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Sample records for monolayer modified ag

  1. 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

  2. Quantitative determination of melamine in milk using Ag nanoparticle monolayer film as SERS substrate

    NASA Astrophysics Data System (ADS)

    Li, Ruoping; Yang, Jingliang; Han, Junhe; Liu, Junhui; Huang, Mingju

    2017-04-01

    A Raman method employing silver nanoparticle (Ag NP) monolayer film as Surface-enhanced Raman Scattering (SERS) substrate was presented to rapidly detect melamine in milk. The Ag NPs with 80 nm diameter were modified by polyvinylpyrrolidone to improve their uniformity and chemical stability. The treatment procedure of liquid milk required only addition of acetic acid and centrifugation, and required time is less than 15 min. The Ag NP monolayer film significantly enhanced Raman signal from melamine and allowed experimentally reproducible determination of the melamine concentration. A good linear relationship (R2=0.994) between the concentration and Raman peak intensity of melamine at 681 cm-1 was obtained for melamine concentrations between 0.10 mg L-1 and 5.00 mg L-1. This implies that this method can detect melamine concentrations below 1.0 mg L-1, the concentration currently considered unsafe.

  3. Cobalt monolayer islands on Ag(111) for ORR catalysis.

    PubMed

    Loglio, Francesca; Lastraioli, Elisa; Bianchini, Claudio; Fontanesi, Claudio; Innocenti, Massimo; Lavacchi, Alessandro; Vizza, Francesco; Foresti, Maria Luisa

    2011-08-22

    The design of a catalyst for one of the most important electrocatalytic reactions, the oxygen reduction reaction (ORR), was done following the most recent guidelines of theoretical studies on this topic. Aim of this work was to achieve a synergic effect of two different metals acting on different steps of the ORR. The catalytic activity of Ag, already known and characterized, was enhanced by the presence of a monolayer of cobalt subdivided into nanosized islands. To obtain such a controlled nanostructure, a novel method utilizing self-assembled monolayers (SAMs) as templates was employed. In a recent study, we were able to perform a confined electrodeposition of cobalt onto Ag(111) in a template formed by selectively desorbing a short-chain thiol (3-mercaptopropionic acid, MPA) from binary SAMs using 1-dodecanthiols (DDT). This method allows for an excellent control of the morphology of the deposit by varying the molar ratio of the two thiols. Because cobalt does not deposit on silver at an underpotential, the alternative approach of surface limited redox replacement (SLRR) was used. This method, recently developed by Adžić et al., consists of the use of a monolayer of a third metal, which can be deposited at an underpotential, as a template for the spontaneous deposition of a more noble metal. Herein, we choose zinc as template for the deposition of cobalt. Ag(111) crystals were covered by monolayer islands consisting of cobalt, with the surface atomic ratios ranging from 12 to 39% for cobalt. The catalytic activity of such samples towards ORR was evaluated and the best improvement in activity was found to be that of the sample with a cobalt percentage of approximately 30% with respect to the bare silver, which is in good agreement with theoretical hypotheses.

  4. 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.

  5. 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

  6. Highly conductive and transparent Ag honeycomb mesh fabricated using a monolayer of polystyrene spheres

    NASA Astrophysics Data System (ADS)

    Kwon, Namyong; Kim, Kyohyeok; Sung, Sihyun; Yi, Insook; Chung, Ilsub

    2013-06-01

    We describe the design principles and fabrication of Ag honeycomb mesh as a transparent conductive electrode using a polystyrene (PS) sphere template. Monolayers of PS spheres with different diameters, such as 600 nm, 3 μm, and 10 μm, are studied as templates to form Ag mesh with high transmittance. Since the parasitic Ag islands degrade the transmittance, both heat pretreatment and wet etching are used to control the area covered by parasitic Ag islands. The trade-off between transmittance and conductivity forces us to use larger diameter PS spheres. Ten-micron PS spheres are chosen as the template for the PS sphere monolayer, and heat pretreatment and Ag wet etching are used to demonstrate that the Ag honeycomb mesh transparent electrodes have high performance. The transmittance and the sheet resistance are 83% and 20 Ω/sq, which are comparable to commercial ITO electrodes.

  7. Superstrong encapsulated monolayer graphene by the modified anodic bonding.

    PubMed

    Jung, Wonsuk; Yoon, Taeshik; Choi, Jongho; Kim, Soohyun; Kim, Yong Hyup; Kim, Taek-Soo; Han, Chang-Soo

    2014-01-07

    We report a superstrong adhesive of monolayer graphene by modified anodic bonding. In this bonding, graphene plays the role of a superstrong and ultra-thin adhesive between SiO2 and glass substrates. As a result, monolayer graphene presented a strong adhesion energy of 1.4 J m(-2) about 310% that of van der Waals bonding (0.45 J m(-2)) to SiO2 and glass substrates. This flexible solid state graphene adhesive can tremendously decrease the adhesive thickness from about several tens of μm to 0.34 nm for epoxy or glue at the desired bonding area. As plausible causes of this superstrong adhesion, we suggest conformal contact with the rough surface of substrates and generation of C-O chemical bonding between graphene and the substrate due to the bonding process, and characterized these properties using optical microscopy, atomic force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy.

  8. 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.

  9. Surface-enhanced Raman scattering-active gold nanoparticles modified with a monolayer of silver film.

    PubMed

    Chang, Chun-Chao; Yang, Kuang-Hsuan; Liu, Yu-Chuan; Yu, Chung-Chin; Wu, Yi-Hao

    2012-11-07

    As shown in the literature, electrochemical underpotential deposition (UPD) offers the ability to deposit up to a monolayer of one metal onto a more noble metal with a flat surface. In this work, we develop an electrochemical pathway to prepare more surface-enhanced Raman scattering (SERS)-active substrates with Ag UPD-modified Au nanoparticles (NPs) by using sonoelectrochemical deposition-dissolution cycles (SEDDCs). Encouragingly, the SERS of Rhodamine 6G (R6G) adsorbed on these Ag UPD-modified Au NPs exhibits a higher intensity by ca. 12-fold magnitude, as compared with that of R6G adsorbed on unmodified Au NPs. The prepared SERS-active substrate demonstrates a large Raman scattering enhancement for R6G with a detection limit of 2 × 10(-14) M and an enhancement factor of 5.0 × 10(8). Also, the strategy proposed in this work to improve the SERS effects by using UPD Ag based on SEDDCs has an effect on the smaller probe molecules of 2,2'-bipyridine (BPy).

  10. Scanning Electrochemical Microscopy of DNA Monolayers Modified with Nile Blue

    PubMed Central

    Gorodetsky, Alon A.; Hammond, William J.; Hill, Michael G.; Slowinski, Krzysztof; Barton, Jacqueline K.

    2009-01-01

    Scanning electrochemical microscopy (SECM) is used to probe long-range charge transport (CT) through DNA monolayers containing the redox-active Nile Blue (NB) intercalator covalently affixed at a specific location in the DNA film. At substrate potentials negative of the formal potential of covalently attached NB, the electrocatalytic reduction of Fe(CN)63− generated at the SECM tip is observed only when NB is located at the DNA/solution interface; for DNA films containing NB in close proximity to the DNA/electrode interface, the electrocatalytic effect is absent. This behavior is consistent with both rapid DNA-mediated CT between the NB intercalator and the gold electrode as well as a rate-limiting electron transfer between NB and the solution phase Fe(CN)63−. The DNA-mediated nature of the catalytic cycle is confirmed through sequence-specific and localized detection of attomoles of TATA-binding protein, a transcription factor that severely distorts DNA upon binding. Importantly, the strategy outlined here is general and allows for the local investigation of the surface characteristics of DNA monolayers both in the absence and in the presence of DNA binding proteins. These experiments highlight the utility of DNA-modified electrodes as versatile platforms for SECM detection schemes that take advantage of CT mediated by the DNA base pair stack. PMID:19053641

  11. Underpotential deposition of thallium, lead, and cadmium at silver electrodes modified with self-assembled monolayers of (3-mercaptopropyl)trimethoxysilane.

