-covered contract. Full coverage applies to contractor business units that— (1) Receive a single CAS-covered contract award of $50 million or more; or (2) Received $50 million or more in net CAS-covered awards during its preceding cost accounting period. (b) Modified coverage. (1...

48 CFR 9903.201-2 - Types of CAS coverage.

Code of Federal Regulations, 2014 CFR

2014-10-01

... later award of a CAS-covered contract. Full coverage applies to contractor business units that— (1) Receive a single CAS-covered contract award of $50 million or more; or (2) Received $50 million or more in net CAS-covered awards during its preceding cost accounting period. (b) Modified coverage. (1...

45 CFR 2540.220 - Under what circumstances and subject to what conditions are participants in Corporation-assisted...

Code of Federal Regulations, 2011 CFR

2011-10-01

... coverage. (1) If a State, local or private program provides for health insurance for the full-time... program provides health insurance coverage for the full-time participant, the sponsor must also continue... Selection and Treatment of Participants § 2540.220 Under what circumstances and subject to what conditions...

45 CFR 2540.220 - Under what circumstances and subject to what conditions are participants in Corporation-assisted...

Code of Federal Regulations, 2010 CFR

2010-10-01

... coverage. (1) If a State, local or private program provides for health insurance for the full-time... program provides health insurance coverage for the full-time participant, the sponsor must also continue... Selection and Treatment of Participants § 2540.220 Under what circumstances and subject to what conditions...

5 CFR 875.405 - If I marry, may my new spouse apply for coverage?

Code of Federal Regulations, 2010 CFR

2010-01-01

... from the date of your marriage and will be subject to the underwriting requirements in force for the... abbreviated underwriting because of your marriage. You may apply for coverage along with your spouse, but full... with full underwriting at any time following the marriage. (b) The new spouse and other qualified...

Surface states and annihilation characteristics of positrons trapped at the oxidized Cu(100) surface

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Weiss, A. H.

2013-06-01

In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Oxidation of the Cu(100) surface has been studied by performing an ab-initio investigation of the stability and electronic structure of the Cu(100) missing row reconstructed surface at various on-surface and subsurface oxygen coverages ranging from 0.5 to 1.5 monolayers using density functional theory (DFT). All studied structures have been found to be energetically more favorable as compared to structures formed by purely on-surface oxygen adsorption. The observed decrease in the positron work function when oxygen atoms occupy on-surface and subsurface sites has been attributed to a significant charge redistribution within the first two layers, buckling effects within each layer and an interlayer expansion. The computed positron binding energy, positron surface state wave function, and annihilation probabilities of the surface trapped positrons with relevant core electrons demonstrate their sensitivity to oxygen coverage, atomic structure of the topmost layers of surfaces, and charge transfer effects. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). The results presented provide an explanation for the changes observed in the probability of annihilation of surface trapped positrons with Cu 3p core-level electrons as a function of annealing temperature.

Self assembly of oppositely charged latex particles at oil-water interface.

PubMed

Nallamilli, Trivikram; Ragothaman, Srikanth; Basavaraj, Madivala G

2017-01-15

In this study we explore the self assembly of oppositely charged latex particles at decane water interfaces. Two spreading protocols have been proposed in this context. In the first method oppositely charged particles are mixed prior to spreading at the interface, this is called "premixed-mixtures". In the second protocol negatively charged particles are first spread at the interface at known coverage followed by spreading positively charged particles at known coverage and this is called "sequential-mixtures". In premixed mixtures depending on particle mixing ratio (composition) and total surface coverage a number of 2d structures ranging from 2d crystals, aggregate-crystal coexistence and 2d-gels are observed. A detailed phase diagram of this system has been explored. In sequential-mixtures for the first time we observed a new phase in colloidal monolayers called 2d-bi crystalline domains. These structures consisted regions of two crystal phases of oppositely charged particles separated by a one dimensional chain of alternating positive and negative particles. Phase diagram of this system has also been explored at various combinations of first spread and second spread particles. A possible mechanism leading to formation of these 2d bi crystalline structures has been discussed. A direct visualization of breakage and reformation of particle barriers separating the crystal phases has been demonstrated through videos. Effect of salt in the water sub phase and particle hydrophobicity on domain formation is also investigated. Copyright © 2016 Elsevier Inc. All rights reserved.

Electronic structure of dense Pb overlayers on Si(111) investigated using angle-resolved photoemission

NASA Astrophysics Data System (ADS)

Choi, W. H.; Koh, H.; Rotenberg, E.; Yeom, H. W.

2007-02-01

Dense Pb overlayers on Si(111) are important as the wetting layer for anomalous Pb island growth as well as for their own complex “devil’s-staircase” phases. The electronic structures of dense Pb overlayers on Si(111) were investigated in detail by angle-resolved photoemission. Among the series of ordered phases found recently above one monolayer, the low-coverage 7×3 and the high-coverage 14×3 phases are studied; they are well ordered and form reproducibly in large areas. The band dispersions and Fermi surfaces of the two-dimensional (2D) electronic states of these overlayers are mapped out. A number of metallic surface-state bands are identified for both phases with complex Fermi contours. The basic features of the observed Fermi contours can be explained by overlapping 2D free-electron-like Fermi circles. This analysis reveals that the 2D electrons near the Fermi level of the 7×3 and 14×3 phases are mainly governed by strong 1×1 and 3×3 potentials, respectively. The origins of the 2D electronic states and their apparent Fermi surface shapes are discussed based on recent structure models.

Proton dynamics and surface heterogeneity of silica gel with adsorbed benzene below one monolayer coverage

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

Peterson, E.M.; O'Reilly, D.E.; Tsangb), T.

1979-04-01

Proton and deuteron NMR relaxation times of C/sub 6/H/sub 6/, C/sub 6/D/sub 6/, and mixtures of these molecules have been measured on a superpure silica gel (SPSG) and a sample of a Matheson silica gel (MSG) both dehydrated at 600/sup 0/ C and rotational (intramolecular) and translational (intermolecular) correlation times have been computed from the relaxation time data at a statistical coverage theta=0.6. Three kinds of adsorption sites have been observed: (1) A sites, which are probably oxygen vacancies on the surface, (2) B sites which are assigned to paired hydroxyl groups on the surface, and finally (3) C sitesmore » which comprise 80% of the occupied surface and are primarily isolated hydroxyl groups. Rotational and translational motions are highly correlated for the A and B site molecules. The mean number of molecules clustered at the A and B sites are inferred from the intermolecular second moments associated with each of these sites. The surface density of the A sites is 1.1 x 10/sup 12/ cm/sup -2/ for SPSG and 3.1 x 10/sup 12/ cm/sup -2/ for MSG.« less

Sulfate-enhanced catalytic destruction of 1,1,1-trichlorethane over Pt(111).

PubMed

Lee, Adam F; Wilson, Karen

2006-01-19

The catalytic destruction of 1,1,1-trichloroethane (TCA) over model sulfated Pt(111) surfaces has been investigated by fast X-ray photoelectron spectroscopy and mass spectrometry. TCA adsorbs molecularly over SO4 precovered Pt(111) at 100 K, with a saturation coverage of 0.4 monolayer (ML) comparable to that on the bare surface. Surface crowding perturbs both TCA and SO4 species within the mixed adlayer, evidenced by strong, coverage-dependent C 1s and Cl and S 2p core-level shifts. TCA undergoes complete dechlorination above 170 K, accompanied by C-C bond cleavage to form surface CH3, CO, and Cl moieties. These in turn react between 170 and 350 K to evolve gaseous CO2, C2H6, and H2O. Subsequent CH3 dehydrogenation and combustion occurs between 350 and 450 K, again liberating CO2 and water. Combustion is accompanied by SO4 reduction, with the coincident evolution of gas phase SO2 and CO2 suggesting the formation of a CO-SOx surface complex. Reactively formed HCl desorbs in a single state at 400 K. Only trace (<0.06 ML) residual atomic carbon and chlorine remain on the surface by 500 K.

Ultrathin type-II GaSb/GaAs quantum wells grown by OMVPE

NASA Astrophysics Data System (ADS)

Pitts, O. J.; Watkins, S. P.; Wang, C. X.; Stotz, J. A. H.; Meyer, T. A.; Thewalt, M. L. W.

2004-09-01

Heterostructures containing monolayer (ML) and submonolayer GaSb insertions in GaAs were grown using organometallic vapour phase epitaxy. At the GaAs-on-GaSb interface, strong intermixing occurs due to the surface segregation of Sb. To form structures with relatively abrupt interfaces, a flashoff growth sequence, in which growth interruptions are employed to desorb Sb from the surface, was introduced. Reflectance-difference spectroscopy and high-resolution X-ray diffraction data demonstrate that interfacial grading is strongly reduced by this procedure. For layer structures grown with the flashoff sequence, a GaSb coverage up to 1 ML can be obtained in the two-dimensional (2D) growth mode. For uncapped GaSb layers, on the other hand, atomic force microscope images show that the 2D-3D growth mode transition occurs at a submonolayer coverage between 0.3 and 0.5 ML. Low-temperature photoluminescence spectra of multiple quantum well samples grown using the flashoff sequence show a strong quantum well-related peak which shifts to lower energies as the amount of Sb incorporated increases. The PL peak energies are consistent with a type-II band lineup at the GaAs/GaSb interface.

Red-to-Ultraviolet Emission Tuning of Two-Dimensional Gallium Sulfide/Selenide.

PubMed

Jung, Chan Su; Shojaei, Fazel; Park, Kidong; Oh, Jin Young; Im, Hyung Soon; Jang, Dong Myung; Park, Jeunghee; Kang, Hong Seok

2015-10-27

Graphene-like two-dimensional (2D) nanostructures have attracted significant attention because of their unique quantum confinement effect at the 2D limit. Multilayer nanosheets of GaS-GaSe alloy are found to have a band gap (Eg) of 2.0-2.5 eV that linearly tunes the emission in red-to-green. However, the epitaxial growth of monolayers produces a drastic increase in this Eg to 3.3-3.4 eV, which blue-shifts the emission to the UV region. First-principles calculations predict that the Eg of these GaS and GaSe monolayers should be 3.325 and 3.001 eV, respectively. As the number of layers is increased to three, both the direct/indirect Eg decrease significantly; the indirect Eg approaches that of the multilayers. Oxygen adsorption can cause the direct/indirect Eg of GaS to converge, resulting in monolayers with a strong emission. This wide Eg tuning over the visible-to-UV range could provide an insight for the realization of full-colored flexible and transparent light emitters and displays.

COMPASS Final Report: Lunar Network Satellite-High Rate (LNS-HR)

NASA Technical Reports Server (NTRS)

oleson, Steven R.; McGuire, Melissa L.

2012-01-01

Two design options were explored to address the requirement to provide lunar piloted missions with continuous communications for outpost and sortie missions. Two unique orbits were assessed, along with the appropriate spacecraft (S/C) to address these requirements. Both constellations (with only two S/C each) provide full time coverage (24 hr/7 d) for a south polar base and also provide continuous 7 day coverage for sorties for specified sites and periodic windows. Thus a two-satellite system can provide full coverage for sorties for selected windows of opportunity without reconfiguring the constellation.

The Mental and Physical Health Consequences of Changes in Private Insurance Before and After Early Retirement

PubMed Central

2016-01-01

Objectives. This study evaluated the impact of private insurance coverage on the symptoms of depression, activities of daily living (ADLs), and instrumental activities of daily living (IADLs) in the years leading up to Medicare eligibility focusing on the transition from full-time work to early full retirement. Method. The Health and Retirement Study was used to (a) estimate 2-stage selection equations of (i) the transition to retirement and (ii) current insurance status, and (b) the impact of insurance coverage on health, net of endogeneity associated retirement and insurance coverage. Results. Employment-based insurance coverage was generally associated with better health. Moreover, being without employment-based insurance was particularly problematic during the transition to retirement. Non-group insurance only moderated the association between losing employment-based insurance and IADLs. Discussion. Results indicated that private insurance coverage is an important contextual factor for the health of early retirees. Those who maintain steady coverage tend to fare the best in retirement. This highlights the dynamic nature of changes in health in later life. PMID:25819976

Benefits | NREL

Science.gov Websites

benefits package for full- and part-time employees includes medical, dental, and vision coverage effective assignment of 12 months or longer are eligible for: Medical/Dental Insurance Vision Coverage Personal Time

Out-of-Pocket Financial Burden for Low-Income Families with Children: Socioeconomic Disparities and Effects of Insurance

PubMed Central

Galbraith, Alison A; Wong, Sabrina T; Kim, Sue E; Newacheck, Paul W

2005-01-01

Objective To determine whether socioeconomic disparities exist in the financial burden of out-of-pocket (OOP) health care expenditures for families with children, and whether health insurance coverage decreases financial burden for low-income families. Data Source The Household Component of the 2001 Medical Expenditure Panel Survey. Study Design Cross-sectional family-level analysis. We used bivariate statistics to examine whether financial burden varied by poverty level. Multivariate regression models were used to assess whether family insurance coverage was associated with level of financial burden for low-income families. The main outcome was financial burden, defined as the proportion of family income spent on OOP health care expenditures, including premiums, for all family members. Data Collection/Extraction We aggregated annual OOP expenditures for all members of 4,531 families with a child <18 years old. Family insurance coverage was categorized as follows: (1) all members publicly insured all year, (2) all members privately insured all year, (3) all members uninsured all year, (4) partial coverage, or (5) mix of public and private with no uninsured periods. Principal Findings A regressive gradient was noted for financial burden across income groups, with families with incomes <100 percent of the Federal Poverty Level (FPL) spending a mean of $119.66 OOP per $1,000 of family income and families with incomes 100–199 percent FPL spending $66.30 OOP per $1,000, compared with $37.75 for families with incomes >400 percent FPL. For low-income families (<200 percent FPL), there was a 785 percent decrease in financial burden for those with full-year public coverage compared with those with full-year private insurance (p<.001). Conclusions Socioeconomic disparities exist in the financial burden of OOP health care expenditures for families with children. For low-income families, full-year public coverage provides significantly greater protection from financial burden than full-year private coverage. PMID:16336545

Out-of-pocket financial burden for low-income families with children: socioeconomic disparities and effects of insurance.

PubMed

Galbraith, Alison A; Wong, Sabrina T; Kim, Sue E; Newacheck, Paul W

2005-12-01

To determine whether socioeconomic disparities exist in the financial burden of out-of-pocket (OOP) health care expenditures for families with children, and whether health insurance coverage decreases financial burden for low-income families. The Household Component of the 2001 Medical Expenditure Panel Survey. Cross-sectional family-level analysis. We used bivariate statistics to examine whether financial burden varied by poverty level. Multivariate regression models were used to assess whether family insurance coverage was associated with level of financial burden for low-income families. The main outcome was financial burden, defined as the proportion of family income spent on OOP health care expenditures, including premiums, for all family members. We aggregated annual OOP expenditures for all members of 4,531 families with a child <18 years old. Family insurance coverage was categorized as follows: (1) all members publicly insured all year, (2) all members privately insured all year, (3) all members uninsured all year, (4) partial coverage, or (5) mix of public and private with no uninsured periods. A regressive gradient was noted for financial burden across income groups, with families with incomes <100 percent of the Federal Poverty Level (FPL) spending a mean of 119.66 US dollars OOP per 1,000 US dollars of family income and families with incomes 100-199 percent FPL spending 66.30 US dollars OOP per 1,000 US dollars, compared with 37.75 US dollars for families with incomes >400 percent FPL. For low-income families (<200 percent FPL), there was a 785 percent decrease in financial burden for those with full-year public coverage compared with those with full-year private insurance (p < .001). Socioeconomic disparities exist in the financial burden of OOP health care expenditures for families with children. For low-income families, full-year public coverage provides significantly greater protection from financial burden than full-year private coverage.

ISS and TPD study of the adsorption and interaction of CO and H2 on polycrystalline Pt

NASA Technical Reports Server (NTRS)

Melendez, Orlando; Hoflund, Gar B.; Schryer, David R.

1990-01-01

The adsorption and interaction of CO and H2 on polycrystalline Pt has been studied using ion scattering spectroscopy (ISS) and temperature programmed desorption (TPD). The ISS results indicate that the initial CO adsorption on Pt takes place very rapidly and saturates the Pt surface with coverage close to a monolayer. ISS also shows that the CO molecules adsorb at an angular orientation from the surface normal and perhaps parallel to the surface. A TPD spectrum obtained after coadsorbing C-12 O-16 and C-13 O-18 on Pt shows no isotopic mixing, which is indicative of molecular CO adsorption. TPD spectra obtained after coadsorbing H2 and CO on polycrystalline Pt provides evidence for the formation of a CO-H surface species.

The important role of water in growth of monolayer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Kastl, Christoph; Chen, Christopher T.; Kuykendall, Tevye; Shevitski, Brian; Darlington, Thomas P.; Borys, Nicholas J.; Krayev, Andrey; Schuck, P. James; Aloni, Shaul; Schwartzberg, Adam M.

2017-06-01

2D transition metal dichalcogenides (TMDs) are commonly grown by chemical vapor deposition using transition metal oxides as solid precursors. Despite the widespread use of this technique, challenges in reproducibility, coverage, and material quality are pervasive, suggestive of unknown and uncontrolled process parameters. In this communication, we demonstrate the impact of water vapor on this growth process. Our results show a direct correlation between gas phase water content and the morphology of TMD films. In particular, we show that the presence of water enhances volatilization, and therefore the vapor transport of tungsten and molybdenum oxide. Surprisingly, we find that water not only plays an important role in volatilization but is also compatible with TMD growth. In fact, carefully controlled humidity can consistently produce high quality, luminescent materials.

Remediation of phosphate-contaminated water by electrocoagulation with aluminium, aluminium alloy and mild steel anodes.

PubMed

Vasudevan, Subramanyan; Lakshmi, Jothinathan; Jayaraj, Jeganathan; Sozhan, Ganapathy

2009-05-30

The present study provides an electrocoagulation process for the remediation of phosphate-contaminated water using aluminium, aluminium alloy and mild steel as the anodes and stainless steel as the cathode. The various parameters like effect of anode materials, effect of pH, concentration of phosphate, current density, temperature and co-existing ions, and so forth, and the adsorption capacity was evaluated using both Freundlich and Langmuir isotherm models. The adsorption of phosphate preferably fitting the Langmuir adsorption isotherm suggests monolayer coverage of adsorbed molecules. The results showed that the maximum removal efficiency of 99% was achieved with aluminium alloy anode at a current density of 0.2 A dm(-2), at a pH of 7.0. The adsorption process follows second-order kinetics.

Formation of atomically smooth epitaxial metal films on a chemically reactive interface: Mg on Si(111)

NASA Astrophysics Data System (ADS)

Özer, Mustafa M.; Weitering, Hanno H.

2013-07-01

Deposition of Mg on Si(111)7 × 7 produces an epitaxial magnesium silicide layer. Under identical annealing conditions, the thickness of this Mg2Si(111) layer increases with deposition amount, reaching a maximum of 4 monolayer (ML) and decreasing to ˜3 ML at higher Mg coverage. Excess Mg coalesces into atomically flat, crystalline Mg(0001) films. This surprising growth mode can be attributed to the accidental commensurability of the Mg(0001), Si(111), and Mg2Si(111) interlayer spacing and the concurrent minimization of in-plane Si mass transfer and domain-wall energies. The commensurability of the interlayer spacing defines a highly unique solid-phase epitaxial growth process capable of producing trilayer structures with atomically abrupt interfaces and atomically smooth surface morphologies.

Interfacial properties at the organic-metal interface probed using quantum well states

NASA Astrophysics Data System (ADS)

Lin, Meng-Kai; Nakayama, Yasuo; Wang, Chin-Yung; Hsu, Jer-Chia; Pan, Chih-Hao; Machida, Shin-ichi; Pi, Tun-Wen; Ishii, Hisao; Tang, S.-J.

2012-10-01

Using angle-resolved photoemission spectroscopy, we investigated the interfacial properties between the long-chain normal-alkane molecule n-CH3(CH2)42CH3 [tetratetracontane (TTC)] and uniform Ag films using the Ag quantum well states. The entire quantum well state energy band dispersions were observed to shift toward the Fermi level with increasing adsorption coverage of TTC up to 1 monolayer (ML). However, the energy shifts upon deposition of 1 ML of TTC are approximately inversely dependent on the Ag film thickness, indicating a quantum-size effect. In the framework of the pushback and image-force models, we applied the Bohr-Sommerfeld quantization rule with the modified Coulomb image potential for the phase shift at the TTC/Ag interface to extract the dielectric constant for 1 ML of TTC.

DNA adsorption characteristics of hollow spherule allophane nano-particles.

PubMed

Matsuura, Yoko; Iyoda, Fumitoshi; Arakawa, Shuichi; John, Baiju; Okamoto, Masami; Hayashi, Hidetomo

2013-12-01

To understand the propensity of natural allophane to adsorb the DNA molecules, the adsorption characteristics were assessed against natural allophane (AK70), using single-stranded DNA (ss-DNA) and adenosine 5'-monophosphate (5'-AMP) as a reference molecule. The adsorption capacity of ss-DNA on AK70 exhibited one order of magnitude lower value as compared with that of 5'-AMP. The adsorption capacity of ss-DNA decreased with increasing pH due to the interaction generated between phosphate groups of ss-DNA and functional Al-OH groups on the wall perforations through deprotonating, associated with higher energy barrier for the adsorption of ss-DNA. The adsorption morphologies consisting of the individual ss-DNA with mono-layer coverage of the clustered allophane particle were observed successfully through transmission electron microscopy analysis. © 2013.

Role of stable and metastable Mg-H complexes in p-type GaN for cw blue laser diodes

NASA Astrophysics Data System (ADS)

Castiglia, A.; Carlin, J.-F.; Grandjean, N.

2011-05-01

Secondary ion mass spectroscopy (SIMS) and capacitance-voltage measurements were combined to thoroughly study Mg doping in GaN layers grown by metal organic vapor phase epitaxy. First we found that the Mg steady-state incorporation regime occurs for a surface coverage of 0.3 monolayer. Additionally SIMS indicates that H incorporates proportionally with Mg until a certain [Mg] where [H] saturates. After thermal activation, [H] while being much lower still scales with [Mg]. These results suggest that H combines with Mg to form two different types of Mg-H complexes: a metastable one leading to the Mg acceptor after annealing, the other one (dominating at high [Mg]) being stable and electrically inactive. The obtained results allowed us optimizing doping conditions for blue laser diodes.

Tuning the ultrafast photodissociation dynamics of CH3Br on ultrathin MgO films by reducing the layer thickness to the 2D limit

NASA Astrophysics Data System (ADS)

Vaida, Mihai E.; Bernhardt, Thorsten M.

2017-11-01

The femtosecond-laser induced photodissociation of CH3Br adsorbed at sub-monolayer coverage on a solid surface was investigated by time-resolved pump-probe mass spectrometry. To tune the interaction of the CH3Br molecules with the substrate, an Mo(1 0 0) surface was covered with ultrathin insulating MgO layers of variable thickness. By gradually decreasing the magnesia layer thickness to the 2D limit the photodissociation dynamics observed by detection of the methyl fragment indicates an energetic lowering of the relevant methyl bromide excited states due to the increasing spatial proximity of the metallic support. Potential orientational effects of the methyl bromide adsorption geometry are also considered.

Controllable deposition of platinum layers on oxide surfaces for the synthesis of fuel cell catalysts

DOE PAGES

Vukmirovic, Miomir B.; Kuttiyiel, Kurian A.; Meng, Hui; ...

