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Sample records for monolayer modified ag

  1. Oxidized Monolayers of Epitaxial Silicene on Ag(111)

    NASA Astrophysics Data System (ADS)

    Johnson, Neil W.; Muir, David I.; Moewes, Alexander

    2016-03-01

    The properties of epitaxial silicene monolayers on Ag(111) at various levels of oxidation are determined through complementary density functional theory calculations and soft X-ray spectroscopy experiments. Our calculations indicate that moderate levels of oxidation do not cause a significant bandgap opening in the epitaxial silicene monolayer, suggesting that oxygen functionalization is not a viable mechanism for bandgap tuning while the silicene monolayer remains on its metallic substrate. In addition, moderate oxidation is calculated to strongly distort the hexagonal Si lattice, causing it to cluster in regions of highest oxygen adatom concentration but retain its 2D sheet structure. However, our experiments reveal that beam-induced oxidation is consistent with the formation of islands of bulk-like SiO2. Complete exposure of the monolayer to ambient conditions results in a fully oxidized sample that closely resembles bulk SiO2, of which a significant portion is completely detached from the substrate.

  2. Oxidized Monolayers of Epitaxial Silicene on Ag(111)

    PubMed Central

    Johnson, Neil W.; Muir, David I.; Moewes, Alexander

    2016-01-01

    The properties of epitaxial silicene monolayers on Ag(111) at various levels of oxidation are determined through complementary density functional theory calculations and soft X-ray spectroscopy experiments. Our calculations indicate that moderate levels of oxidation do not cause a significant bandgap opening in the epitaxial silicene monolayer, suggesting that oxygen functionalization is not a viable mechanism for bandgap tuning while the silicene monolayer remains on its metallic substrate. In addition, moderate oxidation is calculated to strongly distort the hexagonal Si lattice, causing it to cluster in regions of highest oxygen adatom concentration but retain its 2D sheet structure. However, our experiments reveal that beam-induced oxidation is consistent with the formation of islands of bulk-like SiO2. Complete exposure of the monolayer to ambient conditions results in a fully oxidized sample that closely resembles bulk SiO2, of which a significant portion is completely detached from the substrate. PMID:26936144

  3. Oxidized Monolayers of Epitaxial Silicene on Ag(111).

    PubMed

    Johnson, Neil W; Muir, David I; Moewes, Alexander

    2016-03-03

    The properties of epitaxial silicene monolayers on Ag(111) at various levels of oxidation are determined through complementary density functional theory calculations and soft X-ray spectroscopy experiments. Our calculations indicate that moderate levels of oxidation do not cause a significant bandgap opening in the epitaxial silicene monolayer, suggesting that oxygen functionalization is not a viable mechanism for bandgap tuning while the silicene monolayer remains on its metallic substrate. In addition, moderate oxidation is calculated to strongly distort the hexagonal Si lattice, causing it to cluster in regions of highest oxygen adatom concentration but retain its 2D sheet structure. However, our experiments reveal that beam-induced oxidation is consistent with the formation of islands of bulk-like SiO2. Complete exposure of the monolayer to ambient conditions results in a fully oxidized sample that closely resembles bulk SiO2, of which a significant portion is completely detached from the substrate.

  4. High Temperature Ferromagnetism in a GdAg2 Monolayer.

    PubMed

    Ormaza, M; Fernández, L; Ilyn, M; Magaña, A; Xu, B; Verstraete, M J; Gastaldo, M; Valbuena, M A; Gargiani, P; Mugarza, A; Ayuela, A; Vitali, L; Blanco-Rey, M; Schiller, F; Ortega, J E

    2016-07-13

    Materials that exhibit ferromagnetism, interfacial stability, and tunability are highly desired for the realization of emerging magnetoelectronic phenomena in heterostructures. Here we present the GdAg2 monolayer alloy, which possesses all such qualities. By combining X-ray absorption, Kerr effect, and angle-resolved photoemission with ab initio calculations, we have investigated the ferromagnetic nature of this class of Gd-based alloys. The Curie temperature can increase from 19 K in GdAu2 to a remarkably high 85 K in GdAg2. We find that the exchange coupling between Gd atoms is barely affected by their full coordination with noble metal atoms, and instead, magnetic coupling is effectively mediated by noble metal-Gd hybrid s,p-d bands. The direct comparison between isostructural GdAu2 and GdAg2 monolayers explains how the higher degree of surface confinement and electron occupation of such hybrid s,p-d bands promote the high Curie temperature in the latter. Finally, the chemical composition and structural robustness of the GdAg2 alloy has been demonstrated by interfacing them with organic semiconductors or magnetic nanodots. These results encourage systematic investigations of rare-earth/noble metal surface alloys and interfaces, in order to exploit them in magnetoelectronic applications. PMID:27247988

  5. Comparison of electronic structure between monolayer silicenes on Ag (111)

    NASA Astrophysics Data System (ADS)

    Chun-Liang, Lin; Ryuichi, Arafune; Maki, Kawai; Noriaki, Takagi

    2015-08-01

    The electronic structures of monolayer silicenes (4 × 4 and ) grown on Ag (111) surface are studied by scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations. While both phases have similar electronic structures around the Fermi level, significant differences are observed in the higher energy unoccupied states. The DFT calculations show that the contributions of Si 3pz orbitals to the unoccupied states are different because of their different buckled configurations. Project supported by the Ministry of Education, Culture, Sports, Science and Technology (MEXT) through Grants-in-Aid for Scientific Research (Grant Nos. 24241040 and 25110008) and the World Premier International Research Center Initiative (WPI), MEXT, Japan.

  6. Exploring Ag(111) Substrate for Epitaxially Growing Monolayer Stanene: A First-Principles Study

    NASA Astrophysics Data System (ADS)

    Gao, Junfeng; Zhang, Gang; Zhang, Yong-Wei

    2016-07-01

    Stanene, a two-dimensional topological insulator composed of Sn atoms in a hexagonal lattice, is a promising contender to Si in nanoelectronics. Currently it is still a significant challenge to achieve large-area, high-quality monolayer stanene. We explore the potential of Ag(111) surface as an ideal substrate for the epitaxial growth of monolayer stanene. Using first-principles calculations, we study the stability of the structure of stanene in different epitaxial relations with respect to Ag(111) surface, and also the diffusion behavior of Sn adatom on Ag(111) surface. Our study reveals that: (1) the hexagonal structure of stanene monolayer is well reserved on Ag(111) surface; (2) the height of epitaxial stanene monolayer is comparable to the step height of the substrate, enabling the growth to cross the surface step and achieve a large-area stanene; (3) the perfect lattice structure of free-standing stanene can be achieved once the epitaxial stanene monolayer is detached from Ag(111) surface; and finally (4) the diffusion barrier of Sn adatom on Ag(111) surface is found to be only 0.041 eV, allowing the epitaxial growth of stanene monolayer even at low temperatures. Our above revelations strongly suggest that Ag(111) surface is an ideal candidate for growing large-area, high-quality monolayer stanene.

  7. Exploring Ag(111) Substrate for Epitaxially Growing Monolayer Stanene: A First-Principles Study

    PubMed Central

    Gao, Junfeng; Zhang, Gang; Zhang, Yong-Wei

    2016-01-01

    Stanene, a two-dimensional topological insulator composed of Sn atoms in a hexagonal lattice, is a promising contender to Si in nanoelectronics. Currently it is still a significant challenge to achieve large-area, high-quality monolayer stanene. We explore the potential of Ag(111) surface as an ideal substrate for the epitaxial growth of monolayer stanene. Using first-principles calculations, we study the stability of the structure of stanene in different epitaxial relations with respect to Ag(111) surface, and also the diffusion behavior of Sn adatom on Ag(111) surface. Our study reveals that: (1) the hexagonal structure of stanene monolayer is well reserved on Ag(111) surface; (2) the height of epitaxial stanene monolayer is comparable to the step height of the substrate, enabling the growth to cross the surface step and achieve a large-area stanene; (3) the perfect lattice structure of free-standing stanene can be achieved once the epitaxial stanene monolayer is detached from Ag(111) surface; and finally (4) the diffusion barrier of Sn adatom on Ag(111) surface is found to be only 0.041 eV, allowing the epitaxial growth of stanene monolayer even at low temperatures. Our above revelations strongly suggest that Ag(111) surface is an ideal candidate for growing large-area, high-quality monolayer stanene. PMID:27373464

  8. Comparison of a Fluorinated Aryl Thiol Self-Assembled Monolayer with Its Hydrogenated Counterpart on Polycrystalline Ag Substrates

    SciTech Connect

    Schalnat, Matthew C.; Pemberton, Jeanne E.

    2010-07-20

    The effects of perfluorination of aryl thiols on surface coverage, surface electronic properties, and molecular orientation of self-assembled monolayers of thiophenol (TP) and pentafluorothiophenol (F5TP) on polycrystalline Ag were evaluated using linear sweep voltammetry, ultraviolet photoelectron spectroscopy (UPS), and surface Raman spectroscopy, respectively. Electrochemical reductive desorption by linear sweep voltammetry indicates a surface coverage for the TP monolayer of (5.07 ± 1.29) × 10-10 mol/cm2, equating to a molecular area of 32.8 ± 8.3 Å2, and a surface coverage for the F5TP monolayer of (1.95 ± 0.59) × 10-10 mol/cm2, equating to an area of 85.2 ± 25.8 Å2/molecule. TP-modified Ag exhibits a change in work function (ΔΦ) of -0.64 eV relative to bare Ag, whereas F5TP-modified Ag exhibits a ΔΦ of +0.54 eV relative to bare Ag. Quantitative analysis of the UPS and reductive desorption results yields molecular pictures of the proposed interfaces with TP molecules tilted <20° from the surface normal in a herringbone pattern spaced 6.4 Å apart and F5TP molecules in a more disordered arrangement tilted 67° from the surface normal with an intermolecular distance of 10.4 Å. Qualitative surface Raman spectroscopic analysis of in-plane and out-of-plane modes for these systems confirms that TP molecules are oriented more vertical than F5TP molecules in these monolayers.

  9. ELECTROCATALYSIS ON SURFACES MODIFIED BY METAL MONOLAYERS DEPOSITED AT UNDERPOTENTIALS.

    SciTech Connect

    ADZIC,R.

    2000-12-01

    The remarkable catalytic properties of electrode surfaces modified by monolayer amounts of metal adatoms obtained by underpotential deposition (UPD) have been the subject of a large number of studies during the last couple of decades. This interest stems from the possibility of implementing strictly surface modifications of electrocatalysts in an elegant, well-controlled way, and these bi-metallic surfaces can serve as models for the design of new catalysts. In addition, some of these systems may have potential for practical applications. The UPD of metals, which in general involves the deposition of up to a monolayer of metal on a foreign substrate at potentials positive to the reversible thermodynamic potential, facilitates this type of surface modification, which can be performed repeatedly by potential control. Recent studies of these surfaces and their catalytic properties by new in situ surface structure sensitive techniques have greatly improved the understanding of these systems.

  10. Scanning tunnelling spectroscopy and Raman spectroscopy of monolayer silicene on Ag(111)

    NASA Astrophysics Data System (ADS)

    Díaz Álvarez, A.; Zhu, T.; Nys, J. P.; Berthe, M.; Empis, M.; Schreiber, J.; Grandidier, B.; Xu, T.

    2016-11-01

    Low temperature scanning tunnelling spectroscopy and Raman spectroscopy were used to study the electronic and vibrational properties of silicene formed on the Ag(111) surface for coverage up to one monolayer in the temperature range 230-250 °C. The tunnelling spectra reveal the strong contribution of silver states in the measured density of states around the Fermi level. The Raman spectra are found to evolve as a function of the submonolayer coverages, giving rise at one monolayer coverage to peaks that are characteristic of chemical bonds with distorted sp3 hybrid orbitals. Such properties account for the electronic transparency of the silicene/Ag(111) interface.

  11. Deposition of Ag nanoparticles on fluoroalkylsilane self-assembled monolayers with varying chain length

    NASA Astrophysics Data System (ADS)

    Zuo, Juan; Keil, Patrick; Valtiner, Markus; Thissen, Peter; Grundmeier, Guido

    2008-12-01

    Silver nanoparticles were prepared by means of electron beam evaporation of silver on top of self-assembled fluoroalkylsilane monolayers with different fluoroalkyl chain length. The surface properties of the different self-assembled monolayers (SAMs) were evaluated by surface energy measurements and X-ray photoelectron spectroscopy. The morphology of the silver nanostructures, characterized by their size, size distribution, shape and interparticle separation, was observed to be dependent on the chemical composition, fluoroalkyl chain length and surface energy of the sub-layer as well as the degradation of the monolayer during the deposition process. The resulting morphology of the evaporated Ag nanostructures on the different surfaces could be explained based on the basis of surface energy and the role of ordering, disordering and defects of the monolayers caused by the impinging silver atoms during evaporation. Depending on the fluoroalkyl chain length significant changes in the chemical and physical structure of the SAMs after the evaporation process could be detected.

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

    NASA Astrophysics Data System (ADS)

    Yan, Ling-Hao; Wu, Rong-Ting; Bao, De-Liang; Ren, Jun-Hai; Zhang, Yan-Fang; Zhang, Hai-Gang; Huang, Li; Wang, Ye-Liang; Du, Shi-Xuan; Huan, Qing; Gao, Hong-Jun

    2015-07-01

    Adsorption behavior of Fe atoms on a metal-free naphthalocyanine (H2Nc) 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 were adsorbed on the centers of H2Nc molecules and formed Fe-H2Nc complexes at low coverage. DFT calculations show that Fe sited in the center of the molecule is the most stable configuration, in good agreement with the experimental observations. After an Fe-H2Nc complex monolayer was formed, the extra Fe atoms self-assembled to Fe clusters of uniform size and adsorbed dispersively at the interstitial positions of Fe-H2Nc complex monolayer. Therefore, the H2Nc 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. Project supported by the National Natural Science Foundation of China (Grant Nos. 61390501, 51325204, and 11204361), the National Basic Research Program of China (Grant Nos. 2011CB808401 and 2011CB921702), the National Key Scientific Instrument and Equipment Development Project of China (Grant No. 2013YQ1203451), the National Supercomputing Center in Tianjin, China, and the Chinese Academy of Sciences.

  13. Bimetallic PdAg nanoparticle arrays from monolayer films of diblock copolymer micelles

    NASA Astrophysics Data System (ADS)

    Ehret, E.; Beyou, E.; Mamontov, G. V.; Bugrova, T. A.; Prakash, S.; Aouine, M.; Domenichini, B.; Cadete Santos Aires, F. J.

    2015-07-01

    The self-assembly technique provides a highly efficient route to generate well-ordered structures on a nanometer scale. In this paper, well-ordered arrays of PdAg alloy nanoparticles on flat substrates with narrow distributions of particle size (6-7 nm) and interparticle spacing (about 60 nm) were synthesized by the block copolymer micelle approach. A home-made PS-b-P4VP diblock copolymer was prepared to obtain a micellar structure in toluene. Pd and Ag salts were then successfully loaded in the micellar core of the PS-b-P4VP copolymer. A self-assembled monolayer of the loaded micelles was obtained by dipping the flat substrate in the solution. At this stage, the core of the micelles was still loaded with the metal precursor rather than with a metal. Physical and chemical reducing methods were used to reduce the metal salts embedded in the P4VP core into PdAg nanoparticles. HRTEM and EDX indicated that Pd-rich PdAg alloy nanoparticles were synthesized by chemical or physical reduction; UV-visible spectroscopy observations confirmed that metallic PdAg nanoparticles were quickly formed after chemical reduction; XPS measurements revealed that the PdAg alloy nanoparticles were in a metallic state after a short time of exposure to O2 plasma and after hydrazine reduction.

  14. Manipulation resolves non-trivial structure of corrole monolayer on Ag(111)

    NASA Astrophysics Data System (ADS)

    Tebi, Stefano; Aldahhak, Hazem; Serrano, Giulia; Schöfberger, Wolfgang; Rauls, Eva; Gero Schmidt, Wolf; Koch, Reinhold; Müllegger, Stefan

    2016-01-01

    Non-trivial arrangement of molecules within a molecular network complicates structure determination due to interdigitation, partial overlap, or stacking. We demonstrate that combined imaging and lateral manipulation with a scanning tunneling microscope resolves the intricate structure of a molecular network in two-dimensions in a straightforward manner. The network, formed by a monolayer of 5,10,15-tris(pentafluorophenyl)-corrole molecules on Ag(111), is manipulated for the first time with single-molecule precision. Our results reveal a shingle-like packing of partially overlapping corrole molecules. Density functional theory calculations support our findings.

  15. Oligoethylene-bridged diferrocene on Ag(110): Monolayer structures and adsorbate-induced faceting

    SciTech Connect

    Zhong, D. Y.; Fuchs, H.; Wang, W. C.; Dou, R. F.; Chi, L. F.; Wedeking, K.; Erker, G.

    2007-11-15

    The self-assembly of a ferrocene (Fc) derivative, oligoethylene-bridged diferrocene (diFc), Fc(CH{sub 2}){sub 14}Fc, on Ag(110) surface has been investigated by scanning tunneling microscopy (STM) under ultrahigh vacuum. Three ordered structures, the majority {beta} and the minorities {alpha} and {gamma}, are formed at monolayer coverage. In {alpha} and {gamma}, a unit cell contains one molecule and the molecules are parallel to each other so that the distances between Fc groups and between oligoethylene chains are reduced. A unit cell contains five molecules in {beta}: four of them are parallel to each other but not parallel to the fifth. The interaction between diFc and Ag(110), which is relatively strong in comparison to the intermolecular interaction, is dominant for the assembly of the ordered structures. The adsorption of diFc molecules induces the reorganization of substrate steps, which prefer to follow the directions of the superstructure lattice vectors, i.e. ({+-}1,2) and ({+-}3,2) of the Ag(110) surface. The (12 13-1) facet is formed due to step bunching at regions with high step density. By using in situ STM, the process of step reorganization and faceting has been observed in real time. It is concluded that the Ag adatoms play a key role on the substrate reorganization.

  16. Computer simulations of the Adsorption of Xenon onto a C60 monolayer on Ag (111)

    NASA Astrophysics Data System (ADS)

    Gatica, Silvina; Cole, Milton; Diehl, Renee

    2007-03-01

    We performed Grand Canonical Monte Carlo simulations to study the adsorption of Xenon on a substrate composed of C60 molecules placed on top of a Ag(111) surface. The C60 molecules form a commensurate structure at a distance of 0.227 nm above the Ag surface. The interaction potential between the Xe atoms and the substrate has two contributions: from the C60 molecules and from the Ag atoms. In the simulations, the interaction with the Ag surface was computed using an ab initio van der Waals potential, varying as 1/d^3. The interaction between the Xe atoms and each C60 molecule was computed using a potential previously developed by Hernandez et.al. (E. S. Hernandez, M. W. Cole and M. Boninsegni, ``Wetting of spherical surfaces by quantum fluids'', J. Low Temp. Phys. 134, 309-314 (2004)), who integrated the Lennard Jones interaction over the surface of a spherical buckyball. The total potential has especially attractive 3-fold sites, positioned 0.4 nm above the point between each three buckyballs. The low coverage uptake populates those sites, and then continues forming a monolayer. The adsorption isotherms show several steps, typical of substrates that have distinct adsorption sites. We compare the results with the experimental data.

  17. Ordered array of Ag semishells on different diameter monolayer polystyrene colloidal crystals: An ultrasensitive and reproducible SERS substrate.

    PubMed

    Yi, Zao; Niu, Gao; Luo, Jiangshan; Kang, Xiaoli; Yao, Weitang; Zhang, Weibin; Yi, Yougen; Yi, Yong; Ye, Xin; Duan, Tao; Tang, Yongjian

    2016-09-02

    Ag semishells (AgSS) ordered arrays for surface-enhanced Raman scattering (SERS) spectroscopy have been prepared by depositing Ag film onto polystyrene colloidal particle (PSCP) monolayer templates array. The diversified activity for SERS activity with the ordered AgSS arrays mainly depends on the PSCP diameter and Ag film thickness. The high SERS sensitivity and reproducibility are proved by the detection of rhodamine 6G (R6G) and 4-aminothiophenol (4-ATP) molecules. The prominent enhancements of SERS are mainly from the "V"-shaped or "U"-shaped nanogaps on AgSS, which are experimentally and theoretically investigated. The higher SERS activity, stability and reproducibility make the ordered AgSS a promising choice for practical SERS low concentration detection applications.

  18. Ordered array of Ag semishells on different diameter monolayer polystyrene colloidal crystals: An ultrasensitive and reproducible SERS substrate

    PubMed Central

    Yi, Zao; Niu, Gao; Luo, Jiangshan; Kang, Xiaoli; Yao, Weitang; Zhang, Weibin; Yi, Yougen; Yi, Yong; Ye, Xin; Duan, Tao; Tang, Yongjian

    2016-01-01

    Ag semishells (AgSS) ordered arrays for surface-enhanced Raman scattering (SERS) spectroscopy have been prepared by depositing Ag film onto polystyrene colloidal particle (PSCP) monolayer templates array. The diversified activity for SERS activity with the ordered AgSS arrays mainly depends on the PSCP diameter and Ag film thickness. The high SERS sensitivity and reproducibility are proved by the detection of rhodamine 6G (R6G) and 4-aminothiophenol (4-ATP) molecules. The prominent enhancements of SERS are mainly from the “V”-shaped or “U”-shaped nanogaps on AgSS, which are experimentally and theoretically investigated. The higher SERS activity, stability and reproducibility make the ordered AgSS a promising choice for practical SERS low concentration detection applications. PMID:27586562

  19. Ordered array of Ag semishells on different diameter monolayer polystyrene colloidal crystals: An ultrasensitive and reproducible SERS substrate.

    PubMed

    Yi, Zao; Niu, Gao; Luo, Jiangshan; Kang, Xiaoli; Yao, Weitang; Zhang, Weibin; Yi, Yougen; Yi, Yong; Ye, Xin; Duan, Tao; Tang, Yongjian

    2016-01-01

    Ag semishells (AgSS) ordered arrays for surface-enhanced Raman scattering (SERS) spectroscopy have been prepared by depositing Ag film onto polystyrene colloidal particle (PSCP) monolayer templates array. The diversified activity for SERS activity with the ordered AgSS arrays mainly depends on the PSCP diameter and Ag film thickness. The high SERS sensitivity and reproducibility are proved by the detection of rhodamine 6G (R6G) and 4-aminothiophenol (4-ATP) molecules. The prominent enhancements of SERS are mainly from the "V"-shaped or "U"-shaped nanogaps on AgSS, which are experimentally and theoretically investigated. The higher SERS activity, stability and reproducibility make the ordered AgSS a promising choice for practical SERS low concentration detection applications. PMID:27586562

  20. Ordered array of Ag semishells on different diameter monolayer polystyrene colloidal crystals: An ultrasensitive and reproducible SERS substrate

    NASA Astrophysics Data System (ADS)

    Yi, Zao; Niu, Gao; Luo, Jiangshan; Kang, Xiaoli; Yao, Weitang; Zhang, Weibin; Yi, Yougen; Yi, Yong; Ye, Xin; Duan, Tao; Tang, Yongjian

    2016-09-01

    Ag semishells (AgSS) ordered arrays for surface-enhanced Raman scattering (SERS) spectroscopy have been prepared by depositing Ag film onto polystyrene colloidal particle (PSCP) monolayer templates array. The diversified activity for SERS activity with the ordered AgSS arrays mainly depends on the PSCP diameter and Ag film thickness. The high SERS sensitivity and reproducibility are proved by the detection of rhodamine 6G (R6G) and 4-aminothiophenol (4-ATP) molecules. The prominent enhancements of SERS are mainly from the “V”-shaped or “U”-shaped nanogaps on AgSS, which are experimentally and theoretically investigated. The higher SERS activity, stability and reproducibility make the ordered AgSS a promising choice for practical SERS low concentration detection applications.

  1. From monomer to monolayer: a global optimisation study of (ZnO)n nanoclusters on the Ag surface.

    PubMed

    Demiroglu, Ilker; Woodley, Scott M; Sokol, Alexey A; Bromley, Stefan T

    2014-12-21

    We employ global optimisation to investigate how oxide nanoclusters of increasing size can best adapt their structure to lower the system energy when interacting with a realistic extended metal support. Specifically, we focus on the (ZnO)@Ag(111) system where experiment has shown that the infinite Ag(111)-supported ZnO monolayer limit corresponds to an epitaxially 7 : 8 matched graphene-like (Zn(3)O(3))-based hexagonal sheet. Using a two-stage search method based on classical interatomic potentials and then on more accurate density functional theory, we report global minina candidate structures for Ag-supported (ZnO)n cluster with sizes ranging from n = 1-24. Comparison with the respective global minina structure of free space (ZnO)n clusters reveals that the surface interaction plays a decisive role in determining the lowest energy Ag-supported (ZnO)n cluster structures. Whereas free space (ZnO)n clusters tend to adopt cage-like bubble structures as they grow larger, Ag-supported (ZnO)n clusters of increasing size become progressively more like planar cuts from the infinite graphene-like ZnO single monolayer. This energetic favourability for planar hexagonal Ag-supported clusters over their 3D counterparts can be partly rationalised by the ZnO-Ag(111) epitaxial matching and the increased number of close interactions with the Ag surface. Detailed analysis shows that this tendency can also be attributed to the capacity of 2D clusters to distort to improve their interaction with the Ag surface relative to more rigid 3D bubble cluster isomers. For the larger sized clusters we find that the adsorption energies and most stable structural types appear to be rather converged confirming that our study makes a bridge between the Ag-supported ZnO monomer and the infinite Ag-supported ZnO monolayer.

  2. Crystalline monolayer surface of liquid Au-Cu-Si-Ag-Pd: Metallic glass former

    SciTech Connect

    Mechler, S; Yahel, E; Pershan, P S; Meron, M; Lin, B

    2012-02-06

    It is demonstrated by means of x-ray synchrotron reflectivity and diffraction that the surface of the liquid phase of the bulk metallic glass forming alloy Au49Cu26.9Si16.3Ag5.5Pd2.3 consists of a two-dimensional crystalline monolayer phase for temperatures of up to about 50 K above the eutectic temperature. The present alloy as well as glass forming Au82Si18 and Au-Si-Ge alloys containing small amounts of Ge are the only metallic liquids to exhibit surface freezing well above the melting temperature. This suggests that the phenomena of surface freezing in metallic liquids and glass forming ability are related and probably governed by similar physical properties.

  3. Ag on Pt(111): Changes in Electronic and CO Adsorption Properties upon PtAg/Pt(111) Monolayer Surface Alloy Formation.

    PubMed

    Diemant, Thomas; Schüttler, Konstantin M; Behm, R Jürgen

    2015-10-01

    The electronic and chemical (adsorption) properties of bimetallic Ag/Pt(111) surfaces and their modification upon surface alloy formation, that is, during intermixing of Ag and Pt atoms in the top atomic layer upon annealing, were studied by X-ray photoelectron spectroscopy (XPS) and, using CO as probe molecule, by temperature-programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRRAS), respectively. The surface alloys are prepared by deposition of sub-monolayer Ag amounts on a Pt(111) surface at room temperature, leading to extended Ag monolayer islands on the substrate, and subsequent annealing of these surfaces. Surface alloy formation starts at ≈600-650 K, which is evidenced by core-level shifts (CLSs) of the Ag(3d5/2 ) signal. A distinct change of the CO adsorption properties is observed when going to the intermixed PtAg surface alloys. Most prominently, we find the growth of a new desorption feature at higher temperature (≈550 K) in the TPD spectra upon surface alloy formation. This goes along with a shift of the COad -related IR bands to lower wave number. Surface alloy formation is almost completed after heating to 700 K.

  4. The protonation state of thiols in self-assembled monolayers on roughened Ag/Au surfaces and nanoparticles.

    PubMed

    Bandyopadhyay, Sabyasachi; Chattopadhyay, Samir; Dey, Abhishek

    2015-10-14

    The protonation state of thiols in self-assembled monolayers (SAMs) on Ag and Au surfaces and nanoparticles (NPs) has been an issue of contestation. It has been recently demonstrated that deuterating the thiol proton produces ostentatious changes in the Raman spectra of thiols and can be used to detect the presence of the thiol functional group. Surface enhanced Raman spectroscopy (SERS) of H/D substituted aliphatic thiols on Ag surfaces clearly shows the presence of S-H vibration between 2150-2200 cm(-1) which shifts by 400 cm(-1) upon deuteration and a simultaneous >20 cm(-1) shift in the C-S vibration of thiol deuteration. Large shifts (>15 cm(-1)) in the C-S vibration are also observed for alkyl thiol SAMs on Au surfaces. Alternatively, neither the S-H vibration nor the H/D isotope effect on the C-S vibration is observed for alkyl thiol SAMs on Ag/Au NPs. XPS data on Ag/Au surfaces bearing aliphatic thiol SAMs show the presence of both protonated and deprotonated thiols while on Ag/Au NPs only deprotonated thiols are detected. These data suggest that aliphatic thiol SAMs on Au/Ag surfaces are partially protonated whereas they are totally deprotonated on Au/Ag NPs. Aromatic PhSH SAMs on Ag/Au surfaces and Ag/Au NPs do not show these vibrations or H/D shifts as well indicating that the thiols are deprotonated at these interfaces.

  5. Mn Monolayer Modified Rh for Syngas-to-Ethanol Conversion: A First-Principles Study

    SciTech Connect

    Li, Fengyu; Jiang, Deen; Zeng, X.C.; Chen, Zhongfang

    2012-01-01

    Rh is unique in its ability to convert syngas to ethanol with the help of promoters. We performed systematic first-principles computations to examine the catalytic performance of pure and Mn modified Rh(100) surfaces for ethanol formation from syngas. CO dissociation on the surface as well as CO insertion between the chemisorbed CH{sub 3} and the surface are the two key steps. The CO dissociation barrier on the Mn monolayer modified Rh(100) surface is remarkably lowered by {approx}1.5 eV compared to that on Rh(100). Moreover, the reaction barrier of CO insertion into the chemisorbed CH{sub 3} group on the Mn monolayer modified Rh(100) surface is 0.34 eV lower than that of methane formation. Thus the present work provides new mechanistic insight into the role of Mn promoters in improving Rh's selectivity to convert syngas to ethanol.

  6. Self-assembled monolayer films of C[sub 60]/on cysteamine-modified gold

    SciTech Connect

    Caldwell, W.B.; Chen, K.; Mirkin, C.A.; Babinec, S.J. Dow Chemical Company, Midland, MI )

    1993-08-01

    Self-assembled monolayer films (SAMs) of C[sub 60] on cysteamine-modified and cysteamine/ethanethiol-modified Au are reported. The monolayers were characterized via contact angle measurements, X-ray photoelectron spectroscopy, electrochemistry, and quartz crystal microbalance (QCM) measurements. C[sub 60] surface coverage (2.0 [times] 10[sup [minus]10] mol/cm[sup 2]) for a film formed on pure cysteamine was determined by QCM measurements and compares remarkably well with monolayer coverage (1.9 [times] 10[sup [minus]10] mol/cm[sup 2]) predicted by a model based on crystallographic data for C[sub 60]. These experiments demonstrate the utility of the QCM in characterizing and monitoring the growth of fullerene SAMs. C[sub 60] SAMs formed on pure cysteamine yield strikingly different electrochemical responses than those formed on prelayers consisting of varying ratios of ethanethiol and cysteamine and previously reported monolayers of C[sub 60] on (aminopropyl)silanized oxide surfaces. Although the C[sub 60] SAMs are stable under ambient conditions, the fullerenes may be desorbed from the surface through electrochemical reduction of the films for extended periods of time (> 10 min). 11 refs., 2 figs.

  7. Raman gas sensing of modified Ag nanoparticle SERS

    NASA Astrophysics Data System (ADS)

    Myoung, NoSoung; Yoo, Hyung Keun; Hwang, In-Wook

    2014-03-01

    Recent progress in modified Surface Enhanced Raman Scattering (SERS) using Ag nanoparticles makes them promising optical technique for direct gas sensing of interest. However, SERS has been shown to provide sub ppb level detection of the compounds in the vapor phase. The major problem with the sensitivity scaling-up was in the development of fabrication technology for stability and reproducibility of SERS substrates. We report an optimization of 1-propanethiol coated multiple Ag nanoparticle layers on SiO2 substrate as well as new records of real-time, simultaneous vapor phase detection of toluene and 1-2 dichlorobenzene by the radiation of fiber optic coupled 785 nm diode laser and spectrograph. Multiple depositions of Ag NPs were loaded on SiO2 and soaked in 1-propanethiol solution for 24 hours to modify the surface into hydrophobic due to the characteristics of vapor phase of our interests. Raman bands at 1003 cm-1 and 1130 cm-1 for toluene and 12DCB, respectively were compared to 1089 cm-1 and each gas concentration in 1000 mL flask were calculated as a function of each vapor phase ratio. The saturation of toluene and 12DCB were limited only by 800 ppm and the detectable range was 0.6-800 ppm.

  8. Development of a DNA Sensor Based on Alkanethiol Self-Assembled Monolayer-Modified Electrodes

    PubMed Central

    Loaiza, Óscar A.; Campuzano, Susana; López-Berlanga, María; Pedrero, María; Pingarrón, José M.

    2005-01-01

    An electrochemical DNA biosensor based on recognition of double or single stranded DNA (ds-DNA/ss-DNA) immobilised on a self-assembled modified gold electrode is presented for denaturalisation and hybridisation detection. DNA is covalently bond on a self assembled 3-mercaptopropionic acid monolayer by using water soluble N-3-(dimethylaminopropyl)-N prime;ethylcarbodiimide hydrochloride (EDC) and N-hydroxisulfosuccinimide (NHSS) as linkers. The interaction between the immobilised DNA and methylene blue (MB) is investigated using square wave voltammetry (SWV). The increase or diminution of peak currents of the MB upon the hybridisation or denaturalisation event at the modified electrode surface is studied.

  9. Electroanalysis of dopamine at a gold electrode modified with N-acetylcysteine self-assembled monolayer.

    PubMed

    Liu, Ting; Li, Meixian; Li, Qianyuan

    2004-07-01

    Voltammetric behavior of dopamine (DA) on a gold electrode modified with the self-assembled monolayer (SAM) of N-acetylcysteine has been investigated, and one pair of well-defined redox peaks of dopamine is obtained at the SAM modified gold electrode. The oxidation peak current increases linearly with the concentration of dopamine in the range of 1.0x10 (-6)to 2.0x10 (-4)moll(-1). The detection limit is 8.0x10(-7)moll(-1). This method will be applicable to the determination of dopamine in injection of dopamine hydrochloride, and the good recovery of dopamine is obtained. Furthermore, The SAM modified gold electrode can resolve well the voltammetric responses of dopamine and ascorbic acid (AA), so it can also be applied to the determination of dopamine in the presence of ascorbic acid.

  10. Study of the scale formation mechanism on gold modified with an alkanethiol monolayer.

    PubMed

    Clément, Maxime; St-Jean, Émilie; Bouchard, Nicolas-Alexandre; Ménard, Hugues

    2013-02-01

    Scaling is a problem in many industrial processes. To control and minimize it, it is important to understand the dynamics of the scale formation. In this paper, the scale formation was examined on two kinds of gold surfaces. One was a pure metallic gold surface, and the other was a gold surface modified with an alkanethiol self-assembled monolayer. A series of surface characterization experiments were performed to ensure a good understanding of the gold-thiol bond stability in a caustic solution.

  11. Dual functions of 2D WS2 and MoS2-WS2 monolayers coupled with a Ag3PO4 photocatalyst

    NASA Astrophysics Data System (ADS)

    Wei, Zeng-Xi; Huang, Wei-Qing; Xu, Liang; Hu, Wangyu; Peng, P.; Huang, Gui-Fang

    2016-09-01

    The photocatalytic performance of semiconductors can be improved by coupling two-dimensional (2D) layered materials. Understanding the underlying mechanism of this phenomenon at the electronic level is important for the development of photocatalysts with a high efficiency. Here, we first present a theoretical elucidation of the dual functions of 2D layered material as a sensitizer and a co-catalyst by performing density functional theory calculations, taking WS2 and a lateral heterogeneous WS2-MoS2 monolayer as examples to couple with a promising photocatalyst Ag3PO4. The band alignment of a staggered type-II is formed between Ag3PO4 and the 2D monolayer with the latter possessing the higher electron affinity, resulting in the robust separation of photoexcited charge carriers between them, and indicating that the 2D monolayer is an effective sensitizer. Interestingly, the W (Mo) atoms, which are catalytically inert in the isolated 2D monolayer, turn into catalytic active sites, making the 2D monolayer a highly active co-catalyst in hybrids. A better photocatalytic performance in the coupled lateral heterogeneous WS2-MoS2 monolayer and Ag3PO4 can be expected. The calculated results can be rationalized by available experiments. These findings provide theoretical evidence supporting the experimental reports and may be used as a foundation for developing highly efficient 2D layered materials-based photocatalysts.

  12. Dual functions of 2D WS2 and MoS2–WS2 monolayers coupled with a Ag3PO4 photocatalyst

    NASA Astrophysics Data System (ADS)

    Wei, Zeng-Xi; Huang, Wei-Qing; Xu, Liang; Hu, Wangyu; Peng, P.; Huang, Gui-Fang

    2016-09-01

    The photocatalytic performance of semiconductors can be improved by coupling two-dimensional (2D) layered materials. Understanding the underlying mechanism of this phenomenon at the electronic level is important for the development of photocatalysts with a high efficiency. Here, we first present a theoretical elucidation of the dual functions of 2D layered material as a sensitizer and a co-catalyst by performing density functional theory calculations, taking WS2 and a lateral heterogeneous WS2–MoS2 monolayer as examples to couple with a promising photocatalyst Ag3PO4. The band alignment of a staggered type-II is formed between Ag3PO4 and the 2D monolayer with the latter possessing the higher electron affinity, resulting in the robust separation of photoexcited charge carriers between them, and indicating that the 2D monolayer is an effective sensitizer. Interestingly, the W (Mo) atoms, which are catalytically inert in the isolated 2D monolayer, turn into catalytic active sites, making the 2D monolayer a highly active co-catalyst in hybrids. A better photocatalytic performance in the coupled lateral heterogeneous WS2–MoS2 monolayer and Ag3PO4 can be expected. The calculated results can be rationalized by available experiments. These findings provide theoretical evidence supporting the experimental reports and may be used as a foundation for developing highly efficient 2D layered materials-based photocatalysts.

  13. Chitosan-modified porous silicon microparticles for enhanced permeability of insulin across intestinal cell monolayers.

    PubMed

    Shrestha, Neha; Shahbazi, Mohammad-Ali; Araújo, Francisca; Zhang, Hongbo; Mäkilä, Ermei M; Kauppila, Jussi; Sarmento, Bruno; Salonen, Jarno J; Hirvonen, Jouni T; Santos, Hélder A

    2014-08-01

    Porous silicon (PSi) based particulate systems are emerging as an important drug delivery system due to its advantageous properties such as biocompatibility, biodegradability and ability to tailor the particles' physicochemical properties. Here, annealed thermally hydrocarbonized PSi (AnnTHCPSi) and undecylenic acid modified AnnTHCPSi (AnnUnTHCPSi) microparticles were developed as a PSi-based platform for oral delivery of insulin. Chitosan (CS) was used to modify the AnnUnTHCPSi microparticles to enhance the intestinal permeation of insulin. Surface modification with CS led to significant increase in the interaction of PSi microparticles with Caco-2/HT-29 cell co-culture monolayers. Compared to pure insulin, the CS-conjugated microparticles significantly improved the permeation of insulin across the Caco-2/HT-29 cell monolayers, with ca. 20-fold increase in the amount of insulin permeated and ca. 7-fold increase in the apparent permeability (P(app)) value. Moreover, among all the investigated particles, the CS-conjugated microparticles also showed the highest amount of insulin associated with the mucus layer and the intestinal Caco-2 cells and mucus secreting HT-29 cells. Our results demonstrate that CS-conjugated AnnUnTHCPSi microparticles can efficiently enhance the insulin absorption across intestinal cells, and thus, they are promising microsystems for the oral delivery of proteins and peptides across the intestinal cell membrane.

  14. Electrical resistivity of nanoporous gold modified with thiol self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Hakamada, Masataka; Kato, Naoki; Mabuchi, Mamoru

    2016-11-01

    The electrical resistivity of nanoporous gold (NPG) modified with thiol self-assembled monolayers (SAMs) has been measured at 298 K using a four-probe method. We found that the adsorption of thiol SAMs increases the electrical resistivity of NPG by up to 22.2%. Dependence of the electrical resistivity on the atmosphere (air or water) was also observed in SAMs-modified NPG, suggesting that the electronic states of the tail groups affect the electrons of the binding sulfur and adjacent surface gold atoms. The present results suggest that adsorption of thiol molecules can influence the behavior of the conducting electrons in NPG and that modification of NPG with SAMs may be useful for environmental sensing.

  15. Calculation of Electrochemical Reorganization Energies for Redox Molecules at Self-Assembled Monolayer Modified Electrodes.

    PubMed

    Ghosh, Soumya; Hammes-Schiffer, Sharon

    2015-01-01

    Electrochemical electron transfer reactions play an important role in energy conversion processes with many technological applications. Electrodes modified by self-assembled monolayers (SAMs) exhibit reduced double layer effects and are used in molecular electronics. An important quantity for calculating the electron transfer rate constant is the reorganization energy, which is associated with changes in the solute geometry and the environment. In this Letter, an approach for calculating the electrochemical reorganization energy for a redox molecule attached to or near a SAM modified electrode is presented. This integral equations formalism polarizable continuum model (IEF-PCM) approach accounts for the detailed electronic structure of the molecule, as well as the contributions from the electrode, SAM, and electronic and inertial solvent responses. The calculated total reorganization energies are in good agreement with experimental data for a series of metal complexes in aqueous solution. This approach will be useful for calculating electron transfer rate constants for molecular electrocatalysts. PMID:26263083

  16. Synthesis of Ag modified vanadium oxide nanotubes and their antibacterial properties

    SciTech Connect

    Li Jing; Zheng Lifang; Zhang Kaifeng; Feng Xiaoqiang; Su Zhongxing Ma Jiantai

    2008-10-02

    Vanadium oxide nanotubes (VO{sub x}-NTs) modified by highly dispersed Ag nanoparticles have been synthesized via a facile silver-mirror reaction. The crucial factors that affected the preparation of the Ag modified vanadium oxide nanotubes (Ag/VO{sub x}-NTs) have been also studied. The dispersion and structure of Ag nanoparticles in the obtained materials were characterized by transmission electron microscopy (TEM), electron diffraction (ED) and X-ray diffraction (XRD). The results showed the distribution and size of the formed Ag particles were greatly influenced by the concentration of AgNO{sub 3} solution. Typically, Ag nanoparticles were well dispersed on the VO{sub x}-NTs with the size range from 3 to 10 nm. The corresponding antibacterial tests demonstrated the as-synthesized Ag/VO{sub x}-NTs exhibited strong antibacterial activity against Escherichia coli (E. coli)

  17. Synthesis, characterization, monolayer assembly and 2D lanthanide coordination of a linear terphenyl-di(propiolonitrile) linker on Ag(111)

    PubMed Central

    Chen, Zhi; Urgel, José I; Écija, David; Fuhr, Olaf; Auwärter, Willi

    2015-01-01

    Summary As a continuation of our work employing polyphenylene-dicarbonitrile molecules and in particular the terphenyl derivative 1 (TDCN), we have synthesized a novel ditopic terphenyl-4,4"-di(propiolonitrile) (2) linker for the self-assembly of organic monolayers and metal coordination at interfaces. The structure of the organic linker 2 was confirmed by single crystal X-ray diffraction analysis (XRD). On the densely packed Ag(111) surface, the terphenyl-4,4"-di(propiolonitrile) linkers self-assemble in a regular, molecular chevron arrangement exhibiting a Moiré pattern. After the exposure of the molecular monolayer to a beam of Gd atoms, the propiolonitrile groups get readily involved in metal–ligand coordination interactions. Distinct coordination motifs evolve with coordination numbers varying between three and six for the laterally-bound Gd centers. The linker molecules retain an overall flat adsorption geometry. However, only networks with restricted local order were obtained, in marked contrast to previously employed, simpler polyphenylene-dicarbonitrile 1 linkers. PMID:25821671

  18. Dual-loss-modulated Q-switched Tm:LuAG laser with AOM and monolayer graphene.

    PubMed

    Luan, Chao; Yang, Ke Jian; Zhao, Jia; Zhao, Sheng Zhi; Qiao, Wen Chao; Li, Tao; Feng, Tian Li; Liu, Cheng; Qiao, Jun Peng; Zheng, Li He; Xu, Jun; Wang, Qing Guo; Su, Liang Bi

    2015-09-20

    A laser-diode-pumped dual-loss-modulated Q-switching Tm:LuAG laser with an acousto-optic modulator (AOM) and monolayer graphene saturable absorber (SA) around 2 μm is presented for the first time to the best of our knowledge. The average output power and the pulse widths for different repetition rates have been measured. In comparison with the singly Q-switching laser with AOM or with monolayer graphene SA, the dual-loss-modulated Q-switching laser could generate shorter pulse width and higher peak power. The maximum pulse width compression ratio was found to be 3.11, and the highest peak power was enhanced 97.4 times. The experimental results show that the dual-loss-modulated technology is an efficient method for compressing the pulse width, improving the peak power, and enhancing the pulse stability for the Q-switched lasers at 2 μm. PMID:26406500

  19. Gold Electrodes Modified with Self-Assembled Monolayers for Measuring L-Ascorbic Acid: An Undergraduate Analytical Chemistry Laboratory Experiment

    ERIC Educational Resources Information Center

    Ito, Takashi; Perera, D. M. Neluni T.; Nagasaka, Shinobu

    2008-01-01

    This article describes an undergraduate electrochemistry laboratory experiment in which the students measure the L-ascorbic acid content of a real sample. Gold electrodes modified with self-assembled monolayers (SAMs) of thioctic acid and cysteamine are prepared to study the effects of surface modification on the electrode reaction of L-ascorbic…

  20. Calculation of Electrochemical Reorganization Energies for Redox Molecules at Self-Assembled Monolayer Modified Electrodes

    SciTech Connect

    Ghosh, Soumya; Hammes-Schiffer, Sharon

    2015-01-02

    Electrochemical electron transfer reactions play an important role in energy conversion processes with many technological applications. Electrodes modified by self-assembled monolayers (SAMs) are useful because the double layer effects are reduced. An important quantity for calculating the electron transfer rate constant is the reorganization energy, which is associated with changes in solute geometry and solvent configuration. In this Letter, an approach for calculating the electrochemical solvent reorganization energy for a redox molecule attached to or near a SAM modified electrode is presented. This integral equations formalism polarizable continuum model (IEF-PCM) approach accounts for the detailed electronic structure of the molecule, as well as the contributions from the electrode, SAM, and electronic and inertial solvent responses. The calculated total reorganization energies are in good agreement with experimental data for a series of metal complex in aqueous solution. This approach will be useful for calculating electron transfer rate constants for molecular electrocatalysts. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  1. Dithiocarbamate Self-Assembled Monolayers as Efficient Surface Modifiers for Low Work Function Noble Metals.

    PubMed

    Meyer, Dominik; Schäfer, Tobias; Schulz, Philip; Jung, Sebastian; Rittich, Julia; Mokros, Daniel; Segger, Ingolf; Maercks, Franziska; Effertz, Christian; Mazzarello, Riccardo; Wuttig, Matthias

    2016-09-01

    Tuning the work function of the electrode is one of the crucial steps to improve charge extraction in organic electronic devices. Here, we show that N,N-dialkyl dithiocarbamates (DTC) can be effectively employed to produce low work function noble metal electrodes. Work functions between 3.1 and 3.5 eV are observed for all metals investigated (Cu, Ag, and Au). Ultraviolet photoemission spectroscopy (UPS) reveals a maximum decrease in work function by 2.1 eV as compared to the bare metal surface. Electronic structure calculations elucidate how the complex interplay between intrinsic dipoles and dipoles induced by bond formation generates such large work function shifts. Subsequently, we quantify the improvement in contact resistance of organic thin film transistor devices with DTC coated source and drain electrodes. These findings demonstrate that DTC molecules can be employed as universal surface modifiers to produce stable electrodes for electron injection in high performance hybrid organic optoelectronics. PMID:27504721

  2. Gold nanoparticles modified electrode via a mercapto-diazoaminobenzene monolayer and its development in DNA electrochemical biosensor.

    PubMed

    Li, Feng; Feng, Yan; Dong, Pingjun; Tang, Bo

    2010-05-15

    A novel protocol for the gold nanoparticles (AuNPs) modification on the electrode surface was proposed, which was based on the self-assembly of AuNPs on the mercapto-diazoaminobenzene monolayer modified electrode. The mercapto-diazoaminobenzene monolayer was obtained by covalent immobilization of 4-aminothiophenol (4-ATP) molecules onto another 4-ATP monolayer functionalized gold electrode by diazotization-coupling reaction. The DNA immobilization and hybridization on the AuNPs modified electrode was further investigated. The prepared AuNPs-ATP-diazo-ATP film demonstrated efficient electron transfer ability for the electroactive species toward the electrode surface due to a large conjugated structure of the mercapto-diazoaminobenzene monolayer. The recognition of fabricated electrochemical DNA biosensor toward complementary single-stranded DNA was determined by differential pulse voltammetry with the use of Co(phen)(3)3+ as an electrochemical indicator. A linear detection range for the complementary target DNA was obtained from 3.01 x 10(-10) to 1.32 x 10(-8) M with a detection limit of 9.10 x 10(-11) M. The fabricated biosensor also possessed good selectivity and could be regenerated easily. PMID:20207131

  3. Thermoelectric properties of CuS/Ag2S nanocomposites synthesed by modified polyol method

    NASA Astrophysics Data System (ADS)

    Tarachand, Sharma, Vikash; Ganesan, V.; Okram, Gunadhor S.

    2016-05-01

    This is the report on successful synthesis of Ag doped CuS nanostructures by modified polyol method. The resulting samples were characterized by powder X-ray diffraction (XRD), energy dispersive X-ray (EDX), atomic force microscopy (AFM) and dynamic light scattering (DLS). Particle size of pure CuS nanoparticles (NPs) was 17 nm, 38 nm and 97 nm as determined from Scherrer formula, AFM and DLS, respectively. Introduction of Ag led to formation of CuS/Ag2S composites. A transition at 55 K in thermopower is ascribed to structural transformation from hexagonal to orthorhombic structure. Further, their thermoelectric properties exhibit remarkable change owing to Ag doping in CuS nanostructures. The power factor improves with increasing Ag content. They reveal that CuS/Ag2S nanocomposites are some of the potential candidates for generation of thermoelectricity in future.

  4. Photocatalytic performance of Ag doped SnO2 nanoparticles modified with curcumin

    NASA Astrophysics Data System (ADS)

    Vignesh, K.; Hariharan, R.; Rajarajan, M.; Suganthi, A.

    2013-07-01

    Visible light active Ag doped SnO2 nanoparticles modified with curcumin (Cur-Ag-SnO2) have been prepared by a combined precipitation and chemical impregnation route. The optical properties, phase structures and morphologies of the as-prepared nanoparticles were characterized using UV-visible diffuse reflectance spectra (UV-vis-DRS), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The surface area was measured by Brunauer. Emmett. Teller (B.E.T) analysis. Compared to bare SnO2, the surface modified photocatalysts (Ag-SnO2 and Cur-Ag-SnO2) showed a red shift in the visible region. The photocatalytic activity was monitored via the degradation of rose bengal (RB) dye and the results revealed that Cur-Ag-SnO2 shows better photocatalytic activity than that of Ag-SnO2 and SnO2. The superior photocatalytic activity of Cur-Ag-SnO2 could be attributed to the effective electron-hole separation by surface modification. The effect of photocatalyst concentration, initial dye concentration and electron scavenger on the photocatalytic activity was examined in detail. Furthermore, the antifungal activity of the photocatalysts and the reusability of Cur-Ag-SnO2 were tested.

  5. Modified embedded-atom potential for B2-MgAg

    NASA Astrophysics Data System (ADS)

    Groh, Sébastien

    2016-08-01

    Interatomic potentials for pure Ag and Mg-Ag alloy have been developed in the framework of the second nearest-neighbors modified embedded-atom method (MEAM). The validity and the transferability of the Ag potential were obtained by calculating physical, mechanical, thermal, and dislocation related properties. Since the {1 1 1}-generalized stacking fault energy curves obtained from first-principle calculations was used to develop the Ag potential, the critical resolved shear stress to move screw dislocations in Ag single crystal is in good agreement with the experimental data. By combining the ability of the potential to predict the surface energies with its accuracy in describing dislocation properties, the potential is thought to be a predictive model for analyzing the fracture properties of Ag. In addition, the performance of the potential was tested under dynamics conditions by predicting the melting temperature, where a good agreement with experimental value was found. The Ag-MEAM potential was then coupled to an existing Mg-MEAM potential to describe the properties of the binary system MgAg. While the heat of formation, the elastic constants, and the (1 1 0) γ-surface of the MgAg compound in the B2 phase were used to parameterize the potential, heat of formation for MgAg alloys with different stoichiometry, thermal properties of the B2-MgAg compound, as well as dislocation related properties in B2-MgAg compound were tested to validate the transferability of the potential. The heat of formation of Mg5Ag2, MgAg, and MgAg3, the elastic constants and the thermal properties of B2-MgAg obtained with the proposed potential align with first-principles and experimental data. In addition, the core structure of both <0 0 1> and <1 1 1> dislocations in {1 1 0} are in agreement with theoretical predictions, and the magnitudes of the critical resolved shear stress obtained at 0 K for both slip systems partially validate the slip behavior of B2-MgAg

  6. Modified embedded-atom potential for B2-MgAg

    NASA Astrophysics Data System (ADS)

    Groh, Sébastien

    2016-08-01

    Interatomic potentials for pure Ag and Mg–Ag alloy have been developed in the framework of the second nearest-neighbors modified embedded-atom method (MEAM). The validity and the transferability of the Ag potential were obtained by calculating physical, mechanical, thermal, and dislocation related properties. Since the {1 1 1}-generalized stacking fault energy curves obtained from first-principle calculations was used to develop the Ag potential, the critical resolved shear stress to move screw dislocations in Ag single crystal is in good agreement with the experimental data. By combining the ability of the potential to predict the surface energies with its accuracy in describing dislocation properties, the potential is thought to be a predictive model for analyzing the fracture properties of Ag. In addition, the performance of the potential was tested under dynamics conditions by predicting the melting temperature, where a good agreement with experimental value was found. The Ag-MEAM potential was then coupled to an existing Mg-MEAM potential to describe the properties of the binary system MgAg. While the heat of formation, the elastic constants, and the (1 1 0) γ-surface of the MgAg compound in the B2 phase were used to parameterize the potential, heat of formation for MgAg alloys with different stoichiometry, thermal properties of the B2-MgAg compound, as well as dislocation related properties in B2-MgAg compound were tested to validate the transferability of the potential. The heat of formation of Mg5Ag2, MgAg, and MgAg3, the elastic constants and the thermal properties of B2-MgAg obtained with the proposed potential align with first-principles and experimental data. In addition, the core structure of both <0 0 1> and <1 1 1> dislocations in {1 1 0} are in agreement with theoretical predictions, and the magnitudes of the critical resolved shear stress obtained at 0 K for both slip systems partially validate the slip behavior of B2-MgAg

  7. Alkanephosphonates on hafnium-modified gold: a new class of self-assembled organic monolayers.

    PubMed

    Jespersen, Michael L; Inman, Christina E; Kearns, Gregory J; Foster, Evan W; Hutchison, James E

    2007-03-14

    A new method for assembling organic monolayers on gold is reported that employs hafnium ions as linkers between a phosphonate headgroup and the gold surface. Monolayers of octadecylphosphonic acid (ODPA) formed on gold substrates that had been pretreated with hafnium oxychloride are representative of this new class of organic thin films. The monolayers are dense enough to completely block assembly of alkanethiols and resist displacement by alkanethiols. The composition and structure of the monolayers were investigated by contact angle goniometry, XPS, PM-IRRAS, and TOF-SIMS. From these studies, it was determined that this assembly strategy leads to the formation of ODPA monolayers similar in quality to those typically formed on metal oxide substrates. The assembly method allows for the ready generation of patterned surfaces that can be easily prepared by first patterning hafnium on the gold surface followed by alkanephosphonate assembly. Using the bifunctional (thiol-phosphonate) 2-mercaptoethylphosphonic acid (2-MEPA), we show that this new assembly chemistry is compatible with gold-thiol chemistry and use TOF-SIMS to show that the molecule attaches through the phosphonate functionality in the patterned region and through the thiol in the bare gold regions. These results demonstrate the possibility of functionalizing metal substrates with monolayers typically formed on metal oxide surfaces and show that hafnium-gold chemistry is complementary and orthogonal to well-established gold-thiol assembly strategies.

  8. Enhanced visible-light photocatalytic performances of Ag3PO4 surface-modified with small amounts of TiO2 and Ag

    NASA Astrophysics Data System (ADS)

    Wang, Desong; Li, Lei; Luo, Qingzhi; An, Jing; Li, Xueyan; Yin, Rong; Zhao, Mangmang

    2014-12-01

    A novel approach has been developed to prepare an efficient visible-light photocatalyst using Ag3PO4 and TiO2 sol as precursors. First, Ag3PO4 particles were dipped into TiO2 sol for 5 min and were filtered quickly. Second, Ag3PO4 particles adsorbing a small amount of TiO2 sol were aged for 24 h to form TiO2 gel on their surface. Finally, Ag3PO4 particles covered by TiO2 gel were calcined at 450 °C for 2 h to obtain the surface-modified Ag3PO4 sample. The surface-modified Ag3PO4 was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, UV-vis diffuse reflection spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy. The visible-light photocatalytic performances of the surface-modified Ag3PO4 were evaluated by the photodegradation of methyl orange or phenol solution. The results showed that the surface-modified Ag3PO4 exhibited much higher visible-light photocatalytic activity and stability than pure Ag3PO4. As the amount of TiO2 gel on the Ag3PO4 surface increased, the visible-light photocatalytic activity increased first and then decreased. The surface-modification of Ag3PO4 obviously decreased its solubility in water environment due to the protection of TiO2 and Ag nanocrystals on the surface. The visible-light photocatalytic mechanism of the surface-modified Ag3PO4 has been discussed.

  9. Fabrication of a planar-form screen-printed solid electrolyte modified Ag/AgCl reference electrode for application in a potentiometric biosensor.

    PubMed

    Liao, Wei-Yin; Chou, Tse-Chuan

    2006-06-15

    This study features the fabrication of a planar-form, solid electrolyte modified, (PSEM) Ag/AgCl reference electrode using a screen-printing method. The PSEM Ag/AgCl reference electrode uses agar gel as the inner electrolyte and chloroprene rubber for the liquid junction and insulator. These common low-cost materials and the simple fabrication processes involved render the proposed reference electrode an ideal candidate for cost-efficient mass production. It is shown that the developed reference electrode is insensitive to most of the physiologically important ionic species, including Na+, K+, Li+, Ca2+, NH4+, and Cl-, under continuous measurement conditions. Moreover, as with conventional commercial reference electrodes, the proposed reference electrode exhibits a reversible response, which is maintained until the agar gel dries out. The PSEM Ag/AgCl reference electrode is integrated with an iridium oxide modified Pt-based pH indicator electrode to form a chip-type pH biosensor. The performance of this biosensor is consistent with that obtained from a pH meter based on a macroscopic commercial Ag/AgCl reference electrode. The experimental results confirm that the proposed biosensor is capable of providing precise pH measurements of various real samples. Accordingly, the PSEM Ag/AgCl reference electrode presented in this study provides a viable alternative to the macroscopic Ag/AgCl reference electrode used in many conventional chip-based pH sensors.

  10. AG73-modified Bubble liposomes for targeted ultrasound imaging of tumor neovasculature.

    PubMed

    Negishi, Yoichi; Hamano, Nobuhito; Tsunoda, Yuka; Oda, Yusuke; Choijamts, Batsuren; Endo-Takahashi, Yoko; Omata, Daiki; Suzuki, Ryo; Maruyama, Kazuo; Nomizu, Motoyoshi; Emoto, Makoto; Aramaki, Yukihiko

    2013-01-01

    Ultrasound imaging is a widely used imaging technique. The use of contrast agents has become an indispensible part of clinical ultrasound imaging, and molecular imaging via ultrasound has recently attracted significant attention. We recently reported that "Bubble liposomes" (BLs) encapsulating US imaging gas liposomes were suitable for ultrasound imaging and gene delivery. The 12 amino acid AG73 peptide derived from the laminin α1 chain is a ligand for syndecans, and syndecan-2 is highly expressed in blood vessels. In this study, we prepared AG73 peptide-modified BLs (AG73-BLs) and assessed their specific attachment and ultrasound imaging ability for blood vessels in vitro and in vivo. First, we assessed the specific attachment of AG73-BLs in vitro, using flow cytometry and microscopy. AG73-BLs showed specific attachment compared with non-labeled or control peptide-modified BLs. Next, we examined ultrasound imaging in tumor-bearing mice. When BLs were administered, contrast imaging of AG73-BLs was sustainable for up to 4 min, while contrast imaging of non-labeled BLs was not observed. Thus, it is suggested that AG73-BLs may become useful ultrasound contrast agents in the clinic for diagnosis based on ultrasound imaging.

  11. Application of a gold electrode, modified by a self-assembled monolayer of 2-mercaptodecylhydroquinone, to the electroanalysis of hemoglobin.

    PubMed

    Zhang, Jingdong; Seo, Kyoungja; Jeon, Il Cheol

    2003-02-01

    A gold electrode modified by a self-assembled monolayer of 2-mercaptodecylhydroquinone (H(2)Q(CH(2))(10)SH) was applied to investigate the electrochemical response of hemoglobin in aerated buffer solutions. Compared with a bare gold electrode, the monolayer of H(2)Q(CH(2))(10)SH could suppress the reduction wave of dissolved oxygen in the buffer while effectively promoting the rate of electron transfer between hemoglobin and the electrode. Thus, a convenient way for electroanalysis of hemoglobin in air was achieved at the H(2)Q(CH(2))(10)SH/Au electrode. A linear relationship existed between peak current and concentration of hemoglobin in the range 1 x 10(-7)-1 x 10(-6) mol L(-1).

  12. The role of surface Pt on the coadsorption of hydrogen and CO on Pt monolayer film modified Ru(0001) surfaces

    NASA Astrophysics Data System (ADS)

    Diemant, T.; Hartmann, H.; Bansmann, J.; Behm, R. J.

    2016-10-01

    We have investigated the impact and role of the Pt surface modification on the coadsorption of hydrogen and CO on structurally well defined bimetallic Pt monolayer island/film modified Ru(0001) surfaces with Pt contents up to a complete Pt layer, employing temperature programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRRAS). Kinetic limitations in the surface diffusion are shown to play an important role for adsorption at 90 K, and lead to profound effects of the dosing sequence on the adsorption and desorption characteristics. Furthermore, they are responsible for spill-over effects during the TPD measurements, where COad becomes mobile and can spill-over from weakly bonding Pt monolayer areas to strongly bonding Pt-free Ru(0001) areas, which displaces Dad from these surface areas. The present findings are discussed in comparison with previous results on related metallic and bimetallic adsorption and coadsorption systems.

  13. Electronic structures of an epitaxial graphene monolayer on SiC(0001) after metal intercalation (metal = Al, Ag, Au, Pt, and Pd): A first-principles study

    NASA Astrophysics Data System (ADS)

    Hsu, Chia-Hsiu; Lin, Wen-Huan; Ozolins, Vidvuds; Chuang, Feng-Chuan

    2012-02-01

    The atomic structures and electronic properties of metal-intercalated (metal = Al, Ag, Au, Pt, and Pd) graphene monolayers on SiC(0001) were investigated using first-principles calculations. The unique Dirac cone of graphene near the K point reappeared as the graphite layer was intercalated by these metals at a coverage of 3/8 ML. Furthermore, our results show that metal intercalation leads to n-type doping of graphene. The bands contributed from graphene exhibit small splitting after intercalation, whereas the bands contributed from the intercalated metal layer have significant Rashba spin-orbit splittings in all cases except Al.

  14. Characterization and evaluation of a modified PVPA barrier in comparison to Caco-2 cell monolayers for combined dissolution and permeation testing.

    PubMed

    Gantzsch, Sandra P; Kann, Birthe; Ofer-Glaessgen, Monika; Loos, Petra; Berchtold, Harald; Balbach, Stefan; Eichinger, Thomas; Lehr, Claus-Michael; Schaefer, Ulrich F; Windbergs, Maike

    2014-02-10

    Aim of this study was to implement a modified phospholipid vesicle-based permeation assay (PVPA) barrier as alternative to Caco-2 cell monolayers in a combined dissolution and permeation system for testing of solid dosage forms. Commercially available Transwell® inserts were coated with egg phospholipids (Lipoid E 80) and characterized by confocal Raman microscopy. The modified PVPA barrier was then evaluated in permeation studies with solutions of different drugs as well as in combined dissolution and permeation studies utilizing an immediate and an extended release tablet formulation. Raman cross section images demonstrated complete filling of the membrane pores with lipids and the formation of a continuous lipid layer of increasing thickness on top of the membrane during the stepwise coating procedure. Furthermore, it could be shown that this lipid coating remains intact for at least 18h under dynamic flow conditions, significantly exceeding the viability of Caco-2 cell monolayers. Permeability data for both drug solutions as well as for a fast and slow release tablet formulation were in excellent correlation with those data obtained for Caco-2 cell monolayers. Especially under the dynamic flow conditions prevailing in such a setup, the modified PVPA barrier is more robust and easier to handle than epithelial cell monolayers and can be prepared rather easily at a fraction of costs and time. The modified PVPA barrier may therefore represent a valuable alternative to Caco-2 cell monolayers in such context. PMID:24361370

  15. ADO-phosphonic acid self-assembled monolayer modified dielectrics for organic thin film transistors

    NASA Astrophysics Data System (ADS)

    Zhefeng, Li; Xianye, Luo

    2014-10-01

    This study explores a strategy of using the phosphonic acid derivative (11-((12-(anthracen-2-yl)dodecyl)oxy)-11-oxoundecyl) phosphonic acid (ADO-phosphonic acid) as self-assembled monolayers (SAMs) on a Si/SiO2 surface to induce the crystallization of rubrene in vacuum deposited thin film transistors, which showed a field-effect mobility as high as 0.18 cm2/(V·s). It is found that ADO-phosphonic acid SAMs play a unique role in modulating the morphology of rubrene to form a crystalline film in the thin-film transistors.

  16. Sputtered Ag thin films with modified morphologies: Influence on wetting property

    NASA Astrophysics Data System (ADS)

    Dutheil, P.; Thomann, A. L.; Lecas, T.; Brault, P.; Vayer, M.

    2015-08-01

    Silver thin films with thickness ranging from 3 nm to 33 nm were sputter deposited onto silicon wafers and tungsten layers. Those W layers were previously synthesized in the same DC magnetron sputter deposition system with various experimental conditions (argon pressure, target to substrate distance) in order to stabilize different surface morphologies. SEM observations and AFM images showed that the growth mode of Ag films is similar on Si substrates and on the smoothest W layers, whereas it is modified for rough W layers made of sharp grains. The effect of the W layer morphology on Ag film growth was clearly evidenced when the deposition took place at high temperature. It is seen that performing the deposition onto substrates of various morphologies allows tailoring the wetting property of the Ag deposit.

  17. Preparation of vanadium oxide thin films modified with Ag using a hybrid deposition configuration

    NASA Astrophysics Data System (ADS)

    Gonzalez-Zavala, F.; Escobar-Alarcón, L.; Solís-Casados, D. A.; Rivera-Rodríguez, C.; Basurto, R.; Haro-Poniatowski, E.

    2016-04-01

    The application of a hybrid deposition configuration, formed by the interaction of a laser ablation plasma with a flux of atomic vapor, to deposit vanadium oxide thin films modified with different amounts of silver, is reported. The effect of the amount of Ag incorporated in the films on their structural, morphological, compositional and optical properties was studied. The obtained results reveal that films with variable Ag content from 11.7 to 24.6 at.% were obtained. Depending on the silver content, the samples show very different surface morphologies. Optical characterization indicates the presence of nanostructures of Ag. Thin films containing silver exhibit better photocatalytic performances than unmodified V2O5 films. Raman spectra reveal that as the silver content is increased, the signals associated with V2O5 disappear and new modes attributed mainly to silver vanadates appear suggesting the formation of ternary compounds.

  18. Fabrication of a Polyaniline Ultramicroelectrode via a Self Assembled Monolayer Modified Gold Electrode

    PubMed Central

    Bolat, Gulcin; Kuralay, Filiz; Eroglu, Gunes; Abaci, Serdar

    2013-01-01

    Herein, we report a simple and inexpensive way for the fabrication of an ultramicroelectrode and present its characterization by electrochemical techniques. The fabrication of polyaniline UME involves only two steps: modification of a gold (Au) electrode by self assembled monolayers (SAM) and then electrodeposition of polyaniline film on this thiol-coated Au electrode by using cyclic voltammetry and constant potential electrolysis methods. Two types of self-assembled monolayers (4-mercapto-1-butanol, MB, and 11-mercaptoundecanoic acid, MUA) were used, respectively, to see the effect of chain length on microelectrode formation. Microelectrode fabrication and utility of the surface was investigated by cyclic voltammetric measurements in a redox probe. The thus prepared polyaniline microelectrode was then used for DNA immobilization. Discrimination between double-stranded DNA (dsDNA) and single-stranded DNA (ssDNA) was obtained with enhanced electrochemical signals compared to a polyaniline-coated Au electrode. Different modifications on the electrode surfaces were examined using scanning electron microscopy (SEM). PMID:23797740

  19. Ag-modified silicon nanowires substrate for ultrasensitive surface-enhanced raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Shao, Ming-Wang; Zhang, Ming-Liang; Wong, Ning-Bew; Ma, Dorothy Duo-duo; Wang, Hui; Chen, Weiwei; Lee, Shuit-Tong

    2008-12-01

    We report a unique substrate for surface-enhanced raman spectroscopy (SERS) based on silver nanoparticles-embedded silicon nanowires (SiNWs). The SiNWs were prepared by thermal evaporation of SiO powder via oxide-assisted growth, oxide removed with HF, and then used to reduce silver ions to form a highly decorated Ag-embedded surface. Such modified SiNWs substrates yielded ultrahigh SERS sensitivity, which could detect 25μl of 1×10-16M Rhodamine 6G, 1×10-16M crystal violet, and 1×10-14M nicotine in methanol solutions. An Ag-modified SiNW strand could also enable SERS detection of 25μl of 1×10-8mg/ml calf thymus DNA. The possible mechanisms for the ultrahigh SERS sensitivity were discussed.

  20. Ag-Modified In₂O₃/ZnO Nanobundles with High Formaldehyde Gas-Sensing Performance.

    PubMed

    Fang, Fang; Bai, Lu; Song, Dongsheng; Yang, Hongping; Sun, Xiaoming; Sun, Hongyu; Zhu, Jing

    2015-01-01

    Ag-modified In2O3/ZnO bundles with micro/nano porous structures have been designed and synthesized with by hydrothermal method continuing with dehydration process. Each bundle consists of nanoparticles, where nanogaps of 10-30 nm are present between the nanoparticles, leading to a porous structure. This porous structure brings high surface area and fast gas diffusion, enhancing the gas sensitivity. Consequently, the HCHO gas-sensing performance of the Ag-modified In2O3/ZnO bundles have been tested, with the formaldehyde-detection limit of 100 ppb (parts per billion) and the response and recover times as short as 6 s and 3 s, respectively, at 300 °C and the detection limit of 100 ppb, response time of 12 s and recover times of 6 s at 100 °C. The HCHO sensing detect limitation matches the health standard limitation on the concentration of formaldehyde for indoor air. Moreover, the strategy to synthesize the nanobundles is just two-step heating and easy to scale up. Therefore, the Ag-modified In2O3/ZnO bundles are ready for industrialization and practical applications. PMID:26287205

  1. Ag-Modified In₂O₃/ZnO Nanobundles with High Formaldehyde Gas-Sensing Performance.

    PubMed

    Fang, Fang; Bai, Lu; Song, Dongsheng; Yang, Hongping; Sun, Xiaoming; Sun, Hongyu; Zhu, Jing

    2015-08-14

    Ag-modified In2O3/ZnO bundles with micro/nano porous structures have been designed and synthesized with by hydrothermal method continuing with dehydration process. Each bundle consists of nanoparticles, where nanogaps of 10-30 nm are present between the nanoparticles, leading to a porous structure. This porous structure brings high surface area and fast gas diffusion, enhancing the gas sensitivity. Consequently, the HCHO gas-sensing performance of the Ag-modified In2O3/ZnO bundles have been tested, with the formaldehyde-detection limit of 100 ppb (parts per billion) and the response and recover times as short as 6 s and 3 s, respectively, at 300 °C and the detection limit of 100 ppb, response time of 12 s and recover times of 6 s at 100 °C. The HCHO sensing detect limitation matches the health standard limitation on the concentration of formaldehyde for indoor air. Moreover, the strategy to synthesize the nanobundles is just two-step heating and easy to scale up. Therefore, the Ag-modified In2O3/ZnO bundles are ready for industrialization and practical applications.