    PubMed

    Robertson, Joseph W F; Tiani, Domenic J; Pemberton, Jeanne E

    2007-04-10

    Investigation of the underpotential deposition (UPD) of three metals-Tl, Pb, and Cd-on Ag surfaces modified with self-assembled monolayers (SAMs) of (3-mercaptopropyl)trimethoxysilane (3MPT) is reported. On the basis of the observation of negative potential shifts for their UPD processes, Tl and Pb undergo UPD directly on the underlying Ag surface by insertion between the Ag-S bond. This process is proposed to occur by penetration of the 3MPT monolayer by hydrated metal ions through spaces in six-membered siloxane rings that form at the terminus of the 3MPT layer after hydrolysis and condensation. In contrast, Cd does not undergo similarly facile UPD at 3MPT-modified Ag electrodes due to a hydrated ion size too large to fit through these openings. The voltammetric evidence that suggests that the hydrated metal cation size, as described by the Stokes diameter, is the primary determinant of Ag electrode accessibility for UPD through the cross-linked 3MPT layer is further supported by molecular mechanics energy minimization computations of six-membered siloxane rings on each of the three low-index faces of Ag. Finally, the 3MPT monolayer is shown to be exceptionally stable to repeated UPD/stripping cycles of Tl and Pb in contrast to SAMs of similar thickness formed from normal alkanethiols.

  12. Ordered structure upon deposition of Ge on the monolayer silicene on Ag(111)

    NASA Astrophysics Data System (ADS)

    Chen, Han-De; Lin, Dengsung

    The growth of monolayer silicene on Ag (111) has been a hot research in recent years. The akin structure of the same group IV element: Germanene, has also been grown successfully on different metal substrates. In this investigation, Ge has been deposited by molecular beam epitaxy on the monolayer-thick silicene grown on Ag(111). Low-temperature scanning tunneling microscopy (LT-STM) has been employed to observed the surface morphology and atomic structure. On the (3 x 3)Si phase, only one Ge adatom is found on each (3 x 3)Si unit cell on two different sites, A and B. The deposited Ge adatoms prefer to settle around a unit cell that has already incorporated one Ge adatom, thereby forming two domains (3 x 3)A and (3 x 3)B. Results on (r7 x r7)Si superstructure showing local ordering will also be presented.

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2007-11-01

    The self-assembly of a ferrocene (Fc) derivative, oligoethylene-bridged diferrocene (diFc), Fc(CH2)14Fc , on Ag(110) surface has been investigated by scanning tunneling microscopy (STM) under ultrahigh vacuum. Three ordered structures, the majority β and the minorities α and γ , are formed at monolayer coverage. In α and γ , 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 β : 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 (1213-1) 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.

  15. 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

  16. 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.

  17. Direct evidence of interaction-induced Dirac cones in a monolayer silicene/Ag(111) system.

    PubMed

    Feng, Ya; Liu, Defa; Feng, Baojie; Liu, Xu; Zhao, Lin; Xie, Zhuojin; Liu, Yan; Liang, Aiji; Hu, Cheng; Hu, Yong; He, Shaolong; Liu, Guodong; Zhang, Jun; Chen, Chuangtian; Xu, Zuyan; Chen, Lan; Wu, Kehui; Liu, Yu-Tzu; Lin, Hsin; Huang, Zhi-Quan; Hsu, Chia-Hsiu; Chuang, Feng-Chuan; Bansil, Arun; Zhou, X J

    2016-12-20

    Silicene, analogous to graphene, is a one-atom-thick 2D crystal of silicon, which is expected to share many of the remarkable properties of graphene. The buckled honeycomb structure of silicene, along with enhanced spin-orbit coupling, endows silicene with considerable advantages over graphene in that the spin-split states in silicene are tunable with external fields. Although the low-energy Dirac cone states lie at the heart of all novel quantum phenomena in a pristine sheet of silicene, a hotly debated question is whether these key states can survive when silicene is grown or supported on a substrate. Here we report our direct observation of Dirac cones in monolayer silicene grown on a Ag(111) substrate. By performing angle-resolved photoemission measurements on silicene(3 × 3)/Ag(111), we reveal the presence of six pairs of Dirac cones located on the edges of the first Brillouin zone of Ag(111), which is in sharp contrast to the expected six Dirac cones centered at the K points of the primary silicene(1 × 1) Brillouin zone. Our analysis shows clearly that the unusual Dirac cone structure we have observed is not tied to pristine silicene alone but originates from the combined effects of silicene(3 × 3) and the Ag(111) substrate. Our study thus identifies the case of a unique type of Dirac cone generated through the interaction of two different constituents. The observation of Dirac cones in silicene/Ag(111) opens a unique materials platform for investigating unusual quantum phenomena and for applications based on 2D silicon systems.

  18. Direct evidence of interaction-induced Dirac cones in a monolayer silicene/Ag(111) system

    NASA Astrophysics Data System (ADS)

    Feng, Ya; Liu, Defa; Feng, Baojie; Liu, Xu; Zhao, Lin; Xie, Zhuojin; Liu, Yan; Liang, Aiji; Hu, Cheng; Hu, Yong; He, Shaolong; Liu, Guodong; Zhang, Jun; Chen, Chuangtian; Xu, Zuyan; Chen, Lan; Wu, Kehui; Liu, Yu-Tzu; Lin, Hsin; Huang, Zhi-Quan; Hsu, Chia-Hsiu; Chuang, Feng-Chuan; Bansil, Arun; Zhou, X. J.

    2016-12-01

    Silicene, analogous to graphene, is a one-atom-thick 2D crystal of silicon, which is expected to share many of the remarkable properties of graphene. The buckled honeycomb structure of silicene, along with enhanced spin-orbit coupling, endows silicene with considerable advantages over graphene in that the spin-split states in silicene are tunable with external fields. Although the low-energy Dirac cone states lie at the heart of all novel quantum phenomena in a pristine sheet of silicene, a hotly debated question is whether these key states can survive when silicene is grown or supported on a substrate. Here we report our direct observation of Dirac cones in monolayer silicene grown on a Ag(111) substrate. By performing angle-resolved photoemission measurements on silicene(3 × 3)/Ag(111), we reveal the presence of six pairs of Dirac cones located on the edges of the first Brillouin zone of Ag(111), which is in sharp contrast to the expected six Dirac cones centered at the K points of the primary silicene(1 × 1) Brillouin zone. Our analysis shows clearly that the unusual Dirac cone structure we have observed is not tied to pristine silicene alone but originates from the combined effects of silicene(3 × 3) and the Ag(111) substrate. Our study thus identifies the case of a unique type of Dirac cone generated through the interaction of two different constituents. The observation of Dirac cones in silicene/Ag(111) opens a unique materials platform for investigating unusual quantum phenomena and for applications based on 2D silicon systems.

  19. Nondissociative chemisorption of methanethiol on Ag(110): a critical result for self-assembled monolayers.

    PubMed

    Lee, Jae-Gook; Lee, Junseok; Yates, John T

    2004-01-21

    Three definitive experiments have been performed to investigate the possibility of dissociative adsorption of methanethiol (CH3SH) on clean Ag(110). On the clean Ag(110) surface, the adsorption in the first layer occurs to 0.5 ML, producing a (2 x 1) low-energy electron diffraction (LEED) structure. The undissociated molecule desorbs starting at approximately 140 K, and only tiny quantities of other gaseous products are desorbed, and only tiny quantities of S-containing species remain. Using a 50:50% mixture of CH3SD and CD3SH, we find no evidence of S-H or S-D bond scission between these molecules upon desorption. And finally, when the CH3SH molecule is incident on the clean Ag(110) surface in the temperature range of 230-400 K, less than 1% of the incident molecules dissociate to produce adsorbed sulfur-containing species. The results influence our thinking about the surface bonding of alkanethiol-based self-assembled monolayers (SAMs) on noble metals.

  20. Characterization of Two Oxidatively Modified Phospholipids in Mixed Monolayers with DPPC

    PubMed Central

    Sabatini, Karen; Mattila, Juha-Pekka; Megli, Francesco M.; Kinnunen, Paavo K. J.