2016-09-13

Reducing the amount of Pt, the most costly component of both anode and cathode fuel cell catalysts, has attracted considerable attention from the research community. An approach is reported herein to deposit sub-monolayer to multilayer amounts of Pt and other noble metals on metal oxides and oxidized carbon materials. The process is exemplified by Pt deposition on RuO 2(110). The Pt deposit consists of Pt atoms arranged in a c(2×2) array, that is, a 0.25 monolayer (ML). The deposit has lower catalytic activity for the oxygen reduction reaction (ORR) and similar activity for the hydrogen oxidation reaction compared to Pt(111).more » These activities are explained by a large calculated upshift of the d-band center of Pt atoms and larger Pt–Pt interatomic distances than those of Pt(111). A catalyst with Pt coverage larger than 0.25 ML on oxide surfaces and oxidized carbon materials is shown to be active for the ORR as well as for other electrocatalytic reactions. A PtRhSnO 2/C catalyst shows high activity for ethanol oxidation as a result of its ability to effectively cleave the C–C bond in ethanol. Furthermore, Pt deposited on reduced graphene oxide shows high Pt mass ORR activity and good stability.« less

Prototypical Organic–Oxide Interface: Intramolecular Resolution of Sexiphenyl on In 2O 3 (111)

DOE PAGES

Wagner, Margareta; Hofinger, Jakob; Setvin, Martin; ...

2018-03-28

The performance of an organic semiconductor device is critically determined by the geometric alignment, orientation, and ordering of the organic molecules. Although an organic multilayer eventually adopts the crystal structure of the organic material, the alignment and configuration at the interface with the substrate/electrode material are essential for charge injection into the organic layer. This work focuses on the prototypical organic semiconductor para-sexiphenyl (6P) adsorbed on In 2O 3(111), the thermodynamically most stable surface of the material that the most common transparent conducting oxide, indium tin oxide, is based on. The onset of nucleation and formation of the first monolayermore » are followed with atomically resolved scanning tunneling microscopy and noncontact atomic force microscopy (nc-AFM). Annealing to 200 °C provides sufficient thermal energy for the molecules to orient themselves along the high-symmetry directions of the surface, leading to a single adsorption site. The AFM data suggests an essentially planar adsorption geometry. With increasing coverage, the 6P molecules first form a loose network with a poor long-range order. Eventually, the molecules reorient into an ordered monolayer. In conclusion, this first monolayer has a densely packed, well-ordered (2 × 1) structure with one 6P per In 2O 3(111) substrate unit cell, that is, a molecular density of 5.64 × 10 13 cm –2.« less

Prototypical Organic–Oxide Interface: Intramolecular Resolution of Sexiphenyl on In 2O 3 (111)

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

Wagner, Margareta; Hofinger, Jakob; Setvin, Martin

The performance of an organic semiconductor device is critically determined by the geometric alignment, orientation, and ordering of the organic molecules. Although an organic multilayer eventually adopts the crystal structure of the organic material, the alignment and configuration at the interface with the substrate/electrode material are essential for charge injection into the organic layer. This work focuses on the prototypical organic semiconductor para-sexiphenyl (6P) adsorbed on In 2O 3(111), the thermodynamically most stable surface of the material that the most common transparent conducting oxide, indium tin oxide, is based on. The onset of nucleation and formation of the first monolayermore » are followed with atomically resolved scanning tunneling microscopy and noncontact atomic force microscopy (nc-AFM). Annealing to 200 °C provides sufficient thermal energy for the molecules to orient themselves along the high-symmetry directions of the surface, leading to a single adsorption site. The AFM data suggests an essentially planar adsorption geometry. With increasing coverage, the 6P molecules first form a loose network with a poor long-range order. Eventually, the molecules reorient into an ordered monolayer. In conclusion, this first monolayer has a densely packed, well-ordered (2 × 1) structure with one 6P per In 2O 3(111) substrate unit cell, that is, a molecular density of 5.64 × 10 13 cm –2.« less

Mapping nanometric electronic property changes induced by an aryl diazonium sub-monolayer on HOPG.

PubMed

González, M C R; Carro, P; Vázquez, L; Creus, A H

2016-10-26

The morphology as well as the electric and electronic properties of aryl diazonium, in particular 4-nitrobenzene-diazonium (NBD), films on HOPG surfaces have been studied at the nanoscale level. By controlling the 2,2-diphenyl-1-picrylhydrazyl concentration during the NBD film growth, we have been able to control the thickness of the layer. The implications of NBD submonolayer adsorption on the electrical properties of this system have been analysed through Density Functional Theory (DFT) calculations, Atomic Force (AFM), Electric Force (EFM) and Kelvin Probe Force (KPFM) microscopies. DFT simulations showed that the NBD molecule adsorbs almost perpendicularly to the HOPG surface, which was confirmed experimentally through AFM imaging in the dynamic mode. In addition, DFT calculations showed that the adsorbed NBD has an appreciable dipole moment directed towards the HOPG surface and along the vertical direction of the HOPG surface. The existence of this dipole is the origin of the EFM contrast observed between the NBD-free and NBD-covered regions when a bias of -2 V was applied to the tip. Besides, the KPFM measurements show that the NBD adsorption leads to higher work function values, which is in agreement with the DFT calculations. Noticeably, our studies show that the KPFM signal is sensitive to the partial NBD coverage of the HOPG surface below the monolayer level.

A Study to Find Out the Full Immunization Coverage of 12 to 23-month old Children and Areas of Under-Performance using LQAS Technique in a Rural Area of Tripura.

PubMed

Datta, Anjan; Baidya, Subrata; Datta, Srabani; Mog, Chanda; Das, Shampa

2017-02-01

It is very important to analyze the factors which acts as obstacle in achieving 100% immunization among children. Lot Quality Assurance Sampling (LQAS) is one of the effective method to assess such barriers. To assess the full immunization coverage among 12 to 23-month old children of rural field practice area under Department of Community Medicine, Agartala Government Medical College and identify the factors for failure of full immunization. A community based cross-sectional study was conducted from November 2013 to October 2014 on children aged 12 to 23 months old of area under Mohanpur Community health centre. Using LQAS technique 330 samples were selected with multi-stage sampling, each sub-centre being one lot and two calculated to be the decision value. Data was collected using pre-designed pre-tested questionnaire during home visit and verifying immunization card and analysed by computer software SPSS version 21.0. The full immunization coverage among 12 to 23 months old children of Mohanpur area was found as 91.67%. Out of all the 22 sub-centres, 36.36% was found under performing as per pre-fixed criteria and the main reasons for failure of full immunization in those areas are unawareness of need of subsequent doses of vaccines and illness of the children. LQAS is an effective method to identify areas of under-performance even though overall full immunization coverage is high.

Polymeric brushes as functional templates for immobilizing ribonuclease A: study of binding kinetics and activity.

PubMed

Cullen, Sean P; Liu, Xiaosong; Mandel, Ian C; Himpsel, Franz J; Gopalan, Padma

2008-02-05

The ability to immobilize proteins with high binding capacities on surfaces while maintaining their activity is critical for protein microarrays and other biotechnological applications. We employed poly(acrylic acid) (PAA) brushes as templates to immobilize ribonuclease A (RNase A), which is commonly used to remove RNA from plasmid DNA preparations. The brushes are grown by surface-anchored atom-transfer radical polymerization (ATRP) initiators. RNase A was immobilized by both covalent esterification and a high binding capacity metal-ion complexation method to PAA brushes. The polymer brushes immobilized 30 times more enzyme compared to self-assembled monolayers. As the thickness of the brush increases, the surface density of the RNase A increases monotonically. The immobilization was investigated by ellipsometry, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). The activity of the immobilized RNase A was determined using UV absorbance. As much as 11.0 microg/cm(2) of RNase A was bound to PAA brushes by metal-ion complexation compared to 5.8 microg/cm(2) by covalent immobilization which is 30 and 16 times the estimated mass bound in a monolayer. The calculated diffusion coefficient D was 0.63 x 10(-14) cm(2)/s for metal-ion complexation and 0.71 x 10(-14) cm(2)/s for covalent immobilization. Similar values of D indicate that the binding kinetics is similar, but the thermodynamic equilibrium coverage varies with the binding chemistry. Immobilization kinetics and thermodynamics were characterized by ellipsometry for both methods. A maximum relative activity of 0.70-0.80 was reached between five and nine monolayers of the immobilized enzyme. However, the relative activity for covalent immobilization was greater than that of metal-ion complexation. Covalent esterification resulted in similar temperature dependence as free enzyme, whereas metal-ion complexation showed no temperature dependence indicating a significant change in conformation.

Superconductivity proximate to antiferromagnetism in a copper-oxide monolayer grown on Bi2Sr2CaCu2O8 +δ

NASA Astrophysics Data System (ADS)

Wang, Shuai; Zhang, Long; Wang, Fa

2018-01-01

A nodeless superconducting (SC) gap was reported in a recent scanning tunneling spectroscopy experiment of a copper-oxide monolayer grown on a Bi2Sr2CaCu2O8 +δ (Bi2212) substrate [Zhong et al., Sci. Bull. 61, 1239 (2016), 10.1007/s11434-016-1145-4], which is in stark contrast to the nodal d -wave pairing gap in the bulk cuprates. Motivated by this experiment, we first show with first-principles calculations that the tetragonal CuO (T-CuO) monolayer on the Bi2212 substrate is more stable than the commonly postulated CuO2 structure. The T-CuO monolayer is composed of two CuO2 layers sharing the same O atoms. The band structure is obtained by first-principles calculations, and its strong electron correlation is treated with the renormalized mean-field theory. We argue that one CuO2 sublattice is hole doped while the other sublattice remains half filled and may have antiferromagnetic (AF) order. The doped Cu sublattice can show d -wave SC; however, its proximity to the AF Cu sublattice induces a spin-dependent hopping, which splits the Fermi surface and may lead to a full SC gap. Therefore, the nodeless SC gap observed in the experiment could be accounted for by the d -wave SC proximity to an AF order, thus it is extrinsic rather than intrinsic to the CuO2 layers.

Quality and extent of locum tenens coverage in pediatric surgical practices.

PubMed

Nolan, Tracy L; Kandel, Jessica J; Nakayama, Don K

2015-04-01

The prevalence and quality of locum tenens coverage in pediatric surgery have not been determined. An Internet-based survey of American Pediatric Surgical Association members was conducted: 1) practice description; 2) use and frequency of locum tenens coverage; 4) whether the surgeon provided such coverage; and 5) Likert scale responses (strongly disagree, disagree, neutral, agree, strongly agree) to statements addressing its acceptability and quality (two × five contingency table and χ(2) analyses, significance at P < 0.05). Three hundred sixteen of 1163 members (27.2% response rate) responded. One-fourth (24.1%) used a locum tenens regularly. Reasons were long-term inability to recruit a full-time surgeon (35.2%) and short-term vacancies (32.4%). One-fifth (20.4%) did locum tenens work; one-fourth (27.0%) plan to do so in the future. Two-thirds (64.2%) believe that surgical care in a locum tenens situation does not provide the same level of care as a full-time community-based surgeon. Most support locum tenens for short-term coverage (87.3%) and recruitment problems (72.1%), but not long-term vacancies (38.8%; P < 0.001) or permanent coverage (27.0%; P < 0.001). locum tenens coverage is an established feature of pediatric surgery. Most view it as a stopgap solution to the surgical workforce shortage.

Characterizing the mechanics of cultured cell monolayers

PubMed Central

Peter, Loic; Bellis, Julien; Baum, Buzz; Kabla, Alexandre J.; Charras, Guillaume T.

2012-01-01

One-cell-thick monolayers are the simplest tissues in multicellular organisms, yet they fulfill critical roles in development and normal physiology. In early development, embryonic morphogenesis results largely from monolayer rearrangement and deformation due to internally generated forces. Later, monolayers act as physical barriers separating the internal environment from the exterior and must withstand externally applied forces. Though resisting and generating mechanical forces is an essential part of monolayer function, simple experimental methods to characterize monolayer mechanical properties are lacking. Here, we describe a system for tensile testing of freely suspended cultured monolayers that enables the examination of their mechanical behavior at multi-, uni-, and subcellular scales. Using this system, we provide measurements of monolayer elasticity and show that this is two orders of magnitude larger than the elasticity of their isolated cellular components. Monolayers could withstand more than a doubling in length before failing through rupture of intercellular junctions. Measurement of stress at fracture enabled a first estimation of the average force needed to separate cells within truly mature monolayers, approximately ninefold larger than measured in pairs of isolated cells. As in single cells, monolayer mechanical properties were strongly dependent on the integrity of the actin cytoskeleton, myosin, and intercellular adhesions interfacing adjacent cells. High magnification imaging revealed that keratin filaments became progressively stretched during extension, suggesting they participate in monolayer mechanics. This multiscale study of monolayer response to deformation enabled by our device provides the first quantitative investigation of the link between monolayer biology and mechanics. PMID:22991459

Determinants and Coverage of Vaccination in Children in Western Kenya from a 2003 Cross-Sectional Survey

PubMed Central

Calhoun, Lisa M.; van Eijk, Anna M.; Lindblade, Kim A.; Odhiambo, Frank O.; Wilson, Mark L.; Winterbauer, Elizabeth; Slutsker, Laurence; Hamel, Mary J.

2014-01-01

This study assesses full and timely vaccination coverage and factors associated with full vaccination in children ages 12–23 months in Gem, Nyanza Province, Kenya in 2003. A simple random sample of 1,769 households was selected, and guardians were invited to bring children under 5 years of age to participate in a survey. Full vaccination coverage was 31.1% among 244 children. Only 2.2% received all vaccinations in the target month for each vaccination. In multivariate logistic regression, children of mothers of higher parity (odds ratio [OR] = 0.27, 95% confidence interval [95% CI] = 0.13–0.65, P ≤ 0.01), children of mothers with lower maternal education (OR = 0.35, 95% CI = 0.13–0.97, P ≤ 0.05), or children in households with the spouse absent versus present (OR = 0.40, 95% CI = 0.17–0.91, P ≤ 0.05) were less likely to be fully vaccinated. These data serve as a baseline from which changes in vaccination coverage will be measured as interventions to improve vaccination timeliness are introduced. PMID:24343886

Determinants and coverage of vaccination in children in western Kenya from a 2003 cross-sectional survey.

PubMed

Calhoun, Lisa M; van Eijk, Anna M; Lindblade, Kim A; Odhiambo, Frank O; Wilson, Mark L; Winterbauer, Elizabeth; Slutsker, Laurence; Hamel, Mary J

2014-02-01

This study assesses full and timely vaccination coverage and factors associated with full vaccination in children ages 12-23 months in Gem, Nyanza Province, Kenya in 2003. A simple random sample of 1,769 households was selected, and guardians were invited to bring children under 5 years of age to participate in a survey. Full vaccination coverage was 31.1% among 244 children. Only 2.2% received all vaccinations in the target month for each vaccination. In multivariate logistic regression, children of mothers of higher parity (odds ratio [OR] = 0.27, 95% confidence interval [95% CI] = 0.13-0.65, P ≤ 0.01), children of mothers with lower maternal education (OR = 0.35, 95% CI = 0.13-0.97, P ≤ 0.05), or children in households with the spouse absent versus present (OR = 0.40, 95% CI = 0.17-0.91, P ≤ 0.05) were less likely to be fully vaccinated. These data serve as a baseline from which changes in vaccination coverage will be measured as interventions to improve vaccination timeliness are introduced.

Lower lattice thermal conductivity in SbAs than As or Sb monolayers: a first-principles study.

PubMed

Guo, San-Dong; Liu, Jiang-Tao

2017-12-06

Phonon transport in group-VA element (As, Sb and Bi) monolayer semiconductors has been widely investigated in theory, and, of them, monolayer Sb (antimonene) has recently been synthesized. In this work, phonon transport in monolayer SbAs is investigated with a combination of first-principles calculations and the linearized phonon Boltzmann equation. It is found that the lattice thermal conductivity of monolayer SbAs is lower than those of both monolayer As and Sb, and the corresponding sheet thermal conductance is 28.8 W K -1 at room temperature. To understand the lower lattice thermal conductivity in monolayer SbAs than those in monolayer As and Sb, the group velocities and phonon lifetimes of monolayer As, SbAs and Sb are calculated. The calculated results show that the group velocities of monolayer SbAs are between those of monolayer As and Sb, but that the phonon lifetimes of SbAs are smaller than those of both monolayer As and Sb. Hence, the low lattice thermal conductivity in monolayer SbAs is attributed to very small phonon lifetimes. Unexpectedly, the ZA branch has very little contribution to the total thermal conductivity, only 2.4%, which is obviously different from those of monolayer As and Sb with very large contributions. This can be explained by very small phonon lifetimes for the ZA branch of monolayer SbAs. The lower lattice thermal conductivity of monolayer SbAs compared to that of monolayer As or Sb can be understood by the alloying of As (Sb) with Sb (As), which should introduce phonon point defect scattering. We also consider the isotope and size effects on the lattice thermal conductivity. It is found that isotope scattering produces a neglectful effect, and the lattice thermal conductivity with a characteristic length smaller than 30 nm can reach a decrease of about 47%. These results may offer perspectives on tuning the lattice thermal conductivity by the mixture of multiple elements for applications of thermal management and thermoelectricity, and motivate further experimental efforts to synthesize monolayer SbAs.

Full-coverage film cooling. I - Comparison of heat transfer data for three injection angles

NASA Technical Reports Server (NTRS)

Crawford, M. E.; Kays, W. M.; Moffat, R. J.

1980-01-01

Wind tunnel experiments were carried out at Stanford between 1971 and 1977 to study the heat transfer characteristics of full-coverage film cooled surfaces with three geometries; normal-, 30 deg slant-, and 30 deg x 45 deg compound-angled injection. A flat full-coverage section and downstream recovery section comprised the heat transfer system. The experimental objectives were to determine, for each geometry, the effects on surface heat flux of injection blowing ratio, injection temperature ratio, and upstream initial conditions. Spanwise-averaged Stanton numbers were measured for blowing ratios from 0 to 1.3, and for two values of injection temperature at each blowing ratio. The heat transfer coefficient was defined on the basis of a mainstream-to-wall temperature difference. Initial momentum and enthalpy thickness Reynolds numbers were varied from 500 to about 3000.

Surface-Bound Intermediates in Low-Temperature Methanol Synthesis on Copper. Participants and Spectators

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

Yang, Yong; Mei, Donghai; Peden, Charles H.F.

The reactivity of surface adsorbed species present on copper catalysts during methanol synthesis at low temperatures was studied by simultaneous infrared spectroscopy (IR) and mass spectroscopy (MS) measurements during “titration” (transient surface reaction) experiments with isotopic tracing. The results show that adsorbed formate is a major bystander species present on the surface under steady-state methanol synthesis reaction conditions, but it cannot be converted to methanol by reaction with pure H 2, nor with H 2 plus added water. Formate-containing surface adlayers for these experiments were produced during steady state catalysis in (a) H 2:CO 2 (with substantial formate coverage) andmore » (b) moist H 2:CO (with no IR visible formate species). Both these reaction conditions produce methanol at steady state with relatively high rates. Adlayers containing formate were also produced by (c) formic acid adsorption. Various "titration" gases were used to probe these adlayers at modest temperatures (T = 410-450K) and 6 bar total pressure. Methanol gas (up to ~1% monolayer equivalent) was produced in "titration" from the H 2:CO 2 catalytic adlayers by H 2 plus water, but not by dry hydrogen. The decay in the formate IR features accelerated in the presence of added water vapor. The H 2:CO:H 2O catalytic adlayer produced similar methanol titration yields in H 2 plus water but showed no surface formate features in IR (less than 0.2% monolayer coverage). Finally, formate from formic acid chemisorption produced no methanol under any titration conditions. Even under (H 2:CO 2) catalytic reaction conditions, isotope tracing showed that pre-adsorbed formate from formic acid did not contribute to the methanol produced. Although non-formate intermediates exist during low temperature methanol synthesis on copper which can be converted to methanol gas by titration with pure H 2 plus water in sufficient quantities for that intermediate to be observable by IR, formate itself is only a "spectator" in this reaction and gives no observable methanol upon any titration we performed with H 2 or H 2 plus water.« less

Reactive wetting properties of TiO2 nanoparticles predicted by ab initio molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Brandt, Erik G.; Agosta, Lorenzo; Lyubartsev, Alexander P.

2016-07-01

Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity.Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity. Electronic supplementary information (ESI) available: Simulation data on equilibration of energies and structures (root-mean-square-deviations and coordination numbers); radial distribution functions for all O-Ti pairs over the entire data domain; comparison of coordination number distributions for dry and wet nanoparticles; dynamics of water reactivity; high-resolution electron density for the rutile NP. A movie of the simulation trajectory for the rutile (TiO2)24.30H2O system. See DOI: 10.1039/C6NR02791A

Topical Coverage in Introductory Textbooks from the 1980s through the 2000s

ERIC Educational Resources Information Center

Griggs, Richard A.

2014-01-01

To determine how topical coverage in introductory textbooks may have changed from the 1980s to the present, the author examined topic coverage in full-length and brief introductory textbooks from this time period. Because 98% of the teachers use textbooks for the introductory course and the majority do not assign reading beyond the textbook, the…

Oxygen chemisorption on copper (110)

NASA Astrophysics Data System (ADS)

Mundenar, J. M.; Baddorf, A. P.; Plummer, E. W.; Sneddon, L. G.; Didio, R. A.; Zehner, D. M.

1987-09-01

High resolution electron energy loss spectroscopy (EELS) and angle-resolved ultra-violet photoelectron spectroscopy (UPS) have been used: (1) to study a surface phonon of Cu(110) as a function of oxygen coverage, (2) to identify oxygen adsorption site(s) in the p(2×1)O, c(6×2)O, and disordered oxygen overlayer (formed by O 2 exposure at 100 K), and (3) to determine whether molecular adsorption or dissociation of O 2 followed by atomic adsorption occurs after oxygen exposure at 100 K. With EELS, a continuous shift in energy of the surface phonon as a function of oxygen exposure at 300 K is observed. Our EELS data for the p(2×1)O overlayer support previous reports of a single long-bridge adsorption site, while indicating two sites are populated in the c(6×2)O overlayer: a long-bridge site and a four-coordinated site. The long-bridge site is populated at all coverages while the four-coordinated sites is occupied only after high exposures (≥2×10 4 L) at room temperature, or after exposures >2 L at low temperature (100 K). For both conditions the oxygen coverages are greater than 0.5 monolayer. Also, EELS and complementary UPS data clearly show that oxygen adsorbs dissociatively on Cu(110) after O 2 exposure at 100 K. At this temperature, LEED results indicate that the oxygen atoms are adsorbed without long-range order; however, local adsorption sites, which are similar to those in the c(6×2)O surface, are observed.

Ultrafast Multi-Level Logic Gates with Spin-Valley Coupled Polarization Anisotropy in Monolayer MoS2

PubMed Central

Wang, Yu-Ting; Luo, Chih-Wei; Yabushita, Atsushi; Wu, Kaung-Hsiung; Kobayashi, Takayoshi; Chen, Chang-Hsiao; Li, Lain-Jong

2015-01-01

The inherent valley-contrasting optical selection rules for interband transitions at the K and K′ valleys in monolayer MoS2 have attracted extensive interest. Carriers in these two valleys can be selectively excited by circularly polarized optical fields. The comprehensive dynamics of spin valley coupled polarization and polarized exciton are completely resolved in this work. Here, we present a systematic study of the ultrafast dynamics of monolayer MoS2 including spin randomization, exciton dissociation, free carrier relaxation, and electron-hole recombination by helicity- and photon energy-resolved transient spectroscopy. The time constants for these processes are 60 fs, 1 ps, 25 ps, and ~300 ps, respectively. The ultrafast dynamics of spin polarization, valley population, and exciton dissociation provides the desired information about the mechanism of radiationless transitions in various applications of 2D transition metal dichalcogenides. For example, spin valley coupled polarization provides a promising way to build optically selective-driven ultrafast valleytronics at room temperature. Therefore, a full understanding of the ultrafast dynamics in MoS2 is expected to provide important fundamental and technological perspectives. PMID:25656222

Diamondoid monolayers as electron emitters

DOEpatents

Yang, Wanli [El Cerrito, CA; Fabbri, Jason D [San Francisco, CA; Melosh, Nicholas A [Menlo Park, CA; Hussain, Zahid [Orinda, CA; Shen, Zhi-Xun [Stanford, CA

2012-04-10

Provided are electron emitters based upon diamondoid monolayers, preferably self-assembled higher diamondoid monolayers. High intensity electron emission has been demonstrated employing such diamondoid monolayers, particularly when the monolayers are comprised of higher diamondoids. The application of such diamondoid monolayers can alter the band structure of substrates, as well as emit monochromatic electrons, and the high intensity electron emissions can also greatly improve the efficiency of field-effect electron emitters as applied to industrial and commercial applications.