  2. IMPACT OF POLYCYCLIC AROMATIC HYDROCARBONS OF THE ELECTROCHEMICAL RESPONSES OF A FERRICYNIDE PROBE AT TEMPLATE-MODIFIED SELF ASSEMBLED MONOLAYERS ON GOLD ELECTRODES

    EPA Science Inventory

    The impact of pyrene on the electrochemical response of the ferricyanide probe using Self Assembled Monolayer (SAM)-modified gold electrodes was investigated using Cyclic Voltammetry (CV) and Square Wave Voltammetry (SWV). These results suggest the feasibility of using SAMs, par...

  3. Investigation of Ag-TiO2 nanostructures photocatalytic properties prepared by modified dip coating method

    NASA Astrophysics Data System (ADS)

    AlArfaj, Esam

    2016-05-01

    In this article, titanium dioxide and silver nanostructures were deposited on glass substrates using modified sol-gel methods and dip-coating technique. The films were characterised chemically and physically using different techniques (TLC, UV-Vis and XRD) and tested for environmental applications regarding degradation of aromatic hydrocarbons. The photocatalytic activity of the TiO2 nanostructures is tested with different small concentrations of phenol in water and reaction mechanisms discussed. Considerable enhancement is observed in the photodegradation activity of Ag-modified (3 wt.%) TiO2 compared to unmodified TiO2 nanostructures for phenol concentrations within the pseudo-first-order Langmuir-Hinshelwood (LH) model for reaction kinetics. The pseudo-first-order global degradation rate constant increased from <0.005 min-1 for TiO2 to 0.013 min-1 for 3 mol% Ag-modified TiO2. The enhancement is attributed to the incorporation of Ag which promotes the generation of reactive oxygen species and increases the carrier recombination life-time. In addition, Ag has been observed to extend the absorption to the visible region by its surface plasmon resonances and to suppress the anatase-rutile phase transformation. Moreover, TiO2 grain size prepared was found to be 10 nm which maximises the active surface area. For phenol initial concentrations as low as 0.0002 M, saturation trend in the degradation process occurred at 0.00014 M and the reaction rate can be fitted with half-order LH kinetics.

  4. One pot synthesis of Ag nanoparticle modified ZnO microspheres in ethylene glycol medium and their enhanced photocatalytic performance

    SciTech Connect

    Tian Chungui; Li Wei; Pan Kai; Zhang Qi; Tian Guohui; Zhou Wei; Fu Honggang

    2010-11-15

    Ag nanoparticles (NPs) modified ZnO microspheres (Ag/ZnO microspheres) were prepared by a facile one pot strategy in ethylene glycol (EG) medium. The EG played two important roles in the synthesis: it could act as a reaction media for the formation of ZnO and reduce Ag{sup +} to Ag{sup 0}. A series of the characterizations indicated the successful combination of Ag NPs with ZnO microspheres. It was shown that Ag modification could greatly enhance the photocatalytic efficiency of ZnO microspheres by taking the photodegradation of Rhodamine B as a model reaction. With appropriate ratio of Ag and ZnO, Ag/ZnO microspheres showed the better photocatalytic performance than commercial Degussa P-25 TiO{sub 2}. Photoluminescence and surface photovoltage spectra demonstrated that Ag modification could effectively inhibit the recombination of the photoinduced electron and holes of ZnO. This is responsible for the higher photocatalytic activity of Ag/ZnO composites. -- Graphical abstract: A 'one-pot' strategy was developed for preparing the Ag/ZnO microspheres in ethylene glycol. The composites exhibited superior photocatalytic performance for photodegradation of Rhodamine B dye in water. Display Omitted

  5. Two new polyoxometalate-based hybrids consisting of Keggin-type cluster modified by (Ag{sub 4}) group

    SciTech Connect

    Zhao, Xiaofang; Sun, Xiaowei; Han, Zhangang; Zhao, Chuan; Yu, Haitao; Zhai, Xueliang

    2013-11-15

    Two new supramolecular polyoxometalate compounds [Ag{sub 2}(mbpy){sub 3}][Ag(mbpy){sub 2}][PW{sub 12}O{sub 40}] (1) and [Ag{sub 2}(mbpy){sub 3}]{sub 2}[SiW{sub 12}O{sub 40}] (2) (mbpy=4,4'-dimethyl-2,2'-dipyridyl), have been hydrothermally synthesized and characterized by IR, TG, and single-crystal X-ray diffraction techniques. The structural feature of 1–2 is in the cationic moiety of a tetra-core (Ag{sub 4}) cluster through weak Ag…Ag interactions. The silver(I) centers show three-, four- and five-coordinated geometries. In 1 the tetrameric silver atoms in ([Ag{sub 2}(mbpy){sub 3}]{sub 2}){sup 4+} covalently bind to [PW{sub 12}O{sub 40}]{sup 3−} anion via Ag3O bonds, while there is only intermolecular hydrogen bonding between ([Ag{sub 2}(mbpy){sub 3}]{sub 2}){sup 4+} and [SiW{sub 12}O{sub 40}]{sup 4−} in 2. The coordination environments of the tetrameric silver cations have a great influence on the structure richness of the Keggin-based hybrids. The fluorescence properties of compounds 1 and 2 also have been discussed. - Graphical abstract: New polyoxometalate-based hybrids consisting of Keggin-type clusters modified by (Ag{sub 4}) groups had been synthesized and characterized, and their photoluminescence properties were also discussed. Display Omitted - Highlights: • Two Keggin-type polyoxometalates consisting of (Ag{sub 4}) clusters through weak Ag…Ag interactions have been synthesized. • There exist face-to-face and dot-to-face π…π interactions in (Ag-ligand){sub 4} fragment. • The fluorescence properties of (Ag{sub 4}) modified POMs are also discussed.

  6. Collagen-chitosan scaffold modified with Au and Ag nanoparticles: Synthesis and structure

    NASA Astrophysics Data System (ADS)

    Rubina, M. S.; Kamitov, E. E.; Zubavichus, Ya. V.; Peters, G. S.; Naumkin, A. V.; Suzer, S.; Vasil'kov, A. Yu.

    2016-03-01

    Nowadays, the dermal biomimetic scaffolds are widely used in regenerative medicine. Collagen-chitosan scaffold one of these materials possesses antibacterial activity, good compatibility with living tissues and has been already used as a wound-healing material. In this article, collagen-chitosan scaffolds modified with Ag and Au nanoparticles have been synthesized using novel method - the metal-vapor synthesis. The nanocomposite materials are characterized by XPS, TEM, SEM and synchrotron radiation-based X-ray techniques. According to XRD data, the mean size of the nanoparticles (NPs) is 10.5 nm and 20.2 nm in Au-Collagen-Chitosan (Au-CollCh) and Ag-Collagen-Chitosan (Ag-CollCh) scaffolds, respectively in fair agreement with the TEM data. SAXS analysis of the composites reveals an asymmetric size distribution peaked at 10 nm for Au-CollCh and 25 nm for Ag-CollCh indicative of particle's aggregation. According to SEM data, the metal-carrying scaffolds have layered structure and the nanoparticles are rather uniformly distributed on the surface material. XPS data indicate that the metallic nanoparticles are in their unoxidized/neutral states and dominantly stabilized within the chitosan-rich domains.

  7. Electrochemical biosensor modified with dsDNA monolayer for restriction enzyme activity determination.

    PubMed

    Zajda, Joanna; Górski, Łukasz; Malinowska, Elżbieta

    2016-06-01

    A simple and cost effective method for the determination of restriction endonuclease activity is presented. dsDNA immobilized at a gold electrode surface is used as the enzymatic substrate, and an external cationic redox probe is employed in voltammetric measurements for analytical signal generation. The assessment of enzyme activity is based on a decrease of a current signal derived from reduction of methylene blue which is present in the sample solution. For this reason, the covalent attachment of the label molecule is not required which significantly reduces costs of the analysis and simplifies the entire determination procedure. The influence of buffer components on utilized dsDNA/MCH monolayer stability and integrity is also verified. Electrochemical impedance spectroscopy measurements reveal that due to pinhole formation during enzyme activity measurement the presence of any surfactants should be avoided. Additionally, it is shown that the sensitivity of the electrochemical biosensor can be tuned by changing the restriction site location along the DNA length. Under optimal conditions the proposed biosensor exhibits a linear response toward PvuII activity within a range from 0.25 to 1.50 U/μL. PMID:26859430

  8. Electrochemical biosensor modified with dsDNA monolayer for restriction enzyme activity determination.

    PubMed

    Zajda, Joanna; Górski, Łukasz; Malinowska, Elżbieta

    2016-06-01

    A simple and cost effective method for the determination of restriction endonuclease activity is presented. dsDNA immobilized at a gold electrode surface is used as the enzymatic substrate, and an external cationic redox probe is employed in voltammetric measurements for analytical signal generation. The assessment of enzyme activity is based on a decrease of a current signal derived from reduction of methylene blue which is present in the sample solution. For this reason, the covalent attachment of the label molecule is not required which significantly reduces costs of the analysis and simplifies the entire determination procedure. The influence of buffer components on utilized dsDNA/MCH monolayer stability and integrity is also verified. Electrochemical impedance spectroscopy measurements reveal that due to pinhole formation during enzyme activity measurement the presence of any surfactants should be avoided. Additionally, it is shown that the sensitivity of the electrochemical biosensor can be tuned by changing the restriction site location along the DNA length. Under optimal conditions the proposed biosensor exhibits a linear response toward PvuII activity within a range from 0.25 to 1.50 U/μL.

  9. Modified optical absorption of molecules on metallic nanoparticles at sub-monolayer coverage

    NASA Astrophysics Data System (ADS)

    Darby, Brendan L.; Auguié, Baptiste; Meyer, Matthias; Pantoja, Andres E.; Le Ru, Eric C.

    2016-01-01

    Enhanced optical absorption of molecules in the vicinity of metallic nanostructures is key to a number of surface-enhanced spectroscopies and of great general interest to the fields of plasmonics and nano-optics. However, experimental access to this absorbance has long proven elusive. Here, we present direct measurements of the surface absorbance of dye molecules adsorbed onto silver nanospheres and, crucially, at sub-monolayer concentrations where dye-dye interactions become negligible. With a large detuning from the plasmon resonance, distinct shifts and broadening of the molecular resonances reveal the intrinsic properties of the dye in contact with the metal colloid, in contrast to the often studied strong-coupling regime where the optical properties of the dye molecules cannot be isolated. The observation of these shifts together with the ability to routinely measure them has broad implications in the interpretation of experiments involving resonant molecules on metallic surfaces, such as surface-enhanced spectroscopies and many aspects of molecular plasmonics.

  10. Characterization and Evaluation of Reverse Osmosis Membranes Modified with Ag2O Nanoparticles to Improve Performance.

    PubMed

    Al-Hobaib, Abdullah S; Al-Sheetan, Khalid M; Shaik, Mohammed Rafi; Al-Andis, Naser M; Al-Suhybani, M S

    2015-12-01

    The objective of this work was to prepare and characterize a new and highly efficient modified membrane by in situ interfacial polymerization on porous polysulfone supports. The process used m-phenylenediamine and trimesoyl chloride in hexane, incorporating silver oxide Ag2O nanoparticles of varied concentrations from 0.001 to 0.1 wt%. Ag2O nanoparticles were prepared at different sizes varying between 20 and 50 nm. The modified membranes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), transmission electron microscopy (TEM), and contact angle measurement. The results showed a smooth membrane surface and average surface roughness from 31 to 74 nm. Moreover, hydrophilicity improved and the contact angle decreased to 41° at 0.009 wt% silver oxide. The performances of the developed membranes were investigated by measuring permeate fluxes and salt rejection capability by passing NaCl solutions (2000 ppm) through the membranes at 225 psi. The results showed that the flux increased from 26 to 40.5 L/m(2) h, while the salt rejection was high, at 99 %, with 0.003 wt% Ag2O nanoparticles.

  11. Characterization and Evaluation of Reverse Osmosis Membranes Modified with Ag2O Nanoparticles to Improve Performance

    NASA Astrophysics Data System (ADS)

    Al-Hobaib, Abdullah S.; AL-Sheetan, Khalid M.; Shaik, Mohammed Rafi; Al-Andis, Naser M.; Al-Suhybani, M. S.

    2015-09-01

    The objective of this work was to prepare and characterize a new and highly efficient modified membrane by in situ interfacial polymerization on porous polysulfone supports. The process used m-phenylenediamine and trimesoyl chloride in hexane, incorporating silver oxide Ag2O nanoparticles of varied concentrations from 0.001 to 0.1 wt%. Ag2O nanoparticles were prepared at different sizes varying between 20 and 50 nm. The modified membranes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), transmission electron microscopy (TEM), and contact angle measurement. The results showed a smooth membrane surface and average surface roughness from 31 to 74 nm. Moreover, hydrophilicity improved and the contact angle decreased to 41° at 0.009 wt% silver oxide. The performances of the developed membranes were investigated by measuring permeate fluxes and salt rejection capability by passing NaCl solutions (2000 ppm) through the membranes at 225 psi. The results showed that the flux increased from 26 to 40.5 L/m2 h, while the salt rejection was high, at 99 %, with 0.003 wt% Ag2O nanoparticles.

  12. Effects of Oxide-Modified Spherical ZnO on Electrical Properties of Ag/ZnO Electrical Contact Material

    NASA Astrophysics Data System (ADS)

    Wei, Zhijun; Zhang, Lingjie; Shen, Tao; Qiao, Zhengyang; Yang, Hui; Fan, Xianping; Chen, Lawson

    2016-07-01

    Silver-zinc oxide (Ag/ZnO) electrical contact material is widely used as contacts of the medium duty switching devices. Effects of modified ZnO on properties of Ag/ZnO electrical contact material were investigated in this work. NiO and CuO were introduced to modify spherical ZnO by a chemical solution nano-coating method. Ag/ZnO contacts prepared using the modified spherical ZnO were produced by powder metallurgy (PM) method in a muffle furnace in temperature ranges from 750 to 900 °C. Results show that electrical conductivity, stability of relative density, and Vickers' hardness of Ag/ZnO electrical contact material can be improved by the addition of NiO because of the formation of NiO solid solution Zn0.2Ni0.8O. The addition of CuO to Ag/ZnO electrical contact material makes arcing energy and mass loss lower. Since this is attractive for a longer service life, using NiO and CuO co-modified ZnO as a second phase may be a promising way to improve properties of Ag/ZnO electrical contact material. Hence, the presented results could also be useful for the design of a new Ag/ZnO electrical contact material.

  13. Effects of Oxide-Modified Spherical ZnO on Electrical Properties of Ag/ZnO Electrical Contact Material

    NASA Astrophysics Data System (ADS)

    Wei, Zhijun; Zhang, Lingjie; Shen, Tao; Qiao, Zhengyang; Yang, Hui; Fan, Xianping; Chen, Lawson

    2016-09-01

    Silver-zinc oxide (Ag/ZnO) electrical contact material is widely used as contacts of the medium duty switching devices. Effects of modified ZnO on properties of Ag/ZnO electrical contact material were investigated in this work. NiO and CuO were introduced to modify spherical ZnO by a chemical solution nano-coating method. Ag/ZnO contacts prepared using the modified spherical ZnO were produced by powder metallurgy (PM) method in a muffle furnace in temperature ranges from 750 to 900 °C. Results show that electrical conductivity, stability of relative density, and Vickers' hardness of Ag/ZnO electrical contact material can be improved by the addition of NiO because of the formation of NiO solid solution Zn0.2Ni0.8O. The addition of CuO to Ag/ZnO electrical contact material makes arcing energy and mass loss lower. Since this is attractive for a longer service life, using NiO and CuO co-modified ZnO as a second phase may be a promising way to improve properties of Ag/ZnO electrical contact material. Hence, the presented results could also be useful for the design of a new Ag/ZnO electrical contact material.

  14. Direct electrochemical oxidation of S-captopril using gold electrodes modified with graphene-AuAg nanocomposites.

    PubMed

    Pogacean, Florina; Biris, Alexandru R; Coros, Maria; Lazar, Mihaela Diana; Watanabe, Fumiya; Kannarpady, Ganesh K; Al Said, Said A Farha; Biris, Alexandru S; Pruneanu, Stela

    2014-01-01

    In this paper, we present a novel approach for the electrochemical detection of S-captopril based on graphene AuAg nanostructures used to modify an Au electrode. Multi-layer graphene (Gr) sheets decorated with embedded bimetallic AuAg nanoparticles were successfully synthesized catalytically with methane as the carbon source. The two catalytic systems contained 1.0 wt% Ag and 1.0 wt% Au, while the second had a larger concentration of metals (1.5 wt% Ag and 1.5 wt% Au) and was used for the synthesis of the Gr-AuAg-1 and Gr-AuAg-1.5 multicomponent samples. High-resolution transmission electron microscopy analysis indicated the presence of graphene flakes that had regular shapes (square or rectangular) and dimensions in the tens to hundreds of nanometers. We found that the size of the embedded AuAg nanoparticles varied between 5 and 100 nm, with the majority being smaller than 20 nm. Advanced scanning transmission electron microscopy studies indicated a bimetallic characteristic of the metallic clusters. The resulting Gr-AuAg-1 and Gr-AuAg-1.5 samples were used to modify the surface of commonly used Au substrates and subsequently employed for the direct electrochemical oxidation of S-captopril. By comparing the differential pulse voltammograms recorded with the two modified electrodes at various concentrations of captopril, the peak current was determined to be well-defined, even at relatively low concentration (10(-5) M), for the Au/Gr-AuAg-1.5 electrode. In contrast, the signals recorded with the Au/Gr-AuAg-1 electrode were poorly defined within a 5×10(-6) to 5×10(-3) M concentration range, and many of them overlapped with the background. Such composite materials could find significant applications in nanotechnology, sensing, or nanomedicine.

  15. Direct electrochemical oxidation of S-captopril using gold electrodes modified with graphene-AuAg nanocomposites

    PubMed Central

    Pogacean, Florina; Biris, Alexandru R; Coros, Maria; Lazar, Mihaela Diana; Watanabe, Fumiya; Kannarpady, Ganesh K; Al Said, Said A Farha; Biris, Alexandru S; Pruneanu, Stela

    2014-01-01

    In this paper, we present a novel approach for the electrochemical detection of S-captopril based on graphene AuAg nanostructures used to modify an Au electrode. Multi-layer graphene (Gr) sheets decorated with embedded bimetallic AuAg nanoparticles were successfully synthesized catalytically with methane as the carbon source. The two catalytic systems contained 1.0 wt% Ag and 1.0 wt% Au, while the second had a larger concentration of metals (1.5 wt% Ag and 1.5 wt% Au) and was used for the synthesis of the Gr-AuAg-1 and Gr-AuAg-1.5 multicomponent samples. High-resolution transmission electron microscopy analysis indicated the presence of graphene flakes that had regular shapes (square or rectangular) and dimensions in the tens to hundreds of nanometers. We found that the size of the embedded AuAg nanoparticles varied between 5 and 100 nm, with the majority being smaller than 20 nm. Advanced scanning transmission electron microscopy studies indicated a bimetallic characteristic of the metallic clusters. The resulting Gr-AuAg-1 and Gr-AuAg-1.5 samples were used to modify the surface of commonly used Au substrates and subsequently employed for the direct electrochemical oxidation of S-captopril. By comparing the differential pulse voltammograms recorded with the two modified electrodes at various concentrations of captopril, the peak current was determined to be well-defined, even at relatively low concentration (10−5 M), for the Au/Gr-AuAg-1.5 electrode. In contrast, the signals recorded with the Au/Gr-AuAg-1 electrode were poorly defined within a 5×10−6 to 5×10−3 M concentration range, and many of them overlapped with the background. Such composite materials could find significant applications in nanotechnology, sensing, or nanomedicine. PMID:24596464

  16. Submicron patterns obtained by thermal-induced reconstruction of self-assembled monolayer of Ag nanoparticles and their application in SERS

    NASA Astrophysics Data System (ADS)

    Ruan, Weidong; Zhou, Tieli; Cui, Yinqiu; Dong, Yujie; Liu, Zhuo; Dong, Fengxia; Wang, Haiyang; Luan, Xintong; Wang, Xu; Song, Wei; Zhao, Bing

    2014-08-01

    The layer-by-layer (LbL) self-assembly technique was employed for the deposition of poly(diallyldimethylammonium chloride) (PDDA) and triangular Ag nanoplates on glass substrates. A thermal-induced reconstruction of these polyelectrolyte-linked nanoparticle (NP) films was presented. Before the reconstruction, triangular Ag nanoplates were distributed uniformly on the surface with an average interval of 50 ± 15 nm. After the reconstruction, the triangular Ag nanoplates accumulated into discrete stacks with an average interval of 90 ± 25 nm. The temperature-dependent experiments were done and the optimal temperature for the formation of the reconstructed patterns was 120 °C. The possible mechanism of the NP movement and stacking was analyzed. Under the experimental conditions, a hydrophobic environment was formed because of the vacuum and heating. As a result the polyelectrolyte-linked Ag NPs preferred to congregate due to the lowered surface energy. Finally the submicron patterns were formed. The ultraviolet-visible (UV-vis) absorption and surface-enhanced Raman scattering (SERS) properties of the films before and after the reconstruction was investigated. The reconstructed films with submicron patterns had better SERS enhancement ability, which was 1300 times to the original films. The reconstruction method of the monolayer films showed great potential in the surface design and related applications. AFM images were obtained to clarify the three dimensional structures of the reconstructed films obtained at 120 °C. As shown in Fig. 2, the Ag NP stacks had an average diameter of 1.0 ± 0.2 μm and an average height of 170 ± 30 nm. The diameter and height of the stacks were shaped by the aggregates of tens of triangular Ag nanoplates. The AFM cross-sectional contour showed the clear intervals of the stacks, which was corresponding to the SEM characterization.XRD patterns of the polyelectrolyte-linked NP films before and after thermal post-treatment are showed in

  17. Gold nanoparticles modified with self-assembled hybrid monolayer of triblock aptamers as a photoreversible anticoagulant.

    PubMed

    Huang, San-Shan; Wei, Shih-Chun; Chang, Huan-Tsung; Lin, Han-Jia; Huang, Chih-Ching

    2016-01-10

    We demonstrated that thrombin-binding aptamer-conjugated gold nanoparticles (TBA-Au NPs), prepared from a self-assembled hybrid monolayer (SAHM) of triblock aptamers on Au NPs (13 nm), can effectively inhibit thrombin activity toward fibrinogen. The first block poly(adenine) at the end of the triblock TBA was used for the self-assembly on Au NP surface. The second block, in the middle of TBA, was composed of oligonucleotides that could hybridize with each other. The third block, containing TBA15 (15-base, binding to the exosite I of thrombin) and TBA29 (29-base, binding to the exosite II of thrombin) provided bivalent interaction with thrombin. The SAHM triblock aptamers have optimal distances between TBA15 and TBA29, aptamer density, and orientation on the Au NP surfaces. These properties strengthen the interactions with thrombin (Kd=1.5 × 10(-11)M), resulting in an extremely high anticoagulant potency. The thrombin clotting time mediated by SAHM TBA15/TBA29-Au NPs was >10 times longer than that of four commercially available drugs (heparin, argatroban, hirudin, or warfarin). In addition, the rat-tail bleeding assay time further demonstrated that the SAHM TBA15/TBA29-Au NPs were superior to heparin. The SAHM TBA15/TBA29-Au NPs exhibited excellent stability in the human plasma (half-life >14 days) and good biocompatibility (low cytotoxicity and hemolysis). Most interestingly, the inhibition by SAHM TBA15/TBA29-Au NPs was controllable by the irradiation of green laser, via heat transfer-induced TBA release from Au NPs. Therefore, these easily prepared (self-assembled), low cost (non-thiolated aptamer), photo-controllable, multivalent TBA15/TBA29-Au NPs (high density of TBA15/TBA29 on Au NPs) show good potential for the treatment of various diseases related to blood-clotting disorders. Our study opens up the possibility of regulation of molecule binding, protein recognition, and enzyme activity using SAHM aptamer-functionalized nanomaterials.

  18. Gold nanoparticles modified with self-assembled hybrid monolayer of triblock aptamers as a photoreversible anticoagulant.

    PubMed

    Huang, San-Shan; Wei, Shih-Chun; Chang, Huan-Tsung; Lin, Han-Jia; Huang, Chih-Ching

    2016-01-10

    We demonstrated that thrombin-binding aptamer-conjugated gold nanoparticles (TBA-Au NPs), prepared from a self-assembled hybrid monolayer (SAHM) of triblock aptamers on Au NPs (13 nm), can effectively inhibit thrombin activity toward fibrinogen. The first block poly(adenine) at the end of the triblock TBA was used for the self-assembly on Au NP surface. The second block, in the middle of TBA, was composed of oligonucleotides that could hybridize with each other. The third block, containing TBA15 (15-base, binding to the exosite I of thrombin) and TBA29 (29-base, binding to the exosite II of thrombin) provided bivalent interaction with thrombin. The SAHM triblock aptamers have optimal distances between TBA15 and TBA29, aptamer density, and orientation on the Au NP surfaces. These properties strengthen the interactions with thrombin (Kd=1.5 × 10(-11)M), resulting in an extremely high anticoagulant potency. The thrombin clotting time mediated by SAHM TBA15/TBA29-Au NPs was >10 times longer than that of four commercially available drugs (heparin, argatroban, hirudin, or warfarin). In addition, the rat-tail bleeding assay time further demonstrated that the SAHM TBA15/TBA29-Au NPs were superior to heparin. The SAHM TBA15/TBA29-Au NPs exhibited excellent stability in the human plasma (half-life >14 days) and good biocompatibility (low cytotoxicity and hemolysis). Most interestingly, the inhibition by SAHM TBA15/TBA29-Au NPs was controllable by the irradiation of green laser, via heat transfer-induced TBA release from Au NPs. Therefore, these easily prepared (self-assembled), low cost (non-thiolated aptamer), photo-controllable, multivalent TBA15/TBA29-Au NPs (high density of TBA15/TBA29 on Au NPs) show good potential for the treatment of various diseases related to blood-clotting disorders. Our study opens up the possibility of regulation of molecule binding, protein recognition, and enzyme activity using SAHM aptamer-functionalized nanomaterials. PMID:26643617

  19. Detection of saccharides with a fluorescent sensing device based on a gold film modified with 4-mercaptophenylboronic acid monolayer

    NASA Astrophysics Data System (ADS)

    Chen, Shu-Jen; Chang, Jui-Feng; Cheng, Nai-Jen; Yih, Jeng-Nan; Chiu, Kuo-Chi

    2013-09-01

    An extremely sensitive fluorescent sensor based on a phenylboronic acid monolayer was developed for detecting saccharide molecules. The fluorescent sensor was prepared by assembling a monolayer of 4-mercaptophenylboronic acid (4-MPBA) onto a gold-coated compact disk. The change in the fluorescence of the 4-MPBA monolayer was extremely obvious in basic methanolic buffer containing monosaccharides down to the picomolar level. The fluorescence spectra demonstrated that the 4-MPBA monolayer was sensitive to monosaccharides and disaccharides, and the affinity of the monolayer toward saccharides was in the order of glucose < fructose < mannose < galactose < maltose > lactose > sucrose. Additionally, the fluorescence intensity of 4-MPBA monolayer was restorable after cleaning with weak acid, indicating that the reported fluorescent sensor with the detection limit of glucose down to the picomolar level is reusable for sensing saccharides.

  20. Density functional theory calculations of phenol-modified monolayer silicon nanosheets

    NASA Astrophysics Data System (ADS)

    Spencer, Michelle J. S.; Morishita, Tetsuya; Bassett, Michael R.

    2013-12-01

    Silicon nanosheets are one of most exciting recent discoveries, being a two-dimensional form of silicon that is only nanometers thick, with large lateral dimensions. A single atomic layer silicon nanosheet is known as silicene and can be grown with different surface terminations. It has been shown previously that organo-modified silicene can be synthesised with phenyl groups covalently bonded to both sides of the nanosheet, with hydrogen atoms terminating the undercoordinated silicon atoms. In this work, we use density functional theory calculations and ab initio molecular dynamics simulations to determine the effect of hydroxyl (OH) group substitutions on the phenyl-modified silicene. Different positions of the OH groups on the phenyl rings were modelled including ortho-, meta- and para- substituted positions. We found that the meta-substituted position was favoured, followed by the para- then ortho- substituted positions. Our ab initio MD simulations showed that the phenol groups will freely rotate on the nanosheet, aligning so as to form hydrogen bonds between adjacent phenol groups. The unique properties of this material could be useful for future electronic device applications.

  1. Square Wave Voltammetry of TNT at Gold Electrodes Modified with Self-Assembled Monolayers Containing Aromatic Structures

    PubMed Central

    Trammell, Scott A.; Zabetakis, Dan; Moore, Martin; Verbarg, Jasenka; Stenger, David A.

    2014-01-01

    Square wave voltammetry for the reduction of 2,4,6-trinitrotoluene (TNT) was measured in 100 mM potassium phosphate buffer (pH 8) at gold electrodes modified with self-assembled monolayers (SAMs) containing either an alkane thiol or aromatic ring thiol structures. At 15 Hz, the electrochemical sensitivity (µA/ppm) was similar for all SAMs tested. However, at 60 Hz, the SAMs containing aromatic structures had a greater sensitivity than the alkane thiol SAM. In fact, the alkane thiol SAM had a decrease in sensitivity at the higher frequency. When comparing the electrochemical response between simulations and experimental data, a general trend was observed in which most of the SAMs had similar heterogeneous rate constants within experimental error for the reduction of TNT. This most likely describes a rate limiting step for the reduction of TNT. However, in the case of the alkane SAM at higher frequency, the decrease in sensitivity suggests that the rate limiting step in this case may be electron tunneling through the SAM. Our results show that SAMs containing aromatic rings increased the sensitivity for the reduction of TNT when higher frequencies were employed and at the same time suppressed the electrochemical reduction of dissolved oxygen. PMID:25549081

  2. Molecular structure and vibrations of NTCDA monolayers on Ag(111) from density-functional theory and infrared absorption spectroscopy.

    PubMed

    Tonner, Ralf; Rosenow, Phil; Jakob, Peter

    2016-02-17

    The structure and vibrational properties of the metal-organic interface of 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) on Ag(111) were analysed using Fourier-transform infrared absorption spectroscopy in conjunction with density functional theory calculations including dispersion forces (PBE-D3). Mode assignments and polarizations as well as molecular distortions were determined for four adsorption geometries of NTCDA on top and bridge sites aligned either parallel or perpendicular to the Ag rows and compared to accurate calculations of the free molecule. This enables an in-depth understanding of surface effects on the computed and experimental vibrational spectra of the adsorbed NTCDA molecule. The molecule-substrate interaction comprises two major and equally important contributions: non-directional van der Waals forces between molecule and surface, and covalent bonding of the acyl oxygen atoms with underlying Ag atoms, which is quantified by charge-transfer analysis. Furthermore, adsorption energy calculations showed that the molecular axis of flat-lying NTCDA is oriented preferably in parallel to the Ag rows. The molecule is subject to particular distortions from the planar gas phase structure with covalent bonding leading to downward bending of the acyl oxygen atoms and Pauli repulsion to upward bending of the carbon core. In parallel, strong buckling of the silver surface was identified. As found in previous studies, the lowest unoccupied molecular orbital (LUMO) of the molecule slips below the Fermi level and becomes partially populated upon adsorption. Excitation of totally symmetric vibrational modes then leads to substantial interfacial dynamical charge transfer, which is convincingly reproduced in the calculated IR spectra.

  3. Mass preparation and novel visible light photocatalytic activity of C and Ag Co-modified ZnO nanocrystals.

    PubMed

    Zhang, Xiao-Yan; Deng, Ya-Juan; Liu, Jin-Ku; Lu, Yi; Yang, Xiao-Hong

    2015-12-01

    A combustion method was developed to synthesize the C and Ag co-modified ZnO NCs to enhance its photocatalytic efficiency and practicability. The results showed that the doped Ag was significant to promote the photocatalytic activity, and the optimum content was 2% molar ratio of Ag to Zn atom. The degradation rate under visible light increased by 150% compared with C-ZnO NCs, while by more 1233.3% than pure ZnO photocatalyst. There were some new little particles with grain size about 10 nm on the C-ZnO NCs surface, which may state for the existence of Ag atoms. The synergy effect of Ag and carbon elements was proposed to explain the mechanism of enhanced photocatalytic performance under visible light irradiation. PMID:26254866

  4. An in situ study on the coalescence of monolayer-protected Au-Ag nanoparticle deposits upon heating

    PubMed Central

    2014-01-01

    The structural evolution of thiolate-protected nanoparticles of gold, silver, and their alloys with various Au/Ag ratios (3:1, 1:1, and 1:3) upon heating was investigated by means of in situ synchrotron radiation X-ray diffraction. The relationships between the coalescence and composition of nanoparticles, as well as the surfactant reactions, were clarified. Experimental results show that there existed a critical temperature ranging from 120°C to 164°C, above which the tiny broad X-ray diffraction peaks became sharp and strong due to particle coalescence. The coalescence temperatures for alloy nanoparticle deposits were clearly lower than those for pure metals, which can be ascribed to the rivalry between the thermodynamic effect due to alloying and the interactions between surface-assembled layers and the surface atoms of the nanoparticles. The strong affinity of thiolates to Ag and thus complex interactions give rise to a greater energy barrier for the coalescence of nanoparticles into the bulk and subsequent high coalescence temperature. The influences of particle coalescence on the optical and electrical properties of the nanoparticle deposits were also explored. PMID:25246861

  5. Fragmentation and reactivity in collisions of protonated diglycine with chemically modified perfluorinated alkylthiolate-self-assembled monolayer surfaces

    SciTech Connect

    Barnes, George L.; Yang Li; Hase, William L.; Young, Kelsey

    2011-03-07

    Direct dynamics simulations are reported for quantum mechanical (QM)/molecular mechanical (MM) trajectories of N-protonated diglycine (gly{sub 2}-H{sup +}) colliding with chemically modified perfluorinated octanethiolate self-assembled monolayer (SAM) surfaces. The RM1 semiempirical theory is used for the QM component of the trajectories. RM1 activation and reaction energies were compared with those determined from higher-level ab initio theories. Two chemical modifications are considered in which a head group (-COCl or -CHO) is substituted on the terminal carbon of a single chain of the SAM. These surfaces are designated as the COCl-SAM and CHO-SAM, respectively. Fragmentation, peptide reaction with the SAM, and covalent linkage of the peptide or its fragments with the SAM surface are observed. Peptide fragmentation via concerted CH{sub 2}-CO bond breakage is the dominant pathway for both surfaces. HCl formation is the dominant species produced by reaction with the COCl-SAM, while for the CHO-SAM a concerted H-atom transfer from the CHO-SAM to the peptide combined with either a H-atom or radical transfer from the peptide to the surface to form singlet reaction products is the dominant pathway. A strong collision energy dependence is found for the probability of peptide fragmentation, its reactivity, and linkage with the SAM. Surface deposition, i.e., covalent linkage between the surface and the peptide, is compared to recent experimental observations of such bonding by Laskin and co-workers [Phys. Chem. Chem. Phys. 10, 1512 (2008)]. Qualitative differences in reactivity are seen between the COCl-SAM and CHO-SAM showing that chemical identity is important for surface reactivity. The probability of reactive surface deposition, which is most closely analogous to experimental observables, peaks at a value of around 20% for a collision energy of 50 eV.

  6. Second harmonic generation of chiral-modified silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Tao, Yue; Aldea-Nunzi, Gabriela; Rao Bobbara, Sanyasi; Nunzi, Jean-Michel

    2013-10-01

    Various approaches for the optical detection of chiral compounds have been developed due to their natural optical activity. Since the advantages of second harmonic generation (SHG) on noble-metal nanoparticles (NPs) have been observed, it would be interesting to study the nonlinear phenomena from chiral compounds attached Ag NPs. In the present work, we fabricated chiral-modified Ag NPs based on the self-assembly process of cysteine and Ag, and carried out the investigation on SHG on modified and unmodified Ag NPs. For modified Ag NPs, either L-Cysteine (L-C) or D-Cysteine (D-C), as a pair of enantiomers, was applied on top of the Ag NPs. The resulting chiral-modified monolayers of L-C/Ag NPs and D-C/Ag NPs exhibit a reversed optical rotation difference (ORD) at linearly +/-45° polarization of SH, where no such difference exists for Ag NPs alone. SHG efficiently probes and discriminates L-C from D-C monolayers on the modified Ag NPs, which constitutes a simple and sensitive optical diagnostic of chiral molecules.

  7. Determination of Anthracene on Ag-Au Alloy Nanoparticles/Overoxidized-Polypyrrole Composite Modified Glassy Carbon Electrodes

    PubMed Central

    Mailu, Stephen N.; Waryo, Tesfaye T.; Ndangili, Peter M.; Ngece, Fanelwa R.; Baleg, Abd A.; Baker, Priscilla G.; Iwuoha, Emmanuel I.

    2010-01-01

    A novel electrochemical sensor for the detection of anthracene was prepared by modifying a glassy carbon electrode (GCE) with over-oxidized polypyrrole (PPyox) and Ag-Au (1:3) bimetallic nanoparticles (Ag-AuNPs). The composite electrode (PPyox/Ag-AuNPs/GCE) was prepared by potentiodynamic polymerization of pyrrole on GCE followed by its overoxidation in 0.1 M NaOH. Ag-Au bimetallic nanoparticles were chemically prepared by the reduction of AgNO3 and HAuCl4 using C6H5O7Na3 as the reducing agent as well as the capping agent and then immobilized on the surface of the PPyox/GCE. The nanoparticles were characterized by UV-visible spectroscopy technique which confirmed the homogeneous formation of the bimetallic alloy nanoparticles. Transmission electron microscopy showed that the synthesized bimetallic nanoparticles were in the range of 20–50 nm. The electrochemical behaviour of anthracene at the PPyox/Ag-AuNPs/GCE with Ag: Au atomic ratio 25:75 (1:3) exhibited a higher electrocatalytic effect compared to that observed when GCE was modified with each constituent of the composite (i.e., PPyox, Ag-AuNPs) and bare GCE. A linear relationship between anodic current and anthracene concentration was attained over the range of 3.0 × 10−6 to 3.56 × 10−4 M with a detection limit of 1.69 × 10−7 M. The proposed method was simple, less time consuming and showed a high sensitivity. PMID:22163419

  8. Monolayer magnetism of 3d transition metals in Ag, Au, Pd, and Pt hosts: Systematics of local moment variation

    NASA Astrophysics Data System (ADS)

    McHenry, M. E.; MacLaren, J. M.; Clougherty, D. P.

    1991-11-01

    Electronic and magnetic properties of T/Aun, T/Agn (T=Cr, Mn, Fe, Co, and Ni), Fe/Pdn and Fe/Ptn multilayers and sandwiches have been computed using the layer Korringa-Kohn-Rostoker (LKKR) band-structure technique. Enhanced (as compared with bulk) 2D T magnetism is observed in all Cr, Mn, and Fe/host configurations, consistent with weak coupling between Cr, Mn, and Fe d bands and those of the noble metal (NM) hosts and consequently d bandwidths which are exceeded by the exchange splitting. Fe and Cr moments vary systematically with the number of mediating Ag or Au planes and the Fermi energy of the system. These systematics are explained by considering the variation of the Fermi energy (EF) with composition as well as constraints of charge neutrality and strong (single-band) ferromagnetism. For Fe in Pt and Pd hosts, d-d hybridization leads to a nearly invariant Fe moment as a function of the number of mediating Pd or Pt planes but with large induced moments on the host.

  9. Phonon dispersion on Ag (100) surface: A modified analytic embedded atom method study

    NASA Astrophysics Data System (ADS)

    Xiao-Jun, Zhang; Chang-Le, Chen

    2016-01-01

    Within the harmonic approximation, the analytic expression of the dynamical matrix is derived based on the modified analytic embedded atom method (MAEAM) and the dynamics theory of surface lattice. The surface phonon dispersions along three major symmetry directions , and X¯M¯ are calculated for the clean Ag (100) surface by using our derived formulas. We then discuss the polarization and localization of surface modes at points X¯ and M¯ by plotting the squared polarization vectors as a function of the layer index. The phonon frequencies of the surface modes calculated by MAEAM are compared with the available experimental and other theoretical data. It is found that the present results are generally in agreement with the referenced experimental or theoretical results, with a maximum deviation of 10.4%. The agreement shows that the modified analytic embedded atom method is a reasonable many-body potential model to quickly describe the surface lattice vibration. It also lays a significant foundation for studying the surface lattice vibration in other metals. Project supported by the National Natural Science Foundation of China (Grant Nos. 61471301 and 61078057), the Scientific Research Program Funded by Shaanxi Provincial Education Department, China (Grant No. 14JK1301), and the Specialized Research Fund for the Doctoral Program of Higher Education, China (Grant No. 20126102110045).

  10. Enhancement of visible light activity in Ag modified SnO{sub 2}/TiO{sub 2}

    SciTech Connect

    Zhou, Xiufeng; Cao, Jialei; Xu, Mengfei; Wang, Zuoshan; Lu, Juan

    2013-11-15

    Graphical abstract: - Highlights: • Ag modified SnO{sub 2}/TiO{sub 2} nanoparticles were synthesized by a modified sol–gel method. • As-prepared samples have a small and uniform particle size of about 20 nm. • As-prepared samples exhibit an excellent photo-catalytic efficiency on the degradation of MB. • As-prepared samples maintain high photo-chemical stability after 5 catalytic cycles. - Abstract: Ag modified SnO{sub 2}/TiO{sub 2} nanoparticles were successfully prepared by a modified sol–gel method, without adding any acid or alkali. The entire preparation differs from the traditional sol–gel synthesis of TiO{sub 2} that the reaction can get controlled by adjusting the flow speed of water vapor. Ultraviolet–visible diffuse reflectance spectra (UV–vis) and spin-trapping electron paramagnetic resonance (EPR) were used to forecast the photocatalytic activity of the samples, and the results were proved by the degradation of methylene blue solution under visible light. Compared with pure TiO{sub 2}, as-prepared Ag modified SnO{sub 2}/TiO{sub 2} nanoparticles exhibited not only an enhanced photocatalytic activity but also an improved stability. Among all of samples, the composite with 0.5% of Ag and 1% of Sn showed the best photocatalytic performance and stability. Further increasing the Ag proportion will result in the decrease of the photocatalytic activity. A relative mechanism was proposed and discussed in detail.

  11. Voltammetric Detection of Urea on an Ag-Modified Zeolite-Expanded Graphite-Epoxy Composite Electrode

    PubMed Central

    Manea, Florica; Pop, Aniela; Radovan, Ciprian; Malchev, Plamen; Bebeselea, Adriana; Burtica, Georgeta; Picken, Stephen; Schoonman, Joop

    2008-01-01

    In this paper, a modified expanded graphite composite electrode based on natural zeolitic volcanic tuff modified with silver (EG-Ag-Z-Epoxy) was developed. Cyclic voltammetry measurements revealed a reasonably fast electron transfer and a good stability of the electrode in 0.1 M NaOH supporting electrolyte. This modified electrode exhibited moderate electrocatalytic effect towards urea oxidation, allowing its determination in aqueous solution. The linear dependence of the current versus urea concentration was reached using square-wave voltammetry in the concentrations range of urea between 0.2 to 1.4 mM, with a relatively low limit of detection of 0.05 mM. A moderate enhancement of electroanalytical sensitivity for the determination of urea at EG-Ag-Z-Epoxy electrode was reached by applying a chemical preconcentration step prior to voltammetric/amperometric quantification.

  12. Voltammetric studies of Azathioprine on the surface of graphite electrode modified with graphene nanosheets decorated with Ag nanoparticles.

    PubMed

    Asadian, Elham; Iraji Zad, Azam; Shahrokhian, Saeed

    2016-01-01

    By using graphene nanosheets decorated with Ag nanoparticles (AgNPs-G) as an effective approach for the surface modification of pyrolytic graphite electrode (PGE), a sensing platform was fabricated for the sensitive voltammetric determination of Azathioprine (Aza). The prepared AgNPs-G nanosheets were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-vis and Raman spectroscopy techniques. The electrochemical behavior of Aza was investigated by means of cyclic voltammetry. Comparing to the bare PGE, a remarkable enhancement was observed in the response characteristics of Aza on the surface of the modified electrode (AgNPs-G/PGE) as well as a noticeable decrease in its reduction overpotential. These results can be attributed to the incredible enlargement in the microscopic surface area of the electrode due to the presence of graphene nanosheets together with strong adsorption of Aza on its surface. The effect of experimental parameters such as accumulation time, the amount of modifier suspension and pH of the supporting electrolyte were also optimized toward obtaining the maximum sensitivity. Under the optimum conditions, the calibration curve studies demonstrated that the peak current increased linearly with Aza concentrations in the range of 7 × 10(-7) to 1 × 10(-4)mol L(-1) with the detection limit of 68 nM. Further experiments revealed that the modified electrode can be successfully applied for the accurate determination of Aza in pharmaceutical preparations.

  13. Efficient inverted organic light-emitting devices with self or intentionally Ag-doped interlayer modified cathode

    SciTech Connect

    Liu, Wenbo; Liu, Shihao; Yu, Jing; Zhang, Wei; Wen, Xuemei; Yin, Yongming; Zhang, Letian; Chen, Ping; Xie, Wenfa

    2014-03-03

    Green phosphorescent inverted organic light-emitting devices (IOLEDs) with self or intentionally Ag-doped interlayer modified cathode were demonstrated. The IOLEDs show low driving voltage and high efficiency. For example, the efficiency of inverted bottom-emitting OLED with ITO cathode is comparable with the conventional bottom-emitting OLED with ITO anode. The top-emitting IOLED with Ag cathode shows high current efficiency of 76.4 cd/A which is 2.38 times of that of the conventional bottom-emitting OLED with ITO anode. The results indicate that the electron injection from cathode was observably improved by the Ag-doped interlayer and such interlayer is cathode independent relatively.

  14. Antimicrobial activity and cytocompatibility of Ag plasma-modified hierarchical TiO2 film on titanium surface.

    PubMed

    Li, Jinhua; Liu, Xuanyong; Qiao, Yuqin; Zhu, Hongqin; Ding, Chuanxian

    2014-01-01

    To improve the antimicrobial ability and cytocompatibility of biomedical titanium implants, many efforts have been made to modify their surface topography and chemical composition. In this work, Ag plasma-modified hierarchical TiO2 film was fabricated on titanium surface via acid etching to produce micropit, hydrothermal treatment to generate TiO2 nanorod and subsequent plasma immersion ion implantation process to impregnate Ag into TiO2 surface. In view of the potential clinical applications, their antimicrobial activity, bioactivity and cytocompatibility were systematically evaluated. The hierarchical TiO2 film showed enhanced bioactivity and bacteriostatic effect on both microbes due to more negative zeta potential, constructing the first defense line against microbial adhesion by electrostatic repulsion. Addition of embedded Ag remarkably enhanced the antimicrobial efficiency toward both microbes based on Schottky contact without Ag(+) release, establishing the second defense line targeting microbial membrane. Furthermore, the addition of Ag degraded the bioactivity very little and exerted nearly no adverse or even promoted effect on MG63 cell functions, including adhesion, spreading and proliferation. This work illustrates a two-defense-line antimicrobial activity in darkness with both prior electrostatic repulsion to inhibit most microbes adhesion and posterior biocidal action to kill residual ones that luckily infiltrated through the first defense line, and provide proof of concept using both clinically relevant human pathogens. In conclusion, the Ag-embedded hierarchical TiO2 film with excellent antimicrobial activity, bioactivity and cytocompatibility provides a promising candidate for orthopedic and dental implants. PMID:24077111

  15. Amperometric detection of Sudan I in red chili powder samples using Ag nanoparticles decorated graphene oxide modified glassy carbon electrode.

    PubMed

    Prabakaran, E; Pandian, K

    2015-01-01

    A simple and sensitive electrochemical method was developed to determine the concentration of Sudan I in chili powder based on silver nanoparticles decorated graphene oxide modified glassy carbon electrode (AgNPs@GO/GCE). The voltammetry behaviour of Sudan I on modified GCE was investigated in phosphate buffer medium (PBS) with various pH ranges and the electron transfer properties were studied. It is found that the AgNPs@GO/GCE can catalyse the reduction of azo group, -N=N- followed by electrochemical oxidation of (-)OH group present in Sudan I dye molecule. Quantitative detection of Sudan I present in food products was carried out by amperometry method in which reduction potential was fixed at -0.77 V vs. Ag/AgCl. The amperometry method showed an excellent performance with a sensitivity of 6.83 μA mM(-1) and a detection limit of 11.4 × 10(-7)ML(-1). A linear calibration graph was constructed in the ranging 3.90 × 10(-6) to 3.19 × 10(-5)ML(-1). The method was successfully applied for the determination of Sudan I in red chili powder samples. PMID:25053046

  16. Amperometric detection of Sudan I in red chili powder samples using Ag nanoparticles decorated graphene oxide modified glassy carbon electrode.

    PubMed

    Prabakaran, E; Pandian, K

    2015-01-01

    A simple and sensitive electrochemical method was developed to determine the concentration of Sudan I in chili powder based on silver nanoparticles decorated graphene oxide modified glassy carbon electrode (AgNPs@GO/GCE). The voltammetry behaviour of Sudan I on modified GCE was investigated in phosphate buffer medium (PBS) with various pH ranges and the electron transfer properties were studied. It is found that the AgNPs@GO/GCE can catalyse the reduction of azo group, -N=N- followed by electrochemical oxidation of (-)OH group present in Sudan I dye molecule. Quantitative detection of Sudan I present in food products was carried out by amperometry method in which reduction potential was fixed at -0.77 V vs. Ag/AgCl. The amperometry method showed an excellent performance with a sensitivity of 6.83 μA mM(-1) and a detection limit of 11.4 × 10(-7)ML(-1). A linear calibration graph was constructed in the ranging 3.90 × 10(-6) to 3.19 × 10(-5)ML(-1). The method was successfully applied for the determination of Sudan I in red chili powder samples.

  17. Ag-Modified In2O3/ZnO Nanobundles with High Formaldehyde Gas-Sensing Performance

    PubMed Central

    Fang, Fang; Bai, Lu; Song, Dongsheng; Yang, Hongping; Sun, Xiaoming; Sun, Hongyu; Zhu, Jing

    2015-01-01

    Ag-modified In2O3/ZnO bundles with micro/nano porous structures have been designed and synthesized with by hydrothermal method continuing with dehydration process. Each bundle consists of nanoparticles, where nanogaps of 10–30 nm are present between the nanoparticles, leading to a porous structure. This porous structure brings high surface area and fast gas diffusion, enhancing the gas sensitivity. Consequently, the HCHO gas-sensing performance of the Ag-modified In2O3/ZnO bundles have been tested, with the formaldehyde-detection limit of 100 ppb (parts per billion) and the response and recover times as short as 6 s and 3 s, respectively, at 300 °C and the detection limit of 100 ppb, response time of 12 s and recover times of 6 s at 100 °C. The HCHO sensing detect limitation matches the health standard limitation on the concentration of formaldehyde for indoor air. Moreover, the strategy to synthesize the nanobundles is just two-step heating and easy to scale up. Therefore, the Ag-modified In2O3/ZnO bundles are ready for industrialization and practical applications. PMID:26287205

  18. Influence of alkyl chain length on calcium phosphate deposition onto titanium surfaces modified with alkylphosphonic acid monolayers.

    PubMed

    Wu, Jiang; Hirata, Isao; Zhao, Xianghui; Gao, Bo; Okazaki, Masayuki; Kato, Koichi

    2013-08-01

    Much attention has been paid to the modification of a titanium surface with an alkylphosphonic acid (PA)-based self-assembled monolayer (SAM) to accelerate hydroxyapatite (HA) deposition on the surface. In order to further accelerate the rate of HA deposition, we examined here the effect of alkyl chain length of SAMs on the formation of a HA layer. PAs with three different alkyl chain lengths (3, 6, and 16 methylene units) were used for the preparation of a SAM on titanium. The titanium specimens with monolayers were soaked in a simulated body fluid under physiological conditions for 4 weeks. The deposited substances were analyzed by scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. These analyses revealed that the formation of PA SAMs accelerate the deposition of poorly crystallized HA, in an alkyl chain length-dependent manner. Among PAs studied here, PA containing a 16-carbon alkyl chain gave rise to the titanium surface most effective for the deposition of HA.

  19. Facile synthesis of nano silver ferrite (AgFeO₂) modified with chitosan applied for biothiol separation.

    PubMed

    Abdelhamid, Hani Nasser; Wu, Hui-Fen

    2014-12-01

    Silver iron oxide nanoparticles (AgFeO2 NPs) with narrow size distribution have been synthesized, characterized and was applied for biothiols separation. AgFeO2 and AgFeO2 modified chitosan (AgFeO2@CTS NPs) were synthesized using a hydrothermal method and then characterized by electron microscopy (transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy dispersive X-ray (EDX)), X-ray diffraction (XRD), and Fourier transform infrared (FTIR). Different biological thiols (dithiothreitol, glutathione, thiabendazole, and sulfamethizole) were investigated and characterized using matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) and surface assisted laser desorption/ionization mass spectrometry (SALDI-MS). The new material displays dual functionality; 1) for separation and 2) can be served as the matrices for SALDI-MS. Data showed a clear background in the case of nanomaterials compared to conventional matrices (mefenamic acid and 2,5-dihydroxybenzoic acid (DHB) for MALDI-MS).

  20. Highly Sensitive Aluminium(III) Ion Sensor Based on a Self-assembled Monolayer on a Gold Nanoparticles Modified Screen-printed Carbon Electrode.

    PubMed

    See, Wong Pooi; Heng, Lee Yook; Nathan, Sheila

    2015-01-01

    A new approach for the development of a highly sensitive aluminium(III) ion sensor via the preconcentration of aluminium(III) ion with a self-assembled monolayer on a gold nanoparticles modified screen-printed carbon electrode and current mediation by potassium ferricyanide redox behavior during aluminium(III) ion binding has been attempted. A monolayer of mercaptosuccinic acid served as an effective complexation ligand for the preconcentration of trace aluminium; this led to an enhancement of aluminium(III) ion capture and thus improved the sensitivity of the sensor with a detection limit of down to the ppb level. Under the optimum experimental conditions, the sensor exhibited a wide linear dynamic range from 0.041 to 12.4 μM. The lower detection limit of the developed sensor was 0.037 μM (8.90 ppb) using a 10 min preconcentration time. The sensor showed excellent selectivity towards aluminium(III) ion over other interference ions.

  1. An overwhelmingly selective colorimetric sensor for Ag(+) using a simple modified polyacrylonitrile fiber.

    PubMed

    Xing, Xiaoli; Yang, Huixiao; Tao, Minli; Zhang, Wenqin

    2015-10-30

    A carboxymethyl-dithiocarbamate immobilized polyacrylonitrile fiber colorimetric sensor has been synthesized. This fiber sensor exhibits excellent selectivity and sensitivity for Ag(+) in aqueous solution with a remarkable color change from light pink to red-brown over a wide pH range of 2-12. The sensor responds selectively to Ag(+) in the presence of other ions, including Mg(2+), Al(3+), Ca(2+), Cr(3+), Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Pb(2+). The colorimetric sensor has an extremely fast response time (10s) and a low visual limit of detection (5.53×10(-12) mol/L). The fiber sensor also undergoes an obvious color change in the presence of Ag(+) solutions containing EDTA, NaCl or NaBr. Density functional theory optimization reveals that the sensor and Ag(+) interact via a seven-membered ring complexation mechanism.

  2. An overwhelmingly selective colorimetric sensor for Ag(+) using a simple modified polyacrylonitrile fiber.

    PubMed

    Xing, Xiaoli; Yang, Huixiao; Tao, Minli; Zhang, Wenqin

    2015-10-30

    A carboxymethyl-dithiocarbamate immobilized polyacrylonitrile fiber colorimetric sensor has been synthesized. This fiber sensor exhibits excellent selectivity and sensitivity for Ag(+) in aqueous solution with a remarkable color change from light pink to red-brown over a wide pH range of 2-12. The sensor responds selectively to Ag(+) in the presence of other ions, including Mg(2+), Al(3+), Ca(2+), Cr(3+), Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Pb(2+). The colorimetric sensor has an extremely fast response time (10s) and a low visual limit of detection (5.53×10(-12) mol/L). The fiber sensor also undergoes an obvious color change in the presence of Ag(+) solutions containing EDTA, NaCl or NaBr. Density functional theory optimization reveals that the sensor and Ag(+) interact via a seven-membered ring complexation mechanism. PMID:25967097

  3. 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.

  4. 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. PMID:26625272

  5. Detection of HbsAg and hATIII genetically modified goats (Caprahircus) by loop-mediated isothermal amplification.

    PubMed

    Tao, Chenyu; Zhang, Qingde; Zhai, Shanli; Liu, Bang

    2013-11-01

    In this study, sensitive and rapid detection systems were designed using a loop-mediated isothermal amplification (LAMP) method to detect the genetically modified goats. A set of 4 primers were designed for each exogenous nucleic acids HBsAg and hATIII. The DNA samples were first amplified with the outer and inner primers and released a single-stranded DNA,of which both ends were stem-loop structure. Then one inner primer hybridized with the loop, and initiated displacement synthesis in less than 1 h. The result could be visualized by both agarose gel electrophoresis and unaided eyes directly after adding SYBR GREEN 1. The detection limit of LAMP was ten copies of target molecules, indicating that LAMP was tenfold more sensitive than the classical PCR. Furthermore, all the samples of genetically modified goats were tested positively by LAMP, and the results demonstrated that the LAMP was a rapid and sensitive method for detecting the genetically modified organism.

  6. Thermodynamics of the adsorption of organic molecules on graphitized carbon black modified with a monolayer of 5-hydroxy-6-methyluracil

    NASA Astrophysics Data System (ADS)

    Gus'kov, V. Yu.; Ivanov, S. P.; Shaikhitdinova, Yu. F.; Kudasheva, F. Kh.

    2016-10-01

    Thermodynamic characteristics of the adsorption of alkanes, alcohols, arenes, and esters on graphitized carbon black with a deposited monolayer (0.17%) of 5-hydroxy-6-methyluracil are studied by means of inverse gas chromatography at infinite dilution. It is established that size effects (violation of the additivity of molar changes in internal energy and the entropy of adsorption for pairs of molecules of one homologous series that differ by one methyl group) are observed when organic molecules are adsorbed on the surface of the resulting adsorbent. The size effects are similar to those observed when 1% 5-hydroxy-6-methyluracil is deposited on graphitized carbon black. It is concluded that the observed violation of additivity is associated with cavities in the supramolecular structure.

  7. Substituent-Controlled Reversible Switching of Charge Injection Barrier Heights at Metal/Organic Semiconductor Contacts Modified with Disordered Molecular Monolayers.

    PubMed

    Nouchi, Ryo; Tanimoto, Takaaki

    2015-07-28

    Electrically stimulated switching of a charge injection barrier at the interface between an organic semiconductor and an electrode modified with a disordered monolayer (DM) is studied by using various benzenethiol derivatives as DM molecules. The switching behavior is induced by a structural change in the DM molecules and is manifested as a reversible inversion of the polarity of DM-modified Au electrode/rubrene/DM-modified Au electrode diodes. The switching direction is found to be dominantly determined by the push-back effect of the thiol bonding group, while the terminal group modulates the switching strength. A device with 1,2-benzenedithiol DMs exhibited the highest switching ratios of 20, 10(2), and 10(3) for the switching voltages of 3, 5, and 7 V, respectively. A variation in the tilt angle of benzenethiol DMs due to the application of 7 V is estimated to be smaller than 23.6° by model calculations. This study offers an understanding for obtaining highly stable operations of organic electronic devices, especially with molecular modification layers. PMID:26161447

  8. Investigation of Pd-Modified Ag-CuO Air Braze Filler Metals

    SciTech Connect

    Darsell, Jens T.; Hardy, John S.; Kim, Jin Yong; Weil, K. Scott

    2006-01-10

    Palladium was added as a ternary component to a series of silver - copper oxide alloys in an effort to increase the use temperature of these materials for potential ceramic air brazing applications. Large portions of the silver component of the Ag-CuO system were substituted by palladium forming the following alloys: (100-y)[(100-z)Pd - (z)Ag] - (y)CuOx where y = 0 - 34 mol% CuOx, z = 50 - 100 mol% silver, and x = 0, 0.5, and 1, denoting copper metal, Cu2O, or CuO. From differential scanning calorimetry, it was determined that the addition of palladium causes an increase in the solidus and liquidus temperatures of the resulting Pd-Ag-CuO brazes. In general, the liquidus was found to increase by approximately 220°C for the (100-y)(25Pd - 75Ag) - (z)CuOx filler metal compositions relative to comparable Ag-CuOx alloys. Likewise, the solidus was found to increase for these alloys, respectively by 185°C and 60°C, respectively for CuOx contents of y = 0 - 1mol% and 4 - 10 mol%. For the (100-y)(50Pd - 50Ag) - (y)CuOx alloys, the solidus increased between 280 - 390°C over a copper oxide compositional range of x = 0 to 8 mol%. It was determined from sessile drop experiments that palladium causes an increase in the wetting angle for all of the samples tested. Alloy compositions of (100-y)(25Pd - 75Ag) - (y)CuOx displayed increased wetting angles of 5-20° relative to comparable binary compositions. (100-y)(50Pd - 50Ag) - (y)CuOx alloys exhibited an increase in contact angle of 10-60° and compositions containing less than 10 mol% CuOx were not able to wet the substrate. Scanning electron microscopy indicates that the microstructure of the braze consists of Ag-Pd solid solution with CuOx precipitates. In general, a reaction layer consisting of CuAlO2 forms adjacent to the alumina substrate. However, the formation of this layer is apparently hindered by the addition of large amounts of palladium, causing poor wetting behavior, as denoted by substantial porosity found along

  9. A highly sensitive hydrogen peroxide sensor based on (Ag-Au NPs)/poly[o-phenylenediamine] modified glassy carbon electrode.

    PubMed

    Shamsipur, Mojtaba; Karimi, Ziba; Amouzadeh Tabrizi, Mahmoud

    2015-11-01

    Herein, the poly(o-phenylenediamine) decorated with gold-silver nanoparticle (Ag-Au NPs) nanocomposite modified glassy carbon was used for the determination of hydrogen peroxide. Electrochemical experiments indicated that the proposed sensor possesses an excellent sensitivity toward the reduction of hydrogen peroxide. The resulting sensor exhibited a good response to hydrogen peroxide over linear range from 0.2 to 60.0μM with a limit of detection of 0.08μM, good reproducibility, long-term stability and negligible interference from ascorbic acid, uric acid and dopamine. The proposed sensor was successfully applied to the determination of hydrogen peroxide in human serum sample.

  10. Changes in the microbiological and chemical characteristics of white bread during storage in paper packages modified with Ag/TiO2-SiO2, Ag/N-TiO2 or Au/TiO2.

    PubMed

    Peter, Anca; Mihaly-Cozmuta, Leonard; Mihaly-Cozmuta, Anca; Nicula, Camelia; Ziemkowska, Wanda; Basiak, Dariusz; Danciu, Virginia; Vulpoi, Adriana; Baia, Lucian; Falup, Anca; Craciun, Grigore; Ciric, Alexandru; Begea, Mihaela; Kiss, Claudia; Vatuiu, Daniela

    2016-04-15

    Microbiological and chemical characteristics of white bread during storage in paper-packages modified with Ag/TiO2-SiO2, Ag/N-TiO2 or Au/TiO2 were investigated. The whiteness and the water retention of the modified packages were slightly superior to those exhibited by the reference sample, as the color of the composite was lighter. The water retention was very good especially for the Ag/TiO2-SiO2-paper. These improvements can be associated with the high specific surface area and with the low agglomeration tendency of Ag nanoparticles in comparison with the Au ones. The preservation activity of the composites for the bread storage is positively influenced by photoactivity and presence of nano-Ag. Packages Ag/TiO2-SiO2-paper and Ag/N-TiO2-paper can find their applicability for extending the shelf life of bread by 2 days as compared with the unmodified paper-package. No influence of the Au/TiO2 on the extending the shelf life of bread was observed. PMID:26617018

  11. Changes in the microbiological and chemical characteristics of white bread during storage in paper packages modified with Ag/TiO2-SiO2, Ag/N-TiO2 or Au/TiO2.

    PubMed

    Peter, Anca; Mihaly-Cozmuta, Leonard; Mihaly-Cozmuta, Anca; Nicula, Camelia; Ziemkowska, Wanda; Basiak, Dariusz; Danciu, Virginia; Vulpoi, Adriana; Baia, Lucian; Falup, Anca; Craciun, Grigore; Ciric, Alexandru; Begea, Mihaela; Kiss, Claudia; Vatuiu, Daniela

    2016-04-15

    Microbiological and chemical characteristics of white bread during storage in paper-packages modified with Ag/TiO2-SiO2, Ag/N-TiO2 or Au/TiO2 were investigated. The whiteness and the water retention of the modified packages were slightly superior to those exhibited by the reference sample, as the color of the composite was lighter. The water retention was very good especially for the Ag/TiO2-SiO2-paper. These improvements can be associated with the high specific surface area and with the low agglomeration tendency of Ag nanoparticles in comparison with the Au ones. The preservation activity of the composites for the bread storage is positively influenced by photoactivity and presence of nano-Ag. Packages Ag/TiO2-SiO2-paper and Ag/N-TiO2-paper can find their applicability for extending the shelf life of bread by 2 days as compared with the unmodified paper-package. No influence of the Au/TiO2 on the extending the shelf life of bread was observed.

  12. Fano Resonance and Spectrally Modified Photoluminescence Enhancement in Monolayer MoS2 Integrated with Plasmonic Nanoantenna Array.

    PubMed

    Lee, Bumsu; Park, Joohee; Han, Gang Hee; Ee, Ho-Seok; Naylor, Carl H; Liu, Wenjing; Johnson, A T Charlie; Agarwal, Ritesh

    2015-05-13

    The manipulation of light-matter interactions in two-dimensional atomically thin crystals is critical for obtaining new optoelectronic functionalities in these strongly confined materials. Here, by integrating chemically grown monolayers of MoS2 with a silver-bowtie nanoantenna array supporting narrow surface-lattice plasmonic resonances, a unique two-dimensional optical system has been achieved. The enhanced exciton-plasmon coupling enables profound changes in the emission and excitation processes leading to spectrally tunable, large photoluminescence enhancement as well as surface-enhanced Raman scattering at room temperature. Furthermore, due to the decreased damping of MoS2 excitons interacting with the plasmonic resonances of the bowtie array at low temperatures stronger exciton-plasmon coupling is achieved resulting in a Fano line shape in the reflection spectrum. The Fano line shape, which is due to the interference between the pathways involving the excitation of the exciton and plasmon, can be tuned by altering the coupling strengths between the two systems via changing the design of the bowties lattice. The ability to manipulate the optical properties of two-dimensional systems with tunable plasmonic resonators offers a new platform for the design of novel optical devices with precisely tailored responses.

  13. Hot compression deformation behavior and a modified physically-based constitutive model of Cu-6 %Ag alloy

    NASA Astrophysics Data System (ADS)

    Meng, Lie; Wang, Menghan; Liu, Xiao; Wang, Fenglin

    2016-04-01

    In order to reveal the flow characteristics of Cu-6 %Ag alloy on the condition of hot deformation, the isothermal compression experiments are carried out at the temperatures of 973-1123 K under strain rates of 0.01-10 s-1. The effects of deformation condition on the hot compression deformation behavior are investigated. The low instability strain (ɛ i) behavior at high strain rate (10 s-1) is discussed in this paper. According to the experiment results and analyses, the deformation twinning and inhomogeneous grains are thought to be the possible reasons for low strain cracking. Then, a modified physically based constitutive model is established. The strain for maximum softening rate (\\varepsilon_{ *} ) is quoted in the constitutive equation which is proved that there is a nearly linear relationship between { ln }\\varepsilon_{ *} and { ln }Z . What's more, the correlation coefficient (R) and the average absolute relative error (AARE) are used to evaluate the accuracy of the established constitutive model. The values of R and AARE are 0.99612 and 3.47 %, respectively, which show that the modified constitutive model can exactly reveal the flow stress of Cu-6 %Ag alloy.

  14. Surface-enhanced Raman scattering of 4-mercaptobenzoic acid and hemoglobin adsorbed on self-assembled Ag monolayer films with different shapes

    NASA Astrophysics Data System (ADS)

    Zhu, Shuangmei; Fan, Chunzhen; Wang, Junqiao; He, Jinna; Liang, Erjun

    2014-06-01

    Polyvinylpyrrolidone (PVP)-protected silver nanostructures of various shapes, including nanocubes, nanospheres, and hybrid shapes with nanospheres and nanorods, on the surface of glass or Si substrates (PVP-Ag films) are prepared by using electrostatic self-assembly. With 4-mercaptobenzoic acid (4-MBA) as a probe molecule, it is demonstrated that the PVP-protected silver nanocubes films (PVP-Ag NCs) have better surface-enhanced Raman scattering (SERS) activity with an order of magnitude larger enhancement factors (EF) than the PVP-protected silver nanospheres films and the PVP-protected silver hybrid shapes films, which is confirmed by our numerical simulations. The EF of 4-MBA on the PVP-Ag NCs film are up to ~5.38 × 106, and the detection limit is at least down to ~10-8 M. The uniformity and reproducibility of the SERS signals on PVP-Ag NCs film are tested by point-to-point and batch-to-batch measurements. Meanwhile, the PVP-Ag films are also shown to be an excellent SERS substrate with good biocompatibility for hemoglobin detection. It is shown that the PVP-Ag NCs films can be used as excellent SERS substrate with good activity, uniformity, reproducibility, and biocompatibility and are promising for a myriad of chemical and biochemical sensing applications.

  15. Electrochemical Properties of a Thiol Monolayers Coated Gold Electrode Modified with Osmium Gel Membrane as Enzyme Sensor

    NASA Astrophysics Data System (ADS)

    Yabutani, Tomoki; Okada, Nobuyuki; Maruyama, Kenichi; Motonaka, Junko

    The electrochemical behavior of an enzyme sensor for glucose using a gold electrode modified with thiol self-assembled membrane and osmium complex gel as an electron transferring mediator has further been investigated by electrochemical analysis. The gold electrode was initially coated with aminomethanethiol self assembling mono layer membrane(thiol-SAM) and then immobilized with glucose oxidase using poly(vinylpyridine-co-allylamine) (PVP-co-AA), gel coordinated with osmium bipyridine complexes (GOD/Os-PVP-co-AA gel). The cleaning condition of the surface of the Au electrode prior to coating thiol SAM was optimized for reduction of interference caused by concomitant compounds. It was found that interfering influence was most efficiently reduced in the case of use of the Au electrode immersed into nitric acid. The current ratio with a thiol coated gold electrode modified with Os-PVP-co-AA gel in glucose solution in the presence to absence of ascorbic acid, acetaminophen, and uric acid (ID+I/II) was 1.006, 1.014, and 1.018, respectively. The peak current response of glucose in the electrode modified with thiol SAM was dropped to 60 98% as compared with that without thiol SAM.

  16. A novel Ag+ cation sensor based on polyamidoamine dendrimer modified with 1,8-naphthalimide derivatives

    NASA Astrophysics Data System (ADS)

    Dodangeh, Mohammad; Gharanjig, Kamaladin; Arami, Mokhtar

    2016-02-01

    In this study, 4-amino-1,8-naphthalimide-conjugated polyamidoamine dendrimer was synthesized and characterized and its potentiality as a cation sensor was investigated. 4-Amino-1,8-naphthalic anhydride reacted with polyamidoamine dendrimer and the product was characterized using FTIR, 1H NMR, 13C NMR and melting point analysis method. The synthesized compound was applied to detect various cations in water media and N,N-dimethylformamide (DMF) via monitoring the quenching of the fluorescence intensity. Furthermore, various metal cations including Cu2 +, Ni2 +, Zn2 +, Pb2 +,Ca2 +, Ba2 +, Cd2 +, Hg2 +, Fe2 +, Fe3 + and Ag+ were tested. The complexes formed between the synthesized compound and metal cations in solution and their effects on Photoinduced Electron Transfer (PET) process were investigated regarding the potential application of the newly-synthesized dendrimer as a colorimetric and fluorescent sensor for such cations. The results clearly confirmed that the 1,8-naphthalimide groups surrounding the central dendrimer core showed strong green fluorescence emission at 553 nm. This effect considerably decreased with the introduction of all cations, except Ag+ where the fluorescence quenching effect was remarkable and more dominant. Therefore, it can be concluded that the synthesized dye has the potentiality of being a highly sensitive and selective fluorescence sensor for Ag+ cation.