    2006-01-01

    The properties of two oxidatively modified phospholipids viz. 1-palmitoyl-2-(9′-oxo-nonanoyl)-sn-glycero-3-phosphocholine (PoxnoPC) and 1-palmitoyl-2-azelaoyl-sn-glycero-3-phosphocholine (PazePC), were investigated using a Langmuir balance, recording force-area (π-A) isotherms and surface potential ψ. In mixed monolayers with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) a progressive disappearance of the liquid expanded-liquid condensed transition and film expansion was observed with increasing content of the oxidized phospholipids. The above is in agreement with fluorescence microscopy of the monolayers, which revealed an increase in the liquid expanded region of DPPC monolayers. At a critical pressure πs ∼ 42 mN/m both Poxo- and PazePC induced a deflection in the π-A isotherms, which could be rationalized in terms of reorientation of the oxidatively modified acyl chains into aqueous phase (adaptation of the so-called extended conformation), followed upon further film compression by solubilization of the oxidized phospholipids into the aqueous phase. Surface potential displayed a discontinuity at the same value of area/molecule, corresponding to the loss of the oxidized phospholipids from the monolayers. Our data support the view that lipid oxidation modifies both the small-scale structural dynamics of biological membranes as well as their more macroscopic lateral organization. Accordingly, oxidatively modified lipids can be expected to influence the organization and functions of membrane associated proteins. PMID:16581831

  1. Overpotential deposition of Ag monolayer and bilayer on Au(1 1 1) mediated by Pb adlayer underpotential deposition/stripping cycles

    NASA Astrophysics Data System (ADS)

    Wang, J. X.; Ocko, B. M.; Adzic, R. R.

    2003-08-01

    Ultra-thin Ag films on the Au(1 1 1) surface were prepared via overpotential deposition (OPD) in the presence of Pb 2+ ions. By carrying out repetitive Pb adlayer underpotential deposition (UPD) and stripping cycles during Ag bulk deposition, the two-dimensional growth of Ag films was significantly enhanced in high OPD. The Ag monolayer sample was made by comparing the voltammetry curves, in which the signatures for Pb adlayer UPD on Au(1 1 1) changed to that on Ag(1 1 1). As demonstrated by the X-ray specular reflectivity measurements, nearly complete monolayer and bilayer films can be made with optimized deposition procedures. On subatomic scale, however, we found that these films have significant higher root-mean-square displacement amplitudes than those underpotentially deposited Ag monolayer and bilayer on either Au(1 1 1) or Pt(1 1 1).

  2. 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.

  3. High sensitive self-assembled monolayer modified solid mounted resonator for organophosphate vapor detection

    NASA Astrophysics Data System (ADS)

    Wang, Jingjing; Chen, Da; Gan, Yaoguo; Sun, Xuejun; Jin, Yingying

    2011-02-01

    We fabricated a self-assembled monolayer (SAM) modified solid mounted resonator (SMR) for organophosphate vapor detection. The SMR device consisted of a piezoelectric stack and an all-metal Bragg's reflector. The electrode surface is chemically modified with a Cu2+/11-mercaptoundecanoic acid SAM to capture organophosphate compounds. After chemical modification, both the resonance frequency and the Q-factor decrease. Fourier transform infrared external reflection spectroscopy was performed to verify the formation of SAM. Adsorption of organophosphate compounds onto the SAM increases its mass, and the resonance frequency proportionally goes down. The testing results show that the modified SMR can yield a rapid, sensitive, reversible and reproducible response to nerve-agent (dimethyl methyl phosphonate) vapor. This study proves that using the SAM modified SMR to detect trace organophosphate vapor is feasibility.

  4. Comparative study of electroless copper film on different self-assembled monolayers modified ABS substrate.

    PubMed

    Xu, Jiushuai; Fan, Ruibin; Wang, Jiaolong; Jia, Mengke; Xiong, Xuanrui; Wang, Fang

    2014-04-15

    Copper films were grown on (3-Mercaptopropyl)trimethoxysilane (MPTMS), (3-Aminopropyl)triethoxysilane (APTES) and 6-(3-(triethoxysilyl)propylamino)-1,3,5- triazine-2,4-dithiol monosodium (TES) self-assembled monolayers (SAMs) modified acrylonitrile-butadiene-styrene (ABS) substrate via electroless copper plating. The copper films were examined using scanning electron microscopy (SEM) and X-ray diffraction (XRD). Their individual deposition rate and contact angle were also investigated to compare the properties of SAMs and electroless copper films. The results indicated that the formation of copper nuclei on the TES-SAMs modified ABS substrate was faster than those on the MPTMS-SAMs and APTES-SAMs modified ABS substrate. SEM images revealed that the copper film on TES-SAM modified ABS substrate was smooth and uniform, and the density of copper nuclei was much higher. Compared with that of TES-SAMs modified resin, the coverage of copper nuclei on MPTMS and APTES modified ABS substrate was very limited and the copper particle size was too big. The adhesion property test demonstrated that all the SAMs enhanced the interfacial interaction between copper plating and ABS substrate. XRD analysis showed that the copper film deposited on SAM-modified ABS substrate had a structure with Cu(111) preferred orientation, and the copper film deposited on TES-SAMs modified ABS substrate is better than that deposited on MPTMS-SAMs or APTES-SAMs modified ABS resins in electromigrtion resistance.

  5. 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.

  6. 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.

  7. 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.

  8. Adsorption geometry and electronic properties of flat-lying monolayers of tetracene on the Ag(111) surface

    NASA Astrophysics Data System (ADS)

    Zaitsev, N. L.; Nechaev, I. A.; Höfer, U.; Chulkov, E. V.

    2016-10-01

    The geometrical and electronic properties of the monolayer (ML) of tetracene (Tc) molecules on Ag(111) are systematically investigated by means of DFT calculations with the use of a localized basis set. The bridge and hollow adsorption positions of the molecule in the commensurate γ -Tc/Ag(111) are revealed to be the most stable and equally favorable irrespective to the approximation chosen for the exchange-correlation functional. The binding energy is entirely determined by the long-range dispersive interaction. The former lowest unoccupied molecular orbital remains being unoccupied in the case of γ -Tc/Ag(111) as well as in the α phase with increased coverage. The unit cell of the α phase with point-on-line registry was adapted for calculations based on the available experimental data and computed structures of the γ phase. The calculated position of the Tc/Ag(111) interface state is found to be noticeably dependent on the lattice constant of the substrate, however its energy shift with respect to the Shockley surface state of the unperturbed clean side of the slab is sensitive only to the adsorption distance and in good agreement with the experimentally measured energy shift.

  9. 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.

  10. Self-assembled Monolayer Mediated Surface Environment Modification of Poly(vinylpyrrolidone)-Coated Hollow Au-Ag Nanoshells for Enhanced Loading of Hydrophobic Drug and Efficient Multimodal Therapy.

    PubMed

    Jang, Hongje; Kim, Dong-Eun; Min, Dal-Hee

    2015-06-17

    Hollow Au-Ag bimetallic nanoshell possessing hydrophobic interior space and hydrophilic exterior surface was prepared and its application as a chemo-thermo-gene therapeutic agent based on its high payload of multiple drugs having different water solubility was demonstrated. The multifunctional drug delivery system is based on the hydrophobic interior created by the self-assembled monolayer (SAM) of hexanethiol onto the inner surface of the hollow metallic nanoshells whereas the outer surface was mostly coated by hydrophilic biocompatible polymer. The nanoshells having surface environment modified by hexanethiol SAMs provided high capacity both for hydrophilic DNAzyme (Dz) to induce gene silencing and for hydrophobic SN38 (7-ethyl-10-hydroxycamptothecin), anticancer drug. The release of the loaded Dz and SN38 was independently triggered by an acidic environment and by photothermal temperature elevation upon irradiation, respectively. The chemo-thermo-gene multitherapy based on the present nanoshells having modified surface environment showed high efficacy in quantitative cell-based assays using Huh7 human liver cell containing hepatitis C viral NS3 gene replicon RNA.

  11. 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)

  12. Electrochemical sensor for immunoassay of carcinoembryonic antigen based on thionine monolayer modified gold electrode.