Diamondoid monolayers as electron emitters

DOEpatents

Yang, Wanli; Fabbri, Jason D.; Melosh, Nicholas A.; Hussain, Zahid; Shen, Zhi-Xun

2013-10-29

Provided are electron emitters based upon diamondoid monolayers, preferably self-assembled higher diamondoid monolayers. High intensity electron emission has been demonstrated employing such diamondoid monolayers, particularly when the monolayers are comprised of higher diamondoids. The application of such diamondoid monolayers can alter the band structure of substrates, as well as emit monochromatic electrons, and the high intensity electron emissions can also greatly improve the efficiency of field-effect electron emitters as applied to industrial and commercial applications.

Monolayer coated aerogels and method of making

DOEpatents

Zemanian, Thomas Samuel [Richland, WA; Fryxell, Glen [Kennwick, WA; Ustyugov, Oleksiy A [Spokane, WA

2006-03-28

Aerogels having a monolayer coating are described. The aerogel and a monolayer forming precursor are provided in a supercritical fluid, whereupon the aerogel and the monolayer forming precursor are reacted in said supercritical fluid to form a covalent bond between the aerogel and the monolayer forming precursor. Suitable aerogels are ceramic oxides such as silica, alumina, aluminosilicate, and combinations thereof. Suitable monolayer forming precursors include alkyl silanes, chlorosilanes, boranes, chloroboranes, germanes, and combinations thereof. The method may also include providing a surface preparation agent such as water, or hydroetching an aerogel to enhance the coating of the monolayer.

Asymmetric or symmetric bilayer formation during oblique drop impact depends on rheological properties of saturated and unsaturated lipid monolayers.

PubMed

Vranceanu, Marcel; Terinte, Nicoleta; Nirschl, Hermann; Leneweit, Gero

2011-02-01

Bilayer structures are formed by approaching two liquid surfaces with phospholipid monolayers, which are brought into contact by oblique drop impact on a liquid surface. Asymmetric bilayers can be produced by the coupling of drop and target monolayers. In contrast, symmetric bilayers or multilayers are formed by collapse of the compressed target monolayer. We show that under all studied conditions bilayer/multilayer synthesis takes place. The experimental conditions for the synthesis of asymmetric or symmetric bilayers are described quantitatively in terms of the surface rheological (surface elasticity and dilational viscosity) and the hydrodynamical parameters (Weber number and impact angle). The composition and mechanical properties of the phospholipid monolayers strongly influences the patterns of drop impact and the bilayer/multilayer formation. Cholesterol stiffens unsaturated phospholipid monolayers and fluidifies saturated monolayers. All monolayers form asymmetric vesicle-like structures, which are stable in the aqueous medium. Additionally, unsaturated phospholipid monolayers without cholesterol form symmetric vesicles by folding parts of the target monolayer. Sufficient presence of cholesterol in unsaturated phospholipid monolayers inhibits the folding of the target monolayer and the subsequent formation of symmetric bilayers. The rheological properties of saturated and unsaturated phospholipid monolayers and their mixtures with cholesterol are discussed. Based on drop impact results it is shown that the state of a so far undefined region in the DPPC/cholesterol phase diagram is a fluid phase. Copyright © 2010 Elsevier Inc. All rights reserved.

Selectivity and Sensitivity of Ultrathin Monolayer Electrodes

NASA Astrophysics Data System (ADS)

Cheng, Quan

The objective of this work is to build a molecular architecture on the electrode surface with a well-defined morphology and desirable electrochemical characteristics. The goal is accomplished by means of self-assembly of thioctic acid, a sulfur-terminated organic molecule with a short alkyl chain and a hydrophilic carboxylic headgroup, on a gold electrode. Characterization of the monolayer structure and the electrochemical response of the monolayer electrodes is performed by means of capacitance measurements and voltammetry. Investigation of the capacitance of the self-assembled monolayers provides insight into the macroscopic permeability of the films and reveals that penetration of solvent/ions into the thioctic acid monolayer film occurs extensively. Voltammetric results demonstrate that permselectivity of the monolayer electrode can be obtained as a result of the induced electrostatic interactions between the monolayer interface and the electroactive species. Measurement of the voltammetric response of the redox probes at the monolayers as a function of the electrolyte concentration and composition is used to qualitatively analyze the effect of electrolyte on response. A model describing the role of the interfacial charge in the electrochemical response of the monolayers as a function of the solution composition and surface smoothness is proposed. A strategy is developed to further explore the applications of the monolayer electrodes to control the electrochemical response of the biological molecules such as catecholamines. The ability to control the surface hydrophobicity of the monolayer electrodes through coadsorption of thioctic acid and hexanethiol, to display different electrochemical properties towards biological molecules is tested. The optimum conditions for detection of the biological molecules on the monolayer electrodes are discussed. In order to pursue selective analysis in microenvironments, the thioctic acid monolayer formed on the ultramicroelectrodes (UME) is investigated, demonstrating high permselectivity and high sensitivity of the monolayer modified UMEs. Because of the more effective mass transport to the UMEs, effects of electrolyte on the monolayer response can be characterized facilely. Amperometric pH sensing on the thioctic acid UMEs using a redox mediator is discussed. Finally, the thioctic acid monolayer microelectrode is applied to investigate direct electrochemistry of a redox protein, cytochrome c. A sketch for developing a biosensor via mediation effects using the monolayer assembly is proposed.

The role of retiree health insurance in the early retirement of public sector employees.

PubMed

Shoven, John B; Slavov, Sita Nataraj

2014-12-01

Most government employees have access to retiree health coverage, which provides them with group health coverage even if they retire before Medicare eligibility. We study the impact of retiree health coverage on the labor supply of public sector workers between the ages of 55 and 64. We find that retiree health coverage raises the probability of stopping full time work by 4.3 percentage points (around 38 percent) over two years among public sector workers aged 55-59, and by 6.7 percentage points (around 26 percent) over two years among public sector workers aged 60-64. In the younger age group, retiree health insurance mostly seems to facilitate transitions to part-time work rather than full retirement. However, in the older age group, it increases the probability of stopping work entirely by 4.3 percentage points (around 22 percent). Copyright © 2014 Elsevier B.V. All rights reserved.

Fluorine atom abstraction by Si(100). I. Experimental

NASA Astrophysics Data System (ADS)

Tate, M. R.; Gosalvez-Blanco, D.; Pullman, D. P.; Tsekouras, A. A.; Li, Y. L.; Yang, J. J.; Laughlin, K. B.; Eckman, S. C.; Bertino, M. F.; Ceyer, S. T.

1999-08-01

In the interaction of low energy F2 with Si(100) at 250 K, a dissociative chemisorption mechanism called atom abstraction is identified in which only one of the F atoms is adsorbed while the other F atom is scattered into the gas phase. The dynamics of atom abstraction are characterized via time-of-flight measurements of the scattered F atoms. The F atoms are translationally hyperthermal but only carry a small fraction (˜3%) of the tremendous exothermicity of the reaction. The angular distribution of F atoms is unusually broad for the product of an exothermic reaction. These results suggest an "attractive" interaction potential between F2 and the Si dangling bond with a transition state that is not constrained geometrically. These results are in disagreement with the results of theoretical investigations implying that the available potential energy surfaces are inadequate to describe the dynamics of this gas-surface interaction. In addition to single atom abstraction, two atom adsorption, a mechanism analogous to classic dissociative chemisorption in which both F atoms are adsorbed onto the surface, is also observed. The absolute probability of the three scattering channels (single atom abstraction, two atom adsorption, and unreactive scattering) for an incident F2 are determined as a function of F2 exposure. The fluorine coverage is determined by integrating the reaction probabilities over F2 exposure, and the reaction probabilities are recast as a function of fluorine coverage. Two atom adsorption is the dominant channel [P2=0.83±0.03(95%, N=9)] in the limit of zero coverage and decays monotonically to zero. Single atom abstraction is the minor channel (P1=0.13±0.03) at low coverage but increases to a maximum (P1=0.35±0.08) at about 0.5 monolayer (ML) coverage before decaying to zero. The reaction ceases at 0.94±0.11(95%, N=9) ML. Thermal desorption and helium diffraction confirm that the dangling bonds are the abstraction and adsorption sites. No Si lattice bonds are broken, in contrast to speculation by other investigators that the reaction exothermicity causes lattice disorder.

A Study to Find Out the Full Immunization Coverage of 12 to 23-month old Children and Areas of Under-Performance using LQAS Technique in a Rural Area of Tripura

PubMed Central

Baidya, Subrata; Datta, Srabani; Mog, Chanda; Das, Shampa

2017-01-01

Introduction It is very important to analyze the factors which acts as obstacle in achieving 100% immunization among children. Lot Quality Assurance Sampling (LQAS) is one of the effective method to assess such barriers. Aim To assess the full immunization coverage among 12 to 23-month old children of rural field practice area under Department of Community Medicine, Agartala Government Medical College and identify the factors for failure of full immunization. Materials and Methods A community based cross-sectional study was conducted from November 2013 to October 2014 on children aged 12 to 23 months old of area under Mohanpur Community health centre. Using LQAS technique 330 samples were selected with multi-stage sampling, each sub-centre being one lot and two calculated to be the decision value. Data was collected using pre-designed pre-tested questionnaire during home visit and verifying immunization card and analysed by computer software SPSS version 21.0. Results The full immunization coverage among 12 to 23 months old children of Mohanpur area was found as 91.67%. Out of all the 22 sub-centres, 36.36% was found under performing as per pre-fixed criteria and the main reasons for failure of full immunization in those areas are unawareness of need of subsequent doses of vaccines and illness of the children. Conclusion LQAS is an effective method to identify areas of under-performance even though overall full immunization coverage is high. PMID:28384892

Miscibility of binary monolayers at the air-water interface and interaction of protein with immobilized monolayers by surface plasmon resonance technique.

PubMed

Wang, Yuchun; Du, Xuezhong

2006-07-04

The miscibility and stability of the binary monolayers of zwitterionic dipalmitoylphosphatidylcholine (DPPC) and cationic dioctadecyldimethylammonium bromide (DOMA) at the air-water interface and the interaction of ferritin with the immobilized monolayers have been studied in detail using surface pressure-area isotherms and surface plasmon resonance technique, respectively. The surface pressure-area isotherms indicated that the binary monolayers of DPPC and DOMA at the air-water interface were miscible and more stable than the monolayers of the two individual components. The surface plasmon resonance studies indicated that ferritin binding to the immobilized monolayers was primarily driven by the electrostatic interaction and that the amount of adsorbed protein at saturation was closely related not only to the number of positive charges in the monolayers but also to the pattern of positive charges at a given mole fraction of DOMA. The protein adsorption kinetics was determined by the properties of the monolayers (i.e., the protein-monolayer interaction) and the structure of preadsorbed protein molecules (i.e., the protein-protein interaction).

Full-coverage film cooling: 3-dimensional measurements of turbulence structure and prediction of recovery region hydrodynamics

NASA Technical Reports Server (NTRS)

Yavuzkurt, S.; Moffat, R. J.; Kays, W. M.

1979-01-01

Hydrodynamic measurements were made with a triaxial hot-wire in the full-coverage region and the recovery region following an array of injection holes inclined downstream, at 30 degrees to the surface. The data were taken under isothermal conditions at ambient temperature and pressure for two blowing ratios: M = 0.9 and M = 0.4. Profiles of the three main velocity components and the six Reynolds stresses were obtained at several spanwise positions at each of the five locations down the test plate. A one-equation model of turbulence (using turbulent kinetic energy with an algebraic mixing length) was used in a two-dimensional computer program to predict the mean velocity and turbulent kinetic energy profiles in the recovery region. A new real-time hotwire scheme was developed to make measurements in the three-dimensional turbulent boundary layer over the full-coverage surface.

Transmission Magnitude and Phase Control for Polarization-Preserving Reflectionless Metasurfaces

NASA Astrophysics Data System (ADS)

Kwon, Do-Hoon; Ptitcyn, Grigorii; Díaz-Rubio, Ana; Tretyakov, Sergei A.

2018-03-01

For transmissive applications of electromagnetic metasurfaces, an array of subwavelength Huygens' meta-atoms are typically used to eliminate reflection and achieve a high-transmission power efficiency together with a wide transmission phase coverage. We show that the underlying principle of low reflection and full control over transmission is asymmetric scattering into the specular reflection and transmission directions that results from a superposition of symmetric and antisymmetric scattering components, with Huygens' meta-atoms being one example configuration. Available for oblique illumination in TM polarization, a meta-atom configuration comprising normal and tangential electric polarizations is presented, which is capable of reflectionless, full-power transmission and a 2 π transmission phase coverage as well as full absorption. For lossy metasurfaces, we show that a complete phase coverage is still available for reflectionless designs for any value of absorptance. Numerical examples in the microwave and optical regimes are provided.

National, State, and Selected Local Area Vaccination Coverage Among Children Aged 19-35 Months - United States, 2014.

PubMed

Hill, Holly A; Elam-Evans, Laurie D; Yankey, David; Singleton, James A; Kolasa, Maureen

2015-08-28

The reduction in morbidity and mortality associated with vaccine-preventable diseases in the United States has been described as one of the 10 greatest public health achievements of the first decade of the 21st century. A recent analysis concluded that routine childhood vaccination will prevent 322 million cases of disease and about 732,000 early deaths among children born during 1994-2013, for a net societal cost savings of $1.38 trillion. The National Immunization Survey (NIS) has monitored vaccination coverage among U.S. children aged 19-35 months since 1994. This report presents national, regional, state, and selected local area vaccination coverage estimates for children born from January 2011 through May 2013, based on data from the 2014 NIS. For most vaccinations, there was no significant change in coverage between 2013 and 2014. The exception was hepatitis A vaccine (HepA), for which increases were observed in coverage with both ≥1 and ≥2 doses. As in previous years, <1% of children received no vaccinations. National coverage estimates indicate that the Healthy People 2020 target* of 90% was met for ≥3 doses of poliovirus vaccine (93.3%), ≥1 dose of measles, mumps, and rubella vaccine (MMR) (91.5%), ≥3 doses of hepatitis B vaccine (HepB) (91.6%), and ≥1 dose of varicella vaccine (91.0%). Coverage was below target for ≥4 doses of diphtheria, tetanus, and acellular pertussis vaccine (DTaP), the full series of Haemophilus influenzae type b (Hib) vaccine, hepatitis B (HepB) birth dose,† ≥4 doses pneumococcal conjugate vaccine (PCV), ≥2 doses of HepA, the full series of rotavirus vaccine, and the combined vaccine series.§ Examination of coverage by child's race/ethnicity revealed lower estimated coverage among non-Hispanic black children compared with non-Hispanic white children for several vaccinations, including DTaP, the full series of Hib, PCV, rotavirus vaccine, and the combined series. Children from households classified as below the federal poverty level had lower estimated coverage for almost all of the vaccinations assessed, compared with children living at or above the poverty level. Significant variation in coverage by state¶ was observed for several vaccinations, including HepB birth dose, HepA, and rotavirus. High vaccination coverage must be maintained across geographic and sociodemographic groups if progress in reducing the impact of vaccine-preventable diseases is to be sustained.

Electron-stimulated reactions in nanoscale water films adsorbed on (alpha)-Al2O3(0001)

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

Petrik, Nikolay G.; Kimmel, Gregory A.

2018-05-11

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D2O) films adsorbed on -Al2O3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products ( D2, O2 and D¬2O) and the total sputtering yield increased with increasing D2O coverage up to ~15 water monolayers (i.e. ~15 1015 cm-2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D2O and H2O) demonstrated that the highest water decomposition yields occurred at the interfaces of the nanoscalemore » water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO2(110) interfaces. We propose that the relatively low activity of Al2O3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the molecular hydrogen.« less

Measurement of inelastic cross sections for low-energy electron scattering from DNA bases.

PubMed

Michaud, Marc; Bazin, Marc; Sanche, Léon

2012-01-01

To determine experimentally the absolute cross sections (CS) to deposit various amount of energies into DNA bases by low-energy electron (LEE) impact. Electron energy loss (EEL) spectra of DNA bases were recorded for different LEE impact energies on the molecules deposited at very low coverage on an inert argon (Ar) substrate. Following their normalisation to the effective incident electron current and molecular surface number density, the EEL spectra were then fitted with multiple Gaussian functions in order to delimit the various excitation energy regions. The CS to excite a molecule into its various excitation modes were finally obtained from computing the area under the corresponding Gaussians. The EEL spectra and absolute CS for the electronic excitations of pyrimidine and the DNA bases thymine, adenine, and cytosine by electron impacts below 18 eV were reported for the molecules deposited at about monolayer coverage on a solid Ar substrate. The CS for electronic excitations of DNA bases by LEE impact were found to lie within the 10(216) to 10(218) cm(2) range. The large value of the total ionisation CS indicated that ionisation of DNA bases by LEE is an important dissipative process via which ionising radiation degrades and is absorbed in DNA.

Measurement of inelastic cross sections for low-energy electron scattering from DNA bases

PubMed Central

Michaud, Marc; Bazin, Marc.; Sanche, Léon

2013-01-01

Purpose Determine experimentally the absolute cross sections (CS) to deposit various amount of energies into DNA bases by low-energy electron (LEE) impact. Materials and methods Electron energy loss (EEL) spectra of DNA bases are recorded for different LEE impact energies on the molecules deposited at very low coverage on an inert argon (Ar) substrate. Following their normalisation to the effective incident electron current and molecular surface number density, the EEL spectra are then fitted with multiple Gaussian functions in order to delimit the various excitation energy regions. The CS to excite a molecule into its various excitation modes are finally obtained from computing the area under the corresponding Gaussians. Results The EEL spectra and absolute CS for the electronic excitations of pyrimidine and the DNA bases thymine, adenine, and cytosine by electron impacts below 18 eV are reported for the molecules deposited at about monolayer coverage on a solid Ar substrate. Conclusions The CS for electronic excitations of DNA bases by LEE impact are found to lie within the 10−16 – 10−18 cm2 range. The large value of the total ionisation CS indicates that ionisation of DNA bases by LEE is an important dissipative process via which ionising radiation degrades and is absorbed in DNA. PMID:21615242

Electron-stimulated reactions in nanoscale water films adsorbed on α-Al 2 O 3 (0001)

DOE PAGES

Petrik, Nikolay G.; Kimmel, Greg A.

2018-04-11

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D 2O) films adsorbed on an α-Al 2O 3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products (D 2, O 2 and D 2O) and the total sputtering yield increased with increasing D 2O coverage up to ~15 water monolayers (i.e. ~15 x 10 15 cm -2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D 2O and H 2O) demonstrated thatmore » the highest water decomposition yields occurred at the interfaces of the nanoscale water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO 2(110) interfaces. Here, we propose that the relatively low activity of Al 2O 3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the formation of molecular hydrogen.« less

Electron-stimulated reactions in nanoscale water films adsorbed on α-Al 2 O 3 (0001)

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

Petrik, Nikolay G.; Kimmel, Greg A.

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D 2O) films adsorbed on an α-Al 2O 3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products (D 2, O 2 and D 2O) and the total sputtering yield increased with increasing D 2O coverage up to ~15 water monolayers (i.e. ~15 x 10 15 cm -2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D 2O and H 2O) demonstrated thatmore » the highest water decomposition yields occurred at the interfaces of the nanoscale water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO 2(110) interfaces. Here, we propose that the relatively low activity of Al 2O 3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the formation of molecular hydrogen.« less

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.

Full coverage of perovskite layer onto ZnO nanorods via a modified sequential two-step deposition method for efficiency enhancement in perovskite solar cells

NASA Astrophysics Data System (ADS)

Ruankham, Pipat; Wongratanaphisan, Duangmanee; Gardchareon, Atcharawon; Phadungdhitidhada, Surachet; Choopun, Supab; Sagawa, Takashi

2017-07-01

Full coverage of perovskite layer onto ZnO nanorod substrates with less pinholes is crucial for achieving high-efficiency perovskite solar cells. In this work, a two-step sequential deposition method is modified to achieve an appropriate property of perovskite (MAPbI3) film. Surface treatment of perovskite layer and its precursor have been systematically performed and their morphologies have been investigated. By pre-wetting of lead iodide (PbI2) and letting it dry before reacting with methylammonium iodide (MAI) provide better coverage of perovskite film onto ZnO nanorod substrate than one without any treatment. An additional MAI deposition followed with toluene drop-casting technique on the perovskite film is also found to increase the coverage and enhance the transformation of PbI2 to MAPbI3. These lead to longer charge carrier lifetime, resulting in an enhanced power conversion efficiency (PCE) from 1.21% to 3.05%. The modified method could been applied to a complex ZnO nanorods/TiO2 nanoparticles substrate. The enhancement in PCE to 3.41% is observed. These imply that our introduced method provides a simple way to obtain the full coverage and better transformation to MAPbI3 phase for enhancement in performances of perovskite solar cells.

Fe3O4/γ-Fe2O3 nanoparticle multilayers deposited by the Langmuir-Blodgett technique for gas sensors application.

PubMed

Capone, S; Manera, M G; Taurino, A; Siciliano, P; Rella, R; Luby, S; Benkovicova, M; Siffalovic, P; Majkova, E

2014-02-04

Fe3O4/γ-Fe2O3 nanoparticles (NPs) based thin films were used as active layers in solid state resistive chemical sensors. NPs were synthesized by high temperature solution phase reaction. Sensing NP monolayers (ML) were deposited by Langmuir-Blodgett (LB) techniques onto chemoresistive transduction platforms. The sensing ML were UV treated to remove NP insulating capping. Sensors surface was characterized by scanning electron microscopy (SEM). Systematic gas sensing tests in controlled atmosphere were carried out toward NO2, CO, and acetone at different concentrations and working temperatures of the sensing layers. The best sensing performance results were obtained for sensors with higher NPs coverage (10 ML), mainly for NO2 gas showing interesting selectivity toward nitrogen oxides. Electrical properties and conduction mechanisms are discussed.

Epitaxy of Fe/Cu/Si(1 1 1) ultrathin films: an Auger electron diffraction study

NASA Astrophysics Data System (ADS)

Castrucci, P.; Gunnella, R.; Bernardini, R.; Montecchiari, A.; Carboni, R.; De Crescenzi, M.

2001-06-01

Epitaxial Fe films, with thickness in the range between 1 and 50 ML (monolayer, ML), were grown in ultrahigh vacuum conditions on the 7×7 reconstructed (1 1 1)-Si surface. The films were evaporated on a Cu thick buffer layer to avoid iron silicides formation. Auger electron diffraction (AED) technique has been used to investigate the growth of the pseudomorphic film of fcc γ-Fe(1 1 1) and the successive growth of bcc Fe(1 1 0) domains in the Kurdjumov-Sachs orientation. The early stages of growth have been carefully investigated through AED to assess the pseudomorphism of iron γ-phase. AED patterns clearly show the presence of diffraction features that are fingerprints of the existence of a few bcc arranged atomic structures even for 1 ML iron coverage.

Auger electron diffraction study of the growth of Fe(001) films on ZnSe(001)

NASA Astrophysics Data System (ADS)

Jonker, B. T.; Prinz, G. A.