  17. Selective recovery of Ag(I) coordination anion from simulate nickel electrolyte using corn stalk based adsorbent modified by ammonia-thiosemicarbazide.

    PubMed

    Xiong, Ying; Wan, Li; Xuan, Jing; Wang, Yongwei; Xing, Zhiqing; Shan, Weijun; Lou, Zhenning

    2016-01-15

    In nickel electrolyte, Ag(I) was present at trace level concentration (10-20 mg L(-1)) and existed in the form of AgCli(1-i) coordination anion, instead of Ag(+) positive ion usually in several sources. In the present study, TSC-NH3-OCS adsorbent based on natural corn stalk modified by ammonia (NH3)-thiosemicarbazide (TSC) was synthesized and characterized using some instrumental techniques. The TSC-NH3-OCS adsorbent could selectively adsorb Ag(I) as AgCl(i)(1-i) coordination anion from the Ag(I)-Cu(II)-Ni(II) simulate nickel electrolyte, especially in the case of the very high levels of Cu(II) and Ni(II), which significantly outperforms the commercial available resins. The adsorption mechanism was believed to be electrostatic interaction of the protonated bands of AgCl4(3-) with protonated thiol form of the thioamide units by FTIR and XPS analysis. The maximum adsorption capacity in the Ag(I) single and Ag(I)-Cu(II)-Ni(II) ternary system were obtained and calculated as 153.54 and 46.69 mg g(-1), respectively. The reasons that the maximum adsorption capacity of AgCl(i)(1-i) from the single and ternary system varied widely could be explained by adsorption kinetic and thermodynamic results. In addition, three successive sorption/desorption cycle runs from ternary system were performed which indicated that the TSC-NH3-OCS adsorbent has a good performance for recovery Ag(I) from simulate nickel electrolyte.

  18. Selective recovery of Ag(I) coordination anion from simulate nickel electrolyte using corn stalk based adsorbent modified by ammonia-thiosemicarbazide.

    PubMed

    Xiong, Ying; Wan, Li; Xuan, Jing; Wang, Yongwei; Xing, Zhiqing; Shan, Weijun; Lou, Zhenning

    2016-01-15

    In nickel electrolyte, Ag(I) was present at trace level concentration (10-20 mg L(-1)) and existed in the form of AgCli(1-i) coordination anion, instead of Ag(+) positive ion usually in several sources. In the present study, TSC-NH3-OCS adsorbent based on natural corn stalk modified by ammonia (NH3)-thiosemicarbazide (TSC) was synthesized and characterized using some instrumental techniques. The TSC-NH3-OCS adsorbent could selectively adsorb Ag(I) as AgCl(i)(1-i) coordination anion from the Ag(I)-Cu(II)-Ni(II) simulate nickel electrolyte, especially in the case of the very high levels of Cu(II) and Ni(II), which significantly outperforms the commercial available resins. The adsorption mechanism was believed to be electrostatic interaction of the protonated bands of AgCl4(3-) with protonated thiol form of the thioamide units by FTIR and XPS analysis. The maximum adsorption capacity in the Ag(I) single and Ag(I)-Cu(II)-Ni(II) ternary system were obtained and calculated as 153.54 and 46.69 mg g(-1), respectively. The reasons that the maximum adsorption capacity of AgCl(i)(1-i) from the single and ternary system varied widely could be explained by adsorption kinetic and thermodynamic results. In addition, three successive sorption/desorption cycle runs from ternary system were performed which indicated that the TSC-NH3-OCS adsorbent has a good performance for recovery Ag(I) from simulate nickel electrolyte. PMID:26368801

  19. Enhanced photovoltaic performance of QDSSCs via modifying ZnO photoanode with a 3-PPA self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Yang, Lili; Chen, Gang; Sun, Yunfei; Han, Donglai; Yang, Shuo; Gao, Ming; Wang, Zhe; Zou, Ping; Luan, Hongmei; Kong, Xiangwang; Yang, Jinghai

    2015-02-01

    A SAMs layer of 3-PPA with a phosphonic acid headgroup and carboxylic acid tailgroups has been used to modify the surface of ZnO nanorods photoanode in CdS quantum dots sensitized solar cells. Its effects on the photovoltic performance have been investigated in detail by adjusting the concentration and deposition time of 3-PPA. Especially, we utilize ultraviolet photoelectron spectroscopy to characterize the variation of band alignment after introducing 3-PPA layer in the solar cells. The results reveal that the 3-PPA not only suppress the electron-hole recombination process due to its passivation on the surface defects, but forms an energy barrier to efficiently retard the back transfer of electrons, which finally results in the enhancement of conversion efficiency of solar cells.

  20. Enhanced photocatalytic, electrochemical and photoelectrochemical properties of TiO2 nanotubes arrays modified with Cu, AgCu and Bi nanoparticles obtained via radiolytic reduction

    NASA Astrophysics Data System (ADS)

    Nischk, Michał; Mazierski, Paweł; Wei, Zhishun; Siuzdak, Katarzyna; Kouame, Natalie Amoin; Kowalska, Ewa; Remita, Hynd; Zaleska-Medynska, Adriana

    2016-11-01

    TiO2 nanotubes arrays (NTs), obtained via electrochemical anodization of Ti foil, were modified with monometallic (Cu, Bi) and bimetallic (AgCu) nanoparticles. Different amounts of metals' precursors were deposited on the surface of NTs by the spin-coating technique, and the reduction of metals was performed via gamma radiolysis. Surface modification of titania was studied by EDS and XPS analysis. The results show that AgCu nanoparticles exist in a Agcore-Cushell form. Photocatalytic activity was examined under UV irradiation and phenol was used as a model pollutant of water. Over 95% of phenol degradation was achieved after 60 min of irradiation for almost all examined samples, but only slight difference in degradation efficiency (about 3%) between modified and bare NTs was observed. However, the initial phenol degradation rate and TOC removal efficiency was significantly enhanced for the samples modified with 0.31 and 0.63 mol% of Bi as well as for all the samples modified with Cu and AgCu nanoparticles in comparison with bare titania nanotubes. The saturated photocurrent, under the influence of simulated solar light irradiation, for the most active Bi- and AgCu-modified samples, was over two times higher than for pristine NTs. All the examined materials were resistant towards photocorrosion processes that enables their application for long term processes induced by light.

  1. Strong improvements of localized surface plasmon resonance sensitivity by using Au/Ag bimetallic nanostructures modified with polydopamine films.

    PubMed

    Jia, Kun; Khaywah, Mohammad Y; Li, Yugang; Bijeon, Jean L; Adam, Pierre M; Déturche, Régis; Guelorget, Bruno; François, Manuel; Louarn, Guy; Ionescu, Rodica E

    2014-01-01

    In the present work, the standard monometallic localized surface plasmon resonance (LSPR) biosensing sensitivity is highly improved when using a new system based on glass substrates modified with high-temperature annealed gold/silver bimetallic nanoparticles (Au/Ag bimetallic NPs) coated with polydopamine films before biomolecule specific immobilization. Thus, different zones of bimetallic NPs are spatially created onto a glass support thanks to a commercial transmission electron microscopy (TEM) grid marker in combination with two sequential evaporations of continuous films of gold (4 nm) and silver (2 nm) and followed by annealing at 500 °C for 8 h. By using the scanning electron microscopy (SEM), it is found that annealed Au/Ag bimetallic NPs have uniform size and shape distribution that exhibited a sharper well-defined LSPR resonant peak when compared with that of monometallic Au NPs and thereby contributing to an improved sensitivity in LSPR biosensor application. The controlled micropatterns consisting of bimetallic particles are used in the construction of LSPR biochips for high-throughput detection of different concentrations of a model antigen named bovine serum albumin (BSA) on a single glass sample, with a lower limit of detection of 0.01 ng/mL under the optimized conditions.

  2. Au-loaded TiO2 and Ag-loaded TiO2 synthesized by modified sol-gel/impregnation method as photocatalysts

    NASA Astrophysics Data System (ADS)

    Ninsonti, Hathaithip; Sriwichai, Saengrawee; Wetchakun, Natda; Kangwansupamonkon, Wiyong; Phanichphant, Sukon

    2016-02-01

    In this work, Au-loaded TiO2 and Ag-loaded TiO2 nanoparticles were synthesized by modified sol-gel method together with impregnation method. The samples were characterized by their physicochemical properties using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy in order to obtain the correlation between structure and photocatalytic properties. XRD results indicated unloaded TiO2, Au-loaded TiO2 and Ag-loaded TiO2 nanoparticles were all in the anatase phase with average crystallite size in the range of 10-13 nm. In addition, XPS analysis confirmed the presence of Au and Ag elements in Au-loaded TiO2 and Ag-loaded TiO2 nanoparticles, respectively. The photocatalytic activities of TiO2, Au-loaded TiO2 and Ag-loaded TiO2 nanoparticles were evaluated through the mineralization of formic acid under UV-light illumination. The results showed that Au-loading and Ag-loading could effectively improve the photocatalytic activities of TiO2. Furthermore, Au-loaded TiO2 exhibited a higher photocatalytic activity than Ag-loaded TiO2.

  3. Graphite-like C3N4 modified Ag3PO4 nanoparticles with highly enhanced photocatalytic activities under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Xiu, Zhiliang; Bo, Hai; Wu, Yongzhong; Hao, Xiaopeng

    2014-01-01

    Graphite-like C3N4 (g-C3N4) modified Ag3PO4 nanoparticles with highly enhanced photocatalytic activities under visible light irradiation (λ ≥ 400 nm) compared to the bare Ag3PO4 nanoparticles were prepared by a facile chemisorption method. The resulting C3N4/Ag3PO4 composite photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and ultraviolet-visible diffuse reflectance spectra (DRS). Enhanced charge separation efficiency was confirmed by electrochemical impedance spectroscopy (EIS) measurements. The enhanced photocatalytic activities were mainly ascribed to the synergistic effect between C3N4 and Ag3PO4 which led to an improved separation efficiency of electron-hole pairs. The high-efficient hybrid photocatalysts are expected to show considerable potential applications in wastewater treatment and water splitting.

  4. Structural and electrical properties of microwave processed Ag modified KNN-LS ceramics.

    PubMed

    Palei, Prakash; Kumar, Pawan; Agrawal, Dinesh K

    2012-01-01

    Microwave processing steps of 0.95[(K0.5Na0.5)0.94Ag0.06NbO3]-0.05[LiSbO3]/(KNAN-LS) lead free ferroelectric ceramics were optimized for better densification and electrical properties. Calcination temperature and time for single perovskite phase formation were optimized and found to be 850 degrees C for 60 min., respectively. Crystal structural study revealed the presence of mixed structure in the microwave processed (MWP) KNAN-LS ceramics. The sintering of the KNAN-LS ceramics was carried out at 1080 degrees C for 10 min, 20 min and 30 min, respectively, and the sample sintered for 20 min exhibited best properties.

  5. AC loss in stacks of Bi-2223/Ag tapes modified with ferromagnetic covers at the edges

    NASA Astrophysics Data System (ADS)

    Safran, S.; Gömöry, F.; Gencer, Ali

    2010-10-01

    We investigated the magnetization loss of stacked Bi-2223/Ag tapes with a ferromagnetic cover on the edges. Such modification has been found recently to reduce the AC loss of a single tape; however, the behavior in a coil winding could be different. With experiments and numerical calculations we show that a ferromagnetic cover on the edges of a superconducting tape could reduce its magnetization loss also when the tapes are arranged in a stack. The effect is weaker for larger numbers of tapes but nevertheless remained significant in a stack of four tapes, which was the maximum number studied here. The effects observed experimentally are nicely explained by the results of numerical calculations.

  6. Perforated monolayers

    SciTech Connect

    Regen, S.L.

    1989-12-01

    The goals of this DOE-sponsored program are to create novel organic thin films that possess well-defined and adjustable molecular pores; i.e. perforated monolayers,'' and to use such film for fabricating composite membranes that have unique permeation characteristics. The specific strategy that has been adopted involves (1) the synthesis of surfactant molecules bearing internal pores, i.e., porous surfactants,'' (2) the assembly of such molecules at an air--water interface, and (3) the stabilization of the resulting assembly via polymerization, before or after transfer to a macroporous support. Research that has been carried out to date has demonstrated the feasibility of using suitably designed calix(n)arene molecules as a basis for constructing perforated monolayers. Specifically, a broad range of calix(n)arenes have been mercurated with mercury trifluoracetate, and used to form polymerized and porous monolayers at the air--water interface. In related studies, p-tert- butylcalix(6)arene has been shown to produce stable monolayers at the air--water interface; removal of the p-tert-butyl groups afford a unique vesicle-forming surfactant, calix(6)arene.

  7. Immobilization of horseradish peroxidase to a nano-Au monolayer modified chitosan-entrapped carbon paste electrode for the detection of hydrogen peroxide.

    PubMed

    Lei, Cun-Xi; Hu, Shun-Qin; Shen, Guo-Li; Yu, Ru-Qin

    2003-04-10

    A procedure for fabricating an enzyme electrode has been described based on the effective immobilization of horseradish peroxidase (HRP) to a nano-scaled particulate gold (nano-Au) monolayer modified chitosan-entrapped carbon paste electrode (CCPE). The high affinity of chitosan entrapped in CCPE for nano-Au associated with its amino groups has been utilized to realize the use of nano-Au as an intermediator to retain high bioactivity of the enzyme. Hydrogen peroxide (H(2)O(2)) was determined in the presence of hydroquinone as a mediator to transfer electrons between the electrode and HRP. The HRP immobilized on nano-Au displayed excellent electrocatalytical activity to the reduction of H(2)O(2). The effects of experimental variables such as the operating potential of the working electrode, mediator concentration and pH of measuring solution were investigated for optimum analytical performance by using an amperometric method. The enzyme electrode provided a linear response to hydrogen peroxide over a concentration range of 1.22 x 10(-5)-2.43 x 10(-3) mol l(-1) with a sensitivity of 0.013 A l mol(-1) cm(-2) and a detection limit of 6.3 micromol l(-1) based on signal per noise =3. The apparent Michaelis-Menten constant (K(m)(app)) for the sensor was found to be 0.36 mmol l(-1). The lifetime, fabrication reproducibility and measurement repeatability were evaluated with satisfactory results. The analysis results of real sample by this sensor were in satisfactory agreement with those of the potassium permanganate titration method. PMID:18968988

  8. Effect of surface chemical composition on the surface potential and iso-electric point of silicon substrates modified with self-assembled monolayers.

    PubMed

    Kuo, Che-Hung; Chang, Hsun-Yun; Liu, Chi-Ping; Lee, Szu-Hsian; You, Yun-Wen; Shyue, Jing-Jong

    2011-03-01

    Self-assembled monolayer (SAM)-modified nano-materials are a new technology to deliver drug molecules. While the majority of these depend on covalently immobilizing molecules on the surface, it is proposed that electrostatic interactions may be used to deliver drugs. By tuning the surface potential of solid substrates with SAMs, drug molecules could be either absorbed on or desorbed from substrates through the difference in electrostatic interactions around the selected iso-electric point (IEP). In this work, the surface of silicon substrates was tailored with various ratios of 3-aminopropyltrimethoxysilane (APTMS) and 3-mercaptopropyltrimethoxysilane (MPTMS), which form amine- and thiol-bearing SAMs, respectively. The ratio of the functional groups on the silicon surface was quantified by X-ray photoelectron spectrometry (XPS); in general, the deposition kinetics of APTMS were found to be faster than those of MPTMS. Furthermore, for solutions with high MPTMS concentrations, the relative deposition rate of APTMS increased dramatically due to the acid-base reaction in the solution and subsequent electrostatic interactions between the molecules and the substrate. The zeta potential in aqueous electrolytes was determined with an electro-kinetic analyzer. By depositing SAMs of binary functional groups in varied ratios, the surface potential and IEP of silicon substrates could be fine-tuned. For <50% amine concentration in SAMs, the IEP changed linearly with the chemical composition from <2 to 7.18. For higher amine concentrations, the IEP slowly increased with concentration to 7.94 because the formation of hydrogen-bonding suppressed the subsequent protonation of amines.

  9. Electrochemical degradation of carbamazepine using modified electrode with graphene-AuAg composite

    NASA Astrophysics Data System (ADS)

    Pogacean, F.; Biris, A. R.; Socaci, C.; Floare-Avram, V.; Rosu, M. C.; Coros, M.; Pruneanu, S.

    2015-12-01

    Carbamazepine is a pharmaceutical drug which has been detected in surface and drinking water primarily due to human usage but also from the accidental disposal of pharmaceuticals into sewers. We have developed a graphene-modified electrode which was tested at the detection and degradation of carbamazepine. The oxidation process was studied by cyclic voltammetry in aqueous and organic solutions. The electrochemical degradation of carbamazepine was performed by polarizing the working electrode at a certain potential, for different times (from 5 to 60 minutes). The degradation efficiency was highly dependent on the type of solution and on the supporting electrolyte.

  10. Perforated monolayers

    SciTech Connect

    Regen, S.L.

    1992-01-01

    Our research over this past grant period has focused on (1) developing methods for making in situ permeation measurements at the air-water interface, (2) defining the structural and conformational behavior of selected calix(4)arenes, (3) defining the metal complexation properties of certain upper-rim functionalized calix(4)arenes, and (4) synthesizing a broad series of polymerizable calixarenes, to be used for constructing perforated monolayers and multilayers.

  11. Amperometric sensing of anti-HIV drug zidovudine on Ag nanofilm-multiwalled carbon nanotubes modified glassy carbon electrode.

    PubMed

    Rafati, Amir Abbas; Afraz, Ahmadreza

    2014-06-01

    The zidovudine (ZDV) is the first drug approved for the treatment of HIV virus infection. The detection and determination of this drug are very importance in human serum because of its undesirable effects. A new ZDV sensor was fabricated on the basis of nanocomposite of silver nanofilm (Ag-NF) and multiwalled carbon nanotubes (MWCNTs) immobilized on glassy carbon electrode (GCE). The modified electrodes were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), cyclic voltammetry (CV), and linear sweep voltammetry (LSV) techniques. Results showed that the electrodeposited silver has a nanofilm structure and further electrochemical studies showed that the prepared nanocomposite has high electrocatalytic activity and is appropriate for using in sensors. The amperometric technique under optimal conditions is used for the determination of ZDV ranging from 0.1 to 400ppm (0.37μM-1.5mM) with a low detection limit of 0.04ppm (0.15μM) (S/N=3) and good sensitivity. The prepared sensor possessed accurate and rapid response to ZDV and shows an average recovery of 98.6% in real samples.

  12. Antifungal activity of Ag:hydroxyapatite thin films synthesized by pulsed laser deposition on Ti and Ti modified by TiO2 nanotubes substrates

    NASA Astrophysics Data System (ADS)

    Eraković, S.; Janković, A.; Ristoscu, C.; Duta, L.; Serban, N.; Visan, A.; Mihailescu, I. N.; Stan, G. E.; Socol, M.; Iordache, O.; Dumitrescu, I.; Luculescu, C. R.; Janaćković, Dj.; Miškovic-Stanković, V.

    2014-02-01

    Hydroxyapatite (HA) is a widely used biomaterial for implant thin films, largely recognized for its excellent capability to chemically bond to hard tissue inducing the osteogenesis without immune response from human tissues. Nowadays, intense research efforts are focused on development of antimicrobial HA doped thin films. In particular, HA doped with Ag (Ag:HA) is expected to inhibit the attachment of microbes and contamination of metallic implant surface. We herewith report on nano-sized HA and Ag:HA thin films synthesized by pulsed laser deposition on pure Ti and Ti modified with 100 nm diameter TiO2 nanotubes (fabricated by anodization of Ti plates) substrates. The HA-based thin films were characterized by SEM, AFM, EDS, FTIR, and XRD. The cytotoxic activity was tested with HEp2 cells against controls. The antifungal efficiency of the deposited layers was tested against the Candida albicans and Aspergillus niger strains. The Ti substrates modified with TiO2 nanotubes covered with Ag:HA thin films showed the highest antifungal activity.

  13. Study of Ag-Pd bimetallic nanoparticles modified glassy carbon electrode for detection of L-cysteine

    NASA Astrophysics Data System (ADS)

    Murugavelu, M.; Karthikeyan, B.

    2014-11-01

    Ag-Pd bimetallic nanoparticles (Ag-Pd BNPs) as an enhanced sensing material with improved electronic transmission rates in the electrochemical sensing of L-cysteine (L-cys) has been reported. The morphology of Ag-Pd BNPs was characterized with X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and cyclic voltammetry (CV). Oxidation of L-cys on Ag-Pd BNPs is investigated in detail by discussing the effect of the structure and from the electrocatalytic oxidation of L-cys. We found that the Ag-Pd BNPs exhibited high electrocatalytic activity towards L-cys oxidation in neutral condition and could be used for the development of nonenzymatic L-cys sensor. Based on the efficient catalytic ability of Ag-Pd BNPs, the fabricated biosensor exhibited a wide linear range of responses to the L-cys with the concentration detection limit of nearly down to 2 mM with fast response time.

  14. Detection of Molecular Monolayers by Optical Second-Harmonic Generation

    SciTech Connect

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

    1980-12-22

    Second harmonic generation is shown to be sensitive enough to detect molecular monolayers adsorbed on a silver surface. Adsorption of AgCl and pyridine on silver during and after an electrolytic cycle can be easily observed,

  15. Perforated monolayers

    SciTech Connect

    Regen, S.L.

    1992-12-01

    Goal of this research program is to create ultrathin organic membranes that possess uniform and adjustable pores ( < 7[angstrom] diameter). Such membranes are expected to possess high permeation selectivity (permselectivity) and high permeability, and to provide the basis for energy-efficient methods of molecular separation. Work carried out has demonstrated feasibility of using perforated monolayer''-based composites as molecular sieve membranes. Specifically, composite membranes derived from Langmuir-Blodgett multilayers of the calix[6]arene-based surfactant shown below plus poly[l-(trimethylsilyl)-l-propyne] (PTMSP) were found to exhibit sieving behavior towards He, N[sub 2] and SF[sub 6]. Results of derivative studies that have also been completed are also described in this report.

  16. Enhancement of critical current density in YBa2Cu3O7-dgr thin films grown using PLD on YSZ (001) surface modified with Ag nano-dots

    NASA Astrophysics Data System (ADS)

    Ionescu, M.; Li, A. H.; Zhao, Y.; Liu, H. K.; Crisan, A.

    2004-07-01

    Y123 thin films were grown by pulsed laser deposition (PLD) on YSZ (001) substrate. Prior to the film deposition, a discontinuous layer of Ag was deposited on the substrate, also using PLD, in the form of separate islands. Atomic force microscopy (AFM) investigation of the Ag layer showed that its morphology consisted of self-assembled islands of nanometre size, randomly distributed on the surface of the substrate, called nano-dots. The Y123 superconducting films grown on such a surface were characterized using AFM, x-ray diffraction, secondary electron microscopy, ac susceptibility and dc magnetization. The results show that there is no significant difference in surface morphology, crystallographic orientation, phase composition or superconducting transition temperature between the Y123 films grown on YSZ (001) with an Ag nano-dots layer and a control Y123 film grown on a virgin YSZ (001) surface. On the other hand, at 77 K, the magnetic critical current density ( J_c^m ) was three times higher for the Y123 film grown on YSZ with the modified (001) surface than for the film grown on YSZ with a virgin (001) surface. At 5 K the enhancement of J_c^m was approximately seven times, at both low and high fields. This suggests an increase in pinning, caused presumably by point defects formed in the Y123 film above the Ag islands.

  17. Bienzyme HRP-GOx-modified gold nanoelectrodes for the sensitive amperometric detection of glucose at low overpotentials.

    PubMed

    Delvaux, Marc; Walcarius, Alain; Demoustier-Champagne, Sophie

    2005-02-15

    Gold nanotubular electrode ensembles were prepared by using electroless deposition of the metal within the pores of polycarbonate track-etched membranes. Mono-enzyme (GOx) and monolayer/bilayer bienzyme (GOx/HRP) bioelectrodes were prepared by immobilizing the enzymes onto gold nanotubes surfaces modified with mercaptoethylamine. Batch amperometric responses to glucose for the different bioelectrodes were determined and compared. The response of the two geometries (monolayer and bilayer) of the bienzyme electrodes was shown to vary with regard to sensitivity at detection potentials above 0V. On the contrary, at detection potentials below 0V, no noticeable influence of the configuration of the bienzyme on the response intensity was observed. The mono-enzyme (650 microAmM-1 in benzoquinone (BQ) at -0.8 V versus Ag/AgCl) and the two bienzyme bioelectrodes (+/-400 microAmM-1 in hydroquinone (H2Q) at -0.2V versus Ag/AgCl) display remarkable sensitivities compared to a classical GOx-modified gold macroelectrode (13 microAmM-1 in BQ at -0.8 V versus Ag/AgCl). A remarkable feature of the bienzyme electrodes is the possibility to detect glucose at very low applied potentials where the noise level and interferences from other electro-oxidizable compounds are minimal. Another important characteristic of the monolayer bienzyme electrode is the possible existence of a direct electronic communication between HRP and the transducer surface.

  18. Improved performance of Ag-doped TiO2 synthesized by modified sol-gel method as photoanode of dye-sensitized solar cell

    NASA Astrophysics Data System (ADS)

    Gupta, Arun Kumar; Srivastava, Pankaj; Bahadur, Lal

    2016-08-01

    Ag-doped TiO2 with Ag content ranging from 1 to 7 mol% was synthesized by a modified sol-gel route, and its performance as the photoanode of dye-sensitized solar cells (DSSCs) was compared with undoped TiO2 photoanode. Titanium(IV)isopropoxide was used as precursor and hexamethylenetetramine as the capping agent. XRD results show the formation of TiO2 nanoparticles with an average crystallite size of 5 nm (1 % Ag-doped TiO2) and 9 nm (undoped TiO2), respectively. The TiO2 nanopowder was used to prepare its thin film photoelectrode using doctor's blade method. Significant improvement in light-to-energy conversion efficiency was achieved when thin films of 1 % Ag-doped TiO2 were applied as photoanode in DSSC taking N719 as the sensitizer dye. As evidenced by EIS measurements, the electron lifetime of DSSC with Ag-doped TiO2 increased from 1.33 (for undoped TiO2) to 2.05 ms. The short-circuit current density ( J sc), open-circuit voltage ( V oc), fill factor (FF) and the overall energy conversion efficiency ( η) were 1.07 mA cm-2, 0.72 V, 0.73 and 0.40 %, respectively, with the use of 1 % Ag-doped TiO2 photoanode, whereas with undoped TiO2 under similar conditions, J sc = 0.63 mA cm-2, V oc = 0.70 V, fill factor 0.45 and conversion efficiency 0.14 % could be obtained. Therefore, compared with the reference DSSC containing an undoped TiO2 photoanode, the power conversion efficiency of the cell based on Ag-doped TiO2 has been remarkably enhanced by ~70 %. The substantial improvement in the device performance is attributed to the reduced band-gap energy, retarded charge recombination and greater surface coverage of the sensitizing dye over Ag-doped TiO2, which ultimately resulted in improved IPCE, J SC and η values.

  19. Improvement of BCG protective efficacy with a novel chimpanzee adenovirus and a modified vaccinia Ankara virus both expressing Ag85A

    PubMed Central

    Stylianou, E.; Griffiths, K.L.; Poyntz, H.C.; Harrington-Kandt, R.; Dicks, M.D.; Stockdale, L.; Betts, G.; McShane, H.

    2015-01-01

    A replication-deficient chimpanzee adenovirus expressing Ag85A (ChAdOx1.85A) was assessed, both alone and in combination with modified vaccinia Ankara also expressing Ag85A (MVA85A), for its immunogenicity and protective efficacy against a Mycobacterium tuberculosis (M.tb) challenge in mice. Naïve and BCG-primed mice were vaccinated or boosted with ChAdOx1.85A and MVA85A in different combinations. Although intranasally administered ChAdOx1.85A induced strong immune responses in the lungs, it failed to consistently protect against aerosol M.tb challenge. In contrast, ChAdOx1.85A followed by MVA85A administered either mucosally or systemically, induced strong immune responses and was able to improve the protective efficacy of BCG. This vaccination regime has consistently shown superior protection over BCG alone and should be evaluated further. PMID:26478198

  20. Photo-reduction of bromate in drinking water by metallic Ag and reduced graphene oxide (RGO) jointly modified BiVO4 under visible light irradiation.

    PubMed

    Chen, Fei; Yang, Qi; Zhong, Yu; An, Hongxue; Zhao, Jianwei; Xie, Ting; Xu, Qiuxiang; Li, Xiaoming; Wang, Dongbo; Zeng, Guangming

    2016-09-15

    Bromate (BrO3(-)), an oxyhalide disinfection by-product (DBP) in drinking water, has been demonstrated to be carcinogenic and genotoxic. In the current work, metallic Ag and reduced graphene oxide (RGO) co-modified BiVO4 was successfully synthesized by a stepwise chemical method coupling with a photo-deposition process and applied in the photo-reduction of BrO3(-) under visible light irradiation. In this composite, metallic Ag acted as an electron donor or mediator and RGO enhanced the BrO3(-) adsorption onto the surface of catalysts as well as an electron acceptor to restrict the recombination of photo-generated electron-hole pairs. The Ag@BiVO4@RGO composite exhibited greater photo-reduction BrO3(-) performance than pure BiVO4, Ag@BiVO4 and RGO@BiVO4 under identical experimental conditions: initial BrO3(-) concentration 150 μg/L, catalyst dosage 0.5 g/L, pH 7.0 and visible light (λ > 420 nm). The photoluminescence spectra (PL), electron-spin resonance (ESR), photocurrent density (PC) and electrochemical impedance spectroscopy (EIS) measurements indicated that the modified BiVO4 enhanced the photo-generated electrons and separated the electron-hole pairs. The photocatalytic reduction efficiency for BrO3(-) removal decreased with the addition of electron quencher K2S2O8, suggesting that electrons were the primary factor in this photo-reduction process. The declining photo-reduction efficiency of BrO3(-) in tap water should attribute to the consumption of photo-generated electrons by coexisting anions and the adsorption of dissolved organic matter (DOM) on graphene surface. The overall results indicate a promising application potential for photo-reduction in the DBPs removal from drinking water.

  1. Photo-reduction of bromate in drinking water by metallic Ag and reduced graphene oxide (RGO) jointly modified BiVO4 under visible light irradiation.

    PubMed

    Chen, Fei; Yang, Qi; Zhong, Yu; An, Hongxue; Zhao, Jianwei; Xie, Ting; Xu, Qiuxiang; Li, Xiaoming; Wang, Dongbo; Zeng, Guangming

    2016-09-15

    Bromate (BrO3(-)), an oxyhalide disinfection by-product (DBP) in drinking water, has been demonstrated to be carcinogenic and genotoxic. In the current work, metallic Ag and reduced graphene oxide (RGO) co-modified BiVO4 was successfully synthesized by a stepwise chemical method coupling with a photo-deposition process and applied in the photo-reduction of BrO3(-) under visible light irradiation. In this composite, metallic Ag acted as an electron donor or mediator and RGO enhanced the BrO3(-) adsorption onto the surface of catalysts as well as an electron acceptor to restrict the recombination of photo-generated electron-hole pairs. The Ag@BiVO4@RGO composite exhibited greater photo-reduction BrO3(-) performance than pure BiVO4, Ag@BiVO4 and RGO@BiVO4 under identical experimental conditions: initial BrO3(-) concentration 150 μg/L, catalyst dosage 0.5 g/L, pH 7.0 and visible light (λ > 420 nm). The photoluminescence spectra (PL), electron-spin resonance (ESR), photocurrent density (PC) and electrochemical impedance spectroscopy (EIS) measurements indicated that the modified BiVO4 enhanced the photo-generated electrons and separated the electron-hole pairs. The photocatalytic reduction efficiency for BrO3(-) removal decreased with the addition of electron quencher K2S2O8, suggesting that electrons were the primary factor in this photo-reduction process. The declining photo-reduction efficiency of BrO3(-) in tap water should attribute to the consumption of photo-generated electrons by coexisting anions and the adsorption of dissolved organic matter (DOM) on graphene surface. The overall results indicate a promising application potential for photo-reduction in the DBPs removal from drinking water. PMID:27311108

  2. Enzyme-modified nanoparticles using biomimetically synthesized silica.

    PubMed

    Zamora, Patricia; Narváez, Arántzazu; Domínguez, Elena

    2009-09-01

    The entrapment of enzymes within biomimetic silica nanoparticles offers unique and simple immobilization protocols that merge the stability of proteins confined in solid phases with the high loading and reduced diffusion limitations inherent to nano-sized structures. Herein, we report on the biomimetic silica entrapment of chemically derivatized horseradish peroxidase for amperometric sensing applications. Scanning electron microscopy shows evidence of the formation of enzyme-modified nanospheres using poly(ethylenimine) as a template for silicic acid condensation. When these nanospheres are directly deposited on graphite electrodes, chemically modified anionic peroxidase shows direct electron transfer at 0 mV vs Ag|AgCl. Microgravimetric measurements as well as SEM images demonstrate that negatively charged peroxidase is also entrapped when silica precipitates at gold electrodes are modified with a self-assembled monolayer of poly(ethylenimine). Electrostatic interactions may play a crucial role for efficient enzyme entrapment and silica condensation at the PEI template monolayer. The in-situ biomimetically synthesized peroxidase nanospheres are catalytically active, enabling direct bioelectrocatalysis at 0 mV vs Ag|AgCl with long-term stability.

  3. Extracellular Polymeric Substances (EPS) of Freshwater Biofilms Stabilize and Modify CeO2 and Ag Nanoparticles

    PubMed Central

    Kroll, Alexandra; Behra, Renata; Kaegi, Ralf; Sigg, Laura

    2014-01-01

    Streams are potential receiving compartments for engineered nanoparticles (NP). In streams, NP may remain dispersed or settle to the benthic compartment. Both dispersed and settling NP can accumulate in benthic biofilms called periphyton that are essential to stream ecosystems. Periphytic organisms excrete extracellular polymeric substances (EPS) that interact with any material reaching the biofilms. To understand the interaction of NP with periphyton it is therefore crucial to study the interaction of NP with EPS. We investigated the influence of EPS on the physicochemical properties of selected NP (CeO2, Ag) under controlled conditions at pH 6, 7.6, 8.6 and light or dark exposure. We extracted EPS from five different periphyton communities, characterized the extracts, and exposed CeO2 and carbonate-stabilized Ag NP (0.5 and 5 mg/L, both 25 nm primary particle size) and AgNO3 to EPS (10 mg/L) over two weeks. We measured NP size distribution, shape, primary particle size, surface plasmon resonance, and dissolution. All EPS extracts were composed of biopolymers, building blocks of humic substances, low molecular weight (Mr) acids, and small amphiphilic or neutral compounds in varying concentrations. CeO2 NP were stabilized by EPS independent of pH and light/dark while dissolution increased over time in the dark at pH 6. EPS induced a size increase in Ag NP in the light with decreasing pH and the formation of metallic Ag NP from AgNO3 at the same conditions via EPS-enhanced photoreduction. NP transformation and formation were slower in the extract with the lowest biopolymer and low Mr acid concentrations. Periphytic EPS in combination with naturally varying pH and light/dark conditions influence the properties of the Ag and CeO2 NP tested and thus the exposure conditions within biofilms. Our results indicate that periphytic organisms may be exposed to a constantly changing mixture of engineered and naturally formed Ag NP and Ag+. PMID:25333364

  4. Ag electrode modified with polyhexamethylene biguanide stabilized silver nanoparticles: a new type of SERS substrates for detection of enzymatically generated thiocholine

    NASA Astrophysics Data System (ADS)

    Tepanov, A. A.; Nechaeva, N. L.; Prokopkina, T. A.; Kudrinskiy, A. A.; Kurochkin, I. N.; Lisichkin, G. V.

    2015-11-01

    The detection of thiocholine is one of the most widespread techniques for estimation of the cholinesterase activity - acetylcholinesterase and butyrylcholinesterase. Both cholinesterases can be inhibited by organophosphates and carbamates and accordingly can be considered for estimation of these pollutants in the environment. In the current work, SERS spectroscopy was applied for the thiocholine detection. The Ag electrodes modified with silver nanoparticles stabilized by polyhexamethylene biguanide were for the first time suggested as SERS-substrates for that purpose. Such electrodes can be applicable for SERS detection of submicromolar concentrations of thiocholine.

  5. Preparation and optimization of a bienzymic biosensor based on self-assembled monolayer modified gold electrode for alcohol and glucose detection.

    PubMed

    Asav, Engin; Akyilmaz, Erol

    2010-01-15

    The aim of this project was to develop a bienzymic biosensor, which was based on co-immobilization of alcohol oxidase and glucose oxidase on the same electrode by formation of self-assembled monolayer (SAM) for selective determination of ethanol and glucose. In the biosensor construction the enzymes and the mediator, tetrathiafulvalene (TTF), were immobilized with cross-linking agents glutaraldehyde and cysteamine by forming a self-assembled monolayer (SAM) on a gold disc electrode. Amounts of ethanol and glucose were amperometrically detected by monitoring current values at reduction potential of TTF(+), 0.1V. Decreases in biosensor responses were linearly related to glucose concentrations between 0.1 and 1.0 mM and ethanol concentrations between 1.0 and 10 mM. Limits of detection of the biosensor for ethanol and glucose were calculated to be 0.75 and 0.03 mM, respectively. In the optimization studies of the biosensor some parameters such as optimum pH, optimum temperature, enzyme amount, effect of TTF concentration and duration of SAM formation were investigated. PMID:19819124

  6. Diffusion across the modified polyethylene separator GX in the heat-sterilizable AgO-Zn battery

    NASA Technical Reports Server (NTRS)

    Lutwack, R.

    1973-01-01

    Models of diffusion across an inert membrane have been studied using the computer program CINDA. The models were constructed to simulate various conditions obtained in the consideration of the diffusion of Ag (OH)2 ions in the AgO-Zn battery. The effects on concentrations across the membrane at the steady state and on the fluxout as a function of time were used to examine the consequences of stepwise reducing the number of sources of ions, of stepwise blocking the source and sink surfaces, of varying the magnitude of the diffusion coefficient for a uniform membrane, of varying the diffusion coefficient across the membrane, and of excluding volumes to diffusion.

  7. Destabilization of Ag nanoislands on Ag(100) by adsorbed sulfur

    SciTech Connect

    Shen, Mingmin; Russell, Selena M.; Liu, Da-Jiang; Thiel, Patricia A.

    2011-10-17

    Sulfur accelerates coarsening of Ag nanoislands on Ag(100) at 300 K, and this effect is enhanced with increasing sulfur coverage over a range spanning a few hundredths of a monolayer, to nearly 0.25 monolayers. We propose that acceleration of coarsening in this system is tied to the formation of AgS{sub 2} clusters primarily at step edges. These clusters can transport Ag more efficiently than can Ag adatoms (due to a lower diffusion barrier and comparable formation energy). The mobility of isolated sulfur on Ag(100) is very low so that formation of the complex is kinetically limited at low sulfur coverages, and thus enhancement is minimal. However, higher sulfur coverages force the population of sites adjacent to step edges, so that formation of the cluster is no longer limited by diffusion of sulfur across terraces. Sulfur exerts a much weaker effect on the rate of coarsening on Ag(100) than it does on Ag(111). This is consistent with theory, which shows that the difference between the total energy barrier for coarsening with and without sulfur is also much smaller on Ag(100) than on Ag(111).

  8. Amperometric biosensor of SnO2 thin film modified by Pd, In and Ag nanostructure synthesized by CSP method

    NASA Astrophysics Data System (ADS)

    Hassan, Marwa Abdul Muhsien; Hateef, Areej Adnan; Majeed, Aseel Mustafa Abdul; Al-Jabiry, Ali Jasim Mohammed; Jameel, Sabah; Hussian, Haidar Abdul Razaq Abdul

    2013-10-01

    Palladium, Indium and Silver-doped SnO2 thin film was deposited by chemical spray pyrolysis on ITO and porous silicon substrates to be a fast MgSO4·7H2O amperometric biosensor. The prepared SnO2 films were doped by dipping in palladium chloride PdCl2, indium chloride, InCl3 and silver nitrides AgNO3 dissolved in ethanol C2H5OH. The structural and optical properties of the prepared films were studied. The sensitivity behaviors of SnO2, SnO2: Pd, SnO2: In and SnO2: Ag based on the amperometric biosensor to MgSO4·7H2O salts were investigated at room temperature with different doping.

  9. Local structure analysis of NaNbO3 and AgNbO3 modified by Li substitution

    NASA Astrophysics Data System (ADS)

    Yoneda, Yasuhiro; Aoyagi, Rintaro; Fu, Desheng

    2016-10-01

    We analyzed the local structures of NaNbO3 and AgNbO3 by combining the X-ray absorption fine structure (XAFS) and atomic pair-distribution function (PDF) techniques. NaNbO3 is known to be an antiferroelectric material at room temperature. It also undergoes a diffuse phase transition, in which orthorhombic and rhombohedral phases coexist over a wide temperature range. We found a disordered feature in the nearest-neighbor bond distance corresponding to the Nb-O bonds. The disordered bond distribution disappeared when Li was substituted for Na. A similar disorder feature was found in AgNbO3. The disordered site can be specified by combining XAFS and PDF techniques. The sequences of disordered and complex phase transitions are attributable to the competition between the tolerance of the AO12 cage and the tilt of NbO6 octahedra.

  10. Modifying the Surface of a Rashba-Split Pb-Ag Alloy Using Tailored Metal-Organic Bonds

    NASA Astrophysics Data System (ADS)

    Stadtmüller, Benjamin; Seidel, Johannes; Haag, Norman; Grad, Lisa; Tusche, Christian; van Straaten, Gerben; Franke, Markus; Kirschner, Jürgen; Kumpf, Christian; Cinchetti, Mirko; Aeschlimann, Martin

    2016-08-01

    Hybridization-related modifications of the first metal layer of a metal-organic interface are difficult to access experimentally and have been largely neglected so far. Here, we study the influence of specific chemical bonds (as formed by the organic molecules CuPc and PTCDA) on a Pb-Ag surface alloy. We find that delocalized van der Waals or weak chemical π -type bonds are not strong enough to alter the alloy, while localized σ -type bonds lead to a vertical displacement of the Pb surface atoms and to changes in the alloy's surface band structure. Our results provide an exciting platform for tuning the Rashba-type spin texture of surface alloys using organic molecules.

  11. Photocatalytic Properties of TiO2 Thin Films Modified with Ag and Pt Nanoparticles Deposited by Gas Flow Sputtering.

    PubMed

    Maicu, M; Glöss, D; Frach, Peter; Hecker, D; Gerlach, G; Córdoba, José M

    2015-09-01

    In this work, a gas flow sputtering (GFS) process which allows the production and deposition of metal nanoparticles (NPs) in a vacuum environment is described. Aim of the study is to prove the potential of this technology for the fabrication of new TiO2 films with enhanced photocatalytic properties. For this purpose, Ag and Pt NPs have been produced and deposited on photocatalytic float glass coated with TiO2 thin films by magnetron sputtering. The influence of the process parameters and of the metal amount on the final properties of the particles (quantity, size, size distribution, oxidation state etc.,) was widely investigated. Moreover, the effect of the NPs on the photocatalytic activity of the resulting materials was evaluated for the case of the decomposition of stearic acid (SA) during UV-A irradiation. The reduction of the water contact angle (WCA) during the irradiation period was measured in order to test the photo-induced super-hydrophilicity (PSH).

  12. Modifying the Surface of a Rashba-Split Pb-Ag Alloy Using Tailored Metal-Organic Bonds.

    PubMed

    Stadtmüller, Benjamin; Seidel, Johannes; Haag, Norman; Grad, Lisa; Tusche, Christian; van Straaten, Gerben; Franke, Markus; Kirschner, Jürgen; Kumpf, Christian; Cinchetti, Mirko; Aeschlimann, Martin

    2016-08-26

    Hybridization-related modifications of the first metal layer of a metal-organic interface are difficult to access experimentally and have been largely neglected so far. Here, we study the influence of specific chemical bonds (as formed by the organic molecules CuPc and PTCDA) on a Pb-Ag surface alloy. We find that delocalized van der Waals or weak chemical π-type bonds are not strong enough to alter the alloy, while localized σ-type bonds lead to a vertical displacement of the Pb surface atoms and to changes in the alloy's surface band structure. Our results provide an exciting platform for tuning the Rashba-type spin texture of surface alloys using organic molecules. PMID:27610875

  13. Modifying the Surface of a Rashba-Split Pb-Ag Alloy Using Tailored Metal-Organic Bonds.

    PubMed

    Stadtmüller, Benjamin; Seidel, Johannes; Haag, Norman; Grad, Lisa; Tusche, Christian; van Straaten, Gerben; Franke, Markus; Kirschner, Jürgen; Kumpf, Christian; Cinchetti, Mirko; Aeschlimann, Martin

    2016-08-26

    Hybridization-related modifications of the first metal layer of a metal-organic interface are difficult to access experimentally and have been largely neglected so far. Here, we study the influence of specific chemical bonds (as formed by the organic molecules CuPc and PTCDA) on a Pb-Ag surface alloy. We find that delocalized van der Waals or weak chemical π-type bonds are not strong enough to alter the alloy, while localized σ-type bonds lead to a vertical displacement of the Pb surface atoms and to changes in the alloy's surface band structure. Our results provide an exciting platform for tuning the Rashba-type spin texture of surface alloys using organic molecules.

  14. Phonon spectra and temperature variation of bulk properties of Cu, Ag, Au and Pt using Sutton-Chen and modified Sutton-Chen potentials

    NASA Astrophysics Data System (ADS)

    Januszko, A.; Bose, S. K.

    2015-07-01

    Three potentials of the Finnis-Sinclair type are studied with regard to their suitability for predicting bulk thermal and elastic properties of fcc metals Cu, Ag, Au and Pt over a wide temperature range. We start with a particular parametrization of the Finnis-Sinclair model known as the Sutton-Chen potential and a later version of the same, known as the quantum Sutton-Chen potential. The quasiharmonic lattice dynamics method is used to study the temperature variation of the thermodynamic properties. Both models are found to yield poor results for thermal expansion, which can be traced to rapid softening of transverse phonon frequencies with increasing lattice parameter. The form of the Sutton-Chen potential is modified here to seek improvement in the agreement between quasiharmonic calculations and experimental data. It is found that the modified potential better predicts bulk properties in nearly all cases studied. Significant improvement is seen over the Sutton-Chen potential, while lesser but still substantial improvement is observed over the Quantum-Sutton Chen potential.

  15. Photocatalytic Properties of TiO2 Thin Films Modified with Ag and Pt Nanoparticles Deposited by Gas Flow Sputtering.

    PubMed

    Maicu, M; Glöss, D; Frach, Peter; Hecker, D; Gerlach, G; Córdoba, José M

    2015-09-01

    In this work, a gas flow sputtering (GFS) process which allows the production and deposition of metal nanoparticles (NPs) in a vacuum environment is described. Aim of the study is to prove the potential of this technology for the fabrication of new TiO2 films with enhanced photocatalytic properties. For this purpose, Ag and Pt NPs have been produced and deposited on photocatalytic float glass coated with TiO2 thin films by magnetron sputtering. The influence of the process parameters and of the metal amount on the final properties of the particles (quantity, size, size distribution, oxidation state etc.,) was widely investigated. Moreover, the effect of the NPs on the photocatalytic activity of the resulting materials was evaluated for the case of the decomposition of stearic acid (SA) during UV-A irradiation. The reduction of the water contact angle (WCA) during the irradiation period was measured in order to test the photo-induced super-hydrophilicity (PSH). PMID:26716202

  16. Semifluorinated Alkylphosphonic Acids Form High-Quality Self-Assembled Monolayers on Ag-Coated Yttrium Barium Copper Oxide Tapes and Enable Filamentization of the Tapes by Microcontact Printing.

    PubMed

    Park, Chul Soon; Lee, Han Ju; Lee, Dahye; Jamison, Andrew C; Galstyan, Eduard; Zagozdzon-Wosik, Wanda; Freyhardt, Herbert C; Jacobson, Allan J; Lee, T Randall

    2016-08-30

    A custom-designed semifluorinated phosphonic acid, (9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,16-heptadecafluorohexadecyl)phosphonic acid (F8H8PA), and a normal hexadecylphosphonic acid (H16PA) were synthesized and used to generate self-assembled monolayers (SAMs) on commercially available yttrium barium copper oxide (YBCO) tapes. In this study, we wished to evaluate the effectiveness of these monolayer films as coatings for selectively etching YBCO. Initial films formed by solution deposition and manual stamping using a non-patterned polydimethylsiloxane stamp allowed for a comparison of the film-formation characteristics. The resulting monolayers were characterized by X-ray photoelectron spectroscopy (XPS), contact angle goniometry, and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). To prepare line-patterned (filamentized) YBCO tapes, standard microcontact printing (μ-CP) procedures were used. The stamped patterns on the YBCO tapes were characterized by scanning electron microscopy (SEM) before and after etching to confirm the effectiveness of the patterning process on the YBCO surface and energy-dispersive X-ray spectroscopy (EDX) to obtain the atomic composition of the exposed interface. PMID:27482760

  17. Controlling Assembly of Mixed Thiol Monolayers on Silver Nanoparticles to Tune Their Surface Properties

    PubMed Central

    2012-01-01

    Modifying the surfaces of metal nanoparticles with self-assembled monolayers of functionalized thiols provides a simple and direct method to alter their surface properties. Mixed self-assembled monolayers can extend this approach since, in principle, the surfaces can be tuned by altering the proportion of each modifier that is adsorbed. However, this works best if the composition and microstructure of the monolayers can be controlled. Here, we have modified preprepared silver colloids with binary mixtures of thiols at varying concentrations and modifier ratios. Surface-enhanced Raman spectroscopy was then used to determine the effect of altering these parameters on the composition of the resulting mixed monolayers. The data could be explained using a new model based on a modified competitive Langmuir approach. It was found that the composition of the mixed monolayer only reflected the ratio of modifiers in the feedstock when the total amount of modifier was sufficient for approximately one monolayer coverage. At higher modifier concentrations the thermodynamically favored modifier dominated, but working at near monolayer concentrations allowed the surface composition to be controlled by changing the ratios of modifiers. Finally, a positively charged porphyrin probe molecule was used to investigate the microstructure of the mixed monolayers, i.e., homogeneous versus domains. In this case the modifier domains were found to be <2 nm. PMID:22500816

  18. Sensitive Glycoprotein Sandwich Assays by the Synergistic Effect of In Situ Generation of Raman Probes and Plasmonic Coupling of Ag Core-Au Satellite Nanostructures.

    PubMed

    Bi, Xiaoshuang; Li, Xueyuan; Chen, Dong; Du, Xuezhong

    2016-05-01

    Sensitive surface-enhanced Raman scattering (SERS) assays of glycoproteins have been proposed using p-aminothiophenol (PATP)-embedded Ag core-Au satellite nanostructures modified with p-mercaptophenylboronic acid (PMBA) and the self-assembled monolayer of PMBA on a smooth gold-coated wafer. The apparent Raman probe PATP on the surfaces of the Ag cores underwent a photodimerization to generate 4,4'-dimercaptoazobenzene (DMAB) in situ upon excitation of laser, and the in situ generated DMAB acted as the actual Raman probe with considerably strong SERS signals, which was further enhanced by the plasmonic coupling of the Ag core-Au satellite nanostructures due to the synergistic effect. The sandwich assays of glycoproteins showed high sensitivity and excellent selectivity against nonglycoproteins. The Ag core-Au satellite SERS nanostructures can be used for highly sensitive SERS assays of other analytes.

  19. Multifunctional self-assembled monolayers

    SciTech Connect

    Zawodzinski, T.; Bar, G.; Rubin, S.; Uribe, F.; Ferrais, J.

    1996-06-01

    This is the final report of at three year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The specific goals of this research project were threefold: to develop multifunctional self-assembled monolayers, to understand the role of monolayer structure on the functioning of such systems, and to apply this knowledge to the development of electrochemical enzyme sensors. An array of molecules that can be used to attach electrochemically active biomolecules to gold surfaces has been synthesized. Several members of a class of electroactive compounds have been characterized and the factors controlling surface modification are beginning to be characterized. Enzymes have been attached to self-assembled molecules arranged on the gold surface, a critical step toward the ultimate goal of this project. Several alternative enzyme attachment strategies to achieve robust enzyme- modified surfaces have been explored. Several means of juxtaposing enzymes and mediators, electroactive compounds through which the enzyme can exchange electrons with the electrode surface, have also been investigated. Finally, the development of sensitive biosensors based on films loaded with nanoscale-supported gold particles that have surface modified with the self-assembled enzyme and mediator have been explored.

  20. Methods of making monolayers

    DOEpatents

    Alford, Kentin L.; Simmons, Kevin L.; Samuels, William D.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon; Fryxell, Glen E.

    2009-09-15

    The invention pertains to methods of forming monolayers on various surfaces. The surfaces can be selected from a wide array of materials, including, for example, aluminum dioxide, silicon dioxide, carbon and SiC. The substrates can be planar or porous. The monolayer is formed under enhanced pressure conditions. The monolayer contains functionalized molecules, and accordingly functionalizes a surface of the substrate. The properties of the functionalized substrate can enhance the substrate's applicability for numerous purposes including, for example, utilization in extracting contaminants, or incorporation into a polymeric matrix.

  1. Methods of making monolayers

    DOEpatents

    Alford, Kentin L.; Simmons, Kevin L.; Samuels, William D.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon; Fryxell, Glen E.

    2009-12-08

    The invention pertains to methods of forming monolayers on various surfaces. The surfaces can be selected from a wide array of materials, including, for example, aluminum dioxide, silicon dioxide, carbon and SiC. The substrates can be planar or porous. The monolayer is formed under enhanced pressure conditions. The monolayer contains functionalized molecules, and accordingly functionalizes a surface of the substrate. The properties of the functionalized substrate can enhance the substrate's applicability for numerous purposes including, for example, utilization in extracting contaminants, or incorporation into a polymeric matrix.

  2. Simultaneous enzymatic and SERS properties of bifunctional chitosan-modified popcorn-like Au-Ag nanoparticles for high sensitive detection of melamine in milk powder.

    PubMed

    Li, Junrong; Zhang, Guannan; Wang, Lihua; Shen, Aiguo; Hu, Jiming

    2015-08-01

    In this work, we suggest a chitosan-modified popcorn-like Au-Ag nanoparticles (CSPNPs) based assay for high sensitive detection of melamine, in which CSPNPs not only provide with an intrinsic peroxidase-like activity but also act as surface enhanced Raman scattering (SERS) substrates. CSPNPs can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 to the charge transfer complex (CTC), which contributes to a tremendous surface-enhanced resonant Raman scattering (SERRS) signals with 632.8 nm laser excitation. The target molecule melamine can generate an additional compound with H2O2, which means the available amount of H2O2 for the oxidation of TMB reduced. Correspondingly, the SERRS intensity of CTC is decreased. The decreased Raman intensity is proportional to the concentration of melamine over a wide range from 10 nM to 50 μM (R(2)=0.989), with a limit of detection (LOD) of 8.51 nM. Moreover, the proposed highly selective method is fully capable of rapid, separation-free detection of melamine in milk powder. PMID:26048843

  3. Structural, thermal, laser damage, photoconductivity, NLO and mechanical properties of modified vertical Bridgman method grown AgGa0.5In0.5Se2 single crystal

    NASA Astrophysics Data System (ADS)

    Vijayakumar, P.; Ramasamy, P.

    2016-08-01

    AgGa0.5In0.5Se2 single crystal was grown using modified vertical Bridgman method. The structural perfection of the AgGa0.5In0.5Se2 single crystal has been analyzed by high-resolution X-ray diffraction rocking curve measurements. The structural and compositional uniformities of AgGa0.5In0.5Se2 were studied using Raman scattering spectroscopy at room temperature. The FWHM of the Γ1 (W1) and Γ5L (Γ15) measured at different regions of the crystal confirms that the composition throughout its length is fairly uniform. Thermal properties of the as-grown crystal, including specific heat, thermal diffusivity and thermal conductivity have been investigated. The multiple shot surface laser damage threshold value was measured using Nd:YAG laser. Photoconductivity measurements with different temperatures have confirmed the positive photoconducting behavior. Second harmonic generation (SHG) on powder samples has been measured using the Kurtz and Perry technique and the results display that AgGa0.5In0.5Se2 is a phase-matchable NLO material. The hardness behavior has been measured using Vickers micro hardness measurement and the indentation size effect has been observed. The classical Meyer's law, propositional resistance model and modified propositional resistance model have been used to analyse the micro hardness behavior.

  4. Ultrasensitive electrochemical immunoassay for CEA through host-guest interaction of β-cyclodextrin functionalized graphene and Cu@Ag core-shell nanoparticles with adamantine-modified antibody.

    PubMed

    Gao, Jian; Guo, Zhankui; Su, Fengjie; Gao, Liang; Pang, Xuehui; Cao, Wei; Du, Bin; Wei, Qin

    2015-01-15

    A novel non-enzymatic immunoassay was designed for ultrasensitive electrochemical detection of carcino-embryonic antigen (CEA) using β-cyclodextrin functionalized Cu@Ag (Cu@Ag-CD) core-shell nanoparticles as labels and β-cyclodextrin functionalized graphene nanosheet (CD-GN) as sensor platform. CD-GN has excellent conductivity which promoted the electric transmission between base solution and electrode surface and enhanced sensitivity of immunosensor. In addition, owing to supramolecular recognition of CD-GN for the guest molecule, quite a few synthesized adamantine-modified primary antibodies (ADA-Ab1) were immobilized on the CD-GN by supramolecular host-guest interaction between CD and ADA. Cu@Ag-CD as a signal tag could be captured by ADA-modified secondary antibody (ADA-Ab2) through a host-guest interaction, leading to a large loading of Cu@Ag nanoparticles with high electrical conductivity and catalytic activity. The fabricated immunosensor exhibits excellent analytical performance for the measurement of CEA with wide range linear (0.0001-20 ng/mL), low detection limit (20 fg/mL), good sensitivity, reproducibility and stability, which provide an enormous application prospect in clinical diagnostics.

  5. Disinfection of Escherichia coli Gram negative bacteria using surface modified TiO2: optimization of Ag metallization and depiction of charge transfer mechanism.

    PubMed

    Gomathi Devi, LakshmipathiNaik; Nagaraj, Basavalingaiah

    2014-01-01

    The antibacterial activity of silver deposited TiO2 (Ag-TiO2 ) against Gram negative Escherichia coli bacteria was investigated by varying the Ag metal content from 0.10 to 0.50% on the surface of TiO2 . Ag depositions by the photoreduction method were found to be stable. Surface silver metallization was confirmed by EDAX and XPS studies. Photoluminescence studies show that the charge carrier recombination is less for 0.1% Ag-TiO2 and this catalyst shows superior bactericidal activity under solar light irradiation compared to Sol gel TiO2 (SG-TiO2 ) due to the surface plasmon effect. The energy levels of deposited Ag are dependent on the Ag content and it varies from -4.64 eV to -1.30 eV with respect to the vacuum energy level based on atomic silver to bulk silver deposits. The ability of electron transfer from Ag deposit to O2 depends on the position of the energy levels. The 0.25% and 0.50% Ag depositions showed detrimental effect on bactericidal activity due to the mismatch of energy levels. The effect of the EROS (External generation of the Reactive Oxygen Species by 0.1% Ag-TiO2 ) and IROS (Interior generation of Reactive Oxygen Species within the bacteria) on the bactericidal inactivation is discussed in detail. PMID:24995499

  6. 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.

  7. Diamondoid monolayers as electron emitters

    DOEpatents

    Yang, Wanli; Fabbri, Jason D.; Melosh, Nicholas A.; Hussain, Zahid; Shen, Zhi-Xun

    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.

  8. Controlling self assembled monolayers

    NASA Astrophysics Data System (ADS)

    Wei, Yanhu

    2007-12-01

    In this thesis, we demonstrate novel methods of controlling the morphology of self-assembled monolayers at the solution-graphite interface. Scanning tunneling microscopy is used to evaluate the capacity of chain length and weak dipolar interactions to direct packing and neighboring chain selection within monolayers. We designed and synthesized a series of 1,5-substituted anthracene derivatives and investigated the relationship between side chain structure and monolayer morphology. We report that the morphology of monolayers formed on HOPG from symmetrically substituted anthracene derivatives switches from a 2D racemate to a 2D conglomerate by the addition of a single methylene unit to each side chain, i.e., by changing the side chain lengths from even to odd. We introduced ether groups into the side chains of anthracene derivatives in an attempt to use dipolar interactions to alter monolayer morphology. We report that the insertion of electronegative oxygen atoms into the side chains of anthracene derivatives can disturb the odd - even effect of chain length and influence monolayer morphology. By introducing a proper number of ether groups at specific side chain locations, we designed two self-repelling and complementary chains: COC12OC and C2OC10OC 2. COC12OC (or C2OC10OC2) chains repel themselves but select the other C2OC10OC 2 (or COC12OC) chains as their neighbors in self-assembled monolayers. Taking into account chain length matching and dipolar complementary as mechanisms for adjacent side chain selection, we designed and synthesized two symmetrical anthracenes 12 (COC12OC-An-COC 12OC), 13 (C2OC10OC2-An-C 2OC10OC2) and two unsymmetrical anthracenes 15 (C11OC-An-COC12OC) and 16 (C 18OC2-An-C2OC10OC2). Using a mixture solution of these molecules, we prepared a highly ordered AABB monolayer pattern in which paired rows of 15 alternate with paired rows of 16, and a highly ordered AAB monolayer pattern in which rows consisting of 12 are sandwiched between paired

  9. Synthesis, structure and electrochemistry of Ag-modified LiMn{sub 2}O{sub 4} cathode materials for lithium-ion batteries

    SciTech Connect

    Zhou Wenjia; He Benlin; Li Hulin

    2008-08-04

    Spinel lithium manganese oxide was prepared by sol-gel method and a series of Ag/LiMn{sub 2}O{sub 4} composites with different Ag additive contents were prepared by thermal decomposition of AgNO{sub 3} added to the pure LiMn{sub 2}O{sub 4} powders. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDAX) and various electrochemical measurement methods were used to examine the structural and electrochemical characteristics of the Ag/LiMn{sub 2}O{sub 4} composite powders. Phase analysis showed that Ag particles were dispersed on the surface of LiMn{sub 2}O{sub 4} instead of entering the spinel structure. According to the electrochemical tests results, it is clearly to see that Ag additives efficiently improved the cycling stability, reversibility and high-rate discharge capacity of pristine LiMn{sub 2}O{sub 4} by increasing the electrical conductivity between LiMn{sub 2}O{sub 4} particles, decreasing the polarization of cathode and reducing the dissolution of Mn. Meanwhile the influence of the Ag additive contents on the electrochemical properties of the Ag/LiMn{sub 2}O{sub 4} composites is also investigated in detail.

  10. Nucleation and Growth of Cu-Al Intermetallics in Al-Modified Sn-Cu and Sn-Ag-Cu Lead-Free Solder Alloys

    NASA Astrophysics Data System (ADS)

    Reeve, Kathlene N.; Anderson, Iver E.; Handwerker, Carol A.

    2015-03-01

    Lead-free solder alloys Sn-Cu (SC) and Sn-Ag-Cu (SAC) are widely used by the microelectronics industry, but enhanced control of the microstructure is needed to improve solder performance. For such control, nucleation and stability of Cu-Al intermetallic compound (IMC) solidification catalysts were investigated by variation of the Cu (0.7-3.0 wt.%) and Al (0.0-0.4 wt.%) content of SC + Al and SAC + Al alloys, and of SAC + Al ball-grid array (BGA) solder joints. All of the Al-modified alloys produced Cu-Al IMC particles with different morphologies and phases (occasionally non-equilibrium phases). A trend of increasing Cu-Al IMC volume fraction with increasing Al content was established. Because of solidification of non-equilibrium phases in wire alloy structures, differential scanning calorimetry (DSC) experiments revealed delayed, non-equilibrium melting at high temperatures related to quenched-in Cu-Al phases; a final liquidus of 960-1200°C was recorded. During cooling from 1200°C, the DSC samples had the solidification behavior expected from thermodynamic equilibrium calculations. Solidification of the ternary alloys commenced with formation of ternary β and Cu-Al δ phases at 450-550°C; this was followed by β-Sn, and, finally, Cu6Sn5 and Cu-Al γ1. Because of the presence of the retained, high-temperature phases in the alloys, particle size and volume fraction of the room temperature Cu-Al IMC phases were observed to increase when the alloy casting temperature was reduced from 1200°C to 800°C, even though both temperatures are above the calculated liquidus temperature of the alloys. Preliminary electron backscatter diffraction results seemed to show Sn grain refinement in the SAC + Al BGA alloy.

  11. 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.

  12. Revealing the substrate origin of the linear dispersion of silicene/Ag(111).

    PubMed

    Chen, M X; Weinert, M

    2014-09-10

    The band structure of the recently synthesized (3 × 3) silicene monolayer on (4 × 4) Ag(111) is investigated using density functional theory. A k-projection technique that includes the k⊥-dependence of the surface bands is used to separate the contributions arising from the silicene and the substrate, allowing a consistent comparison between the calculations and the angle-resolved photoemission experiments. Our calculations not only reproduce the observed gap and linear dispersion across the K point of (1 × 1) silicene but also demonstrate that these originate from the k⊥-dependence of Ag(111) substrate states (modified by interactions with the silicene) and not from a Dirac state.

  13. Direct evidence of metallic bands in a monolayer boron sheet

    NASA Astrophysics Data System (ADS)

    Feng, Baojie; Zhang, Jin; Liu, Ro-Ya; Iimori, Takushi; Lian, Chao; Li, Hui; Chen, Lan; Wu, Kehui; Meng, Sheng; Komori, Fumio; Matsuda, Iwao

    2016-07-01

    The search for metallic boron allotropes has attracted great attention in the past decades and recent theoretical works predict the existence of metallicity in monolayer boron. Here, we synthesize the β12-sheet monolayer boron on a Ag(111) surface and confirm the presence of metallic boron-derived bands using angle-resolved photoemission spectroscopy. The Fermi surface is composed of one electron pocket at the S ¯ point and a pair of hole pockets near the X ¯ point, which is supported by the first-principles calculations. The metallic boron allotrope in β12 sheet opens the way to novel physics and chemistry in material science.

  14. Pentagonal monolayer crystals of carbon, boron nitride, and silver azide

    SciTech Connect

    Yagmurcukardes, M. Senger, R. T.; Sahin, H.; Kang, J.; Torun, E.; Peeters, F. M.

    2015-09-14

    In this study, we present a theoretical investigation of structural, electronic, and mechanical properties of pentagonal monolayers of carbon (p-graphene), boron nitride (p-B{sub 2}N{sub 4} and p-B{sub 4}N{sub 2}), and silver azide (p-AgN{sub 3}) by performing state-of-the-art first principles calculations. Our total energy calculations suggest feasible formation of monolayer crystal structures composed entirely of pentagons. In addition, electronic band dispersion calculations indicate that while p-graphene and p-AgN{sub 3} are semiconductors with indirect bandgaps, p-BN structures display metallic behavior. We also investigate the mechanical properties (in-plane stiffness and the Poisson's ratio) of four different pentagonal structures under uniaxial strain. p-graphene is found to have the highest stiffness value and the corresponding Poisson's ratio is found to be negative. Similarly, p-B{sub 2}N{sub 4} and p-B{sub 4}N{sub 2} have negative Poisson's ratio values. On the other hand, the p-AgN{sub 3} has a large and positive Poisson's ratio. In dynamical stability tests based on calculated phonon spectra of these pentagonal monolayers, we find that only p-graphene and p-B{sub 2}N{sub 4} are stable, but p-AgN{sub 3} and p-B{sub 4}N{sub 2} are vulnerable against vibrational excitations.

  15. A highly sensitive self assembled monolayer modified copper doped zinc oxide nanofiber interface for detection of Plasmodium falciparum histidine-rich protein-2: Targeted towards rapid, early diagnosis of malaria.

    PubMed

    Brince Paul, K; Kumar, Sanni; Tripathy, Suryasnata; Vanjari, Siva Rama Krishna; Singh, Vikrant; Singh, Shiv Govind

    2016-06-15

    Rapid, ultrasensitive diagnostic/triaging kits for early detection of malarial parasites are critical for prevention of malarial epidemic, especially in developing and tropical countries. Unlike traditional microscopic diagnosis, these kits rely on the detection of antigens specific to malarial parasites. One such antigen which is routinely used in these diagnostic kits is Histidine-rich protein-2; a protein synthesized and released into the blood stream by the parasite Plasmodium falciparum. In this paper, we demonstrate an ultrasensitive nanobiosensor detection platform for Histidine-rich protein-2 having a limit of detection of attogram/ml. This nanobiosensor platform comprises of Mercaptopropylphosphonic acid functionalized copper doped zinc oxide nanofibers synthesized by electrospinning technique. Ultrasensitivity of attogram/ml can be attributed to the complimentary effects of Mercaptopropylphosphonic acid and copper doping in zinc oxide. Mercaptopropylphosphonic acid enhances the functional groups required for immobilizing antibody. Copper doping in zinc oxide not only increases the conductivity of the nanofibers but also pre-concentrates the target analyte onto the Mercaptopropylphosphonic acid treated nanofiber surface due to inherent electric field generated at the copper/zinc oxide heterojunction interface. The impedimetric detection response of copper-doped zinc oxide nanofiber modified electrode shows excellent sensitivity (28.5 kΩ/(gm/ml)/cm(2)) in the detection ranges of 10 ag/ml-10 µg/ml, and a detection limit of 6 attogram/ml. In addition, the proposed biosensor is highly selective to targeted HRP2 protein with a relative standard deviation of 1.9% in the presence of various interference of nonspecific molecules. To the best of our knowledge, this biosensor shows the lowest detection limit of malarial parasites reported in the literature spanning different nanomaterials and different detection mechanisms. Since the nanobiosensor platform is

  16. A highly sensitive self assembled monolayer modified copper doped zinc oxide nanofiber interface for detection of Plasmodium falciparum histidine-rich protein-2: Targeted towards rapid, early diagnosis of malaria.

    PubMed

    Brince Paul, K; Kumar, Sanni; Tripathy, Suryasnata; Vanjari, Siva Rama Krishna; Singh, Vikrant; Singh, Shiv Govind

    2016-06-15

    Rapid, ultrasensitive diagnostic/triaging kits for early detection of malarial parasites are critical for prevention of malarial epidemic, especially in developing and tropical countries. Unlike traditional microscopic diagnosis, these kits rely on the detection of antigens specific to malarial parasites. One such antigen which is routinely used in these diagnostic kits is Histidine-rich protein-2; a protein synthesized and released into the blood stream by the parasite Plasmodium falciparum. In this paper, we demonstrate an ultrasensitive nanobiosensor detection platform for Histidine-rich protein-2 having a limit of detection of attogram/ml. This nanobiosensor platform comprises of Mercaptopropylphosphonic acid functionalized copper doped zinc oxide nanofibers synthesized by electrospinning technique. Ultrasensitivity of attogram/ml can be attributed to the complimentary effects of Mercaptopropylphosphonic acid and copper doping in zinc oxide. Mercaptopropylphosphonic acid enhances the functional groups required for immobilizing antibody. Copper doping in zinc oxide not only increases the conductivity of the nanofibers but also pre-concentrates the target analyte onto the Mercaptopropylphosphonic acid treated nanofiber surface due to inherent electric field generated at the copper/zinc oxide heterojunction interface. The impedimetric detection response of copper-doped zinc oxide nanofiber modified electrode shows excellent sensitivity (28.5 kΩ/(gm/ml)/cm(2)) in the detection ranges of 10 ag/ml-10 µg/ml, and a detection limit of 6 attogram/ml. In addition, the proposed biosensor is highly selective to targeted HRP2 protein with a relative standard deviation of 1.9% in the presence of various interference of nonspecific molecules. To the best of our knowledge, this biosensor shows the lowest detection limit of malarial parasites reported in the literature spanning different nanomaterials and different detection mechanisms. Since the nanobiosensor platform is

  17. Citrate-reduced silver hydrosol modified with omega-mercaptoalkanoic acids self-assembled monolayers as a substrate for surface-enhanced resonance Raman scattering. A study with cytochrome c.