    PubMed

    Dai, Zong; Chen, Jin; Yan, Feng; Ju, Huangxian

    2005-01-01

    A sensor based on thionine monolayer modified gold electrode for determination of carcinoembryonic antigen (CEA) in human serum is proposed. The sensor is prepared by covalently binding thionine to a cysteamine self-assembled monolayer with p-phthaloyl chloride as a linkage, which gives a surface coverage of 8.97+/-3.28 x 10(-12)mol/cm(2) for thionine. The electrochemistry of the immobilized thionine displays a surface-controlled electrode process with an average electron transfer rate constant of 1.47+/-0.84 s(-1). Based on an electrochemical enzyme-linked immunoassay by using the immobilized thionine as an electron transfer mediator between the electrode and the horseradish peroxidase (HRP) labeled anti-CEA antibody, a calibration curve with two linear ranges from 0.6 to 17 and 17 to 200 ng/mL and a detection limit of 0.2 ng/mL for CEA determination is obtained in pH 4.2 PBS containing 2.0 mmol/L H(2)O(2) and 0.5 mol/L NaCl. The sensor shows a good accuracy. The precision and reproducibility are acceptable with the intra-assay CV of 4.9% and 5.9% at 10 and 100 ng/mL CEA concentrations, respectively, and the inter-assays CV of 7.8% at 100 ng/mL CEA. The response of thionine modified electrode shows only 1.6% decrease after 100 replicate measurements and the storage stability is acceptable in a pH 7.0 PBS at 4 degrees C for 1 week. The method avoids the addition of electron transfer mediator to the solution, thus is much simpler. The proposed method would be valuable for the diagnosis and monitoring of carcinoma and its metastasis.

  13. 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…

  14. A perfect wetting of Mg monolayer on Ag(111) under atomic scale investigation: First principles calculations, scanning tunneling microscopy, and Auger spectroscopy.

    PubMed

    Migaou, Amani; Sarpi, Brice; Guiltat, Mathilde; Payen, Kevin; Daineche, Rachid; Landa, Georges; Vizzini, Sébastien; Hémeryck, Anne

    2016-05-21

    First principles calculations, scanning tunneling microscopy, and Auger spectroscopy experiments of the adsorption of Mg on Ag(111) substrate are conducted. This detailed study reveals that an atomic scale controlled deposition of a metallic Mg monolayer perfectly wets the silver substrate without any alloy formation at the interface at room temperature. A liquid-like behavior of the Mg species on the Ag substrate is highlighted as no dot formation is observed when coverage increases. Finally a layer-by-layer growth mode of Mg on Ag(111) can be predicted, thanks to density functional theory calculations as observed experimentally.

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

    PubMed

    Chen, Zhi; Klyatskaya, Svetlana; Urgel, José I; Écija, David; Fuhr, Olaf; Auwärter, Willi; Barth, Johannes V; Ruben, Mario

    2015-01-01

    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.

  16. 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.

  17. Enzyme monolayer- and bilayer-modified tin oxide electrodes for the determination of hydrogen peroxide and glucose

    SciTech Connect

    Tatsuma, Tetsu; Okawa, Yusuke; Watanabe, Tadashi )

    1989-11-01

    An enzyme-based amperometric biosensor for hydrogen peroxide was developed, employing a horseradish peroxidase (HRP) monolayer covalently attached to a tin oxide electrode and a dissolved electron mediator. The sensor can determine hydrogen peroxide at levels down to 10{sup {minus}8} M and can be applied to a flow system. Stability of the electrode, kinetics of the surface process, and the efficiencies of different mediators were studied. As an extension, glucose oxidase (GOx) was chemically bound to the HRP-modified electrode. A GOx/HRP bilayer-modified electrode thus obtained exhibits much better performance in glucose detection limit, sensitivity, and response speed than previously reported GOx monolayer-modified electrodes.

  18. Improved DET communication between cellobiose dehydrogenase and a gold electrode modified with a rigid self-assembled monolayer and green metal nanoparticles: The role of an ordered nanostructuration.

    PubMed

    Bollella, P; Mazzei, F; Favero, G; Fusco, G; Ludwig, R; Gorton, L; Antiochia, R

    2017-02-15

    Efficient direct electron transfer (DET) between cellobiose dehydrogenase from Corynascus thermophilus (CtCDH) and a novel gold electrode platform, obtained by covalent linking of green AuNPs and AgNPs modified with a dithiol self-assembled monolayer, consisting of biphenyl-4,4'-dithiol (BPDT), was presented. The green AuNPs and AgNPs were synthesized using quercetin as reducing agent at room temperature. TEM experiments showed that the AuNPs and AgNPs were circular in shape with an average diameter of 5 and 8nm, respectively. Cyclic voltammetry of CtCDH immobilized onto the AuNPs/BPDT/AuE and the AgNPs/BPDT/AuE electrode platforms were carried out and compared with naked AuE, BPDT/AuE, AuNPs/AuE, and AgNPs/AuE. A pair of well-defined redox waves in neutral pH solution due to efficient DET of CtCDH was present with both MNPs/BPDT/AuE platforms. No DET communication was found with platforms without MNPs linked to BPDT. The apparent heterogeneous electron transfer rate constants (kS) of CtCDH were calculated to be 21.5±0.8s(-1) and 10.3±0.7s(-1), for the AuNPs/BPDT/AuE and the AgNPs/BPDT/AuE platforms, respectively. The modified electrodes were successively used to develop an eco-friendly biosensor for lactose detection. The CtCDH/AuNPs/BPDT/AuE based biosensor showed the best analytical performances with an excellent stability, a detection limit of 3µM, a linear range between 5 and 400µM and a sensitivity of 27.5±2.5µAcm(-2)mM(-1). Such performances were favorably compared with other lactose biosensors reported in literature. The biosensor was successively tested to quantify lactose content in real milk and cream samples. No significant interference present in the sample matrices was observed.

  19. 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

    2016-09-06

    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.

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

    SciTech Connect

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

    2016-09-06

    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.

  1. Improving performance, stability, and processability of OFETs with printed Ag electrodes by means of a novel, multipurpose self-assembled monolayer (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Alt, Milan; Jesper, Malte; Schinke, Janusz; Hillebrandt, Sabina; Reiser, Patrick; Rödlmeier, Tobias; Angelova, Iva; Hamburger, Manuel; Lemmer, Ulrich; Hernandez-Sosa, Gerardo; Lovrincic, Robert

    2016-11-01

    We present a novel SAM-forming molecule bisjulolidyldisulfide that reduces the WF of metal surfaces by 1.2 eV and can lower the barrier for electron injection to organic semiconductors. Applied to Au and Ag surfaces, including inkjet-printed Ag on PET, we characterized bisjulolidyldisulfide monolayers by means of photoelectron spectroscopy (PES) and sessile drop technique, as well as their influence on the performance of n-type OFETs. Next a strong reduction of the contact resistance by two orders of magnitude, we found that this SAM treatment extends the shelf lifetime of ambient-stored OFET devices. Also, it improves the wettability and thereby facilitates solution processing of a subsequent layer with respect to the untreated surface. The full electrical functionality of bisjulolidyldisulfide SAMs was found to become manifest with only one minute of immersion in ethanol solution. PES measurements suggests that the surface coverage is thorough on Au, but only fractional on Ag, especially on printed Ag. However, the quality of SAM-treated bottom contacts in n-type OFETs is very similar for all three investigated metal surfaces (Au and Ag evaporated and printed Ag). This is especially important for printed Ag-electrodes, as their surface was found to be significantly worse for device performance in comparison to their evaporated Ag counterpart. Using this surface treatment we realized integrated unipolar n-type ring oscillators with inkjet printed Ag electrodes.