1991-03-01

The growth of Fe films on ZnSe(001) epilayers and bulk GaAs(001) substrates has been studied to determine the mode of film growth, the formation of the interface, and the structure of the overlayer at the 1-10 monolayer level. Auger electron diffraction (AED), x-ray photoelectron spectroscopy (XPS), and reflection high-energy electron diffraction data are obtained for incremental deposition of the Fe(001) overlayer. The coverage dependence of the AED forward scattering peaks reveals a predominantly layer-by-layer mode of film growth at 175 °C on ZnSe, while a more three-dimensional growth mode occurs on the oxide-desorbed GaAs(001) substrate. XPS studies of the semiconductor 3d levels indicate that the Fe/ZnSe interface is less reactive than the Fe/GaAs interface.

Thermomechanical Response of Self-Assembled Nanoparticle Membranes

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

Wang, Yifan; Chan, Henry; Narayanan, Badri

2017-07-21

Monolayers composed of colloidal nanoparticles, with a thickness of less than 10 nm, have remarkable mechanical moduli and can suspend over micrometer-sized holes to form free-standing membranes. In this paper, we discuss experiment's and coarse-grained molecular dynamics simulations characterizing the thermomechanical properties of these self-assembled nanoparticle membranes. These membranes remain strong and resilient up to temperatures much higher than previous simulation predictions and exhibit an unexpected hysteretic behavior during the first heating cooling cycle. We show this hysteretic behavior can be explained by an asymmetric ligand configuration from the self assembly process and can be controlled by changing the ligandmore » coverage or cross-linking the ligand molecules. Finally, we show the screening effect of water molecules on the ligand interactions can strongly affect the moduli and thermomechanical behavior.« less

Identification of Au–S complexes on Au(100)

DOE PAGES

Walen, Holly; Liu, Da -Jiang; Oh, Junepyo; ...

2016-01-25

In this study, using a combination of scanning tunneling microscopy and density functional theory (DFT) calculations, we have identified a set of related Au–S complexes that form on Au(100), when sulfur adsorbs and lifts the hexagonal surface reconstruction. The predominant complex is diamond-shaped with stoichiometry Au 4S 5. All of the complexes can be regarded as combinations of S–Au–S subunits. The complexes exist within, or at the edges of, p(2 × 2) sulfur islands that cover the unreconstructed Au regions, and are observed throughout the range of S coverage examined in this study, 0.009 to 0.12 monolayers. A qualitative modelmore » is developed which incorporates competitive formation of complexes, Au rafts, and p(2 × 2) sulfur islands, as Au atoms are released by the surface structure transformation.« less

Angle-resolved and core-level photoemission study of interfacing the topological insulator Bi1.5Sb0.5Te1.7Se1.3 with Ag, Nb, and Fe

NASA Astrophysics Data System (ADS)

de Jong, N.; Frantzeskakis, E.; Zwartsenberg, B.; Huang, Y. K.; Wu, D.; Hlawenka, P.; Sańchez-Barriga, J.; Varykhalov, A.; van Heumen, E.; Golden, M. S.

2015-08-01

Interfaces between a bulk-insulating topological insulator (TI) and metallic adatoms have been studied using high-resolution, angle-resolved, and core-level photoemission. Fe, Nb, and Ag were evaporated onto Bi1 .5Sb0 .5Te1 .7Se1 .3 (BSTS) surfaces both at room temperature and 38 K. The coverage and temperature dependence of the adsorption and interfacial formation process have been investigated, highlighting the effects of the overlayer growth on the occupied electronic structure of the TI. For all coverages at room temperature and for those equivalent to less than 0.2 monolayer at low temperature all three metals lead to a downward shift of the TI bands with respect to the Fermi level. At room temperature Ag appears to intercalate efficiently into the van der Waals gap of BSTS, accompanied by low-level substitution for the Te/Se atoms of the termination layer of the crystal. This Te/Se substitution with silver increases significantly for low temperature adsorption, and can even dominate the electrostatic environment of the Bi/Sb atoms in the BSTS near-surface region. On the other hand, Fe and Nb evaporants remain close to the termination layer of the crystal. On room temperature deposition, they initially substitute isoelectronically for Bi as a function of coverage, before substituting for Te/Se atoms. For low temperature deposition, Fe and Nb are too immobile for substitution processes and show a behavior consistent with clustering on the surface. For both Ag and Fe/Nb, these differing adsorption pathways still lead to the qualitatively similar and remarkable behavior for low temperature deposition that the chemical potential first moves downward (p -type dopant behavior) and then upward (n -type behavior) on increasing coverage.

Methanol oxidation on stoichiometric and oxygen-rich RuO2(110).

PubMed

Rai, Rahul; Weaver, Jason F

2017-07-26

We used temperature-programmed reaction spectroscopy (TPRS) to investigate the adsorption and oxidation of methanol on stoichiometric and O-rich RuO 2 (110) surfaces. We find that the complete oxidation of CH 3 OH is strongly preferred on stoichiometric RuO 2 (110) during TPRS for initial CH 3 OH coverages below ∼0.33 ML (monolayer), and that partial oxidation to mainly CH 2 O becomes increasingly favored with increasing CH 3 OH coverage from 0.33 to 1.0 ML. We present evidence that an adsorbed CH 2 O 2 species serves as the key intermediate to complete oxidation and that CH 2 O 2 formation is intrinsically facile but becomes limited by the availability of bridging O-atoms on stoichiometric RuO 2 (110) at initial CH 3 OH coverages above 0.33 ML. We show that methanol molecules adsorbed in excess of 0.33 ML dehydrogenate to mainly CH 2 O and desorb during TPRS, with adsorbed CH 3 O groups mediating the evolution of both CH 2 O and CH 3 OH. We find that O-rich RuO 2 (110) surfaces are also highly active toward methanol oxidation and that selectivity toward the complete oxidation of methanol increases markedly with increasing coverage of on-top O-atoms (O ot ) on RuO 2 (110). Our results demonstrate that CH 3 OH species adsorbed within O ot -rich domains react efficiently during TPRS, in parallel with reaction of CH 3 OH adsorbed initially on cus-Ru sites. The data suggests that the facile hydrogenation of O ot atoms and the resulting desorption of H 2 O at low-temperature (<∼400 K) provides an efficient pathway for restoring reactive O-atoms and thereby promoting complete oxidation of methanol on the O-rich RuO 2 (110) surface.

The interaction of insulin, glucose, and insulin-glucose mixtures with a phospholipid monolayer.

PubMed

Shigenobu, Hayato; McNamee, Cathy E

2012-12-15

We determined how glucose or insulin interacts with a phospholipid monolayer at the air/water interface and explained these mechanisms from a physico-chemical point of view. The 1,2-dipalmitoyl-2-sn-glycero-3-phosphatidylcholine (DPPC) monolayer at an air/water interface acted as a model membrane, which allowed the effect of the molecular packing density in the monolayer on the interactions to be determined. The interaction of glucose, insulin, and a mixture of glucose and insulin to the DPPC monolayer were investigated via surface pressure-area per molecule Langmuir isotherms and fluorescence microscopy. Glucose adsorbed to the underside of the DPPC monolayer, while insulin was able to penetrate through the monolayer when the phospholipid molecules were not densely packed. The presence of a mixture of insulin and glucose affected the molecular packing in the DPPC monolayer differently than the pure insulin or glucose solutions, and the glucose-insulin mixture was seen to be able to penetrate through the monolayer. These results indicated that glucose and insulin interact with one another, giving a material that may then transported through a pore in the monolayer or through the spaces between the molecules of the monolayer. Copyright © 2012 Elsevier Inc. All rights reserved.

Interlayer orientation-dependent light absorption and emission in monolayer semiconductor stacks

PubMed Central

Heo, Hoseok; Sung, Ji Ho; Cha, Soonyoung; Jang, Bo-Gyu; Kim, Joo-Youn; Jin, Gangtae; Lee, Donghun; Ahn, Ji-Hoon; Lee, Myoung-Jae; Shim, Ji Hoon; Choi, Hyunyong; Jo, Moon-Ho

2015-01-01

Two-dimensional stacks of dissimilar hexagonal monolayers exhibit unusual electronic, photonic and photovoltaic responses that arise from substantial interlayer excitations. Interband excitation phenomena in individual hexagonal monolayer occur in states at band edges (valleys) in the hexagonal momentum space; therefore, low-energy interlayer excitation in the hexagonal monolayer stacks can be directed by the two-dimensional rotational degree of each monolayer crystal. However, this rotation-dependent excitation is largely unknown, due to lack in control over the relative monolayer rotations, thereby leading to momentum-mismatched interlayer excitations. Here, we report that light absorption and emission in MoS2/WS2 monolayer stacks can be tunable from indirect- to direct-gap transitions in both spectral and dynamic characteristics, when the constituent monolayer crystals are coherently stacked without in-plane rotation misfit. Our study suggests that the interlayer rotational attributes determine tunable interlayer excitation as a new set of basis for investigating optical phenomena in a two-dimensional hexagonal monolayer system. PMID:26099952

Plasma immersion ion implantation of polyurethane shape memory polymer: Surface properties and protein immobilization

NASA Astrophysics Data System (ADS)

Cheng, Xinying; Kondyurin, Alexey; Bao, Shisan; Bilek, Marcela M. M.; Ye, Lin

2017-09-01

Polyurethane-type shape memory polymers (SMPU) are promising biomedical implant materials due to their ability to recover to a predetermined shape from a temporary shape induced by thermal activation close to human body temperature and their advantageous mechanical properties including large recovery strains and low recovery stresses. Plasma Immersion Ion Implantation (PIII) is a surface modification process using energetic ions that generates radicals in polymer surfaces leading to carbonisation and oxidation and the ability to covalently immobilise proteins without the need for wet chemistry. Here we show that PIII treatment of SMPU significantly enhances its bioactivity making SMPU suitable for applications in permanent implantable biomedical devices. Scanning Electron Microscopy (SEM), contact angle measurements, surface energy measurements, attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterise the PIII modified surface, including its after treatment aging kinetics and its capability to covalently immobilise protein directly from solution. The results show a substantial improvement in wettability and dramatic changes of surface chemical composition dependent on treatment duration, due to the generation of radicals and subsequent oxidation. The SMPU surface, PIII treated for 200s, achieved a saturated level of covalently immobilized protein indicating that a full monolayer coverage was achieved. We conclude that PIII is a promising and efficient surface modification method to enhance the biocompatibility of SMPU for use in medical applications that demand bioactivity for tissue integration and stability in vivo.

A Novel Deployment Scheme Based on Three-Dimensional Coverage Model for Wireless Sensor Networks

PubMed Central

Xiao, Fu; Yang, Yang; Wang, Ruchuan; Sun, Lijuan

2014-01-01

Coverage pattern and deployment strategy are directly related to the optimum allocation of limited resources for wireless sensor networks, such as energy of nodes, communication bandwidth, and computing power, and quality improvement is largely determined by these for wireless sensor networks. A three-dimensional coverage pattern and deployment scheme are proposed in this paper. Firstly, by analyzing the regular polyhedron models in three-dimensional scene, a coverage pattern based on cuboids is proposed, and then relationship between coverage and sensor nodes' radius is deduced; also the minimum number of sensor nodes to maintain network area's full coverage is calculated. At last, sensor nodes are deployed according to the coverage pattern after the monitor area is subdivided into finite 3D grid. Experimental results show that, compared with traditional random method, sensor nodes number is reduced effectively while coverage rate of monitor area is ensured using our coverage pattern and deterministic deployment scheme. PMID:25045747

Early Impacts of the Affordable Care Act on Health Insurance Coverage in Medicaid Expansion and Non-Expansion States.

PubMed

Courtemanche, Charles; Marton, James; Ukert, Benjamin; Yelowitz, Aaron; Zapata, Daniela

2017-01-01

The Affordable Care Act (ACA) aimed to achieve nearly universal health insurance coverage in the United States through a combination of insurance market reforms, mandates, subsidies, health insurance exchanges, and Medicaid expansions, most of which took effect in 2014. This paper estimates the causal effects of the ACA on health insurance coverage in 2014 using data from the American Community Survey. We utilize difference-in-difference-in-differences models that exploit cross-sectional variation in the intensity of treatment arising from state participation in the Medicaid expansion and local area pre-ACA uninsured rates. This strategy allows us to identify the effects of the ACA in both Medicaid expansion and non-expansion states. Our preferred specification suggests that, at the average pre-treatment uninsured rate, the full ACA increased the proportion of residents with insurance by 5.9 percentage points compared to 2.8 percentage points in states that did not expand Medicaid. Private insurance expansions from the ACA were due to increases in both employer-provided and non-group coverage. The coverage gains from the full ACA were largest for those without a college degree, non-whites, young adults, unmarried individuals, and those without children in the home. We find no evidence that the Medicaid expansion crowded out private coverage.

Fractographic study of the behavior of different ceramic veneers on full coverage crowns in relation to supporting core materials

PubMed Central

Agustín-Panadero, Rubén; Román-Rodriguez, Juan L.; Solá-Ruíz, María F.; Granell-Ruíz, María; Fons-Font, Antonio

2013-01-01

Objectives: To observe porcelain veneer behavior of zirconia and metal-ceramic full coverage crowns when subjected to compression testing, comparing zirconia cores to metal cores. Study Design: The porcelain fracture surfaces of 120 full coverage crowns (60 with a metal core and 60 with a zirconia core) subjected to static load (compression) testing were analyzed. Image analysis was performed using macroscopic processing with 8x and 12x enlargement. Five samples from each group were prepared and underwent scanning electron microscope (SEM) analysis in order to make a fractographic study of fracture propagation in the contact area and composition analysis in the most significant areas of the specimen. Results: Statistically significant differences in fracture type (cohesive or adhesive) were found between the metal-ceramic and zirconia groups: the incidence of adhesive fracture was seen to be greater in metal-ceramic groups (92%) and cohesive fracture was more frequent in zirconium oxide groups (72%). The fracture propagation pattern was on the periphery of the contact area in the full coverage crown restorations selected for fractographic study. Conclusions: The greater frequency of cohesive fracture in restorations with zirconia cores indicates that their behavior is inadequate compared to metal-ceramic restorations and that further research is needed to improve their clinical performance. Key words:Zirconia, zirconium oxide, fractography, composition, porcelain veneers, fracture, cohesive, adhesive. PMID:24455092

From porphyrins to pyrphyrins: adsorption study and metalation of a molecular catalyst on Au(111)

NASA Astrophysics Data System (ADS)

Mette, Gerson; Sutter, Denys; Gurdal, Yeliz; Schnidrig, Stephan; Probst, Benjamin; Iannuzzi, Marcella; Hutter, Jürg; Alberto, Roger; Osterwalder, Jürg

2016-04-01

The molecular ligand pyrphyrin, a tetradentate bipyridine based macrocycle, represents an interesting but widely unexplored class of molecules. It resembles the well-known porphyrin, but consists of pyridyl subunits instead of pyrroles. Metal complexes based on pyrphyrin ligands have recently shown promise as water reduction catalysts in homogeneous photochemical water splitting reactions. In this study, the adsorption and metalation of pyrphyrin on a single crystalline Au(111) surface is investigated in an ultrahigh vacuum by means of scanning tunneling microscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy and density functional theory. Pyrphyrin coverages of approximately one monolayer and less are obtained by sublimation of the molecules on the substrate kept at room temperature. The molecules self-assemble in two distinct phases of long-range molecular ordering depending on the surface coverage. The deposition of cobalt metal and subsequent annealing lead to the formation of Co-ligated pyrphyrin molecules accompanied by a pronounced change of the molecular self-assembly. Electronic structure calculations taking the herringbone reconstruction of Au(111) into account show that the molecules are physisorbed, but preferred adsorption sites are identified where Co and the N atoms of the two terminal cyano groups are optimally coordinated to the surface Au atoms. An intermediate state of the metalation reaction is observed and the reaction steps for the Co metalation of pyrphyrin molecules on Au(111) are established in a joint experimental and computational effort.The molecular ligand pyrphyrin, a tetradentate bipyridine based macrocycle, represents an interesting but widely unexplored class of molecules. It resembles the well-known porphyrin, but consists of pyridyl subunits instead of pyrroles. Metal complexes based on pyrphyrin ligands have recently shown promise as water reduction catalysts in homogeneous photochemical water splitting reactions. In this study, the adsorption and metalation of pyrphyrin on a single crystalline Au(111) surface is investigated in an ultrahigh vacuum by means of scanning tunneling microscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy and density functional theory. Pyrphyrin coverages of approximately one monolayer and less are obtained by sublimation of the molecules on the substrate kept at room temperature. The molecules self-assemble in two distinct phases of long-range molecular ordering depending on the surface coverage. The deposition of cobalt metal and subsequent annealing lead to the formation of Co-ligated pyrphyrin molecules accompanied by a pronounced change of the molecular self-assembly. Electronic structure calculations taking the herringbone reconstruction of Au(111) into account show that the molecules are physisorbed, but preferred adsorption sites are identified where Co and the N atoms of the two terminal cyano groups are optimally coordinated to the surface Au atoms. An intermediate state of the metalation reaction is observed and the reaction steps for the Co metalation of pyrphyrin molecules on Au(111) are established in a joint experimental and computational effort. Electronic supplementary information (ESI) available: More details and results of the XPS experiments and the DFT calculation including also the coordinates of the calculated configurations. See DOI: 10.1039/C5NR08953K

Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles

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

Zhang, Honghu; Nayak, Srikanth; Wang, Wenjie

Here, we report on pH- and salt-responsive assembly of nanoparticles capped with polyelectrolytes at vapor–liquid interfaces. Two types of alkylthiol-terminated poly(acrylic acid) (PAAs, varying in length) are synthesized and used to functionalize gold nanoparticles (AuNPs) to mimic similar assembly effects of single-stranded DNA-capped AuNPs using synthetic polyelectrolytes. Using surface-sensitive X-ray scattering techniques, including grazing incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that PAA-AuNPs spontaneously migrate to the vapor–liquid interfaces and form Gibbs monolayers by decreasing the pH of the suspension. The Gibbs monoalyers show chainlike structures of monoparticle thickness. The pH-induced self-assembly is attributed to themore » protonation of carboxyl groups and to hydrogen bonding between the neighboring PAA-AuNPs. In addition, we show that adding MgCl 2 to PAA-AuNP suspensions also induces adsorption at the interface and that the high affinity between magnesium ions and carboxyl groups leads to two- and three-dimensional clusters that yield partial surface coverage and poorer ordering of NPs at the interface. We also examine the assembly of PAA-AuNPs in the presence of a positively charged Langmuir monolayer that promotes the attraction of the negatively charged capped NPs by electrostatic forces. Our results show that synthetic polyelectrolyte-functionalized nanoparticles exhibit interfacial self-assembly behavior similar to that of DNA-functionalized nanoparticles, providing a pathway for nanoparticle assembly in general.« less

Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles

DOE PAGES

Zhang, Honghu; Nayak, Srikanth; Wang, Wenjie; ...

2017-10-06

Here, we report on pH- and salt-responsive assembly of nanoparticles capped with polyelectrolytes at vapor–liquid interfaces. Two types of alkylthiol-terminated poly(acrylic acid) (PAAs, varying in length) are synthesized and used to functionalize gold nanoparticles (AuNPs) to mimic similar assembly effects of single-stranded DNA-capped AuNPs using synthetic polyelectrolytes. Using surface-sensitive X-ray scattering techniques, including grazing incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that PAA-AuNPs spontaneously migrate to the vapor–liquid interfaces and form Gibbs monolayers by decreasing the pH of the suspension. The Gibbs monoalyers show chainlike structures of monoparticle thickness. The pH-induced self-assembly is attributed to themore » protonation of carboxyl groups and to hydrogen bonding between the neighboring PAA-AuNPs. In addition, we show that adding MgCl 2 to PAA-AuNP suspensions also induces adsorption at the interface and that the high affinity between magnesium ions and carboxyl groups leads to two- and three-dimensional clusters that yield partial surface coverage and poorer ordering of NPs at the interface. We also examine the assembly of PAA-AuNPs in the presence of a positively charged Langmuir monolayer that promotes the attraction of the negatively charged capped NPs by electrostatic forces. Our results show that synthetic polyelectrolyte-functionalized nanoparticles exhibit interfacial self-assembly behavior similar to that of DNA-functionalized nanoparticles, providing a pathway for nanoparticle assembly in general.« less

Regular Nanoscale Protein Patterns via Directed Adsorption through Self-Assembled DNA Origami Masks.

PubMed

Ramakrishnan, Saminathan; Subramaniam, Sivaraman; Stewart, A Francis; Grundmeier, Guido; Keller, Adrian

2016-11-16

DNA origami has become a widely used method for synthesizing well-defined nanostructures with promising applications in various areas of nanotechnology, biophysics, and medicine. Recently, the possibility to transfer the shape of single DNA origami nanostructures into different materials via molecular lithography approaches has received growing interest due to the great structural control provided by the DNA origami technique. Here, we use ordered monolayers of DNA origami nanostructures with internal cavities on mica surfaces as molecular lithography masks for the fabrication of regular protein patterns over large surface areas. Exposure of the masked sample surface to negatively charged proteins results in the directed adsorption of the proteins onto the exposed surface areas in the holes of the mask. By controlling the buffer and adsorption conditions, the protein coverage of the exposed areas can be varied from single proteins to densely packed monolayers. To demonstrate the versatility of this approach, regular nanopatterns of four different proteins are fabricated: the single-strand annealing proteins Redβ and Sak, the iron-storage protein ferritin, and the blood protein bovine serum albumin (BSA). We furthermore demonstrate the desorption of the DNA origami mask after directed protein adsorption, which may enable the fabrication of hierarchical patterns composed of different protein species. Because selectivity in adsorption is achieved by electrostatic interactions between the proteins and the exposed surface areas, this approach may enable also the large-scale patterning of other charged molecular species or even nanoparticles.

Structural, electronic and magnetic properties of Au-based monolayer derivatives in honeycomb structure

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

Kapoor, Pooja, E-mail: pupooja16@gmail.com; Sharma, Munish; Ahluwalia, P. K.

2016-05-23

We present electronic properties of atomic layer of Au, Au{sub 2}-N, Au{sub 2}-O and Au{sub 2}-F in graphene-like structure within the framework of density functional theory (DFT). The lattice constant of derived monolayers are found to be higher than the pristine Au monolayer. Au monolayer is metallic in nature with quantum ballistic conductance calculated as 4G{sub 0}. Similarly, Au{sub 2}-N and Au{sub 2}-F monolayers show 4G{sub 0} and 2G{sub 0} quantum conductance respectively while semiconducting nature with calculated band gap of 0.28 eV has been observed for Au{sub 2}-O monolayer. Most interestingly, half metalicity has been predicted for Au{sub 2}-Nmore » and Au{sub 2}-F monolayers. Our findings may have importance for the application of these monolayers in nanoelectronic and spintronics.« less

Theory-Guided Innovation of Noncarbon Two-Dimensional Nanomaterials

DTIC Science & Technology

2016-05-24

unique structures and exceptional properties, such as Be5C2 monolayers with quasi -planaer pentacoordinate carbon, FeB6 monolayers hypercoordinate...properties, such as Be5C2 monolayers with quasi -planaer pentacoordinate carbon, FeB6 monolayers hypercoordinate transition metal, semiconducting Group 15...theoretical and experimental studies, we have developed a convenient chemical approach to etch hexagonal boron nitride monolayers to achieve holes

Lipid monolayer structure and interactions in the presence of peptides and proteins

NASA Astrophysics Data System (ADS)

Freites, Juan Alfredo

Structural aspects of two simple model systems, protein-lipid monolayer and peptide-lipid monolayer, were studied by experimental and computer simulation techniques. In both cases, both the choice of system and the approach employed to studying it, were motivated by specific biological problems. The interaction of annexin A1 with monolayers of dipalmitoylphosphatidylcholine (DPPC) was studied by fluorescence microscopy as a function of lipid monolayer phase and pH. It was shown that the annexin A1-DPPC interaction depends strongly on both the domain structure and phase behavior of the DPPC monolayer, and only weakly on the subphase pH. Annexin A1 was found to be line-active, adsorbing preferentially at phase boundaries. Also, annexin A1 was found to form networks in the presence of a domain structure in the lipid monolayer. Molecular dynamics simulations were carried out on a model system composed of a surfactant protein B peptide, SP-B1--25, and a monolayer of hexadecanoic acid. A detailed structural characterization was performed as a function of the lipid monolayer specic area. It was found that the peptide remains inserted in the monolayer up to values of specific area corresponding to an untilted condensed phase of the pure hexadecanoic acid monolayer. The system remains stable by altering the conformational order of both the anionic lipid monolayer and the peptide secondary structure, and effectively constitutes a unique disordered lipid-peptide monolayer phase. Two elements appear to be key for the constitution of this phase: an electrostatic interaction between the cationic residues of the peptide with the anionic headgroups of the lipids, and an exclusion of the aromatic residues on the hydrophobic end of the peptide from the hydrophilic and aqueous regions of the system. A direct comparison between molecular dynamics simulations and laboratory experiments was performed for hexadecanoic acid monolayer systems. In order to simulate specific points on the surface pressure vs. area isotherm, an algorithm for the control of surface pressure was developed based on previous work by Martyna, Tobias and Klein. The algorithm was implemented and tested with the hexadecanoic acid monolayer system.