    PubMed

    Bonifacio, Alois; van der Sneppen, Lineke; Gooijer, Cees; van der Zwan, Gert

    2004-07-01

    A new citrate-reduced silver hydrosol coated with omega-mercaptoalkanoic acids (mercaptopropionic and mercaptoundecanoic acids) self-assembled monolayers was prepared and characterized with surface-enhanced Raman spectroscopy. The structure and the quality of the coating monolayers are discussed and compared to similar coated and uncoated silver hydrosols previously developed. As an application, the new hydrosol was used as a biocompatible and efficient metal substrate for a surface-enhanced resonance Raman scattering (SERRS) study of cytochrome c. The high-quality SERRS spectra reported of cytochrome c (obtained using only 1 microL of a micromolar cytochrome solution) are discussed and compared with data available from literature studies.

  18. Superatomic S(2) silver clusters stabilized by a thiolate-phosphine monolayer: insight into electronic and optical properties of Ag14(SC6H3F2)12(PPh3)8 and Ag16(SC6H3F2)14(DPPE)4.

    PubMed

    Gell, Lars; Lehtovaara, Lauri; Häkkinen, Hannu

    2014-09-18

    The electronic structure of two recently crystallographically solved, thiolate-phosphine protected silver clusters Ag14 and Ag16 are analyzed via density functional theory (DFT) and their optical excitations are analyzed from time-dependent DFT perturbation theory. Both clusters can be characterized as having the S(2) free-electron configuration in the metal core, which is the first time such a configuration is confirmed for structurally known ligand-protected noble metal clusters. However, their different core shapes and ligand layer induce significantly different optical spectra. Performance of gradient-corrected DFT functionals is discussed and it is shown that the asymptotically correct Leeuwen-Baerends LB94 functional reproduces the optical spectrum of Ag14 in a good agreement with experiment. Choice of the functional becomes important for clusters where the optical transitions are dominated by the electron-rich ligand layer.

  19. Reversible Association of Nitro Compounds with p-Nitrothiophenol Modified on Ag Nanoparticles/Graphene Oxide Nanocomposites through Plasmon Mediated Photochemical Reaction.

    PubMed

    Lin, Tsung-Wu; Tasi, Ting-Ti; Chang, Po-Ling; Cheng, Hsiu-Yao

    2016-03-01

    Because localized surface plasmon resonance in nanostructures of noble metals is accompanied by interesting physical effects such as optical near-field enhancement, heat release, and the generation of hot electrons, it has been employed in a wide range of applications, including plasmon-assisted chemical reactions. Here, we use a composite of silver nanoparticles and graphene oxide (Ag@GO) as the catalytic as well as the analytic platform for plasmon-assisted chemical reactions. Through time-dependent surface-enhanced Raman scattering experiments, it is found that p-nitrothiophenol (pNTP) molecules on Ag@GO can be associated with nitro compounds such as nitrobenzene and 1-nitropropane to form azo compounds when aided by the plasmons. Furthermore, the reaction rate can be modulated by varying the wavelength and power of the excitation laser as well as the nitro compounds used. In addition, the aforementioned coupling reaction can be reversed. We demonstrate that the oxidation of azo compounds on Ag@GO using KMnO4 leads to the dissociation of the N═N double bond in the azo compounds and that the rate of bond dissociation can be accelerated significantly via laser irradiation. Furthermore, the pNTP molecules on Ag@GO can be recovered after the oxidation reaction. Finally, we demonstrate that the plasmon-assisted coupling reaction allows for the immobilization of nitro-group-containing fluorophores at specific locations on Ag@GO.

  20. Reversible Association of Nitro Compounds with p-Nitrothiophenol Modified on Ag Nanoparticles/Graphene Oxide Nanocomposites through Plasmon Mediated Photochemical Reaction.

    PubMed

    Lin, Tsung-Wu; Tasi, Ting-Ti; Chang, Po-Ling; Cheng, Hsiu-Yao

    2016-03-01

    Because localized surface plasmon resonance in nanostructures of noble metals is accompanied by interesting physical effects such as optical near-field enhancement, heat release, and the generation of hot electrons, it has been employed in a wide range of applications, including plasmon-assisted chemical reactions. Here, we use a composite of silver nanoparticles and graphene oxide (Ag@GO) as the catalytic as well as the analytic platform for plasmon-assisted chemical reactions. Through time-dependent surface-enhanced Raman scattering experiments, it is found that p-nitrothiophenol (pNTP) molecules on Ag@GO can be associated with nitro compounds such as nitrobenzene and 1-nitropropane to form azo compounds when aided by the plasmons. Furthermore, the reaction rate can be modulated by varying the wavelength and power of the excitation laser as well as the nitro compounds used. In addition, the aforementioned coupling reaction can be reversed. We demonstrate that the oxidation of azo compounds on Ag@GO using KMnO4 leads to the dissociation of the N═N double bond in the azo compounds and that the rate of bond dissociation can be accelerated significantly via laser irradiation. Furthermore, the pNTP molecules on Ag@GO can be recovered after the oxidation reaction. Finally, we demonstrate that the plasmon-assisted coupling reaction allows for the immobilization of nitro-group-containing fluorophores at specific locations on Ag@GO. PMID:26977529

  1. Normal-incidence steering effect in crystal growth: Ag/Ag(100)

    SciTech Connect

    Montalenti, F.; Voter, A. F.

    2001-08-15

    During crystal growth by vapor deposition, normal incident atoms are deflected toward three-dimensional surface structures. The effect becomes strong when the atoms are deposited with a low initial kinetic energy. At low T this steering effect induces an instability in the growth process, causing a perfectly flat surface to become rough after a few monolayers are deposited. Quantitative results for the initial stages of growth of Ag/Ag(100) at T{approx}0 K are presented.

  2. Surface-enhanced Raman scattering from AgNP-graphene-AgNP sandwiched nanostructures

    NASA Astrophysics Data System (ADS)

    Wu, Jian; Xu, Yijun; Xu, Pengyu; Pan, Zhenghui; Chen, Sheng; Shen, Qishen; Zhan, Li; Zhang, Yuegang; Ni, Weihai

    2015-10-01

    We developed a facile approach toward hybrid AgNP-graphene-AgNP sandwiched structures using self-organized monolayered AgNPs from wet chemical synthesis for the optimized enhancement of the Raman response of monolayer graphene. We demonstrate that the Raman scattering of graphene can be enhanced 530 fold in the hybrid structure. The Raman enhancement is sensitively dependent on the hybrid structure, incident angle, and excitation wavelength. A systematic simulation is performed, which well explains the enhancement mechanism. Our study indicates that the enhancement resulted from the plasmonic coupling between the AgNPs on the opposite sides of graphene. Our approach towards ideal substrates offers great potential to produce a ``hot surface'' for enhancing the Raman response of two-dimensional materials.We developed a facile approach toward hybrid AgNP-graphene-AgNP sandwiched structures using self-organized monolayered AgNPs from wet chemical synthesis for the optimized enhancement of the Raman response of monolayer graphene. We demonstrate that the Raman scattering of graphene can be enhanced 530 fold in the hybrid structure. The Raman enhancement is sensitively dependent on the hybrid structure, incident angle, and excitation wavelength. A systematic simulation is performed, which well explains the enhancement mechanism. Our study indicates that the enhancement resulted from the plasmonic coupling between the AgNPs on the opposite sides of graphene. Our approach towards ideal substrates offers great potential to produce a ``hot surface'' for enhancing the Raman response of two-dimensional materials. Electronic supplementary information (ESI) available: Additional SEM images, electric field enhancement profiles, Raman scattering spectra, and structure-dependent peak ratios. See DOI: 10.1039/c5nr04500b

  3. Temperature dependent effects during Ag deposition on Cu(110)

    SciTech Connect

    Taylor, T.N.; Muenchausen, R.E.; Hoffbauer, M.A.; Denier van der Gon, A.W.; van der Veen, J.F.; FOM-Instituut voor Atoom-en Molecuulfysica, Amsterdam )

    1989-01-01

    The composition, structure, and morphology of ultrathin films grown by Ag deposition on Cu(110) were monitored as a function of temperature using low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), and medium energy ion scattering (MEIS). Aligned backscattering measurements with 150 keV He ions indicate that the Ag resides on top of the Cu and there is no significant surface compound formation. Measurements with LEED show that the Ag is initially confined to the substrate troughs. Further deposition forces the Ag out of the troughs and results in a split c(2 {times} 4) LEED pattern, which is characteristic of a distorted Ag(111) monolayer template. As verified by both AES and MEIS measurements, postmonolayer deposition of Ag on Cu(110) at 300K leads to a pronounced 3-dimensional clustering. Ion blocking analysis of the Ag clusters show that the crystallites have a (110)-like growth orientation, implying that the Ag monolayer template undergoes a rearrangement. These data are confirmed by low temperature LEED results in the absence of clusters, which indicate that Ag multilayers grow from a Ag--Cu interface where the Ag is captured in the troughs. Changes observed in the film structure and morphology are consistent with a film growth mechanism that is driven by overlayer strain response to the substrate corrugation. 16 refs., 4 figs.

  4. Pt monolayer coating on complex network substrate with high catalytic activity for the hydrogen evolution reaction

    PubMed Central

    Li, Man; Ma, Qiang; Zi, Wei; Liu, Xiaojing; Zhu, Xuejie; Liu, Shengzhong (Frank)

    2015-01-01

    A deposition process has been developed to fabricate a complete-monolayer Pt coating on a large-surface-area three-dimensional (3D) Ni foam substrate using a buffer layer (Ag or Au) strategy. The quartz crystal microbalance, current density analysis, cyclic voltammetry integration, and X-ray photoelectron spectroscopy results show that the monolayer deposition process accomplishes full coverage on the substrate and the deposition can be controlled to a single atomic layer thickness. To our knowledge, this is the first report on a complete-monolayer Pt coating on a 3D bulk substrate with complex fine structures; all prior literature reported on submonolayer or incomplete-monolayer coating. A thin underlayer of Ag or Au is found to be necessary to cover a very reactive Ni substrate to ensure complete-monolayer Pt coverage; otherwise, only an incomplete monolayer is formed. Moreover, the Pt monolayer is found to work as well as a thick Pt film for catalytic reactions. This development may pave a way to fabricating a high-activity Pt catalyst with minimal Pt usage. PMID:26601247

  5. Surface-engineered growth of AgIn₅S₈ crystals.

    PubMed

    Lai, Chia-Hung; Chiang, Ching-Yeh; Lin, Po-Chang; Yang, Kai-Yu; Hua, Chi Chung; Lee, Tai-Chou

    2013-05-01

    The growth of semiconductor crystals and thin films plays an essential role in industry and academic research. Considering the environmental damage caused by energy consumption during their fabrication, a simpler and cheaper method is desired. In fact, preparing semiconductor materials at lower temperatures using solution chemistry has potential in this research field. We found that solution chemistry, the physical and chemical properties of the substrate surface, and the phase diagram of the multicomponent compound semiconductor have a decisive influence on the crystal structure of the material. In this study, we used self-assembled monolayers (SAMs) to modify the silicon/glass substrate surface and effectively control the density of the functional groups and surface energy of the substrates. We first employed various solutions to grow octadecyltrichlorosilane (OTS), 3-mercaptopropyl-trimethoxysilane (MPS), and mixed OTS-MPS SAMs. The surface energy can be adjusted between 24.9 and 50.8 erg/cm(2). Using metal sulfide precursors in appropriate concentrations, AgIn5S8 crystals can be grown on the modified substrates without any post-thermal treatment. We can easily adjust the nucleation in order to vary the density of AgIn5S8 crystals. Our current process can achieve AgIn5S8 crystals of a maximum of 1 μm in diameter and a minimum crystal density of approximately 0.038/μm(2). One proof-of-concept experiment demonstrated that the material prepared from this low temperature process showed positive photocatalytic activity. This method for growing crystals can be applied to the green fabrication of optoelectronic materials.

  6. A light-modified ferroelectric resistive switching behavior in Ag/BaMoO{sub 4}/FTO device at ambient temperature

    SciTech Connect

    Zhao, W.X.; Sun, B.; Liu, Y.H.; Wei, L.J.; Li, H.W.; Chen, P.

    2014-12-15

    BaMoO{sub 4} powder was prepared by a facile hydrothermal synthesis. And the BaMoO{sub 4}/FTO device was fabricated by a spin-coated method, in which the thickness of BaMoO{sub 4} layer is about 20 µm. The bipolar resistive switching effect has been observed in Ag/BaMoO{sub 4}/FTO device. Moreover, the resistive switching effect of the device is greatly improved by white light irradiation. The resistive switching behavior is explained by the polarization reversal that changes the charge distribution and modulates the Schottky barriers. - Graphical abstract: We fabricate a resistive switching device based on Ag/BaMoO{sub 4}/FTO, the device shows superior white-light controlled bipolar resistive switching memristive characteristics. - Highlights: • The BaMoO{sub 4} nanosquares powder was prepared by a hydrothermal synthesis. • The resistive switching of the Ag/BaMoO{sub 4}/FTO device was observed for the first time. • It is shown that the resistive switching is greatly improved under the white light irradiation. • The mechanism of resistive switching is attributed to the ferroelectric polarization reversal.

  7. Growth of a collapsing Langmuir monolayer

    SciTech Connect

    Kundu, S.; Datta, A.; Hazra, S.

    2006-05-15

    Langmuir monolayers of stearic acid on Co ions in the aqueous subphase have been deposited at different stages of constant pressure collapse, on hydrophilic Si(001) using a modified version of the inverse Langmuir-Schaefer method of horizontal deposition. The electron density profiles (EDPs) along the depth of the deposited films, extracted from the x-ray reflectivity data, show that a monolayer to bi-molecular layer transformation takes place after collapse. The molecules in the lower monolayer have asymmetric configurations with head groups touching water and tails in air, whereas molecules in the upper layer are in symmetric configurations with tails on both sides of the heads. Atomic force microscopy images of the deposited films after collapse, however, show nearly circular islands of height more than that of the bimolecular layer observed in the EDP. As pressure increases, ridges are seen to coexist with these islands. Although the coverage of such islands and ridges is low, they play an important role in determining the growth mode. The growth of the wetting and island layers, taken together, has a striking similarity with the Stranski-Krastanow mode, observed usually for heteroepitaxial growth.

  8. Electroanalytical applications of cationic self-assembled monolayers: square-wave voltammetric determination of dopamine and ascorbate.

    PubMed

    Raj, C R; Tokuda, K; Ohsaka, T

    2001-03-01

    Gold electrodes modified with cationic self-assembled monolayers (SAMs) of 2,2'-dithiobisethaneamine (CYST) and 6,6'-dithiobishexaneamine (DTH) were used for the simultaneous determination of dopamine (DA) and ascorbate (AA). The cationic SAM modified electrodes have several advantages over the bare electrode for the oxidation of AA. A very large (approximately 450 mV) decrease in the overpotential for the oxidation of AA when compared with the bare electrode has been observed at the cationic monolayer-modified electrode. The electrostatic interaction of negatively charged AA with the monolayer shift the oxidation peak potential of AA to less positive potential and enhances the peak current. On the other hand, the positively charged DA is repelled from the monolayer and the oxidation potential shifts to more positive potential when compared to the bare electrode. The electrochemical oxidation of AA at the mixed monolayer of CYST and diethyl disulfide (DEDS) supports the influence of cationic terminal group of the monolayer on the oxidation of AA. Since the oxidation of AA occurs well before the oxidation potential of DA is reached, the homogeneous catalytic oxidation of AA by the oxidized DA has been advantageously eliminated at the monolayer-modified electrode. The cationic self-assembled monolayers successfully detect DA in the presence of high concentration of AA. The sensitivity of the electrode modified with CYST monolayer was found to be 0.036 and 0.021 microA/microM towards AA and DA, respectively.

  9. Bright white-light emission from Ag/SiO2/CdS-ZnS core/shell/shell plasmon couplers

    NASA Astrophysics Data System (ADS)

    Liao, Chen; Tang, Luping; Gao, Xiaoqin; Xu, Ruilin; Zhang, Huichao; Yu, Yongya; Lu, Changgui; Cui, Yiping; Zhang, Jiayu

    2015-12-01

    Well-defined plasmon couplers (PCs) that comprise a Ag core overcoated with a SiO2 shell with controlled thickness, followed by a monolayer of CdS-ZnS core-shell quantum dots (QDs) were synthesized to modify the emission from trap-rich CdS-ZnS QDs by adjusting the distance between the QDs and Ag nanoparticles (NPs). When the thickness of the SiO2 shell was 10 nm, because the shell could effectively suppress the non-radiative energy transfer from the semiconductor QDs to the metal NPs and the localized surface plasmon resonance (LSPR) of the Ag NPs spectrally matched the emission peak of the CdS-ZnS QDs to bring about strong plasmon coupling, optimum enhancements of the surface state emission (SSE) (17 times) and band-edge emission (BEE) (4 times) were simultaneously realized and the SSE to BEE intensity ratio was increased to 55%. As a result, a bright white-light source with 1931 Commission Internationale d'Eclairage (CIE) chromaticity coordinates of (0.32, 0.34) was realized by the superposition of the two emissions. The experimental results from Ag/SiO2/CdSe-ZnS and the Ag/SiO2/CdS:Mn-ZnS core/shell/shell PCs indicated that suppressing the non-radiative decay rate (knr) was the underlying mechanism for plasmon coupling fluorescence enhancement.

  10. Scanning tunneling microscopy studies of mixed self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Raigoza, Annette Fernandez

    This thesis examines the formation of multicomponent self-assembled mono-layers (SAMs) on the Au(111) surface using scanning tunneling microscopy. Two methods, sequential adsorption and coadsorption, are used to create these mixed SAMs. In the sequential adsorption experiments, a clean Au(111)-on-mica sub-strate is exposed to the first molecular species and then this adsorbate-covered sample is exposed to the second molecular species. Alternately, in the coadsorption experiments, a gold surface is exposed to both adsorbates simultaneously. Exposing a coronene- or dithiocarbamate-covered surface to excess thiol in the vapor phase results in a drastic restructuring of the initial surface. This is primarily driven by the kinetics of the octanethiol monolayer formation process, but the extent to which this happens is dependent on the molecule-molecule and molecule-surface interactions of the adsorbate due to the initial coverage and order of the monolayer. An octanethiolate monolayer is also substantially modified when immersed in a solution containing dithiocarbamate (DTC). Defects in the octanethiol monolayer are prime sites for molecular exchange. A surplus of DTC in the solution drives substitution that can lead to the complete removal of thiol from the surface. When a Au(111) surface is exposed to solutions containing both octanethiol and dithiocarbamate (DTC), both molecular species compete for available ad- sorption sites. At equal octanethiol-to-DTC ratios, molecular exchange hinders octanethiol monolayer formation. Higher octanethiol concentration in solution results in the incorporation of thiol into the resulting monolayer, with a strong dependence on the chain length of the DTC molecules.

  11. Phenomenological Modeling for Langmuir Monolayers

    NASA Astrophysics Data System (ADS)

    Baptiste, Dimitri; Kelly, David; Safford, Twymun; Prayaga, Chandra; Varney, Christopher N.; Wade, Aaron

    Experimentally, Langmuir monolayers have applications in molecular optical, electronic, and sensor devices. Traditionally, Langmuir monolayers are described by a rigid rod model where the rods interact via a Leonard-Jones potential. Here, we propose effective phenomenological models and utilize Monte Carlo simulations to analyze the phase behavior and compare with experimental isotherms. Research reported in this abstract was supported by UWF NIH MARC U-STAR 1T34GM110517-01.

  12. Phase Transitions in Dipalmitoylphosphatidylcholine Monolayers.

    PubMed

    Zuo, Yi Y; Chen, Rimei; Wang, Xianju; Yang, Jinlong; Policova, Zdenka; Neumann, A Wilhelm

    2016-08-23

    A self-assembled phospholipid monolayer at an air-water interface is a well-defined model system for studying surface thermodynamics, membrane biophysics, thin-film materials, and colloidal soft matter. Here we report a study of two-dimensional phase transitions in the dipalmitoylphosphatidylcholine (DPPC) monolayer at the air-water interface using a newly developed methodology called constrained drop surfactometry (CDS). CDS is superior to the classical Langmuir balance in its capacity for rigorous temperature control and leak-proof environments, thus making it an ideal alternative to the Langmuir balance for studying lipid polymorphism. In addition, we have developed a novel Langmuir-Blodgett (LB) transfer technique that allows the direct transfer of lipid monolayers from the droplet surface under well-controlled conditions. This LB transfer technique permits the direct visualization of phase coexistence in the DPPC monolayer. With these technological advances, we found that the two-dimensional phase behavior of the DPPC monolayer is analogous to the three-dimensional phase transition of a pure substance. This study has implications in the fundamental understanding of surface thermodynamics as well as applications such as self-assembled monolayers and pulmonary surfactant biophysics. PMID:27479299

  13. Structure and Function Evolution of Thiolate Monolayers on Gold

    SciTech Connect

    Grant Alvin Edwards

    2006-05-01

    The use of n-alkanethiolate self-assembled monolayers on gold has blossomed in the past few years. These systems have functioned as models for common interfaces. Thiolate monolayers are ideal because they are easily modified before or after deposition. The works contained within this dissertation include interfacial characterization (inbred reflection absorption spectroscopy, ellipsometry, contact angle, scanning probe microscopy, and heterogeneous electron-transfer kinetics) and various modeling scenarios. The results of these characterizations present ground-breaking insights into the structure, function, and reproducible preparation of these monolayers. Surprisingly, three interfacial properties (electron-transfer, contact angle, and ellipsometry) were discovered to depend directly on the odd-even character of the monolayer components. Molecular modeling was utilized to investigate adlayer orientation, and suggests that these effects are adlayer structure specific. Finally, the electric force microscopy and theoretical modeling investigations of monolayer samples are presented, which show that the film dielectric constant, thickness, and dipole moment directly affect image contrast. In addition, the prospects for utilization of this emerging technique are outlined.

  14. Facile tuning of superhydrophobic states with Ag nanoplates.

    SciTech Connect

    Sun, Y.; Qiao, R.; Clemson Univ.

    2008-01-01

    GaAs wafers have been decorated with Ag nanoplates through direct galvanic reaction between aqueous AgNO{sub 3} solutions and GaAs, resulting in Ag nanoplate/GaAs composite surfaces with varying hydrophobocity after the Ag nanoplates are coated with self-assembled monolayers of alkyl thiol molecules. By carefully controlling the reaction conditions, such as growth time and concentration of the AgNO{sub 3} solution, the size, thickness, and surface roughness of the individual Ag nanoplates can be tuned in order to produce different topographic structures and roughness of the composite surfaces, which in turn influences the hydrophobicity of the surfaces. The as-synthesized composite surfaces have been found to exhibit various levels of hydrophobicity and different wetting states such as the Wenzel wetting state, Cassie impregnating wetting state, and Cassie nonwetting state. The relationship between surface structure and hydrophobic state is also discussed.

  15. Evidence for graphite-like hexagonal AlN nanosheets epitaxially grown on single crystal Ag(111)

    NASA Astrophysics Data System (ADS)

    Tsipas, P.; Kassavetis, S.; Tsoutsou, D.; Xenogiannopoulou, E.; Golias, E.; Giamini, S. A.; Grazianetti, C.; Chiappe, D.; Molle, A.; Fanciulli, M.; Dimoulas, A.

    2013-12-01

    Ultrathin (sub-monolayer to 12 monolayers) AlN nanosheets are grown epitaxially by plasma assisted molecular beam epitaxy on Ag(111) single crystals. Electron diffraction and scanning tunneling microscopy provide evidence that AlN on Ag adopts a graphite-like hexagonal structure with a larger lattice constant compared to bulk-like wurtzite AlN. This claim is further supported by ultraviolet photoelectron spectroscopy indicating a reduced energy bandgap as expected for hexagonal AlN.

  16. Nano-scale characterization of binary self-assembled monolayers under an ambient condition with STM and TERS.

    PubMed

    Horimoto, Noriko N; Tomizawa, Shigeru; Fujita, Yasuhiko; Kajimoto, Shinji; Fukumura, Hiroshi

    2014-09-01

    Gold surfaces were modified by benzyl-mercaptan (BM) and then partly replaced with benzenethiol (BT), which formed binary self-assembled monolayers (SAM). Initially BT randomly replaced BM in the monolayer, but at long exchange times >15 nm radius domains were observed with specific relative composition of BT and BM.

  17. Nd-doped ZnO monolayer: High Curie temperature and large magnetic moment

    NASA Astrophysics Data System (ADS)

    Tan, Changlong; Sun, Dan; Zhou, Long; Tian, Xiaohua; Huang, Yuewu

    2016-10-01

    We performed first-principles calculations within density-functional theory to study the structural, electronic, and magnetic properties of Nd-doped ZnO monolayer. The calculated results reveal that Nd-doped ZnO monolayer exhibits stable room temperature ferromagnetism with a large saturation magnetic moment of 3.99 μB per unit in ZnO monolayer. The magnetic property is contributed to the localized f sates of Nd atoms. When two Zn atoms are substituted by two Nd dopants, they tend to form ferromagnetic (FM) coupling and the estimated Curie temperature is higher than room temperature. More interesting, the impurity bands appear within the band gap of ZnO monolayer due to the introduction of Nd dopant. Our results may provide a reference for modifying the material property of ZnO monolayer and are promising as nanoscale building block in spintronic devices.

  18. Correcting the AGS depolarizing resonances

    SciTech Connect

    Ratner, L.G.

    1986-01-01

    For the 1986 AGS run, the technique of correcting an imperfection resonance using a beat harmonic instead of the direct harmonic was applied and found to be useful in achieving a 22 GeV/c polarized beam. Both conventional and modified techniques are explained. (LEW)

  19. Self-Assembled Monolayers of Oligophenylenecarboxylic Acids on Silver Formed at the Liquid-Solid Interface.

    PubMed

    Aitchison, Hannah; Lu, Hao; Hogan, Simon W L; Früchtl, Herbert; Cebula, Izabela; Zharnikov, Michael; Buck, Manfred

    2016-09-20

    A series of para-oligophenylene mono- and dicarboxylic acids (R-(C6H4)nCOOH, n = 1-3, R = H,COOH) was studied. Adsorbed on Au(111)/mica modified by an underpotential deposited bilayer of Ag, the self-assembled monolayers (SAMs) were analyzed by near-edge X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and scanning tunneling microscopy. In all cases SAMs are formed with molecules adopting an upright orientation and anchored to the substrate by a carboxylate. Except benzoic acid, all SAMs could be imaged at molecular resolution, which revealed highly crystalline layers with a dense molecular packing. The structures of the SAMs are described by a rectangular (5 × √3) unit cell for the prevailing phase of the monocarboxylic acids and an oblique ([Formula: see text]) unit cell for the dicarboxylic acids, thus evidencing a pronounced influence of the second COOH moiety on the SAM structure. Density functional theory calculations suggest that hydrogen bonding between the SAM-terminating COOH moieties accounts for the difference. Contrasting other classes of SAMs, the systems studied here are determined by intermolecular interactions whereas molecule-substrate interactions play a secondary role. Thus, eliminating problems arising from the mismatch between the molecular and the substrate lattices, coordinatively bonded carboxylic acids on silver should provide considerable flexibility in the design of SAM structures. PMID:27588836

  20. Monolayer coated aerogels and method of making

    DOEpatents

    Zemanian, Thomas Samuel; Fryxell, Glen; Ustyugov, Oleksiy A.

    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.

  1. Improving the Dielectric Properties of Ethylene-Glycol Alkanethiol Self-Assembled Monolayers

    PubMed Central

    2014-01-01

    Self-assembled monolayers (SAMs) can be formed at the interface between solids and fluids, and are often used to modify the surface properties of the solid. One of the most widely employed SAM systems is exploiting thiol-gold chemistry, which, together with alkane-chain-based molecules, provides a reliable way of SAM formation to modify the surface properties of electrodes. Oligo ethylene-glycol (OEG) terminated alkanethiol monolayers have shown excellent antifouling properties and have been used extensively for the coating of biosensor electrodes to minimize nonspecific binding. Here, we report the investigation of the dielectric properties of COOH-capped OEG monolayers and demonstrate a strategy to improve the dielectric properties significantly by mixing the OEG SAM with small concentrations of 11-mercaptoundecanol (MUD). The monolayer properties and composition were characterized by means of impedance spectroscopy, water contact angle, ellipsometry and X-ray photoelectron spectroscopy. An equivalent circuit model is proposed to interpret the EIS data and to determine the conductivity of the monolayer. We find that for increasing MUD concentrations up to about 5% the resistivity of the SAM steadily increases, which together with a considerable decrease of the phase of the impedance, demonstrates significantly improved dielectric properties of the monolayer. Such monolayers will find widespread use in applications which depend critically on good dielectric properties such as capacitive biosensor. PMID:24447311

  2. Covalently networked monolayer-protected nanoparticle films.

    PubMed

    Tognarelli, D J; Miller, Robert B; Pompano, Rebecca R; Loftus, Andrew F; Sheibley, Daniel J; Leopold, Michael C

    2005-11-22

    Covalently networked films of nanoparticles can be assembled on various substrates from functionalized monolayer-protected clusters (MPCs) via ester coupling reactions. Exposure of a specifically modified substrate to alternating solutions of 11-mercaptoundecanoic acid exchanged and 11-mercaptoundecanol exchanged MPCs, in the presence of ester coupling reagents, 1,3-dicyclohexylcarbodiimide and 4-(dimethylamino)pyridine, results in the formation of a multilayer film with ester bridges between individual nanoparticles. These films can be grown in a controlled manner to various thicknesses and exhibit certain properties that are consistent with films having other types of interparticle connectivity, including chemical vapor response behavior and quantized double layer charging. Ester coupling of MPCs into assembled films is a straightforward and highly versatile approach that results in robust films that can endure harsher chemical environments than other types of films. The stability of these covalent films is assessed and compared to other more traditional MPC film assemblies.

  3. Adsorption of sulfur on Ag(100)

    SciTech Connect

    Russell, Selena M.; Shen, Mingmin; Liu, Da-Jiang; Thiel, Patricia A.

    2010-12-17

    We have used scanning tunneling microscopy and density Functional theory to investigate the structures formed by sulfur on Ag(100). As indicated by previous low-energy electron diffraction studies, the main phases have unit cells of p(2 x 2) and ({radical}17 x {radical}17)R14{sup o}. We show that the latter is a reconstruction. The favored structural model is one in which 5 Ag atoms are missing from the (100) surface plane per unit cell. The ejected Ag atoms combine with sulfur to form islands of the reconstructed phase on the terraces. The ({radical}17 x {radical}17)R14{sup o} phase coexists with the p(2 x 2), at sulfur coverages slightly above 0.25 monolayers. In addition, chain-like structures are observed in STM, both at room temperature (where they are dynamic) and below (where they are not). These results are compared with relevant literature for copper surfaces.

  4. Biointerfaces on indium-tin oxide prepared from organophosphonic acid self-assembled monolayers.

    PubMed

    Chockalingam, Muthukumar; Magenau, Astrid; Parker, Stephen G; Parviz, Maryam; Vivekchand, S R C; Gaus, Katharina; Gooding, J Justin

    2014-07-22

    Herein we show the development of biointerfaces on indium-tin oxide (ITO) surfaces prepared from organophosphonate self-assembled monolayers. The interfaces were prepared in a stepwise fabrication procedure containing a base monolayer modified with oligo(ethylene oxide) species to which biological recognition ligands were attached. The density of ligands was controlled by varying the ratio of two oligo(ethylene oxide) species such that only one is compatible with further coupling. The final biointerface on ITO was assessed using cell adhesion studies, which showed that the biointerfaces prepared on ITO performed similarly to equivalent monolayers on gold or silicon.

  5. Monolayer-induced band shifts at Si(100) and Si(111) surfaces

    SciTech Connect

    Mäkinen, A. J. Kim, Chul-Soo; Kushto, G. P.

    2014-01-27

    We report our study of the interfacial electronic structure of Si(100) and Si(111) surfaces that have been chemically modified with various organic monolayers, including octadecene and two para-substituted benzene derivatives. X-ray photoelectron spectroscopy reveals an upward band shift, associated with the assembly of these organic monolayers on the Si substrates, that does not correlate with either the dipole moment or the electron withdrawing/donating character of the molecular moieties. This suggests that the nature and quality of the self-assembled monolayer and the intrinsic electronic structure of the semiconductor material define the interfacial electronic structure of the functionalized Si(100) and Si(111) surfaces.

  6. Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

    DOE PAGESBeta

    Song, Wentao; Leung, Kevin; Shao, Qian; Gaskell, Karen J.; Reutt-Robey, Janice E.

    2016-09-15

    The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF)2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF)2, through the saturation monolayer limit, in which these two chemical species phasemore » separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF)2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.« less

  7. Electromelting of Confined Monolayer Ice

    NASA Astrophysics Data System (ADS)

    Qiu, Hu; Guo, Wanlin

    2013-05-01

    In sharp contrast to the prevailing view that electric fields promote water freezing, here we show by molecular dynamics simulations that monolayer ice confined between two parallel plates can melt into liquid water under a perpendicularly applied electric field. The melting temperature of the monolayer ice decreases with the increasing strength of the external field due to the field-induced disruption of the water-wall interaction induced well-ordered network of the hydrogen bond. This electromelting process should add an important new ingredient to the physics of water.

  8. Electromelting of confined monolayer ice.

    PubMed

    Qiu, Hu; Guo, Wanlin

    2013-05-10

    In sharp contrast to the prevailing view that electric fields promote water freezing, here we show by molecular dynamics simulations that monolayer ice confined between two parallel plates can melt into liquid water under a perpendicularly applied electric field. The melting temperature of the monolayer ice decreases with the increasing strength of the external field due to the field-induced disruption of the water-wall interaction induced well-ordered network of the hydrogen bond. This electromelting process should add an important new ingredient to the physics of water. PMID:23705718

  9. Influence of self-assembled monolayer surface chemistry on Candida antarctica lipase B adsorption and specific activity

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Immobilization of Candida antarctica B lipase was examined on gold surfaces modified with either methyl- or hydroxyl-terminated self-assembled alkylthiol monolayers (SAMs), representing hydrophobic and hydrophilic surfaces, respectively. Lipase adsorption was monitored gravimetrically using a quart...

  10. Characterization of heterojunctions via x-ray and uv photoemission spectroscopy: energy level implications for single and mixed monolayer SAMs, cadmium selenide nanoparticle films, and organic semiconductor depositions

    NASA Astrophysics Data System (ADS)

    Graham, Amy L.

    This work has centered on the interface dipoles arising at heterojunctions between metals, semiconductor nanoparticles, self-assembled monolayers, and organic semiconductor materials. Alkanethiol self-assembled monolayers, CdSe nanocrystals, and the organic semiconductors zinc phthalocyanine (ZnPc) and Buckminster fullerene (C60) were the basis of these investigations. UV photoemission spectroscopy has proven to be an invaluable tool to observe the vacuum level shifts for these analyses while using XPS to corroborate surface structure. With a full evaluation of these surfaces, the shifts in the vacuum level, valence ionizations, and core ionizations, the impact of these interfaces, as well as their influence on the subsequent deposition of organic semiconductor layers is established. Alkanethiols possessing varying dipole moments were examined on gold and silver substrates. The viability of these alkanethiols was demonstrated to predictively adjust the work function of these metals as a function of their intrinsic dipole moments projected to surface normal, and established differences between Ag---S and Au---S bonds. The capability of the SAMs to modify the work function of gold provided an opportunity for mixed monolayers of the alkanethiols to produce a precise range of work functions by minimal adjustments of solution concentration, which were examined with a simple point dipole model. Photoemission spectroscopy offers a thorough analysis of CdSe nanoparticle films. Despite a plethora of research on these nanocrystals, there still is controversy on the magnitude of the shift in the valence band with diameter. In our research we found the majority of the valence band shift could be attributed to the interface dipole, ignored previously. Meanwhile, the valence band tethered films was obscured by the sulfur of the thiol tether. Finally, organic semiconductor layers deposited on SAMs on gold exhibited various interface dipole effects at these heterojunctions. Charge

  11. Ubiquitous pentacene monolayer on metals deposited onto pentacene films.

    PubMed

    Jaeckel, B; Sambur, J B; Parkinson, B A

    2007-11-01

    Photoelectron spectroscopy (XPS and UPS) was used to study the deposition of metal layers (Ag, Cu, and Au) onto pentacene films. Very low work functions were measured (PhiAg = 3.91 eV, PhiCu = 3.93 eV, and PhiAu = 4.3 eV) for all of the metals, in agreement with results from the literature. The intensities of the C 1s core-level signals from pentacene that were monitored during stepwise metal deposition leveled off at a value of about 30% of a thick pentacene film. This C 1s intensity is comparable to that of one monolayer of pentacene deposited onto the respective metal. The valence band spectra of metals deposited onto pentacene and spectra collected for pentacene deposited onto bare metal surfaces are very similar. These findings lead to the conclusion that approximately one monolayer of pentacene is always present on top of the freshly deposited metal film, which explains the very low work function of the metals when they are deposited onto organic films. We expect similar behavior with other nonreactive metals deposited onto stable organic layers.

  12. General synthesis of noble metal (Au, Ag, Pd, Pt) nanocrystal modified MoS2 nanosheets and the enhanced catalytic activity of Pd-MoS2 for methanol oxidation.

    PubMed

    Yuwen, Lihui; Xu, Fei; Xue, Bing; Luo, Zhimin; Zhang, Qi; Bao, Biqing; Su, Shao; Weng, Lixing; Huang, Wei; Wang, Lianhui

    2014-06-01

    A general and facile method for water-dispersed noble metal (Au, Ag, Pd, Pt) nanocrystal modified MoS2 nanosheets (NM-MoS2 NSs) has been developed. By using sodium carboxymethyl cellulose as a stabilizer, well-dispersed NM-MoS2 NSs with homogeneously deposited noble metal nanocrystals (NM NCs) can be synthesized in aqueous solutions. Due to the transition from the semiconducting 2H phase to the metallic 1T phase, the chemically exfoliated MoS2 (ce-MoS2) NSs have improved electrochemical activity. The partially metallic nature of the ce-MoS2 NSs and the catalytic activity of the NM NCs synergistically make NM-MoS2 NSs a potential electrochemical catalyst. For the first time, Pd-MoS2 NSs were used as an electrocatalyst for methanol oxidation in alkaline media. The results showed that Pd-MoS2 NSs have enhanced catalytic activity with 2.8-fold anodic peak current mass density compared to a commercial Pd/C catalyst, suggesting potential for application in direct methanol fuel cells (DMFCs).

  13. AGS II

    SciTech Connect

    Palmer, R.B.

    1984-01-01

    Interest in rare K decays, neutrino oscillations and other fields have generated an increasing demand for running, and improved intensity and duty cycle, at the AGS. Current projects include acceleration of polarized protons and light ions (up to mass 32). Future plans are for a booster to increase intensity and allow heavy ions (up to mass 200), and a stretcher to give 100% duty cycle. A later upgrade could yield an average current of 32 ..mu.. amps. 6 figures, 2 tables.

  14. Nanosized insulin-complexes based on biodegradable amine-modified graft polyesters poly[vinyl-3-(diethylamino)-propylcarbamate-co-(vinyl acetate)-co-(vinyl alcohol)]-graft-poly(L-lactic acid): protection against enzymatic degradation, interaction with Caco-2 cell monolayers, peptide transport and cytotoxicity.

    PubMed

    Simon, Michael; Behrens, Isabel; Dailey, Lea Anne; Wittmar, Matthias; Kissel, Thomas

    2007-05-01

    Non-parenteral insulin delivery by the oral route is limited by epithelial barriers and enzymatic degradation. Nanosized insulin-complexes based on amine modified comb-like polyesters were designed to overcome these barriers. Protection of insulin in nanocomplexes (NC) from enzymatic degradation was investigated. The interaction with enterocyte-like Caco-2 cells in terms of cytotoxicity, transport through and uptake in the cell layers was evaluated by measuring transepithelial electrical resistance (TEER), release of lactate dehydrogenase (LDH) and insulin transport. The protection capacity of NC and their interaction with Caco-2 cells varied strongly as a function of lactide-grafting (hydrophobicity). With increasing lactide-grafting (P(26) < or = P(26)-1(LL) < or = P(26)-2(LL)) NC protected up to 95% of the insulin against degradation by trypsin. Transport and uptake into cell monolayers increased with higher l-lactid grafting. About 25% of a 1.25mg/ml TRITC-insulin NC dispersion with P(26)-2(LL) was recovered in Caco-2 cells after 90 min. A concentration dependent cytotoxicity profile was observed showing elevated LDH release and decreased TEER values. The cytotoxicity correlates with the surfactant like character of the polymers, decreasing the surface tension to 46 mN/m for the amphiphilic P(26)-2(LL). The observed TEER decrease was reversible after 20 h, suggesting that the biodegradable comb-polyesters offer a promising approach to overcome mucosal barriers.

  15. Aminopropyltrimethoxysilane- and aminopropyltrimethoxysilane-silver-modified montmorillonite for the removal of nitrate ions.

    PubMed

    Gatti, Marcela N; Fernández, Laura G; Sánchez, María P; Parolo, M Eugenia

    2016-10-01

    A natural clay (Mn) modified with γ-aminopropyltrimethoxysilane (Mn-S) and silver (Mn-S-Ag) were evaluated as a potential adsorption media for nitrate removal from water. These materials were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, zeta-potential, thermogravimetric analysis, scanning electron microscopy and elemental analyses. First, the adsorption capacity of the Mn-S clay for Ag(+) was studied. The cation adsorption capacity was almost three times greater for Mn-S than for Mn because a metal-amino group complex is favored. Second, the nitrate adsorption on Mn-S and Mn-S-Ag was studied as a function of contact time, pH, temperature and adsorbent dosage using batch techniques. In the absence of Ag(+), [Formula: see text] adsorption was high at low pH and the amount of adsorbed nitrate decreased as the pH increased. For the Mn-S, the following monolayer adsorption capacities were obtained: Qmax = 0.80, 0.72 and 0.68 mmol [Formula: see text]/g at pH 3, 5 and 7, respectively, whereas for the Mn-S-Ag the values obtained were: Qmax = 0.77, 0.74 and 0.42 mmol [Formula: see text]/g at pH 3, 5 and 7, respectively. From the results obtained, [Formula: see text] adsorption occurs over [Formula: see text] surface groups without involving the Ag(+) cation in the adsorption process.

  16. Construction of a new selective coated disk electrode for Ag (I) based on modified polypyrrole-carbon nanotubes composite with new lariat ether.

    PubMed

    Abbaspour, A; Tashkhourian, J; Ahmadpour, S; Mirahmadi, E; Sharghi, H; Khalifeh, R; Shahriyari, M R

    2014-01-01

    A poly (vinyl chloride) (PVC) matrix membrane ion-selective electrode for silver (I) ion is fabricated based on modified polypyrrole - multiwalled carbon nanotubes composite with new lariat ether. This sensor has a Nernstian slope of 59.4±0.5mV/decade over a wide linear concentration range of 1.0×10(-7) to 1.0×10(-1)molL(-1) for silver (I) ion. It has a short response time of about 8.0s and can be used for at least 50days. The detection limit is 9.3×10(-8)molL(-1) for silver (I) ion, and the electrode was applicable in the wide pH range of 1.6 -7.7. The electrode shows good selectivity for silver ion against many cations such as Hg (II), which usually imposes serious interference in the determination of silver ion concentration. The use of multiwalled carbon nanotubes (MWCNTs) in a polymer matrix improves the linear range and sensitivity of the electrode. In addition by coating the solid contact with a layer of the polypyrrole (Ppy) before coating the membrane on it, not only did it reduce the drift in potential, but a shorter response time was also resulted. The proposed electrode was used as an indicator electrode for potentiometric titration of silver ions with chloride anions and in the titration of mixed halides. This electrode was successfully applied for the determination of silver ions in silver sulphadiazine as a burning cream.

  17. Surfactant role of Ag atoms in the growth of Si layers on Si(111)√3×√3-Ag substrates

    SciTech Connect

    Yamagami, Tsuyoshi; Sone, Junki; Nakatsuji, Kan; Hirayama, Hiroyuki

    2014-10-13

    The growth of Si layers on Si(111)√3×√3-Ag substrates was studied for coverages of up to a few mono-layers. Atomically flat islands were observed to nucleate in the growth at 570 K. The top surfaces of the islands were covered in Ag atoms and exhibited a √3×√3 reconstruction with the same surface state dispersions as Si(111)√3×√3-Ag substrates. These results indicate that the Ag atoms on the substrate always hop up to the top of the Si layers.

  18. First-principles study of the contractive reconstruction of gold and silver monolayers on gold, silver and aluminum

    SciTech Connect

    Takeuchi, Noboru.

    1990-11-16

    Using first-principles calculations in conjunction with modeling techniques, the author has investigated the structures of Au and Ag monolayers on a number of metal surfaces. Au(100) has a c(26 {times} 68) surface unit cell and the reconstruction has been interpreted as the top layer transforming to a contracted hexagonal-close-packed layer, superimposed on the square lattice of the underlying substrate atoms. Similar reconstructions have been observed on the 5d fcc metals Ir and Pt, but not in the 4d Rh, Pd, and Ag. The author studied the energetics of a monolayer of Au and Ag using first-principles calculations. The author found that it is energetically favorable for both Au and Ag to transform from a square to hexagonal arrangement and to contract to a higher surface density, but Au gains substantially more energy than Ag. This is true both for a monolayer in isolation as well as on top of a jellium surface. The author also calculated the mismatch energy (energy loss when the top layer loses registry with the substrate) for Au and Ag, and found that Ag has a slightly higher mismatch energy. The first-principles results thus offer a strong indication that Au(100) can reconstruct but Ag will not. The reconstruction is further studied with a 2 dimensional Frenkel-Kontorowa model, with parameters extracted from the total energy calculations. The author found that it is indeed energetically favorable for the top layer of Au(100), but not for Ag, to transform to a hexagonal-close-packed structure and contract. 85 refs., 34 figs., 8 tabs.

  19. Convective microsphere monolayer deposition

    NASA Astrophysics Data System (ADS)

    Gilchrist, James

    2011-03-01

    There is perhaps no simpler way of modifying surface chemistry and morphology than surface deposition of particles. Micron-sized microspheres were deposited into thin films via rapid convective deposition, similar to the `coffee ring effect' using a similar method to that studied by Prevo and Velev, Langmuir, 2003. By varying deposition rate and blade angle, the optimal operating ranges in which 2D close-packed arrays of microspheres existed were obtained. Self-assembly of colloidal particles through a balance of electrostatic and capillary forces during solvent evaporation was revealed. These interactions were explored through a model comparing the residence time of a particle in the thin film and the characteristic time of capillary-driven crystallization to describe the morphology and microstructure of deposited particles. Co-deposition of binary suspensions of micron and nanoscale particles was tailored to generate higher-quality surface coatings and a simple theory describes the immergence of instabilities that result in formation of stripes. Optical and biomedical applications that utilize the described nanoscale control over surface morphology will also be discussed.

  20. Plasmon-assisted photocurrent generation from silver nanoparticle monolayers combined with porphyrins via their different chain-length alkylcarboxylates.

    PubMed

    Kakuta, Takayoshi; Kon, Hiroki; Kajikawa, Azusa; Kanaizuka, Katsuhiko; Yagyu, Shigeta; Miyake, Ryosuke; Ishizakil, Manabu; Uruma, Keirei; Togashi, Takanari; Sakamoto, Masatomi; Kurihara, Masato

    2014-06-01

    Three-typed porphyrin derivatives with a different chain-length alkylcarboxylic acid as their peripheral anchor group have been prepared. Anodic photocurrents were observed in a simple system where the porphyrin derivatives were directly anchored on an indium tin oxide (ITO) electrode. Cathodic photocurrents and their plasmon-assisted enhancement appeared from an Ag nanoparticle (Ag NP) composite monolayer combined with the porphyrin derivatives on the ITO electrode. In the photocurrent generation mechanism, Ag NPs played both the roles as photon- and energy-transfer to the porphyrin derivatives. The plasmon-assisted enhancement was affected by the chain-lengths of the peripheral anchor groups. PMID:24738356

  1. Dependence of the band structure of C-60 monolayers on molecularorientations and doping observed by angle resolved photoemission

    SciTech Connect

    Brouet, V.; Yang, W.L.; Zhou, X.J.; Hussain, Z.; Shen, Z.X.

    2008-01-17

    We present angle resolved photoemission studies of C60monolayers deposited on Ag surfaces. The electronic structure of thesemonolayers is derived from the partial filling of the narrow, 6-folddegenerated, C60 conduction band. By comparing the band structure in twomonolayers deposited, respectively, on Ag(111) and Ag(100), we show thatthe molecular degree of freedom, in this case the relative orientationsbetween C60 molecules, is essential to describe the band structure. Wefurther show that the evolution of the band as a function of doping doesnot follow a rigid band-filling picture. Phase separation is observedbetween a metallic and an insulating phase, which might be a result ofstrong correlations.

  2. Atomistic simulation of the electronic states of adatoms in monolayer MoS2

    NASA Astrophysics Data System (ADS)

    Chang, Jiwon; Larentis, Stefano; Tutuc, Emanuel; Register, Leonard F.; Banerjee, Sanjay K.

    2014-04-01

    Using an ab initio density functional theory based electronic structure method, we study the effects of adatoms on the electronic properties of monolayer transition metal dichalcogenide Molybdenum-disulfide (MoS2). We consider the 1st (Li, Na, K) and 7th (F, Cl, Br) column atoms and metals (Sc, Ti, Ta, Mo, Pd, Pt, Ag, Au). Three high symmetry sites for the adatom on the surface of monolayer MoS2 are examined as starting points to search for the most energetically stable configuration for each adatom-monolayer MoS2 system, as well as the type of associated bonding. For the most stable adatom positions, we characterize the emergence of adatom-induced electronic states including any dopant states.

  3. Structure and Long-Term Stability of Alkylphosphonic Acid Monolayers on SS316L Stainless Steel.

    PubMed

    Kosian, Medea; Smulders, Maarten M J; Zuilhof, Han

    2016-02-01

    Surface modification of stainless steel (SS316L) to improve surface properties or durability is an important avenue of research, as SS316L is widely used in industry and science. We studied, therefore, the formation and stability of a series of organic monolayers on SS316L under industrially relevant conditions. These included acidic (pH 3), basic (pH 11), neutral (Milli-Q water), and physiological conditions [10 mM phosphate-buffered saline (PBS)], as well as dry heating (120 °C). SS316L was modified with alkylphosphonic acids of chain length (CH2)n with n varying between 3 and 18. While alkylphosphonic acids of all chain lengths formed self-assembled monolayers with hydrophobic properties, only monolayers of chain lengths 12-18 formed ordered monolayers, as evidenced by static water contact angle (SCA), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and infrared reflection absorption spectroscopy (IRRAS). A long-term stability study revealed the excellent stability of monolayers with chain lengths 12-18 for up to 30 days in acid, neutral, and physiological solutions, and for up to 7 days under dry heating. Under strong basic conditions a partial breakdown of the monolayer was observed, especially for the shorter chain lengths. Finally, the effect of multivalent surface attachment on monolayer stability was explored by means of a series of divalent bisphosphonic acids. PMID:26771302

  4. Multifunctional Self-Assembled Monolayers for Organic Field-Effect Transistors

    NASA Astrophysics Data System (ADS)

    Cernetic, Nathan

    Organic field effect transistors (OFETs) have the potential to reach commercialization for a wide variety of applications such as active matrix display circuitry, chemical and biological sensing, radio-frequency identification devices and flexible electronics. In order to be commercially competitive with already at-market amorphous silicon devices, OFETs need to approach similar performance levels. Significant progress has been made in developing high performance organic semiconductors and dielectric materials. Additionally, a common route to improve the performance metric of OFETs is via interface modification at the critical dielectric/semiconductor and electrode/semiconductor interface which often play a significant role in charge transport properties. These metal oxide interfaces are typically modified with rationally designed multifunctional self-assembled monolayers. As means toward improving the performance metrics of OFETs, rationally designed multifunctional self-assembled monolayers are used to explore the relationship between surface energy, SAM order, and SAM dipole on OFET performance. The studies presented within are (1) development of a multifunctional SAM capable of simultaneously modifying dielectric and metal surface while maintaining compatibility with solution processed techniques (2) exploration of the relationship between SAM dipole and anchor group on graphene transistors, and (3) development of self-assembled monolayer field-effect transistor in which the traditional thick organic semiconductor is replaced by a rationally designed self-assembled monolayer semiconductor. The findings presented within represent advancement in the understanding of the influence of self-assembled monolayers on OFETs as well as progress towards rationally designed monolayer transistors.

  5. Monolayer-Mediated Patterning of Electroceramic Thin Films

    SciTech Connect

    Clem, P.G.; Payne, D.A.

    1998-10-11

    Integrated electroceramic thin film devices on semiconductor and insulator substrates feature a variety of attractive attributes, including high capacitance density, nonvolatile memory, sensor/actuator ability, and other unique electronic and optical properties. The ability to pattern such ceramic materials atop semiconductor substrates, thus, is a critical technology. Patterned oxide thin film devices are typically formed by uniform film deposition followed by somewhat complicated post-deposition ion-beam or chemical etching in a controlled environment. We review here the development of an ambient atmosphere technique which allows selective deposition of electroceramic thin layers without such post-deposition etching. In this method, substrate surfaces are selectively functionalized with hydrophobic self-assembled monolayer to modify the adhesion of subsequently deposited solution-derived electroceramics. The selective fictionalization is achieved through microcontact printing (v-CP) of self-assembled monolayer of the chemical octadecyltrichlorosilane on substrates of technical interest. Subsequent sol-gel deposition of ceramic oxides on these functionalized substrates, followed by lift-off from the monolayer, yields high quality, patterned oxide thin layers only on the unfunctionalized regions. A variety of micron- scale dielectric oxide devices have been fabricated using this process, with lateral resolution as fine as 0.5Lm. In this paper, we review the monolayer patterning and electrical behavior of several patterned electroceramic thin films, including Pb(Zr,Ti)03 [PZT], LiNb03, and Ta205. An applied device example is also presented in combination with selective MOCVD deposition of metal electrodes: integrated, fully monolayer-patterned Pt//PZT//PSi(Si(100) ferroelectric memory cells.

  6. Effect of Ag+ and PO43‑ ratios on the microstructure and photocatalytic activity of Ag3PO4

    NASA Astrophysics Data System (ADS)

    Qin, Jiaqian; Zhang, Xinyu; Yang, Chengwu; Song, Aijun; Zhang, Bing; Rajendran, Saravanan; Ma, Mingzhen; Liu, Riping

    2016-09-01

    In this work, the catalyst silver phosphate (Ag3PO4) with different initial ratios of Ag+ and PO43‑ in aqueous solution was synthesized by a simple precipitation method from AgNO3 and NH4H2PO4 which were used as the precursor. After that, the prepared samples were characterized by different techniques such as field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), UV-visible diffuse reflectance spectroscopy (UV-DRS) and decomposition evolution of rhodamine B (RhB) solution. The results indicate that the initial ratios of Ag+/PO43‑ in aqueous solution can modify the morphology and also it can significantly affect the photocatalytic performance. During photocatalytic process, the rich Ag+ ion Ag3PO4 can form the surface plasmon resonance (SPR) of Ag nanoparticles, which inhibit the reduction of Ag3PO4 resulting in higher photocatalytic activity and stability.

  7. Comparison of the early stages of condensation of Cu and Ag on Mo/100/ with Cu and Ag on W/100/

    NASA Technical Reports Server (NTRS)

    Soria, F.; Poppa, H.

    1980-01-01

    The adsorption and condensation of Cu and Ag, up to several monolayers in thickness, onto Mo(100) has been observed at pressures below 2 times 10 to the -10th torr in a study that used combined LEED, Auger, TDS (Thermal Desorption Spectroscopy), and work function measurements in a single experimental setup. The results show that Cu behaves similarly on Mo(100) and W(100) substrates, while some differences are found for Ag adsorption.

  8. Fabrication of Sn-3.5Ag Eutectic Alloy Powder by Annealing Sub-Micrometer Sn@Ag Powder Prepared by Citric Acid-Assisted Ag Immersion Plating.

    PubMed

    Chee, Sang-Soo; Choi, Eun Byeol; Lee, Jong-Hyun

    2015-11-01

    A Sn-3.5Ag eutectic alloy powder has been developed by chemically synthesizing sub-micrometer Sn@Ag powder at room temperature. This synthesis was achieved by first obtaining a sub-micrometer Sn powder for the core using a modified variant of the polyol method, and then coating this with a uniformly thin and continuous Ag layer through immersion plating in 5.20 mM citric acid. The citric acid was found to play multiple roles in the Ag coating process, acting as a chelating agent, a reducing agent and a stabilizer to ensure coating uniformity; and as such, the amount used has an immense influence on the coating quality of the Ag shells. It was later verified by transmission electron microscopy and X-ray diffraction analysis that the coated Ag layer transfers to the Sn core via diffusion to form an Ag3Sn phase at room temperature. Differential scanning calorimetry also revealed that the synthesized Sn@Ag powder is nearly transformed into Sn-3.5Ag eutectic alloy powder upon annealing three times at a temperature of up to 250 degrees C, as evidenced by a single melting peak at 220.5 degrees C. It was inferred from this that Sn-3.5Ag eutectic alloy powder can be successfully prepared through the synthesis of core Sn powders by a modified polyol method, immersion plating using citric acid, and annealing, in that order.

  9. Preparation, characterization, and photocatalytic activity of porous AgBr@Ag and AgBrI@Ag plasmonic photocatalysts

    NASA Astrophysics Data System (ADS)

    Yang, Fan; Tian, Baozhu; Zhang, Jinlong; Xiong, Tianqing; Wang, Tingting

    2014-02-01

    Porous AgBr@Ag and AgBrI@Ag plasmonic photocatalysts were synthesized by a multistep route, including a dealloying method to prepare porous Ag, a transformation from Ag to AgBr and AgBrI, and a photo-reduction process to form Ag nanoparticles on the surface of AgBr and AgBrI. It was found that the porous structure kept unchanged during Ag was transferred into AgBr, AgBrI, AgBr@Ag, and AgBrI@Ag. Both porous AgBr@Ag and porous AgBrI@Ag showed much higher visible-light photocatalytic activity than cubic AgBr@Ag for the degradation of methyl orange, which is because the interconnected pore channels not only provide more reactive sites but also favor the transportation of photo-generated electrons and holes. For AgBrI@Ag, AgBrI solid solution formed at the interface of AgBr and AgI, and the phase junction can effectively separate the photo-generated electrons and holes, favorable to the improvement of photocatalytic activity. The optimal I content for obtaining the highest activity is ∼10 at.%.

  10. Structure and shear response of lipid monolayers

    SciTech Connect

    Dutta, P.; Ketterson, J.B.

    1990-02-01

    Organic monolayers and multilayers are both scientifically fascinating and technologically promising; they are, however, both complex systems and relatively inaccessible to experimental probes. In this Progress Report, we describe our X-ray diffraction studies, which have given us substantial new information about the structures and phase transitions in monolayers on the surface of water; our use of these monolayers as a unique probe of the dynamics of wetting and spreading; and our studies of monolayer mechanical properties using a simple but effective technique available to anyone using the Wilhelmy method to measure surface tension.

  11. Stability of antibacterial self-assembled monolayers on hydroxyapatite.

    PubMed

    Torres, Nelson; Oh, Sunho; Appleford, Mark; Dean, David D; Jorgensen, James H; Ong, Joo L; Agrawal, C Mauli; Mani, Gopinath

    2010-08-01

    Open fractures are common in battlefields, motor vehicle accidents, gunshot wounds, sports injuries, and high-energy falls. Such fractures are treated using hydroxyapatite (HA)-based bone graft substitutes. However, open fracture wounds are highly susceptible to bacterial infections. Hence, this study was focused on incorporating antibacterial properties to HA using silver (Ag) carrying self-assembled monolayers (SAMs). Also, the stability of Ag carrying SAMs on HA was investigated under sterilization and physiological conditions. Initially, the -COOH terminated phosphonic acid SAMs of two different chain lengths (11 carbon atoms - shorter chain and 16 carbon atoms - longer chain) were deposited on HA. Antibacterial SAMs (ASAMs) were prepared by chemically attaching Ag to shorter and longer chain SAMs coated HA. X-ray photoelectron spectroscopy, atomic force microscopy, and contact angle goniometry collectively confirmed the attachment of Ag onto SAMs coated HA. The bacterial adhesion study showed that the adherence of Staphylococcus aureus was significantly reduced on ASAMs coated HA when compared to control-HA. The stability studies showed that gas plasma, dry heat and autoclave degraded most of the ASAMs on HA. UV irradiation did not damage the shorter chain ASAMs as vigorously as other treatments, while it degraded the longer chain ASAMs completely. Ethylene oxide treatment did not degrade the longer chain ASAMs unlike all other treatments but it severely damaged the shorter chain ASAMs. Both shorter and longer chain ASAMs significantly desorbed from the HA surfaces under physiological conditions although longer chain ASAMs exhibited better stability than shorter chain ASAMs. This study demonstrated the potential for using ASAMs to provide antibacterial properties to HA and the need for developing techniques to improve stability of SAMs under sterilization and physiological conditions. PMID:20188873

  12. Electrochemical Potential Stabilization of Reconstructed Au(111) Structure by Monolayer Coverage with Graphene.

    PubMed

    Yasuda, Satoshi; Kumagai, Ryota; Nakashima, Koji; Murakoshi, Kei

    2015-09-01

    The electrochemical properties of a monolayer graphene grown on a Au(111) electrode were studied using cyclic voltammetry (CV) and electrochemical scanning tunneling microscopy (EC-STM). CV and EC-STM measurements in 0.1 M H2SO4 aqueous solution revealed that graphene grown on the reconstructed (22 × √3) Au(111) structure effectively inhibited potential-induced structural transitions between reconstructed (22 × √3) and unreconstructed (1 × 1), and the adsorption/desorption of SO4(2-) ions, which are intrinsic behavior of the bare Au(111) surface. The underlying reconstructed structure was significantly stabilized by covering with monolayer graphene over a wide potential range between -0.2 V and +1.35 V vs Ag/AgCl (saturated KCl), which is much wider than that for bare Au(111) (-0.2 to + 0.35 V vs Ag/AgCl (saturated KCl)). Such high stability has not been reported to date; therefore, these results are considered to be important for understanding the fundamentals of surface reconstruction and also serve to open a new branch of electrochemistry related to graphene/metal-electrolyte interfaces. PMID:26279244

  13. Monolayer Silane-Coated, Water-Soluble Quantum Dots.

    PubMed

    Zhang, Xi; Shamirian, Armen; Jawaid, Ali M; Tyrakowski, Christina M; Page, Leah E; Das, Adita; Chen, Ou; Isovic, Adela; Hassan, Asra; Snee, Preston T

    2015-12-01

    A one-step method to produce ≈12 nm hydrodynamic diameter water-soluble CdSe/ZnS quantum dots (QDs), as well as CdS/ZnS, ZnSe/ZnMnS/ZnS, AgInS2 /ZnS, and CuInS2 /ZnS QDs, by ligand exchange with a near-monolayer of organosilane caps is reported. The method cross-links the surface-bound silane ligands such that the samples are stable on the order of months under ambient conditions. Furthermore, the samples may retain a high quantum yield (60%) over this time. Several methods to functionalize aqueous QD dispersions with proteins and fluorescent dyes have been developed with reaction yields as high as 97%. PMID:26476710

  14. Raman modes of exfoliated black phosphorus down to the monolayer

    NASA Astrophysics Data System (ADS)

    Phaneuf-L'Heureux, Anne-Laurence; Favron, Alexandre; Gaufres, Etienne; Martel, Richard; Francoeur, Sebastien

    2015-03-01

    Exfoliated black phosphorus layers, or 2D-phosphane, are a lamellar direct-gap semiconductor providing high mobilities and enabling a thickness-controlled band gap tunability ranging from 0.3 up to about 2 eV. Using Raman spectroscopy, we have studied vibrational modes of pristine and non-oxidized 2D-phosphane as a function of the number of layers involved (n), and also as a function of temperature, polarization, and excitation wavelength. The evolution of the width and of the frequency of Ag2 as a function of n presents a clear non-monotonic dependence. This can be explained by the presence of new nearly-degenerate Raman-allowed modes that are symmetry-forbidden in both bulk and monolayer samples. We also present Raman spectra of few-layer samples for excitation wavelengths in the viscinity of the expected band gap.

  15. Monolayer Silane-Coated, Water-Soluble Quantum Dots.

    PubMed

    Zhang, Xi; Shamirian, Armen; Jawaid, Ali M; Tyrakowski, Christina M; Page, Leah E; Das, Adita; Chen, Ou; Isovic, Adela; Hassan, Asra; Snee, Preston T

    2015-12-01

    A one-step method to produce ≈12 nm hydrodynamic diameter water-soluble CdSe/ZnS quantum dots (QDs), as well as CdS/ZnS, ZnSe/ZnMnS/ZnS, AgInS2 /ZnS, and CuInS2 /ZnS QDs, by ligand exchange with a near-monolayer of organosilane caps is reported. The method cross-links the surface-bound silane ligands such that the samples are stable on the order of months under ambient conditions. Furthermore, the samples may retain a high quantum yield (60%) over this time. Several methods to functionalize aqueous QD dispersions with proteins and fluorescent dyes have been developed with reaction yields as high as 97%.

  16. Seeded growth of robust SERS-active 2D Au@Ag nanoparticulate films

    SciTech Connect

    Baker, Gary A; Dai, Sheng; Hagaman, Edward {Ed} W; Mahurin, Shannon Mark; Zhu, Haoguo; Bao, Lili

    2008-01-01

    We demonstrate herein a novel and versatile solution-based methodology for fabricating self-organized two-dimensional (2D) Au nanoparticle arrays on glass using in situ nucleation at an aminosilane monolayer followed by seeded, electroless growth; subsequent deposition of Ag produced Au{at}Ag core-shell nanoparticulate films which proved highly promising as surface-enhanced Raman scattering (SERS) platforms.

  17. Molecular Packing of Functionalized Fluorinated Lipids in Langmuir Monolayers

    SciTech Connect

    Landsberg, Michael J.; Ruggles, Jeremy L.; Hussein, Waleed M.; McGeary, Ross P.; Gentle, Ian R.; Hankamer, Ben

    2012-01-20

    Fluorinated amphipaths are a fascinating class of compounds, which, despite significant challenges associated with their syntheses, have found use across a number of areas of biotechnology. Applications range from the in vitro stabilization of membrane proteins to the development of enhanced stability intravenous drug and gene delivery systems. More recently, monolayer-forming fluorinated lipids have found use in the 2D crystallization of detergent-solubilized hydrophobic or partially hydrophobic proteins at the air-water interface. In this study, we investigate the surface properties of a novel suite of monolayer forming, partially fluorinated lipids. These modular lipid structures contain a densely fluorinated insertion in the hydrocarbon tail and a synthetically modifiable headgroup. Analyses of surface-pressure area isotherms and X-ray reflectometry profiles reveal that the lipids spread into fluid monolayers and are more compressible than their non-fluorinated counterparts. Furthermore, the data support a model whereby the partially fluorinated chains of the lipid tails form a film which is fundamentally incompatible with detergents and other destabilizing amphipaths.

  18. Haemoglobin synthesis in K562 erythroleukaemia cells is affected by intimate contact with monolayers of various human cell types.

    PubMed

    Zuhrie, S R; Pearson, J D; Wickramasinghe, S N

    1988-01-01

    The haemoglobin content of K562 erythroleukaemia cells was affected by co-culture over monolayers of various human cell types. Haemoglobin synthesis was increased after co-culture with umbilical-cord-derived endothelial cells and most monolayers of bone-marrow-derived macrophages, and inhibited after co-culture with two fibroblast lines, blood-monocyte-derived macrophages, a neuroglial cell line (U-251 MG) and most monolayers of bone-marrow-derived stromal cells. These effects were modified when a thin layer of agar was placed over the monolayers. Cell-free culture media conditioned by all but two of the seven types of monolayer studied inhibited haemoglobin synthesis by K562 cells; those conditioned by blood-monocyte-derived macrophages and two of 11 monolayers of bone-marrow-derived macrophages stimulated haemoglobin synthesis. Thus, the haemoglobin content of K562 cells appeared to be influenced both by intimate contact between K562 cells and the cells of the monolayers and by humoral factors released by the monolayers. The data support the concept that erythroid differentiation is partly dependent on intimate contact between erythroid progenitor cells and microenvironmental cells.

  19. Stilling Waves with Ordered Molecular Monolayers

    ERIC Educational Resources Information Center

    Vitz, Ed

    2008-01-01

    A demonstration of the damping effect of an oil monolayer on water waves is described. The history of this remarkable demonstration--with a 2000 (or more) year span--and a brief explanation in terms of the properties of water and the monolayer are presented. If a layer of olive oil, one molecule thick (about one-ten millionth of a centimeter), is…

  20. Cell adhesion on a polymerized peptide-amphiphile monolayer.

    PubMed

    Biesalski, Markus A; Knaebel, Alexandra; Tu, Raymond; Tirrell, Matthew

    2006-03-01

    We report the synthesis and characterization of a stable polymerized monolayer of peptide-amphihiles on a planar solid support that promotes mouse fibroblast cell adhesion and spreading. Peptide-amphiphiles consisting of a polymerizable fatty acid attached to a short RGD containing peptide sequence are self-assembled and polymerized at the water-air interface by means of the Langmuir- Blodgett technique. The surface concentration of the peptide-amphiphile is varied by co-spreading the peptide-amphiphile with an analogous non-modified polymerizable amphiphile at the water/air interface, prior to UV light-induced polymerization. The polymerized monolayer is transferred onto a hydrophobized smooth mica surface and the resulting surfaces have been investigated with respect to directing the cell adhesion and spreading of mouse fibroblast cells in a serum-free medium. Fibroblast cells adhere and spread on surfaces exposing the bioactive ligand but do not spread on reference surfaces without peptide. We find a maximum number of adherent cells at rather high peptide surface concentrations of about 10 mol% in the mixed monolayer, equivalent to more than 50 pmol/cm2 peptide on the surface of the film. We attribute this finding to a limited accessibility of the ligands by the integrins. Because of the stability of the polymerized peptide-amphiphile monolayer, these surfaces can be re-seeded multiple times with cells, i.e. adherent cells can be removed from the surface, the surface can be sterilized and cells can be re-attached. PMID:16157369

  1. Binary functionalization of H:Si(111) surfaces by alkyl monolayers with different linker atoms enhances monolayer stability and packing.

    PubMed

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

    2016-05-14

    Alkyl monolayer modified Si forms a class of inorganic-organic hybrid materials with applications across many technologies such as thin-films, fuel/solar-cells and biosensors. Previous studies have shown that the linker atom, through which the monolayer binds to the Si substrate, and any tail group in the alkyl chain, can tune the monolayer stability and electronic properties. In this paper we study the H:Si(111) surface functionalized with binary SAMs: these are composed of alkyl chains that are linked to the surface by two different linker groups. Aiming to enhance SAM stability and increase coverage over singly functionalized Si, we examine with density functional theory simulations that incorporate vdW interactions, a range of linker groups which we denote as -X-(alkyl) with X = CH2, O(H), S(H) or NH(2) (alkyl = C6 and C12 chains). We show how the stability of the SAM can be enhanced by adsorbing alkyl chains with two different linkers, e.g. Si-[C, NH]-alkyl, through which the adsorption energy is increased compared to functionalization with the individual -X-alkyl chains. Our results show that it is possible to improve stability and optimum coverage of alkyl functionalized SAMs linked through a direct Si-C bond by incorporating alkyl chains linked to Si through a different linker group, while preserving the interface electronic structure that determines key electronic properties. This is important since any enhancement in stability and coverage to give more densely packed monolayers will result in fewer defects. We also show that the work function can be tuned within the interval of 3.65-4.94 eV (4.55 eV for bare H:Si(111)).

  2. Facile synthesis of ternary Ag/AgBr-Ag2CO3 hybrids with enhanced photocatalytic removal of elemental mercury driven by visible light.