  2. Direct Electron Transfer of Hemoglobin on Manganese III Oxide-Ag Nanofibers Modified Glassy Carbon Electrode

    PubMed Central

    Negahdary, Masoud; Mazaheri, Gholamreza; Rad, Somyyeh; Hadi, Mohammadreza; Malekzadeh, Roya; Saadatmand, Mohammad Mahdi; Rezaei-Zarchi, Saeed; Pishbin, Fariba; Khosravian-hemami, Mojdeh

    2012-01-01

    We investigated the electrochemical behavior of hemoglobin by glassy carbon electrode modified with Mn2O3-Ag nanofibers. The Mn2O3-Ag nanofibers were used as facilitator electron transfer between Hb and glassy-carbon-modified electrode. The Mn2O3-Ag nanofibers are studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The hemoglobin showed a quasireversible electrochemical redox behavior with a formal potential of −49 mV (versus Ag/AgCl) in 0.1 M potassium phosphate buffer solution at pH 7.0. The designed biosensor possesses good stability and reproducibility and achieves 95% of the steady-state current in less than five seconds. PMID:22550487

  3. MIES investigation of alkanethiol monolayers self-assembled on Au(111) and Ag(111) surfaces

    NASA Astrophysics Data System (ADS)

    Heinz, Bertram; Morgner, Harald

    1997-02-01

    Self-assembled monolayers of alkanethiols (SH(CH 2) mCH 3, m=7,8,9,11,15,17) have been prepared to study their electronic properties by means of metastable induced electron spectroscopy (MIES). The thermal metastable helium atoms used as projectiles in this technique interact exclusively with molecular orbitals exposed at the top of the film, which makes the method perfectly surface sensitive. Access of metastable helium atoms to the methyl group or to the CH 2-groups of the alkyl chain depends strongly on the orientation of the molecular axis. The MIE-spectrum of nonanethiol on Au(111) and the MIE-spectrum of hexadecane physisorbed on graphite served as references for upright aligned and flat lying alkyl chains. Both MIE-spectra can be related to the electronic bandstructure of polyethylene. Electron emission originating from the upright methyl groups and flat lying CH 2-groups is distinguished by characteristic intensities in the MIE-spectra. On this basis, a quantity R has been introduced as a measure for the molecular orientation of the alkyl chain at the top surface of the films. The evolution of R with respect to different molecular assemblies of the alkyl chains is consistent with XPS, LEED and UPS results. Within the series of dense and ordered alkanethiol films on gold and silver R decreases monotonously upon increasing the alkyl chain length. This behaviour indicates either the emergence of CH 2-groups at the cost of methyl groups at the top surface or a decreasing degree of orientational order of the methyl groups or both in the case of longer alkyl chains.

  4. Copper Contamination of Self-Assembled Organic Monolayer Modified Silicon Surfaces Following a "Click" Reaction Characterized with LAPS and SPIM.

    PubMed

    Wu, Fan; Zhang, De-Wen; Wang, Jian; Watkinson, Michael; Krause, Steffi

    2017-04-04

    A copper(I)-catalyzed azide alkyne cycloaddition (CuAAC) reaction combined with microcontact printing was used successfully to pattern alkyne-terminated self-assembled organic monolayer-modified silicon surfaces. Despite the absence of a copper peak in X-ray photoelectron spectra, copper contamination was found and visualized using light-addressable potentiometric sensors (LAPS) and scanning photo-induced impedance microscopy (SPIM) after the "click"-modified silicon surfaces were rinsed with hydrochloric acid (HCl) solution, which was frequently used to remove copper residues in the past. Even cleaning with an ethylenediaminetetraacetic acid (EDTA) solution did not remove the copper residue completely. Different strategies for avoiding copper contamination, including the use of bulky chelators for the copper(I) catalyst and rinsing with different reagents, were tested. Only cleaning of the silicon surfaces with an EDTA solution containing trifluoroacetic acid (TFA) after the click modification proved to be an effective method as confirmed by LAPS and SPIM results, which showed the expected potential shift due to the surface charge introduced by functional groups in the monolayer and allowed, for the first time, imaging the impedance of an organic monolayer.

  5. Self-assembled monolayer modified MoO3/Au/MoO3 multilayer anodes for high performance OLEDs

    NASA Astrophysics Data System (ADS)

    Jeong, Daekyun; Lim, Chefwi; Kim, Myeonggi; Jeong, Kyunghoon; Kim, Jae-Hun; Kim, Jiyoung; Park, Jin-Goo; Min, Kyeong-Sik; Lee, Jaegab

    2017-01-01

    We control the work function and the surface energy of the MoO3/Au/MoO3 (MAM) anode of OLEDs by modifying the top MoO3 layer via vapor phase deposition. The performance and stability of the device are significantly altered depending on the dipole direction of the selfassembled monolayer (SAM) with permanent dipole moment inserted between N,N'-Bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine (NPB) film and a MAM anode as well as on the interfacial wetting between the SAM and NPB layer. A CF3-terminated monolayer on a MAM electrode improved the performance and stability of the OLEDs relative to a reference device with only a MAM electrode, demonstrating that coating with SAMs via vapor phase deposition is an effective method to engineer the interface of MAM electrode optoelectronic devices. [Figure not available: see fulltext.

  6. Synthesis of Ag2O and Ag co-modified flower-like SnS2 composites with enhanced photocatalytic activity under solar light irradiation

    NASA Astrophysics Data System (ADS)

    Deng, Lu; Zhu, Zhenfeng; Liu, Liu; Liu, Hui

    2017-01-01

    Three-dimensional Ag2O and Ag co-modified flower-like SnS2 composites have been synthesized through a facile hydrothermal and photoreduction process. The physical and chemical properties of Ag2O and Ag co-modified flower-like SnS2 composites were carefully studied by using XRD, SEM, TEM, UV-vis diffuse reflectance spectra (DRS) and XPS. The photocatalytic activity of the as-prepared products was evaluated by photocatalytic decolorization of Rhodamine B (Rh B) aqueous solution at ambient temperature under solar light irradiation. The photocatalytic result shows that Ag2O and Ag co-modified flower-like SnS2 composites exhibit enhanced photocatalytic activity compared with that of pure SnS2. Three of the Ag2O and Ag co-modified flower-like SnS2 composites form the Z-scheme systems, because of their unique charge-carrier transfer process, the oxidation/reduction ability of photogenerated holes and electrons could be enhanced. Therefore, the new Ag2O and Ag co-modified flower-like SnS2 composites possess a favorable photocatalytic activity, and it can be a promising candidate for the solar energy conversion process.

  7. 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

  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. Scalable Synthesis of Ag Networks with Optimized Sub-monolayer Au-Pd Nanoparticle Covering for Highly Enhanced SERS Detection and Catalysis

    PubMed Central

    Li, Tianyu; Vongehr, Sascha; Tang, Shaochun; Dai, Yuming; Huang, Xiao; Meng, Xiangkang

    2016-01-01

    Highly porous tri-metallic AgxAuyPdz networks with a sub-monolayer bimetallic Au-Pd nanoparticle coating were synthesized via a designed galvanic replacement reaction of Ag nanosponges suspended in mixed solutions of HAuCl4 and K2PdCl4. The resulting networks’ ligaments have a rough surface with bimetallic nanoparticles and nanopores due to removal of Ag. The surface morphology and composition are adjustable by the temperature and mixed solutions’ concentration. Very low combined Au and Pd atomic percentage (1−x) where x is atomic percentage of Ag leads to sub-monolayer nanoparticle coverings allowing a large number of active boundaries, nanopores, and metal-metal interfaces to be accessible. Optimization of the Au/Pd atomic ratio y/z obtains large surface-enhanced Raman scattering detection sensitivity (at y/z = 5.06) and a higher catalytic activity (at y/z = 3.55) toward reduction reactions as benchmarked with 4-nitrophenol than for most bimetallic catalysts. Subsequent optimization of x (at fixed y/z) further increases the catalytic activity to obtain a superior tri-metallic catalyst, which is mainly attributed to the synergy of several aspects including the large porosity, increased surface roughness, accessible interfaces, and hydrogen absorption capacity of nanosized Pd. This work provides a new concept for scalable synthesis and performance optimization of tri-metallic nanostructures. PMID:27845400

  10. Scalable Synthesis of Ag Networks with Optimized Sub-monolayer Au-Pd Nanoparticle Covering for Highly Enhanced SERS Detection and Catalysis

    NASA Astrophysics Data System (ADS)

    Li, Tianyu; Vongehr, Sascha; Tang, Shaochun; Dai, Yuming; Huang, Xiao; Meng, Xiangkang

    2016-11-01

    Highly porous tri-metallic AgxAuyPdz networks with a sub-monolayer bimetallic Au-Pd nanoparticle coating were synthesized via a designed galvanic replacement reaction of Ag nanosponges suspended in mixed solutions of HAuCl4 and K2PdCl4. The resulting networks’ ligaments have a rough surface with bimetallic nanoparticles and nanopores due to removal of Ag. The surface morphology and composition are adjustable by the temperature and mixed solutions’ concentration. Very low combined Au and Pd atomic percentage (1‑x) where x is atomic percentage of Ag leads to sub-monolayer nanoparticle coverings allowing a large number of active boundaries, nanopores, and metal-metal interfaces to be accessible. Optimization of the Au/Pd atomic ratio y/z obtains large surface-enhanced Raman scattering detection sensitivity (at y/z = 5.06) and a higher catalytic activity (at y/z = 3.55) toward reduction reactions as benchmarked with 4-nitrophenol than for most bimetallic catalysts. Subsequent optimization of x (at fixed y/z) further increases the catalytic activity to obtain a superior tri-metallic catalyst, which is mainly attributed to the synergy of several aspects including the large porosity, increased surface roughness, accessible interfaces, and hydrogen absorption capacity of nanosized Pd. This work provides a new concept for scalable synthesis and performance optimization of tri-metallic nanostructures.