Generation of the displacement current by the transformation of J-aggregates in spreading monolayers of squarylium dye

NASA Astrophysics Data System (ADS)

Iwamoto, Mitsumasa; Majima, Yutaka; Hirayama, Fuminori; Furuki, Makoto; Pu, Lyong Sun

1992-07-01

Maxwell displacement currents generated from monolayers of squarylium dye with propyl groups (SQ) and from mixed monolayers with arachidic acid were investigated during the course of monolayer compression in connection with the formation of J-aggregates in the monolayers. Abrupt changes in the generation of displacement current were observed for monolayers of SQ due to the transformation between two types of J-aggregates with different absorption spectra. In contrast, for mixed monolayers with arachidic acid which show no transition of J-aggregates, abrupt changes in the displacement current were not observed. It was concluded that displacement current measurement is effective in the detection of the transformation of the molecular arrangement in aggregates.

Chain Stretching and Order-Disorder Transitions in Block Copolymer Monolayers and Multilayers

NASA Astrophysics Data System (ADS)

Kramer, Edward J.; Mishra, Vindhya; Stein, Gila E.; Sohn, Karen E.; Hur, Sumi; Fredrickson, Glenn H.; Cochran, Eric W.

2009-03-01

Both monolayers of block copolymer cylinders and spheres undergo order to disorder transitions (ODT) at temperatures well below those of the bulk. Monolayers of PS-b-P2VP cylinders undergo a ``nematic'' to ``isotropic'' transition at temperatures about 20 K below the bulk ODT while monolayers of PS-b-P2VP with P2VP spheres undergo a 2D crystal to hexatic transition at least 10 K below the bulk ODT. Bilayers of each structure disorder at temperatures well above that of the monolayers. While one is tempted to attribute all of the difference to the fact that ordered monolayers are quasi 2 dimensional while bilayers are not, an alternative explanation exists. In the cylinder monolayer the corona PS chains must stretch to fill a nearly square cross-section domain rather than a hexagonal one in the bulk, while the corona PS chains in a sphere monolayer must stretch to fill a hexagonal prism rather than an octahedron in the bulk. The more non-uniform stretching of the chains in the monolayer should increase its free energy and decrease its order-disorder temperature.

Protonation of octadecylamine Langmuir monolayer by adsorption of halide counterions

NASA Astrophysics Data System (ADS)

Sung, Woongmo; Avazbaeva, Zaure; Lee, Jonggwan; Kim, Doseok

Langmuir monolayer consisting of octadecylamine (C18H37NH2, ODA) was investigated by heterodyne vibrational sum-frequency generation (HD-VSFG) spectroscopy in conjunction with surface pressure-area (π- A) isotherm, and the result was compared with that from cationic-lipid (DPTAP) Langmuir monolayer. In case of ODA monolayer on pure water, both SF intensity of water OH band and the surface pressure were significantly smaller than those of the DPTAP monolayer implying that only small portion of the amine groups (-NH3+ is protonated in the monolayer. In the presence of sodium halides (NaCl and NaI) in the subphase water, it was found that the sign of Imχ (2) of water OH band remained the same as that of the ODA monolayer on pure water, but there was a substantial increase in the SF amplitude. From this, we propose that surface excess of the halide counterions (Cl- and I-) makes the solution condition near the ODA monolayer/water interface more acidic so that ODA molecules in the monolayer are more positively charged, which works to align the water dipoles at the interface.

Robust nanofabrication of monolayer MoS2 islands with strong photoluminescence enhancement via local anodic oxidation

NASA Astrophysics Data System (ADS)

Fernandes, Thales F. D.; Gadelha, Andreij de C.; Barboza, Ana P. M.; Paniago, Roberto M.; Campos, Leonardo C.; Soares Guimarães, Paulo S.; de Assis, Pierre-Louis; Neves, Bernardo R. A.

2018-04-01

In this work, we demonstrate the nanofabrication of monolayer MoS2 islands using local anodic oxidation of few-layer and bulk MoS2 flakes. The nanofabricated islands present true monolayer Raman signal and photoluminescence intensity up to two orders of magnitude larger than that of a pristine monolayer. This technique is robust enough to result in monolayer islands without the need of meticulously fine-tuning the oxidation process, thus providing a fast and reliable way of creating monolayer regions with enhanced optical properties and with controllable size, shape, and position.

DNA-modified electrodes fabricated using copper-free click chemistry for enhanced protein detection.

PubMed

Furst, Ariel L; Hill, Michael G; Barton, Jacqueline K

2013-12-31

A method of DNA monolayer formation has been developed using copper-free click chemistry that yields enhanced surface homogeneity and enables variation in the amount of DNA assembled; extremely low-density DNA monolayers, with as little as 5% of the monolayer being DNA, have been formed. These DNA-modified electrodes (DMEs) were characterized visually, with AFM, and electrochemically, and were found to facilitate DNA-mediated reduction of a distally bound redox probe. These low-density monolayers were found to be more homogeneous than traditional thiol-modified DNA monolayers, with greater helix accessibility through an increased surface area-to-volume ratio. Protein binding efficiency of the transcriptional activator TATA-binding protein (TBP) was also investigated on these surfaces and compared to that on DNA monolayers formed with standard thiol-modified DNA. Our low-density monolayers were found to be extremely sensitive to TBP binding, with a signal decrease in excess of 75% for 150 nM protein. This protein was detectable at 4 nM, on the order of its dissociation constant, with our low-density monolayers. The improved DNA helix accessibility and sensitivity of our low-density DNA monolayers to TBP binding reflects the general utility of this method of DNA monolayer formation for DNA-based electrochemical sensor development.

Testing the effectiveness of monolayers under wind and wave conditions.

PubMed

Palada, C; Schouten, P; Lemckert, C

2012-01-01

Monolayers are highly desirable for their evaporation reducing capabilities due to their relatively minimal cost and ease of application. Despite these positive attributes, monolayers have consistently failed to perform effectively due to the harsh wind and wave conditions prevalent across real-world water reserves. An exhaustive and consistent study testing the influence of wind and wave combinations on monolayer performance has yet to be presented in the literature. To remedy this, the effect of simultaneous wind and wave conditions on a benchmark high-performance monolayer (octadecanol suspension, CH(3)(CH(2))(16)CH(2)OH) has been analysed. Subjected only to waves, the monolayer remained intact due to its innate ability to compress and expand. However, the constant simultaneous application of wind and waves caused the monolayer to break up and gather down-wind where it volatilised over time. At wind speeds above 1.3 m s(-1) the monolayer was completely ineffective. For wind speeds below this threshold, the monolayer had an influence on the evaporation rate dependent on wind speed. From these results a series of application protocols can now be developed for the optimised deployment of monolayers in real-world water reserves. This will be of interest to private, commercial and government organisations involved in the storage and management of water resources.

Part II: diffraction from two-dimensional cholera toxin crystals bound to their receptors in a lipid monolayer.

PubMed

Miller, C E; Majewski, J; Watkins, E B; Weygand, M; Kuhl, T L

2008-07-01

The structure of cholera toxin (CTAB(5)) bound to its putative ganglioside receptor, galactosyl-N-acetylgalactosaminyl (N-acetyl-neuraminyl) galactosylglucosylceramide (GM(1)), in a lipid monolayer at the air-water interface has been studied utilizing grazing incidence x-ray diffraction. Cholera toxin is one of very few proteins to be crystallized in two dimensions and characterized in a fully hydrated state. The observed grazing incidence x-ray diffraction Bragg peaks indicated cholera toxin was ordered in a hexagonal lattice and the order extended 600-800 A. The pentameric binding portion of cholera toxin (CTB(5)) improved in-plane ordering over the full toxin (CTAB(5)) especially at low pH. Disulfide bond reduction (activation of the full toxin) also increased the protein layer ordering. These findings are consistent with A-subunit flexibility and motion, which cause packing inefficiencies and greater disorder of the protein layer. Corroborative out-of-plane diffraction (Bragg rod) analysis indicated that the scattering units in the cholera layer with CTAB(5) shortened after disulfide bond reduction of the A subunit. These studies, together with Part I results, revealed key changes in the structure of the cholera toxin-lipid system under different pH conditions.

Full membrane spanning self-assembled monolayers as model systems for UHV-based studies of cell-penetrating peptides

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

Franz, Johannes; Graham, Daniel J.; Schmüser, Lars

2015-03-01

Biophysical studies of the interaction of peptides with model membranes provide a simple yet effective approach to understand the transport of peptides and peptide based drug carriers across the cell membrane. Therein, the authors discuss the use of self-assembled monolayers fabricated from the full membrane-spanning thiol (FMST) 3-((14-((4'-((5-methyl-1-phenyl-35-(phytanyl)oxy-6,9,12,15,18,21,24,27,30,33,37-undecaoxa-2,3-dithiahenpentacontan-51-yl)oxy)-[1,1'-biphenyl]-4-yl)oxy)tetradecyl)oxy)-2-(phytanyl)oxy glycerol for ultrahigh vacuum (UHV) based experiments. UHV-based methods such as electron spectroscopy and mass spectrometry can provide important information about how peptides bind and interact with membranes, especially with the hydrophobic core of a lipid bilayer. Moreover, near-edge x-ray absorption fine structure spectra and x-ray photoelectron spectroscopy (XPS) data showed thatmore » FMST forms UHV-stable and ordered films on gold. XPS and time of flight secondary ion mass spectrometry depth profiles indicated that a proline-rich amphipathic cell-penetrating peptide, known as sweet arrow peptide is located at the outer perimeter of the model membrane.« less

Introduction to Special Issue on Education and Health.

ERIC Educational Resources Information Center

Kiker, B. F.

1998-01-01

Introduces a special issue devoted to education-health linkages. The scope of coverage is quite broad. Papers treat education's connections with specific health-related behaviors, full-time employees' health insurance coverage, medical care/lifestyle choices, nurses' wage profiles, low birthweight children's capabilities, smoking decisions,…

Unanticipated C=C bonds in covalent monolayers on silicon revealed by NEXAFS.

PubMed

Lee, Michael V; Lee, Jonathan R I; Brehmer, Daniel E; Linford, Matthew R; Willey, Trevor M

2010-02-02

Interfaces are crucial to material properties. In the case of covalent organic monolayers on silicon, molecular structure at the interface controls the self-assembly of the monolayers, which in turn influences the optical properties and electrical transport. These properties intrinsically affect their application in biology, tribology, optics, and electronics. We use near-edge X-ray absorption fine structure spectroscopy to show that the most basic covalent monolayers formed from 1-alkenes on silicon retain a double bond in one-fifth to two-fifths of the resultant molecules. Unsaturation in the predominantly saturated monolayers will perturb the regular order and affect the dependent properties. The presence of unsaturation in monolayers produced by two different methods also prompts the re-evaluation of other radical-based mechanisms for forming covalent monolayers on silicon.

Tennessee health plan tobacco cessation coverage.

PubMed

Kolade, Folasade M

2014-01-01

To evaluate the smoking cessation coverage available from public and private Tennessee health plans. Cross-sectional study. The sampling frame for private plans was a register of licensed plans obtained from the Tennessee Commerce Department. Government websites and reports provided TennCare data. Data were abstracted from plan manuals and formularies for benefit year 2012. Classification of coverage included comprehensive-all seven recommended medications plus individual and group counseling; moderate-at least two forms of nicotine replacement therapy (NRT) plus bupropion and varenicline and one form of counseling; inadequate-at least one treatment, or none-no medications or counseling, or coverage only for pregnant women. Of nine private plans, one provided comprehensive coverage; two, moderate coverage; four, inadequate coverage, as did TennCare; and two plans provided no coverage. Over 362,800 smokers had inadequate access to cessation treatments under TennCare, while 119,094 smokers had inadequate or no cessation coverage under private plans. In 2012, Tennessee fell short of Healthy People goals for total managed care and comprehensive TennCare coverage of smoking cessation. If Tennessee mandates that all health plans provide full coverage, 481,900 smokers may immediately be in a better position to quit. © 2013 Wiley Periodicals, Inc.

Mechanistic Study of Nitric Oxide Reduction by Hydrogen on Pt(100) (I): A DFT Analysis of the Reaction Network

DOE PAGES

Bai, Yunhai; Mavrikakis, Manos

2017-05-08

Periodic, self-consistent density functional theory (DFT-GGA, PW91) calculations are used to study the reaction mechanism for nitric oxide (NO) reduction by hydrogen (H 2) on Pt(100). Energetics of various N–O activation paths, including both direct and hydrogen-assisted N–O bond-breaking paths, and the formation of three different N-containing products (N 2, N 2O, and NH3), are systematically studied. On the basis of our analysis, NO* dissociation has a lower barrier than NO* hydrogenation to HNO* or NOH*, and therefore, the direct NO dissociation path is predicted to dominate N–O activation on clean Pt(100). The reaction of atomic N* with N* andmore » NO* is proposed as the mechanism for N 2 and N 2O formation, respectively. NH 3 formation from N* via three successive hydrogenation steps is also studied and is found to be kinetically more difficult than N 2 and N 2O formation from N*. Finally, NO adsorption phase diagrams on Pt(100) are constructed, and these phase diagrams suggest that, at low temperatures (e.g., 400 K), the Pt(100) surface may be covered by half a monolayer of NO. We propose that high NO coverage might affect the NO + H 2 reaction mechanism, and therefore, one should explicitly take the NO coverage into consideration in first-principles studies to determine the reaction mechanism on catalyst surfaces under reaction conditions. In conclusion, a detailed analysis of high NO coverage effects on the reaction mechanism will be presented in a separate contribution.« less

Mechanistic Study of Nitric Oxide Reduction by Hydrogen on Pt(100) (I): A DFT Analysis of the Reaction Network

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

Bai, Yunhai; Mavrikakis, Manos

Periodic, self-consistent density functional theory (DFT-GGA, PW91) calculations are used to study the reaction mechanism for nitric oxide (NO) reduction by hydrogen (H 2) on Pt(100). Energetics of various N–O activation paths, including both direct and hydrogen-assisted N–O bond-breaking paths, and the formation of three different N-containing products (N 2, N 2O, and NH3), are systematically studied. On the basis of our analysis, NO* dissociation has a lower barrier than NO* hydrogenation to HNO* or NOH*, and therefore, the direct NO dissociation path is predicted to dominate N–O activation on clean Pt(100). The reaction of atomic N* with N* andmore » NO* is proposed as the mechanism for N 2 and N 2O formation, respectively. NH 3 formation from N* via three successive hydrogenation steps is also studied and is found to be kinetically more difficult than N 2 and N 2O formation from N*. Finally, NO adsorption phase diagrams on Pt(100) are constructed, and these phase diagrams suggest that, at low temperatures (e.g., 400 K), the Pt(100) surface may be covered by half a monolayer of NO. We propose that high NO coverage might affect the NO + H 2 reaction mechanism, and therefore, one should explicitly take the NO coverage into consideration in first-principles studies to determine the reaction mechanism on catalyst surfaces under reaction conditions. In conclusion, a detailed analysis of high NO coverage effects on the reaction mechanism will be presented in a separate contribution.« less

Selective Capture of Glycoproteins Using Lectin-modified Nanoporous Gold Monolith

PubMed Central

Alla, Allan J.; d’Andrea, Felipe B.; Bhattarai, Jay K.; Cooper, Jared A.; Tan, Yih Horng; Demchenko, Alexei V.; Stine, Keith J.

2015-01-01

The surface of nanoporous gold (np-Au) monoliths was modified via a flow method with the lectin Concanavalin A (Con A) to develop a substrate for separation and extraction of glycoproteins. Self-assembled monolayers (SAMs) of lipoic acid (LA) on the np-Au monoliths were prepared followed by activation of the terminal carboxyl groups to create amine reactive esters that were utilized in the immobilization of Con A. Thermogravimetric analysis (TGA) was used to determine the surface coverages of LA and Con A on np-Au monoliths which were found to be 1.31 × 1018 molecules m−2 and 1.85 × 1015 molecules m−2, respectively. An in situ solution depletion method was developed that enabled surface coverage characterization without damaging the substrate and suggesting the possibility of regeneration. Using this method, the surface coverages of LA and Con A were found to be 0.989 ×1018 molecules m−2 and 1.32 × 1015 molecules m−2, respectively. The selectivity of the Con A-modified np-Au monolith for the high mannose-containing glycoprotein ovalbumin (OVA) versus negative control non-glycosylated bovine serum albumin (BSA) was demonstrated by the difference in the ratio of the captured molecules to the immobilized Con A molecules, with OVA:Con A = 2.3 and BSA:Con A = 0.33. Extraction of OVA from a 1:3 mole ratio mixture with BSA was demonstrated by the greater amount of depletion of OVA concentration during the circulation with the developed substrate. A significant amount of captured OVA was eluted using α-methyl mannopyranoside as a competitive ligand. This work is motivated by the need to develop new materials for chromatographic separation and extraction substrates for use in preparative and analytical procedures in glycomics. PMID:26554297

Scaling of the structural characteristics of nanoholes created by local droplet etching

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

Heyn, Ch.; Schnüll, S.; Hansen, W.

2014-01-14

We study the tuneability of nanoholes created by local droplet etching of AlGaAs surfaces with Al droplets at varied coverage θ of the deposited droplet material and process temperature T. For the contact angle of the as-grown droplets a mean value of 66° is determined, which depends neither on θ nor on T. The experimental results on the hole structural characteristics are interpreted in terms of scaling models yielding a general form f(θ,T)∝θ{sup q}exp(E/[k{sub B}T]), with constants q and E and Boltzmann's constant k{sub B}. In detail, the hole density varies from N = 4.0 × 10{sup 6} up to 1.5 × 10{sup 8} cm{sup −2}, andmore » the scaling parameters are q = 0 and E = E{sub N} = 2.46 eV. The hole diameter varies from 50 up to 190 nm with scaling parameters q = 1/3 and E = −E{sub N}/3. Moreover, the hole depth varies from 9 up to 125 nm with q = 2/3 and E = −1.73 eV. Furthermore, a threshold coverage of at least 0.2 monolayers (ML) must be deposited before hole formation takes place. In situ electron diffraction indicates that these 0.2 ML are consumed for a surface reconstruction change from (3 × 1) to (2 × 1). For coverages above 2.0 ML holes with a bimodal depth distribution are observed.« less

The effect of oxygen vacancies on the binding interactions of NH3 with rutile TiO2(110) -1×1

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

Kim, Boseong; Li, Zhenjun; Kay, Bruce D.

2012-11-21

A series of NH3 temperature-programmed desorption (TPD) spectra was taken after the NH3 dose at 70 K on rutile TiO2(110)-1×1 surfaces with the oxygen vacancy (VO) concentrations of ~0% (p-TiO2) and 5% (r-TiO2), respectively, to study the effect of VO’s on the desorption energy of NH3 as a function of the coverage, θ. Our results show that at zero coverage limit, the desorption energy of NH3 on r-TiO2 is 115 kJ/mol, which is 10 kJ/mol less than that on p-TiO2. The desorption energy from the Ti4+ sites decreases with increasing θ due to the repulsive NH3 - NH3 interactions andmore » approaches ~ 55 kJ/mol upon the saturation of Ti4+ sites (θ = 1 monolayer, ML) on both p- and r-TiO2. The absolute saturation coverage is determined to be about 10% smaller on r-TiO2 than that on p-TiO2. Further, the trailing edges of the NH3 TPD spectra on the hydroxylated TiO2(110) (h-TiO2) appear to be the same as that on r-TiO2 while those on oxidized TiO2(110) (o-TiO2) shift to higher temperatures. We present the detailed analysis of the results and reconcile the observed differences based on the repulsive adsorbate-adsorbate interactions between neighboring NH3 molecules and the surface charge associated with the presence of VO’s. Besides NH3, no other reaction products are observed in the TPD spectra.« less

Scanning force microscopy and fluorescence microscopy of microcontact printed antibodies and antibody fragments.

PubMed

LaGraff, John R; Chu-LaGraff, Quynh

2006-05-09

Unlabeled primary immunoglobulin G (IgG) antibodies and its F(ab')2 and Fc fragments were attached to oxygen-plasma-cleaned glass substrates using either microcontact printing (MCP) or physical adsorption during bath application from dilute solutions. Fluorescently labeled secondary IgGs were then bound to surface-immobilized IgG, and the relative surface coverage was determined by measuring the fluorescence intensity. Results indicated that the surface coverage of IgG increased with increasing protein solution concentration for both MCP and bath-applied IgG and that a greater concentration of IgG was transferred to a glass substrate using MCP than during physisorption during bath applications. Scanning force microscopy (SFM) showed that patterned MCP IgG monolayers were 5 nm in height, indicating that IgG molecules lie flat on the substrate. After incubation with a secondary IgG, the overall line thickness increased to around 15 nm, indicating that the secondary IgG was in a more vertical orientation with respect to the substrate. The surface roughness of these MCP patterned IgG bilayers as measured by SFM was observed to increase with increasing surface coverage. Physisorption of IgG to both unmodified patterned polydimethylsiloxane (PDMS) stamps and plasma-cleaned glass substrates was modeled by Langmuir adsorption kinetics yielding IgG binding constants of K(MCP) = 1.7(2) x 10(7) M(-1) and K(bath) = 7.8(7) x 10(5) M(-1), respectively. MCP experiments involving primary F(ab')2 and Fc fragments incubated in fluorescently labeled fragment-specific secondary IgGs were carried out to test for the function and orientation of IgG. Finally, possible origins of MCP stamping defects such as pits, pull outs, droplets, and reverse protein transfer are discussed.

Strain and electric field induced metallization in the GaX (X = N, P, As & Sb) monolayer

NASA Astrophysics Data System (ADS)

Bahuguna, Bhagwati Prasad; Saini, L. K.; Sharma, Rajesh O.; Tiwari, Brajesh

2018-05-01

We investigate the strain and electric field dependent electronic properties of two dimensional Ga-based group III-V monolayer from the first-principles approach within density functional theory. The energy bandgap of GaX monolayer increases upto the certain value of compressive strain and then decreases. On the other hand, the energy bandgap of GaX monolayer is monotonically decreased with increasing tensile strain and become metallic at the higher value. Furthermore, the perpendicular electric field decreases the energy band gap of unstrained GaX monolayer and shows semiconductor to metal transition. These results suggest that the nature of energy bands and value of energy bandgap in GaX monolayer can be tuned by the biaxial mechanical strain or perpendicular electrical field. Additionally, we have also studied the optical response of unstrained GaX monolayer in term of optical conductivity. These findings may provide valuable information to develop the Ga-based optoelectronic devices and further the understanding of the GaX monolayer.