    PubMed

    Zhang, Anchao; Zhang, Lixiang; Lu, Hao; Chen, Guoyan; Liu, Zhichao; Xiang, Jun; Sun, Lushi

    2016-08-15

    A novel technique for photocatalytic removal of elemental mercury (Hg(0)) using visible-light-driven Ag/AgBr-Ag2CO3 hybrids was proposed. The ternary Ag/AgBr-Ag2CO3 hybrids were synthesized by a simple modified co-precipitation method and characterized by N2 adsorption-desorption, scanning electron microscope (SEM), X-ray diffraction (XRD), UV-vis diffused reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) techniques. The effects of AgBr content, fluorescent lamp (FSL) irradiation, solution temperature, SO2 and NO on Hg(0) removal were investigated in detail. Furthermore, a possible reaction mechanism for higher Hg(0) removal was proposed, and the simultaneous removal of Hg(0), SO2 and NO was studied. The results showed that a high efficiency of Hg(0) removal was obtained by using Ag/AgBr-Ag2CO3 hybrids under fluorescent lamp irradiation. The AgBr content, FSL irradiation, solution temperature, and SO2 all exhibited significant effects on Hg(0) removal, while NO had slight effect on Hg(0) removal. The addition of Ca(OH)2 demonstrated a little impact on Hg(0) removal and could significantly improve the SO2-resistance performance of Ag/AgBr(0.7)-Ag2CO3 hybrid. The characterization results exhibited that hydroxyl radical (OH), superoxide radical (O2(-)), hole (h(+)), and Br(0), were reactive species responsible for removing Hg(0), and the h(+) played a key role in Hg(0) removal. PMID:27135702

  3. Metallurgical characterization of experimental Ag-based soldering alloys

    PubMed Central

    Ntasi, Argyro; Al Jabbari, Youssef S.; Silikas, Nick; Al Taweel, Sara M.; Zinelis, Spiros

    2014-01-01

    Aim To characterize microstructure, hardness and thermal properties of experimental Ag-based soldering alloys for dental applications. Materials and methods Ag12Ga (AgGa) and Ag10Ga5Sn (AgGaSn) were fabricated by induction melting. Six samples were prepared for each alloy and microstructure, hardness and their melting range were determined by, scanning electron microscopy, energy dispersive X-ray (EDX) microanalysis, X-ray diffraction (XRD), Vickers hardness testing and differential scanning calorimetry (DSC). Results Both alloys demonstrated a gross dendritic microstructure while according to XRD results both materials consisted predominately of a Ag-rich face centered cubic phase The hardness of AgGa (61 ± 2) was statistically lower than that of AgGaSn (84 ± 2) while the alloys tested showed similar melting range of 627–762 °C for AgGa and 631–756 °C for AgGaSn. Conclusion The experimental alloys tested demonstrated similar microstructures and melting ranges. Ga and Sn might be used as alternative to Cu and Zn to modify the selected properties of Ag based soldering alloys. PMID:25382945

  4. Structural and electronic properties of ultrathin picene films on the Ag(100) surface

    NASA Astrophysics Data System (ADS)

    Kelly, Simon J.; Sorescu, Dan C.; Wang, Jun; Archer, Kaye A.; Jordan, Kenneth D.; Maksymovych, Petro

    2016-10-01

    Using scanning tunneling microscopy and electronic structure calculations, we investigated the assembly and electronic properties of picene molecules on the Ag(100), Ag(111), and Cu(111) surfaces, with particular emphasis on Ag(100). In each case, picene molecules are found to lie parallel to the surface at coverages up to half a monolayer and to adopt alternating parallel and tilted orientations at full monolayer coverage. In the latter case, the arrangement of the molecules is roughly similar to that in the bulk crystal. On the metal surfaces considered, the growth mode of picene is quite different from that of its structural isomer pentacene, which forms a bilayer overlayer on top of a dense monolayer of flat-lying molecules on metal surfaces. Tunneling spectroscopy measurements provide estimates of the energies of several low-lying unfilled molecular orbitals as well as of the highest occupied molecular orbital of the absorbed picene molecules. From analysis of these results, we establish that the on-site Coulomb repulsion for picene decreases by ~ 2 eV in going from the gas phase to the full monolayer on Ag(100), bringing it close to that of the undoped bulk crystal.

  5. THE TWO-DIMENSIONAL VALENCE ELECTRONIC STRUCTURE OF A MONOLYAER OF Ag ON Cu(00l)

    SciTech Connect

    Tobin, J.G.; Robey, S.W.; Shirley, D.A.

    1985-05-01

    The metal overlayer system c(10x2)Ag/Cu(001) was studied at coverages near one monolayer with angle-resolved photoemission. The observed spectroscopic features indicate a two-dimensional d-band electronic structure that can be interpreted using a model with planar, hexagonal symmetry in which crystal field effects dominate over spin-orbit effects.

  6. Structure-property Relationships for Methyl-terminated Alkyl Self-assembled Monolayers

    SciTech Connect

    F DelRio; D Rampulla; C Jaye; G Stan; R Gates; D Fischer; R Cook

    2011-12-31

    Structure-property relationships for methyl-terminated alkyl self-assembled monolayers (SAMs) are developed using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and atomic force microscopy (AFM). NEXAFS C K-edge spectra are used to compute the dichroic ratio, which provides a quantitative measure of the molecular structure. AFM data are analyzed with an elastic adhesive contact model, modified by a first-order elastic perturbation method to include substrate effects, to extract the monolayer mechanical properties. Using this approach, the measured mechanical properties are not influenced by the substrate, which allows universal structure-property relationships to be developed for methyl-terminated alkyl SAMs.

  7. Lateral Interactions in Monolayer Thick Mercury Films

    NASA Astrophysics Data System (ADS)

    Kime, Yolanda Jan

    An understanding of lateral adatom-adatom interactions is often an important part of understanding electronic structure and adsorption energetics in monolayer thick films. In this dissertation I use angle-resolved photoemission and thermal desorption spectroscopies to explore the relationship between the adatom-adatom interaction and other characteristics of the adlayer, such as electronic structure, defects, or coexistent structural phases in the adlayer. Since Hg binds weakly to many substrates, the lateral interactions are often a major contribution to the dynamics of the overlayer. Hg adlayer systems are thus ideal for probing lateral interactions. The electronic structures of Hg adlayers on Ag(100), Cu(100), and Cu_3Au(100) are studied with angle-resolved ultraviolet photoemission. The Hg atomic 5d_{5/2} electronic band is observed to split into two levels following adsorption onto some surfaces. The energetic splitting of the Hg 5d_{5/2} level is found to be directly correlated to the adlayer homogeneous strain energy. The existence of the split off level also depends on the order or disorder of the Hg adlayer. The energetics of Hg adsorption on Cu(100) are probed using thermal desorption spectroscopy. Two different ordered adlayer structures are observed for Hg adsorption on Cu(100) at 200 K. Under some adsorption conditions and over a range of exposures, the two phases are seen to coexist on the surface prior to the thermal desorption process. A phase transition from the more dense to the less dense phase is observed to occur during the thermal desorption process. Inherent differences in defect densities are responsible for the observed differences between lateral interactions measured previously with equilibrium (atom beam scattering) and as measured by the non-equilibrium (thermal desorption) technique reported here. Theoretical and experimental evidence for an indirect through-metal interaction between adatoms is also discussed. Although through

  8. Role of metal contacts in designing high-performance monolayer n-type WSe2 field effect transistors.

    PubMed

    Liu, Wei; Kang, Jiahao; Sarkar, Deblina; Khatami, Yasin; Jena, Debdeep; Banerjee, Kaustav

    2013-05-01

    This work presents a systematic study toward the design and first demonstration of high-performance n-type monolayer tungsten diselenide (WSe2) field effect transistors (FET) by selecting the contact metal based on understanding the physics of contact between metal and monolayer WSe2. Device measurements supported by ab initio density functional theory (DFT) calculations indicate that the d-orbitals of the contact metal play a key role in forming low resistance ohmic contacts with monolayer WSe2. On the basis of this understanding, indium (In) leads to small ohmic contact resistance with WSe2 and consequently, back-gated In-WSe2 FETs attained a record ON-current of 210 μA/μm, which is the highest value achieved in any monolayer transition-metal dichalcogenide- (TMD) based FET to date. An electron mobility of 142 cm(2)/V·s (with an ON/OFF current ratio exceeding 10(6)) is also achieved with In-WSe2 FETs at room temperature. This is the highest electron mobility reported for any back gated monolayer TMD material till date. The performance of n-type monolayer WSe2 FET was further improved by Al2O3 deposition on top of WSe2 to suppress the Coulomb scattering. Under the high-κ dielectric environment, electron mobility of Ag-WSe2 FET reached ~202 cm(2)/V·s with an ON/OFF ratio of over 10(6) and a high ON-current of 205 μA/μm. In tandem with a recent report of p-type monolayer WSe2 FET ( Fang , H . et al. Nano Lett. 2012 , 12 , ( 7 ), 3788 - 3792 ), this demonstration of a high-performance n-type monolayer WSe2 FET corroborates the superb potential of WSe2 for complementary digital logic applications.

  9. Herringbone and triangular patterns of dislocations in Ag, Au, and AgAu alloy films on Ru(0001).

    SciTech Connect

    Thayer, Gayle Echo; de la Figuera, Juan; Bartelt, Norman Charles; Carter, C. Barrington; Hwang, R. Q.; Thurmer, Konrad; Ling, W. L.; Hamilton, John C.; McCarty, Kevin F.

    2008-10-01

    We have studied the dislocation structures that occur in films of Ag, Au, and Ag{sub 0.5}Au{sub 0.5} alloy on a Ru(0001) substrate. Monolayer (ML) films form herringbone phases while films two or more layers thick contain triangular patterns of dislocations. We use scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) to determine how the film composition affects the structure and periodicity of these ordered structures. One layer of Ag forms two different herringbone phases depending on the exact Ag coverage and temperature. Low-energy electron microscopy (LEEM) establishes that a reversible, first-order phase transition occurs between these two phases at a certain temperature. We critically compare our 1 ML Ag structures to conflicting results from an X-ray scattering study [H. Zajonz et al., Phys. Rev. B 67 (2003) 155417]. Unlike Ag, the herringbone phases of Au and AgAu alloy are independent of the exact film coverage. For two layer films in all three systems, none of the dislocations in the triangular networks thread into the second film layer. In all three systems, the in-plane atomic spacing of the second film layer is nearly the same as in the bulk. Film composition does, however, affect the details of the two layer structures. Ag and Au films form interconnected networks of dislocations, which we refer to as 'trigons.' In 2 ML AgAu alloy, the dislocations form a different triangular network that shares features of both trigon and moire structures. Yet another well-ordered structure, with square symmetry, forms at the boundaries of translational trigon domains in 2 ML Ag films but not in Au films.

  10. Morphological transitions in polymer monolayers under compression.

    PubMed

    Srivastava, S; Basu, J K; Sprung, M; Wang, J

    2009-05-01

    We present a systematic investigation of morphological transitions in poly vinylacetate Langmuir monolayers. On compression, the polymer monolayer is converted to a continuous membrane with a thickness of approximately 2-3 nm. Above a certain surface concentration the monolayer, on water, undergoes a morphological transition-buckling, leading to formation of striped patterns of period of lambda(b) approximately 160 nm, as determined from in situ grazing incidence small angle x-ray scattering measurements. The obtained value is much smaller than what has been typically observed for Langmuir monolayers on water or thin films on soft substrates. Using existing theories for buckling of fluidlike films on fluid substrates, we obtain very low values of bending rigidity and Young's modulus of the polymer monolayer compared to that observed earlier for lipid or polymeric monolayers. Since buckling in these monolayers occurs only above a certain surface concentration, we have looked at the possibility that the buckling in these films occurs due to changes in their mechanical properties under compression. Using the model of Huang and Suo of buckling of solidlike films on viscoelastic substrates, we find values of the mechanical properties, which are much closer to the bulk values but still significantly lower. Although the reduction could be along the lines of what has been observed earlier for ultrathin polymer film or surface layers of polymers, the possibility of micromechanical effects also determining the buckling in such polymer monolayers cannot be ruled out. We have provided possible explanation of the buckling of the poly vinylacetate monolayers in terms of the change in isothermal compression modulus with surface concentration. PMID:19425809

  11. Synthesis of Ag-coated polystyrene colloids by an improved surface seeding and shell growth technique

    SciTech Connect

    Tian Chungui; Wang Enbo . E-mail: wangenbo@public.cc.jl.cn; Kang Zhenhui; Mao Baodong; Zhang Chao; Lan Yang; Wang Chunlei; Song Yanli

    2006-11-15

    In this paper, an improved surface seeding and shell growth technique was developed to prepare Ag-polystyrene core shell composite. Polyethyleneimine (PEI) could act as the linker between Ag ions (Ag nanoparticles) and polystyrene (PS) colloids and the reducing agent in the formation of Ag nanoparticles. Due to the multi-functional characteristic of PEI, Ag seeds formed in-situ and were immobilized on the surface of PEI-modified PS colloids and no free Ag clusters coexist with the Ag 'seeding' PS colloids in the system. Then, the additional agents could be added into the resulting dispersions straightly to produce a thick Ag nanoshell. The Ag nanoshell with controllable thickness was formed on the surface of PS by the 'one-pot' surface seeding and shell growth method. The Ag-coverage increased gradually with the increasing of mass ratio of AgNO{sub 3}/PS. The optical properties of the Ag-PS colloids could be tailored by changing the coverage of Ag. - Graphical abstract: An improved surface seeding and shell growth technique was developed to prepare Ag-polystyrene core shell composite. The optical properties of the Ag-PS colloids could be tailored by changing the coverage of Ag. Display Omitted.

  12. DNA-modified Electrodes Fabricated using Copper-Free Click Chemistry for Enhanced Protein Detection

    PubMed Central

    Furst, Ariel L.; Hill, Michael G.; Barton, Jacqueline K.

    2014-01-01

    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. PMID:24328347

  13. Effects of irradiated biodegradable polymer in endothelial cell monolayer formation

    NASA Astrophysics Data System (ADS)

    Arbeitman, Claudia R.; del Grosso, Mariela F.; Behar, Moni; García Bermúdez, Gerardo

    2013-11-01

    In this work we study cell adhesion, proliferation and cell morphology of endothelial cell cultured on poly-L-lactide acid (PLLA) modified by heavy ion irradiation. Thin films of PLLA samples were irradiated with sulfur (S) at energies of 75 MeV and gold (Au) at 18 MeV ion-beams. Ion beams were provided by the Tandar (Buenos Aires, Argentina) and Tandetron (Porto Alegre, Brazil) accelerators, respectively. The growth of a monolayer of bovine aortic endothelial cells (BAEC) onto unirradiated and irradiated surfaces has been studied by in vitro techniques in static culture. Cell viability and proliferation increased on modified substrates. But the results on unirradiated samples, indicate cell death (necrosis/apoptosis) with the consequent decrease in proliferation. We analyzed the correlation between irradiation parameters and cell metabolism and morphology.

  14. Electrochemical Deposition Of Thiolate Monolayers On Metals

    NASA Technical Reports Server (NTRS)

    Porter, Marc D.; Weissharr, Duane E.

    1995-01-01

    Electrochemical method devised for coating metal (usually, gold) surfaces with adherent thiolate monolayers. Affords greater control over location and amount of material deposited and makes it easier to control chemical composition of deposits. One important potential use for this method lies in fabrication of chemically selective thin-film resonators for microwave oscillators used to detect pollutants: monolayer formulated to bind selectively pollutant chemical species of interest, causing increase in mass of monolayer and corresponding decrease in frequency of resonance. Another important potential use lies in selective chemical derivatization for purposes of improving adhesion, lubrication, protection against corrosion, electrocatalysis, and electroanalysis.

  15. Structural prediction for scandium carbide monolayer sheet

    NASA Astrophysics Data System (ADS)

    Ma, Hong-Man; Wang, Jing; Zhao, Hui-Yan; Zhang, Dong-Bo; Liu, Ying

    2016-09-01

    A two-dimensional tetragonal scandium carbide monolayer sheet has been constructed and studied using density functional theory. The results show that the scandium carbide sheet is stable and exhibits a novel tetracoordinated quasiplanar structure, as favored by the hybridization between Sc-3d orbitals and C-2p orbitals. Calculations of the phonon dispersion as well as molecular dynamics simulations also demonstrate the structural stability of this scandium carbide monolayer sheet. Electronic properties show that the scandium carbide monolayer sheet is metallic and non-magnetic.

  16. Drug induced `softening' in phospholipid monolayers

    NASA Astrophysics Data System (ADS)

    Basak, Uttam Kumar; Datta, Alokmay; Bhattacharya, Dhananjay

    2015-06-01

    Compressibility measurements on Langmuir monolayers of the phospholipid Dimystoryl Phospatidylcholine (DMPC) in pristine form and in the presence of the Non-steroidal Anti-inflammatory Drug (NSAID) Piroxicam at 0.025 drug/lipid (D/L) molecular ratio at different temperatures, show that the monolayer exhibits large increase (and subsequent decrease) in compressibility due to the drug in the vicinity of the Liquid Expanded - Liquid Condensed (LE-LC) phase transition. Molecular dynamics simulations of the lipid monolayer in presence of drug molecules show a disordering of the tail tilt, which is consistent with the above result.

  17. Individual and collective electronic properties of Ag nanocrystals

    SciTech Connect

    Kim, S.H.; Medeiros-Ribeiro, G.; Ohlberg, D.A.A.; Williams, R.S.; Heath, J.R.

    1999-11-25

    The authors report on the electronic transport properties of individual alkanethiol-passivated Ag nanocrystals and their superlattices. Isolated Ag particles with diameters in the range of 2.7--4.8 nm supported by a metallic substrate passivated with an organic layer show a Coulomb gap. Monolayer films of Ag particles exhibit four distinct electronic signatures, two of which have not been previously reported, depending on their structures. In two-dimensional ordered superlattices of octanethiol-capped 4.8 nm diameter nanocrystals on graphite, the strong interparticle electronic coupling produces metallic films. A disordered monolayer of dodecanethiol-capped 6.6 nm diameter nanocrystals exhibits a temperature-dependent differential conductance, which is attributed to the localized states formed by the disorder in the lattice. For two-dimensional ordered superlattices of pentanethiol- and hexanethiol-capped 2.7 nm diameter Ag particles. It was shown that the films are insulating, and individual nanocrystals maintain their individual electronic identity. Two different types of insulating films have been observed: one with electronically homogeneous nanocrystals in a close-packed lattice and the other with sublattices of electronically distinct monocrystals within a square lattice. The relationship of the Coulomb blockade and nanocrystal ordering to the electronic behavior of this class of architectonic materials are discussed.

  18. Annealing effect of ultrathin Ag films on Ni/Pt(111)

    SciTech Connect

    Su, C.W.; Yo, H.Y.; Chen, Y.J.; Shern, C.S.

    2005-06-15

    The epitaxial growth and alloy formation of Ag-capped layer on Ni/Pt(111) surface were investigated using Auger electron spectroscopy, ultraviolet photoelectron spectroscopy, and low-energy electron diffraction. The growth of Ag on one ML Ni/Pt(111) transforms from layer-by-layer mode into three-dimensional island mode after the growth of one atomic monolayer of Ag. The starting temperature for the alloy formation of Ni-Pt is dependent of the thickness of Ni films. The interface compositions after the high-temperature annealing were studied with the depth-profile analysis of Ar ion sputtering.

  19. Effects of lung surfactant proteins, SP-B and SP-C, and palmitic acid on monolayer stability.

    PubMed Central

    Ding, J; Takamoto, D Y; von Nahmen, A; Lipp, M M; Lee, K Y; Waring, A J; Zasadzinski, J A

    2001-01-01

    Langmuir isotherms and fluorescence and atomic force microscopy images of synthetic model lung surfactants were used to determine the influence of palmitic acid and synthetic peptides based on the surfactant-specific proteins SP-B and SP-C on the morphology and function of surfactant monolayers. Lung surfactant-specific protein SP-C and peptides based on SP-C eliminate the loss to the subphase of unsaturated lipids necessary for good adsorption and respreading by inducing a transition between monolayers and multilayers within the fluid phase domains of the monolayer. The morphology and thickness of the multilayer phase depends on the lipid composition of the monolayer and the concentration of SP-C or SP-C peptide. Lung surfactant protein SP-B and peptides based on SP-B induce a reversible folding transition at monolayer collapse that allows all components of surfactant to be retained at the interface during respreading. Supplementing Survanta, a clinically used replacement lung surfactant, with a peptide based on the first 25 amino acids of SP-B also induces a similar folding transition at monolayer collapse. Palmitic acid makes the monolayer rigid at low surface tension and fluid at high surface tension and modifies SP-C function. Identifying the function of lung surfactant proteins and lipids is essential to the rational design of replacement surfactants for treatment of respiratory distress syndrome. PMID:11325728

  20. AGS experiments - 1994, 1995, 1996

    SciTech Connect

    Depken, J.C.

    1997-01-01

    This report contains the following information on the Brookhaven AGS Accelerator complex: FY 1996 AGS schedule as run; FY 1997 AGS schedule (working copy); AGS beams 1997; AGS experimental area FY 1994 physics program; AGS experimental area FY 1995 physics program; AGS experimental area FY 1996 physics program; AGS experimental area FY 1997 physics program (in progress); a listing of experiments by number; two-phage summaries of each experiment begin here, also ordered by number; listing of publications of AGS experiments begins here; and listing of AGS experimenters begins here.

  1. Electronic, transport, and optical properties of bulk and mono-layer PdSe{sub 2}

    SciTech Connect

    Sun, Jifeng; Shi, Hongliang; Siegrist, Theo; Singh, David J.

    2015-10-12

    The electronic and optical properties of bulk and monolayer PdSe{sub 2} are investigated using first-principles calculations. Using the modified Becke-Johnson potential, we find semiconductor behavior for both bulk and monolayer PdSe{sub 2} with indirect gap values of 0.03 eV for bulk and 1.43 eV for monolayer, respectively. Our sheet optical conductivity results support this observation and show similar anisotropic feature in the 2D plane. We further study the thermoelectric properties of the 2D PdSe{sub 2} using Blotzmann transport model and find interestingly high Seebeck coefficients (>200 μV/K) for both p- and n-type up to high doping level (∼2 × 10{sup 13} cm{sup −2}) with an anisotropic character in an electrical conductivity suggesting better thermoelectric performance along y direction in the plane.

  2. Electronic, transport, and optical properties of bulk and mono-layer PdSe2

    DOE PAGESBeta

    Sun, Jifeng; Shi, Hongliang; Siegrist, Theo; Singh, David J.

    2015-10-13

    In this study, the electronic and optical properties of bulk and monolayer PdSe2 are investigated using firstprinciples calculations. Using the modified Becke-Johnson potential, we find semiconductor behavior for both bulk and monolayer PdSe2 with indirect gap values of 0.03 eV for bulk and 1.43 eV for monolayer, respectively. Our sheet optical conductivity results support this observation and show similar anisotropic feature in the 2D plane. We further study the thermoelectric properties of the 2D PdSe2 using Blotzmann transport model and find interestingly high Seebeck coefficients (>200 μV/K) for both p- and n-type up to high doping level (–2 x 1013more » cm2) with an anisotropic character in an electrical conductivity suggesting better thermoelectric performance along y direction in the plane.V« less

  3. Laser-Induced Spallation of Microsphere Monolayers.

    PubMed

    Hiraiwa, Morgan; Stossel, Melicent; Khanolkar, Amey; Wang, Junlan; Boechler, Nicholas

    2016-08-01

    The detachment of a semiordered monolayer of polystyrene microspheres adhered to an aluminum-coated glass substrate is studied using a laser-induced spallation technique. The microsphere-substrate adhesion force is estimated from substrate surface displacement measurements obtained using optical interferometry, and a rigid-body model that accounts for the inertia of the microspheres. The estimated adhesion force is compared with estimates obtained using an adhesive contact model together with interferometric measurements of the out-of-plane microsphere contact resonance, and with estimated work of adhesion values for the polystyrene-aluminum interface. Scanning electron microscope images of detached monolayer regions reveal a unique morphology, namely, partially detached monolayer flakes composed of single hexagonal close packed crystalline domains. This work contributes to the fields of microsphere adhesion and contact dynamics, and demonstrates a unique monolayer delamination morphology. PMID:27409715

  4. Monolayer graphene from a green solid precursor

    NASA Astrophysics Data System (ADS)

    Kalita, Golap; Wakita, Koichi; Umeno, Masayoshi

    2011-06-01

    Monolayer and bilayer graphene sheets are synthesized by simple control pyrolysis of solid botanical derivative camphor (C 10H 16O), a green and renewable carbon source. Raman studies show much intense 2D peak than that of G peak, signifying presence of monolayer graphene. Transmission electron microscopic study shows predominately monolayer or bilayer graphene sheets, while trilayer graphene sheet were also observed. Synthesized graphene film on copper foil is transferred to poly(ethylene terephthalate) substrate to fabricate transparent electrode. Electrical and optical measurement shows a sheet resistance of 860 Ω/sq with a transmittance of 91% at 550 nm wavelength of the graphene film. The technique to fabricate monolayer or bilayer graphene based film from camphor is both viable and scalable for potential large area electronic applications.

  5. Accurate Molecular Dimensions from Stearic Acid Monolayers.

    ERIC Educational Resources Information Center

    Lane, Charles A.; And Others

    1984-01-01

    Discusses modifications in the fatty acid monolayer experiment to reduce the inaccurate moleculary data students usually obtain. Copies of the experimental procedure used and a Pascal computer program to work up the data are available from the authors. (JN)

  6. Large Friction Anisotropy of a Polydiacetylene Monolayer

    SciTech Connect

    Burns, A.R.; Carpick, R.W.; Sasaki, D.Y.

    1999-05-11

    Friction force microscopy measurements of a polydiacetylene monolayer film reveal a 300% friction anisotropy that is correlated with the film structure. The film consists of a monolayer of the red form of N-(2-ethanol)- 10,12 pentacosadiynamide, prepared on a Langmuir trough and deposited on a mica substrate. As confirmed by atomic force microscopy and fluorescence microscopy, the monolayer consists of domains of linearly oriented conjugated backbones with pendant hydrocarbon side chains above and below the backbones. Maximum friction occurs when the sliding direction is perpendicular to the backbone. We propose that the backbones impose anisotropic packing of the hydrocarbon side chains which leads to the observed friction anisotropy. Friction anisotropy is therefore a sensitive, optically-independent indicator of polymer backbone direction and monolayer structural properties.

  7. Multicellular density fluctuations in epithelial monolayers

    NASA Astrophysics Data System (ADS)

    Zehnder, Steven M.; Wiatt, Marina K.; Uruena, Juan M.; Dunn, Alison C.; Sawyer, W. Gregory; Angelini, Thomas E.

    2015-09-01

    Changes in cell size often accompany multicellular motion in tissue, and cell number density is known to strongly influence collective migration in monolayers. Density fluctuations in other forms of active matter have been explored extensively, but not the potential role of density fluctuations in collective cell migration. Here we investigate collective motion in cell monolayers, focusing on the divergent component of the migration velocity field to probe density fluctuations. We find spatial patterns of diverging and converging cell groups throughout the monolayers, which oscillate in time with a period of approximately 3-4 h. Simultaneous fluorescence measurements of a cytosol dye within the cells show that fluid passes between groups of cells, facilitating these oscillations in cell density. Our findings reveal that cell-cell interactions in monolayers may be mediated by intercellular fluid flow.

  8. Nonequilibrium bubbles in a flowing langmuir monolayer.

    PubMed

    Muruganathan, Rm; Khattari, Z; Fischer, Th M

    2005-11-24

    We investigate the nonequilibrium behavior of two-dimensional gas bubbles in Langmuir monolayers. A cavitation bubble is induced in liquid expanded phase by locally heating a Langmuir monolayer with an IR-laser. At low IR-laser power the cavitation bubble is immersed in quiescent liquid expanded monolayer. At higher IR-laser power thermo capillary flow around the laser-induced cavitation bubble sets in. The thermo capillary flow is caused by a temperature dependence of the gas/liquid line tension. The slope of the line tension with temperature is determined by measuring the thermo capillary flow velocity. Thermodynamically stable satellite bubbles are generated by increasing the surface area of the monolayer. Those satellite bubbles collide with the cavitation bubble. Upon collision the satellite bubbles either coalesce with the cavitation bubble or slide past the cavitation bubble. Moreover we show that the satellite bubbles can also be produced by the emission from the laser-induced cavitation bubbles.

  9. Evidence of silicene in honeycomb structures of silicon on Ag(111).

    PubMed

    Feng, Baojie; Ding, Zijing; Meng, Sheng; Yao, Yugui; He, Xiaoyue; Cheng, Peng; Chen, Lan; Wu, Kehui

    2012-07-11

    In the search for evidence of silicene, a two-dimensional honeycomb lattice of silicon, it is important to obtain a complete picture for the evolution of Si structures on Ag(111), which is believed to be the most suitable substrate for growth of silicene so far. In this work we report the finding and evolution of several monolayer superstructures of silicon on Ag(111), depending on the coverage and temperature. Combined with first-principles calculations, the detailed structures of these phases have been illuminated. These structures were found to share common building blocks of silicon rings, and they evolve from a fragment of silicene to a complete monolayer silicene and multilayer silicene. Our results elucidate how silicene forms on Ag(111) surface and provides methods to synthesize high-quality and large-scale silicene.

  10. Quantifying the origin of released Ag+ ions from nanosilver.

    PubMed

    Sotiriou, Georgios A; Meyer, Andreas; Knijnenburg, Jesper T N; Panke, Sven; Pratsinis, Sotiris E

    2012-11-13

    Nanosilver is most attractive for its bactericidal properties in modern textiles, food packaging, and biomedical applications. Concerns, however, about released Ag(+) ions during dispersion of nanosilver in liquids have limited its broad use. Here, nanosilver supported on nanostructured silica is made with closely controlled Ag size both by dry (flame aerosol) and by wet chemistry (impregnation) processes without any surface functionalization that could interfere with its ion release. It is characterized by electron microscopy, atomic absorption spectroscopy, and X-ray diffraction, and its Ag(+) ion release in deionized water is monitored electrochemically. The dispersion method of nanosilver in solutions affects its dissolution rate but not the final Ag(+) ion concentration. By systematically comparing nanosilver size distributions to their equilibrium Ag(+) ion concentrations, it is revealed that the latter correspond precisely to dissolution of one to two surface silver oxide monolayers, depending on particle diameter. When, however, the nanosilver is selectively conditioned by either washing or H(2) reduction, the oxide layers are removed, drastically minimizing Ag(+) ion leaching and its antibacterial activity against E. coli . That way the bactericidal activity of nanosilver is confined to contact with its surface rather than to rampant ions. This leads to silver nanoparticles with antibacterial properties that are essential for medical tools and hospital applications.

  11. Mass spectrometric analysis of monolayer protected nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhu, Zhengjiang

    Monolayer protected nanoparticles (NPs) include an inorganic core and a monolayer of organic ligands. The wide variety of core materials and the tunable surface monolayers make NPs promising materials for numerous applications. Concerns related to unforeseen human health and environmental impacts of NPs have also been raised. In this thesis, new analytical methods based on mass spectrometry are developed to understand the fate, transport, and biodistributions of NPs in the complex biological systems. A laser desorption/ionization mass spectrometry (LDI-MS) method has been developed to characterize the monolayers on NP surface. LDI-MS allows multiple NPs taken up by cells to be measured and quantified in a multiplexed fashion. The correlations between surface properties of NPs and cellular uptake have also been explored. LDI-MS is further coupled with inductively coupled plasma mass spectrometry (ICP-MS) to quantitatively measure monolayer stability of gold NPs (AuNPs) and quantum dots (QDs), respectively, in live cells. This label-free approach allows correlating monolayer structure and particle size with NP stability in various cellular environments. Finally, uptake, distribution, accumulation, and excretion of NPs in higher order organisms, such as fish and plants, have been investigated to understand the environmental impact of nanomaterials. The results indicate that surface chemistry is a primary determinant. NPs with hydrophilic surfaces are substantially less toxic and present a lower degree of bioaccumulation, making these nanomaterials attractive for sustainable nanotechnology.

  12. Surface properties of substituted-benzenethiol monolayers on gold and silver: Work function, wettability, and surface tension

    NASA Astrophysics Data System (ADS)

    Tatara, Shingo; Kuzumoto, Yasutaka; Kitamura, Masatoshi

    2016-03-01

    The surface properties, including work function and wettability, of Au and Ag surfaces modified with various substituted benzenethiols have been investigated. Whereas the work functions of the modified Au surfaces ranged from 4.42 to 5.48 eV, those of the modified Ag surfaces ranged from 3.99 to 5.77 eV. The highest work function of 5.77 eV was obtained on the Ag surface modified with pentafluorobenzenethiol, and the lowest work function of 3.99 eV was obtained on the Ag surface modified with 4-methylbenzenethiol. The water contact angle on modified Au surfaces was found to be in a wide range from 30.9 to 88.3°. The water contact angle on the Au surface modified with a substituted benzenethiol was close to that on the Ag surface modified with the same benzenethiol. Furthermore, the tension of the modified Au surfaces was estimated from their contact angles of water and ethylene glycol.

  13. Aqueous electrodeposition of Ge monolayers.

    PubMed

    Liang, Xuehai; Kim, Youn-Geun; Gebergziabiher, Daniel K; Stickney, John L

    2010-02-16

    The electrodeposition of germanium on Au(111) in aqueous solutions has been investigated by means of cyclic voltammetry, Auger electron spectroscopy, and in situ scanning tunneling microscopy (STM). The data yield a picture of germanium deposition, which starts with the formation of two well-ordered hydroxide phases, with 1/3 ML and 4/9 ML coverages upon initial reduction of the Ge(IV) species (probably H(2)GeO(3) at pH 4.7). Those structures appear to result from a three-electron reduction to form surface-limited structures with (square root(3) x square root(3))R30 degrees or (3 x 3) unit cells, respectively. Further reduction, probably in a two-electron process from the hydroxide structures, resulted in a germanium hydride structure, again surface-limited, with a coverage of close to 0.8 ML. The hydride structure is very flat, though with the periodic modulation characteristic of a Moiré pattern. Longer deposition times and lower potentials resulted in increased coverage of Ge in some cases, but with apparently limited coverage as a function of pH. The maximum Ge coverage, about 4 ML, was observed using a pH 9.32 deposition solution. At potentials negative of the Moiré pattern, about -850 mV versus Ag/AgCl, a "corruption" of the smooth Moiré pattern occurred. This roughening appears to mark the initial formation of a Au-Ge alloy, accounting for the observation of coverage in excess of that needed to form the Moiré pattern at some pH values.

  14. Polarized proton acceleration program at the AGS

    SciTech Connect

    Lee, Y.Y.

    1981-01-01

    The unexpected importance of high energy spin effects and the success of the ZGS in correcting many intrinsic and imperfection depolarizing resonances led us to attempt to accelerate polarized protons in the AGS. A multi-university/laboratory collaborative effort involving Argonne, Brookhaven, Michigan, Rice and Yale is underway to improve and modify to accelerate polarized protons. From the experience at the ZGS and careful studies made us confident of the feasibility of achieving a polarization of over 60 percent up to 26 GeV/c with an intensity of 10/sup 11/ approx. 10/sup 12/ per pulse. The first polarized proton acceleration at the AGS is expected in 1983.

  15. RESONANT EXTRACTION PARAMETERS FOR THE AGS BOOSTER.

    SciTech Connect

    BROWN,K.A.; CULLEN,J.; GLENN,J.W.; MAPES,M.; MARNERIS,I.; TSOUPAS,N.; SNYDSTRUP,L.; VAN ASSELT,W.

    2001-06-18

    Brookhaven's AGS Booster is the injector for the AGS. It is being modified to send resonant extracted heavy ions to a new beam line, the Booster Applications Facility (BAF). The design of the resonant extraction system for BAF was described in [1]. This note will give a more detailed description of the system and describe the predicted resonant beam time structure. We will describe tune space manipulations necessary to extract the resonant beam at the maximum Booster rigidity, schemes for performing resonant extraction, and describe the modifications required to perform bunched beam extraction to the BAF facility.

  16. Geometry optimization and structural distribution of silver clusters from Ag 170 to Ag 310

    NASA Astrophysics Data System (ADS)

    Shao, Xueguang; Yang, Xiaoli; Cai, Wensheng

    2008-07-01

    Silver clusters in the size range of 170-310 were optimized with a modified dynamic lattice search (DLS) method. Considering the computational complexity, only 21 clusters of several tens and magic numbers of atoms were investigated. The interaction of silver atoms is modeled by the Gupta potential. Results show that, between the 21 clusters, nine fcc and twelve m-Dh structures are obtained. Compared with the structures adopted by Ag 13 to Ag 160, the main motif is still m-Dh in the range of Ag 170-Ag 310, but the ratio of fcc structures obviously increases. It can, therefore, be deduced that the fcc motif is more stable for larger size silver clusters.

  17. Atomic force microscopy electrostatic nanolithography on self-assembled monolayer of organo-mercaptan molecules

    NASA Astrophysics Data System (ADS)

    Reagan, Michael A.; Juhl, Shane; Umemura, Kazuo

    2005-03-01

    We report a novel technique for manipulating SAM molecules at the nanoscale. An initial stage, the AFM probe induces local modification of the self-assembled monolayer involving cleavage of the sulfur-metal bond. This leads to depressions appearing on the surface's topography images followed by the removal (diffusion) of the desorbed specie. It is known from the macroscopic scale electrochemical experiments that oxidative desorption of the organo-mercaptans from the gold surface takes place at potentials greater than +0.8 V (vs. Ag/AgCl) in aqueous KOH solutions. This corresponds to about -3.9 V in the absolute potential scale. A weak positive bias of the metal substrate is expected to result in the dissociative electron transfer from the mercaptan to the gold, taking place in the surface region localized near the scanning probe tip, where the water can be condensed from the ambient environment forming a nanoscale electrochemical cell.

  18. Evidence for superconductivity in Li-decorated monolayer graphene.

    PubMed

    Ludbrook, B M; Levy, G; Nigge, P; Zonno, M; Schneider, M; Dvorak, D J; Veenstra, C N; Zhdanovich, S; Wong, D; Dosanjh, P; Straßer, C; Stöhr, A; Forti, S; Ast, C R; Starke, U; Damascelli, A

    2015-09-22

    Monolayer graphene exhibits many spectacular electronic properties, with superconductivity being arguably the most notable exception. It was theoretically proposed that superconductivity might be induced by enhancing the electron-phonon coupling through the decoration of graphene with an alkali adatom superlattice [Profeta G, Calandra M, Mauri F (2012) Nat Phys 8(2):131-134]. Although experiments have shown an adatom-induced enhancement of the electron-phonon coupling, superconductivity has never been observed. Using angle-resolved photoemission spectroscopy (ARPES), we show that lithium deposited on graphene at low temperature strongly modifies the phonon density of states, leading to an enhancement of the electron-phonon coupling of up to λ ≃ 0.58. On part of the graphene-derived π*-band Fermi surface, we then observe the opening of a Δ ≃ 0.9-meV temperature-dependent pairing gap. This result suggests for the first time, to our knowledge, that Li-decorated monolayer graphene is indeed superconducting, with Tc ≃ 5.9 K.

  19. Evidence for superconductivity in Li-decorated monolayer graphene

    PubMed Central

    Ludbrook, B. M.; Levy, G.; Nigge, P.; Zonno, M.; Schneider, M.; Dvorak, D. J.; Veenstra, C. N.; Zhdanovich, S.; Wong, D.; Dosanjh, P.; Straßer, C.; Stöhr, A.; Forti, S.; Ast, C. R.; Starke, U.; Damascelli, A.

    2015-01-01

    Monolayer graphene exhibits many spectacular electronic properties, with superconductivity being arguably the most notable exception. It was theoretically proposed that superconductivity might be induced by enhancing the electron–phonon coupling through the decoration of graphene with an alkali adatom superlattice [Profeta G, Calandra M, Mauri F (2012) Nat Phys 8(2):131–134]. Although experiments have shown an adatom-induced enhancement of the electron–phonon coupling, superconductivity has never been observed. Using angle-resolved photoemission spectroscopy (ARPES), we show that lithium deposited on graphene at low temperature strongly modifies the phonon density of states, leading to an enhancement of the electron–phonon coupling of up to λ≃0.58. On part of the graphene-derived π∗-band Fermi surface, we then observe the opening of a Δ≃0.9-meV temperature-dependent pairing gap. This result suggests for the first time, to our knowledge, that Li-decorated monolayer graphene is indeed superconducting, with Tc≃5.9 K. PMID:26351697

  20. Vibrational properties of an adamantane monolayer on a gold surface

    NASA Astrophysics Data System (ADS)

    Sakai, Yuki; Nguyen, Giang D.; Capaz, Rodrigo B.; Coh, Sinisa; Pechenezhskiy, Ivan V.; Hong, Xiaoping; Crommie, Michael F.; Wang, Feng; Saito, Susumu; Louie, Steven G.; Cohen, Marvin L.

    2014-03-01

    We study the vibrational properties of an adamantane monolayer on a Au(111) surface. The IR spectrum of a self-assembled monolayer of adamantane on Au(111) is measured by a newly developed infrared scanning tunneling microscopy (IRSTM) technique. We analyze the IR spectrum of this system by a density functional theory and find that the IR spectrum is severely modified by both adamantane-gold and adamantane-adamantane interactions. One of three gas-phase C-H bond stretching modes is significantly red-shifted due to the molecule-substrate interactions. The intermolecular interactions cause a suppression of the IR intensity of another gas-phase IR peak. The techniques used in this work can be applied for an independent estimate of molecule-substrate and intermolecular interactions in related diamondoid/metal-substrate systems. This work was supported by NSF grant No. DMR10-1006184 and U.S. DOE under Contract No. DE-AC02-05CH11231.

  1. Evidence for hybrid surface metallic band in (4 × 4) silicene on Ag(111)

    SciTech Connect

    Tsoutsou, D. Xenogiannopoulou, E.; Golias, E.; Tsipas, P.; Dimoulas, A.

    2013-12-02

    The electronic band structure of monolayer (4 × 4) silicene on Ag(111) is imaged by angle resolved photoelectron spectroscopy. A dominant hybrid surface metallic band is observed to be located near the bulk Ag sp-band which is also faintly visible. The two-dimensional character of the hybrid band has been distinguished against the bulk character of the Ag(111) sp-band by means of photon energy dependence experiments. The surface band exhibits a steep linear dispersion around the K{sup ¯}{sub Ag} point and has a saddle point near the M{sup ¯}{sub Ag} point of Ag(111) resembling the π-band dispersion in graphene.

  2. Aging of Transition Metal Dichalcogenide Monolayers.

    PubMed

    Gao, Jian; Li, Baichang; Tan, Jiawei; Chow, Phil; Lu, Toh-Ming; Koratkar, Nikhil

    2016-02-23

    Two-dimensional sheets of transition metal dichalcogenides are an emerging class of atomically thin semiconductors that are considered to be "air-stable", similar to graphene. Here we report that, contrary to current understanding, chemical vapor deposited transition metal dichalcogenide monolayers exhibit poor long-term stability in air. After room-temperature exposure to the environment for several months, monolayers of molybdenum disulfide and tungsten disulfide undergo dramatic aging effects including extensive cracking, changes in morphology, and severe quenching of the direct gap photoluminescence. X-ray photoelectron and Auger electron spectroscopy reveal that this effect is related to gradual oxidation along the grain boundaries and the adsorption of organic contaminants. These results highlight important challenges associated with the utilization of transition metal dichalcogenide monolayers in electronic and optoelectronic devices. We also demonstrate a potential solution to this problem, featuring encapsulation of the monolayer sheet by a 10-20 nm thick optically transparent polymer (parylene C). This strategy is shown to successfully prevent the degradation of the monolayer material under accelerated aging (i.e., high-temperature, oxygen-rich) conditions.

  3. Aging of Transition Metal Dichalcogenide Monolayers.

    PubMed

    Gao, Jian; Li, Baichang; Tan, Jiawei; Chow, Phil; Lu, Toh-Ming; Koratkar, Nikhil

    2016-02-23

    Two-dimensional sheets of transition metal dichalcogenides are an emerging class of atomically thin semiconductors that are considered to be "air-stable", similar to graphene. Here we report that, contrary to current understanding, chemical vapor deposited transition metal dichalcogenide monolayers exhibit poor long-term stability in air. After room-temperature exposure to the environment for several months, monolayers of molybdenum disulfide and tungsten disulfide undergo dramatic aging effects including extensive cracking, changes in morphology, and severe quenching of the direct gap photoluminescence. X-ray photoelectron and Auger electron spectroscopy reveal that this effect is related to gradual oxidation along the grain boundaries and the adsorption of organic contaminants. These results highlight important challenges associated with the utilization of transition metal dichalcogenide monolayers in electronic and optoelectronic devices. We also demonstrate a potential solution to this problem, featuring encapsulation of the monolayer sheet by a 10-20 nm thick optically transparent polymer (parylene C). This strategy is shown to successfully prevent the degradation of the monolayer material under accelerated aging (i.e., high-temperature, oxygen-rich) conditions. PMID:26808328

  4. Nonlinear optical techniques for surface studies. [Monolayers

    SciTech Connect

    Shen, Y.R.

    1981-09-01

    Recent effort in developing nonlinear optical techniques for surface studies is reviewed. Emphasis is on monolayer detection of adsorbed molecules on surfaces. It is shown that surface coherent antiStokes Raman scattering (CARS) with picosecond pulses has the sensitivity of detecting submonolayer of molecules. On the other hand, second harmonic or sum-frequency generation is also sensitive enough to detect molecular monolayers. Surface-enhanced nonlinear optical effects on some rough metal surfaces have been observed. This facilitates the detection of molecular monolayers on such surfaces, and makes the study of molecular adsorption at a liquid-metal interface feasible. Advantages and disadvantages of the nonlinear optical techniques for surface studies are discussed.

  5. Electromagnetic interference shielding effectiveness of monolayer graphene.

    PubMed

    Hong, Seul Ki; Kim, Ki Yeong; Kim, Taek Yong; Kim, Jong Hoon; Park, Seong Wook; Kim, Joung Ho; Cho, Byung Jin

    2012-11-16

    We report the first experimental results on the electromagnetic interference (EMI) shielding effectiveness (SE) of monolayer graphene. The monolayer CVD graphene has an average SE value of 2.27 dB, corresponding to ~40% shielding of incident waves. CVD graphene shows more than seven times (in terms of dB) greater SE than gold film. The dominant mechanism is absorption rather than reflection, and the portion of absorption decreases with an increase in the number of graphene layers. Our modeling work shows that plane-wave theory for metal shielding is also applicable to graphene. The model predicts that ideal monolayer graphene can shield as much as 97.8% of EMI. This suggests the feasibility of manufacturing an ultrathin, transparent, and flexible EMI shield by single or few-layer graphene. PMID:23085718

  6. AgRISTARS

    NASA Technical Reports Server (NTRS)

    1984-01-01

    An introduction to the overall AgRISTARS program, a general statement on progress, and separate summaries of the activities of each project, with emphasis on the technical highlights are presented. Organizational and management information on AgRISTARS is included in the appendices, as is a complete bibliography of publication and reports.

  7. Adherence of Mycoplasma hyopneumoniae to cell monolayers.

    PubMed

    Zielinski, G C; Young, T; Ross, R F; Rosenbusch, R F

    1990-03-01

    This work was an attempt to develop an in vitro adherence model for Mycoplasma hyopneumoniae, using monolayers of human and porcine lung fibroblasts and porcine kidney cells. Mycoplasma hyopneumoniae grown in Friis mycoplasma broth was radiolabeled with 35[S]-methionine, washed, concentrated, and inoculated on the monolayers. After 15 minutes of centrifugation to facilitate adherence, monolayers were washed 3 times, dissolved with 0.1N NaOH, and suspended in scintillation liquid, and the radioactivity was determined in a liquid scintillation counter. Adherence, measured as a percentage of counts added, varied according to the mycoplasma strain and the cell line used. Comparison of strains J, 144L, and 232 of M hyopneumoniae revealed 7.5 +/- 5.9, 31.9 +/- 13, and 9.6 +/- 5% adherence to porcine kidney cells, respectively. Slightly different, but proportionally the same relationships were obtained with swine or human fibroblasts. Adherence was decreased slightly by repeated washings of the mycoplasma-treated cell monolayers; however, a plateau was reached, indicating irreversibility of the adherence process. Pretreatment of cell monolayers with nonlabeled organisms substantially blocked adherence by labeled organisms. Dilution of labeled organisms resulted in an increased proportion adhering. Therefore, it appears that the adherence was a receptor-dependent event. Treatment of the mycoplasmas with trypsin prior to the inoculation of monolayers resulted in a marked reduction in adherence. Treatment of the mycoplasmas with hyperimmune swine serum against M hyopneumoniae or normal swine serum resulted in 80 to 90% reduction of adherence; however, no inhibition occurred when mycoplasmas were treated with purified IgG from the hyperimmune serum.

  8. Two-photon Photo-emission of Ultrathin Film PTCDA Morphologies on Ag(111)

    SciTech Connect

    Yang, Aram; Yang, Aram; Shipman, Steven T.; Garrett-Roe, Sean; Johns, James; Strader, Matt; Szymanski, Paul; Muller, Eric; Harris, Charles B.

    2007-11-29

    Morphology- and layer-dependent electronic structure and dynamics at the PTCDA/Ag(111) interface have been studied with angle-resolved two-photon photoemission. In Stranski-Krastanov growth modes, the exposed wetting layer inhibited the evolution of the vacuum level and valence band to bulk values. For layer-by-layer growth, we observed the transition of electron structure from monolayer to bulk values within eight monolayers. Effective masses and lifetimes of the conduction band and the n=1 image potential state were measured to be larger for disordered layers. The effective mass was interpreted in the context of charge mobility measurements.

  9. Supramolecular engineering through temperature-induced chemical modification of 2H-tetraphenylporphyrin on Ag(111): flat phenyl conformation and possible dehydrogenation reactions.

    PubMed

    Di Santo, Giovanni; Blankenburg, Stephan; Castellarin-Cudia, Carla; Fanetti, Mattia; Borghetti, Patrizia; Sangaletti, Luigi; Floreano, Luca; Verdini, Alberto; Magnano, Elena; Bondino, Federica; Pignedoli, Carlo A; Nguyen, Manh-Thuong; Gaspari, Roberto; Passerone, Daniele; Goldoni, Andrea

    2011-12-16

    Scratching the surface: Formation of a monolayer of 2H-tetraphenylporphyrins (2H-TPP) on Ag(111), either by sublimation of a multilayer in the range 525-600 K or by annealing (at the same temperature) a monolayer deposited at room temperature, induces a chemical modification of the molecules. Rotation of the phenyl rings into a flat conformation is observed and tentatively explained, by using DFT calculations, as a peculiar reaction due to molecular dehydrogenation. PMID:22113855

  10. Supramolecular engineering through temperature-induced chemical modification of 2H-tetraphenylporphyrin on Ag(111): flat phenyl conformation and possible dehydrogenation reactions.

    PubMed

    Di Santo, Giovanni; Blankenburg, Stephan; Castellarin-Cudia, Carla; Fanetti, Mattia; Borghetti, Patrizia; Sangaletti, Luigi; Floreano, Luca; Verdini, Alberto; Magnano, Elena; Bondino, Federica; Pignedoli, Carlo A; Nguyen, Manh-Thuong; Gaspari, Roberto; Passerone, Daniele; Goldoni, Andrea

    2011-12-16

    Scratching the surface: Formation of a monolayer of 2H-tetraphenylporphyrins (2H-TPP) on Ag(111), either by sublimation of a multilayer in the range 525-600 K or by annealing (at the same temperature) a monolayer deposited at room temperature, induces a chemical modification of the molecules. Rotation of the phenyl rings into a flat conformation is observed and tentatively explained, by using DFT calculations, as a peculiar reaction due to molecular dehydrogenation.

  11. AGS experiments: 1993 - 1994 - 1995

    SciTech Connect

    Depken, J.C.

    1996-04-01

    This report contains: FY 1995 AGS Schedule as Run; FY 1996-97 AGE Schedule (working copy); AGS Beams 1995; AGS Experimental Area FY 1993 Physics Program; AGS Experimental Area FY 1994 Physics Program; AGS Experimental Area FY 1995 Physics Program; AGS Experimental Area FY 1996 Physics Program (In progress); A listing of experiments by number; Two-page summaries of each experiment begin here, also ordered by number; Listing of publications of AGS experiments begins here; and Listing of AGS experimenters begins here. This is the twelfth edition.

  12. Organic chemistry on surfaces: Direct cyclopropanation by dihalocarbene addition to vinyl terminated self-assembled monolayers (SAMs)

    PubMed Central

    Adamkiewicz, Malgorzata

    2014-01-01

    Summary C11-Vinyl-terminated self-assembled monolayers (SAMs) on silica surfaces are successfully modified in C–C bond forming reactions with dihalocarbenes to generate SAMs, terminated with dihalo- (fluoro, chloro, bromo) cyclopropane motifs with about 30% surface coverage. PMID:25550756

  13. Desorption of oxygen from alloyed Ag/Pt(111)

    SciTech Connect

    Jankowski, Maciej; Wormeester, Herbert Zandvliet, Harold J. W.; Poelsema, Bene

    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}) 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.

  14. Monolayer Topological Insulators: Silicene, Germanene, and Stanene

    NASA Astrophysics Data System (ADS)

    Ezawa, Motohiko

    2015-12-01

    We report the recent progress on the theoretical aspects of monolayer topological insulators including silicene, germanene and stanene, which are monolayer honeycomb structures of silicon, germanium and tin, respectively. They show quantum spin Hall effects in nature due to the spin-orbit interaction. The band gap can be tuned by applying perpendicular electric field, which induces a topological phase transition. We also analyze the topological properties of generic honeycomb systems together with the classification of topological insulators. Phase diagrams of topological insulators and superconductors in honeycomb systems are explicitly determined. We also investigate topological electronics including a topological field-effect transistor, the topological Kirchhoff's law and the topological spin-valleytronics.

  15. Low temperature photoresponse of monolayer tungsten disulphide

    SciTech Connect

    Cao, Bingchen; Shen, Xiaonan; Shang, Jingzhi; Cong, Chunxiao; Yang, Weihuang; Eginligil, Mustafa E-mail: meginligil@ntu.edu.sg; Yu, Ting E-mail: meginligil@ntu.edu.sg

    2014-11-01

    High photoresponse can be achieved in monolayers of transition metal dichalcogenides. However, the response times are inconveniently limited by defects. Here, we report low temperature photoresponse of monolayer tungsten disulphide prepared by exfoliation and chemical vapour deposition (CVD) method. The exfoliated device exhibits n-type behaviour; while the CVD device exhibits intrinsic behaviour. In off state, the CVD device has four times larger ratio of photoresponse for laser on/off and photoresponse decay–rise times are 0.1 s (limited by our setup), while the exfoliated device has few seconds. These findings are discussed in terms of charge trapping and localization.

  16. Nonlinear optical studies of organic monolayers

    SciTech Connect

    Shen, Y.R.

    1988-02-01

    Second-order nonlinear optical effects are forbidden in a medium with inversion symmetry, but are necessarily allowed at a surface where the inversion summary is broken. They are often sufficiently strong so that a submonolayer perturbation of the surface can be readily detected. They can therefore be used as effective tools to study monolayers adsorbed at various interfaces. We discuss here a number of recent experiments in which optical second harmonic generation (SHG) and sum-frequency generation (SFG) are employed to probe and characterize organic monolayers. 15 refs., 5 figs.

  17. Monochromatic electron photoemission from diamondoid monolayers

    SciTech Connect

    Yang, Wanli; Yang, Wanli L.; Fabbri, J.D.; Willey, T.M.; Lee, J.R.I.; Dahl, J.E.; Carlson, R.M.K.; Schreiner, P.R.; Fokin, A.A.; Tkachenko, B.A.; Fokina, N.A.; Meevasana, W.; Mannella, N.; Tanaka, K.; Zhou, X.J.; van Buuren, T.; Kelly, M.A.; Hussain, Z.; Melosh, N.A.; Shen, Z.-X.

    2007-02-27

    We found monochromatic electron photoemission from large-area self-assembled monolayers of a functionalized diamondoid, [121]tetramantane-6-thiol. Photoelectron spectra of the diamondoid monolayers exhibited a peak at the low-kinetic energy threshold; up to 68percent of all emitted electrons were emitted within this single energy peak. The intensity of the emission peak is indicative of diamondoids being negative electron affinity materials. With an energy distribution width of less than 0.5 electron volts, this source of monochromatic electrons may find application in technologies such as electron microscopy, electron beam lithography, and field-emission flatpanel displays.

  18. Active Tensile Modulus of an Epithelial Monolayer

    NASA Astrophysics Data System (ADS)

    Vincent, Romaric; Bazellières, Elsa; Pérez-González, Carlos; Uroz, Marina; Serra-Picamal, Xavier; Trepat, Xavier

    2015-12-01

    A general trait of cell monolayers is their ability to exert contractile stresses on their surroundings. The scaling laws that link such contractile stresses with the size and geometry of constituent cells remain largely unknown. In this Letter, we show that the active tension of an epithelial monolayer scales linearly with the size of the constituent cells, a surprisingly simple relationship. The slope of this relationship defines an active tensile modulus, which depends on the concentration of myosin and spans more than 2 orders of magnitude across cell types and molecular perturbations.

  19. Correlational switching between 3{times}1 and 6{times}1 surface reconstructions on Si(111) with submonolayer Ag adsorption

    SciTech Connect

    Kempa, K.; Broido, D.A.; Weitering, H.H. |

    1996-07-01

    Electron correlations are strongly enhanced in low dimensional systems. Taking correlations as the dominant mechanism, we provide and explanation of the recently observed electrostatically enforced structural phase transition (3x1 to 6x1) on a Si(111) surface with sub-monolayer Ag adsorption.

  20. Single-crystalline octahedral Au-Ag nanoframes.

    PubMed

    Hong, Xun; Wang, Dingsheng; Cai, Shuangfei; Rong, Hongpan; Li, Yadong

    2012-11-01

    We report the formation of single-crystalline octahedral Au-Ag nanoframes by a modified galvanic replacement reaction. Upon sequential addition of AgNO(3), CuCl, and HAuCl(4) to octadecylamine solution, truncated polyhedral silver nanoparticles formed first and then changed into octahedral Au-Ag nanoframes, without requiring a conventional Ag removal step with additional oxidation etchant. The nanoframes have 12 sides, and all of the eight {111} faces are empty. The side grows along the [110] direction, and the diameter is less than 10 nm. The selective gold deposition on the high-energy (110) surface, the diffusion, and the selective redeposition of Au and Ag atoms are the key reasons for the formation of octahedral nanoframes.

  1. Electrodeposition of gold nanoparticles on aryl diazonium monolayer functionalized HOPG surfaces.

    PubMed

    González, M C R; Orive, A G; Salvarezza, R C; Creus, A H

    2016-01-21

    Gold nanoparticle electrodeposition on a modified HOPG surface with a monolayer organic film based on aryl diazonium chemistry has been studied. This organic monolayer is electrochemically grown with the use of 2,2-diphenyl-1-picrylhydrazyl (DPPH), a radical scavenger. The electrodeposition of gold on this modified surface is highly favored resulting in an AuNP surface density comparable to that found on glassy carbon. AuNPs grow only in the areas covered by the organic monolayer leaving free clean HOPG zones. A progressive mechanism for the nucleation and growth is followed giving hemispherical AuNPs, homogeneously distributed on the surface and their sizes can be well controlled by the applied electrodeposition potential. By using AFM, C-AFM and electrochemical measurements with the aid of two redox probes, namely Fe(CN)6(4-)/Fe(CN)6(3-) and dopamine, relevant results about the electrochemical modified surface as well as the gold nanoparticles electrodeposited on them are obtained.

  2. Surface enhanced Raman scattering of monolayer MX2 with metallic nano particles

    PubMed Central

    Zhang, Duan; Wu, Ye-Cun; Yang, Mei; Liu, Xiao; Coileáin, Cormac Ó; Abid, Mourad; Abid, Mohamed; Wang, Jing-Jing; Shvets, Igor; Xu, Hongjun; Chun, Byong Sun; Liu, Huajun; Wu, Han-Chun

    2016-01-01

    Monolayer transition metal dichalcogenides MX2 (M = Mo, W; X = S) exhibit remarkable electronic and optical properties, making them candidates for application within flexible nano-optoelectronics. The ability to achieve a high optical signal, while quantitatively monitoring strain in real-time is the key requirement for applications in flexible sensing and photonics devices. Surface-enhanced Raman scattering (SERS) allows us to achieve both simultaneously. However, the SERS depends crucially on the size and shape of the metallic nanoparticles (NPs), which have a large impact on its detection sensitivity. Here, we investigated the SERS of monolayer MX2, with particular attention paid to the effect of the distribution of the metallic NPs. We show that the SERS depends crucially on the distribution of the metallic NPs and also the phonon mode of the MX2. Moreover, strong coupling between MX2 and metallic NPs, through surface plasmon excitation, results in splitting of the and modes and an additional peak becomes apparent. For a WS2-Ag system the intensity of the additional peak increases exponentially with local strain, which opens another interesting window to quantitatively measure the local strain using SERS. Our experimental study may be useful for the application of monolayer MX2 in flexible nano-optoelectronics. PMID:27457808

  3. Surface enhanced Raman scattering of monolayer MX2 with metallic nano particles.

    PubMed

    Zhang, Duan; Wu, Ye-Cun; Yang, Mei; Liu, Xiao; Coileáin, Cormac Ó; Abid, Mourad; Abid, Mohamed; Wang, Jing-Jing; Shvets, Igor; Xu, Hongjun; Chun, Byong Sun; Liu, Huajun; Wu, Han-Chun

    2016-01-01

    Monolayer transition metal dichalcogenides MX2 (M = Mo, W; X = S) exhibit remarkable electronic and optical properties, making them candidates for application within flexible nano-optoelectronics. The ability to achieve a high optical signal, while quantitatively monitoring strain in real-time is the key requirement for applications in flexible sensing and photonics devices. Surface-enhanced Raman scattering (SERS) allows us to achieve both simultaneously. However, the SERS depends crucially on the size and shape of the metallic nanoparticles (NPs), which have a large impact on its detection sensitivity. Here, we investigated the SERS of monolayer MX2, with particular attention paid to the effect of the distribution of the metallic NPs. We show that the SERS depends crucially on the distribution of the metallic NPs and also the phonon mode of the MX2. Moreover, strong coupling between MX2 and metallic NPs, through surface plasmon excitation, results in splitting of the and modes and an additional peak becomes apparent. For a WS2-Ag system the intensity of the additional peak increases exponentially with local strain, which opens another interesting window to quantitatively measure the local strain using SERS. Our experimental study may be useful for the application of monolayer MX2 in flexible nano-optoelectronics. PMID:27457808

  4. Surface enhanced Raman scattering of monolayer MX2 with metallic nano particles

    NASA Astrophysics Data System (ADS)

    Zhang, Duan; Wu, Ye-Cun; Yang, Mei; Liu, Xiao; Coileáin, Cormac Ó.; Abid, Mourad; Abid, Mohamed; Wang, Jing-Jing; Shvets, Igor; Xu, Hongjun; Chun, Byong Sun; Liu, Huajun; Wu, Han-Chun

    2016-07-01

    Monolayer transition metal dichalcogenides MX2 (M = Mo, W; X = S) exhibit remarkable electronic and optical properties, making them candidates for application within flexible nano-optoelectronics. The ability to achieve a high optical signal, while quantitatively monitoring strain in real-time is the key requirement for applications in flexible sensing and photonics devices. Surface-enhanced Raman scattering (SERS) allows us to achieve both simultaneously. However, the SERS depends crucially on the size and shape of the metallic nanoparticles (NPs), which have a large impact on its detection sensitivity. Here, we investigated the SERS of monolayer MX2, with particular attention paid to the effect of the distribution of the metallic NPs. We show that the SERS depends crucially on the distribution of the metallic NPs and also the phonon mode of the MX2. Moreover, strong coupling between MX2 and metallic NPs, through surface plasmon excitation, results in splitting of the and modes and an additional peak becomes apparent. For a WS2-Ag system the intensity of the additional peak increases exponentially with local strain, which opens another interesting window to quantitatively measure the local strain using SERS. Our experimental study may be useful for the application of monolayer MX2 in flexible nano-optoelectronics.

  5. Kinetics of self-assembled monolayer formation on individual nanoparticles.

    PubMed

    Smith, Jeremy G; Jain, Prashant K

    2016-08-24

    Self-assembled monolayer (SAM) formation of alkanethiols on nanoparticle surfaces is an extensively studied surface reaction. But the nanoscale aspects of the rich microscopic kinetics of this reaction may remain hidden due to ensemble-averaging in colloidal samples, which is why we investigated in real-time how alkanethiol SAMs form on a single Ag nanoparticle. From single-nanoparticle trajectories obtained using in situ optical spectroscopy, the kinetics of SAM formation appears to be limited by the growth of the layer across the nanoparticle surface. A significant spread in the growth kinetics is seen between nanoparticles. The single-nanoparticle rate distributions suggest two distinct modes for SAM growth: spillover of adsorbed thiols from the initial binding sites on the nanoparticle and direct adsorption of thiol from solution. At low concentrations, wherein direct adsorption from solution is not prevalent and growth takes place primarily by adsorbate migration, the SAM formation rate was less variable from one nanoparticle to another. On the other hand, at higher thiol concentrations, when both modes of growth were operative, the population of nanoparticles with inherent variations in surface conditions and/or morphology exhibited a heterogeneous distribution of rates. These new insights into the complex dynamics of SAM formation may inform synthetic strategies for ligand passivation and functionalization of nanoparticles and models of reactive adsorption and catalysis on nanoparticles. PMID:27523488

  6. Kinetics-controlled growth of bimetallic RhAg on Au nanorods and their catalytic properties

    NASA Astrophysics Data System (ADS)

    Ye, Wei; Guo, Xia; Xie, Fang; Zhu, Rui; Zhao, Qing; Yang, Jian

    2014-03-01

    Controlled growth of hybrid metallic nanocomposites for a desirable structure in a combination of selected components is highly important for their applications. Herein, the controllable growth of RhAg on the gold nanorods is achieved from the dumbbell-like RhAg-tipped nanorods to the brushy RhAg-coated nanorods, or the rod-like Au@Ag-Rh nanorattles. These different growth modes of RhAg on the gold nanorods are correlated with the reducing kinetics of RhCl3 and AgNO3. In view of the promising catalytic properties of Rh, the gold nanorods modified by RhAg in different structures are examined as catalysts for the oxidation of o-phenylenediamine. It is found that brushy RhAg-coated nanorods present a higher catalytic efficiency than dumbbell-like RhAg-tipped nanorods and rod-like Au@Ag-Rh nanorattles. These results would benefit the overgrowth control on the one-dimensional metallic nanorods and the rational design of new generation heterogeneous catalysts and optical devices.Controlled growth of hybrid metallic nanocomposites for a desirable structure in a combination of selected components is highly important for their applications. Herein, the controllable growth of RhAg on the gold nanorods is achieved from the dumbbell-like RhAg-tipped nanorods to the brushy RhAg-coated nanorods, or the rod-like Au@Ag-Rh nanorattles. These different growth modes of RhAg on the gold nanorods are correlated with the reducing kinetics of RhCl3 and AgNO3. In view of the promising catalytic properties of Rh, the gold nanorods modified by RhAg in different structures are examined as catalysts for the oxidation of o-phenylenediamine. It is found that brushy RhAg-coated nanorods present a higher catalytic efficiency than dumbbell-like RhAg-tipped nanorods and rod-like Au@Ag-Rh nanorattles. These results would benefit the overgrowth control on the one-dimensional metallic nanorods and the rational design of new generation heterogeneous catalysts and optical devices. Electronic

  7. Design and compressibility of Langmuir monolayers from organometallic nanocyclic complexes

    NASA Astrophysics Data System (ADS)

    Grushevskaya, H. V.; Krylova, N. G.; Lipnevich, I. V.

    2016-08-01

    We propose to control design of organometallic conducting Langmuir monolayer by utilizing geometrodynamic approach. By means of this approach the compressibility of the monolayer, which consists of molecules of thiophene-pyrrole series oligomer with covalently bound hydrophobic alkyl chain, has been analyzed for different subphase with iron salts. It has been discovered that the monolayers are polymerized and turn into monolayers of nanocyclic organometallic coordination compounds at a two-dimensional phase transition of the first order.

  8. Glitter in a 2D monolayer.

    PubMed

    Yang, Li-Ming; Dornfeld, Matthew; Frauenheim, Thomas; Ganz, Eric

    2015-10-21

    We predict a highly stable and robust atomically thin gold monolayer with a hexagonal close packed lattice stabilized by metallic bonding with contributions from strong relativistic effects and aurophilic interactions. We have shown that the framework of the Au monolayer can survive 10 ps MD annealing simulations up to 1400 K. The framework is also able to survive large motions out of the plane. Due to the smaller number of bonds per atom in the 2D layer compared to the 3D bulk we observe significantly enhanced energy per bond (0.94 vs. 0.52 eV per bond). This is similar to the increase in bond strength going from 3D diamond to 2D graphene. It is a non-magnetic metal, and was found to be the global minima in the 2D space. Phonon dispersion calculations demonstrate high kinetic stability with no negative modes. This 2D gold monolayer corresponds to the top monolayer of the bulk Au(111) face-centered cubic lattice. The close-packed lattice maximizes the aurophilic interactions. We find that the electrons are completely delocalized in the plane and behave as 2D nearly free electron gas. We hope that the present work can inspire the experimental fabrication of novel free standing 2D metal systems.

  9. Monolayer phase coarsening using oscillatory flow

    NASA Astrophysics Data System (ADS)

    Leung, J.; Lopez, J. M.; Vogel, M. J.

    2005-11-01

    The co-existing phase domains of monolayers commonly observed via microscope are examined on flowing systems. Recent evidence shows that co-existing phase domains have profound effects on monolayer response to bulk flow. The present flow geometry consists of an open-top rectangular cavity in which the flow is driven by the periodic oscillation of the floor in its own plane. The oscillation of the floor dilates and compresses any film at the gas/liquid interface while still maintaining an essentially flat interface. A range of flow conditions (oscillation frequency and amplitude) is chosen so that the flow remains essentially two-dimensional. Measurements at the interface, initially covered by an insoluble monolayer (vitamin K1 or stearic acid), are made using a Brewster angle microscope system with a pulsed laser. Various phenomena such as fragmentation (breaking up of co-existing domains into finer ones) had previously been observed in sheared monolayer flows. In this new flow regime, we have seen dramatic coarsening of the domains. Interesting relaxation behavior at short and long time scales will also be discussed.

  10. Adsorption of Ions at Uncharged Insoluble Monolayers.

    PubMed

    Peshkova, Tatyana V; Minkov, Ivan L; Tsekov, Roumen; Slavchov, Radomir I

    2016-09-01

    A method is proposed for the experimental determination of the adsorption of inorganic electrolytes at a surface covered with insoluble surfactant monolayer. This task is complicated by the fact that the change of the salt concentration alters both chemical potentials of the electrolyte and the surfactant. Our method resolves the question by combining data for the surface pressure versus area of the monolayer at several salt concentrations with data for the equilibrium spreading pressure of crystals of the surfactant (used to fix a standard state). We applied the method to alcohols spread at the surface of concentrated halide solutions. The measured salt adsorption is positive and has nonmonotonic dependence on the area per surfactant molecule. For the liquid expanded film, depending on the concentration, there is one couple of ions adsorbed per each 3-30 surfactant molecules. We analyzed which ion, the positive or the negative, stands closer to the surface, by measuring the effect of NaCl on the Volta potential of the monolayer. The potentiometric data suggest that Na(+) is specifically adsorbed, while Cl(-) remains in the diffuse layer, i.e., the surface is positively charged. The observed reverse Hofmeister series of the adsorptions of NaF, NaCl, and NaBr suggests the same conclusion holds for all these salts. The force that causes the adsorption of Na(+) seems to be the interaction of the ion with the dipole moment of the monolayer. PMID:27529571

  11. Hydrolytic kinetics of biodegradable polyester monolayers

    SciTech Connect

    Lee, W.K.; Gardella, J.A. Jr.

    2000-04-04

    The rate of hydrolysis of Langmuir monolayer films of a series of biodegradable polyesters was investigated at the air/water interface. The present study investigated parameters such as degradation medium, pH, and time. The hydrolysis of polyester monolayers strongly depended on both the degradation medium used to control subphase pH and the concentration of active ions. Under the conditions studied here, polymer monolayers showed faster hydrolysis when they were exposed to a basic subphase rather than that of acidic or neutral subphase. The basic (pH = 10) hydrolysis of [poly(l-lactide)/polycaprolactone](l-PLA/PCL 1/1 by mole) blend was faster than that of each homopolymer at the initial stage. This result is explained by increasing numbers of base attack sites per unit area owing to the very slow hydrolysis of PCL, a dilution effect on the concentration of l-PLA monolayers. Conversely the hydrolytic behavior of l-lactide-co-caprolactone (1/1 by mole) was similar to that of PCL even though the chemical compositions of the blend and the copolymer are very similar to each other. The resistance of the copolymer to hydrolysis might be attributed to the hydrophobicity and the steric hindrance of caprolactone unit in the copolymer.

  12. Nanotubes based on monolayer blue phosphorus

    NASA Astrophysics Data System (ADS)

    Montes, E.; Schwingenschlögl, U.

    2016-07-01

    We demonstrate structural stability of monolayer zigzag and armchair blue phosphorus nanotubes by means of molecular dynamics simulations. The vibrational spectrum and electronic band structure are determined and analyzed as functions of the tube diameter and axial strain. The nanotubes are found to be semiconductors with a sensitive indirect band gap that allows flexible tuning.