  11. Optical properties of a-C:H thin films modified by Ti and Ag

    NASA Astrophysics Data System (ADS)

    Prikhodko, Oleg Yu.; Mikhailova, Svetlana L.; Mukhametkarimov, Ershan C.; Maksimova, Suyumbika Ya.; Manabaev, Nurlan K.; Dauthan, Kuanysh

    2016-09-01

    Structure and optical properties of amorphous diamond-like carbon (a-C: H) thin films modified with Ag, Ti and Ag + Ti metal impurities are studied. The films were prepared by ion-plasma magnetron sputtering of combined polycrystalline graphite and metal target in the mixture of Ar and CH4 gases. AFM, SEM and TEM methods show that a-C:H<Ag+Ti> films are heterogeneous, nanostructured and characterized by the presence of silver nanoclusters on the surface sized 60 nm and both Ti and Ag nanoclusters with a mean size (2 ÷ 3) nm in the bulk of films. It was found that in a- C:H<Ag+Ti> films as well as in a-C:H<Ag> films plasma resonance absorption due to excitation of surface plasmons in silver nanoclusters in the visible region of spectrum takes place. Intensity of the resonance absorption in the a- C:H<Ag+Ti> films increases with increase in concentration of silver. The results are important for produce of nanomaterials with nonlinear optical properties based on the amorphous diamond-like carbon films containing metal nanoclusters.

  12. Alkaline phosphatase based amperometric biosensor immobilized by cysteamine-glutaraldehyde modified self-assembled monolayer.

    PubMed

    Yorganci, Emine; Akyilmaz, Erol

    2011-10-01

    Alkaline phosphatase (ALP) was immobilized with cross-linking agents glutaraldehyde and cysteamine by forming a self-assembled monolayer on a screen printed gold electrode. ALP converts p-nitrophenyl phosphate to p-nitrophenol and phosphate. p-Nitrophenol loses H(+) ion and turns into the negatively charged compound p-nitrophenolate at medium pH. As a result, the unstable product formed is measured chronoamperometrically at an application potential of + 0.95 V. The biosensor response depends linearly on p-nitrophenyl phosphate concentration between 0.05 - 0.6 mM with a response time of 40 seconds. Detection limit of the biosensor is 0.033 mM.

  13. Multifold Electrical Conductance Enhancements at Metal-Bismuth Telluride Interfaces Modified Using an Organosilane Monolayer.

    PubMed

    Cardinal, Thomas; Kwan, Matthew; Borca-Tasciuc, Theodorian; Ramanath, Ganpati

    2017-01-25

    Controlling electrical transport across metal-thermoelectric interfaces is key to realizing high efficiency devices for solid state refrigeration and waste-heat harvesting. We obtain up to 17-fold increases in electrical contact conductivity Σc by inserting a mercaptan-terminated organosilane monolayer at Cu-Bi2Te3 and Ni-Bi2Te3 interfaces, yielding similar Σc for both metals by offsetting an otherwise 7-fold difference. The Σc improvements are underpinned by silane-moiety-induced inhibition of Cu diffusion, promotion of high-conductivity interfacial nickel telluride formation, and mercaptan-induced reduction of Bi2Te3 surface oxides. Our findings should enable incorporating nanomolecular layers with appropriately chosen terminal moieties in thermoelectric device metallization schemes without metal diffusion barriers.

  14. 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...

  15. 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.

  16. Super-Hydrophobic/Icephobic Coatings Based on Silica Nanoparticles Modified by Self-Assembled Monolayers

    PubMed Central

    Liu, Junpeng; Janjua, Zaid A.; Roe, Martin; Xu, Fang; Turnbull, Barbara; Choi, Kwing-So; Hou, Xianghui

    2016-01-01

    A super-hydrophobic surface has been obtained from nanocomposite materials based on silica nanoparticles and self-assembled monolayers of 1H,1H,2H,2H-perfluorooctyltriethoxysilane (POTS) using spin coating and chemical vapor deposition methods. Scanning electron microscope images reveal the porous structure of the silica nanoparticles, which can trap small-scale air pockets. An average water contact angle of 163° and bouncing off of incoming water droplets suggest that a super-hydrophobic surface has been obtained based on the silica nanoparticles and POTS coating. The monitored water droplet icing test results show that icing is significantly delayed by silica-based nano-coatings compared with bare substrates and commercial icephobic products. Ice adhesion test results show that the ice adhesion strength is reduced remarkably by silica-based nano-coatings. The bouncing phenomenon of water droplets, the icing delay performance and the lower ice adhesion strength suggest that the super-hydrophobic coatings based on a combination of silica and POTS also show icephobicity. An erosion test rig based on pressurized pneumatic water impinging impact was used to evaluate the durability of the super-hydrophobic/icephobic coatings. The results show that durable coatings have been obtained, although improvement will be needed in future work aiming for applications in aerospace. PMID:28335360

  17. 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.

  18. Electron Transfer Mechanism in Gold Surface Modified with Self-Assembly Monolayers from First Principles

    NASA Astrophysics Data System (ADS)

    Lima, Filipe C. D. A.; Iost, Rodrigo M.; Crespilho, Frank N.; Caldas, Marília J.; Calzolari, Arrigo; Petrilli, Helena M.

    2013-03-01

    We report the investigation of electron tunneling mechanism of peptide ferrocenyl-glycylcystamine self-assembled monolayers (SAMs) onto Au (111) electrode surfaces. Recent experimental investigations showed that electron transfer in peptides can occur across long distances by separating the donor from the acceptor. This mechanism can be further fostered by the presence of electron donor terminations of Fc terminal units on SAMs but the charge transfer mechanism is still not clear. We study the interaction of the peptide ferrocenyl-glycylcystamine on the Au (111) from first principles calculations to evaluate the electron transfer mechanism. For this purpose, we used the Kohn Sham (KS) scheme for the Density Functional Theory (DFT) as implemented in the Quantum-ESPRESSO suit of codes, using Vandebilt ultrasoft pseudopotentials and GGA-PBE exchange correlation functional to evaluate the ground-state atomic and electronic structure of the system. The analysis of KS orbital at the Fermi Energy showed high electronic density localized in Fc molecules and the observation of a minor contribution from the solvent and counter ion. Based on the results, we infer evidences of electron tunneling mechanism from the molecule to the Au(111). We acknowledge FAPESP for grant support. Also, LCCA/USP, RICE and CENAPAD for computational resources.

  19. Photoinduced anisotropy of second-harmonic generation from azobenzene-modified alkylsiloxane monolayers

    NASA Astrophysics Data System (ADS)

    Yi, Y. W.; Furtak, T. E.; Farrow, M. J.; Walba, D. M.