GaAs monolayer: Excellent SHG responses and semi metallic to metallic transition modulated by vacancy effect

NASA Astrophysics Data System (ADS)

Rozahun, Ilmira; Bahti, Tohtiaji; He, Guijie; Ghupur, Yasenjan; Ablat, Abduleziz; Mamat, Mamatrishat

2018-05-01

Monolayer materials are considered as a promising candidate for novel applications due to their attractive magnetic, electronic and optical properties. Investigation on nonlinear optical (NLO) properties and effect of vacancy on monolayer materials are vital to property modulations of monolayers and extending their applications. In this work, with the aid of first-principles calculations, the crystal structure, electronic, magnetic, and optical properties of GaAs monolayers with the vacancy were investigated. The result shows gallium arsenic (GaAs) monolayer produces a strong second harmonic generation (SHG) response. Meanwhile, the vacancy strongly affects structural, electronic, magnetic and optical properties of GaAs monolayers. Furthermore, arsenic vacancy (VAs) brings semi metallic to metallic transition, while gallium vacancy (VGa) causes nonmagnetic to magnetic conversion. Our result reveals that GaAs monolayer possesses application potentials in Nano-amplifying modulator and Nano-optoelectronic devices, and may provide useful guidance in designing new generation of Nano-electronic devices.

Investigating Alkylsilane Monolayer Tribology at a Single-Asperity Contact with Molecular Dynamics Simulation.

PubMed

Summers, Andrew Z; Iacovella, Christopher R; Cummings, Peter T; McCabe, Clare

2017-10-24

Chemisorbed monolayer films are known to possess favorable characteristics for nanoscale lubrication of micro- and nanoelectromechanical systems (MEMS/NEMS). Prior studies have shown that the friction observed for monolayer-coated surfaces features a strong dependence on the geometry of contact. Specifically, tip-like geometries have been shown to penetrate into monolayer films, inducing defects in the monolayer chains and leading to plowing mechanisms during shear, which result in higher coefficients of friction (COF) than those observed for planar geometries. In this work, we use molecular dynamics simulations to examine the tribology of model silica single-asperity contacts under shear with monolayer-coated substrates featuring various film densities. It is observed that lower monolayer densities lead to reduced COFs, in contrast to results for planar systems where COF is found to be nearly independent of monolayer density. This is attributed to a liquid-like response to shear, whereby fewer defects are imparted in monolayer chains from the asperity, and chains are easily displaced by the tip as a result of the higher free volume. This transition in the mechanism of molecular plowing suggests that liquid-like films should provide favorable lubrication at single-asperity contacts.

Sodium adsorption and diffusion on monolayer black phosphorus with intrinsic defects

NASA Astrophysics Data System (ADS)

Sun, Xiaoli; Wang, Zhiguo

2018-01-01

Monolayer black phosphorus is a potential anode material for rechargeable ion batteries. In this work, the effects of intrinsic defects including mono-vacancy (MV), di-vacancy, and Stone-Wales (SW) defects on the adsorption and diffusion of sodium on monolayer black phosphorus were investigated using first-principles calculations. The adsorption energies for sodium on monolayer black phosphorus are in the range of -1.80 to -0.56 eV, which is lower than the value of -0.48 eV for sodium adsorbed on pristine monolayer phosphorus. This indicates that these defects can enhance the adsorption of sodium on monolayer black phosphorus. The diffusivity of sodium on monolayer phosphorus with SW and MV defects is 2.35 × 10-4-3.36 × 10-6 cm2/s, and 7.38 × 10-5-1.48 × 10-9 cm2/s, respectively. Although these values are smaller than that of the pristine monolayer phosphorus at 7.38 × 10-5 cm2/s, defects are inevitably introduced during these fabrication processes. These diffusivity values are reasonable for defective monolayer phosphorus used as an effective anode for sodium ion batteries.

Limited Area Coverage/High Resolution Picture Transmission (LAC/HRPT) data vegetative index calculation processor user's manual

NASA Technical Reports Server (NTRS)

Obrien, S. O. (Principal Investigator)

1980-01-01

The program, LACVIN, calculates vegetative indexes numbers on limited area coverage/high resolution picture transmission data for selected IJ grid sections. The IJ grid sections were previously extracted from the full resolution data tapes and stored on disk files.

Molecular organization of phospholipid monolayers on the water surface by Maxwell displacement current measurement

NASA Astrophysics Data System (ADS)

Sulaiman, Khaulah; Majid, Wan Haliza Abdul; Muhamad, Muhamad Rasat

2006-02-01

The monolayer of organic molecules at the air-water interface has been studied using the Maxwell displacement current (MDC) technique. The materials used in this study were the biological materials of phosphatidyl ethanolamine (PE) and phosphatidic acids (PA). The configuration of the experimental set-up consists of the metal/air-gap/monolayer/metal coupled with the Langmuir method. This measurement enables the detection of current without destroying the monolayer. The phase transition and molecular orientation of the phospholipid monolayers were investigated using MDC measurement without mechanical contact between electrodes and the materials. Direct evidence of phase transition from gaseous to the polar ordering phase can be obtained across phospholipid monolayers even though at very low surface pressure. Relaxation process of the phospholipid monolayers was investigated by using the step compression on the MDC signals.

Measuring the equation of state for a 2D colloidal membrane: A microfluidic approach to buffer exchange

NASA Astrophysics Data System (ADS)

Balchunas, Andrew; Cabanas, Rafael; Fraden, Seth; Dogic, Zvonimir

Previous work has shown that monodisperse rod-like colloidal particles, such as a filamentous bacteriophage, self assemble into a 2D monolayer smectic in the presence of a non-adsorbing depleting polymer. These structures have the same functional form of bending rigidity and lateral compressibility as conventional lipid bi-layers, so we name the monolayer smectic a colloidal membrane. We have developed a microfluidic device such that the osmotic pressure acting on a colloidal membrane may be controlled via a full in situ buffer exchange. Rod density within individual colloidal membranes was measured as a function of osmotic pressure and a first order phase transition, from 2D fluid to 2D solid, was observed. kon and koff rates of rod to membrane binding were measured by lowering the osmotic pressure until membrane evaporation occurred.

Model dielectric function for 2D semiconductors including substrate screening

NASA Astrophysics Data System (ADS)

Trolle, Mads L.; Pedersen, Thomas G.; Véniard, Valerie

2017-01-01

Dielectric screening of excitons in 2D semiconductors is known to be a highly non-local effect, which in reciprocal space translates to a strong dependence on momentum transfer q. We present an analytical model dielectric function, including the full non-linear q-dependency, which may be used as an alternative to more numerically taxing ab initio screening functions. By verifying the good agreement between excitonic optical properties calculated using our model dielectric function, and those derived from ab initio methods, we demonstrate the versatility of this approach. Our test systems include: Monolayer hBN, monolayer MoS2, and the surface exciton of a 2 × 1 reconstructed Si(111) surface. Additionally, using our model, we easily take substrate screening effects into account. Hence, we include also a systematic study of the effects of substrate media on the excitonic optical properties of MoS2 and hBN.

Shallow Heavily Doped n++ Germanium by Organo-Antimony Monolayer Doping.

PubMed

Alphazan, Thibault; Díaz Álvarez, Adrian; Martin, François; Grampeix, Helen; Enyedi, Virginie; Martinez, Eugénie; Rochat, Névine; Veillerot, Marc; Dewitte, Marc; Nys, Jean-Philippe; Berthe, Maxime; Stiévenard, Didier; Thieuleux, Chloé; Grandidier, Bruno

2017-06-14

Functionalization of Ge surfaces with the aim of incorporating specific dopant atoms to form high-quality junctions is of particular importance for the development of solid-state devices. In this study, we report the shallow doping of Ge wafers with a monolayer doping strategy that is based on the controlled grafting of Sb precursors and the subsequent diffusion of Sb into the wafer upon annealing. We also highlight the key role of citric acid in passivating the surface before its reaction with the Sb precursors and the benefit of a protective SiO 2 overlayer that enables an efficient incorporation of Sb dopants with a concentration higher than 10 20 cm -3 . Microscopic four-point probe measurements and photoconductivity experiments show the full electrical activation of the Sb dopants, giving rise to the formation of an n++ Sb-doped layer and an enhanced local field-effect passivation at the surface of the Ge wafer.

Effective lattice Hamiltonian for monolayer tin disulfide: Tailoring electronic structure with electric and magnetic fields

NASA Astrophysics Data System (ADS)

Yu, Jin; van Veen, Edo; Katsnelson, Mikhail I.; Yuan, Shengjun

2018-06-01

The electronic properties of monolayer tin dilsulfide (ML -Sn S2 ), a recently synthesized metal dichalcogenide, are studied by a combination of first-principles calculations and tight-binding (TB) approximation. An effective lattice Hamiltonian based on six hybrid s p -like orbitals with trigonal rotation symmetry are proposed to calculate the band structure and density of states for ML -Sn S2 , which demonstrates good quantitative agreement with relativistic density-functional-theory calculations in a wide energy range. We show that the proposed TB model can be easily applied to the case of an external electric field, yielding results consistent with those obtained from full Hamiltonian results. In the presence of a perpendicular magnetic field, highly degenerate equidistant Landau levels are obtained, showing typical two-dimensional electron gas behavior. Thus, the proposed TB model provides a simple way in describing properties in ML -Sn S2 .

First principles study of gallium cleaning for hydrogen-contaminated α-Al2O3(0001) surfaces.

PubMed

Yang, Rui; Rendell, Alistair P

2013-05-15

The use of gallium for cleaning hydrogen-contaminated Al2O3 surfaces is explored by performing first principles density functional calculations of gallium adsorption on a hydrogen-contaminated Al-terminated α-Al2O3(0001) surface. Both physisorbed and chemisorbed H-contaminated α-Al2O3(0001) surfaces with one monolayer (ML) gallium coverage are investigated. The thermodynamics of gallium cleaning are considered for a variety of different asymptotic products, and are found to be favorable in all cases. Physisorbed H atoms have very weak interactions with the Al2O3 surface and can be removed easily by the Ga ML. Chemisorbed H atoms form stronger interactions with the surface Al atoms. Bonding energy analysis and departure simulations indicate, however, that chemisorbed H atoms can be effectively removed by the Ga ML. Copyright © 2013 Wiley Periodicals, Inc.

Scanning Tunneling Microscopy Analysis of a Pentacene/Graphene/SiC(0001) system

NASA Astrophysics Data System (ADS)

Yost, Andrew; Suzer, Ozgun; Smerdon, Joseph; Chien, Teyu; Guest, Jeffrey

2014-03-01

A complete understanding of the structure of molecular assemblies, as well as an understanding of donor-acceptor interactions is crucial in the development of emergent molecular electronics technologies such as organic photovoltaics. The pentacene (C22H14) is a good electron donor in Pentacene-C60 system, which is a model system of an organic photovoltaic cell.. Here we present scanning tunneling microscopy studies of the pentacene(Pn) molecule on Graphene(G) that is epitaxially grown on SiC(0001). In addition to the morphologies reported in literature, several new structures of Pn on on G/SiC(0001) were observed with different periodicity and registry both in monolayer and bilayer coverages of molecules on the surface. Preliminary scanning tunneling spectroscopy of the molecular system is also discussed; well-isolated states and a large HOMO-LUMO gap indicate the Pn is weakly coupled to the grapheme and underlying substrate.

Concentration transient analysis of antimony surface segregation during Si(100) molecular beam epitaxy

NASA Technical Reports Server (NTRS)

Markert, L. C.; Greene, J. E.; Ni, W.-X.; Hansson, G. V.; Sundgren, J.-E.

1991-01-01

Antimony surface segregation during Si(100) molecular beam epitaxy (MBE) was investigated at temperatures T(sub s) = 515 - 800 C using concentration transient analysis (CTA). The dopant surface coverage Theta, bulk fraction gamma, and incorporation probability sigma during MBE were determined from secondary-ion mass spectrometry depth profiles of modulation-doped films. Programmed T(sub s) changes during growth were used to trap the surface-segregated dopant overlayer, producing concentration spikes whose integrated area corresponds to Theta. Thermal antimony doping by coevaporation was found to result in segregation strongly dependent on T(sub s) with Theta(sub Sb) values up to 0.9 monolayers (ML): in films doped with Sb(+) ions accelerated by 100 V, Theta(sub Sb) was less than or equal to 4 x 10(exp -3) ML. Surface segregation of coevaporated antimony was kinematically limited for the film growth conditions in these experiments.

Adsorption of xenon and krypton on shales

NASA Technical Reports Server (NTRS)

Podosek, F. A.; Bernatowicz, T. J.; Kramer, F. E.

1981-01-01

A method that uses a mass spectrometer as a manometer is employed in the measurement of Xe and Kr adsorption parameters on shales and related samples, where gas partial pressures were lower than 10 to the -11th atm, corresponding adsorption coverages are only small fractions of a monolayer, and Henry's Law behavior is expected and observed. Results show heats of adsorption in the 2-7 kcal/mol range, and Henry constants at 0-25 C of 1 cu cm STP/g per atmosphere are extrapolated. Although the adsorption properties obtained are variable by sample, the range obtained suggests that shales may be capable of an equilibrium adsorption with modern air high enough to account for a significant fraction of the atmospheric inventory of Xe, and perhaps even of Kr. This effect will nevertheless not account for the factor-of-25 defficiency of atmospheric Xe, in comparison with the planetary gas patterns observed in meteorites.

Applications of surface analysis and surface theory in tribology

NASA Technical Reports Server (NTRS)

Ferrante, John

1988-01-01

Tribology, the study of adhesion, friction and wear of materials is a complex field which requires a knowledge of solid state physics, surface physics, chemistry, material science and mechanical engineering. It has been dominated, however, by the more practical need to make equipment work. With the advent of surface analysis and advances in surface and solid state theory, a new dimension has been added to the analysis of interactions at tribological interfaces. In this paper the applications of tribological studies and their limitations are presented. Examples from research at the NASA Lewis Research Center are given. Emphasis is on fundamental studies involving the effects of monolayer coverage and thick films on friction and wear. A summary of the current status of theoretical calculations of defect energetics is presented. In addition, some new theoretical techniques which enable simplified quantitative calculations of adhesion, fracture and friction are discussed.

The study of 'microsurfaces' using thermal desorption spectroscopy

NASA Technical Reports Server (NTRS)

Thomas, M. E.; Poppa, H.; Pound, G. M.

1979-01-01

The use of a newly combined ultrahigh vacuum technique for studying continuous and particulate evaporated thin films using thermal desorption spectroscopy (TDS), transmission electron microscopy (TEM), and transmission electron diffraction (TED) is discussed. It is shown that (1) CO thermal desorption energies of epitaxially deposited (111) Ni and (111) Pd surfaces agree perfectly with previously published data on bulk (111) single crystal, (2) contamination and surface structural differences can be detected using TDS as a surface probe and TEM as a complementary technique, and (3) CO desorption signals from deposited metal coverages of one-thousandth of a monolayer should be detectable. These results indicate that the chemisorption properties of supported 'microsurfaces' of metals can now be investigated with very high sensitivity. The combined use of TDS and TEM-TED experimental methods is a very powerful technique for fundamental studies in basic thin film physics and in catalysis.

Strong Coupling of Localized Surface Plasmons to Excitons in Light-Harvesting Complexes

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

Tsargorodska, Anna; Cartron, Michaël L.; Vasilev, Cvetelin

Gold nanostructure arrays exhibit surface plasmon resonances that split after attaching light harvesting complexes 1 and 2 (LH1 and LH2) from purple bacteria. The splitting is attributed to strong coupling between the localized surface plasmon resonances and excitons in the light-harvesting complexes. Wild-type and mutant LH1 and LH2 from Rhodobacter sphaeroides containing different carotenoids yield different splitting energies, demonstrating that the coupling mechanism is sensitive to the electronic states in the light harvesting complexes. Plasmon–exciton coupling models reveal different coupling strengths depending on the molecular organization and the protein coverage, consistent with strong coupling. Strong coupling was also observed formore » self-assembling polypeptide maquettes that contain only chlorins. However, it is not observed for monolayers of bacteriochlorophyll, indicating that strong plasmon–exciton coupling is sensitive to the specific presentation of the pigment molecules.« less

Applications of surface analysis and surface theory in tribology

NASA Technical Reports Server (NTRS)

Ferrante, John

1989-01-01

Tribology, the study of adhesion, friction and wear of materials, is a complex field which requires a knowledge of solid state physics, surface physics, chemistry, material science, and mechanical engineering. It has been dominated, however, by the more practical need to make equipment work. With the advent of surface analysis and advances in surface and solid-state theory, a new dimension has been added to the analysis of interactions at tribological interfaces. In this paper the applications of tribological studies and their limitations are presented. Examples from research at the NASA Lewis Research Center are given. Emphasis is on fundamental studies involving the effects of monolayer coverage and thick films on friction and wear. A summary of the current status of theoretical calculations of defect energetics is presented. In addition, some new theoretical techniques which enable simplified quantitative calculations of adhesion, fracture, and friction are discussed.

Solid oxide fuel cell cathode with oxygen-reducing layer

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

Surdoval, Wayne A.; Berry, David A.; Shultz, Travis

The disclosure provides a SOFC comprised of an electrolyte, anode, and cathode, where the cathode comprises an MIEC and an oxygen-reducing layer. The oxygen-reducing layer is in contact with the MIEC, and the MIEC is generally between and separating the oxygen-reducing layer and the electrolyte. The oxygen-reducing layer is comprised of single element oxides, single element carbonates, or mixtures thereof, and has a thickness of less than about 30 nm. In a particular embodiment, the thickness is less than 5 nm. In another embodiment, the thickness is about 3 monolayers or less. The oxygen-reducing layer may be a continuous filmmore » or a discontinuous film with various coverage ratios. The oxygen-reducing layer at the thicknesses described may be generated on the MIEC surface using means known in the art such as, for example, ALD processes.« less

Study of fission-product segregation in used CANDU fuel by X-ray photoelectron spectroscopy (XPS) II

NASA Astrophysics Data System (ADS)

Hocking, William H.; Duclos, A. Michael; Johnson, Lawrence H.

1994-03-01

A thorough investigation of the grain-boundary chemistry of used CANDU fuel from one intact element has been conducted by X-ray photoelectron spectroscopy (XPS). Selected findings from more extensive XPS measurements on other used CANDU fuels exposed to storage conditions are included for comparison. Cesium, rubidium, tellurium and barium have been commonly observed, often reaching high degrees of surface enrichment, although their relative abundances can vary widely with a complex dependence on the fuel irradiation history. Lower concentrations of cadmium, molybdenum, strontium and iodine have also been occasionally detected. Except for iodine, chemical-shift data are indicative of oxidized species, possibly uranates. Segregation at monolayer-level coverages has been demonstrated by sequential XPS analysis and argon-ion sputtering. Calculations based on an idealized thin-film model are consistent with the depth profiles. The interpretation of these results is discussed in the context of previous studies, especially on LWR fuels.

Strong Coupling of Localized Surface Plasmons to Excitons in Light-Harvesting Complexes

DOE PAGES

Tsargorodska, Anna; Cartron, Michaël L.; Vasilev, Cvetelin; ...

2016-09-30

Gold nanostructure arrays exhibit surface plasmon resonances that split after attaching light harvesting complexes 1 and 2 (LH1 and LH2) from purple bacteria. The splitting is attributed to strong coupling between the localized surface plasmon resonances and excitons in the light-harvesting complexes. Wild-type and mutant LH1 and LH2 from Rhodobacter sphaeroides containing different carotenoids yield different splitting energies, demonstrating that the coupling mechanism is sensitive to the electronic states in the light harvesting complexes. Plasmon–exciton coupling models reveal different coupling strengths depending on the molecular organization and the protein coverage, consistent with strong coupling. Strong coupling was also observed formore » self-assembling polypeptide maquettes that contain only chlorins. However, it is not observed for monolayers of bacteriochlorophyll, indicating that strong plasmon–exciton coupling is sensitive to the specific presentation of the pigment molecules.« less

Disappearing Enantiomorphs: Single Handedness in Racemate Crystals.

PubMed

Parschau, Manfred; Ernst, Karl-Heinz

2015-11-23

Although crystallization is the most important method for the separation of enantiomers of chiral molecules in the chemical industry, the chiral recognition involved in this process is poorly understood at the molecular level. We report on the initial steps in the formation of layered racemate crystals from a racemic mixture, as observed by STM at submolecular resolution. Grown on a copper single-crystal surface, the chiral hydrocarbon heptahelicene formed chiral racemic lattice structures within the first layer. In the second layer, enantiomerically pure domains were observed, underneath which the first layer contained exclusively the other enantiomer. Hence, the system changed from a 2D racemate into a 3D racemate with enantiomerically pure layers after exceeding monolayer-saturation coverage. A chiral bias in form of a small enantiomeric excess suppressed the crystallization of one double-layer enantiomorph so that the pure minor enantiomer crystallized only in the second layer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extremely high efficient nanoreactor with Au@ZnO catalyst for photocatalysis

NASA Astrophysics Data System (ADS)

Su, Chung-Yi; Yang, Tung-Han; Gurylev, Vitaly; Huang, Sheng-Hsin; Wu, Jenn-Ming; Perng, Tsong-Pyng

2015-10-01

We fabricated a photocatalytic Au@ZnO@PC (polycarbonate) nanoreactor composed of monolayered Au nanoparticles chemisorbed on conformal ZnO nanochannel arrays within the PC membrane. A commercial PC membrane was used as the template for deposition of a ZnO shell into the pores by atomic layer deposition (ALD). Thioctic acid (TA) with sufficient steric stabilization was used as a molecular linker for functionalization of Au nanoparticles in a diameter of 10 nm. High coverage of Au nanoparticles anchored on the inner wall of ZnO nanochannels greatly improved the photocatalytic activity for degradation of Rhodamine B. The membrane nanoreactor achieved 63% degradation of Rhodamine B within only 26.88 ms of effective reaction time owing to its superior mass transfer efficiency based on Damköhler number analysis. Mass transfer limitation can be eliminated in the present study due to extremely large surface-to-volume ratio of the membrane nanoreactor.

In-situ laser nano-patterning for ordered InAs/GaAs(001) quantum dot growth

NASA Astrophysics Data System (ADS)

Zhang, Wei; Shi, Zhenwu; Huo, Dayun; Guo, Xiaoxiang; Zhang, Feng; Chen, Linsen; Wang, Qinhua; Zhang, Baoshun; Peng, Changsi

2018-04-01

A study of in-situ laser interference nano-patterning on InGaAs wetting layers was carried out during InAs/GaAs (001) quantum dot molecular beam epitaxy growth. Periodic nano-islands with heights of a few atomic layers were obtained via four-beam laser interference irradiation on the InGaAs wetting layer at an InAs coverage of 0.9 monolayer. The quantum dots nucleated preferentially at edges of nano-islands upon subsequent deposition of InAs on the patterned surface. When the nano-islands are sufficiently small, the patterned substrate could be spontaneously re-flattened and an ordered quantum dot array could be produced on the smooth surface. This letter discusses the mechanisms of nano-patterning and ordered quantum dot nucleation in detail. This study provides a potential technique leading to site-controlled, high-quality quantum dot fabrication.

3D reconstruction of pentacene structural organization in top-contact OTFTs via resonant soft X-ray reflectivity

NASA Astrophysics Data System (ADS)

Capelli, Raffaella; Nardi, Marco Vittorio; Toccoli, Tullio; Verucchi, Roberto; Dinelli, Franco; Gelsomini, Carolina; Koshmak, Konstantin; Giglia, Angelo; Nannarone, Stefano; Pasquali, Luca

2018-01-01

Herein, we describe the use of soft X-ray reflectivity at the carbon K-edge to study the molecular organization (orientation, structure, and morphology) of pentacene active films in a top-contact transistor geometry. This technique is not affected by sample charging, and it can be applied in the case of insulating substrates. In addition, the sampling depth is not limited to the near-surface region, giving access to buried device interfaces (metal/organic and dielectric/organic). Spectral lineshape simulations, based on ab-initio calculations using a realistic 3D layer-by-layer model, allow us to unravel the details of the molecular organization in all the specific and crucial areas of the active film, overcoming the limitations of conventional approaches. The tilt angle of the long molecular axis in the whole film is found to progressively decrease with respect to the substrate normal from 25° to 0° with the increasing film thickness. A full vertical alignment, optimal for in-plane charge hopping, is reached only after the complete formation of the first five monolayers. Remarkably, starting from the first one in contact with the dielectric substrate, all the monolayers in the stack show a change in orientation with the increasing thickness. On the other hand, at the buried interface with a gold top-contact, the molecules assume a flat orientation that only propagates for two or three monolayers into the organic film. Top-contact devices with the highest performances can thus be obtained using films of at least ten monolayers. This explains the observed thickness dependence of charge mobility in pentacene transistors.