  13. Adsorption of Ions at Uncharged Insoluble Monolayers

    NASA Astrophysics Data System (ADS)

    Peshkova, T. V.; Minkov, I. L.; Tsekov, R.; Slavchov, R. I.

    2016-08-01

    A method is proposed for the experimental determination of the adsorption of inorganic electrolytes at a surface covered with insoluble surfactant monolayer. This task is complicated by the fact that the change of the salt concentration alters both chemical potentials of the electrolyte and the surfactant. Our method resolves the question by combining data for the surface pressure versus area of the monolayer at several salt concentrations with data for the equilibrium spreading pressure of crystals of the surfactant (used to fix a standard state). We applied the method to alcohols spread at the surface of concentrated halide solutions. The measured salt adsorption is positive and has nonmonotonic dependence on the area per surfactant molecule. For the liquid expanded film, depending on the concentration, there is one couple of ions adsorbed per each 3–30 surfactant molecules. We analyzed which ion, the positive or the negative, stands closer to the surface, by measuring the effect of NaCl on the Volta potential of the monolayer. The potentiometric data suggest that Na+ is specifically adsorbed, while Cl– remains in the diffuse layer, i.e., the surface is positively charged. The observed reverse Hofmeister series of the adsorptions of NaF, NaCl, and NaBr suggests the same conclusion holds for all these salts. The force that causes the adsorption of Na+ seems to be the interaction of the ion with the dipole moment of the monolayer.

  14. Convective Assembly of a Particle Monolayer.

    PubMed

    Fleck, N A; McMeeking, R M; Kraus, T

    2015-12-29

    Recently, the steady-state process of convective assembly has emerged as a viable production route for colloidal monolayers. The present study models the regions of particle assembly: Region I comprises convective concentration of a particle suspension in a liquid below a meniscus, Region II comprises permeation of fluid through the dense particle monolayer, and Region III comprises capillary densification. For each region, the dominant physics and nondimensional groups are identified, and quantitative models are derived to describe the evolution of microstructure in terms of the main process parameters. The concentration profile within the assembly zone of Region I is predicted, including the role of a concentration-dependent diffusion constant and the shape of the meniscus. The fluid flow through the assembled monolayer is treated in Region II, along with a stability calculation to reveal that isolated particle clusters do not survive on top of the monolayer. The physics of capillary crystallization is addressed in Region III, with an emphasis on the density of cracks that emerge. The Peclet number and Capillary number both play important roles but in different regions of the assembly process.

  15. CO Oxidation Prefers the Eley-Rideal or Langmuir-Hinshelwood Pathway: Monolayer vs Thin Film of SiC.

    PubMed

    Sinthika, S; Vala, Surya Teja; Kawazoe, Y; Thapa, Ranjit

    2016-03-01

    Using the first-principles approach, we investigated the electronic and chemical properties of wurtzite silicon carbide (2H-SiC) monolayer and thin film structures and substantiated their catalytic activity toward CO oxidation. 2H-SiC monolayer, being planar, is quite stable and has moderate binding with O2, while CO interacts physically; thus, the Eley-Rideal (ER) mechanism prevails over the Langmuir-Hinshelwood (LH) mechanism with an easily cleared activation barrier. Contrarily, 2H-SiC thin film, which exhibits a nonplanar structure, allows moderate binding of both CO and O2 on its surface, thus favoring the LH mechanism over the ER one. Comprehending these results leads to a better understanding of the reaction mechanisms involving structural contrast. Weak overlapping between the 2p(z)(C) and 3p(z)(Si) orbitals of the SiC monolayer system has been found to be the primary reason to revert the active site toward sp(3) hybridization, during interaction with the molecules. In addition, the influences of graphite and Ag(111) substrates on the CO oxidation mechanism were also studied, and it is observed that the ER mechanism is preserved on SiC/G system, while CO oxidation on the SiC/Ag(111) system follows the LH mechanism. The calculated Sabatier activities of the SiC catalysts show that the catalysts are very efficient in catalyzing CO oxidation.

  16. CO Oxidation Prefers the Eley-Rideal or Langmuir-Hinshelwood Pathway: Monolayer vs Thin Film of SiC.

    PubMed

    Sinthika, S; Vala, Surya Teja; Kawazoe, Y; Thapa, Ranjit

    2016-03-01

    Using the first-principles approach, we investigated the electronic and chemical properties of wurtzite silicon carbide (2H-SiC) monolayer and thin film structures and substantiated their catalytic activity toward CO oxidation. 2H-SiC monolayer, being planar, is quite stable and has moderate binding with O2, while CO interacts physically; thus, the Eley-Rideal (ER) mechanism prevails over the Langmuir-Hinshelwood (LH) mechanism with an easily cleared activation barrier. Contrarily, 2H-SiC thin film, which exhibits a nonplanar structure, allows moderate binding of both CO and O2 on its surface, thus favoring the LH mechanism over the ER one. Comprehending these results leads to a better understanding of the reaction mechanisms involving structural contrast. Weak overlapping between the 2p(z)(C) and 3p(z)(Si) orbitals of the SiC monolayer system has been found to be the primary reason to revert the active site toward sp(3) hybridization, during interaction with the molecules. In addition, the influences of graphite and Ag(111) substrates on the CO oxidation mechanism were also studied, and it is observed that the ER mechanism is preserved on SiC/G system, while CO oxidation on the SiC/Ag(111) system follows the LH mechanism. The calculated Sabatier activities of the SiC catalysts show that the catalysts are very efficient in catalyzing CO oxidation. PMID:26866799

  17. Ab initio study of ZrO2 monolayers epitaxial on Si

    NASA Astrophysics Data System (ADS)

    Dogan, Mehmet; Kumah, Divine; Ahn, Charles; Walker, Frederick; Ismail-Beigi, Sohrab

    Growing thin films of crystalline metal oxides on semiconductors has been of much scientific interest because of their applications in electronic devices. One research goal is to achieve ferroelectricity in a crystalline and thin oxide film that is epitaxial on a semiconductor. This would enable the realization of non-volatile field-effect transistors where the state is encoded in the polarization direction of the oxide. We study oxides that are not ferroelectric in the bulk but become ferroelectric as an ultra-thin film on a semiconductor. Recent advances in epitaxial growth methods permit fabrication of such systems. We use density functional theory to study the interface between ZrO2 monolayers and Si (001). These monolayers have multiple metastable states. We present an analysis of these configurations and energy barriers between them. We consider the likely experimental situation where different configurations coexist to form a multi-domain system, and investigate domain dynamics. Furthermore, we demonstrate that the ZrO2 monolayers can be used as a buffer layer to induce ferroelectricity in perovskite oxides such as SrTiO3 on Si. We also show that these monolayers modify the transport properties of Si which would allow for the desired device applications. This work is supported by the National Science Foundation through Grant MRSEC NSF DMR-1119826.

  18. A computer model of engineered cardiac monolayers.

    PubMed

    Kim, Jong M; Bursac, Nenad; Henriquez, Craig S

    2010-05-19

    Engineered monolayers created using microabrasion and micropatterning methods have provided a simplified in vitro system to study the effects of anisotropy and fiber direction on electrical propagation. Interpreting the behavior in these culture systems has often been performed using classical computer models with continuous properties. However, such models do not account for the effects of random cell shapes, cell orientations, and cleft spaces inherent in these monolayers on the resulting wavefront conduction. This work presents a novel methodology for modeling a monolayer of cardiac tissue in which the factors governing cell shape, cell-to-cell coupling, and degree of cleft space are not constant but rather are treated as spatially random with assigned distributions. This modeling approach makes it possible to simulate wavefront propagation in a manner analogous to performing experiments on engineered monolayer tissues. Simulated results are compared to previously published measured data from monolayers used to investigate the role of cellular architecture on conduction velocities and anisotropy ratios. We also present an estimate for obtaining the electrical properties from these networks and demonstrate how variations in the discrete cellular architecture affect the macroscopic conductivities. The simulations support the common assumption that under normal ranges of coupling strength, tissues with relatively uniform distributions of cell shapes and connectivity can be represented using continuous models with conductivities derived from random discrete cellular architecture using either global or local estimates. The results also reveal that in the presence of abrupt changes in cell orientation, local estimates of tissue properties predict smoother changes in conductivity that may not adequately predict the discrete nature of propagation at the transition sites. PMID:20441739

  19. Terrace-dependent nucleation of small Ag clusters on a five-fold icosahedral quasicrystal surface

    SciTech Connect

    Unal, B.; Evans, J.W.; Lograsso, T.A.; Ross, A.R.; Jenks, C.J.; Thiel, P.A.

    2007-07-21

    Nucleation of Ag islands on the five-fold surface of icosahedral Al-Pd-Mn is influenced strongly by trap sites. Submonolayers of Ag prepared by deposition at 365 K and with a flux of 1 x 10{sup -3} monolayers/s exhibit a variation in Ag island densities across different terraces. Comparisons with previous work and with rate equation analysis indicate that trap sites are not saturated under these experimental conditions and that the difference in island densities is not necessarily due to variation in trap densities. While it could have a number of different origins, our results point to a terrace-dependent value of the effective diffusion barrier for Ag adatoms.

  20. Chemically modified polypyrrole

    SciTech Connect

    Inagaki, T.; Skotheim, T.A.; Lee, H.S.; Okamoto, Y.; Samuelson, L.; Tripathy, S.

    1988-01-01

    Polypyrrole (PPy) films have been systematically modified with electroactive groups in the ..beta..-position to design electrode materials with specific electrochemical and surface active properties. Electrochemical copolymerization of pyrrole and 3-(6-ferrocenyl,6-hydroxyhexyl)pyrrole (P-6-Fc) yields a ferrocene functionalized polypyrrole with a controlled amount to ferrocene functionalization. And also, copolymers of pyrrole and 3-(4-(2,5- dimethoxyphenyl)butyl)pyrrole (P-MP) can be made by electrochemical polymerization and converted to the copolymers containing pH dependent electroactive hydroquinone moieties. Derivatized pyrroles have also been incorporated into Langmuir-Blodgett film structures. The surface pressure-area isotherms of 3-(13-ferrocenyl,13-hydroxytridecy)pyrrole (P-13-Fc) and the mixed monolayer of P-13-Fc and 3-n-hexadecylpyrrole (HDP) are shown. 17 refs., 4 figs.

  1. Impedance studies of the cell Ag/AgI/Ag beta alumina/AgI/Ag. Technical report No. 15, August 1987-August 1988

    SciTech Connect

    Breiter, M.W.; Drstak, H.; Maly-Schreiber, M.

    1988-07-01

    The construction of the cell Ag/AgI/Ag beta alumina/AgI/Ag is described. The impedance of this cell was measured between .001 and 10000 Hz at temperatures between 20 and 550 C. At temperatures below 100 C the cell impedance is determined to a large extent by the bulk resistance of the AgI layer and to a smaller extent by the impedance of the interface Ag/Agi. At temperatures between 160 and 350 C the impedance is controlled by the bulk resistance of the Ag beta alumina and an impedance due to contact problems between Ag and AgI. The bulk resistance of the beta' alumina becomes predominant between 350 and 550 C. A hindrance due to the transfer of silver ions from AgI to Ag beta' alumina was not observable in the whole temperature range.

  2. Ligand Replacement Approach to Raman-Responded Molecularly Imprinted Monolayer for Rapid Determination of Penicilloic Acid in Penicillin.

    PubMed

    Zhang, Liying; Jin, Yang; Huang, Xiaoyan; Zhou, Yujie; Du, Shuhu; Zhang, Zhongping

    2015-12-01

    Penicilloic acid (PA) is a degraded byproduct of penicillin and often causes fatal allergies to humans, but its rapid detection in penicillin drugs remains a challenge due to its similarity to the mother structure of penicillin. Here, we reported a ligand-replaced molecularly imprinted monolayer strategy on a surface-enhanced Raman scattering (SERS) substrate for the specific recognition and rapid detection of Raman-inactive PA in penicillin. The bis(phenylenediamine)-Cu(2+)-PA complex was first synthesized and stabilized onto the surface of silver nanoparticle film that was fabricated by a bromide ion-added silver mirror reaction. A molecularly imprinted monolayer was formed by the further modification of alkanethiol around the stabilized complex on the Ag film substrate, and the imprinted recognition site was then created by the replacement of the complex template with Raman-active probe molecule p-aminothiophenol. When PA rebound into the imprinted site in the alkanethiol monolayer, the SERS signal of p-aminothiophenol exhibited remarkable enhancement with a detection limit of 0.10 nM. The imprinted monolayer can efficiently exclude the interference of penicillin and thus provides a selective determination of 0.10‰ (w/w) PA in penicillin, which is about 1 order of magnitude lower than the prescribed residual amount of 1.0‰. The strategy reported here is simple, rapid and inexpensive compared to the traditional chromatography-based methods. PMID:26545037

  3. Ligand Replacement Approach to Raman-Responded Molecularly Imprinted Monolayer for Rapid Determination of Penicilloic Acid in Penicillin.

    PubMed

    Zhang, Liying; Jin, Yang; Huang, Xiaoyan; Zhou, Yujie; Du, Shuhu; Zhang, Zhongping

    2015-12-01

    Penicilloic acid (PA) is a degraded byproduct of penicillin and often causes fatal allergies to humans, but its rapid detection in penicillin drugs remains a challenge due to its similarity to the mother structure of penicillin. Here, we reported a ligand-replaced molecularly imprinted monolayer strategy on a surface-enhanced Raman scattering (SERS) substrate for the specific recognition and rapid detection of Raman-inactive PA in penicillin. The bis(phenylenediamine)-Cu(2+)-PA complex was first synthesized and stabilized onto the surface of silver nanoparticle film that was fabricated by a bromide ion-added silver mirror reaction. A molecularly imprinted monolayer was formed by the further modification of alkanethiol around the stabilized complex on the Ag film substrate, and the imprinted recognition site was then created by the replacement of the complex template with Raman-active probe molecule p-aminothiophenol. When PA rebound into the imprinted site in the alkanethiol monolayer, the SERS signal of p-aminothiophenol exhibited remarkable enhancement with a detection limit of 0.10 nM. The imprinted monolayer can efficiently exclude the interference of penicillin and thus provides a selective determination of 0.10‰ (w/w) PA in penicillin, which is about 1 order of magnitude lower than the prescribed residual amount of 1.0‰. The strategy reported here is simple, rapid and inexpensive compared to the traditional chromatography-based methods.

  4. Ordered surface alloy formation of immiscible metals: The case of Pb deposited on Ag(111)

    SciTech Connect

    Dalmas, J.; Oughaddou, H.; Leandri, C.; Gay, J-M.; Le Lay, G.; Treglia, G.; Aufray, B.; Bunk, O.

    2005-10-15

    The deposition of 1/3 Pb monolayer at room temperature onto Ag(111) leads to a ({radical}(3)x{radical}(3))R30 deg. superstructure. We present here a detailed structural study of this surface structure by synchrotron radiation surface x ray diffraction (SR-SXRD) and scanning tunnel microscopy (STM). We show that Pb atoms are embedded into the silver top surface layer forming an ordered Ag{sub 2}Pb surface alloy despite the strong tendency of the system to phase separate in the bulk. Quenched molecular dynamics simulations allow us to interpret this ordering reversal, in terms of size-mismatch induced surface alloying.

  5. Growth mode and structures of silicene on the Ag(1 1 1) surface

    NASA Astrophysics Data System (ADS)

    Lee, Guo-Wei; Chen, Han-De; Lin, Deng-Sung

    2015-11-01

    Low-temperature scanning tunneling microscopy (LT-STM) and ab initio density functional theory (DFT) calculations have been utilized to explore the growth processes and atomic structure of silicene on the Ag(1 1 1) surface. STM images reveal an etching growth mode in the sub-monolayer range. The results confirm the existence of various overlayer structures reported previously and that the lattice parameters of several overlayer structures at sub-monolayer coverages are close to the corresponding substrate supercells. However, detailed analysis of domain boundaries and Moiré-like superstructure in the STM images strongly suggest that the overlayer structures and the substrate lattices have no coincident relationships. Preliminary results of DFT calculations show that the changes in total energy upon translational displacement of the (3 × 3)Si silicene supercells with respect to the Ag(1 1 1) lattice is within a few tens of meV/Si atom.

  6. Nanosphere monolayer on a transducer for enhanced detection of gaseous heavy metal.

    PubMed

    Sabri, Ylias M; Kandjani, Ahmad Esmaielzadeh; Ippolito, Samuel J; Bhargava, Suresh K

    2015-01-28

    This study reports for the first time that polystyrene monodispersed nanosphere monolayer (PS-MNM) based Au (Au-MNM) and Ag (Ag-MNM) nanostructures deposited on quartz crystal microbalance (QCM) transducers can be used for nonoptical based chemical sensing with extremely high sensitivity and selectivity. This was demonstrated by exposing the Au-MNM and Ag-MNM based QCMs to low concentrations of Hg(0) vapor in the presence interferent gas species (i.e., H2O, NH3, volatile organics, etc.) at operating temperatures of 30 and 75 °C. At 30 °C, the Au-MNM and Ag-MNM based QCMs showed ∼16 and ∼20 times higher response magnitude toward Hg(0) vapor concentration of 3.26 mg/m(3) (364 parts per billion by volume (ppbv)) relative to their unmodified control counterparts, respectively. The results indicated that the extremely high sensitivity was not due to the increased surface area (only 4.62 times increase) but due to their long-range interspatial order and high number of surface defect formation which are selectively active toward Hg(0) vapor sorption. The Au-MNM and Ag-MNM also had more than an order of magnitude lower detection limits (<3 ppbv) toward Hg(0) vapor compared to their unmodified control counterparts (>30 ppbv). When the operating temperature was increased from 30 to 75 °C, it was found that the sensors exhibited lower drift, better accuracy, and better selectivity toward Hg(0) vapor but at the compromise of higher detection limits. The high repeatability (84%), accuracy (97%), and stability of Au-MNM in particular make it practical to potentially be used as nonspectroscopic based Hg(0) vapor sensor in many industries either as mercury emission monitoring or as part of a mercury control feedback system.

  7. Nanosphere monolayer on a transducer for enhanced detection of gaseous heavy metal.

    PubMed

    Sabri, Ylias M; Kandjani, Ahmad Esmaielzadeh; Ippolito, Samuel J; Bhargava, Suresh K

    2015-01-28

    This study reports for the first time that polystyrene monodispersed nanosphere monolayer (PS-MNM) based Au (Au-MNM) and Ag (Ag-MNM) nanostructures deposited on quartz crystal microbalance (QCM) transducers can be used for nonoptical based chemical sensing with extremely high sensitivity and selectivity. This was demonstrated by exposing the Au-MNM and Ag-MNM based QCMs to low concentrations of Hg(0) vapor in the presence interferent gas species (i.e., H2O, NH3, volatile organics, etc.) at operating temperatures of 30 and 75 °C. At 30 °C, the Au-MNM and Ag-MNM based QCMs showed ∼16 and ∼20 times higher response magnitude toward Hg(0) vapor concentration of 3.26 mg/m(3) (364 parts per billion by volume (ppbv)) relative to their unmodified control counterparts, respectively. The results indicated that the extremely high sensitivity was not due to the increased surface area (only 4.62 times increase) but due to their long-range interspatial order and high number of surface defect formation which are selectively active toward Hg(0) vapor sorption. The Au-MNM and Ag-MNM also had more than an order of magnitude lower detection limits (<3 ppbv) toward Hg(0) vapor compared to their unmodified control counterparts (>30 ppbv). When the operating temperature was increased from 30 to 75 °C, it was found that the sensors exhibited lower drift, better accuracy, and better selectivity toward Hg(0) vapor but at the compromise of higher detection limits. The high repeatability (84%), accuracy (97%), and stability of Au-MNM in particular make it practical to potentially be used as nonspectroscopic based Hg(0) vapor sensor in many industries either as mercury emission monitoring or as part of a mercury control feedback system. PMID:25562372

  8. The enhanced SERS effect of Ag/ZnO nanoparticles through surface hydrophobic modification

    NASA Astrophysics Data System (ADS)

    Li, Zhenjiang; Zhu, Kaixing; Zhao, Qian; Meng, Alan

    2016-07-01

    Ag/ZnO nanocomposites modified by a mixture of stearic acid (SA) and polyvinylpyrrolidone (PVP) were obtained using a heating reflux method. Fourier transform infrared spectroscopy (FT-IR) suggests that organic SA/PVP was bonded onto the surface of Ag/ZnO nanocrystals, converting the wettability property of the nanostructures from hydrophilic to hydrophobic. The modified Ag/ZnO nanostructures were confirmed as effective Raman substrates, with a 3-fold signal enhancement compared to the ordinary hydrophilic Ag/ZnO substrate for detecting Rh B molecules due to the hydrophobic condensation effect. It is expected that the modified Ag/ZnO nanoparticles have potential for SERS-based rapid detection of molecules.

  9. Thermodynamics of the adsorption of organic compounds from the gas phase over a monolayer of liquid crystal formed on the surface of a carbon adsorbent

    NASA Astrophysics Data System (ADS)

    Kopytin, K. A.; Bykov, E. S.; Onuchak, L. A.; Kudryashov, S. Yu.; Kuvshinova, S. A.; Burmistrov, V. A.

    2015-04-01

    Inverse gas-solid chromatography is used to study the adsorption of vapors of organic compounds with different structures and polarities on a carbon adsorbent modified with a monolayer of 4-(3-hydroxypropyloxy)-4'-formylazobenzene (HPOFAB) polar LIQUID crystal. The resulting thermodynamic characteristics of adsorption on the original and modified adsorbents are compared. The effect the nature and structure of adsorbate molecules and the liquid crystal modifier have on the thermodynamic characteristics of adsorption is considered.

  10. Application of a Newly Developed High-Sensitivity HBsAg Chemiluminescent Enzyme Immunoassay for Hepatitis B Patients with HBsAg Seroclearance

    PubMed Central

    Shinkai, Noboru; Matsuura, Kentaro; Sugauchi, Fuminaka; Watanabe, Tsunamasa; Murakami, Shuko; Iio, Etsuko; Ogawa, Shintaro; Nojiri, Shunsuke; Joh, Takashi

    2013-01-01

    We modified and automated a highly sensitive chemiluminescent enzyme immunoassay (CLEIA) for surface antigen (HBsAg) detection using a combination of monoclonal antibodies, each for a specific epitope of HBsAg, and by improving an earlier conjugation technique. Of 471 hepatitis B virus (HBV) carriers seen in our hospital between 2009 and 2012, 26 were HBsAg seronegative as determined by the Abbott Architect assay. The Lumipulse HBsAg-HQ assay was used to recheck those 26 patients who demonstrated seroclearance by the Abbott Architect assay. The performance of the Lumipulse HBsAg-HQ assay was compared with that of a quantitative HBsAg detection system (Abbott Architect) and the Roche Cobas TaqMan HBV DNA assay (CTM) (lower limit of detection, 2.1 log copies/ml) using blood serum samples from patients who were determined to be HBsAg seronegative by the Abbott Architect assay. Ten patients had spontaneous HBsAg loss. Of 8 patients treated with nucleotide analogues (NAs), two were HBsAg seronegative after stopping lamivudine therapy and 6 were HBsAg seronegative during entecavir therapy. Eight acute hepatitis B (AH) patients became HBsAg seronegative. Of the 26 patients, 16 were HBsAg positive by the Lumipulse HBsAg-HQ assay but negative by the Abbott Architect assay. The differences between the two assays in terms of detectable HBsAg persisted over the long term in the spontaneous loss group (median, 10 months), the NA-treated group (2.5 months), and the AH group (0.5 months). In 9 patients, the Lumipulse HBsAg-HQ assay detected HBsAg when HBV DNA was negative by the CTM assay. HBsAg was also detected by the Lumipulse HBsAg-HQ assay in 4 patients with an anti-HBs concentration of >10 mIU/ml, 3 of whom had no HBsAg escape mutations. The automatic, highly sensitive HBsAg CLEIA Lumipulse HBsAg-HQ is a convenient and precise assay for HBV monitoring. PMID:23946517

  11. Application of a newly developed high-sensitivity HBsAg chemiluminescent enzyme immunoassay for hepatitis B patients with HBsAg seroclearance.

    PubMed

    Shinkai, Noboru; Matsuura, Kentaro; Sugauchi, Fuminaka; Watanabe, Tsunamasa; Murakami, Shuko; Iio, Etsuko; Ogawa, Shintaro; Nojiri, Shunsuke; Joh, Takashi; Tanaka, Yasuhito

    2013-11-01

    We modified and automated a highly sensitive chemiluminescent enzyme immunoassay (CLEIA) for surface antigen (HBsAg) detection using a combination of monoclonal antibodies, each for a specific epitope of HBsAg, and by improving an earlier conjugation technique. Of 471 hepatitis B virus (HBV) carriers seen in our hospital between 2009 and 2012, 26 were HBsAg seronegative as determined by the Abbott Architect assay. The Lumipulse HBsAg-HQ assay was used to recheck those 26 patients who demonstrated seroclearance by the Abbott Architect assay. The performance of the Lumipulse HBsAg-HQ assay was compared with that of a quantitative HBsAg detection system (Abbott Architect) and the Roche Cobas TaqMan HBV DNA assay (CTM) (lower limit of detection, 2.1 log copies/ml) using blood serum samples from patients who were determined to be HBsAg seronegative by the Abbott Architect assay. Ten patients had spontaneous HBsAg loss. Of 8 patients treated with nucleotide analogues (NAs), two were HBsAg seronegative after stopping lamivudine therapy and 6 were HBsAg seronegative during entecavir therapy. Eight acute hepatitis B (AH) patients became HBsAg seronegative. Of the 26 patients, 16 were HBsAg positive by the Lumipulse HBsAg-HQ assay but negative by the Abbott Architect assay. The differences between the two assays in terms of detectable HBsAg persisted over the long term in the spontaneous loss group (median, 10 months), the NA-treated group (2.5 months), and the AH group (0.5 months). In 9 patients, the Lumipulse HBsAg-HQ assay detected HBsAg when HBV DNA was negative by the CTM assay. HBsAg was also detected by the Lumipulse HBsAg-HQ assay in 4 patients with an anti-HBs concentration of >10 mIU/ml, 3 of whom had no HBsAg escape mutations. The automatic, highly sensitive HBsAg CLEIA Lumipulse HBsAg-HQ is a convenient and precise assay for HBV monitoring.

  12. Morphology, dimension, and composition dependence of thermodynamically preferred atomic arrangements in Ag-Pt nanoalloys.

    PubMed

    Deng, Lei; Deng, Huiqiu; Xiao, Shifang; Tang, Jianfeng; Hu, Wangyu

    2013-01-01

    The present article is on Metropolis Monte Carlo simulations coupled with semiempirical potentials to obtain the thermodynamically preferred configurations of Ag-Pt nanoalloys. The effects of particle size, morphology or alloy composition on the surface segregation and the chemical ordering patterns were investigated. Surface segregation of Ag is observed in all Ag-Pt nanoalloys. Such segregation develops quickly as the increase of particle sizes or global Ag composition. Generally, Ag surface enrichment is more apparent for more open particles except for large sized icosahedron (ICO) nanoalloys. The most energetically favorable chemical ordering patterns gradually evolve from Pt-core/Ag-shell to onion-like structures when the global Ag composition increases. Due to the site preference of Ag segregation, the presence of partly alloyed facets and Ag blocked vertices or edges at low global Ag compositions can modify the electronic and geometric structures on the nanoalloys' surface. The coupling between Pt and Ag sites is a topic of particular interest for catalysis. The detailed atomistic understanding of atomic arrangements in Ag-Pt nanoalloys is essential to intelligently design robust and active nanocatalysts with a low cost. PMID:24015590

  13. Multifunctional and Stable Monolayers on Carbon: A Simple and Reliable Method for Backfilling Sparse Layers Grafted from Protected Aryldiazonium Ions.

    PubMed

    Lee, Lita; Gunby, Nathaniel R; Crittenden, Deborah L; Downard, Alison J

    2016-03-22

    A new strategy for preparation of robust multifunctional low nanometer thickness monolayers on carbon substrates is presented. Beginning with protected aryldiazonium salts, sparse monolayers of ethynyl-, amino-, and carboxy-terminated tethers are covalently anchored to the surface. The layers are then backfilled with a second modifier via the nucleophilic addition of an amine derivative to the surface. Through use of electroactive moieties coupled to the tethers, and an electroactive amine for backfilling, electrochemical measurements reveal that backfilling approximately doubles the surface concentration of the monolayer. Cyclic voltammetry of solution-based redox probes at the modified surfaces is consistent with the expected blocking properties at various stages of surface preparation. Fractional surface coverages of the layers are estimated using electrochemically determined surface concentrations of modifiers and computationally derived modifier footprints. Assuming free rotation of the coupled ferrocenyl or nitrophenyl groups leads to physically unreasonable fractional surface coverages, indicating that these larger modifiers must be rotationally restricted. Using a conformationally constrained model produces lower bound estimates of the total fractional surface coverage close to 0.4, with tether-only coverages close to 0.2. The backfilled tether layers constitute practical platforms for controlled construction of complex interfaces with many potential applications including sensing, molecular electronics, and catalysis.

  14. Valley-Polarized Exciton-Polaritons in a Monolayer Semiconductor Embedded in a Microcavity

    NASA Astrophysics Data System (ADS)

    Chen, Yen-J.; Stanev, Teodor K.; Stern, Nathaniel P.; Cain, Jeffrey D.; Dravid, Vinayak P.

    Two-dimensional transition metal dichalcogenides (TMDs) are semiconductors that exhibit degenerate, but inequivalent, valleys at their K-point band gaps which selectively couple to circularly-polarized light fields. Coherent hybrid states of light and matter, exciton-polaritons, have been observed when monolayer TMDs strongly interact with photon fields in a microcavity. The degree of polarization is determined by the relative rates of exciton and intervalley relaxation, which can be modified for microcavity exciton-polaritons. Preservation of valley-polarization in a microcavity at room temperature is compared to the nearly zero polarization for bare monolayer MoS2 on SiO2, demonstrating cavity-modified relaxation dynamics of the coherent valley-specific exciton-polaritons. These results suggest promising opto-electronic applications for valley-based polaritonic and photonic devices integrating monolayer TMDs. This work is supported by the U.S. Department of Energy (BES DE-SC0012130) and the National Science Foundation MRSEC program (DMR-1121262). N.P.S. is an Alfred P. Sloan Research Fellow.

  15. Electronic, transport, and optical properties of bulk and mono-layer PdSe2

    SciTech Connect

    Sun, Jifeng; Shi, Hongliang; Siegrist, Theo; Singh, David J.

    2015-10-13

    In this study, the electronic and optical properties of bulk and monolayer PdSe2 are investigated using firstprinciples calculations. Using the modified Becke-Johnson potential, we find semiconductor behavior for both bulk and monolayer PdSe2 with indirect gap values of 0.03 eV for bulk and 1.43 eV for monolayer, respectively. Our sheet optical conductivity results support this observation and show similar anisotropic feature in the 2D plane. We further study the thermoelectric properties of the 2D PdSe2 using Blotzmann transport model and find interestingly high Seebeck coefficients (>200 μV/K) for both p- and n-type up to high doping level (–2 x 1013 cm2) with an anisotropic character in an electrical conductivity suggesting better thermoelectric performance along y direction in the plane.V

  16. Structure and bonding in photodiffused amorphous Ag-GeSe/sub 2/ thin films

    SciTech Connect

    Fischer-Colbrie, A.; Bienenstock, A.; Fuoss, P.H.; Marcus, M.A.

    1988-12-15

    Grazing-incidence x-ray scattering (GIXS) techniques have been used to study the local and intermediate-range order in photodiffused amorphous Ag-GeSe/sub 2/ thin films and a variety of Ag-Ge-Se alloys. Using synchrotron-radiation sources, the GIXS technique can be used in conjunction with radial-distribution-function analysis, differential anomalous x-ray scattering, and differential distribution-function analysis to study the structure of very thin amorphous films. With these techniques, we have determined that the local atomic structure of Ag-GeSe/sub 2/ films satisfies a model where Se-Ag dative bonds are formed, one Se-Ag covalent bond is formed for each Ag atom added (below a critical composition), and Ge-Ge bonds are created as Ag is added. This last result significantly modifies the intermediate-range order in this system.

  17. The effect of β-sitosterol on the properties of cholesterol/phosphatidylcholine/ganglioside monolayers--the impact of monolayer fluidity.

    PubMed

    Hąc-Wydro, Katarzyna

    2013-10-01

    In this paper the influence of one of phytosterols, namely β-sitosterol on cholesterol (Chol)/phosphatidylcholine (PC)/ganglioside (GM3) monolayers was examined to find the correlation between the properties of model system and the effect of phytocompound. The studied monolayers differed in condensation and fluidity, which were modified by the structure of phosphatidylcholine. It was found that the incorporation of β-sitosterol into cholesterol/phosphatidylcholine/ganglioside films changes their morphology, condensation and interactions between the lipids. The substitution of cholesterol more strongly decreased the condensation and stability of the film containing PC molecules having monounsaturated chains than more densely packed monolayer composed of saturated phosphatidylcholine. However, thorough analysis of data obtained so far suggests that the magnitude of β-sitosterol effect is determined by the composition of the system rather than its fluidity itself. Moreover, the results collected herein correlate well with the findings that phytosterol more strongly inhibits the growth of cancer cells, which at a given proportion of cholesterol to phospholipids in membranes, have more unsaturated fatty acids within phospholipids molecules.

  18. Molecular Dynamics in Self-Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    Bochinski, Jason; Stevens, Derrick; Scott, Mary; Guy, Laura; Dedeugd, Casey; Clarke, Laura

    2007-03-01

    Silane self-assembled monolayers (SAMs) are an important tool for both scientific research and technological applications. Despite their widespread use, few experimental investigations have addressed molecular motion within these films, which offer a unique and useful physical system for fundamental scientific studies, such as observing dipolar and other glass transitions in two-dimensions. In addition, relaxations such as ``rotator'' phases where molecular groups rotate in a plane parallel to the surface have been correlated with film conductivity, adhesive, and wetting properties. We utilize surface-sensitive, dielectric relaxation spectroscopy to probe molecular motion as a function of temperature within silane chemistry-based monolayers formed upon interdigitated electrodes. Our latest results exploring a previously published motion as well as comparisons to linear polymer films will be discussed.

  19. Fracture Characteristics of Monolayer CVD-Graphene

    PubMed Central

    Hwangbo, Yun; Lee, Choong-Kwang; Kim, Sang-Min; Kim, Jae-Hyun; Kim, Kwang-Seop; Jang, Bongkyun; Lee, Hak-Joo; Lee, Seoung-Ki; Kim, Seong-Su; Ahn, Jong-Hyun; Lee, Seung-Mo

    2014-01-01

    We have observed and analyzed the fracture characteristics of the monolayer CVD-graphene using pressure bulge testing setup. The monolayer CVD-graphene has appeared to undergo environmentally assisted subcritical crack growth in room condition, i.e. stress corrosion cracking arising from the adsorption of water vapor on the graphene and the subsequent chemical reactions. The crack propagation in graphene has appeared to be able to be reasonably tamed by adjusting applied humidity and stress. The fracture toughness, describing the ability of a material containing inherent flaws to resist catastrophic failure, of the CVD-graphene has turned out to be exceptionally high, as compared to other carbon based 3D materials. These results imply that the CVD-graphene could be an ideal candidate as a structural material notwithstanding environmental susceptibility. In addition, the measurements reported here suggest that specific non-continuum fracture behaviors occurring in 2D monoatomic structures can be macroscopically well visualized and characterized. PMID:24657996

  20. Piezoelectric monolayers as nonlinear energy harvesters.

    PubMed

    López-Suárez, Miquel; Pruneda, Miguel; Abadal, Gabriel; Rurali, Riccardo

    2014-05-01

    We study the dynamics of h-BN monolayers by first performing ab-initio calculations of the deformation potential energy and then solving numerically a Langevine-type equation to explore their use in nonlinear vibration energy harvesting devices. An applied compressive strain is used to drive the system into a nonlinear bistable regime, where quasi-harmonic vibrations are combined with low-frequency swings between the minima of a double-well potential. Due to its intrinsic piezoelectric response, the nonlinear mechanical harvester naturally provides an electrical power that is readily available or can be stored by simply contacting the monolayer at its ends. Engineering the induced nonlinearity, a 20 nm2 device is predicted to harvest an electrical power of up to 0.18 pW for a noisy vibration of 5 pN. PMID:24722065

  1. Electrochemical detection of aqueous Ag+ based on Ag+-assisted ligation reaction

    PubMed Central

    Miao, Peng; Han, Kun; Wang, Bidou; Luo, Gangyin; Wang, Peng; Chen, Mingli; Tang, Yuguo

    2015-01-01

    In this work, a novel strategy to fabricate a highly sensitive and selective biosensor for the detection of Ag+ is proposed. Two DNA probes are designed and modified on a gold electrode surface by gold-sulfur chemistry and hybridization. In the presence of Ag+, cytosine-Ag+-cytosine composite forms and facilitates the ligation event on the electrode surface, which can block the release of electrochemical signals labeled on one of the two DNA probes during denaturation process. Ag+ can be sensitively detected with the detection limit of 0.1 nM, which is much lower than the toxicity level defined by U.S. Environmental Protection Agency. This biosensor can easily distinguish Ag+ from other interfering ions and the performances in real water samples are also satisfactory. Moreover, the two DNA probes are designed to contain the recognition sequences of a nicking endonuclease, and the ligated DNA can thus be cleaved at the original site. Therefore, the electrode can be regenerated, which allows the biosensor to be reused for additional tests. PMID:25779347

  2. Atomistic simulations of langmuir monolayer collapse.

    PubMed

    Lorenz, Christian D; Travesset, Alex

    2006-11-21

    Monolayers at the vapor/water interface collapse by exploring the third dimension at sufficient lateral compression, either by forming three-dimensional structures or by solubilization into the aqueous solution. In this paper, we provide an atomistic description of collapse from molecular dynamics (MD) simulations. More specifically, we investigate monolayers of arachidic acids spread on pure water and in an aqueous solution with Ca2+ ions in the subphase. In both cases, it is found that the collapsed systems generally lead to the formation of multilayer structures, which in the system with Ca2+ ions, proceeds by an intermediate regime where the monolayer exhibits significant roughness (of the order of 4 A). If no roughness is present, the system forms collapsed structures into the aqueous solution. The computational cost of atomic MD limits our simulations to relatively small system sizes, fast compression rates, and temporal scales on the order of a nanosecond. We discuss the issues caused by these limitations and present a detailed discussion of how the collapse regime proceeds at long time scales. We conclude with a summary of the implications of our results for further theoretical and experimental studies. PMID:17106994

  3. Investigation on gallium ions impacting monolayer graphene

    SciTech Connect

    Wu, Xin; Zhao, Haiyan Yan, Dong; Pei, Jiayun

    2015-06-15

    In this paper, the physical phenomena of gallium (Ga{sup +}) ion impacting monolayer graphene in the nanosculpting process are investigated experimentally, and the mechanisms are explained by using Monte Carlo (MC) and molecular dynamics (MD) simulations. Firstly, the MC method is employed to clarify the phenomena happened to the monolayer graphene target under Ga{sup +} ion irradiation. It is found that substrate has strong influence on the damage mode of graphene. The mean sputtering yield of graphene under 30 keV Ga{sup +} ion irradiation is 1.77 and the least ion dose to completely remove carbon atoms in graphene is 21.6 ion/nm{sup 2}. Afterwards, the focused ion beam over 21.6 ion/nm{sup 2} is used for the irradiation on a monolayer graphene supported by SiO2 experimentally, resulting in the nanostructures, i.e., nanodot and nanowire array on the graphene. The performances of the nanostructures are characterized by atomic force microscopy and Raman spectrum. A plasma plume shielding model is put forward to explain the nanosculpting results of graphene under different irradiation parameters. In addition, two damage mechanisms are found existing in the fabrication process of the nanostructures by using empirical MD simulations. The results can help us open the possibilities for better control of nanocarbon devices.

  4. Intrinsic structural defects in monolayer molybdenum disulfide

    SciTech Connect

    Zhou, Wu; Idrobo Tapia, Juan C

    2013-01-01

    Monolayer molybdenum disulfide (MoS2) is a two-dimensional direct band gap semiconductor with distinctive mechanical, electronic, optical and chemical properties that can be utilized for novel nanoelectronics and optoelectronics devices. The performance of these electronic devices strongly depends on the quality and defect morphology of the MoS2 layers. Yet, little is known about the atomic structure of defects present in monolayer MoS2 and their influences on the material properties. Here we provide a systematic study of various intrinsic structural defects, including point defects, grain boundaries, and edges, in chemical vapor phase grown monolayer MoS2 via direct atomic resolution imaging, and explore their energy landscape and electronic properties using first-principles calculations. We discover that one-dimensional metallic wires can be created via two different types of 60 grain boundaries consisting of distinct 4-fold ring chains. A new type of edge reconstruction, representing a transition state during growth, was also identified, providing insights into the material growth mechanism. The atomic scale study of structural defects presented here brings new opportunities to tailor the properties of MoS2 via controlled synthesis and defect engineering.

  5. Exploring atomic defects in molybdenum disulphide monolayers

    PubMed Central

    Hong, Jinhua; Hu, Zhixin; Probert, Matt; Li, Kun; Lv, Danhui; Yang, Xinan; Gu, Lin; Mao, Nannan; Feng, Qingliang; Xie, Liming; Zhang, Jin; Wu, Dianzhong; Zhang, Zhiyong; Jin, Chuanhong; Ji, Wei; Zhang, Xixiang; Yuan, Jun; Zhang, Ze

    2015-01-01

    Defects usually play an important role in tailoring various properties of two-dimensional materials. Defects in two-dimensional monolayer molybdenum disulphide may be responsible for large variation of electric and optical properties. Here we present a comprehensive joint experiment–theory investigation of point defects in monolayer molybdenum disulphide prepared by mechanical exfoliation, physical and chemical vapour deposition. Defect species are systematically identified and their concentrations determined by aberration-corrected scanning transmission electron microscopy, and also studied by ab-initio calculation. Defect density up to 3.5 × 1013 cm−2 is found and the dominant category of defects changes from sulphur vacancy in mechanical exfoliation and chemical vapour deposition samples to molybdenum antisite in physical vapour deposition samples. Influence of defects on electronic structure and charge-carrier mobility are predicted by calculation and observed by electric transport measurement. In light of these results, the growth of ultra-high-quality monolayer molybdenum disulphide appears a primary task for the community pursuing high-performance electronic devices. PMID:25695374

  6. Controlling surface functionality through generation of thiol groups in a self-assembled monolayer.

    SciTech Connect

    Lud, S. Q.; Neppl, S.; Richter, G.; Bruno, P.; Gruen, D. M.; Jordan, R.; Feulner, P.; Stutzmann, M.; Garrido, J. A.; Materials Science Division; Technische Univ. Munchen

    2010-01-01

    A lithographic method to generate reactive thiol groups on functionalized synthetic diamond for biosensor and molecular electronic applications is developed. We demonstrate that ultrananocrystalline diamond (UNCD) thin films covalently functionalized with surface-generated thiol groups allow controlled thiol-disulfide exchange surface hybridization processes. The generation of the thiol functional head groups was obtained by irradiating phenylsulfonic acid (PSA) monolayers on UNCD surfaces. The conversion of the functional headgroup of the self-assembled monolayer was verified by using X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and fluorescence microscopy. Our findings indicate the selective generation of reactive thiol surface groups. Furthermore, we demonstrate the grafting of yeast cytochrome c to the thiol-modified diamond surface and the electron transfer between protein and electrode.

  7. Monolayer-Mediated Growth of Organic Semiconductor Films with Improved Device Performance.

    PubMed

    Huang, Lizhen; Hu, Xiaorong; Chi, Lifeng

    2015-09-15

    Increased interest in wearable and smart electronics is driving numerous research works on organic electronics. The control of film growth and patterning is of great importance when targeting high-performance organic semiconductor devices. In this Feature Article, we summarize our recent work focusing on the growth, crystallization, and device operation of organic semiconductors intermediated by ultrathin organic films (in most cases, only a monolayer). The site-selective growth, modified crystallization and morphology, and improved device performance of organic semiconductor films are demonstrated with the help of the inducing layers, including patterned and uniform Langmuir-Blodgett monolayers, crystalline ultrathin organic films, and self-assembled polymer brush films. The introduction of the inducing layers could dramatically change the diffusion of the organic semiconductors on the surface and the interactions between the active layer with the inducing layer, leading to improved aggregation/crystallization behavior and device performance. PMID:25992464

  8. Morphology control of perovskite light-emitting diodes by using amino acid self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Wang, Nana; Cheng, Lu; Si, Junjie; Liang, Xiaoyong; Jin, Yizheng; Wang, Jianpu; Huang, Wei

    2016-04-01

    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 MAPbBr3 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 cd m-2.

  9. Phase transitions of an ionic liquid self-assembled monolayer on Au.

    PubMed

    Branca, Mathieu; Correia-Ledo, Debby; Bolduc, Olivier R; Ratel, Mathieu; Schmitzer, Andreea R; Masson, Jean-Francois

    2011-07-01

    The properties of a surface modified with an ionic liquid self-assembled monolayer (IL-SAM) can be tuned by simply changing the deposition temperature. Mid-IR, SERS, and molecular modelling demonstrated that 1-(12-mercaptododecyl)-3-methylimidazolium bromide (MDMIBr) exhibited a crystalline monolayer for deposition temperatures below 25 °C. Above 25 °C, the aliphatic chain collapsed into a disordered conformation. At 40 °C, another phase transition occurs due to the imidazolium group tilting parallel to the surface. Consequently, the wettability of IL-SAM was tuned over a broad range of contact angle (from 20° to nearly 40°) by varying the deposition temperature. Permeation of redox mediators to a Au electrode coated with MDMIBr strongly depends on the net charge of the redox mediator. Electron transfer was excellent for neutral and negatively charged redox mediators on electrodes coated with IL-SAM regardless of deposition temperature. PMID:21625701

  10. Crystalline Gibbs monolayers of DNA-capped nanoparticles at the air-liquid interface.

    PubMed

    Campolongo, Michael J; Tan, Shawn J; Smilgies, Detlef-M; Zhao, Mervin; Chen, Yi; Xhangolli, Iva; Cheng, Wenlong; Luo, Dan

    2011-10-25

    Using grazing-incidence small-angle X-ray scattering in a special configuration (parallel SAXS, or parSAXS), we mapped the crystallization of DNA-capped nanoparticles across a sessile droplet, revealing the formation of crystalline Gibbs monolayers of DNA-capped nanoparticles at the air-liquid interface. We showed that the spatial crystallization can be regulated by adjusting both ionic strength and DNA sequence length and that a modified form of the Daoud-Cotton model could describe and predict the resulting changes in interparticle spacing. Gibbs monolayers at the air-liquid interface provide an ideal platform for the formation and study of equilibrium nanostructures and may afford exciting routes toward the design of programmable 2D plasmonic materials and metamaterials.

  11. Mono-layer BC2 a high capacity anode material for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Hardikar, Rahul; Samanta, Atanu; Han, Sang Soo; Lee, Kwang-Ryeol; Singh, Abhishek

    2015-04-01

    Mono-layer of graphene with high surface area compared to the bulk graphite phase, shows less Li uptake. The Li activity or kinetics can be modified via defects and/or substitutional doping. Boron and Nitrogen are the best known dopants for carbonaceous anode materials. In particular, boron doped graphene shows higher capacity and better Li adsorption compared to Nitrogen doped graphene. Here, using first principles density functional theory calculations, we study the spectrum of boron carbide (BCx) mono-layer phases in order to estimate the maximum gravimetric capacity that can be achieved by substitutional doping in graphene. Our results show that uniformly boron doped BC2 phase shows a high capacity of? 1400 mAh/g, much higher than previously reported capacity of BC3. Supported by Korea Institute of Science and Technology.

  12. Characterization of organosulfur monolayer formation at gold electrodes

    SciTech Connect

    Tani Woods, N.

    1996-08-01

    Among the many types of organic films, covalently-attached organosulfur monolayers have attracted a great deal of attention. The authors have focused their interest on the fundamental characterization of spontaneously adsorbed organosulfur monolayers. An introductory chapter presents general aspects of monolayer preparation and characterization, followed by a few examples that illustrate the range of applications of these films. This thesis contains two papers. In the first paper, three analogous monolayer precursors are studied to determine their similarities and differences in the monolayer structure. A GC-MS analysis of products form the chemisorption process and open circuit potential measurements are used to derive possible mechanisms behind monolayer formation. The second paper focuses on monolayers formed from thioctic acid, including its characterization and application to cytochrome c electrochemistry. Although thiols and disulfides have been extensively studied as monolayer precursors, thioctic acid is particularly interesting because the disulfide functionality of this asymmetric molecule is contained in a strained five-membered ring. Given the ring strain, steric bulk and asymmetry of the molecule, the study of these monolayers lend insight into the factors important for the formation of organosulfur monolayers. This thesis concludes with a general summary and directions for future studies. 40 refs.

  13. Monolayer MXenes: promising half-metals and spin gapless semiconductors

    NASA Astrophysics Data System (ADS)

    Gao, Guoying; Ding, Guangqian; Li, Jie; Yao, Kailun; Wu, Menghao; Qian, Meichun

    2016-04-01

    Half-metals and spin gapless semiconductors are promising candidates for spintronic applications due to the complete (100%) spin polarization of electrons around the Fermi level. Based on recent experimental and theoretical findings of graphene-like monolayer transition metal carbides and nitrides (also known as MXenes), we demonstrate using first-principles calculations that monolayers Ti2C and Ti2N exhibit nearly half-metallic ferromagnetism with the magnetic moments of 1.91 and 1.00μB per formula unit, respectively, while monolayer V2C is a metal with unstable antiferromagnetism, and monolayer V2N is a nonmagnetic metal. Interestingly, under a biaxial strain, there is a phase transition from a nearly half-metal to truly half-metal, spin gapless semiconductor, and metal for monolayer Ti2C. Monolayer Ti2N is still a nearly half-metal under a suitable biaxial strain. Large magnetic moments can be induced by the biaxial tensile and compressive strains for monolayer V2C and V2N, respectively. We also show that the structures of these four monolayer MXenes are stable according to the calculated formation energy and phonon spectrum. Our investigations suggest that, unlike monolayer graphene, monolayer MXenes Ti2C and Ti2N without vacancy, doping or external electric field exhibit intrinsic magnetism, especially the half-metallic ferromagnetism and spin gapless semiconductivity, which will stimulate further studies on possible spintronic applications for new two-dimensional materials of MXenes.

  14. 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

  15. Enhanced Ag(+) Ion Release from Aqueous Nanosilver Suspensions by Absorption of Ambient CO2.

    PubMed

    Fujiwara, Kakeru; Sotiriou, Georgios A; Pratsinis, Sotiris E

    2015-05-19

    Nanosilver with closely controlled average particle diameter (7-30 nm) immobilized on nanosilica is prepared and characterized by X-ray diffraction, N2 adsorption, and transmission electron microscopy. The presence of Ag2O on the as-prepared nanosilver surface is confirmed by UV-vis spectroscopy and quantified by thermogravimetric analysis and mass spectrometry. The release of Ag(+) ions in deionized water is monitored electrochemically and traced quantitatively to the dissolution of a preexisting Ag2O monolayer on the nanosilver surface. During this dissolution, the pH of the host solution rapidly increases, suppressing dissolution of the remaining metallic Ag. When, however, a nanosilver suspension is exposed to a CO2-containing atmosphere, like ambient air during its storage or usage, then CO2 is absorbed by the host solution decreasing its pH and contributing to metallic Ag dissolution and further leaching of Ag(+) ions. So the release of Ag(+) ions from the above closely sized nanosilver solutions in the absence and presence of CO2 as well as under synthetic air containing 200-1800 ppm of CO2 is investigated along with the solution pH and related to the antibacterial activity of nanosilver.

  16. Luminescent and structural properties of ZnO-Ag films

    SciTech Connect

    Khomchenko, V. S. Kushnirenko, V. I. Papusha, V. P.; Savin, A. K.; Lytvyn, O. S.

    2010-05-15

    ZnO-Ag thin films were prepared by a two-stage method on glass and sapphire substrates. Ag doping was carried out by a method of close space sublimation at atmospheric pressure. The film thickness is varied from 0.6 to 7 {mu}m. The structural and radiative properties were explored by X-ray diffraction technique, atomic force microscopy, photoluminescence and cathodoluminescence spectroscopy. The influence of the fabricating conditions on the properties of ZnO-Ag films is studied. It is found that the Ag doping modifies the crystalline structure of the films and promotes the oriented growth of monocrystalline blocks with the size of 500-2000 nm in the [0002] direction. Improvement of the crystalline quality correlates with the change of the radiative characteristics of the films. The origin of emission centers is discussed.

  17. Monolayer cultivation of osteoprogenitors shortens duration of the embryonic stem cell test while reliably predicting developmental osteotoxicity.

    PubMed

    zur Nieden, Nicole I; Davis, Lesley A; Rancourt, Derrick E

    2010-11-01

    Osteotoxic compounds administered during pregnancy can initiate skeletal congenital anomalies in the embryo. In vitro, developmental osteotoxicity of a compound can be predicted with the embryonic stem cell test (EST), the only in vitro embryotoxicity model identified to date that entirely abrogates the use of animals. Although the previously identified endpoint osteocalcin mRNA expression robustly predicts developmental osteotoxicity, it can only be assayed after 5 weeks of in vitro culture with existing embryoid body (EB)-based differentiation protocols. Therefore, the goal of this study was to characterize novel earlier endpoints of developmental osteotoxicity for the EST. The currently used EB-based differentiation protocol was modified so that a monolayer culture of pre-differentiated cells was inoculated. The expression profile of five bone-specific mRNAs, including osteocalcin, over the course of 30 differentiation days suggested an acceleration of pre-osteoblast specification in the monolayer over the EB-based protocol. Similarly, calcification was already visible after 14 days of culture in monolayer cultures. Employing image and absorption-based techniques to measure the degree of mineralization in these cells after compound treatment, the three compounds Penicillin G, 5-fluorouracil (5-FU) and all-trans retinoic acid (RA) were then tested after 14 days in monolayer cultures and compared to embryoid body-based differentiations at day 30. By modifying the culture the three test substances were classified correctly into non- or strong osteotoxic. Moreover, we were successful in shortening the assay duration from 30 to 14 days.

  18. Supported lipid monolayer with improved nanomechanical stability: effect of polymerization.

    PubMed

    El Zein, Racha; Dallaporta, Hervé; Charrier, Anne M

    2012-06-21

    We study the effect of polymerization on the nanomechanical stability of supported lipid monolayers consisting of 1,2-di-(10Z,12Z-tricosadiynoyl)-sn-glycero-3-phosphocholine by means of force mapping using an atomic force microscope. For both nonpolymerized and polymerized lipid monolayers, we investigate the break-through forces required to rupture the monolayers for a whole range of loading velocities. We show that the average break-through force exerted by the tip and required to penetrate the monolayer has a logarithmic dependence on the loading rate. Both Young moduli and intrinsic Gibbs energies have been determined for the nonpolymerized and polymerized lipid monolayers, and we show a drastic effect of polymerization on the nanomechanical stability of the monolayer with an increase by a factor of ∼100 for the young modulus and ∼3 for the intrinsic Gibbs activation energy.

  19. Modified cyanobacteria

    DOEpatents

    Vermaas, Willem F J.

    2014-06-17

    Disclosed is a modified photoautotrophic bacterium comprising genes of interest that are modified in terms of their expression and/or coding region sequence, wherein modification of the genes of interest increases production of a desired product in the bacterium relative to the amount of the desired product production in a photoautotrophic bacterium that is not modified with respect to the genes of interest.

  20. Asymmetric printing of molecules and zeolites on self assembled monolayers.

    PubMed

    Kehr, Nermin Seda; Schäfer, Andreas; Ravoo, Bart Jan; De Cola, Luisa

    2010-04-01

    Microcontact printing (mCP) is used to immobilize dyes and peptides asymmetrically, by a "peptide coupling" reaction, on monolayers of zeolite L crystals in the contact area between the stamp and the surface of the monolayer. Chemically patterned surfaces of monolayers of zeolite L crystals are obtained by using patterned stamps with different ink solutions. Additional printing of functionalized nano-objects on SAMs of zeolite L crystals is demonstrated.

  1. Epitaxial Templating of C60 with a Molecular Monolayer.

    PubMed

    Rochford, L A; Jones, T S; Nielsen, C B

    2016-09-01

    Commensurate epitaxial monolayers of truxenone on Cu (111) were employed to template the growth of monolayer and bilayer C60. Through the combination of STM imaging and LEED analysis we have demonstrated that C60 forms a commensurate 8 × 8 overlayer on truxenone/Cu (111). Bilayers of C60 retain the 8 × 8 periodicity of templated monolayers and although Kagome lattice arrangements are observed these are explained with combinations of 8 × 8 symmetry. PMID:27540868

  2. A simple way to prepare Cupric oleate capped AgI nanoparticles

    SciTech Connect

    Song Meirong; Zhang Zhijun . E-mail: s234soow@henu.edu.cn

    2004-12-02

    Cupric oleate capped AgI (Cu(OA){sub 2}-AgI) nanoparticles were prepared by a simple method and they have good dispersibility in organic solvents. X-ray diffraction (XRD), transmission electron microscope (TEM), FTIR, X-ray photoelectron spectrometer (XPS) and ultraviolet-visible (UV-vis) spectrometer were used to characterize the Cu(OA){sub 2}-AgI nanoparticles. The results show that the mean size is about 80 nm; the modified reagent has been chemically bonded on the surface of AgI. In addition, new absorption peaks in the UV region appear.

  3. Carbon phosphide monolayers with superior carrier mobility

    NASA Astrophysics Data System (ADS)

    Wang, Gaoxue; Pandey, Ravindra; Karna, Shashi P.

    2016-04-01

    Two dimensional (2D) materials with a finite band gap and high carrier mobility are sought after materials from both fundamental and technological perspectives. In this paper, we present the results based on the particle swarm optimization method and density functional theory which predict three geometrically different phases of the carbon phosphide (CP) monolayer consisting of sp2 hybridized C atoms and sp3 hybridized P atoms in hexagonal networks. Two of the phases, referred to as α-CP and β-CP with puckered or buckled surfaces are semiconducting with highly anisotropic electronic and mechanical properties. More remarkably, they have the lightest electrons and holes among the known 2D semiconductors, yielding superior carrier mobility. The γ-CP has a distorted hexagonal network and exhibits a semi-metallic behavior with Dirac cones. These theoretical findings suggest that the binary CP monolayer is a yet unexplored 2D material holding great promise for applications in high-performance electronics and optoelectronics.Two dimensional (2D) materials with a finite band gap and high carrier mobility are sought after materials from both fundamental and technological perspectives. In this paper, we present the results based on the particle swarm optimization method and density functional theory which predict three geometrically different phases of the carbon phosphide (CP) monolayer consisting of sp2 hybridized C atoms and sp3 hybridized P atoms in hexagonal networks. Two of the phases, referred to as α-CP and β-CP with puckered or buckled surfaces are semiconducting with highly anisotropic electronic and mechanical properties. More remarkably, they have the lightest electrons and holes among the known 2D semiconductors, yielding superior carrier mobility. The γ-CP has a distorted hexagonal network and exhibits a semi-metallic behavior with Dirac cones. These theoretical findings suggest that the binary CP monolayer is a yet unexplored 2D material holding great

  4. Au@Ag core/shell cuboids and dumbbells: Optical properties and SERS response

    NASA Astrophysics Data System (ADS)

    Khlebtsov, Boris N.; Liu, Zhonghui; Ye, Jian; Khlebtsov, Nikolai G.

    2015-12-01

    Recent studies have conclusively shown that the plasmonic properties of Au nanorods can be finely controlled by Ag coating. Here, we investigate the effect of asymmetric silver overgrowth of Au nanorods on their extinction and surface-enhanced Raman scattering (SERS) properties for colloids and self-assembled monolayers. Au@Ag core/shell cuboids and dumbbells were fabricated through a seed-mediated anisotropic growth process, in which AgCl was reduced by use of Au nanorods with narrow size and shape distribution as seeds. Upon tailoring the reaction rate, monodisperse cuboids and dumbbells were synthesized and further transformed into water-soluble powders of PEGylated nanoparticles. The extinction spectra of AuNRs were in excellent agreement with T-matrix simulations based on size and shape distributions of randomly oriented particles. The multimodal plasmonic properties of the Au@Ag cuboids and dumbbells were investigated by comparing the experimental extinction spectra with finite-difference time-domain (FDTD) simulations. The SERS efficiencies of the Au@Ag cuboids and dumbbells were compared in two options: (1) individual SERS enhancers in colloids and (2) self-assembled monolayers formed on a silicon wafer by drop casting of nanopowder solutions mixed with a drop of Raman reporters. By using 1,4-aminothiophenol Raman reporter molecules, the analytical SERS enhancement factor (AEF) of the colloidal dumbbells was determined to be 5.1×106, which is an order of magnitude higher than the AEF=4.0×105 for the cuboids. This difference can be explained by better fitting of the dumbbell plasmon resonance to the excitation laser wavelength. In contrast to the colloidal measurements, the AEF=5×107 of self-assembled cuboid monolayers was almost twofold higher than that for dumbbell monolayers, as determined with rhodamine 6G Raman reporters. According to TEM data and electromagnetic simulations, the better SERS response of the self-assembled cuboids is due to uniform

  5. Diacetylene mixed Langmuir monolayers for interfacial polymerization.

    PubMed

    Ariza-Carmona, Luisa; Rubia-Payá, Carlos; García-Espejo, G; Martín-Romero, María T; Giner-Casares, Juan J; Camacho, Luis

    2015-05-19

    Polydiacetylene (PDA) and its derivatives are promising materials for applications in a vast number of fields, from organic electronics to biosensing. PDA is obtained through polymerization of diacetylene (DA) monomers, typically using UV irradiation. DA polymerization is a 1-4 addition reaction with both initiation and growth steps with topochemical control, leading to the "blue" polymer form as primary reaction product in bulk and at interfaces. Herein, the diacetylene monomer 10,12-pentacosadiynoic acid (DA) and the amphiphilic cationic N,N'-dioctadecylthiapentacarbocyanine (OTCC) have been used to build a mixed Langmuir monolayer. The presence of OTCC imposes a monolayer supramolecular structure instead of the typical trilayer of pure DA. Surface pressure, Brewster angle microscopy, and UV-vis reflection spectroscopy measurements, as well as computer simulations, have been used to assess in detail the supramolecular structure of the DA:OTCC Langmuir monolayer. Our experimental results indicate that the DA and OTCC molecules are sequentially arranged, with the two OTCC alkyl chains acting as spacing diacetylene units. Despite this configuration is expected to prevent photopolymerization of DA, the polymerization takes place without phase segregation, thus exclusively leading to the red polydiacetylene form. We propose a simple model for the initial formation of the "blue" or "red" PDA forms as a function of the relative orientation of the DA units. The structural insights and the proposed model concerning the supramolecular structure of the "blue" and "red" forms of the PDA are aimed at the understanding of the relation between the molecular and macroscopical features of PDAs.

  6. Ag Division States Philosophy

    ERIC Educational Resources Information Center

    American Vocational Journal, 1976

    1976-01-01

    The discussion which took place during the American Vocational Association's (AVA) Agriculture Division meeting at the 1975 AVA Convention is summarized, and the statement of vo-ag education philosophy (including 13 key concepts), which was passed during the convention, is presented. (AJ)

  7. Graphoepitaxy for Pattern Multiplication of Nanoparticle Monolayers

    NASA Astrophysics Data System (ADS)

    Ferraro, Mark E.; Bonnecaze, Roger T.; Truskett, Thomas M.

    2014-08-01

    We compute the free energy minimizing structures of particle monolayers in the presence of enthalpic barriers of a finite height βVext using classical density functional theory and Monte Carlo simulations. We show that a periodic square template with dimensions up to at least 10 times the particle diameter disrupts the formation of the entropically favored hexagonally close-packed 2D lattice in favor of a square lattice. The results illustrate how graphoepitaxy can successfully order nanoparticulate films into desired patterns many times smaller than those of the prepatterned template.

  8. Processing of monolayer materials via interfacial reactions

    DOEpatents

    Sutter, Peter Werner; Sutter, Eli Anguelova

    2014-05-20

    A method of forming and processing of graphene is disclosed based on exposure and selective intercalation of the partially graphene-covered metal substrate with atomic or molecular intercalation species such as oxygen (O.sub.2) and nitrogen oxide (NO.sub.2). The process of intercalation lifts the strong metal-carbon coupling and restores the characteristic Dirac behavior of isolated monolayer graphene. The interface of graphene with metals or metal-decorated substrates also provides for controlled chemical reactions based on novel functionality of the confined space between a metal surface and a graphene sheet.

  9. Cell Volume Fluctuations in MDCK Monolayers

    PubMed Central

    Zehnder, Steven M.; Suaris, Melanie; Bellaire, Madisonclaire M.; Angelini, Thomas E.

    2015-01-01

    Cells moving collectively in tissues constitute a form of active matter, in which collective motion depends strongly on driven fluctuations at the single-cell scale. Fluctuations in cell area and number density are often seen in monolayers, yet their role in collective migration is not known. Here we study density fluctuations at the single- and multicell level, finding that single-cell volumes oscillate with a timescale of 4 h and an amplitude of 20%; the timescale and amplitude are found to depend on cytoskeletal activity. At the multicellular scale, density fluctuations violate the central limit theorem, highlighting the role of nonequilibrium driving forces in multicellular density fluctuations. PMID:25606673

  10. Fibrinogen monolayer characterization by colloid deposition.

    PubMed

    Nattich-Rak, Małgorzata; Adamczyk, Zbigniew; Wasilewska, Monika; Sadowska, Marta

    2013-09-24

    Colloid particle deposition was applied to characterize bovine and human fibrinogen (Fb) monolayers on mica produced by controlled adsorption under diffusion transport at pH 3.5. The surface concentration of Fb was determined by AFM enumeration of single molecules adsorbed over the substrate surface. The electrokinetic properties of Fb monolayers for various ionic strength were studied using the in situ streaming potential measurements. It was shown that Fb adsorbs irreversibly on mica for a broad range of ionic strength of 4 × 10(-4) to 0.15 M, NaCl. The overcharging of initially negative mica surface occurred for fibrinogen surface concentrations higher than 1400 μm(-2). The orientation of fibrinogen molecules in the monolayers was evaluated by the colloid deposition method involving negatively charged polystyrene latex microspheres, 820 nm in diameter. An anomalous deposition of negative latex particles on substrates exhibiting a negative zeta potential was observed, which contradicts the mean-field DLVO predictions. Measurable deposition was observed even at low ionic strength where the minimum approach distance of latex particles to the interface exceeds 70 nm (for 6 × 10(-4) M NaCl). This confirms that, at this pH, fibrinogen molecules adsorb end-on on mica assuming extended conformations with the positive charge located mostly in the end part of the αA chains. This agrees with previous experimental and theoretical results discussed in the literature (Santore, M. M.; Wertz Ch. F. Protein spreading kinetics at liquid-solid interfaces via an adsorption probe method. Langmuir 2005, 21, 10172-10178 (experimental); Adamczyk, Z.; Barbasz, J.; Cieśla, M.; Mechanisms of fibrinogen adsorption at solid substrates. Langmuir, 2011, 25, 6868-6878 (theoretical)). This unusual latex deposition on Fb monolayers was quantitatively interpreted in terms of the model developed in ref 55 (Jin, X.; Wang, N. H. L.; Tarjus, G.; Talbot, J. Irreversible adsorption on nonuniform

  11. Sub-monolayer film growth of a volatile lanthanide complex on metallic surfaces

    PubMed Central

    Chen, Jinjie; Edelmann, Kevin; Wulfhekel, Wulf

    2015-01-01

    Summary We deposited a volatile lanthanide complex, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)terbium(III), onto metal surfaces of Cu(111), Ag(111) and Au(111) in vacuum and observed well-ordered sub-monolayer films with low temperature (5 K) scanning tunneling microscopy. The films show a distorted three-fold symmetry with a commensurate structure. Scanning tunneling spectroscopy reveals molecular orbitals delocalized on the ligands of the molecule. Our results imply that this complex can be transferred onto the metal substrates without molecular decomposition or contamination of the surface. This new rare-earth-based class of molecules broadens the choice of molecular magnets to study with scanning tunneling microscopy. PMID:26733215

  12. Freeze-dried PVP-Ag+ precursors to novel AgBr/AgCl-Ag hybrid nanocrystals for visible-light-driven photodegradation of organic pollutants

    NASA Astrophysics Data System (ADS)

    Chen, Deliang; Chen, Qianqian; Zhang, Wenjie; Ge, Lianfang; Shao, Gang; Fan, Bingbing; Lu, Hongxia; Zhang, Rui; Yang, Daoyuan; Shao, Guosheng

    2015-04-01

    AgBr/AgCl-Ag nanocrystals with various molar Br-to-Ag ratios (RBr/Ag = 0, 1/3, 1/2, 2/3, 1) and different photoreduction times (0-20 min) were synthesized via stepwise liquid-solid reactions using the freeze-dried PVP-Ag+ hybrid as the Ag source, followed by a photoreduction reaction. The AgBr/AgCl-Ag7.5(1:2) nanocrystals obtained take on a spherical morphology with a particle-size range of 58 ± 15 nm. The photocatalytic performance of AgBr/AgCl-Ag nanocrystals was evaluated by photodegrading organic dyes, 4-chlorophenol and isopropanol under artificial visible light (λ ⩾ 420 nm, 100 mW cm-2). For the decomposition of rhodamine B, the AgBr/AgCl-Ag7.5(1:2) nanocrystals has a photodegradation rate of ∼0.87 min-1, ∼159 times higher than that (∼0.0054 min-1) of TiO2 (P25), whereas the AgCl-Ag and AgBr-Ag nanocrystals have photodegradation rates of 0.35 min-1 and 0.45 min-1, respectively. The efficient separation of photogenerated electron-hole pairs in the ternary system consisting of AgBr, AgCl and Ag species plays a key role in the enhancement of photocatalytic performance.

  13. Functionalization of Ag nanoparticles using local hydrophilic pool segment designed on their particle surface

    NASA Astrophysics Data System (ADS)

    Iijima, Motoyuki; Kurumiya, Aki; Esashi, Junki; Miyazaki, Hayato; Kamiya, Hidehiro

    2014-10-01

    The preparation of SiO2-coated Ag nanoparticles dispersible in various organic solvents has been achieved using a solgel reaction of tetraethylorthosilicate (TEOS), in the localized hydrophilic pool segments designed on Ag nanoparticle surfaces. First, oleylamine-capped core Ag nanoparticles were synthesized, followed by ligand exchange with polyethyleneimine (PEI) and further adsorption of an anionic surfactant comprising hydrophilic polyethylene glycol (PEG) chains and hydrophobic alkyl chains, which has previously been reported to improve the stability of nanoparticles in various solvents. Then, a reaction of TEOS with the localized hydrophilic PEI layer on the Ag nanoparticles' surface was conducted by stirring a toluene/TEOS solution of surface-modified Ag nanoparticles at various temperatures. It was found that a SiO2 layer was successfully formed on Ag nanoparticles when the reaction temperature was increased to 60 °C. It was also found, however, that at this elevated temperature, the primary particle size of Ag nanoparticles increased to several tens of nm, attributable to the dissolution and re-reduction of Ag+. Because the surface modifier, PEI and anionic surfactant all remained on the nanoparticle surface during the SiO2 coating process, the prepared SiO2-coated Ag nanoparticles were found to be dispersible in various organic solvents near to their primary particle size.

  14. Sub-monolayer growth of Ag on flat and nanorippled SiO2 surfaces

    NASA Astrophysics Data System (ADS)

    Bhatnagar, Mukul; Ranjan, Mukesh; Jolley, Kenny; Smith, Roger; Mukherjee, Subroto

    2016-05-01

    In-situ Rutherford Backscattering Spectrometry (RBS) and Molecular Dynamics (MD) simulations have been used to investigate the growth dynamics of silver on a flat and the rippled silica surface. The calculated sticking coefficient of silver over a range of incidence angles shows a similar behaviour to the experimental results for an average surface binding energy of a silver adatom of 0.2 eV. This value was used to parameterise the MD model of the cumulative deposition of silver in order to understand the growth mechanisms. Both the model and the RBS results show marginal difference between the atomic concentration of silver on the flat and the rippled silica surface, for the same growth conditions. For oblique incidence, cluster growth occurs mainly on the leading edge of the rippled structure.