    2003-09-01

    Noncontact alignment of liquid crystal displays offers the advantage of reduced contamination and minimal surface charging. This approach also provides a means of reversible alignment after a device has been assembled. With this objective we have synthesized self-assembled monolayers based on dimethylaminoazobenzene units covalently attached to a glass surface by means of a short alkylsiloxane anchor, a derivatized version of methyl red (d-MR). The resulting architecture favors an orientation in which the axis of the azobenzene group should be nearly parallel to the surface with an isotropic azimuthal distribution. Under illumination with polarized light the trans-cis isomerization and subsequent relaxation serves to wiggle the molecule into an orientation perpendicular to the treatment polarization. We have tested this scenario using optical second harmonic generation and supporting optical techniques. We are able to identify a surface order parameter that characterizes the photoalignment of the azobenzene group, and have shown that the treatment illumination promotes the formation of H aggregates of the azobenzene species. We have also demonstrated that the treated d-MR layer successfully aligns a nematic liquid crystal.

  20. 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.

  1. An efficient visible-light photocatalyst prepared by modifying AgBr particles with a small amount of activated carbon

    SciTech Connect

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

    2016-04-15

    Highlights: • An efficient visible-light photocatalyst was prepared by modifying AgBr particles. • A small amount of activated carbon was used to modify AgBr particles. • The modified AgBr exhibited improved visible-light photocatalytic performances. - Abstract: An efficient visible-light photocatalyst was successfully prepared by modifying AgBr particles with a small amount of activated carbon (AC) via a simple chemical precipitation approach. The AC/AgBr composite was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, UV–vis diffuse reflection spectroscopy, photoluminescence spectroscopy, electrochemical impedance spectroscopy. The photocatalytic performances of the AC/AgBr composite were investigated by evaluating photodegradation of methyl orange (MO) and phenol under visible light irradiation, and the effects of the AC content in the composite, concentrations of AC/AgBr composite and MO, carrier scavengers on MO photodegradation rate were systematically investigated. The results indicated that the modification of AC can hardly change the crystalline and crystal size of AgBr particles, while significantly improve their specific surface areas, visible-light absorption and separation efficiency of photogenerated electron–hole pairs. Compared with pure AgBr, the AC/AgBr composite exhibited drastically enhanced visible-light photocatalytic activity and stability. The photogenerated electrons and holes, hydroxyl radicals are responsible to the photodegradation of organic pollutants, and the photogenerated holes are the main active species. On the basis of the results and the properties of AC and AgBr, the visible-light photocatalytic mechanism of the AC/AgBr composite was discussed.

  2. 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.

  3. Ag Nanoparticles-Modified 3D Graphene Foam for Binder-Free Electrodes of Electrochemical Sensors

    PubMed Central

    Han, Tao; Jin, Jianli; Wang, Congxu; Sun, Youyi; Zhang, Yinghe; Liu, Yaqing

    2017-01-01

    Ag nanoparticles-modified 3D graphene foam was synthesized through a one-step in-situ approach and then directly applied as the electrode of an electrochemical sensor. The composite foam electrode exhibited electrocatalytic activity towards Hg(II) oxidation with high limit of detection and sensitivity of 0.11 µM and 8.0 µA/µM, respectively. Moreover, the composite foam electrode for the sensor exhibited high cycling stability, long-term durability and reproducibility. These results were attributed to the unique porous structure of the composite foam electrode, which enabled the surface of Ag nanoparticles modified reduced graphene oxide (Ag NPs modified rGO) foam to become highly accessible to the metal ion and provided more void volume for the reaction with metal ion. This work not only proved that the composite foam has great potential application in heavy metal ions sensors, but also provided a facile method of gram scale synthesis 3D electrode materials based on rGO foam and other electrical active materials for various applications. PMID:28336878

  4. Ag Nanoparticles-Modified 3D Graphene Foam for Binder-Free Electrodes of Electrochemical Sensors.

    PubMed

    Han, Tao; Jin, Jianli; Wang, Congxu; Sun, Youyi; Zhang, Yinghe; Liu, Yaqing

    2017-02-16

    Ag nanoparticles-modified 3D graphene foam was synthesized through a one-step in-situ approach and then directly applied as the electrode of an electrochemical sensor. The composite foam electrode exhibited electrocatalytic activity towards Hg(II) oxidation with high limit of detection and sensitivity of 0.11 μM and 8.0 μA/μM, respectively. Moreover, the composite foam electrode for the sensor exhibited high cycling stability, long-term durability and reproducibility. These results were attributed to the unique porous structure of the composite foam electrode, which enabled the surface of Ag nanoparticles modified reduced graphene oxide (Ag NPs modified rGO) foam to become highly accessible to the metal ion and provided more void volume for the reaction with metal ion. This work not only proved that the composite foam has great potential application in heavy metal ions sensors, but also provided a facile method of gram scale synthesis 3D electrode materials based on rGO foam and other electrical active materials for various applications.

  5. Electrochemical reduction of CO2 to ethylene glycol on imidazolium ion-terminated self-assembly monolayer-modified Au electrodes in an aqueous solution.

    PubMed

    Tamura, Jun; Ono, Akihiko; Sugano, Yoshitsune; Huang, Chingchun; Nishizawa, Hideyuki; Mikoshiba, Satoshi

    2015-10-21

    Imidazolium ion-terminated self-assembled monolayer (SAM)-modified electrodes achieve CO2 conversion while suppressing hydrogen evolution. Immobile imidazolium ion on gold (Au) electrodes reduce CO2 at low overpotential. The distance between electrode and imidazolium ion separated by alkane thiol affects CO2 reduction activity. CO2 reduction current depends on the tunnel current rate. Although the product of CO2 reduction at the bare Au electrode is CO, SAM-modified electrodes produce ethylene glycol in aqueous electrolyte solution without CO evolution. The faradaic efficiency reached a maximum of 87%. CO2 reduction at SAM-modified electrodes is unaffected by reduction activity of Au electrode. This phenomenon shows that the reaction field of CO2 reduction is not the electrode surface but the imidazolium ion monolayer.

  6. Monolayer anthracene and anthraquinone modified electrodes as platforms for Trametes hirsuta laccase immobilisation.

    PubMed

    Sosna, Maciej; Chrétien, Jean-Mathieu; Kilburn, Jeremy D; Bartlett, Philip N

    2010-09-14

    Surface modification techniques are essential to the construction of enzyme based elements of biofuel cells and biosensors. In this article we report on the preparation and characterisation of modified carbon electrodes which were used as supports for the immobilisation of laccase from Trametes hirsuta. The electrodes were electrochemically modified with diamine or diazonium linkers followed by attachment of either anthracene or anthraquinone head groups using solid phase chemical methodology. These well defined surfaces were found to effectively bind laccase and to provide direct electrical contact to the enzyme active site, as evidenced by XPS, EIS and voltammetry, respectively. The influence of the type of linker and head group on enzyme binding and bioelectrocatalytic activity are evaluated.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. Sensitive detection of clozapine using a gold electrode modified with 16-mercaptohexadecanoic acid self-assembled monolayer.

    PubMed

    Huang, Fei; Qu, Song; Zhang, Song; Liu, Baohong; Kong, Jilie

    2007-04-30

    Clozapine, an effective antipsychotic drug, was found generating a pair of redox peaks at about 0.33-0.4V (versus SCE) at 16-mercaptohexadecanoic acid (i.e. MHA) self-assembled monolayer (SAM) modified gold electrode (i.e. MHA/Au) in 0.05molL(-1) Tris-HCl (pH 8.1) buffer solution. Sensitive and quantitative measurement of clozapine based on anodic peak was established under optimum conditions. The anodic peak current was linear to clozapine concentration in the range from 1x10(-6) to 5x10(-5)molL(-1) with the detection limit of 7x10(-9)molL(-1). This method was successfully applied to the detection of clozapine in drug tablets and proved to be reliable compared with ultraviolet spectrophotometry (UV). The MHA SAM was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), contact angle goniometry, electrochemical impedance spectroscopy (EIS) and electrochemical probe.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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

  20. Hybrid opto-chemical doping in Ag nanoparticle-decorated monolayer graphene grown by chemical vapor deposition probed by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Maiti, R.; Haldar, S.; Majumdar, D.; Singha, A.; Ray, S. K.