Covalently Bound Monomolecular Layers on Si Single Crystals

NASA Astrophysics Data System (ADS)

Chidsey, Christopher E. D.

1996-03-01

Methods and reagents borrowed from the molecular synthetic chemistry of silicon compounds have been used to form covalently bound monomolecular layers on silicon single crystals. Organic monolayers bound covalently to silicon could form the basis for silicon/organic interfaces useful in sensor structures. In a representative reaction, alkyl monolayers with densities approaching that of crystalline polyethylene have been prepared by the radical-initiated insertion of 1-alkenes into the Si-H bonds of hydrogen-terminated Si(111) surfaces footnote M. R. Linford, P. Fenter, P. M. Eisenberger and C. E. D Chidsey, J. Am. Chem. Soc. 117, 3145-3155 (1995). It has recently been found that this insertion reaction can also be initiated by illumination with UV light having sufficient energy to break the Si-H bond. Synchrotron-based high-resolution photoelectron spectroscopy and diffraction have demonstrated the expected Si-C bond in such monolayers footnote J. H. Terry, R. Cao, P. A. Pianetta, M. R. Linford and C. E. D. Chidsey, unpublished results. An alternate approach to similar monolayers has been found to be the chlorination of hydrogen-terminated Si(111) with Cl_2, followed by the nucleophilic displacement of chlorine with alkyl lithium reagents. The well-behaved chemical transformations of the hydrogen-terminated silicon surfaces appear to result from the essentially bulk termination of the silicon lattice with closed-shell silicon hydride "functional groups" on the surface. In addition to the formation of novel organic layers, a full understanding of the reactivity of the hydrogen-terminated silicon surfaces should lead to better control of key technological silicon interfaces such as Si/SiO_2, Si/epi-Si, and Si/metal.

Rec.2100 color gamut revelation using spectrally ultranarrow emitters

NASA Astrophysics Data System (ADS)

Genc, Sinan; Uguz, Mustafa; Yilmaz, Osman; Mutlugun, Evren

2017-11-01

We theoretically simulate the performance of ultranarrow emitters for the first time to achieve record high coverage for the International Telecommunication Union Radiocommunication Sector BT.2100 (Rec.2100) and National Television System Committee (NTSC) color gamut. Our results, employing more than 130-m parameter sets, include the investigation into peak emission wavelength and full width at half maximum (FWHM) values for three primaries that show ultranarrow emitters, i.e., nanoplatelets are potentially promising materials to fully cover the Rec.2100 color gamut. Using ultranarrow emitters having FWHM as low as 6 nm can provide the ability to attain 99.7% coverage area of the Rec.2100 color gamut as well as increasing the NTSC triangle to 133.7% with full coverage. The parameter set that provides possibility to fully reach Rec.2100 also has been shown to match with D65 white light by making use of the correct combination of those three primaries. Furthermore, we investigate the effect of the fourth color component on the CIE 1931 color space without sacrificing the achieved coverage percentages. The investigation into the fourth color component, cyan, is shown for the first time to enhance the Rec.2100 gamut area to 127.7% with 99.9% coverage. The fourth color component also provides an NTSC coverage ratio of 171.5%. The investigation into the potential of emitters with ultranarrow emission bandwidth holds great promise for future display applications.

Association between clean indoor air laws and voluntary smokefree rules in homes and cars.

PubMed

Cheng, Kai-Wen; Okechukwu, Cassandra A; McMillen, Robert; Glantz, Stanton A

2015-03-01

This study examines the influence that smokefree workplaces, restaurants and bars have on the adoption of smokefree rules in homes and cars, and whether there is an association with adopting smokefree rules in homes and cars. Bivariate probit models were used to jointly estimate the likelihood of living in a smokefree home and having a smokefree car as a function of law coverage and other variables. Household data were obtained from the nationally representative Social Climate Survey of Tobacco Control 2001, 2002 and 2004-2009; clean indoor air law data were from the American Nonsmokers' Rights Foundation Tobacco Control Laws Database. 'Full coverage' and 'partial coverage' smokefree legislation is associated with an increased likelihood of having voluntary home and car smokefree rules compared with 'no coverage'. The association between 'full coverage' and smokefree rule in homes and cars is 5% and 4%, respectively, and the association between 'partial coverage' and smokefree rules in homes and cars is 3% and 4%, respectively. There is a positive association between the adoption of smokefree rules in homes and cars. Clean indoor air laws provide the additional benefit of encouraging voluntary adoption of smokefree rules in homes and cars. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

Stability of children's insurance coverage and implications for access to care: evidence from the Survey of Income and Program Participation.

PubMed

Buchmueller, Thomas; Orzol, Sean M; Shore-Sheppard, Lara

2014-06-01

Even as the number of children with health insurance has increased, coverage transitions--movement into and out of coverage and between public and private insurance--have become more common. Using data from 1996 to 2005, we examine whether insurance instability has implications for access to primary care. Because unobserved factors related to parental behavior and child health may affect both the stability of coverage and utilization, we estimate the relationship between insurance and the probability that a child has at least one physician visit per year using a model that includes child fixed effects to account for unobserved heterogeneity. Although we find that unobserved heterogeneity is an important factor influencing cross-sectional correlations, conditioning on child fixed effects we find a statistically and economically significant relationship between insurance coverage stability and access to care. Children who have part-year public or private insurance are more likely to have at least one doctor's visit than children who are uninsured for a full year, but less likely than children with full-year coverage. We find comparable effects for public and private insurance. Although cross-sectional analyses suggest that transitions directly between public and private insurance are associated with lower rates of utilization, the evidence of such an effect is much weaker when we condition on child fixed effects.

Effects of the Affordable Care Act's young adult insurance expansion on prescription drug insurance coverage, utilization, and expenditures.

PubMed

Look, Kevin A; Arora, Prachi

2016-01-01

The US Affordable Care Act (ACA) extended the age of eligibility for young adults to remain on their parents' health insurance plans in order to address the disproportionate number of uninsured young adults in the United States. Effective September 23, 2010, the ACA has required all private health insurance plans to cover dependents until the age of 26. However, it is unknown whether the ACA dependent coverage expansion had an impact on prescription drug insurance or the use of prescription drugs. To evaluate short-term changes in prescription health insurance coverage, prescription drug insurance coverage, prescription drug use, and prescription drug expenditures following implementation of the ACA young adult insurance expansion using national data from 2009 and 2011. Full-year health insurance coverage increased 4.9 percentage points during the study period, which was mainly due to increases in private health insurance among middle- and high-income young adults. In contrast, full-year prescription drug insurance coverage increased 5.5 percentage points and was primarily concentrated among high-income young adults. Although no significant short-term changes in overall prescription drug use were observed, a 30% decrease in out-of-pocket expenditures was seen among young adults. While the main goal of the ACA's young adult insurance expansion was to increase health insurance coverage among young adults, it also had the unintended positive effect of increasing coverage for prescription drug insurance. Additionally, young adults experienced substantial decreases in out-of-pocket spending for prescription drugs. It is important for evaluations of health care policies to assess both intended and unintended outcomes to better understand the implications for the broader health system. Copyright © 2015 Elsevier Inc. All rights reserved.

Does ITV vaginal procedure ensure dosimetric coverage during IMRT of post-operative gynaecological tumours without instructions concerning rectal filling?

PubMed

Verges, Ramona; Giraldo, Alexandra; Seoane, Alejandro; Toral, Elisabet; Ruiz, M Carmen; Pons, Ariadna; Giralt, Jordi

2018-01-01

To find out whether the internal target volume (ITV) vaginal procedure ensures dosimetric coverage during intensity-modulated radiation therapy (IMRT) of post-operative gynaecological tumours without instructions on rectal filling. The ITV vaginal procedure does not necessarily include all movements of the bladder, and does not include changes in the rectal volume. We should know if the vaginal ITV is a useful tool in maintaining CTV coverage during treatment. A retrospective analysis of 24 patients treated between July 2012 and July 2014 with adjuvant IMRT for gynaecological cancer. All patients underwent empty and full bladder CT on simulation (CT-planning) and three weeks later (CT-control). ITV displacement was measured and the 3D vector was calculated. ITV coverage was then evaluated by comparing the volume covered by the prescription isodose on both CT's. Patients were asked to have full bladder but they did not follow recommendations for the rectum. The mean 3D vector was 0.64 ± 0.32 cm (0.09-1.30). The mean ITV coverage loss was 5.8 ± 5.7% (0-20.2). We found a significant positive correlation between the 3D vector and the loss of coverage (Pearson correlation, r  = 0.493, 95% CI: 0.111-0.748, p  = 0.0144). We did not find any significant correlation between the bladder and rectal parameters with the 3D vector and loss of dosimetric coverage. We found a trend between the maximum rectal diameter in CT-planning and 3D vector ( r  = 0.400, 95% CI: -0.004 to 0.692, p  = 0.0529). ITV vaginal procedure contributed to ensuring a good dose coverage without instructions on rectal filling.

[Complete immunization coverage and reasons for non-vaccination in a periurban area of Abidjan].

PubMed

Sackou, K J; Oga, A S S; Desquith, A A; Houenou, Y; Kouadio, K L

2012-10-01

An immunization coverage survey was conducted among children aged 12-59 months in a suburban neighbourhood in Abidjan. The objective was to determine the complete immunization coverage, the reasons for non-vaccination and factors influencing the immunization status of children. The method of exhaustive sampling enabled us to interview the mothers of 669 children using a questionnaire. Overall vaccination coverage was 68.6% with 1.2%, with 1.2% of children never having received vaccine. The logistic regression analysis showed that the level of education, knowledge of the immunization schedule and the marital status of mothers, as well as the type of habitat, were associated with full immunization of children. These determinants must be taken into account to improve vaccination coverage.

Effectiveness of a smartphone app on improving immunization of children in rural Sichuan Province, China: a cluster randomized controlled trial.

PubMed

Chen, Li; Du, Xiaozhen; Zhang, Lin; van Velthoven, Michelle Helena; Wu, Qiong; Yang, Ruikan; Cao, Ying; Wang, Wei; Xie, Lihui; Rao, Xiuqin; Zhang, Yanfeng; Koepsell, Jeanne Catherine

2016-08-31

The aim of this study was to assess the effectiveness of an EPI smartphone application (EPI app) on improving vaccination coverage in rural Sichuan Province, China. This matched-pair cluster randomized controlled study included 32 village doctors, matched in 16 pairs, and took place from 2013 to 2015. Village doctors in the intervention group used the EPI app and reminder text messages while village doctors in the control group used their usual procedures and text messages. The primary outcome was full vaccination coverage with all five vaccines (1 dose of BCG, 3 doses of hepatitis B, 3 doses of OPV, 3 doses of DPT and 1 dose of measles vaccine), and the secondary outcome was coverage with each dose of the five individual vaccines. We also conducted qualitative interviews with village doctors to understand perceptions on using the EPI app and how this changed their vaccination work. The full vaccination coverage increased statistically significant from baseline to end-line in both the intervention (67 % [95 % CI:58-75 %] to 84 % [95 % CI:76-90 %], P = 0.028) and control group (71 % [95 % CI:62-79 %] to 82 % [95 % CI:74-88 %], P = 0.014). The intervention group had higher increase in full vaccination coverage from baseline to end-line compared to the control group (17 % vs 10 %), but this was not statistically significant (P = 0.164). Village doctors found it more convenient to use the EPI app to manage child vaccination and also reported saving time by looking up information of caregivers and contacting caregivers for overdue vaccinations quicker. However, village doctors found it hard to manage children who migrated out of the counties. This study showed that an app and text messages can be used by village doctors to improve full vaccination coverage, though no significant increase in vaccination coverage was found when assessing the effect of the app on its own. Village doctors using EPI app reported having improved their working efficiency of managing childhood vaccination. Future studies should be conducted to evaluate the impact of more integrated approach of mHealth intervention on child immunization. Chinese Clinical Trials Registry (ChiCTR): ChiCTR-TRC- 13003960 , registered on December 6, 2013.

29 CFR 801.3 - Coverage.

Code of Federal Regulations, 2012 CFR

2012-07-01

... employer engaged in or affecting commerce or in the production of goods for commerce.” (Section 3 of EPPA; 29 U.S.C. 2002.) In interpreting the phrase “affecting commerce” in other statutes, courts have found coverage to be coextensive with the full scope of the Congressional power to regulate commerce. See, for...

Optical properties of two-dimensional GaS and GaSe monolayers

NASA Astrophysics Data System (ADS)

Jappor, Hamad Rahman; Habeeb, Majeed Ali

2018-07-01

Optical properties of GaS and GaSe monolayers are investigated using first-principles calculations. The optical properties are studied up to 35 eV. Precisely, our results demonstrated that the optical properties appearance of GaS monolayer is comparative with GaSe monolayer with few informations contrasts. Moreover, the absorption begins in the visible region, although the peaks in the ultraviolet (UV) region. The refractive index values are 1.644 (GaS monolayer) and 2.01 (GaSe monolayer) at zero photon energy limit and increase to 2.092 and 2.698 respectively and both located in the visible region. Furthermore, we notice that the optical properties of both monolayers are obtained in the ultraviolet range and the results are significant. Accordingly, it can be used as a highly promising material in the solar cell, ultraviolet optical nanodevices, nanoelectronics, optoelectronic, and photocatalytic applications.

The ferromagnetic monolayer Fe(110) on W(110)

NASA Astrophysics Data System (ADS)

Gradmann, U.; Liu, G.; Elmers, H. J.; Przybylski, M.

1990-07-01

Ferromagnetic order in the pseudomorphic monolayer Fe(110) on W(110) was analyzed experimentally using Conversion Electron Mössbauer Spectroscopy (CEMS) and Torsion Oscillation Magnetometry (TOM). The monolayer is thermodynamically stable, crystallizes to large monolayer patches at elevated temperatures and therefore forms an excellent approximation to the ideal monolayer structure. It is ferromagnetic below a Curie-temperature T c,mono, which is given by (282±3) K for the Ag-coated layer, (290±10) K for coating by Cu, Ag or Au and ≈210 K for the free monolayer. For the Ag-coated monolayer, ground state hyperfine field B hf (0)=(11.9±0.3) T and magnetic moment per atom μ=2.53 μB could be determined, in fair agreement with theoretical predictions. Unusual properties of the phase transition are detected by the combination of both experimental techniques. Strong magnetic anisotropies, which are essential for ferromagnetic order, are determined by CEMS.

First-principles study on the electronic, optical, and transport properties of monolayer α- and β-GeSe

DOE PAGES

Xu, Yuanfeng; Zhang, Hao; Shao, Hezhu; ...

2017-12-15

The extraordinary properties and the novel applications of black phosphorene induce the research interest in the monolayer group-IV monochalcogenides. Here using first-principles calculations, we systematically investigate the electronic, transport, and optical properties of monolayer α- and β-GeSe, revealing a direct band gap of 1.61 eV for monolayer α-GeSe and an indirect band gap of 2.47 eV for monolayer β-GeSe. For monolayer β-GeSe, the electronic/hole transport is anisotropic, with an extremely high electron mobility of 2.93×104cm2/Vs along the armchair direction, comparable to that of black phosphorene. However, for β-GeSe, robust band gaps nearly independent of the applied tensile strain along themore » armchair direction are observed. Both monolayer α- and β-GeSe exhibit anisotropic optical absorption in the visible spectrum.« less

Modeling the self-assembly of functionalized fullerenes on solid surfaces using Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Bubnis, Gregory J.

Since their discovery 25 years ago, carbon fullerenes have been widely studied for their unique physicochemical properties and for applications including organic electronics and photovoltaics. For these applications it is highly desirable for crystalline fullerene thin films to spontaneously self-assemble on surfaces. Accordingly, many studies have functionalized fullerenes with the aim of tailoring their intermolecular interactions and controlling interactions with the solid substrate. The success of these rational design approaches hinges on the subtle interplay of intermolecular forces and molecule-substrate interactions. Molecular modeling is well-suited to studying these interactions by directly simulating self-assembly. In this work, we consider three different fullerene functionalization approaches and for each approach we carry out Monte Carlo simulations of the self-assembly process. In all cases, we use a "coarse-grained" molecular representation that preserves the dominant physical interactions between molecules and maximizes computational efficiency. The first approach we consider is the traditional gold-thiolate SAM (self-assembled monolayer) strategy which tethers molecules to a gold substrate via covalent sulfur-gold bonds. For this we study an asymmetric fullerene thiolate bridged by a phenyl group. Clusters of 40 molecules are simulated on the Au(111) substrate at different temperatures and surface coverage densities. Fullerenes and S atoms are found to compete for Au(111) surface sites, and this competition prevents self-assembly of highly ordered monolayers. Next, we investigate self-assembled monolayers formed by fullerenes with hydrogen-bonding carboxylic acid substituents. We consider five molecules with different dimensions and symmetries. Monte Carlo cooling simulations are used to find the most stable solid structures of clusters adsorbed to Au(111). The results show cases where fullerene-Au(111) attraction, fullerene close-packing, and hydrogen-bonding interactions can cooperate to guide self-assembly or compete to hinder it. Finally, we consider three bis-fullerene molecules, each with a different "bridging group" covalently joining two fullerenes. To effectively study the competing "standing-up" and "lying-down" morphologies, we use Monte Carlo simulations in conjunction with replica exchange and force field biasing methods. For clusters adsorbed to smooth model surfaces, we determine free energy landscapes and demonstrate their utility for rationalizing and predicting self-assembly.

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

Yu, Yao; Chen, Josephine; Leary, Celeste I.

Radiation of the low neck can be accomplished using split-field intensity-modulated radiation therapy (sf-IMRT) or extended-field intensity-modulated radiation therapy (ef-IMRT). We evaluated the effect of these treatment choices on target coverage and thyroid and larynx doses. Using data from 14 patients with cancers of the oropharynx, we compared the following 3 strategies for radiating the low neck: (1) extended-field IMRT, (2) traditional split-field IMRT with an initial cord-junction block to 40 Gy, followed by a full-cord block to 50 Gy, and (3) split-field IMRT with a full-cord block to 50 Gy. Patients were planned using each of these 3 techniques.more » To facilitate comparison, extended-field plans were normalized to deliver 50 Gy to 95% of the neck volume. Target coverage was assessed using the dose to 95% of the neck volume (D{sub 95}). Mean thyroid and larynx doses were computed. Extended-field IMRT was used as the reference arm; the mean larynx dose was 25.7 ± 7.4 Gy, and the mean thyroid dose was 28.6 ± 2.4 Gy. Split-field IMRT with 2-step blocking reduced laryngeal dose (mean larynx dose 15.2 ± 5.1 Gy) at the cost of a moderate reduction in target coverage (D{sub 95} 41.4 ± 14 Gy) and much higher thyroid dose (mean thyroid dose 44.7 ± 3.7 Gy). Split-field IMRT with initial full-cord block resulted in greater laryngeal sparing (mean larynx dose 14.2 ± 5.1 Gy) and only a moderately higher thyroid dose (mean thyroid dose 31 ± 8 Gy) but resulted in a significant reduction in target coverage (D{sub 95} 34.4 ± 15 Gy). Extended-field IMRT comprehensively covers the low neck and achieves acceptable thyroid and laryngeal sparing. Split-field IMRT with a full-cord block reduces laryngeal doses to less than 20 Gy and spares the thyroid, at the cost of substantially reduced coverage of the low neck. Traditional 2-step split-field IMRT similarly reduces the laryngeal dose but also reduces low-neck coverage and delivers very high doses to the thyroid.« less

Morphological variation of stimuli-responsive polypeptide at air-water interface

NASA Astrophysics Data System (ADS)

Shin, Sungchul; Ahn, Sungmin; Cheng, Jie; Chang, Hyejin; Jung, Dae-Hong; Hyun, Jinho

2016-12-01

The morphological variation of stimuli-responsive polypeptide molecules at the air-water interface as a function of temperature and compression was described. The surface pressure-area (π-A) isotherms of an elastin-like polypeptide (ELP) monolayer were obtained under variable external conditions, and Langmuir-Blodgett (LB) monolayers were deposited onto a mica substrate for characterization. As the compression of the ELP monolayer increased, the surface pressure increased gradually, indicating that the ELP monolayer could be prepared with high stability at the air-water interface. The temperature in the subphase of the ELP monolayer was critical in the preparation of LB monolayers. The change in temperature induced a shift in the π-A isotherms as well as a change in ELP secondary structures. Surprisingly, the compression of the ELP monolayer influenced the ELP secondary structure due to the reduction in the phase transition temperature with decreasing temperature. The change in the ELP secondary structure formed at the air-water interface was investigated by surface-enhanced Raman scattering. Moreover, the morphology of the ELP monolayer was subsequently imaged using atomic force microscopy. The temperature responsive behavior resulted in changes in surface morphology from relatively flat structures to rugged labyrinth structures, which suggested conformational changes in the ELP monolayers.

Biodegradation of artificial monolayers applied to water storages to reduce evaporative loss.

PubMed

Pittaway, P; Herzig, M; Stuckey, N; Larsen, K

2015-01-01

Repeat applications of an artificial monolayer to the interfacial boundary layer of large agricultural water storages during periods of high evaporative demand remains the most commercially feasible water conservation strategy. However, the interfacial boundary layer (or microlayer) is ecologically distinct from subsurface water, and repeat monolayer applications may adversely affect microlayer processes. In this study, the natural cleansing mechanisms operating within the microlayer were investigated to compare the biodegradability of two fatty alcohol (C16OH and C18OH) and one glycol ether (C18E1) monolayer compound. The C16OH and C18OH compounds were more susceptible to microbial degradation, but the C18E1 compound was most susceptible to indirect photodegradation. On clean water the surface pressure and evaporation reduction achieved with a compressed C18E1 monolayer was superior to the C18OH monolayer, but on brown water the surface pressure dropped rapidly. These results suggest artificial monolayers are readily degraded by the synergy between photo and microbial degradation. The residence time of C18OH and C18E1 monolayers on clear water is sufficient for cost-effective water conservation. However, the susceptibility of C18E1 to photodegradation indicates the application of this monolayer to brown water may not be cost-effective.

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

Das, Kaushik, E-mail: kaushikdas2089@gmail.com; Kundu, Sarathi

Long chain fatty acid molecules (e.g., stearic and behenic acids) form a monolayer on water surface in the presence of Ba{sup 2+} ions at low subphase pH (≈ 5.5) and remain as a monolayer before collapse generally occurs at higher surface pressure (π{sub c} > 50 mN/m). Monolayer formation is verified from the surface pressure vs. area per molecule (π-A) isotherms and also from the atomic force microscopy (AFM) analysis of the films deposited by single upstroke of hydrophilic Si (001) substrate through the monolayer covered water surface. At high subphase pH (≈ 9.5), barium stearate molecules form multilayer structuremore » at lower surface pressure which is verified from the π-A isotherms and AFM analysis of the film deposited at 25 mN/m. Such monolayer to multilayer structure formation or monolayer collapse at lower surface pressure is unusual as at this surface pressure generally fatty acid salt molecules form a monolayer on the water surface. Formation of bidentate chelate coordination in the metal containing headgroups is the reason for such monolayer to multilayer transition. However, for longer chain barium behenate molecules only monolayer structure is maintained at that high subphase pH (≈ 9.5) due to the presence of relatively more tail-tail hydrophobic interaction.« less

First-principles study on the structure and electronic property of gas molecules adsorption on Ge2Li2 monolayer

NASA Astrophysics Data System (ADS)

Hu, Yiwei; Long, Linbo; Mao, Yuliang; Zhong, Jianxin

2018-06-01

Using first-principles methods, we have studied the adsorption of gas molecules (CO2, CH4, H2S, H2 and NH3) on two dimensional Ge2Li2 monolayer. The adsorption geometries, adsorption energies, charge transfer, and band structures of above mentioned gas molecules adsorption on Ge2Li2 monolayer are analyzed. It is found that the adsorption of CO2 on Ge2Li2 monolayer is a kind of strong chemisorption, while other gas molecules such as CH4, H2S, H2 and NH3 are physisorption. The strong covalent binding is formed between the CO2 molecule and the nearest Ge atom in Ge2Li2 monolayer. This adsorption of CO2 molecule on Ge2Li2 monolayer leads to a direct energy gap of 0.304 eV. Other gas molecules exhibit mainly ionic binding to the nearest Li atoms in Ge2Li2 monolayer, which leads to indirect energy gap after adsorptions. Furthermore, it is found that the work function of Ge2Li2 monolayer is sensitive with the variation of adsorbents. Our results reveal that the Ge2Li2 monolayer can be used as a kind of nano device for gas molecules sensor.