  15. Impact of Anchoring Groups on Ballistic Transport: Single Molecule vs Monolayer Junctions

    PubMed Central

    2015-01-01

    Tuning the transport properties of molecular junctions by chemically modifying the molecular structure is one of the key challenges for advancing the field of molecular electronics. In the present contribution, we investigate current–voltage characteristics of differently linked metal–molecule–metal systems that comprise either a single molecule or a molecular assembly. This is achieved by employing density functional theory in conjunction with a Green’s function approach. We show that the conductance of a molecular system with a specific anchoring group is fundamentally different depending on whether a single molecule or a continuous monolayer forms the junction. This is a consequence of collective electrostatic effects that arise from dipolar elements contained in the monolayer and from interfacial charge rearrangements. As a consequence of these collective effects, the “ideal” choice for an anchoring group is clearly different for monolayer and single molecule devices. A particularly striking effect is observed for pyridine-docked systems. These are subject to Fermi-level pinning at high molecular packing densities, causing an abrupt increase of the junction current already at small voltages. PMID:26401191

  16. Synthesis and Optical Control of Circular Polarization in monolayer Tungsten Disulfide

    NASA Astrophysics Data System (ADS)

    McCreary, Kathleen; Hanbicki, Aubrey; Jonker, Berend; Currie, Marc; Kioseoglou, George

    The unique electronic band structure in single layer WS2 provides the ability to selectively populate a desired valley by exciting with circularly polarized light. The valley population is reflected through the circular polarization of photoluminescence (PL). We investigate the circularly polarized PL in WS2 monolayers synthesized using chemical vapor deposition (CVD). The resulting polarization is strongly dependent on the sample preparation. As-grown CVD WS2 (still on the growth substrate) exhibits low polarized emission, regardless of laser excitation or laser power. Removing WS2 from the growth substrate and repositioning on the same substrate significantly impacts the optical properties. In transferred films, the excitonic state is optically controlled via high-powered laser exposure such that subsequent PL is solely from either the charged exciton state or the neutral exciton state. Neutral excitonic emission exhibits zero polarization whereas the trion polarization can exceed 25% at room temperature. The removal process may modify the strain, sample-to-substrate distance, and chemical doping in the WS2 monolayer, and work is underway to determine how these factors influence the valley populations. These results demonstrate a new method to control the excitonic state and PL polarization in monolayer WS2. . Supported by core programs at NRL and the NRL Nanoscience Institute, and by the Air Force Office of Scientific Research #AOARD 14IOA018-134141.

  17. MoS2 monolayers on nanocavities: enhancement in light-matter interaction

    NASA Astrophysics Data System (ADS)

    Janisch, Corey; Song, Haomin; Zhou, Chanjing; Lin, Zhong; Elías, Ana Laura; Ji, Dengxin; Terrones, Mauricio; Gan, Qiaoqiang; Liu, Zhiwen

    2016-06-01

    Two-dimensional (2D) atomic crystals and van der Waals heterostructures constitute an emerging platform for developing new functional ultra-thin electronic and optoelectronic materials for novel energy-efficient devices. However, in most thin-film optical applications, there is a long-existing trade-off between the effectiveness of light-matter interactions and the thickness of semiconductor materials, especially when the materials are scaled down to atom thick dimensions. Consequently, enhancement strategies can introduce significant advances to these atomically thick materials and devices. Here we demonstrate enhanced absorption and photoluminescence generation from MoS2 monolayers coupled with a planar nanocavity. This nanocavity consists of an alumina nanolayer spacer sandwiched between monolayer MoS2 and an aluminum reflector, and can strongly enhance the light-matter interaction within the MoS2, increasing the exclusive absorption of monolayer MoS2 to nearly 70% at a wavelength of 450 nm. The nanocavity also modifies the spontaneous emission rate, providing an additional design freedom to control the interaction between light and 2D materials.

  18. Electrodeposition of gold templated by patterned thiol monolayers

    NASA Astrophysics Data System (ADS)

    She, Zhe; Di Falco, Andrea; Hähner, Georg; Buck, Manfred

    2016-06-01

    The electrochemical deposition of Au onto Au substrates modified by self-assembled monolayers (SAMs) was studied by linear sweep voltammetry (LSV), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Patterned SAMs exhibiting electrochemical contrast were prepared by two different methods. One used microcontact printing (μCP) to generate a binary SAM of ω-(4‧-methyl-biphenyl-4-yl)-propane thiol (CH3-C6H4-C6H4-(CH2)3-SH, MBP3) and octadecane thiol (CH3(CH2)17SH, ODT). Templated by the SAM, a gold microelectrode structure was electrodeposited featuring a line 15 μm wide and 3 mm long. After transfer to an epoxy substrate the structure proved to be electrically conductive across the full length. The other patterning method applied electron beam lithography (EBL) where electrochemical contrast was achieved by crosslinking molecules in a single component SAM of MBP3. An electron dose above 250 mC/cm2 results in a high deposition contrast. The choice of parameters for the deposition/lift-off process is found to be more critical for Au compared to Cu studied previously. The origin of the differences and implications for nanoscale patterning are discussed.

  19. Monte Carlo study of electron transport in monolayer silicene

    NASA Astrophysics Data System (ADS)

    Borowik, Piotr; Thobel, Jean-Luc; Adamowicz, Leszek

    2016-11-01

    Electron mobility and diffusion coefficients in monolayer silicene are calculated by Monte Carlo simulations using simplified band structure with linear energy bands. Results demonstrate reasonable agreement with the full-band Monte Carlo method in low applied electric field conditions. Negative differential resistivity is observed and an explanation of the origin of this effect is proposed. Electron mobility and diffusion coefficients are studied in low applied electric field conditions. We demonstrate that a comparison of these parameter values can provide a good check that the calculation is correct. Low-field mobility in silicene exhibits {T}-3 temperature dependence for nondegenerate electron gas conditions and {T}-1 for higher electron concentrations, when degenerate conditions are imposed. It is demonstrated that to explain the relation between mobility and temperature in nondegenerate electron gas the linearity of the band structure has to be taken into account. It is also found that electron-electron scattering only slightly modifies low-field electron mobility in degenerate electron gas conditions.

  20. Asphaltene Adsorption onto Self-Assembled Monolayers of Mixed Aromatic

    SciTech Connect

    Turgman-Cohen, S.; Smith, M; Fischer, D; Kilpatrick, P; Genzer, J

    2009-01-01

    The adsorption of asphaltenes onto flat solid surfaces modified with mixed self-assembled monolayers (SAMs) of aliphatic and aromatic trichlorosilanes with varying wettabilities, aromaticities, and thicknesses is tested. The mixed SAMs are characterized by means of contact angle to assess hydrophobicity and molecular and chemical uniformity, spectroscopic ellipsometry to measure the thickness of the films, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy to assess chemical and molecular composition. The molecular characteristics of the adsorbed asphaltene layer and the extent of asphaltene adsorption are determined using NEXAFS and spectroscopic ellipsometry, respectively. The SAMs are formed by depositing phenyl-, phenethyl-, butyl-, and octadecyl- trichlorosilanes from toluene solutions onto silica-coated substrates; the chemical composition and the wettability of the SAM surface is tuned systematically by varying the trichlorosilane composition in the deposition solutions. The adsorption of asphaltenes on the substrates does not correlate strongly with the SAM chemical composition. Instead, the extent of asphaltene adsorption decreases with increasing SAM thickness. This observation suggests that the leading interaction governing the adsorption of asphaltenes is their interaction with the polar silica substrate and that the chemical composition of the SAM is of secondary importance.

  1. Embedding Ba Monolayers and Bilayers in Boron Carbide Nanowires.

    PubMed

    Yu, Zhiyang; Luo, Jian; Shi, Baiou; Zhao, Jiong; Harmer, Martin P; Zhu, Jing

    2015-11-26

    Aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) was employed to study the distribution of barium atoms on the surfaces and in the interiors of boron carbide based nanowires. Barium based dopants, which were used to control the crystal growth, adsorbed to the surfaces of the boron-rich crystals in the form of nanometer-thick surficial films (a type of surface complexion). During the crystal growth, these dopant-based surface complexions became embedded inside the single crystalline segments of fivefold boron-rich nanowires collectively, where they were converted to more ordered monolayer and bilayer modified complexions. Another form of bilayer complexion stabilized at stacking faults has also been identified. Numerous previous works suggested that dopants/impurities tended to segregate at the stacking faults or twinned boundaries. In contrast, our study revealed the previously-unrecognized possibility of incorporating dopants and impurities inside an otherwise perfect crystal without the association to any twin boundary or stacking fault. Moreover, we revealed the amount of barium dopants incorporated was non-equilibrium and far beyond the bulk solubility, which might lead to unique properties.

  2. Embedding Ba Monolayers and Bilayers in Boron Carbide Nanowires

    NASA Astrophysics Data System (ADS)

    Yu, Zhiyang; Luo, Jian; Shi, Baiou; Zhao, Jiong; Harmer, Martin P.; Zhu, Jing

    2015-11-01

    Aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) was employed to study the distribution of barium atoms on the surfaces and in the interiors of boron carbide based nanowires. Barium based dopants, which were used to control the crystal growth, adsorbed to the surfaces of the boron-rich crystals in the form of nanometer-thick surficial films (a type of surface complexion). During the crystal growth, these dopant-based surface complexions became embedded inside the single crystalline segments of fivefold boron-rich nanowires collectively, where they were converted to more ordered monolayer and bilayer modified complexions. Another form of bilayer complexion stabilized at stacking faults has also been identified. Numerous previous works suggested that dopants/impurities tended to segregate at the stacking faults or twinned boundaries. In contrast, our study revealed the previously-unrecognized possibility of incorporating dopants and impurities inside an otherwise perfect crystal without the association to any twin boundary or stacking fault. Moreover, we revealed the amount of barium dopants incorporated was non-equilibrium and far beyond the bulk solubility, which might lead to unique properties.

  3. Embedding Ba Monolayers and Bilayers in Boron Carbide Nanowires

    PubMed Central

    Yu, Zhiyang; Luo, Jian; Shi, Baiou; Zhao, Jiong; Harmer, Martin P.; Zhu, Jing

    2015-01-01

    Aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) was employed to study the distribution of barium atoms on the surfaces and in the interiors of boron carbide based nanowires. Barium based dopants, which were used to control the crystal growth, adsorbed to the surfaces of the boron-rich crystals in the form of nanometer-thick surficial films (a type of surface complexion). During the crystal growth, these dopant-based surface complexions became embedded inside the single crystalline segments of fivefold boron-rich nanowires collectively, where they were converted to more ordered monolayer and bilayer modified complexions. Another form of bilayer complexion stabilized at stacking faults has also been identified. Numerous previous works suggested that dopants/impurities tended to segregate at the stacking faults or twinned boundaries. In contrast, our study revealed the previously-unrecognized possibility of incorporating dopants and impurities inside an otherwise perfect crystal without the association to any twin boundary or stacking fault. Moreover, we revealed the amount of barium dopants incorporated was non-equilibrium and far beyond the bulk solubility, which might lead to unique properties. PMID:26607754

  4. AGS experiments -- 1995, 1996 and 1997

    SciTech Connect

    Depken, J.C.; Presti, P.L.

    1997-12-01

    This report contains (1) FY 1995 AGS schedule as run; (2) FY 1996 AGS schedule as run; (3) FY 1997 AGS schedule as run; (4) FY 1998--1999 AGS schedule (proposed); (5) AGS beams 1997; (6) AGS experimental area FY 1995 physics program; (7) AGS experimental area FY 1996 physics program; (8) AGS experimental area FY 1997 physics program; (9) AGS experimental area FY 1998--1999 physics program (proposed); (10) a listing of experiments by number; (11) two-page summaries of each experiment, in order by number; and (12) listing of publications of AGS experiments.

  5. AGS experiments -- 1991, 1992, 1993. Tenth edition

    SciTech Connect

    Depken, J.C.

    1994-04-01

    This report contains: (1) FY 1993 AGS schedule as run; (2) FY 1994--95 AGS schedule; (3) AGS experiments {ge} FY 1993 (as of 30 March 1994); (4) AGS beams 1993; (5) AGS experimental area FY 1991 physics program; (6) AGS experimental area FY 1992 physics program; (7) AGS experimental area FY 1993 physics program; (8) AGS experimental area FY 1994 physics program (planned); (9) a listing of experiments by number; (10) two-page summaries of each experiment; (11) listing of publications of AGS experiments; and (12) listing of AGS experiments.

  6. Structure and Phase Transitions of Monolayers of Intermediate-length n-alkanes on Graphite Studied by Neutron Diffraction and Molecular Dynamics Simulation

    SciTech Connect

    Taub, H.; Hansen, F.Y.; Diama, Amand; Matthies, Blake; Criswell, Leah; Mo, Haiding; Bai, M; Herwig, Kenneth W

    2009-01-01

    We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C(24)H(50) denoted as C24) and dotriacontane (n-C(32)H(66) denoted as C32) adsorbed on a graphite basal-plane surface. Our measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows of molecules in their all-trans conformation aligned with their long axis parallel to the surface and forming so-called lamellas of width approximately equal to the all-trans length of the molecule. The RC structure is uniaxially commensurate with the graphite surface in its [110] direction such that the distance between molecular rows in a lamella is 4.26 A=sqrt[3a(g)], where a(g)=2.46 A is the lattice constant of the graphite basal plane. Molecules in adjacent rows of a lamella alternate in orientation between the carbon skeletal plane being parallel and perpendicular to the graphite surface. Upon heating, the crystalline monolayers transform to a 'smectic' phase in which the inter-row spacing within a lamella expands by approximately 10% and the molecules are predominantly oriented with the carbon skeletal plane parallel to the graphite surface. In the smectic phase, the MD simulations show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously.

  7. Structure and phase transitions of monolayers of intermediate-length n-alkanes on graphite studied by neutron diffraction and molecular dynamics simulation.

    PubMed

    Diama, A; Matthies, B; Herwig, K W; Hansen, F Y; Criswell, L; Mo, H; Bai, M; Taub, H

    2009-08-28

    We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C(24)H(50) denoted as C24) and dotriacontane (n-C(32)H(66) denoted as C32) adsorbed on a graphite basal-plane surface. Our measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows of molecules in their all-trans conformation aligned with their long axis parallel to the surface and forming so-called lamellas of width approximately equal to the all-trans length of the molecule. The RC structure is uniaxially commensurate with the graphite surface in its [110] direction such that the distance between molecular rows in a lamella is 4.26 A=sqrt[3a(g)], where a(g)=2.46 A is the lattice constant of the graphite basal plane. Molecules in adjacent rows of a lamella alternate in orientation between the carbon skeletal plane being parallel and perpendicular to the graphite surface. Upon heating, the crystalline monolayers transform to a "smectic" phase in which the inter-row spacing within a lamella expands by approximately 10% and the molecules are predominantly oriented with the carbon skeletal plane parallel to the graphite surface. In the smectic phase, the MD simulations show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously.

  8. Interactions of Oxygen and Ethylene with Submonolayer Ag Films Supported on Ni(111)

    SciTech Connect

    Alamgir, F.M.; Senanayake, S.; Rettew, R.E.; Meyer, A.; Chen, T.-L.; Petersburg, C.; Flege, J.I.; Falta, J.

    2011-06-01

    We investigate the oxidation of, and the reaction of ethylene with, Ni(111) with and without sub-monolayer Ag adlayers as a function of temperature. The addition of Ag to Ni(111) is shown to enhance the activity towards the ethylene epoxidation reaction, and increase the temperature at which ethylene oxide is stable on the surface. We present a systematic study of the formation of chemisorbed oxygen on the Ag-Ni(111) surfaces and correlate the presence and absence of O{sup 1-} and O{sup 2-} surface species with the reactivity towards ethylene. By characterizing the samples with low-energy electron microscopy (LEEM) in combination with X-ray photoelectron spectroscopy (XPS), we have identified specific growth of silver on step-edge sites and successfully increased the temperature at which the produced ethylene oxide remains stable, a trait which is desirable for catalysis.

  9. Interactions of Oxygen and Ethylene with Submonolayer Ag Films Supported on Ni(111)

    SciTech Connect

    R Rettew; A Meyer; S Senanayake; T Chen; C Petersburg; J Flege; J Falta; F Alamgir

    2011-12-31

    We investigate the oxidation of, and the reaction of ethylene with, Ni(111) with and without sub-monolayer Ag adlayers as a function of temperature. The addition of Ag to Ni(111) is shown to enhance the activity towards the ethylene epoxidation reaction, and increase the temperature at which ethylene oxide is stable on the surface. We present a systematic study of the formation of chemisorbed oxygen on the Ag-Ni(111) surfaces and correlate the presence and absence of O{sup 1-} and O{sup 2-} surface species with the reactivity towards ethylene. By characterizing the samples with low-energy electron microscopy (LEEM) in combination with X-ray photoelectron spectroscopy (XPS), we have identified specific growth of silver on step-edge sites and successfully increased the temperature at which the produced ethylene oxide remains stable, a trait which is desirable for catalysis.

  10. Carbon phosphide monolayers with superior carrier mobility.

    PubMed

    Wang, Gaoxue; Pandey, Ravindra; Karna, Shashi P

    2016-04-28

    Two dimensional (2D) materials with a finite band gap and high carrier mobility are sought after materials from both fundamental and technological perspectives. In this paper, we present the results based on the particle swarm optimization method and density functional theory which predict three geometrically different phases of the carbon phosphide (CP) monolayer consisting of sp2 hybridized C atoms and sp3 hybridized P atoms in hexagonal networks. Two of the phases, referred to as α-CP and β-CP with puckered or buckled surfaces are semiconducting with highly anisotropic electronic and mechanical properties. More remarkably, they have the lightest electrons and holes among the known 2D semiconductors, yielding superior carrier mobility. The γ-CP has a distorted hexagonal network and exhibits a semi-metallic behavior with Dirac cones. These theoretical findings suggest that the binary CP monolayer is a yet unexplored 2D material holding great promise for applications in high-performance electronics and optoelectronics. PMID:27067002

  11. Predicting Two-Dimensional Silicon Carbide Monolayers.

    PubMed

    Shi, Zhiming; Zhang, Zhuhua; Kutana, Alex; Yakobson, Boris I

    2015-10-27

    Intrinsic semimetallicity of graphene and silicene largely limits their applications in functional devices. Mixing carbon and silicon atoms to form two-dimensional (2D) silicon carbide (SixC1-x) sheets is promising to overcome this issue. Using first-principles calculations combined with the cluster expansion method, we perform a comprehensive study on the thermodynamic stability and electronic properties of 2D SixC1-x monolayers with 0 ≤ x ≤ 1. Upon varying the silicon concentration, the 2D SixC1-x presents two distinct structural phases, a homogeneous phase with well dispersed Si (or C) atoms and an in-plane hybrid phase rich in SiC domains. While the in-plane hybrid structure shows uniform semiconducting properties with widely tunable band gap from 0 to 2.87 eV due to quantum confinement effect imposed by the SiC domains, the homogeneous structures can be semiconducting or remain semimetallic depending on a superlattice vector which dictates whether the sublattice symmetry is topologically broken. Moreover, we reveal a universal rule for describing the electronic properties of the homogeneous SixC1-x structures. These findings suggest that the 2D SixC1-x monolayers may present a new "family" of 2D materials, with a rich variety of properties for applications in electronics and optoelectronics. PMID:26394207

  12. Predicting Two-Dimensional Silicon Carbide Monolayers.

    PubMed

    Shi, Zhiming; Zhang, Zhuhua; Kutana, Alex; Yakobson, Boris I

    2015-10-27

    Intrinsic semimetallicity of graphene and silicene largely limits their applications in functional devices. Mixing carbon and silicon atoms to form two-dimensional (2D) silicon carbide (SixC1-x) sheets is promising to overcome this issue. Using first-principles calculations combined with the cluster expansion method, we perform a comprehensive study on the thermodynamic stability and electronic properties of 2D SixC1-x monolayers with 0 ≤ x ≤ 1. Upon varying the silicon concentration, the 2D SixC1-x presents two distinct structural phases, a homogeneous phase with well dispersed Si (or C) atoms and an in-plane hybrid phase rich in SiC domains. While the in-plane hybrid structure shows uniform semiconducting properties with widely tunable band gap from 0 to 2.87 eV due to quantum confinement effect imposed by the SiC domains, the homogeneous structures can be semiconducting or remain semimetallic depending on a superlattice vector which dictates whether the sublattice symmetry is topologically broken. Moreover, we reveal a universal rule for describing the electronic properties of the homogeneous SixC1-x structures. These findings suggest that the 2D SixC1-x monolayers may present a new "family" of 2D materials, with a rich variety of properties for applications in electronics and optoelectronics.

  13. Phase transformations in binary colloidal monolayers.

    PubMed

    Yang, Ye; Fu, Lin; Marcoux, Catherine; Socolar, Joshua E S; Charbonneau, Patrick; Yellen, Benjamin B

    2015-03-28

    Phase transformations can be difficult to characterize at the microscopic level due to the inability to directly observe individual atomic motions. Model colloidal systems, by contrast, permit the direct observation of individual particle dynamics and of collective rearrangements, which allows for real-space characterization of phase transitions. Here, we study a quasi-two-dimensional, binary colloidal alloy that exhibits liquid-solid and solid-solid phase transitions, focusing on the kinetics of a diffusionless transformation between two crystal phases. Experiments are conducted on a monolayer of magnetic and nonmagnetic spheres suspended in a thin layer of ferrofluid and exposed to a tunable magnetic field. A theoretical model of hard spheres with point dipoles at their centers is used to guide the choice of experimental parameters and characterize the underlying materials physics. When the applied field is normal to the fluid layer, a checkerboard crystal forms; when the angle between the field and the normal is sufficiently large, a striped crystal assembles. As the field is slowly tilted away from the normal, we find that the transformation pathway between the two phases depends strongly on crystal orientation, field strength, and degree of confinement of the monolayer. In some cases, the pathway occurs by smooth magnetostrictive shear, while in others it involves the sudden formation of martensitic plates. PMID:25677504

  14. 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. PMID:24354916

  15. Lateral Heterostructures of Monolayer Transition Metal Dichalcogenides: a First-principles Study

    NASA Astrophysics Data System (ADS)

    Wu, Meng; Cao, Ting; Louie, Steven G.

    Using first-principles calculations, we investigate the electronic structure and optical properties of lateral heterostructures consisting of different monolayer transition metal dichalcogenides (TMDs). We find that the spin-orbital coupling effect plays an important role in modifying the ground-state electronic structure and excited-state properties such as optical responses. The anisotropy of optical absorption is investigated including local-field effects. This work was supported by NSF Grant No. DMR15-1508412, the U.S. DOE under Contract No. DE-AC02-05CH11231. Computational resources have been provided by DOE at Lawrence Berkeley National Laboratory's NERSC facility.

  16. Examining the effects of self-assembled monolayers on nanoporous gold based amperometric glucose biosensors.

    PubMed

    Xiao, Xinxin; Li, Hui; Wang, Meng'en; Zhang, Kai; Si, Pengchao

    2014-01-21

    Nanoporous gold (NPG) based biosensors have been constructed by covalently immobilizing glucose oxidase (GOx) onto self-assembled monolayers (SAMs). With p-benzoquinone (BQ) as a mediator, diffusion behavior and amperometric biosensor performance are evaluated by electrochemical characterization. The enzyme modified electrodes are demonstrated to show a thickness-sensitive behavior. Compared with planar polycrystalline gold, the unique porous structure of NPG has also been characterized via an electrochemical surface reconstruction process. Single-crystal gold-like electrochemical behavior on NPG and a comprehensive understanding of its impacts on sensor performance have been proposed. PMID:24256634

  17. Large work function shift of gold induced by a novel perfluorinated azobenzene-based self-assembled monolayer.

    PubMed

    Crivillers, Núria; Osella, Silvio; Van Dyck, Colin; Lazzerini, Giovanni M; Cornil, David; Liscio, Andrea; Di Stasio, Francesco; Mian, Shabbir; Fenwick, Oliver; Reinders, Federica; Neuburger, Markus; Treossi, Emanuele; Mayor, Marcel; Palermo, Vincenzo; Cacialli, Franco; Cornil, Jérôme; Samorì, Paolo

    2013-01-18

    Tune it with light! Self-assembled monolayers on gold based on a chemisorbed novel azobenzene derivative with a perfluorinated terminal phenyl ring are prepared. The modified substrate shows a significant work function increase compared to the bare metal. The photo-conversion between trans and cis isomers chemisorbed on the surface shows great perspectives for being an accessible route to tune the gold properties by means of light.

  18. Spin-Cast and Patterned Organophosphonate Self-Assembled Monolayer Dielectrics on Metal-Oxide-Activated Si

    SciTech Connect

    O Acton; D Hutchins; L Arnadottir; T Weidner; N Cernetic; G Ting; T Kim; D Castner; H Ma; A Jen

    2011-12-31

    An efficient process is developed for modifying Si with self-assembled monolayers (SAMs) through in situ metal oxide surface activation and microcontact printing or spin-coating of phosphonic-acid-based molecules. The utility of this process is demonstrated by fabricating self-organized and solution-processed low-voltage organic thin-film transistors enabled by patterned and spin-cast phosphonate SAM/metal oxide hybrid dielectrics.

  19. Effect of 45 nm silver nanoparticles (AgNPs) upon the smooth muscle of rat trachea: role of nitric oxide.

    PubMed

    González, Carmen; Salazar-García, Samuel; Palestino, Gabriela; Martínez-Cuevas, Pedro P; Ramírez-Lee, Manuel A; Jurado-Manzano, Brenda B; Rosas-Hernández, Héctor; Gaytán-Pacheco, Noemí; Martel, Guadalupe; Espinosa-Tanguma, Ricardo; Biris, Alexandru S; Ali, Syed F

    2011-12-15

    AgNPs have been used to manufacture nanomaterials with new biophysical properties and functions. However, few experimental approaches have been used to assess their potential toxic or beneficial effects on human health, in association with the size, concentration, and biological target. The aim of this work was to evaluate the effects of the AgNPs on the smooth muscle of rat trachea. A single administration of AgNPs did not modify the smooth muscle tone, but, when the trachea rings were pre-treated with acetylcholine (ACh), AgNPs produced a contractile effect. Simultaneous administration of AgNPs and ACh resulted in a slight increase of smooth muscle contractility induced by ACh. AgNPs pretreatment followed by ACh administration showed that AgNPs exerted an important contraction effect induced by ACh after which muscle tone did not return to the basal level. This effect was associated with an increase in the production of nitric oxide (NO). The contractile response of the AgNPs induced by ACh was completely blocked when the rings were incubated, after the ACh but before the AgNPs administration, with 1400 W (NO blocker). The contractile effect was also abolished by atropine, which suggests that AgNPs alter ACh muscarinic receptor signaling. These data also show that AgNPs modify the contractile action of ACh through NO production and possibly induce hyper-reactivity of tracheal smooth muscle.

  20. Enhanced Selectivity to H2 Formation in Decomposition of HCOOH on the Ag19@Pd60 Core-Shell Nanocluster from First-Principles.

    PubMed

    Cho, Jinwon; Lee, Sangheon; Han, Jonghee; Yoon, Sung Pil; Nam, Suk Woo; Choi, Sun Hee; Hong, Seong-Ahn; Lee, Kwan-Young; Ham, Hyung Chul

    2015-10-01

    In this study, using spin-polarized density functional theory calculation we examined the origin of enhanced catalytic activity toward H2 production from HCOOH in Ag19@Pd60 core-shell nanoclusters (a 79-atom truncated octahedral cluster models). First, we find that the Pd monolayer shell on the Ag core can greatly enhance the selectivity to H2 formation via HCOOH decomposition compared to the pure Pd79 cluster by substantially reducing the binding energy of key intermediate HCOO and in turn the barrier for dehydrogenation. This activity enhancement is related to the modification of d states in the Pd monolayer shell by the strong ligand effect between Ag core and Pd shell, rather than the tensile strain effect by Ag core. In particular, the absence of dz2-r2 density of states near the Fermi level in the Pd monolayer shell (which originated from the substantial charge transfer from Ag to Pd) is the main reason for the increased H2 production from HCOOH decomposition. PMID:26726494

  1. Enhanced Selectivity to H2 Formation in Decomposition of HCOOH on the Ag19@Pd60 Core-Shell Nanocluster from First-Principles.

    PubMed

    Cho, Jinwon; Lee, Sangheon; Han, Jonghee; Yoon, Sung Pil; Nam, Suk Woo; Choi, Sun Hee; Hong, Seong-Ahn; Lee, Kwan-Young; Ham, Hyung Chul

    2015-10-01

    In this study, using spin-polarized density functional theory calculation we examined the origin of enhanced catalytic activity toward H2 production from HCOOH in Ag19@Pd60 core-shell nanoclusters (a 79-atom truncated octahedral cluster models). First, we find that the Pd monolayer shell on the Ag core can greatly enhance the selectivity to H2 formation via HCOOH decomposition compared to the pure Pd79 cluster by substantially reducing the binding energy of key intermediate HCOO and in turn the barrier for dehydrogenation. This activity enhancement is related to the modification of d states in the Pd monolayer shell by the strong ligand effect between Ag core and Pd shell, rather than the tensile strain effect by Ag core. In particular, the absence of dz2-r2 density of states near the Fermi level in the Pd monolayer shell (which originated from the substantial charge transfer from Ag to Pd) is the main reason for the increased H2 production from HCOOH decomposition.

  2. Stabilizing and enhancing activity of Ag as a catalyst for oxygen redaction reaction on hydrogen fuel cell cathodes

    NASA Astrophysics Data System (ADS)

    Stolbov, Sergey; Alcantara Ortigoza, Marisol

    2013-03-01

    Progress in searching for cost-effective and highly active catalysts for the oxygen reduction reaction (ORR) on hydrogen fuel cell cathodes is hindered by the fact that only a few elements (expensive and scarce Pt, Ir, Au) do not dissolve in the reaction environment (acidic medium at the expected operating potential +0.8 to +1.0 V vs SHE). Yet, in this work, we explore silver as an active element for the ORR catalysts. Although the dissolution potential (DP) of elemental Ag is 0.8 V, we rely on our finding that binding of a metal monolayer (ML) to a reactive substrate can significantly increase its DP. Using our approach, we select Ag/Ru/W, Ag/Nb, and Ag/Ta as promising candidates for the ORR catalysts (where Ag and Ru are MLs). Our evaluation of DP within density functional theory (DFT) shows that, indeed, in the selected structures, DP of Ag significantly increases as compared to that of Ag(111) and, in the case of Ag/Nb, even exceeds that of Pt. The ORR free-energy diagrams calculated within DFT suggest that the above systems are more active toward ORR than Pt. We thus predict here three highly active and truly cost-effective ORR catalysts. This work was supported by NSF under Grant CBET-1249134

  3. SYNCHROTRON X - RAY OBSERVATIONS OF A MONOLAYER TEMPLATE FOR MINERALIZATION.

    SciTech Connect

    DIMASI,E.; GOWER,L.B.

    2000-11-27

    Mineral nucleation at a Langmuir film interface has been studied by synchrotron x-ray scattering. Diluted calcium bicarbonate solutions were used as subphases for arachidic and stearic acid monolayers, compressed in a Langmuir trough. Self-assembly of the monolayer template is observed directly, and subsequent crystal growth monitored in-situ.

  4. Hydrogen exchange mass spectrometry of proteins at Langmuir monolayers

    PubMed Central

    Pirrone, Gregory F.; Vernon, Briana C.; Kent, Michael S.; Engen, John R.

    2015-01-01

    Hydrogen exchange (HX) mass spectrometry (MS) is valuable for providing conformational information for proteins/peptides that are very difficult to analyze with other methods such as peripheral membrane proteins and peptides that interact with membranes. We developed a new type of HX MS measurement that integrates Langmuir monolayers. A lipid monolayer was generated, a peptide or protein associated with it, and then the monolayer-associated peptide or protein was exposed to deuterium. The deuterated species was recovered from the monolayer, digested, and deuterium incorporation monitored by MS. Test peptides showed that deuterium recovery in an optimized protocol was equivalent to deuterium recovery in conventional solution HX MS. The reproducibility of the measurements was high despite the requirement of generating a new monolayer for each deuterium labeling time. We validated that known conformational changes in the presence of a monolayer/membrane could be observed with the peptide melittin and the myristoylated protein Arf-1. Results in an accompanying paper show that the method can reveal details of conformational changes in a protein (HIV-1 Nef) which adopts a different conformation depending on if it can insert into the lipid layer. Overall, the HX MS Langmuir monolayer method provided new and meaningful conformational information for proteins that associate with lipid layers. The combination of HX MS results with neutron or X-ray reflection of the same proteins in Langmuir monolayers can be more informative than isolated use of either method. PMID:26134943

  5. Hydrogen Exchange Mass Spectrometry of Proteins at Langmuir Monolayers.

    PubMed

    Pirrone, Gregory F; Vernon, Briana C; Kent, Michael S; Engen, John R

    2015-07-21

    Hydrogen exchange (HX) mass spectrometry (MS) is valuable for providing conformational information for proteins/peptides that are very difficult to analyze with other methods such as peripheral membrane proteins and peptides that interact with membranes. We developed a new type of HX MS measurement that integrates Langmuir monolayers. A lipid monolayer was generated, a peptide or protein associated with it, and then the monolayer-associated peptide or protein was exposed to deuterium. The deuterated species was recovered from the monolayer, digested, and deuterium incorporation monitored by MS. Test peptides showed that deuterium recovery in an optimized protocol was equivalent to deuterium recovery in conventional solution HX MS. The reproducibility of the measurements was high, despite the requirement of generating a new monolayer for each deuterium labeling time. We validated that known conformational changes in the presence of a monolayer/membrane could be observed with the peptide melittin and the myristoylated protein Arf-1. Results in an accompanying paper show that the method can reveal details of conformational changes in a protein (HIV-1 Nef), which adopts a different conformation, depending on whether or not it is able to insert into the lipid layer. Overall, the HX MS Langmuir monolayer method provided new and meaningful conformational information for proteins that associate with lipid layers. The combination of HX MS results with neutron or X-ray reflection of the same proteins in Langmuir monolayers can be more informative than the isolated use of either method.

  6. The disinfection performance and mechanisms of Ag/lysozyme nanoparticles supported with montmorillonite clay.

    PubMed

    Jiang, Jing; Zhang, Chang; Zeng, Guang-Ming; Gong, Ji-Lai; Chang, Ying-Na; Song, Biao; Deng, Can-Hui; Liu, Hong-Yu

    2016-11-01

    The fabrication of montmorillonite (Mt) decorated with lysozyme-modified silver nanoparticles (Ag/lyz-Mt) was reported. The lysozyme (lyz) was served as both reducing and capping reagent. Coupling the bactericidal activity of the lyz with AgNPs, along with the high porous structure and large specific surface area of the Mt, prevented aggregation of AgNPs and promoted nanomaterial-bacteria interactions, resulting in a greatly enhanced bactericidal capability against both Gram positive and Gram negative bacteria. This paper systematically elucidated the bactericidal mechanisms of Ag/lyz-Mt. Direct contact between the Ag/lyz-Mt surface and the bacterial cell was essential to the disinfection. Physical disruption of bacterial membrane was considered to be one of the bactericidal mechanisms of Ag/lyz-Mt. Results revealed that Ag(+) was involved in the bactericidal activity of Ag/lyz-Mt via tests conducted using Ag(+) scavengers. A positive ROS (reactive oxygen species) scavenging test indirectly confirmed the involvement of ROS (O2(-), H2O2, and OH) in the bactericidal mechanism. Furthermore, the concentrations of individual ROS were quantified. Results showed that Ag/lyz-Mt nanomaterial could be a promising bactericide for water disinfection.

  7. The disinfection performance and mechanisms of Ag/lysozyme nanoparticles supported with montmorillonite clay.

    PubMed

    Jiang, Jing; Zhang, Chang; Zeng, Guang-Ming; Gong, Ji-Lai; Chang, Ying-Na; Song, Biao; Deng, Can-Hui; Liu, Hong-Yu

    2016-11-01

    The fabrication of montmorillonite (Mt) decorated with lysozyme-modified silver nanoparticles (Ag/lyz-Mt) was reported. The lysozyme (lyz) was served as both reducing and capping reagent. Coupling the bactericidal activity of the lyz with AgNPs, along with the high porous structure and large specific surface area of the Mt, prevented aggregation of AgNPs and promoted nanomaterial-bacteria interactions, resulting in a greatly enhanced bactericidal capability against both Gram positive and Gram negative bacteria. This paper systematically elucidated the bactericidal mechanisms of Ag/lyz-Mt. Direct contact between the Ag/lyz-Mt surface and the bacterial cell was essential to the disinfection. Physical disruption of bacterial membrane was considered to be one of the bactericidal mechanisms of Ag/lyz-Mt. Results revealed that Ag(+) was involved in the bactericidal activity of Ag/lyz-Mt via tests conducted using Ag(+) scavengers. A positive ROS (reactive oxygen species) scavenging test indirectly confirmed the involvement of ROS (O2(-), H2O2, and OH) in the bactericidal mechanism. Furthermore, the concentrations of individual ROS were quantified. Results showed that Ag/lyz-Mt nanomaterial could be a promising bactericide for water disinfection. PMID:27318738

  8. AGS preinjector improvement

    SciTech Connect

    Alessi, J.G.; Brennan, J.M.; Brown, H.N.; Brodowski, J.; Gough, R.; Kponou, A.; Prelec, K.; Staples, J.; Tanabe, J.; Witkover, R.

    1987-01-01

    In 1984, a polarized H/sup -/ source was installed to permit the acceleration of polarized protons in the AGS, using a low current, 750 keV RFQ Linear Accelerator as the preinjector. This RFQ was designed by LANL and has proved to be quite satisfactory and reliable. In order to improve the reliability and simplify maintenance of the overall AGS operations, it has been decided to replace one of the two 750 keV Cockcroft-Waltons (C-W) with an RFQ. The design of a new high current RFQ has been carried out by LBL and is also being constructed there. This paper describes the preinjector improvement project, centered around that RFQ, which is underway at BNL.

  9. Methylene blue adsorption on a DMPA lipid langmuir monolayer.

    PubMed

    Giner Casares, Juan José; Camacho, Luis; Martín-Romero, Maria Teresa; López Cascales, José Javier

    2010-07-12

    Adsorption of methylene blue (MB) onto a dimyristoylphosphatidic acid (DMPA) Langmuir air/water monolayer is studied by molecular dynamics (MD) simulations, UV reflection spectroscopy and surface potential measurements. The free-energy profile associated with MB transfer from water to the lipid monolayer shows two minima of -66 and -60 kJ mol(-1) for its solid and gas phase, respectively, corresponding to a spontaneous thermodynamic process. From the position of the free-energy minima, it is possible to predict the precise location of MB in the interior of the DMPA monolayer. Thus, MB is accommodated in the phosphoryl or carbonyl region of the DMPA Langmuir air/water interface, depending on the isomorphic state (solid or gas phase, respectively). Reorientation of MB, measured from the bulk solution to the interior of the lipid monolayer, passes from a random orientation in bulk solution to an orientation parallel to the surface of the lipid monolayer when MB is absorbed. PMID:20544777

  10. Methylene blue adsorption on a DMPA lipid langmuir monolayer.

    PubMed

    Giner Casares, Juan José; Camacho, Luis; Martín-Romero, Maria Teresa; López Cascales, José Javier

    2010-07-12

    Adsorption of methylene blue (MB) onto a dimyristoylphosphatidic acid (DMPA) Langmuir air/water monolayer is studied by molecular dynamics (MD) simulations, UV reflection spectroscopy and surface potential measurements. The free-energy profile associated with MB transfer from water to the lipid monolayer shows two minima of -66 and -60 kJ mol(-1) for its solid and gas phase, respectively, corresponding to a spontaneous thermodynamic process. From the position of the free-energy minima, it is possible to predict the precise location of MB in the interior of the DMPA monolayer. Thus, MB is accommodated in the phosphoryl or carbonyl region of the DMPA Langmuir air/water interface, depending on the isomorphic state (solid or gas phase, respectively). Reorientation of MB, measured from the bulk solution to the interior of the lipid monolayer, passes from a random orientation in bulk solution to an orientation parallel to the surface of the lipid monolayer when MB is absorbed.

  11. Monolayer-by-monolayer stacked pyramid-like MoS2 nanodots on monolayered MoS2 flakes with enhanced photoluminescence.

    PubMed

    Yuan, Cailei; Cao, Yingjie; Luo, Xingfang; Yu, Ting; Huang, Zhenping; Xu, Bo; Yang, Yong; Li, Qinliang; Gu, Gang; Lei, Wen

    2015-11-01

    The precise control of the morphology and crystal shape of MoS2 nanostructures is of particular importance for their application in nanoelectronic and optoelectronic devices. Here, we describe a single step route for the synthesis of monolayer-by-monolayer stacked pyramid-like MoS2 nanodots on monolayered MoS2 flakes using a chemical vapor deposition method. First-principles calculations demonstrated that the bandgap of the pyramid-like MoS2 nanodot is a direct bandgap. Enhanced local photoluminescence emission was observed in the pyramid-like MoS2 nanodot, in comparison with monolayered MoS2 flakes. The findings presented here provide new opportunities to tailor the physical properties of MoS2via morphology-controlled synthesis.

  12. Effect of different polymers on morphology and particle size of silver nanoparticles synthesized by modified polyol method

    NASA Astrophysics Data System (ADS)

    Fereshteh, Zeinab; Rojaee, Ramin; Sharifnabi, Ali

    2016-10-01

    In this work, simple, economic, eco-friendly modified method with high efficiency was applied for synthesis of silver nanoparticles (Ag NPs) by using polyethylene glycol (PEG) as a capping agent, reductant, and media agent. In order to preparation uniform and small Ag NPs, the reaction parameters such as type of polymer, AgNO3/Polymer weight concentration ratio, and AgNO3/NaBH4 molar concentration ratio were modified. The best condition was optimized in concentration ratio of AgNO3: PEG: NaBH4 where are 1:10:0.01, respectively with 82% efficiency and 98.95% purity. Therefore, this modified polyol method can also be scaled up for synthesis of Ag NPs appropriately. Due to polymeric coating on the Ag NPs, they can be employed as a promising candidate for drug delivery systems.

  13. Metastability of a Supercompressed Fluid Monolayer

    PubMed Central

    Smith, Ethan C.; Crane, Jonathan M.; Laderas, Ted G.; Hall, Stephen B.

    2003-01-01

    Previous studies showed that monomolecular films of extracted calf surfactant collapse at the equilibrium spreading pressure during quasi-static compressions but become metastable at much higher surface pressures when compressed faster than a threshold rate. To determine the mechanism by which the films become metastable, we studied single-component films of 1-palmitoyl-2-oleoyl phosphatidylcholine (POPC). Initial experiments confirmed similar metastability of POPC if compressed above a threshold rate. Measurements at different surface pressures then showed that rates of collapse, although initially increasing above the equilibrium spreading pressure, reached a sharply defined maximum and then slowed considerably. When heated, rapidly compressed films recovered their ability to collapse with no discontinuous change in area, arguing that the metastability does not reflect transition of the POPC film to a new phase. These observations indicate that in several respects, the supercompression of POPC monolayers resembles the supercooling of three-dimensional liquids toward a glass transition. PMID:14581205

  14. New Monolayered Materials Exhibiting Unusual Electronic Properties

    NASA Astrophysics Data System (ADS)

    Lopez-Bezanilla, Alejandro; Martin, Ivar; Littlewood, Peter B.

    Computationally based approaches are allowing to progress in the discovery and design of nano-scaled materials. Here we propose a series of new mono-layered compounds with exotic properties. By means of density functional theory calculations we demonstrate that the pentagonal arrangement of SiC2 yields an inverted distribution of the p-bands which leads to an unusual electronic behaviour of the material under strain [J. Phys. Chem. C, 2015, 119 (33), pp 19469]. A different pentagonal arrangement of C atoms enables the formation of Dirac cones which, unlike graphene, exhibit a strain-mediated tunable band gap. This work is supported by DOE-BES under Contract No. DE-AC02-06CH11357.

  15. Valley depolarization in monolayer WSe2.

    PubMed

    Yan, Tengfei; Qiao, Xiaofen; Tan, Pingheng; Zhang, Xinhui

    2015-01-01

    We have systematically examined the circular polarization of monolayer WSe2 at different temperature, excitation energy and exciton density. The valley depolarization in WSe2 is experimentally confirmed to be governed by the intervalley electron-hole exchange interaction. More importantly, a non-monotonic dependence of valley circular polarization on the excitation power density has been observed, providing the experimental evidence for the non-monotonic dependence of exciton intervalley scattering rate on the excited exciton density. The physical origination of our experimental observations has been proposed to be in analogy to the D'yakonov-Perel' mechanism that is operative in conventional GaAs quantum well systems. Our experimental results are fundamentally important for well understanding the valley pseudospin relaxation in atomically thin transition metal dichalcogenides. PMID:26490157

  16. Organic Monolayer Protected Topological Surface State.

    PubMed

    Yang, Hung-Hsiang; Chu, Yu-Hsun; Lu, Chun-I; Butler, Christopher John; Sankar, Raman; Chou, Fang-Cheng; Lin, Minn-Tsong

    2015-10-14

    Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA)/Bi2Se3 and Fe/PTCDA/Bi2Se3 heterointerfaces are investigated using scanning tunneling microscopy and spectroscopy. The close-packed self-assembled PTCDA monolayer possesses big molecular band gap and weak molecule-substrate interactions, which leaves the Bi2Se3 topological surface state intact under PTCDA. Formation of Fe-PTCDA hybrids removes interactions between the Fe dopant and the Bi2Se3 surface, such as doping effects and Coulomb scattering. Our findings reveal the functionality of PTCDA to prevent dopant disturbances in the TSS and provide an effective alternative for interface designs of realistic TI devices.

  17. Monolayer semiconductor nanocavity lasers with ultralow thresholds

    DOE PAGESBeta

    Wu, Sanfeng; Buckley, Sonia; Schaibley, John R.; Feng, Liefeng; Yan, Jiaqiang; Mandrus, David G.; Hatami, Fariba; Yao, Wang; Vučković, Jelena; Majumdar, Arka; et al

    2015-03-16

    Engineering the electromagnetic environment of a nanoscale light emitter by a photonic cavity can significantly enhance its spontaneous emission rate through cavity quantum electrodynamics in the Purcell regime. This effect can greatly reduce the lasing threshold of the emitter1–5, providing the ultimate low-threshold laser system with small footprint, low power consumption and ultrafast modulation. A state-of-the-art ultra-low threshold nanolaser has been successfully developed though embedding quantum dots into photonic crystal cavity (PhCC)6–8. However, several core challenges impede the practical applications of this architecture, including the random positions and compositional fluctuations of the dots7, extreme difficulty in current injection8, and lackmore » of compatibility with electronic circuits7,8. Here, we report a new strategy to lase, where atomically thin crystalline semiconductor, i.e., a tungsten-diselenide (WSe2) monolayer, is nondestructively and deterministically introduced as a gain medium at the surface of a pre-fabricated PhCC. A new type of continuous-wave nanolaser operating in the visible regime is achieved with an optical pumping threshold as low as 27 nW at 130 K, similar to the value achieved in quantum dot PhCC lasers7. The key to the lasing action lies in the monolayer nature of the gain medium, which confines direct-gap excitons to within 1 nm of the PhCC surface. The surface-gain geometry allows unprecedented accessibilities to multi-functionalize the gain, enabling electrically pumped operation. Our scheme is scalable and compatible with integrated photonics for on-chip optical communication technologies.« less

  18. Monolayer semiconductor nanocavity lasers with ultralow thresholds

    NASA Astrophysics Data System (ADS)

    Wu, Sanfeng; Buckley, Sonia; Schaibley, John R.; Feng, Liefeng; Yan, Jiaqiang; Mandrus, David G.; Hatami, Fariba; Yao, Wang; Vučković, Jelena; Majumdar, Arka; Xu, Xiaodong

    2015-04-01

    Engineering the electromagnetic environment of a nanometre-scale light emitter by use of a photonic cavity can significantly enhance its spontaneous emission rate, through cavity quantum electrodynamics in the Purcell regime. This effect can greatly reduce the lasing threshold of the emitter, providing a low-threshold laser system with small footprint, low power consumption and ultrafast modulation. An ultralow-threshold nanoscale laser has been successfully developed by embedding quantum dots into a photonic crystal cavity (PCC). However, several challenges impede the practical application of this architecture, including the random positions and compositional fluctuations of the dots, extreme difficulty in current injection, and lack of compatibility with electronic circuits. Here we report a new lasing strategy: an atomically thin crystalline semiconductor--that is, a tungsten diselenide monolayer--is non-destructively and deterministically introduced as a gain medium at the surface of a pre-fabricated PCC. A continuous-wave nanolaser operating in the visible regime is thereby achieved with an optical pumping threshold as low as 27 nanowatts at 130 kelvin, similar to the value achieved in quantum-dot PCC lasers. The key to the lasing action lies in the monolayer nature of the gain medium, which confines direct-gap excitons to within one nanometre of the PCC surface. The surface-gain geometry gives unprecedented accessibility and hence the ability to tailor gain properties via external controls such as electrostatic gating and current injection, enabling electrically pumped operation. Our scheme is scalable and compatible with integrated photonics for on-chip optical communication technologies.

  19. Electronic correlations in monolayer VS2

    NASA Astrophysics Data System (ADS)

    Isaacs, Eric B.; Marianetti, Chris A.

    2016-07-01

    The layered transition metal dichalcogenide vanadium disulfide (VS2), which nominally has one electron in the 3 d shell, is potent for strong-correlation physics and is possibly another realization of an effective one-band model beyond the cuprates. Here monolayer VS2 in both the trigonal prismatic and the octahedral phases is investigated using density functional theory plus Hubbard U (DFT +U ) calculations. Trigonal prismatic VS2 has an isolated low-energy band that emerges from a confluence of crystal-field splitting and direct V-V hopping. Within spin density functional theory, ferromagnetism splits the isolated band of the trigonal prismatic structure, leading to a low-band-gap, S =1/2 , ferromagnetic Stoner insulator; the octahedral phase is higher in energy. Including the on-site interaction U increases the band gap, leads to Mott insulating behavior, and, for sufficiently high values, stabilizes the ferromagnetic octahedral phase. The validity of DFT and DFT +U for these two-dimensional materials with potential for strong electronic correlations is discussed. A clear benchmark is given by examining the experimentally observed charge density wave in octahedral VS2, for which DFT grossly overestimates the bond length differences compared to known experiments; the presence of charge density waves is also probed for the trigonal prismatic phase. Finally, we investigate why only the octahedral phase has been observed in experiments and discuss the possibility of realizing the trigonal prismatic phase. Our work suggests that trigonal prismatic VS2 is a promising candidate for strongly correlated electron physics that, if realized, could be experimentally probed in an unprecedented fashion due to its monolayer nature.

  20. Monolayer semiconductor nanocavity lasers with ultralow thresholds.

    PubMed

    Wu, Sanfeng; Buckley, Sonia; Schaibley, John R; Feng, Liefeng; Yan, Jiaqiang; Mandrus, David G; Hatami, Fariba; Yao, Wang; Vučković, Jelena; Majumdar, Arka; Xu, Xiaodong

    2015-04-01

    Engineering the electromagnetic environment of a nanometre-scale light emitter by use of a photonic cavity can significantly enhance its spontaneous emission rate, through cavity quantum electrodynamics in the Purcell regime. This effect can greatly reduce the lasing threshold of the emitter, providing a low-threshold laser system with small footprint, low power consumption and ultrafast modulation. An ultralow-threshold nanoscale laser has been successfully developed by embedding quantum dots into a photonic crystal cavity (PCC). However, several challenges impede the practical application of this architecture, including the random positions and compositional fluctuations of the dots, extreme difficulty in current injection, and lack of compatibility with electronic circuits. Here we report a new lasing strategy: an atomically thin crystalline semiconductor--that is, a tungsten diselenide monolayer--is non-destructively and deterministically introduced as a gain medium at the surface of a pre-fabricated PCC. A continuous-wave nanolaser operating in the visible regime is thereby achieved with an optical pumping threshold as low as 27 nanowatts at 130 kelvin, similar to the value achieved in quantum-dot PCC lasers. The key to the lasing action lies in the monolayer nature of the gain medium, which confines direct-gap excitons to within one nanometre of the PCC surface. The surface-gain geometry gives unprecedented accessibility and hence the ability to tailor gain properties via external controls such as electrostatic gating and current injection, enabling electrically pumped operation. Our scheme is scalable and compatible with integrated photonics for on-chip optical communication technologies. PMID:25778703

  1. Monolayer semiconductor nanocavity lasers with ultralow thresholds

    SciTech Connect

    Wu, Sanfeng; Buckley, Sonia; Schaibley, John R.; Feng, Liefeng; Yan, Jiaqiang; Mandrus, David G.; Hatami, Fariba; Yao, Wang; Vučković, Jelena; Majumdar, Arka; Xu, Xiaodong

    2015-03-16

    Engineering the electromagnetic environment of a nanoscale light emitter by a photonic cavity can significantly enhance its spontaneous emission rate through cavity quantum electrodynamics in the Purcell regime. This effect can greatly reduce the lasing threshold of the emitter1–5, providing the ultimate low-threshold laser system with small footprint, low power consumption and ultrafast modulation. A state-of-the-art ultra-low threshold nanolaser has been successfully developed though embedding quantum dots into photonic crystal cavity (PhCC)6–8. However, several core challenges impede the practical applications of this architecture, including the random positions and compositional fluctuations of the dots7, extreme difficulty in current injection8, and lack of compatibility with electronic circuits7,8. Here, we report a new strategy to lase, where atomically thin crystalline semiconductor, i.e., a tungsten-diselenide (WSe2) monolayer, is nondestructively and deterministically introduced as a gain medium at the surface of a pre-fabricated PhCC. A new type of continuous-wave nanolaser operating in the visible regime is achieved with an optical pumping threshold as low as 27 nW at 130 K, similar to the value achieved in quantum dot PhCC lasers7. The key to the lasing action lies in the monolayer nature of the gain medium, which confines direct-gap excitons to within 1 nm of the PhCC surface. The surface-gain geometry allows unprecedented accessibilities to multi-functionalize the gain, enabling electrically pumped operation. Our scheme is scalable and compatible with integrated photonics for on-chip optical communication technologies.

  2. Acid monolayer functionalized iron oxide nanoparticle catalysts

    NASA Astrophysics Data System (ADS)

    Ikenberry, Myles

    Superparamagnetic iron oxide nanoparticle functionalization is an area of intensely active research, with applications across disciplines such as biomedical science and heterogeneous catalysis. This work demonstrates the functionalization of iron oxide nanoparticles with a quasi-monolayer of 11-sulfoundecanoic acid, 10-phosphono-1-decanesulfonic acid, and 11-aminoundecanoic acid. The carboxylic and phosphonic moieties form bonds to the iron oxide particle core, while the sulfonic acid groups face outward where they are available for catalysis. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectrometry (XPS), and dynamic light scattering (DLS). The sulfonic acid functionalized particles were used to catalyze the hydrolysis of sucrose at 80° and starch at 130°, showing a higher activity per acid site than the traditional solid acid catalyst Amberlyst-15, and comparing well against results reported in the literature for sulfonic acid functionalized mesoporous silicas. In sucrose catalysis reactions, the phosphonic-sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic-sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. Between the two sulfonic ligands, the phosphonates produced a more tightly packed monolayer, which corresponded to a higher sulfonic acid loading, lower agglomeration, lower recoverability through application of an external magnetic field, and higher activity per acid site for the hydrolysis of starch. Functionalizations with 11-aminoundecanoic acid resulted in some amine groups binding to the surfaces of iron oxide nanoparticles. This amine binding is commonly ignored in iron oxide

  3. Modulating electronic, magnetic and chemical properties of MoS2 monolayer sheets by substitutional doping with transition metals

    NASA Astrophysics Data System (ADS)

    Ma, Dongwei; Ju, Weiwei; Li, Tingxian; Zhang, Xiwei; He, Chaozheng; Ma, Benyuan; Tang, Yanan; Lu, Zhansheng; Yang, Zongxian

    2016-02-01

    Based on first-principles calculations, the effects of substitutional doping with transition-metal (TM) atoms (Co, Ni, Ru, Rh, Pd, Ir, Pt and Au) were investigated on the electronic structure, magnetic property and chemical activity of the molybdenum disulfide (MoS2) monolayer sheet. It is found that all the considered TM atoms are strongly bonded to the sulfur defects. The magnetic properties of MoS2 monolayer sheets can be modulated by embedding TM atoms. The introduced spin magnetic moments are 1.00, 1.00, 1.00, 0.99, and 2.00μB, respectively, for Ir, Rh, Co, Au and Ru doping. The electronic properties of MoS2 monolayer sheets are also significantly changed due to the induced impurity states in the band gap. The chemical activity of the TM-doped MoS2 monolayer sheet (TM-MoS2) is significantly enhanced compared with the undoped sheet. Most TM-MoS2 can strongly adsorb and thus effectively activate the adsorbed O2. It is proposed that the partially occupied d orbitals of the doped TM atoms localized in the vicinity of the Fermi level play a crucial role in adsorbing and activating the adsorbed O2. The adsorption of O2 can in turn modify the electronic structures and magnetic properties of TM-MoS2.

  4. Preparation and antibacterial activities of Ag/Ag+/Ag3+ nanoparticle composites made by pomegranate (Punica granatum) rind extract

    NASA Astrophysics Data System (ADS)

    Yang, Hui; Ren, Yan-yu; Wang, Tao; Wang, Chuang

    Nano-silver and its composite materials are widely used in medicine, food and other industries due to their strong conductivity, size effect and other special performances. So far, more microbial researches have been applied, but a plant method is rarely reported. In order to open up a new way to prepare AgNP composites, pomegranate peel extract was used in this work to reduce Ag+ to prepare Ag/Ag+/Ag3+ nanoparticle composites. UV-Vis was employed to detect and track the reduction of Ag+ and the forming process of AgNPs. The composition, structure and size of the crystal were analyzed by XRD and TEM. Results showed that, under mild conditions, pomegranate peel extract reacted with dilute AgNO3 solution to produce Ag/Ag+/Ag3+ nanoparticle composites. At pH = 8 and 10 mmol/L of AgNO3 concentration, the size of the achieved composites ranged between 15 and 35 nm with spherical shapes and good crystallinity. The bactericidal experiment indicated that the prepared Ag/Ag+/Ag3+ nanoparticles had strong antibacterial activity against gram positive bacteria and gram negative bacteria. FTIR analysis revealed that biological macromolecules with groups of sbnd NH2, sbnd OH, and others were distributed on the surface of the newly synthesized Ag/Ag+/Ag3+ nanoparticles. This provided a useful clue to further study the AgNP biosynthesis mechanism.

  5. The Modeling of Pulmonary Particulate Matter Transport Using Langmuir Monolayers

    NASA Astrophysics Data System (ADS)

    Eaton, Jeremy M.

    The effects of a barrier in proximity to the air-water interface on the dynamics of a Langmuir monolayer system are observed. A monolayer of Survanta, bovine lung surfactant, is deposited onto the interface of an aqueous buffer solution. Polystyrene particles one micron in diameter and tagged with fluorescent carboxylate groups are distributed evenly throughout the monolayer surface. The bead-monolayer system is compressed and expanded to induce folding. A polydimethylsiloxane (PDMS) substrate is placed below the monolayer in the buffer solution to study interactions between the folding monolayer and a barrier. The presence of the substrate is shown to shift surface pressure-area isotherms toward regions of lower area by an average of 8.9 mN/m. The surface of the PDMS substrate can be imaged using fluorescence microscopy to detect the presence of particles or surfactant that may have been transported there from the air-water interface during folding. Images show the transferral of particles and monolayer together suggesting the pinch-off of a fold or the direct interaction of a fold with the barrier.

  6. Adhesive and conformational behaviour of mycolic acid monolayers.

    PubMed

    Zhang, Zhenyu; Pen, Yu; Edyvean, Robert G; Banwart, Steven A; Dalgliesh, Robert M; Geoghegan, Mark

    2010-09-01

    We have studied the pH-dependent interaction between mycolic acid (MA) monolayers and hydrophobic and hydrophilic surfaces using molecular (colloidal probe) force spectroscopy. In both cases, hydrophobic and hydrophilic monolayers (prepared by Langmuir-Blodgett and Langmuir-Schaefer deposition on silicon or hydrophobized silicon substrates, respectively) were studied. The force spectroscopy data, fitted with classical DLVO (Derjaguin, Landau, Verwey, and Overbeek) theory to examine the contribution of electrostatic and van der Waals forces, revealed that electrostatic forces are the dominant contribution to the repulsive force between the approaching colloidal probe and MA monolayers. The good agreement between data and the DLVO model suggest that beyond a few nm away from the surface, hydrophobic, hydration, and specific chemical bonding are unlikely to contribute to any significant extent to the interaction energy between the probe and the surface. The pH-dependent conformation of MA molecules in the monolayer at the solid-liquid interface was studied by ellipsometry, neutron reflectometry, and with a quartz crystal microbalance. Monolayers prepared by the Langmuir-Blodgett method demonstrated a distinct pH-responsive behaviour, while monolayers prepared by the Langmuir-Schaefer method were less sensitive to pH variation. It was found that the attachment of water molecules plays a vital role in determining the conformation of the MA monolayers.

  7. Phosphate Adsorption using Modified Iron Oxide-based Sorbents in Lake Water: Kinetics, Equilibrium, and Column Tests

    EPA Science Inventory

    Adsorption behavior of Bayoxide ® E33 (E33) and three E33-modified sorbents for the removal of phosphate from lake water was investigated in this study. E33-modified sorbents were synthesized by coating with manganese (E33/Mn) and silver (E33/AgI and E33/AgII) nanoparticles. Adso...

  8. Disordered self assembled monolayer dielectric induced hysteresis in organic field effect transistors.

    PubMed

    Padma, N; Saxena, Vibha; Sudarsan, V; Rava, Harshil; Sen, Shaswati

    2014-06-01

    A memory device using an organic field effect transistor (OFET) with copper phthalocyanine (CuPc) as active material was fabricated and studied. For this purpose, SiO2 dielectric surface was modified with a disordered self assembled monolayer (SAM) of octadecyltrichlorosilane (OTS) molecule which was found to induce large disorder in CuPc film thereby generating more traps for charge carriers. Drain current-drain voltage characteristics at zero gate voltage exhibited large hysteresis which was not observed in OFET devices with ordered OTS monolayer modified and unmodified SiO2 dielectrics. The extent of hysteresis and drain current on/off ratio, reading voltage etc. were found to be dependent on the sweep rate/step voltage employed during scanning. Highest hysteresis with on/off ratio of about 240 was obtained for an optimum step voltage of 2 V while it decreased with further reduction in the same. This was attributed to the longer scanning time leading to release of trapped carriers during forward scan itself. The OFET device was found to exhibit excellent memory retention capability where OFF and ON current measured for about 2 hours after stressing the device at write and erase voltages showed good retention of on/off ratio. PMID:24738406

  9. Ultrafast shock compression of self-assembled monolayers: a molecular picture.

    PubMed

    Patterson, James E; Dlott, Dana D

    2005-03-24

    Simulations of self-assembled monolayers (SAMs) are performed to interpret experimental measurements of ultrafast approximately 1 GPa (volume compression deltaV approximately 0.1) planar shock compression dynamics probed by vibrational sum-frequency generation (SFG) spectroscopy (Lagutchev, A. S.; Patterson, J. E.; Huang, W.; Dlott, D. D. J. Phys. Chem. B 2005, 109, XXXX). The SAMs investigated are octadecanethiol (ODT) and pentadecanethiol (PDT) on Au(111) and Ag(111) substrates, and benzyl mercaptan (BMT) on Au(111). In the alkane SAMs, SFG is sensitive to the instantaneous orientation of the terminal methyl; in BMT it is sensitive to the phenyl orientation. Computed structures of alkane SAMs are in good agreement with experiment. In alkanes, the energies of gauche defects increase with increasing number and depth below the methyl plane, with the exception of ODT/Au where both single and double gauche defects at the two uppermost dihedrals have similar energies. Simulations of isothermal uniaxial compression of SAM lattices show that chain and methyl tilting is predominant in PDT/Au, ODT/Ag and PDT/Ag, whereas single and double gauche defect formation is predominant in ODT/Au. Time-resolved shock data showing transient SFG signal loss of ODT/Au and PDT/Au are fit by calculations of the terminal group orientations as a function of deltaV and their contributions to the SFG hyperpolarizability. The highly elastic response of PDT/Au results from shock-generated methyl and chain tilting. The viscoelastic response of ODT/Au results from shock generation of single and double gauche defects. Isothermal compression simulations help explain and fit the time dependence of shock spectra but generally underestimate the magnitude of SFG signal loss because they do not include effects of high-strain-rate dynamics and shock front and surface irregularities. PMID:16863164

  10. Processing of nanoporous Ag layers by potential-controlled displacement (PCD) of Cu.

    PubMed

    Viyannalage, L T; Liu, Y; Dimitrov, N

    2008-08-01

    A cementation-like process taking place under potential control and introduced in this work as a "potential-controlled displacement" (PCD) is developed as a new method for processing of nanoporous Ag structures with controlled roughness (porosity) length scales. Most of the development work is done in a deoxygenated electrolyte containing 1 x 10(-3) M AgClO(4 )+ 5 x 10(-2) M CuSO(4) + 1 x 10(-1) M HClO(4) using a copper rotating disk electrode at 50 rpm. At this electrolyte concentration, the Ag deposition is under diffusion limitations whereas the Cu dissolution displays a typical Butler-Volmer anodic behavior. Thus, a careful choice of the operational current density enables strict control of the ratio between the dissolving and depositing metals as ascertained independently by atomic absorption spectrometry (AAS). The roughness length scale of the resulting surfaces is controlled by a careful selection of the current density applied. The highest surface area and finest morphology is obtained when the atomic ratio of Ag deposition and Cu dissolution becomes 1:1. Preseeding of uniform Ag clusters on the Cu surface made by pulse plating of Ag along with complementary plating and stripping of Pb monolayer is found to yield finer length scale resulting in up to a 67% higher surface area. An electrochemical technique using as a reference value the charge of an underpotentially deposited Pb layer on a flat Ag surface is used for measuring the real surface area. Scanning electron microscopy (SEM) studies are conducted to examine and characterize the deposit morphology of Ag grown by PCD on Cu substrates. PMID:18613704

  11. Nanocavity absorption enhancement for two-dimensional material monolayer systems.

    PubMed

    Song, Haomin; Jiang, Suhua; Ji, Dengxin; Zeng, Xie; Zhang, Nan; Liu, Kai; Wang, Chu; Xu, Yun; Gan, Qiaoqiang

    2015-03-23

    Here we propose a strategy to enhance the light-matter interaction of two-dimensional (2D) material monolayers based on strong interference effect in planar nanocavities, and overcome the limitation between optical absorption and the atomically-thin thickness of 2D materials. By exploring the role of spacer layers with different thicknesses and refractive indices, we demonstrate that a nanocavity with an air spacer layer placed between a graphene monolayer and an aluminum reflector layer will enhance the exclusive absorption in the graphene monolayer effectively, which is particularly useful for the development of atomically-thin energy harvesting/conversion devices.

  12. Molecular beam epitaxy growth of monolayer niobium diselenide flakes

    NASA Astrophysics Data System (ADS)

    Hotta, Takato; Tokuda, Takuto; Zhao, Sihan; Watanabe, Kenji; Taniguchi, Takashi; Shinohara, Hisanori; Kitaura, Ryo

    2016-09-01

    Monolayer niobium diselenide (NbSe2) is prepared through molecular beam epitaxy with hexagonal boron nitride (hBN) as substrates. Atomic force microscopy and the Raman spectroscopy have shown that the monolayer NbSe2 grown on the hBN possesses triangular or truncated triangular shape whose lateral size amounts up to several hundreds of nanometers. We have found that the precisely controlled supply rate and ultraflat surface of hBN plays an important role in the growth of the monolayer NbSe2.

  13. Simulations of calcite crystallization on self-assembled monolayers.

    PubMed

    Freeman, Colin L; Harding, John H; Duffy, Dorothy M

    2008-09-01

    This paper presents simulations of calcium carbonate ordering in contact with self-assembled monolayers. The calculations use potential-based molecular dynamics to model the crystallization of calcium carbonate to calcite expressing both the (00.1) and (01.2) surfaces. The effect of monolayer properties: ionization; epitaxial matching; charge density; and headgroup orientation on the crystallization process are examined in detail. The results demonstrate that highly charged surfaces are vital to stimulate ordering and crystallization. Template directed crystallization requires charge epitaxy between both the crystal surface and the monolayer. The orientation of the headgroup appears to make no contribution to the selection of the crystal surface.

  14. Angle-resolved photoemission study of Ag(1 1 1)

    NASA Astrophysics Data System (ADS)

    Edamoto, K.; Miyazaki, E.; Shimokoshi, K.; Kato, H.

    1990-01-01

    The (1 1 1) face of Ag has been studied by angle-resolved photoemission spectroscopy utilizing synchrotron radiation as the excitation source (25 <= hv <= 50eV). The overlapping Ag 4d bands were deconvolved by the modified FIRO method. The peak positions thus determined are used to map the dispersion curves along the lang1 1 1rang (Γ-L) direction. The results show general agreement with calculated band structure, so far as the energy levels and symmetries are concerned. However, it is found that the density of state effect is dominant in the spectra obtained in the present photon energy region. The emission from the Ag 5s, p bands is observed to be broadened due to the indirect transition process.

  15. Ag-Air Service

    NASA Technical Reports Server (NTRS)

    1981-01-01

    Econ, Inc.'s agricultural aerial application, "ag-air," involves more than 10,000 aircraft spreading insecticides, herbicides, fertilizer, seed and other materials over millions of acres of farmland. Difficult for an operator to estimate costs accurately and decide what to charge or which airplane can handle which assignment most efficiently. Computerized service was designed to improve business efficiency in choice of aircraft and determination of charge rates based on realistic operating cost data. Each subscriber fills out a detailed form which pertains to his needs and then receives a custom-tailored computer printout best suited to his particular business mix.

  16. Hyperfine fields at the (001) Fe/Ag interface.

    NASA Astrophysics Data System (ADS)

    Rodriguez, C. O.; Peltzer Y Blanca, E. L.; Ganduglia-Pirovano, M. V.; Petersen, M.

    2000-03-01

    First principles studies within local spin density functional theory have been performed to calculate and investigate the microscopic origin of Hyperfine Fields (HFF's) of a Cd impurity in bulk Fe and at the (001) interface of Fe/Ag. Monolayer resolved HFF's at this interface have recently been studied using ^111In/^111Cd probe atoms in PAC ( B.U.Runge, M.Dippel, G.Fillebock, K. Jacobs, U. Kohl and G. Schatz, Phys. Rev. Lett. 79), 3054 (1997) determinations. The reduction of the symmetry and the changes in the chemical environment of Cd at each side of the interface as compared to Cd in Fe bulk can be linked to the interpretation of the HFF's.

  17. A sum-frequency generation spectroscopic study of the Gibbs analysis paradox: monolayer or sub-monolayer adsorption?

    PubMed

    Shahir, Afshin Asadzadeh; Nguyen, Khoi Tan; Nguyen, Anh V

    2016-04-01

    The Gibbs adsorption isotherm (GAI) has been considered as the foundation of surfactant adsorption studies for over a century; however, its application in determining the limiting surface excess has recently been intensively discussed, with contradictory experimental evidence either supporting or refuting the theory. The available arguments are based on monolayer adsorption models. In this paper, we experimentally and intellectually propose and validate the contribution of sub-monolayer adsorption to the GAI paradox. We utilize a powerful intrinsically surface-sensitive technique, vibrational sum-frequency generation spectroscopy (SFG), complementing with conventional tensiometric measurements to address these controversies both quantitatively and qualitatively. Our SFG results revealed that the precipitous decrease in surface tension directly corresponds to surface occupancy by adsorbates. In addition, the Gibbs analysis was successfully applied to the soluble monolayer of a surface-active alcohol to full saturation. However, the full saturation of the topmost monolayer does not necessarily mean that the surface adsorption was completed because the adsorption was observed to continuously occur in the sub-monolayer region soon after the topmost monolayer became saturated. Nonetheless, the Gibbs isotherm failed to account for the excess of alcohol adsorbed in this sub-monolayer region. This new concept of surface excess must therefore be treated thermodynamically.

  18. Communication: Structure, formation, and equilibration of ensembles of Ag-S complexes on an Ag surface

    SciTech Connect

    Russell, Selena M.; Kim, Yousoo; Liu, Da-Jiang; Evans, J. W.; Thiel, P. A.

    2013-02-15

    We have utilized conditions of very low temperature (4.7 K) and very low sulfur coverage to isolate and identify Ag-S complexes that exist on the Ag(111) surface. The experimental conditions are such that the complexes form at temperatures above the temperature of observation. These complexes can be regarded as polymeric chains of varying length, with an Ag4S pyramid at the core of each monomeric unit. Steps may catalyze the formation of the chains and this mechanism may be reflected in the chain length distribution.