Mechanical and electronic properties of Janus monolayer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Shi, Wenwu; Wang, Zhiguo

2018-05-01

The mechanical and electronic properties of Janus monolayer transition metal dichalcogenides MXY (M  =  Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W; X/Y  =  S, Se, Te) were investigated using density functional theory. Results show that breaking the out-of-plane structural symmetry can be used to tune the electronic and mechanical behavior of monolayer transition metal dichalcogenides. The band gaps of monolayer WXY and MoXY are in the ranges of 0.16–1.91 and 0.94–1.69 eV, respectively. A semiconductor to metallic phase transition occurred in Janus monolayer MXY (M  =  Ti, Zr and Hf). The monolayers MXY (M  =  V, Nb, Ta and Cr) show metallic characteristics, which show no dependence on the structural symmetry breaking. The mechanical properties of MXY depended on the composition. Monolayer MXY (M  =  Mo, Ti, Zr, Hf and W) showed brittle characteristic, whereas monolayer CrXY and VXY are with ductile characteristic. The in-plane stiffness of pristine and Janus monolayer MXY are in the range between 22 and 158 N m‑1. The tunable electronic and mechanical properties of these 2D materials would advance the development of ultra-sensitive detectors, nanogenerators, low-power electronics, and energy harvesting and electromechanical systems.

Structural and dynamic characteristics in monolayer square ice.

PubMed

Zhu, YinBo; Wang, FengChao; Wu, HengAn

2017-07-28

When water is constrained between two sheets of graphene, it becomes an intriguing monolayer solid with a square pattern due to the ultrahigh van der Waals pressure. However, the square ice phase has become a matter of debate due to the insufficient experimental interpretation and the slightly rhomboidal feature in simulated monolayer square-like structures. Here, we performed classical molecular dynamics simulations to reveal monolayer square ice in graphene nanocapillaries from the perspective of structure and dynamic characteristics. Monolayer square-like ice (instantaneous snapshot), assembled square-rhombic units with stacking faults, is a long-range ordered structure, in which the square and rhombic units are assembled in an order of alternative distribution, and the other rhombic unit forms stacking faults (polarized water chains). Spontaneous flipping of water molecules in monolayer square-like ice is intrinsic and induces transformations among different elementary units, resulting in the structural evolution of monolayer square ice in dynamics. The existence of stacking faults should be attributed to the spontaneous flipping behavior of water molecules under ambient temperature. Statistical averaging results (thermal average positions) demonstrate the inherent square characteristic of monolayer square ice. The simulated data and insight obtained here might be significant for understanding the topological structure and dynamic behavior of monolayer square ice.

Determining the thickness of aliphatic alcohol monolayers covalently attached to silicon oxide surfaces using angle-resolved X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Austin W. H.; Kim, Dongho; Gates, Byron D.

2018-04-01

The thickness of alcohol based monolayers on silicon oxide surfaces were investigated using angle-resolved X-ray photoelectron spectroscopy (ARXPS). Advantages of using alcohols as building blocks for the formation of monolayers include their widespread availability, ease of handling, and stability against side reactions. Recent progress in microwave assisted reactions demonstrated the ease of forming uniform monolayers with alcohol based reagents. The studies shown herein provide a detailed investigation of the thickness of monolayers prepared from a series of aliphatic alcohols of different chain lengths. Monolayers of 1-butanol, 1-hexanol, 1-octanol, 1-decanol, and 1-dodecanol were each successfully formed through microwave assisted reactions and characterized by ARXPS techniques. The thickness of these monolayers consistently increased by ∼1.0 Å for every additional methylene (CH2) within the hydrocarbon chain of the reagents. Tilt angles of the molecules covalently attached to silicon oxide surfaces were estimated to be ∼35° for each type of reagent. These results were consistent with the observations reported for thiol based or silane based monolayers on either gold or silicon oxide surfaces, respectively. The results of this study also suggest that the alcohol based monolayers are uniform at a molecular level.

Growth Mechanism of Transition Metal Dichalcogenide Monolayers: The Role of Self-Seeding Fullerene Nuclei.

PubMed

Cain, Jeffrey D; Shi, Fengyuan; Wu, Jinsong; Dravid, Vinayak P

2016-05-24

Due to their unique optoelectronic properties and potential for next generation devices, monolayer transition metal dichalcogenides (TMDs) have attracted a great deal of interest since the first observation of monolayer MoS2 a few years ago. While initially isolated in monolayer form by mechanical exfoliation, the field has evolved to more sophisticated methods capable of direct growth of large-area monolayer TMDs. Chemical vapor deposition (CVD) is the technique used most prominently throughout the literature and is based on the sulfurization of transition metal oxide precursors. CVD-grown monolayers exhibit excellent quality, and this process is widely used in studies ranging from the fundamental to the applied. However, little is known about the specifics of the nucleation and growth mechanisms occurring during the CVD process. In this study, we have investigated the nucleation centers or "seeds" from which monolayer TMDs typically grow. This was accomplished using aberration-corrected scanning transmission electron microscopy to analyze the structure and composition of the nuclei present in CVD-grown MoS2-MoSe2 alloys. We find that monolayer growth proceeds from nominally oxi-chalcogenide nanoparticles which act as heterogeneous nucleation sites for monolayer growth. The oxi-chalcogenide nanoparticles are typically encased in a fullerene-like shell made of the TMD. Using this information, we propose a step-by-step nucleation and growth mechanism for monolayer TMDs. Understanding this mechanism may pave the way for precise control over the synthesis of 2D materials, heterostructures, and related complexes.

Respiratory syncytial virus infection disrupts monolayer integrity and function in cystic fibrosis airway cells.

PubMed

Kong, Michele; Maeng, Patrick; Hong, Jeong; Szczesniak, Rhonda; Sorscher, Eric; Sullender, Wayne; Clancy, John Paul

2013-09-19

Respiratory Syncytial Virus (RSV) infection is a common contributor to pulmonary symptoms in children with cystic fibrosis (CF). Here we examined RSV infection in immortalized bronchial epithelial cells (CFBE41o-) expressing wild-type (wt) or F508del cystic fibrosis transmembrane conductance regulator (CFTR), for monolayer integrity and RSV replication. CFBE41o- monolayers expressing wt or F508del CFTR were grown on permeable supports and inoculated with RSV A2 strain. Control experiments utilized UV-inactivated RSV and heat-killed RSV. Monolayer resistance and RSV production was monitored for up to six days post-infection. Within 24 h, a progressive decrease in monolayer resistance was observed in RSV infected F508del CFBE41o- cells, while the monolayer integrity of RSV infected wt CFTR CFBE41o- cells remained stable. RSV replication was necessary to disrupt F508del CFBE41o- monolayers as UV-irradiated and heat killed RSV had no effect on monolayer integrity, with an earlier and much more pronounced peak in RSV titer noted in F508del relative to wt CFTR-expressing cells. RSV infection of wt CFBE41o- monolayers also resulted in blunting of CFTR response. These findings identify an enhanced sensitivity of CFBE41o- cells expressing F508del CFTR to RSV infection, replication and monolayer disruption independent of the cellular immune response, and provide a novel mechanism by which cystic fibrosis airway epithelia are susceptible to RSV-dependent injury.

Electrochemical Properties of Organosilane Self Assembled Monolayers on Aluminum 2024

NASA Technical Reports Server (NTRS)

Hintze, Paul E.; Calle, Luz Marina

2004-01-01

Self assembled monolayers are commonly used to modify surfaces. Within the last 15 years, self assembled monolayers have been investigated as a way to protect from corrosion[1,2] or biofouling.[3] In this study, self assembled monolayers of decitriethoxysilane (C10H21Si(OC2H5)3) and octadecyltriethoxysilane (C18H37Si(OC2H5)3) were formed on aluminum 2024-T3. The modified surfaces and bare Al 2024 were characterized by dynamic water contact angle measurements, x-ray photoelectron spectroscopy (XIPS) and infrared spectroscopy. Electrochemical impedance spectroscopy (EIS) in 0.5 M NaCl was used to characterize the monolayers and evaluate their corrosion protection properties. The advancing water contact angle and infrared measurements show that the mono layers form a surface where the hydrocarbon chains are packed and oriented away from the surface, consistent with what is found in similar systems. The contact angle hysteresis measured in these systems is relatively large, perhaps indicating that the hydrocarbon chains are not as well packed as monolayers formed on other substrates. The results of the EIS measurements were modeled using a Randle's circuit modified by changing the capacitor to a constant phase element. The constant phase element values were found to characterize the monolayer. The capacitance of the monolayer modified surface starts lower than the bare Al 2024, but approaches values similar to the bare Al 2024 within 24 hours as the monolayer is degraded. The n values found for bare Al 2024 quickly approach the value of a true capacitor and are greater than 0.9 within hours after the start of exposure. For the monolayer modified structure, n can stay lower than 0.9 for a longer period of time. In fact, n for the monolayer modified surfaces is different from the bare surface even after the capacitance values have converged. This indicates that the deviation from ideal capacitance is the most sensitive indicator of the presence of the monolayer.

Novel color additive for chlorine disinfectants corrects deficiencies in spray surface coverage and wet-contact time and checks for correct chlorine concentration.

PubMed

Tyan, Kevin; Jin, Katherine; Kang, Jason; Kyle, Aaron M

2018-04-18

Bleach sprays suffer from poor surface coverage, dry out before reaching proper contact time, and can be inadvertently over-diluted to ineffective concentrations. Highlight ® , a novel color additive for bleach that fades to indicate elapsed contact time, maintained >99.9% surface coverage over full contact time and checked for correct chlorine concentration. Copyright © 2018 Association for Professionals in Infection Control and Epidemiology, Inc. Published by Elsevier Inc. All rights reserved.

Risk factors for low vaccination coverage among Roma children in disadvantaged settlements in Belgrade, Serbia.

PubMed

Stojanovski, Kristefer; McWeeney, Gerry; Emiroglu, Nedret; Ostlin, Piroska; Koller, Theadora; Licari, Lucianne; Kaluski, Dorit Nitzan

2012-08-10

Full vaccination coverage for children under 59 months of age in Serbia is over 90%. This study assesses vaccination coverage and examines its association with birth registration among Roma children who resided in disadvantaged settlements in Belgrade, Serbia. The First Roma Health and Nutrition Survey in Belgrade settlements, 2009, was conducted among households of 468 Roma children between the ages of 6-59 months. The 2005 WHO Immunization Coverage Cluster Survey sampling methodology was employed. Vaccinations were recorded using children's vaccination cards and through verification steps carried out in the Primary Health Care Centers. For those who had health records the information on vaccination was recorded. About 88% of children had vaccination cards. The mean rate of age appropriate full immunization was 16% for OPV and DTP and 14.3% for MMR. Multivariate analyses indicated that children whose births were registered with the civil authorities were more likely to have their vaccination cards [OR=6.1, CI (2.5, 15.0)] and to have their full, age appropriate, series vaccinations for DTP, OPV, MMR and HepB [OR=3.8, CI (1.5, 10.0), OR=3.2, CI (1.5, 6.6), OR=4.8, CI (1.1, 21.0), OR=5.4, CI (1.4, 21.6), respectively]. The immunization coverage among Roma children in settlements is far below the WHO/UNICEF MDG4 target in achieving prevention and control of vaccine preventable diseases. It demonstrates the need to include "invisible" populations into the health systems in continuous, integrated, comprehensive, accessible and sensitive modes. Copyright © 2012 Elsevier Ltd. All rights reserved.

CMB-S4 and the hemispherical variance anomaly

NASA Astrophysics Data System (ADS)

O'Dwyer, Márcio; Copi, Craig J.; Knox, Lloyd; Starkman, Glenn D.

2017-09-01

Cosmic microwave background (CMB) full-sky temperature data show a hemispherical asymmetry in power nearly aligned with the Ecliptic. In real space, this anomaly can be quantified by the temperature variance in the Northern and Southern Ecliptic hemispheres, with the Northern hemisphere displaying an anomalously low variance while the Southern hemisphere appears unremarkable [consistent with expectations from the best-fitting theory, Lambda Cold Dark Matter (ΛCDM)]. While this is a well-established result in temperature, the low signal-to-noise ratio in current polarization data prevents a similar comparison. This will change with a proposed ground-based CMB experiment, CMB-S4. With that in mind, we generate realizations of polarization maps constrained by the temperature data and predict the distribution of the hemispherical variance in polarization considering two different sky coverage scenarios possible in CMB-S4: full Ecliptic north coverage and just the portion of the North that can be observed from a ground-based telescope at the high Chilean Atacama plateau. We find that even in the set of realizations constrained by the temperature data, the low Northern hemisphere variance observed in temperature is not expected in polarization. Therefore, observing an anomalously low variance in polarization would make the hypothesis that the temperature anomaly is simply a statistical fluke more unlikely and thus increase the motivation for physical explanations. We show, within ΛCDM, how variance measurements in both sky coverage scenarios are related. We find that the variance makes for a good statistic in cases where the sky coverage is limited, however, full northern coverage is still preferable.

Single orientation graphene synthesized on iridium thin films grown by molecular beam epitaxy

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

Dangwal Pandey, A., E-mail: arti.pandey@desy.de; Grånäs, E.; Shayduk, R.

Heteroepitaxial iridium thin films were deposited on (0001) sapphire substrates by means of molecular beam epitaxy, and subsequently, one monolayer of graphene was synthesized by chemical vapor deposition. The influence of the growth parameters on the quality of the Ir films, as well as of graphene, was investigated systematically by means of low energy electron diffraction, x-ray reflectivity, x-ray diffraction, Auger electron spectroscopy, scanning electron microscopy, and atomic force microscopy. Our study reveals (111) oriented iridium films with high crystalline quality and extremely low surface roughness, on which the formation of large-area epitaxial graphene is achieved. The presence of defects,more » like dislocations, twins, and 30° rotated domains in the iridium films is also discussed. The coverage of graphene was found to be influenced by the presence of 30° rotated domains in the Ir films. Low iridium deposition rates suppress these rotated domains and an almost complete coverage of graphene was obtained. This synthesis route yields inexpensive, air-stable, and large-area graphene with a well-defined orientation, making it accessible to a wider community of researchers for numerous experiments or applications, including those which use destructive analysis techniques or irreversible processes. Moreover, this approach can be used to tune the structural quality of graphene, allowing a systematic study of the influence of defects in various processes like intercalation below graphene.« less

Targeted delivery of 10-hydroxycamptothecin to human breast cancers by cyclic RGD-modified lipid-polymer hybrid nanoparticles.

PubMed

Yang, Zhe; Luo, Xingen; Zhang, Xiaofang; Liu, Jie; Jiang, Qing

2013-04-01

Lipid-polymer hybrid nanoparticles (NPs) combining the positive attributes of both liposomes and polymeric NPs are increasingly being considered as promising candidates to carry therapeutic agents safely and efficiently into targeted sites. Herein, a modified emulsification technique was developed and optimized for the targeting lipid-polymer hybrid NPs fabrication; the surface properties and stability of the hybrid NPs were systematically investigated, which confirmed that the hybrid NPs consisted of a poly (lactide-co-glycolide) core with ∼90% surface coverage of the lipid monolayer and a ∼4.4 nm hydrated polyethylene glycol (PEG) shell. Optimization results showed that the lipid:polymer mass ratio and the lipid-PEG:lipid molar ratio could affect the size, lipid association efficiency and stability of hybrid NPs. Furthermore, a model chemotherapy drug, 10-hydroxycamptothecin, was encapsulated into hybrid NPs with a higher drug loading compared to PLGA NPs. Surface modification of the lipid layer and the PEG conjugated targeting ligand did not affect their drug release kinetics. Finally, the cytotoxicity and cellular uptake studies indicated that the lipid coverage and the c(RGDyk) conjugation of the hybrid NPs gained a significantly enhanced ability of cell killing and endocytosis. Our results suggested that lipid-polymer hybrid NPs prepared by the modified emulsion technique have great potential to be utilized as an engineered drug delivery system with precise control ability of surface targeting modification.

Dynamic atomic layer epitaxy of InN on/in +c-GaN matrix: Effect of “In+N” coverage and capping timing by GaN layer on effective InN thickness

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

Yoshikawa, Akihiko, E-mail: yoshi@faculty.chiba-u.jp; Graduate School of Engineering, Kogakuin University, Hachioji, Tokyo 192-0015; Kusakabe, Kazuhide

2016-01-11

The growth front in the self-organizing and self-limiting epitaxy of ∼1 monolayer (ML)-thick InN wells on/in +c-GaN matrix by molecular beam epitaxy (MBE) has been studied in detail, with special attention given to the behavior and role of the N atoms. The growth temperatures of interest are above 600 °C, far higher than the typical upper critical temperature of 500 °C in MBE. It was confirmed that 2 ML-thick InN wells can be frozen/inserted in GaN matrix at 620 °C, but it was found that N atoms at the growth front tend to selectively re-evaporate more quickly than In atoms at temperatures highermore » than 650 °C. As a result, the effective thickness of inserted InN wells in the GaN matrix at 660–670 °C were basically 1 ML or sub-ML, even though they were capped by a GaN barrier at the time of 2 ML “In+N” coverage. Furthermore, it was found that the N atoms located below In atoms in the dynamic atomic layer epitaxy growth front had remarkably weaker bonding to the +c-GaN surface.« less

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.

Full-coverage film cooling on flat, isothermal surfaces: Data and predictions

NASA Technical Reports Server (NTRS)

Crawford, M. E.; Kays, W. M.; Moffat, R. J.

1980-01-01

The heat transfer and fluid mechanics characteristics of full-coverage film cooling were investigated. The results for flat, isothermal plates for three injection geometries (normal, slant, and compound angle) are summarized and data concerning the spanwise distribution of the heat transfer coefficient within the blowing region are presented. Data are also presented for two different numbers of rows of holes (6 and 11). The experimental results summarized can be predicted with a two dimensional boundary layer code, STANCOOL, by providing descriptors of the injection parameters as inputs.

Healthcare financing systems for increasing the use of tobacco dependence treatment.

PubMed

Reda, Ayalu A; Kotz, Daniel; Evers, Silvia M A A; van Schayck, Constant Paul

2012-06-13

We hypothesized that provision of financial assistance for smokers trying to quit, or reimbursement of their care providers, could lead to an increased rate of successful quit attempts. The primary objective of this review was to assess the impact of reducing the costs of providing or using smoking cessation treatment through healthcare financing interventions on abstinence from smoking. The secondary objectives were to examine the effects of different levels of financial support on the use and/or prescription of smoking cessation treatment and on the number of smokers making a quit attempt. We searched the Cochrane Tobacco Addiction Group Specialized Register in April 2012. We considered randomised controlled trials (RCTs), controlled trials and interrupted time series studies involving financial benefit interventions to smokers or their healthcare providers or both. Two reviewers independently extracted data and assessed the quality of the included studies. Risk ratios (RR) were calculated for individual studies on an intention-to-treat basis and meta-analysis was performed using a random-effects model. We included economic evaluations when a study presented the costs and effects of two or more alternatives. We found eleven trials involving financial interventions directed at smokers and healthcare providers.Full financial interventions directed at smokers had a statistically significant favourable effect on abstinence at six months or greater when compared to no intervention (RR 2.45, 95% CI 1.17 to 5.12, I² = 59%, 4 studies). There was also a significant effect of full financial interventions when compared to no interventions on the number of participants making a quit attempt (RR 1.11, 95% CI 1.04 to 1.32, I² = 15%) and use of smoking cessation treatment (NRT: RR 1.83, 95% CI 1.55 to 2.15, I² = 43%; bupropion: RR 3.22, 95% CI 1.41 to 7.34, I² = 71%; behavioural therapy: RR 1.77, 95% CI 1.19 to 2.65). There was no evidence of an effect on smoking cessation when we pooled two trials of financial incentives directed at healthcare providers (RR 1.16, CI 0.98 to 1.37, I² = 0%). Comparisons of full coverage with partial coverage, partial coverage with no coverage, and partial coverage with another partial coverage intervention did not detect significant effects. Comparison of full coverage with partial or no coverage resulted in costs per additional quitter ranging from $119 to $6450. Full financial interventions directed at smokers when compared to no financial interventions increase the proportion of smokers who attempt to quit, use smoking cessation treatments, and succeed in quitting.  The absolute differences are small but the costs per additional quitter are low to moderate. We did not detect an effect on smoking cessation from financial incentives directed at healthcare providers. The methodological qualities of the included studies need to be taken into consideration when interpreting the results.

Interactions of doxorubicin with self-assembled monolayer-modified electrodes: electrochemical, surface plasmon resonance (SPR), and gravimetric studies.

PubMed

Nieciecka, Dorota; Krysinski, Pawel

2011-02-01

We present the results on the partitioning of doxorubicin (DOX), a potent anticancer drug, through the model membrane system, self-assembled monolayers (SAMs) on gold electrodes. The monolayers were formed from alkanethiols of comparable length with different ω-terminal groups facing the aqueous electrolyte: the hydrophobic -CH(3) groups for the case of dodecanethiol SAMs or hydrophilic -OH groups of mercaptoundecanol SAMs. The electrochemical experiments combined with the surface plasmon resonance (SPR) and gravimetric studies show that doxorubicin is likely adsorbed onto the surface of hydrophilic monolayer, while for the case of the hydrophobic one the drug mostly penetrates the monolayer moiety. The adsorption of the drug hinders further penetration of doxorubicin into the monolayer moiety.

A Depth-Adjustment Deployment Algorithm Based on Two-Dimensional Convex Hull and Spanning Tree for Underwater Wireless Sensor Networks.

PubMed

Jiang, Peng; Liu, Shuai; Liu, Jun; Wu, Feng; Zhang, Le

2016-07-14

Most of the existing node depth-adjustment deployment algorithms for underwater wireless sensor networks (UWSNs) just consider how to optimize network coverage and connectivity rate. However, these literatures don't discuss full network connectivity, while optimization of network energy efficiency and network reliability are vital topics for UWSN deployment. Therefore, in this study, a depth-adjustment deployment algorithm based on two-dimensional (2D) convex hull and spanning tree (NDACS) for UWSNs is proposed. First, the proposed algorithm uses the geometric characteristics of a 2D convex hull and empty circle to find the optimal location of a sleep node and activate it, minimizes the network coverage overlaps of the 2D plane, and then increases the coverage rate until the first layer coverage threshold is reached. Second, the sink node acts as a root node of all active nodes on the 2D convex hull and then forms a small spanning tree gradually. Finally, the depth-adjustment strategy based on time marker is used to achieve the three-dimensional overall network deployment. Compared with existing depth-adjustment deployment algorithms, the simulation results show that the NDACS algorithm can maintain full network connectivity with high network coverage rate, as well as improved network average node degree, thus increasing network reliability.