  19. Enhanced Raman scattering and nonlinear conductivity in Ag-doped hollow ZnO microspheres

    NASA Astrophysics Data System (ADS)

    Tringe, Joseph W.; Levie, Harold W.; McCall, Scott K.; Teslich, Nick E.; Wall, Mark A.; Orme, Christine A.; Matthews, Manyalibo J.

    2012-10-01

    Hollow spherical ZnO particles doped with Ag were synthesized with a two-step oxidation and sublimation furnace annealing process. Ag nanoparticle precipitates, as observed by transmission electron microscopy, were present in the polycrystalline ZnO matrix at Ag concentrations below 0.02 mol%, significantly below the 0.8 mol% solubility limit for Ag in ZnO. Enhanced Raman scattering of ZnO phonon modes is observed, increasing with Ag nanoparticle concentration. A further enhancement in Raman scattering due to resonance effects was observed for LO phonons excited by 2.33-eV photons as compared with Raman scattering under 1.96-eV excitation. Room-temperature photoluminescence spectra showed both a near-band-edge emission due to free exciton transitions and a mid-gap transition due to the presence of singly ionized oxygen vacancies. ZnO:Ag particles were measured electrically in a packed column and in monolithic form, and in both cases displayed nonlinear current-voltage characteristics similar to those previously observed in sintered ZnO:Ag monoliths where Ag-enhanced disorder at grain boundaries is thought to control current transport. We demonstrate therefore that Ag simultaneously modifies the electrical and optical properties of ZnO particles through the introduction of vacancies and other defects.

  20. Micropatterning of perfluoroalkyl self-assembled monolayers for arraying proteins and cells on chips

    NASA Astrophysics Data System (ADS)

    Kira, Atsushi; Okano, Kazunori; Hosokawa, Yoichiroh; Naito, Akira; Fuwa, Koh; Yuyama, Jyunpei; Masuhara, Hiroshi

    2009-06-01

    Organosilane self-assembled monolayers (SAMs) with perfluoroalkyl groups ( Rf) on glass surfaces were used for arraying proteins and cells on chips. Quartz crystal microbalance measurements confirmed the inhibition of protein adsorption on Rf-SAM-modified surfaces and showed efficient adsorption on hydroxyl-, carboxyl-, and amino group-modified surfaces. The characteristics of Rf-modified surfaces were evaluated using solvent contact angle measurement and Fourier transform infrared (FTIR) spectroscopy. The Rf surface was highly water- and oil-resistant, as inferred from the contact angles of water, oleic acid, and hexadecane. Specific peaks of IR spectra were detected in the region from 1160 to 1360 cm -1. Etching with dry plasma completely exfoliated the Rf-SAM, exposing the underlying intact glass surface. Modification conditions were optimized using contact angle and FTIR measurements. After dry plasma processing, the contact angles of all solvents became undetectable, and the IR peaks disappeared. Micrometer scale protein and cell patterns can be fabricated using the proposed method. Protein adsorption on micropatterned Rf-SAM-modified chips was evaluated using fluorescence analysis; protein adsorption was easily controlled by patterning Rf-SAM. PC12 and HeLa cells grew well on micropatterned Rf-SAM-modified chips. Micropatterning of Rf-SAM by dry plasma treatment with photolithography is useful for the spatial arrangement of proteins and cells.

  1. Diels-Alder Reaction of Anthranilic Acids: A Versatile Route to Dense Monolayers on Flat Edge and Basal Plane Graphitic Carbon Substrates.

    PubMed

    Farquhar, Anna K; Fitchett, Christopher M; Dykstra, Haidee M; Waterland, Mark R; Brooksby, Paula A; Downard, Alison J

    2016-09-01

    Methods that reliably yield monolayers of covalently anchored modifiers on graphene and other planar graphitic materials are in demand. Covalently bonded groups can add functionality to graphitic carbon for applications ranging from sensing to supercapacitors and can tune the electronic and optical properties of graphene. Limiting modification to a monolayer gives a layer with well-defined concentration and thickness providing a minimum barrier to charge transfer. Here we investigate the use of anthranilic acid derivatives for grafting aryl groups to few layer graphene and pyrolyzed photoresist film (PPF). Under mild conditions, anthranilic acids generate arynes, which undergo Diels-Alder cycloadditions. Using spectroscopy, electrochemistry, and atomic force microscopy, we demonstrate that the reaction yields monolayers of aryl groups on graphene and PPF with maximum surface coverages consistent with densely packed layers. Our study confirms that anthranilic acids offer a convenient route to covalent modification of planar graphitic carbons (both basal and edge plane materials). PMID:27529723

  2. AGS Experiments: 1989, 1990, 1991

    SciTech Connect

    Depken, J.C.

    1992-02-01

    This report contains: Experimental areas layout; table of beam parameters and fluxes; experiment schedule as run''; proposed 1992 schedule; a listing of experiments by number; two-page summaries of each experiment begin here, also ordered by number; publications of AGS Experiments begin here; and list of AGS Experimenters begins here.

  3. AGS Experiments: 1989, 1990, 1991

    SciTech Connect

    Depken, J.C.

    1992-02-01

    This report contains: Experimental areas layout; table of beam parameters and fluxes; experiment schedule ``as run``; proposed 1992 schedule; a listing of experiments by number; two-page summaries of each experiment begin here, also ordered by number; publications of AGS Experiments begin here; and list of AGS Experimenters begins here.

  4. Monolayers of hard rods on planar substrates. I. Equilibrium.

    PubMed

    Oettel, M; Klopotek, M; Dixit, M; Empting, E; Schilling, T; Hansen-Goos, H

    2016-08-21

    The equilibrium properties of hard rod monolayers are investigated in a lattice model (where position and orientation of a rod are restricted to discrete values) as well as in an off-lattice model featuring spherocylinders with continuous positional and orientational degrees of freedom. Both models are treated using density functional theory and Monte Carlo simulations. Upon increasing the density of rods in the monolayer, there is a continuous ordering of the rods along the monolayer normal ("standing up" transition). The continuous transition also persists in the case of an external potential which favors flat-lying rods in the monolayer. This behavior is found in both the lattice and the continuum models. For the lattice model, we find very good agreement between the results from the specific DFT used (lattice fundamental measure theory) and simulations. The properties of lattice fundamental measure theory are further illustrated by the phase diagrams of bulk hard rods in two and three dimensions. PMID:27544121

  5. Molecular motion in alkylsilane self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Stevens, Derrick; Scott, Mary; Guy, Laura; Bochinski, Jason; Clarke, Laura

    2008-03-01

    We have investigated intra-molecular rotation within polar-substituted alkylsilane self-assembled monolayers (SAMs) on fused silica, utilizing surface-sensitive dielectric spectroscopy. Both trichlorosilanes (which allow crosslinking within the SAM) and monochlorosilanes (attached only to the surface) are utilized to grow monolayer and submonolayer films. Dielectric loss spectra as a function of temperature have been obtained for SAMs with varying carbon chain length, surface coverage, and alkyl terminal group. As shown by ellipsometry, contact angle measurements, and AFM, monochlorosilanes form a more disordered monolayer than trichlorosilanes. This more disordered film may result in additional degrees of freedom within the monolayer, or in the language of phase transitions, a rotator phase. Issues such as uncontrolled vertical polymerization and film growth by island formation and their effect on rotational dynamics will be discussed.

  6. Extraordinary room-temperature photoluminescence in triangular WS2 monolayers.

    PubMed

    Gutiérrez, Humberto R; Perea-López, Nestor; Elías, Ana Laura; Berkdemir, Ayse; Wang, Bei; Lv, Ruitao; López-Urías, Florentino; Crespi, Vincent H; Terrones, Humberto; Terrones, Mauricio

    2013-08-14

    Individual monolayers of metal dichalcogenides are atomically thin two-dimensional crystals with attractive physical properties different from those of their bulk counterparts. Here we describe the direct synthesis of WS2 monolayers with triangular morphologies and strong room-temperature photoluminescence (PL). The Raman response as well as the luminescence as a function of the number of S-W-S layers is also reported. The PL weakens with increasing number of layers due to a transition from direct band gap in a monolayer to indirect gap in multilayers. The edges of WS2 monolayers exhibit PL signals with extraordinary intensity, around 25 times stronger than that at the platelet's center. The structure and chemical composition of the platelet edges appear to be critical for PL enhancement.

  7. Growth of rare-earth monolayers on synthetic fluorine mica

    NASA Astrophysics Data System (ADS)

    Tsui, F.; Han, P. D.; Flynn, C. P.

    1993-05-01

    We have grown single-crystal rare-earth films on cleaved faces of synthetic fluorine mica fluorophlogopite by molecular-beam-epitaxy techniques. This has made it possible to measure material properties such as magnetism in monolayer structures.

  8. The Intrinsic Ferromagnetism in a MnO2 Monolayer.

    PubMed

    Kan, M; Zhou, J; Sun, Q; Kawazoe, Y; Jena, P

    2013-10-17

    The Mn atom, because of its special electronic configuration of 3d(5)4s(2), has been widely used as a dopant in various two-dimensional (2D) monolayers such as graphene, BN, silicene and transition metal dichalcogenides (TMDs). The distributions of doped Mn atoms in these systems are highly sensitive to the synthesis process and conditions, thus suffering from problems of low solubility and surface clustering. Here we show for the first time that the MnO2 monolayer, synthetized 10 years ago, where Mn ions are individually held at specific sites, exhibits intrinsic ferromagnetism with a Curie temperature of 140 K, comparable to the highest TC value achieved experimentally for Mn-doped GaAs. The well-defined atomic configuration and the intrinsic ferromagnetism of the MnO2 monolayer suggest that it is superior to other magnetic monolayer materials.

  9. Phase emerging from intramonolayer cycloaddition on micro-patterned monolayer

    SciTech Connect

    Tajuddin, Hairul A.; Manning, Robert J.; Leggett, Graham J.; Williams, Nicholas H.

    2012-11-27

    Cu(I)-catalyzed cycloaddition between azide and acetylene, followed by hydrolysis of ester were performed on micro-patterned self-assembled monolayer to produce smaller features. The reactions were initially performed on mixed monolayers and analysed by water contact angle (CA) and confirmed by X-ray Photoelectron Spectroscopy (XPS). The contact angle measurement has shown a drastic wetting of water on the surface of mixed monolayer indicating that the terminal groups on mixed monolayer has changed into carboxylic acid and hydroxyl terminals. The reactions work in a similar way on micro-patterned SAM and analyzed by using friction force microscope. The emerging of the new lines with high friction force on the border suggested a successful intramonolayer reactions on the border of the patterned SAM.

  10. Phase emerging from intramonolayer cycloaddition on micro-patterned monolayer

    NASA Astrophysics Data System (ADS)

    Tajuddin, Hairul A.; Manning, Robert J.; Leggett, Graham J.; Williams, Nicholas H.

    2012-11-01

    Cu(I)-catalyzed cycloaddition between azide and acetylene, followed by hydrolysis of ester were performed on micro-patterned self-assembled monolayer to produce smaller features. The reactions were initially performed on mixed monolayers and analysed by water contact angle (CA) and confirmed by X-ray Photoelectron Spectroscopy (XPS). The contact angle measurement has shown a drastic wetting of water on the surface of mixed monolayer indicating that the terminal groups on mixed monolayer has changed into carboxylic acid and hydroxyl terminals. The reactions work in a similar way on micro-patterned SAM and analyzed by using friction force microscope. The emerging of the new lines with high friction force on the border suggested a successful intramonolayer reactions on the border of the patterned SAM.

  11. Monolayered mesenchymal stem cells repair scarred myocardium after myocardial infarction.

    PubMed

    Miyahara, Yoshinori; Nagaya, Noritoshi; Kataoka, Masaharu; Yanagawa, Bobby; Tanaka, Koichi; Hao, Hiroyuki; Ishino, Kozo; Ishida, Hideyuki; Shimizu, Tatsuya; Kangawa, Kenji; Sano, Shunji; Okano, Teruo; Kitamura, Soichiro; Mori, Hidezo

    2006-04-01

    Mesenchymal stem cells are multipotent cells that can differentiate into cardiomyocytes and vascular endothelial cells. Here we show, using cell sheet technology, that monolayered mesenchymal stem cells have multipotent and self-propagating properties after transplantation into infarcted rat hearts. We cultured adipose tissue-derived mesenchymal stem cells characterized by flow cytometry using temperature-responsive culture dishes. Four weeks after coronary ligation, we transplanted the monolayered mesenchymal stem cells onto the scarred myocardium. After transplantation, the engrafted sheet gradually grew to form a thick stratum that included newly formed vessels, undifferentiated cells and few cardiomyocytes. The mesenchymal stem cell sheet also acted through paracrine pathways to trigger angiogenesis. Unlike a fibroblast cell sheet, the monolayered mesenchymal stem cells reversed wall thinning in the scar area and improved cardiac function in rats with myocardial infarction. Thus, transplantation of monolayered mesenchymal stem cells may be a new therapeutic strategy for cardiac tissue regeneration. PMID:16582917

  12. Synthesis and characterizations of heterojunction of monolayer semiconductors

    NASA Astrophysics Data System (ADS)

    Lee, Yi-Hsien; Zhang, Xin-Quan; Tseng, Yu-Wen; Huang, Kuan-Hua; Chen, Chun-An; Chen, Bo-Han

    Monolayers of van der Waals materials, including graphene, and MoS2, offered a burgeoning field in fundamental physics, and optoelectronics.[1-5] Recently, atomically thin heterostructures of monolayer TMDc with various geometrical and energy band alignments are expected to be the key materials for next generation flexible optoelectronics. The individual TMDc monolayers can be adjoined vertically or laterally to construct diverse heterostructures which are difficult to reach with the laborious pick up-and-transfer method of the exfoliated flakes. The ability to produce copious amounts of high quality layered heterostructures on diverse surfaces is highly desirable but it has remained a challenging issue. Here, we have achieved a direct synthesis of various heterostructures of monolayer TMDc. The synthesis was performed using CVD with aromatic molecules as seeding promoters. We will discuss possible growth behaviors, and we examine the symmetry and the interface of these heterostructures using optical analysis and scanning TEM.

  13. Interaction of SO 2 with clean and Cs-precovered Ag(100)

    NASA Astrophysics Data System (ADS)

    Höfer, M.; Stolz, H.; Wassmuth, H.-W.

    The present paper gives a first report of our investigations of the adsorption and desorption kinetics of SO 2 on clean and cesiated Ag(100) by means of TPD. Δφ, molecular beam back scattering (MBBS) and isotope exchange experiments, assisted by AES and LEED. On clean Ag(100), SO 2 is adsorbed only at temperatures Tads < 300K. Although the TPD-spectra show similarities to our earlier measurements on clean Ag(100) and Ag(111), where SO 2 was found to be adsorbed molecularly, distinct differences were obtained, especially concerning the SO 2 sticking probability and the SO 2 induced change of the work function. In addition, an exchange of isotopes was observed within the first monolayer. SO 2 adsorption on Cs precovered Ag(100) leads to the formation of additional, Cs-influenced states at higher adsorption energies coexisting with clean silver SO 2 states, indicating a short range Cs sbnd SO 2 interaction. The Cs-influenced states are occupied first, leading to a strong re-increase of the work function.

  14. Substrate-Structure Dependence of Ag Electromigration on Au-Precovered Si(111) Surfaces

    NASA Astrophysics Data System (ADS)

    Shi, Fangxiao; Shiraki, Ichiro; Nagao, Tadaaki; Hasegawa, Shuji

    2000-07-01

    Electromigration of Ag on Au-precovered Si(111) surfaces was investigated by in-situ ultrahigh vacuum scanning electron microscopy and μ-probe reflection-high-energy electron diffraction (RHEED). Migration behaviors of a Ag-film patch strongly depended on Au coverage θAu and corresponding surface structures. When θAu<0.7 monolayer (ML), the patch expanded preferentially towards the cathode to attain a maximum area in which the sum of Ag and Au coverages were always about 1 ML irrespective of θAu, resulting in two-dimensional (2D) alloy phases (showing \\sqrt{3}×\\sqrt{3} RHEED patterns) with different Au/Ag concentration ratios. The largest expansion of the patch area was achieved on a (5× 2+α-\\sqrt{3}×\\sqrt{3})-Au mixed phase structure (θAu˜ 0.7 ML). However, when θAu>0.7 ML, the patch expansion was greatly reduced. Especially on the β-\\sqrt{3}×\\sqrt{3}-Au surface (θAu˜ 1.0 ML), the patch showed no directional expansion towards the cathode. But Ag atoms were observed to migrate inside the patches on all substrates (including the β-\\sqrt{3}×\\sqrt{3}-Au surface) to form 3D islands near terrace edges.

  15. Restructuring hollow Au–Ag nanostructures for improved SERS activity

    NASA Astrophysics Data System (ADS)

    Jiji, S. G.; Gopchandran, K. G.

    2016-10-01

    Hollow Au–Ag nanostructures with improved SERS performance were prepared by using a modified galvanic replacement reaction. The plasmon characteristics of the hollow structures are found to be highly sensitive to the volume of cathode, whether or not a co-reductant was used in the synthesis. It is found that the presence of a co-reductant viz., ascorbic acid (AA) during the reaction make the hollow structures capable to maintain its physical structure even after addition of excess cathode and also it transformes sacrificial templates into highly efficient hollow Au–Ag SERS substrates. In the galvanic replacement reaction conducted in presence of AA, where on one side the removal of Ag atoms make cavities to occur and on the other side a coating on the surface with Au and Ag atoms due to co-reduction take place simultaneously. Morphological observations indicated that it is possible to control the competition between these two mechanisms and to make Au–Ag hollow structures in tune with applications by optimizing the volume of cathode or AA. The SERS activity of these substrates were tested with crystal violet molecule as probe, using two different laser lines, 514 and 784.8 nm. In this report, the enhancement observed for hollow structures fabricated under optimum conditions are in the order of 106. SERS measurements have shown that for a specific volume of cathode, substrates fabricated in presence of AA are superior to the other type and also the increase in enhancement factor is ∼10 fold.

  16. Nonequilibrium 2-Hydroxyoctadecanoic Acid Monolayers: Effect of Electrolytes

    SciTech Connect

    Lendrum, Conrad D.; Ingham, Bridget; Lin, Binhua; Meron, Mati; Toney, Michael F.; McGrath, Kathryn M.

    2012-02-06

    2-Hydroxyacids display complex monolayer phase behavior due to the additional hydrogen bonding afforded by the presence of the second hydroxy group. The placement of this group at the position {alpha} to the carboxylic acid functionality also introduces the possibility of chelation, a utility important in crystallization including biomineralization. Biomineralization, like many biological processes, is inherently a nonequilibrium process. The nonequilibrium monolayer phase behavior of 2-hydroxyoctadecanoic acid was investigated on each of pure water, calcium chloride, sodium bicarbonate and calcium carbonate crystallizing subphases as a precursor study to a model calcium carbonate biomineralizing system, each at a pH of {approx}6. The role of the bicarbonate co-ion in manipulating the monolayer structure was determined by comparison with monolayer phase behavior on a sodium chloride subphase. Monolayer phase behavior was probed using surface pressure/area isotherms, surface potential, Brewster angle microscopy, and synchrotron-based grazing incidence X-ray diffraction and X-ray reflectivity. Complex phase behavior was observed for all but the sodium chloride subphase with hydrogen bonding, electrostatic and steric effects defining the symmetry of the monolayer. On a pure water subphase hydrogen bonding dominates with three phases coexisting at low pressures. Introduction of calcium ions into the aqueous subphase ensures strong cation binding to the surfactant head groups through chelation. The monolayer becomes very unstable in the presence of bicarbonate ions within the subphase due to short-range hydrogen bonding interactions between the monolayer and bicarbonate ions facilitated by the sodium cation enhancing surfactant solubility. The combined effects of electrostatics and hydrogen bonding are observed on the calcium carbonate crystallizing subphase.

  17. Sn-Ag-Cu solders and solder joints: Alloy development, microstructure, and properties

    NASA Astrophysics Data System (ADS)

    Anderson, I. E.; Cook, B. A.; Harringa, J. L.; Terpstra, R. L.

    2002-06-01

    Slow cooling of Sn-Ag-Cu and Sn-Ag-Cu-X (X = Fe, Co) solder-joint specimens made by hand soldering simulated reflow in surface-mount assembly to achieve similar as-solidified joint microstructures for realistic shearstrength testing, using Sn-3.5Ag (wt.%) as a baseline. Minor substitutions of either cobalt or iron for copper in Sn-3.7Ag-0.9Cu refined the joint matrix microstructure, modified the Cu6Sn5 intermetallic phase at the copper substrate/solder interface, and increased the shear strength. At elevated (150°C) temperature, no significant difference in shear strength was found in all of the alloys studied. Ambient temperature shear strength was reduced by largescale tin dendrites in the joint microstructure, especially by the coarse dendrites in solute poor Sn-Ag-Cu.

  18. Trion formation in monolayer transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Kezerashvili, Roman Ya.; Tsiklauri, Shalva M.

    We present three-body calculations for trions binding energy in monolayer transition metal dichalcogenides using the method of hyperspherical harmonics (HH). In numerical calculations for a proper treatment of Coulomb screening in two dimensions we assume that electrons and holes are interacted via Keldysh potential. The convergences of binding energy calculations for the ground state of the trion as a function of the grand angular momentum are studied. For the trion binding energy in MoS2 we obtain 19.2 mev. This value is remarkably close to the experimental one of 18 meV. A comparison with results of other calculations are presented. We also study solutions of a hyperradial equation in a minimal approximation for the ground angular momentum to examine two regimes: a long range and a short range cases when the inter particle distance is much greater and much less than the screening length. For these cases, we find analytical expressions for the energy and wave function for trion states

  19. Endohedral metallofullerenes in self-assembled monolayers.

    PubMed

    Gimenez-Lopez, Maria Del Carmen; Gardener, Jules A; Shaw, Adam Q; Iwasiewicz-Wabnig, Agnieszka; Porfyrakis, Kyriakos; Balmer, Claire; Dantelle, Geraldine; Hadjipanayi, Maria; Crossley, Alison; Champness, Neil R; Castell, Martin R; Briggs, G Andrew D; Khlobystov, Andrei N

    2010-01-01

    A method has been developed for the attachment of a dithiolane group to endohedral metallofullerenes via a 1,3-dipolar cycloaddition reaction. This sulfur-containing functional group serves as an anchor, enabling efficient immobilisation of endohedral fullerenes on Au(111) surfaces at room temperature, directly from the solution phase. The functionalised fullerenes form disordered monolayers that exhibit no long-range ordering, which is attributed to both the strong bonding of the dithiolane anchor to the surface and to the conformational flexibility of the functional group. Endohedral fullerenes Er(3)N@C(80) and Sc(3)N@C(80) have been used as models for functionalisation and subsequent surface deposition. Their chemical reactivity towards dithiolane functionalisation and their surface behaviour have been compared to that of C(60). The endohedral fullerenes appear to be significantly less reactive towards the functionalisation than C(60), however they bind in a similar manner to a gold surface as their dithiolane terminated C(60) counterparts. The optical activity of Er(3)N@C(80) molecules is preserved after attachment of the functional group. We report a splitting of the endohedral Er(3+) emission lines due to the reduction in symmetry of the functionalised fullerene cage, as compared to the highly symmetrical icosahedral C(80) cage of pristine Er(3)N@C(80).

  20. Surface dilatational viscosity of Langmuir monolayers

    NASA Astrophysics Data System (ADS)

    Lopez, Juan; Vogel, Michael; Hirsa, Amir

    2003-11-01

    With increased interest in microfluidic systems, interfacial phenomena is receiving more attention. As the length scales of fluid problems decrease, the surface to volume ratio increases and the coupling between interfacial flow and bulk flow becomes increasingly dominated by effects due to intrinsic surface viscosities (shear and dilatational), in comparison to elastic effects (due to surface tension gradients). The surface shear viscosity is well-characterized, as cm-scale laboratory experiments are able to isolate its effects from other interfacial processes (e.g., in the deep-channel viscometer). The same is not true for the dilatational viscosity, because it acts in the direction of surface tension gradients. Their relative strength scale with the capillary number, and for cm-scale laboratory flows, surface tension effects tend to dominate. In microfluidic scale flows, the scaling favors viscosity. We have devised an experimental apparatus which is capable of isolating and enhancing the effects of dilatational viscosity at the cm scales by driving the interface harmonically in time, while keeping the interface flat. In this talk, we shall present both the theory for how this works as well as experimental measurements of surface velocity from which we deduce the dilatational viscosity of several monolayers on the air-water interface over a substantial range of surface concentrations. Anomalous behavior over some range of concentration, which superficially indicates negative viscosity, maybe explained in terms of compositional effects due to large spatial and temporal variations in concentration and corresponding viscosity.

  1. Technique for etching monolayer and multilayer materials

    DOEpatents

    Bouet, Nathalie C. D.; Conley, Raymond P.; Divan, Ralu; Macrander, Albert

    2015-10-06

    A process is disclosed for sectioning by etching of monolayers and multilayers using an RIE technique with fluorine-based chemistry. In one embodiment, the process uses Reactive Ion Etching (RIE) alone or in combination with Inductively Coupled Plasma (ICP) using fluorine-based chemistry alone and using sufficient power to provide high ion energy to increase the etching rate and to obtain deeper anisotropic etching. In a second embodiment, a process is provided for sectioning of WSi.sub.2/Si multilayers using RIE in combination with ICP using a combination of fluorine-based and chlorine-based chemistries and using RF power and ICP power. According to the second embodiment, a high level of vertical anisotropy is achieved by a ratio of three gases; namely, CHF.sub.3, Cl.sub.2, and O.sub.2 with RF and ICP. Additionally, in conjunction with the second embodiment, a passivation layer can be formed on the surface of the multilayer which aids in anisotropic profile generation.

  2. Magnetoluminescence study of WS2 monolayers

    NASA Astrophysics Data System (ADS)

    Scrace, T.; Tsai, Y.; Barman, B.; Schweidenback, L.; Petrou, A.; Kioseoglou, G.; Hawrylak, P.

    2014-03-01

    We have studied the photoluminescence (PL) spectra[2] from WS2 monolayers in the 5-150 K temperature range in magnetic fields up to 7 tesla applied along the normal to the sample plane. The luminescence was excited by a 488nm linearly polarized laser beam. The PL spectra have two features identified as the neutral (X) and negatively charged (X-) exciton. At zero magnetic field the X- feature has a large (as high as 30%), laser power-dependent circular polarization, in contrast to the small polarization of Xthat does not depend on laser power. The application of an external magnetic field has a profound effect on the circular polarization of the charged exciton. Its polarization increases by 10% at 7 tesla for any laser-power while its energy exhibits a small magnetic splitting (2meV at 7 tesla). On the other hand, the emitted circular polarization of the free exciton is not affected by the external magnetic field. This work has been supported by ONR.

  3. Defect-Tolerant Monolayer Transition Metal Dichalcogenides

    NASA Astrophysics Data System (ADS)

    Pandey, Mohnish; Rasmussen, Filip A.; Kuhar, Korina; Olsen, Thomas; Jacobsen, Karsten W.; Thygesen, Kristian S.

    2016-04-01

    Localized electronic states formed inside the band gap of a semiconductor due to crystal defects can be detrimental to the material's optoelectronic properties. Semiconductors with lower tendency to form defect induced deep gap states are termed defect tolerant. Here we provide a systematic first principles investigation of defect tolerance in 29 monolayer transition metal dichalcogenides (TMDs) of interest for nanoscale optoelectronics. We find that the TMDs based on group VI and X metals form deep gap states upon creation of a chalcogen (S, Se, Te) vacancy while the TMDs based on group IV metals form only shallow defect levels and are thus predicted to be defect tolerant. Interestingly, all the defect sensitive TMDs have valence and conduction bands with very similar orbital composition. This indicates a bonding/anti-bonding nature of the gap which in turn suggests that dangling bonds will fall inside the gap. These ideas are made quantitative by introducing a descriptor that measures the degree of similarity of the conduction and valence band manifolds. Finally, the study is generalized to non-polar nanoribbons of the TMDs where we find that only the defect sensitive materials form edge states within the band gap.

  4. Structural phase transitions in monolayer molybdenum dichalcogenides

    NASA Astrophysics Data System (ADS)

    Choe, Duk-Hyun; Sung, Ha June; Chang, Kee Joo

    2015-03-01

    The recent discovery of two-dimensional materials such as graphene and transition metal dichalcogenides (TMDs) has provided opportunities to develop ultimate thin channel devices. In contrast to graphene, the existence of moderate band gap and strong spin-orbit coupling gives rise to exotic electronic properties which vary with layer thickness, lattice structure, and symmetry. TMDs commonly appear in two structures with distinct symmetries, trigonal prismatic 2H and octahedral 1T phases which are semiconducting and metallic, respectively. In this work, we investigate the structural and electronic properties of monolayer molybdenum dichalcogenides (MoX2, where X = S, Se, Te) through first-principles density functional calculations. We find a tendency that the semiconducting 2H phase is more stable than the metallic 1T phase. We show that a spontaneous symmetry breaking of 1T phase leads to various distorted octahedral (1T') phases, thus inducing a metal-to-semiconductor transition. We discuss the effects of carrier doping on the structural stability and the modification of the electronic structure. This work was supported by the National Research Foundation of Korea (NRF) under Grant No. NRF-2005-0093845 and Samsung Science and Technology Foundation under Grant No. SSTFBA1401-08.

  5. Employing X-ray Photoelectron Spectroscopy for Determining Layer Homogeneity in Mixed Polar Self-Assembled Monolayers

    PubMed Central

    2016-01-01

    Self-assembled monolayers (SAMs) containing embedded dipolar groups offer the particular advantage of changing the electronic properties of a surface without affecting the SAM–ambient interface. Here we show that such systems can also be used for continuously tuning metal work functions by growing mixed monolayers consisting of molecules with different orientations of the embedded dipolar groups. To avoid injection hot-spots when using the SAM-modified electrodes in devices, a homogeneous mixing of the two components is crucial. We show that a combination of high-resolution X-ray photoelectron spectroscopy with state-of-the-art simulations is an ideal tool for probing the electrostatic homogeneity of the layers and thus for determining phase separation processes in polar adsorbate assemblies down to inhomogeneities at the molecular level. PMID:27429041

  6. Covalently anchored carboxyphenyl monolayer via aryldiazonium ion grafting: a well-defined reactive tether layer for on-surface chemistry.

    PubMed

    Lee, Lita; Ma, Haifeng; Brooksby, Paula A; Brown, Simon A; Leroux, Yann R; Hapiot, Philippe; Downard, Alison J

    2014-06-24

    Electrografting of aryl films to electrode surfaces from diazonium ion solutions is a widely used method for preparation of modified electrodes. In the absence of deliberate measures to limit film growth, the usual film structure is a loosely packed multilayer. For some applications, monolayer films are advantageous; our interest is in preparing well-defined monolayers of reactive tethers for further on-surface chemistry. Here, we describe the synthesis of an aryl diazonium salt with a protected carboxylic acid substituent. After electrografting to glassy carbon electrodes and subsequent deprotection, the layer is reacted with amine derivatives. Electrochemistry and atomic force microscopy are used to monitor the grafting, deprotection, and subsequent coupling steps. Attempts to follow the same procedures on gold surfaces suggest that the grafted layer is not stable in these reaction conditions. PMID:24874712

  7. Employing X-ray Photoelectron Spectroscopy for Determining Layer Homogeneity in Mixed Polar Self-Assembled Monolayers.

    PubMed

    Hehn, Iris; Schuster, Swen; Wächter, Tobias; Abu-Husein, Tarek; Terfort, Andreas; Zharnikov, Michael; Zojer, Egbert

    2016-08-01

    Self-assembled monolayers (SAMs) containing embedded dipolar groups offer the particular advantage of changing the electronic properties of a surface without affecting the SAM-ambient interface. Here we show that such systems can also be used for continuously tuning metal work functions by growing mixed monolayers consisting of molecules with different orientations of the embedded dipolar groups. To avoid injection hot-spots when using the SAM-modified electrodes in devices, a homogeneous mixing of the two components is crucial. We show that a combination of high-resolution X-ray photoelectron spectroscopy with state-of-the-art simulations is an ideal tool for probing the electrostatic homogeneity of the layers and thus for determining phase separation processes in polar adsorbate assemblies down to inhomogeneities at the molecular level. PMID:27429041

  8. Surface Charge Transfer Doping of Monolayer Phosphorene via Molecular Adsorption.

    PubMed

    He, Yuanyuan; Xia, Feifei; Shao, Zhibin; Zhao, Jianwei; Jie, Jiansheng

    2015-12-01

    Monolayer phosphorene has attracted much attention owing to its extraordinary electronic, optical, and structural properties. Rationally tuning the electrical transport characteristics of monolayer phosphorene is essential to its applications in electronic and optoelectronic devices. Herein, we study the electronic transport behaviors of monolayer phosphorene with surface charge transfer doping of electrophilic molecules, including 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), NO2, and MoO3, using density functional theory combined with the nonequilibrium Green's function formalism. F4TCNQ shows optimal performance in enhancing the p-type conductance of monolayer phosphorene. Static electronic properties indicate that the enhancement is originated from the charge transfer between adsorbed molecule and phosphorene layer. Dynamic transport behaviors demonstrate that additional channels for hole transport in host monolayer phosphorene were generated upon the adsorption of molecule. Our work unveils the great potential of surface charge transfer doping in tuning the electronic properties of monolayer phosphorene and is of significance to its application in high-performance devices.

  9. C₆₀ fullerene promotes lung monolayer collapse.

    PubMed

    Barnoud, Jonathan; Urbini, Laura; Monticelli, Luca

    2015-03-01

    Airborne nanometre-sized pollutants are responsible for various respiratory diseases. Such pollutants can reach the gas-exchange surface in the alveoli, which is lined with a monolayer of lung surfactant. The relationship between physiological effects of pollutants and molecular-level interactions is largely unknown. Here, we determine the effects of carbon nanoparticles on the properties of a model of lung monolayer using molecular simulations. We simulate phase-separated lipid monolayers in the presence of a model pollutant nanoparticle, C₆₀ fullerene. In the absence of nanoparticles, the monolayers collapse only at very low surface tensions (around 0 mN m(-1)). In the presence of nanoparticles, instead, monolayer collapse is observed at significantly higher surface tensions (up to ca 10 mN m(-1)). Collapse at higher tensions is related to lower mechanical rigidity of the monolayer. It is possible that similar mechanisms operate on lung surfactant in vivo, which suggests that health effects of airborne carbon nanoparticles may be mediated by alterations of the mechanical properties of lung surfactant.

  10. Manipulation of electronic structure in WSe2 monolayer by strain

    NASA Astrophysics Data System (ADS)

    Yang, Cong-xia; Zhao, Xu; Wei, Shu-yi

    2016-11-01

    In this paper, we study the electronic properties of WSe2 monolayer with biaxial tensile strain and compressive strain by using first principles based on the density function theory. Under the biaxial tensile strain, WSe2 monolayer retains direct band gap with increasing strain and the band gap of WSe2 continuously decreases with increasing strain, eventually turn to metal when strain is equal to or more than 13%. Under the biaxial compressive strain, WSe2 monolayer turns to indirect gap and the band gap continuously decreases with increasing strain, finally turn to metal when strain is up to -7%. The strain can reduce the band gap of the WSe2 monolayer regardless of the strain direction. By comparison, we can see that the tensile strain appears to be more effective in reducing the band gap of pristine WSe2 monolayer than the compressive strain from -5% to 5%. But the band gap turns to zero quickly from -6% to -7% under compressive strain, however for tensile strain from 5% to 13%, the band gap decreases slowly. Based on the further analysis of the projected charge density for WSe2 monolayer, the fundamental reason of the change of band structure under biaxial tensile strain is revealed.

  11. Treponema pallidum Invades Intercellular Junctions of Endothelial Cell Monolayers

    NASA Astrophysics Data System (ADS)

    Thomas, D. Denee; Navab, Mahamad; Haake, David A.; Fogelman, Alan M.; Miller, James N.; Lovett, Michael A.

    1988-05-01

    The pathogenesis of syphilis reflects invasive properties of Treponema pallidum, but the actual mode of tissue invasion is unknown. We have found two in vitro parallels of treponemal invasiveness. We tested whether motile T. pallidum could invade host cells by determining the fate of radiolabeled motile organisms added to a HeLa cell monolayer; 26% of treponemes associated with the monolayer in a trypsin-resistant niche, presumably between the monolayer and the surface to which it adhered, but did not attain intracellularity. Attachment of T. pallidum to cultured human and rabbit aortic and human umbilical vein endothelial cells was 2-fold greater than to HeLa cells. We added T. pallidum to aortic endothelial cells grown on membrane filters under conditions in which tight intercellular junctions had formed. T. pallidum was able to pass through the endothelial cell monolayers without altering tight junctions, as measured by electrical resistance. In contrast, heat-killed T. pallidum and the nonpathogen Treponema phagedenis biotype Reiter failed to penetrate the monolayer. Transmission electron micrographs of sections of the monolayer showed T. pallidum in intercellular junctions. Our in vitro observations suggest that these highly motile spirochetes may leave the circulation by invading the junctions between endothelial cells.

  12. High Quality Factor Mechanical Resonators Based on WSe2 Monolayers.

    PubMed

    Morell, Nicolas; Reserbat-Plantey, Antoine; Tsioutsios, Ioannis; Schädler, Kevin G; Dubin, François; Koppens, Frank H L; Bachtold, Adrian

    2016-08-10

    Suspended monolayer transition metal dichalcogenides (TMD) are membranes that combine ultralow mass and exceptional optical properties, making them intriguing materials for opto-mechanical applications. However, the low measured quality factor of TMD resonators has been a roadblock so far. Here, we report an ultrasensitive optical readout of monolayer TMD resonators that allows us to reveal their mechanical properties at cryogenic temperatures. We find that the quality factor of monolayer WSe2 resonators greatly increases below room temperature, reaching values as high as 1.6 × 10(4) at liquid nitrogen temperature and 4.7 × 10(4) at liquid helium temperature. This surpasses the quality factor of monolayer graphene resonators with similar surface areas. Upon cooling the resonator, the resonant frequency increases significantly due to the thermal contraction of the WSe2 lattice. These measurements allow us to experimentally study the thermal expansion coefficient of WSe2 monolayers for the first time. High Q-factors are also found in resonators based on MoS2 and MoSe2 monolayers. The high quality-factor found in this work opens new possibilities for coupling mechanical vibrational states to two-dimensional excitons, valley pseudospins, and single quantum emitters and for quantum opto-mechanical experiments based on the Casimir interaction. PMID:27459399

  13. High Quality Factor Mechanical Resonators Based on WSe2 Monolayers

    PubMed Central

    2016-01-01

    Suspended monolayer transition metal dichalcogenides (TMD) are membranes that combine ultralow mass and exceptional optical properties, making them intriguing materials for opto-mechanical applications. However, the low measured quality factor of TMD resonators has been a roadblock so far. Here, we report an ultrasensitive optical readout of monolayer TMD resonators that allows us to reveal their mechanical properties at cryogenic temperatures. We find that the quality factor of monolayer WSe2 resonators greatly increases below room temperature, reaching values as high as 1.6 × 104 at liquid nitrogen temperature and 4.7 × 104 at liquid helium temperature. This surpasses the quality factor of monolayer graphene resonators with similar surface areas. Upon cooling the resonator, the resonant frequency increases significantly due to the thermal contraction of the WSe2 lattice. These measurements allow us to experimentally study the thermal expansion coefficient of WSe2 monolayers for the first time. High Q-factors are also found in resonators based on MoS2 and MoSe2 monolayers. The high quality-factor found in this work opens new possibilities for coupling mechanical vibrational states to two-dimensional excitons, valley pseudospins, and single quantum emitters and for quantum opto-mechanical experiments based on the Casimir interaction. PMID:27459399

  14. Effect of Ag nanowire addition into nanoparticle paste on the conductivity of Ag patterns printed by gravure offset method.

    PubMed

    Ok, Ki-Hun; Lee, Chan-Jae; Kwak, Min-Gi; Choi, Duck-Kyun; Kim, Kwang-Seok; Jung, Seung-Boo; Kim, Jong-Woong

    2014-11-01

    This paper focuses on the effect of Ag nanowire addition into a commercial Ag nanopaste and the printability evaluation of the mixed paste by the gravure offset printing methodology. Ag nanowires were synthesized by a modified polyol method, and a small amount of them was added into a commercial metallic paste based on Ag nanoparticles of 50 nm in diameter. Two annealing temperatures were selected for comparison, and electrical conductivity was measured by four point probe method. As a result, the hybrid mixture could be printed by the gravure offset method for patterning fine lines up to 15 μm width with sharp edges and scarce spreading. The addition of the Ag nanowires was significantly efficient for enhancement of electrical conductivity of the printed lines annealed at a low temperature (150 degrees C), while the effect was somewhat diluted in case of high temperature annealing (200 degrees C). The experimental results were discussed with the conduction mechanism in the printed conductive circuits with a schematic description of the electron flows in the printed lines.

  15. Switching light with light - advanced functional colloidal monolayers

    NASA Astrophysics Data System (ADS)

    Bley, K.; Sinatra, N.; Vogel, N.; Landfester, K.; Weiss, C. K.

    2013-12-01

    Colloidal monolayers comprising of highly ordered two dimensional crystals are of high interest to generate surface patterns for a variety of different applications. Mostly, unfunctionalized polymer or silica colloids are assembled into monolayers. However, the incorporation of functional molecules into such colloids offers a convenient possibility of implementing additional properties to the two-dimensional crystal. Here, we present the formation of novel functional colloidal monolayers with photoswitchable fluorescence. The miniemulsion polymerization technique was used to incorporate an appropriate dye system of a perylene-based fluorophore and a bis-arylethene as a photochrome in polymeric colloids in defined ratios. Upon irradiation with UV or visible light the photochrome reversibly isomerizes from the ring-closed form, which is able to absorb light of the emission wavelength of the fluorescent dye and the ring-open form, which is not. The fluorescence emission of the dye can thus be reversibly switched on and off with light even when embedded in colloids. The colloids were self-assembled at the air-water interface to produce hexagonally ordered functional monolayers and more complex binary crystals. We investigate in detail the influence of the polymeric matrix on the switching properties of the fluorophore/photochrome system and find that the rate constants for the photoswitching, which all lie in the same range, are less influenced by the polymeric environment than expected. We demonstrate the reversible switching of the fluorescence emission in self-assembled colloidal monolayers. The arrangement of broadly distributed functional colloids into ordered monolayers with high addressability was obtained by the formation of binary colloidal monolayers.Colloidal monolayers comprising of highly ordered two dimensional crystals are of high interest to generate surface patterns for a variety of different applications. Mostly, unfunctionalized polymer or silica

  16. In-situ coherent x-ray scattering from Ag (001) and Ag (111) surfaces in vacuum and gas-phase environments

    NASA Astrophysics Data System (ADS)

    Karl, Robert, Jr.; Barbour, Andi; Komanicky, Vladimir; Zhu, Chenhui; Hennessy, Daniel; You, Hoydoo; Pierce, Michael S.

    2013-03-01

    We have been able to obtain X-ray photon correlation spectroscopy (XPCS) quality data from the Ag (001) and Ag (111) surfaces at two different locations along the specular scattering rod. We observe dynamic behavior related to temperature and gas-phase composition. We will present the methods of the XPCS analysis routines, as they have been adapted to this specific system, and the preliminary results for the dynamics, such as step edge motion, island growth, and surface phase transitions, of the Ag surface features in these different conditions. These dynamics are also q dependent and vary from slow at low q, to faster dynamics at positions near the Ag (001) anti-Bragg scattering position where the experimental sensitivity is sufficient to detect changes at a monolayer level. This indicates that the dynamics involved are occurring right at the surface and do not involve multiple layers. These results will then be compared to our recent similar measurements on the Au (001) surface. The work at Safarik University was supported by Slovak grant VEGA 1/0782/12

  17. Products and Kinetics of the Reactions of an Alkane Monolayer and a Terminal Alkene Monolayer with NO₃ Radicals

    SciTech Connect

    Gross, Simone; Bertram, Allan K.

    2009-01-27

    The reactions of an alkanethiol and a terminal alkenethiol self-assembled monolayer with NO₃ radicals (in the presence of NO₂ and O₂) were studied. For the alkane monolayer, infrared (IR) spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed the formation of organonitrates (RONO₂). The observation of organonitrates is in contrast to the recent X-ray photoelectron spectroscopy (XPS) data, which showed very little nitrogen-containing surface species. The identification of organonitrates may help explain why significant volatilization of the organic chain was not observed in recent studies of alkane monolayer oxidation by NO₃ radicals. The reactive uptake coefficient (g) of NO₃ on alkene monolayers determined in our study is higher than the values obtained in a recent study using liquid and solid alkene bulk films. A possible reason for this difference may be the location of the double bond at the interface. Using the g value determined in our studies, we show that under conditions where NO₃ is high the lifetime of an alkene monolayer in the atmosphere may be short (approximately 20 min). XPS, IR, and ToF-SIMS were used to identify surface functional groups after the oxidation of the alkene monolayers by NO₃. The results are consistent with the formation of C-O, aldehyde/ketone, carboxylic groups, and nitrogen containing species.

  18. The AGS-Booster lattice

    SciTech Connect

    Lee, Y.Y.; Barton, D.S.; Claus, J.; Cottingham, J.G.; Courant, E.D.; Danby, G.T.; Dell, G.F.; Forsyth, E.B.; Gupta, R.C.; Kats, J.

    1987-01-01

    The AGS Booster has three objectives. They are to increase the space charge limit of the AGS, to increase the intensity of the polarized proton beam by accumulating many linac pulses (since the intensity is limited by the polarized ion source), and to reaccelerate heavy ions from the BNL Tandem Van de Graaff before injection into the AGS. The machine is capable of accelerating protons at 7.5 Hertz from 200 MeV to 1.5 GeV or to lower final energies at faster repetition rates. The machine will also be able to accelerate heavy ions from as low as 1 MeV/nucleon to a magnetic rigidity as high as 17.6 Tesla-meters with a one second repetition rate. As an accumulator for polarized protons, the Booster should be able to store the protons at 200 MeV for several seconds. We expect that the Booster will increase the AGS proton intensity by a factor of four, polarized proton intensity by a factor of twenty to thirty, and will also enable the AGS to accelerate all species of heavy ions (at present the AGS heavy ion program is limited to the elements lighter than sulfur because it can only accelerate fully stripped ions). The construction project started in FY 1985 and is expected to be completed in 1989. The purpose of this paper is to provide a future reference for the AGS Booster lattice.

  19. Perforated monolayers: Design and synthesis of porous and cohesive monolayers from mercurated calix(n)arenes

    SciTech Connect

    Markowitz, M.A.; Janout, V.; Regen, S.L. ); Castner, D.G. )

    1989-10-11

    Mercuration of a series of O-alkylated calix(n)arenes (produced via reaction of tetrahydroxycalix(4)arene, pentahydroxylcalix(5)arene, hexahydroxycalix(6)arene, and heptahydroxycalix(7)arene with n-bromobutane and with n-bromohexadecane) afford an homologous series of calixarene-based surfactants that form stable monolayers at the air-water interface. Surface pressure-area isotherms, measured for each calixarene, yield limiting areas that are in excellent agreement with values predicted from space-filling models, if it is assumed that the base of each calixarene is parallel and the alkyl chains are perpendicular to the water surface. Introduction of malonic acid to the aqueous subphase results in a substantial increase in the cohesiveness of films derived from calix(4)arene-, calix(5)arene-, and calix(6)arene-based surfactants, as judged by changes in surface viscosity. X-ray photoelectron spectroscopic analysis of a Langmuir-Blodgett film, produced from a malonic acid stabilized calix(6)arene monolayer, shows a carboxylate/mercury ratio of 0.9.

  20. Ultrafast Dynamics of Plasmon-Exciton Interaction of Ag Nanowire- Graphene Hybrids for Surface Catalytic Reactions.

    PubMed

    Ding, Qianqian; Shi, Ying; Chen, Maodu; Li, Hui; Yang, Xianzhong; Qu, Yingqi; Liang, Wenjie; Sun, Mengtao

    2016-01-01

    Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling. PMID:27601199

  1. Ultrafast Dynamics of Plasmon-Exciton Interaction of Ag Nanowire- Graphene Hybrids for Surface Catalytic Reactions.

    PubMed

    Ding, Qianqian; Shi, Ying; Chen, Maodu; Li, Hui; Yang, Xianzhong; Qu, Yingqi; Liang, Wenjie; Sun, Mengtao

    2016-09-07

    Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling.

  2. Ultrafast Dynamics of Plasmon-Exciton Interaction of Ag Nanowire- Graphene Hybrids for Surface Catalytic Reactions

    PubMed Central

    Ding, Qianqian; Shi, Ying; Chen, Maodu; Li, Hui; Yang, Xianzhong; Qu, Yingqi; Liang, Wenjie; Sun, Mengtao

    2016-01-01

    Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling. PMID:27601199

  3. Preparation and characterization of silver loaded montmorillonite modified with sulfur amino acid

    NASA Astrophysics Data System (ADS)

    Li, Tian; Lin, Oulian; Lu, Zhiyuan; He, Liuimei; Wang, Xiaosheng

    2014-06-01

    The Na+ montmorillonite (MMT) was modified with sulfur containing amino acid (L-cystine, L-cysteine or L-methionine) and characterized by energy dispersive spectrometer (EDS), X-ray diffraction (XRD) and Fourier transform infrared spectrum (FT-IR). The results showed the modification was smooth and the surface condition of MMT was changed with sulfur containing groups. Then silver was loaded on the modified MMTs via ion-exchange reaction under microwave irradiation, the spectra of X-ray photoelectron spectroscopy (XPS), EDS and FT-IR confirmed the successful loading of massive silver and the strong interaction between sulfur and silver, the silver loaded L-cystine modified MMT (Ag@AA-MMT-3) with a silver content of 10.93 wt% was the highest of all. Further more, the Ag@AA-MMT-3 was under the irradiation of a UV lamp to turn silver ions to silver nano particles (Ag NPs). The XPS, specific surface area (SSA), transmission electron microscopy (TEM), XRD patterns and UV-vis spectra proved the existence of uniform nano scaled metallic Ag NPs. By contrast, the UV irradiated Ag@AA-MMT-3 (Ag@AA-MMT-UV) showed a much better slow release property than Ag@AA-MMT-3 or Ag@MMT. The Ag@AA-MMT-UV showing a large inhibition zone and high inhibition ratio presented very good antibacterial property.

  4. Switching light with light - advanced functional colloidal monolayers

    NASA Astrophysics Data System (ADS)

    Bley, K.; Sinatra, N.; Vogel, N.; Landfester, K.; Weiss, C. K.

    2013-12-01

    Colloidal monolayers comprising of highly ordered two dimensional crystals are of high interest to generate surface patterns for a variety of different applications. Mostly, unfunctionalized polymer or silica colloids are assembled into monolayers. However, the incorporation of functional molecules into such colloids offers a convenient possibility of implementing additional properties to the two-dimensional crystal. Here, we present the formation of novel functional colloidal monolayers with photoswitchable fluorescence. The miniemulsion polymerization technique was used to incorporate an appropriate dye system of a perylene-based fluorophore and a bis-arylethene as a photochrome in polymeric colloids in defined ratios. Upon irradiation with UV or visible light the photochrome reversibly isomerizes from the ring-closed form, which is able to absorb light of the emission wavelength of the fluorescent dye and the ring-open form, which is not. The fluorescence emission of the dye can thus be reversibly switched on and off with light even when embedded in colloids. The colloids were self-assembled at the air-water interface to produce hexagonally ordered functional monolayers and more complex binary crystals. We investigate in detail the influence of the polymeric matrix on the switching properties of the fluorophore/photochrome system and find that the rate constants for the photoswitching, which all lie in the same range, are less influenced by the polymeric environment than expected. We demonstrate the reversible switching of the fluorescence emission in self-assembled colloidal monolayers. The arrangement of broadly distributed functional colloids into ordered monolayers with high addressability was obtained by the formation of binary colloidal monolayers.Colloidal monolayers comprising of highly ordered two dimensional crystals are of high interest to generate surface patterns for a variety of different applications. Mostly, unfunctionalized polymer or silica

  5. Mysterious Lattice Rotations in Adsorbed Monolayers

    NASA Astrophysics Data System (ADS)

    Diehl, Renee D.

    1997-03-01

    Lattice rotations due to a mismatch in structure have been observed in film growth for many years, probably beginning in the 1930's with the Nishiyama-Wasserman and Kurdjumov-Sachs orientations observed when fcc(111) films grow on bcc(110) surfaces, or vice versa. Early analysis of this problem was carried out with the aid of Moiré patterns and the observation that the preferred lattice orientations are those which maximize the Moiré fringe spacing. Later energy calculations indicated that the structures which were predicted by the the Moiré technique actually do correspond to energy minima. Epitaxial rotation in adsorbed monolayers is a conceptually simpler problem since in principle it involves only two planes of atoms, and it was first observed in 1977 for Ar on a graphite surface(C. G. Shaw, M. D. Chinn, S. C. Fain, Jr. Phys. Rev. Lett. 41 (1978) 955.). This observation came only a few months after a new theory, based on the expected elastic behavior of an overlayer, was developed by A. D. Novaco and J. P. McTague(A. D. Novaco and J. P. McTague, Phys. Rev. Lett. 38 (1977) 1286.), and the agreement with the experimental results was remarkable. It was later shown that a few symmetry principles similar to those used for the film growth studies sometimes can also predict the observed structures. However, the situation for incommensurate layers physisorbed on metal surfaces currently looks bleak. None of the existing theories or models appears to describe the experimental results. New data for physisorbed gases on metal surfaces will be presented, along with some half-baked (and probably wrong) ideas for what might be happening. This work was supported by NSF.

  6. Adsorption mode of the chiral modifier cinchonidine on Au(1 1 1)

    NASA Astrophysics Data System (ADS)

    Behzadi, B.; Ferri, D.; Baiker, A.; Ernst, K.-H.

    2007-01-01

    The adsorption of the chiral modifier cinchonidine on Au(l 1 1) in UHV has been studied by means of TPD, LEED and XPS. In the monolayer the molecule is bound via nitrogen lone pair electrons of its quinoline part rather than via the π-system of this aromatic moiety. Intact molecular desorption is only observed for the multilayers. Decomposition in the first monolayer upon heating occurs above 400 K, indicating a stronger interaction in the monolayer. No long-range ordered structures were observed via LEED. Long-time exposure leads to rearrangement and further stabilization of the first molecular monolayer. Quinoline is bound to gold via the nitrogen lone pair as well. The binding energy of 9.6 kcal/mol is characteristic for physisorption.

  7. Covalently-layers of PVA and PAA and in situ formed Ag nanoparticles as versatile antimicrobial surfaces.

    PubMed

    Fragal, Vanessa H; Cellet, Thelma S P; Pereira, Guilherme M; Fragal, Elizângela H; Costa, Marco Antonio; Nakamura, Celso Vataru; Asefa, Tewodros; Rubira, Adley F; Silva, Rafael

    2016-10-01

    The in situ synthesis of silver nanoparticles (AgNPs) within covalently-modified poly(ethylene terephthalate) (PET) films possessing ultra-thin layer of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) is successfully demonstrated. The resulting polymeric films are shown to exhibit antimicrobial activities toward Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria and fungus (Candida albicans). To make the films, first PET surfaces were subject to photo-oxidation and subsequent solid-state grafting to attach a PVA layer, followed by a PAA layer. To synthesize the AgNPs inside the films, the PVA and PAA-modified PET was soaked in AgNO3 solution and the polymeric film was modified with the Ag(+) ions via Ag(+)-carboxylate interaction, and then the Ag(+) ions-containing polymer film was subject to either photo-reduction or thermal reduction processes. The PVA and PAA thin layers attached by covalent bonds to the PET surface uniquely promoted not only the in situ synthesis but also the stabilization of AgNPs. The formation of the AgNPs was confirmed by UV-vis spectroscopy or by monitoring the surface plasmon resonance (SPR) peak associated with AgNPs. The resulting PVA and PAA ultrathin layers modified and AgNPs containing PET served as bactericide and fungicide, inhibiting the growth of bacteria and fungi on the surfaces. Given PET's versatility and common use in many commercial processes, the method can be used for producing plastic surfaces with versatile antimicrobial and antibacterial properties. PMID:27196366

  8. Switching light with light--advanced functional colloidal monolayers.

    PubMed

    Bley, K; Sinatra, N; Vogel, N; Landfester, K; Weiss, C K

    2014-01-01

    Colloidal monolayers comprising of highly ordered two dimensional crystals are of high interest to generate surface patterns for a variety of different applications. Mostly, unfunctionalized polymer or silica colloids are assembled into monolayers. However, the incorporation of functional molecules into such colloids offers a convenient possibility of implementing additional properties to the two-dimensional crystal. Here, we present the formation of novel functional colloidal monolayers with photoswitchable fluorescence. The miniemulsion polymerization technique was used to incorporate an appropriate dye system of a perylene-based fluorophore and a bis-arylethene as a photochrome in polymeric colloids in defined ratios. Upon irradiation with UV or visible light the photochrome reversibly isomerizes from the ring-closed form, which is able to absorb light of the emission wavelength of the fluorescent dye and the ring-open form, which is not. The fluorescence emission of the dye can thus be reversibly switched on and off with light even when embedded in colloids. The colloids were self-assembled at the air-water interface to produce hexagonally ordered functional monolayers and more complex binary crystals. We investigate in detail the influence of the polymeric matrix on the switching properties of the fluorophore/photochrome system and find that the rate constants for the photoswitching, which all lie in the same range, are less influenced by the polymeric environment than expected. We demonstrate the reversible switching of the fluorescence emission in self-assembled colloidal monolayers. The arrangement of broadly distributed functional colloids into ordered monolayers with high addressability was obtained by the formation of binary colloidal monolayers. PMID:24227011

  9. Platinum monolayer electrocatalysts for oxygen reduction in fuel cells

    NASA Astrophysics Data System (ADS)

    Zhang, Junliang

    Fuel cells are expected to be one of the major clean energy sources in the near future. However, the slow kinetics of electrocatalytic oxygen reduction reaction (ORR) and the high loading of Pt for the cathode material are the urgent issues to be addressed since they determine the efficiency and the cost of this energy source. In this study, a new approach was developed for designing electrocatalysts for the ORR in fuel cells. These electrocatalysts consist of only one Pt monolayer, or mixed transition metal-Pt monolayer, on suitable carbon-supported metal, or alloy nanoparticles. The synthesis involved depositing a monolayer of Cu on a suitable transition metal or metal alloy surface at underpotentials, followed by galvanic displacement of the Cu monolayer with Pt or mixed metal-Pt. It was found that the electronic properties of Pt monolayer could be fine-tuned by the electronic and geometric effects introduced by the substrate metal (or alloy) and the lateral effects of the neighboring metal atoms. The role of substrates was found reflected in a "volcano" plot of the monolayer activity for the ORR as a function of their calculated d-band centers. The Pt mass-specific activity of the new Pt monolayer electrocatalysts was up to twenty times higher than the state-of-the-art commercial Pt/C catalysts. The enhancement of the activity is caused mainly by decreased formation of PtOH (the blocking species for ORR), and to a lesser degree by the electronic effects. Fuel cell tests showed a very good long term stability of the new electrocatalysts. Our results demonstrated a viable way to designing the electrocatalysts which could successfully alleviate two issues facing the commercialization of fuel cells---the costs of electrocatalysts and their efficiency.

  10. Coexistent compressive and tensile strain in Ag thin films on Si(1 1 1)-(7×7) surfaces

    NASA Astrophysics Data System (ADS)

    Goswami, D. K.; Bhattacharjee, K.; Satpati, B.; Roy, S.; Kuri, G.; Satyam, P. V.; Dev, B. N.

    2007-09-01

    Growth and strain behavior of thin Ag films on Si substrates have been investigated by scanning tunneling microscopy, cross-sectional transmission electron microscopy and high resolution X-ray diffraction studies. Ag islands formed on Si at room temperature growth show strongly preferred heights and flat top. At low coverage [ ≳1 monolayer (ML)], Ag islands with (1 1 1) orientation containing two atomic layers of Ag are overwhelmingly formed [D.K. Goswami, K. Bhattacharjee, B. Satpati, S. Roy, P.V. Satyam, B.N. Dev, Surf. Sci. 601 (2007) 603]. A thicker (40 ML) annealed film shows two closely spaced Ag(1 1 1) diffraction peaks—one weak and broad and the other narrow and more intense. The broad peak corresponds to an average expansion (0.21%) and the narrow intense peak corresponds to a contraction (0.17%) of the Ag(1 1 1) planar spacing compared to the bulk value. This coexistence of compressive and tensile strain can be explained in terms of changes in the Ag lattice during the heating-cooling cycle due to thermal expansion coefficient mismatch between Ag and Si.

  11. Local density of unoccupied states in ion-beam-mixed Pd-Ag alloys

    SciTech Connect

    Chae, K.H.; Jung, S.M.; Lee, Y.S.; Whang, C.N.; Jeon, Y.; Croft, M.; Sills, D.; Ansari, P.H.; Mack, K.

    1996-04-01

    X-ray absorption spectroscopy (XAS) measurements have been used to probe the electronic structure of ion-beam-mixed (IBM) Pd-Ag thin films with bulk alloys being studied for comparison. Pd {ital L}{sub 3} and Ag {ital L}{sub 3} absorption edges for pure Pd, Ag, and Pd{sub 1{minus}{ital x}}Ag{sub {ital x}} alloys are discussed. Structural information from both x-ray diffraction and the XAS fine structure oscillations are discussed. The observed decrease of the white-line feature strength, at the Pd {ital L}{sub 3} edge, indicates that the local density of unoccupied Pd 4{ital d} states declines upon alloying with Ag in a manner similar to that observed in previous bulk studies. However, while the Pd {ital d}-hole count decreases monotonically for bulk alloys, in the IBM alloys it saturates at higher levels in the Ag-rich materials. This disparity is interpreted on the basis of a modified charge transfer due to structural differences in the IBM alloys. The Ag {ital L}{sub 3} near-edge region is largely unchanged in these alloys, indicating that the charge transferred away from the Ag site is dominantly of {ital non}-{ital d} type. Our experimental results are discussed in the context of recent electronic structure calculations and of previous work on this alloy system. {copyright} {ital 1996 The American Physical Society.}

  12. Plasmonic Ag@oxide nanoprisms for enhanced performance of organic solar cells.

    PubMed

    Du, Peng; Jing, Pengtao; Li, Di; Cao, Yinghui; Liu, Zhenyu; Sun, Zaicheng

    2015-05-01

    Localized surface plasmon resonance (LSPR), light scattering, and lowering the series resistance of noble metal nanoparticles (NPs) provide positive effect on the performance of photovoltaic device. However, the exciton recombination on the noble metal NPs accompanying above influences will deteriorate the performance of device. In this report, surface-modified Ag@oxide (TiO2 or SiO2 ) nanoprisms with 1-2 nm shell thickness are developed. The thin film composed of P3HT/Ag@oxides and P3HT:PCBM/Ag@oxides is investigated by absorption, photoluminescence (PL), and transient absorption spectroscopy. The results show a significant absorption, PL enhancement, and long-lived photogenerated polaron in the P3HT/Ag@TiO2 film, indicating the increase of photogenerated exciton population by LSPR of Ag nanoprisms. In the case of P3HT/Ag nanoprisms, partial PL quench and relatively short-lived photogenerated polaron are observed. That indicates that the oxides layer can effectively avoid the exciton recombination. When the Ag@oxide nanoprisms are introduced into the active layer of P3HT:PCBM photovoltaic devices, about 31% of power conversion efficiency enhancement is obtained relative to the reference cell. All these results indicate that Ag@oxides can enhance the performance of the cell, at the same time the ultrathin oxide shell prevents from the exciton recombination.

  13. High-performance polyimide nanocomposites with core-shell AgNWs@BN for electronic packagings

    NASA Astrophysics Data System (ADS)

    Zhou, Yongcun; Liu, Feng

    2016-08-01

    The increasing density of electronic devices underscores the need for efficient thermal management. Silver nanowires (AgNWs), as one-dimensional nanostructures, possess a high aspect ratio and intrinsic thermal conductivity. However, high electrical conductivity of AgNWs limits their application for electronic packaging. We synthesized boron nitride-coated silver nanowires (AgNWs@BN) using a flexible and fast method followed by incorporation into synthetic polyimide (PI) for enhanced thermal conductivity and dielectric properties of nanocomposites. The thinner boron nitride intermediate nanolayer on AgNWs not only alleviated the mismatch between AgNWs and PI but also enhanced their interfacial interaction. Hence, the maximum thermal conductivity of an AgNWs@BN/PI composite with a filler loading up to 20% volume was increased to 4.33 W/m K, which is an enhancement by nearly 23.3 times compared with that of the PI matrix. The relative permittivity and dielectric loss were about 9.89 and 0.015 at 1 MHz, respectively. Compared with AgNWs@SiO2/PI and Ag@BN/PI composites, boron nitride-coated core-shell structures effectively increased the thermal conductivity and reduced the permittivity of nanocomposites. The relative mechanism was studied and discussed. This study enables the identification of appropriate modifier fillers for polymer matrix nanocomposites.

  14. Synthesis and properties of polyamide-Ag2S composite based solar energy absorber surfaces

    NASA Astrophysics Data System (ADS)

    Krylova, Valentina; Baltrusaitis, Jonas

    2013-10-01

    Silver sulfide (Ag2S), an efficient solar light absorber, was synthesized using a modified chemical bath deposition (CBD) method and polyamide 6 (PA) as a host material via solution phase reaction between AgNO3 and Na2S2O3. X-ray diffraction (XRD) data showed a single, α-Ag2S (acanthite), crystalline phase present while surface and bulk chemical analyses, performed using X-ray photoelectron (XPS) and energy dispersive (EDS) spectroscopies, showed 2:1 Ag:S ratio. Direct and indirect bandgaps obtained from Tauc plots were 1.3 and 2.3 eV, respectively. Detailed surface chemical analysis showed the presence of three distinct sulfur species with majority component due to the Ag2S chemical bonds and minority components due to two types of oxygen-sulfur bonds. Conductivity of the resulting composite material was shown to change with the reaction time thus enabling to obtain controlled conductivity composite material. The synthesis method presented is based on the low solubility of Ag2S and is potentially green, no by-product producing, as all Ag2S nucleated outside the host material can be recycled into the process via dissolving it in HNO3.

  15. Ag/TiO{sub 2} nanofiber heterostructures: Highly enhanced photocatalysts under visible light

    SciTech Connect

    Wang Yuan; Liu Lixin; Xu Liang; Meng Chuanmin; Zhu Wenjun

    2013-05-07

    Photocatalysis of TiO{sub 2} has recently drawn considerable attention, while the photoefficiency of TiO{sub 2} is limited by its large band-gap energy and usually fast electron-hole recombination. Here, we present an unconventional heterostructure of Ag nanoparticles modified TiO{sub 2} nanofibers synthesized by one-step electrospinning process, to improve the photoefficiency of TiO{sub 2} host. The efficient promotion of the visible light photocatalysis of Ag/TiO{sub 2} nanofiber heterostructures can be ascribed to the electronic excitation of Ag nanoparticles under visible light and the transfer of the electrons to TiO{sub 2} conduction band, which deeply depends on the number of Ag/TiO{sub 2} junctions and the height of Schottky barrier. The Ag/Ti molar ratio can be easily controlled by the electrospinning process and the Ag/TiO{sub 2} nanofibers with Ag/Ti molar ratio of 0.05 exhibit the highest photocatalytic activity. Simultaneously, the Ag/TiO{sub 2} nanofiber heterostructures show excellent photocatalytic stability.

  16. Theoretical Simulation of isocyanate (NCO) adsorption on the Ag(001) surface

    NASA Astrophysics Data System (ADS)

    Boungou, C. C.; N'dollo, M.; Malonda-Boungou, B. R.; Moussounda, P. S.; Dintzer, T.

    2016-05-01

    The adsorption of isocyanate (NCO) on a Ag (001) surface with different coverages [θ = 0.25, 0.50, 0.75 and 1.00 monolayer (ML)] is studied by using density functional theory and the periodic slab model. Adsorption energies, geometrical parameters and work function changes are calculated. We found that the most energetic sites are the bridge for 0.25 ML and the hollow for 0.50, 0.75 and 1.00 ML. The change in the work function depends on both the adsorption site and the NCO coverage. A detailed analysis of the computed local density of states shows that the NCO π and σ states strongly interact with the Ag (pz, dz2) bands.

  17. Coexistence of multiple silicene phases in silicon grown on Ag(1 1 1).

    PubMed

    Moras, P; Mentes, T O; Sheverdyaeva, P M; Locatelli, A; Carbone, C

    2014-05-01

    Silicene, the silicon equivalent of graphene, is attracting increasing scientific and technological attention in view of the exploitation of its exotic electronic properties. This novel material has been theoretically predicted to exist as a free-standing layer in a low-buckled, stable form, and can be synthesized by the deposition of Si on appropriate crystalline substrates. By employing low-energy electron diffraction and microscopy, we have studied the growth of Si on Ag(1 1 1) and observed a rich variety of rotationally non-equivalent silicene structures. Our results highlight a very complex formation diagram, reflecting the coexistence of different and nearly degenerate silicene phases, whose relative abundance can be controlled by varying the Si coverage and growth temperature. At variance with other studies, we find that the formation of single-phase silicene monolayers cannot be achieved on Ag(1 1 1).

  18. Spin dynamics simulations at AGS

    SciTech Connect

    Huang, H.; MacKay, W.W.; Meot, F.; Roser, T.

    2010-05-23

    To preserve proton polarization through acceleration, it is important to have a correct model of the process. It has been known that with the insertion of the two helical partial Siberian snakes in the Alternating Gradient Synchrotron (AGS), the MAD model of AGS can not deal with a field map with offset orbit. The stepwise ray-tracing code Zgoubi provides a tool to represent the real electromagnetic fields in the modeling of the optics and spin dynamics for the AGS. Numerical experiments of resonance crossing, including spin dynamics in presence of the snakes and Q-jump, have been performed in AGS lattice models, using Zgoubi. This contribution reports on various results so obtained.

  19. High-Efficiency Colloidal Quantum Dot Photovoltaics via Robust Self-Assembled Monolayers.

    PubMed

    Kim, Gi-Hwan; García de Arquer, F Pelayo; Yoon, Yung Jin; Lan, Xinzheng; Liu, Mengxia; Voznyy, Oleksandr; Jagadamma, Lethy Krishnan; Abbas, Abdullah Saud; Yang, Zhenyu; Fan, Fengjia; Ip, Alexander H; Kanjanaboos, Pongsakorn; Hoogland, Sjoerd; Kim, Jin Young; Sargent, Edward H

    2015-11-11

    The optoelectronic tunability offered by colloidal quantum dots (CQDs) is attractive for photovoltaic applications but demands proper band alignment at electrodes for efficient charge extraction at minimal cost to voltage. With this goal in mind, self-assembled monolayers (SAMs) can be used to modify interface energy levels locally. However, to be effective SAMs must be made robust to treatment using the various solvents and ligands required for to fabricate high quality CQD solids. We report robust self-assembled monolayers (R-SAMs) that enable us to increase the efficiency of CQD photovoltaics. Only by developing a process for secure anchoring of aromatic SAMs, aided by deposition of the SAMs in a water-free deposition environment, were we able to provide an interface modification that was robust against the ensuing chemical treatments needed in the fabrication of CQD solids. The energy alignment at the rectifying interface was tailored by tuning the R-SAM for optimal alignment relative to the CQD quantum-confined electron energy levels. This resulted in a CQD PV record power conversion efficiency (PCE) of 10.7% with enhanced reproducibility relative to controls.

  20. Neutrally Charged Gas/Liquid Interface by a Catanionic Langmuir Monolayer

    SciTech Connect

    Vaknin, David; Bu, Wei

    2010-07-23

    Surface-sensitive synchrotron X-ray scattering and spectroscopic experiments were performed to explore the characteristics of Langmuir monolayers of oppositely charged mixed amphiphiles. A premixed (molar 1:1 stearic acid/stearylamine) solution was spread as a monolayer at the gas/liquid interface on pure water and on mono- and divalent salt solutions, revealing that the negatively charged carboxyl groups and positively charged amine groups are miscible into one another and tend to bond together to form a nearly neutral surface. Similar control experiments on pure stearic acid (SA) and stearylamine (ST) were also conducted for comparison. Due to the strong bonding, hexagonal structures in small domains with acyl-chains normal to the liquid surface are formed at zero surface pressures, that is, at molecular areas much larger than those of the densely packed acyl chains. In-plane X-ray diffraction indicates that the catanionic surface is highly ordered and modifies the structure of the water surface and thus can serve as a model system for interactions of an amino acid template with solutes.