    2017-02-01

    The novel opto-chemical doping effect in Ag nanoparticle-decorated monolayer graphene grown by chemical vapor deposition has been investigated using Raman spectroscopy for the first time. We used both noble metal nanoparticles and optical excitation, in a hybrid opto-chemical route, to tune the doping level in graphene. Metal nanoparticle-induced chemical effects and laser power-induced substrate effects alter the doping nature of graphene from p- to n-type. Compared with earlier studies, the proposed method significantly lowers the laser intensity required for optical power-dependent doping, resulting in prevention of damage to the sample due to local heating. Some other interesting observations are the enhanced peak intensity in the Raman spectrum of graphene, enhancement of the D-band intensity and the introduction of G-band splitting. This novel, cheap and easily implemented hybrid optical-chemical doping strategy could be very useful for tuning graphene plasmons on the widely used Si/SiO2 substrates for various photonic device applications.

  1. Hybrid opto-chemical doping in Ag nanoparticle-decorated monolayer graphene grown by chemical vapor deposition probed by Raman spectroscopy.

    PubMed

    Maiti, R; Haldar, S; Majumdar, D; Singha, A; Ray, S K

    2017-02-17

    The novel opto-chemical doping effect in Ag nanoparticle-decorated monolayer graphene grown by chemical vapor deposition has been investigated using Raman spectroscopy for the first time. We used both noble metal nanoparticles and optical excitation, in a hybrid opto-chemical route, to tune the doping level in graphene. Metal nanoparticle-induced chemical effects and laser power-induced substrate effects alter the doping nature of graphene from p- to n-type. Compared with earlier studies, the proposed method significantly lowers the laser intensity required for optical power-dependent doping, resulting in prevention of damage to the sample due to local heating. Some other interesting observations are the enhanced peak intensity in the Raman spectrum of graphene, enhancement of the D-band intensity and the introduction of G-band splitting. This novel, cheap and easily implemented hybrid optical-chemical doping strategy could be very useful for tuning graphene plasmons on the widely used Si/SiO2 substrates for various photonic device applications.

  2. Thermoelectric Generators from AgBiTe and AgSbTe Thin Films Modified by High-Energy Beam

    NASA Astrophysics Data System (ADS)

    Budak, S.; Guner, S.; Muntele, C.; Ila, D.

    2015-06-01

    The ternary chalcogenides AgBiTe2 and AgSbTe2 belong to the family of semiconductors with disordered NaCl cubic structure in which Ag and Sb occupy metal sublattices. Both compounds are very interesting due to their thermoelectric properties. We have grown single-layer AgBiTe and AgSbTe thin films on silicon (Si) and fused silica (Suprasil) substrates using electron beam deposition. High-energy (MeV) Si-ion bombardment was performed on the thin-film samples at five different fluences between 5 × 1013 ions/cm2 and 7 × 1015 ions/cm2. We have measured the thermoelectric efficiency (figure of merit, ZT) of the fabricated thermoelectric devices by measuring the cross-plane thermal conductivity using the third-harmonic (3 ω) method, the cross-plane Seebeck coefficient, and the in-plane electrical conductivity using the van der Pauw method before and after MeV Si-ion bombardment. Rutherford backscattering spectrometry and the Rutherford Universal Manipulation Program (RUMP) simulation package were used to analyze the elemental composition and thickness of the deposited materials on the substrates. The RUMP simulation gave thicknesses for the AgBiTe and AgSbTe thin films of 270 nm and 188 nm, respectively. The figure of merit for AgBiTe started to decrease from the value of 0.37 for the virgin sample after bombardment. We saw similar decreasing behavior for the AgSbTe thin-film system. The figure of merit for AgSbTe started to decrease from the value of 0.88 for the virgin sample after bombardment. MeV Si-ion bombardment caused changes in the thermoelectric properties of the thin films.

  3. Electrochemical and vibrational spectroscopic studies of coadsorption: Formation of mixed monolayers of methylene blue and long-chain dithioethers at sulfur-modified polycrystalline gold surfaces

    SciTech Connect

    Barner, B.J.; Corn, R.M. )

    1990-05-01

    Molecular conformation and order within mixed monolayers of methylene blue, sulfide, and the long-chain dithioether C{sub 14}H{sub 29}SC{sub 2}H{sub 4}SC{sub 14}H{sub 29} adsorbed onto polycrystalline evaporated gold films are studied by using electrochemical methods and ex situ vibrational spectroscopy. The methylene blue dye molecules directly chemisorb onto the sulfur-modified gold surface and do not significantly partition into the alkyl portions of the monolayer. However, upon reduction to leucomethylene blue, the dye molecules do partition into the alkyl subphase. Repeated electrochemical reduction and oxidation of the chemisorbed methylene blue result in an ordering of the adsorbed alkyl chains from a liquid-like structure to a close-packed configuration. The presence of a partial dithioether monolayer also leads to the formation of a stabilized leucomethylene blue film. The variations of the molecular structure observed in these mixed systems arise from the competing processes of chemisorption, aggregation, and hydrophobic solubilization occurring within the thin film.

  4. Determination of anthracene on Ag-Au alloy nanoparticles/overoxidized-polypyrrole composite modified glassy carbon electrodes.

    PubMed

    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 AgNO(3) and HAuCl(4) using C(6)H(5)O(7)Na(3) 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.

  5. 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.

  6. Effect of Time and Deposition Method on Quality of Phosphonic Acid Modifier Self-Assembled Monolayers on Indium Zinc Oxide

    SciTech Connect

    Sang, Lingzi; Knesting, Kristina M.; Bulusu, Anuradha; Sigdel, Ajaya K.; Giordano, Anthony J.; Marder, Seth R.; Berry, Joseph J.; Graham, Samuel; Ginger, David S.; Pemberton, Jeanne E.

    2016-12-15

    Phosphonic acid (PA) self-assembled monolayers (SAMs) are utilized at critical interfaces between transparent conductive oxides (TCO) and organic active layers in organic photovoltaic devices (OPVs). The effects of PA deposition method and time on the formation of close-packed, high-quality monolayers is investigated here for SAMs fabricated by solution deposition, micro-contact printing, and spray coating. The solution deposition isotherm for pentafluorinated benzylphosphonic acid (F5BnPA) on indium-doped zinc oxide (IZO) is studied using polarization modulation-infrared reflection-absorption spectroscopy (PM-IRRAS) at room temperature as a model PA/IZO system. Fast surface adsorption occurs within the first min; however, well-oriented high-quality SAMs are reached only after -48 h, presumably through a continual process of molecular adsorption/desorption and monolayer filling accompanied by molecular reorientation. Two other rapid, soak-free deposition techniques, micro-contact printing and spray coating, are also explored. SAM quality is compared for deposition of phenyl phosphonic acid (PPA), F13-octylphosphonic acid (F13OPA), and pentafluorinated benzyl phosphonic acid (F5BnPA) by solution deposition, micro-contact printing and spray coating using PM-IRRAS. In contrast to micro-contact printing and spray coating techniques, 48-168 h solution deposition at both room temperature and 70 degrees C result in contamination- and surface etch-free close-packed monolayers with good reproducibility. SAMs fabricated by micro-contact printing and spray coating are much less well ordered.

  7. Effect of time and deposition method on quality of phosphonic acid modifier self-assembled monolayers on indium zinc oxide

    NASA Astrophysics Data System (ADS)

    Sang, Lingzi; Knesting, Kristina M.; Bulusu, Anuradha; Sigdel, Ajaya K.; Giordano, Anthony J.; Marder, Seth R.; Berry, Joseph J.; Graham, Samuel; Ginger, David S.; Pemberton, Jeanne E.

    2016-12-01

    Phosphonic acid (PA) self-assembled monolayers (SAMs) are utilized at critical interfaces between transparent conductive oxides (TCO) and organic active layers in organic photovoltaic devices (OPVs). The effects of PA deposition method and time on the formation of close-packed, high-quality monolayers is investigated here for SAMs fabricated by solution deposition, micro-contact printing, and spray coating. The solution deposition isotherm for pentafluorinated benzylphosphonic acid (F5BnPA) on indium-doped zinc oxide (IZO) is studied using polarization modulation-infrared reflection-absorption spectroscopy (PM-IRRAS) at room temperature as a model PA/IZO system. Fast surface adsorption occurs within the first min; however, well-oriented high-quality SAMs are reached only after ∼48 h, presumably through a continual process of molecular adsorption/desorption and monolayer filling accompanied by molecular reorientation. Two other rapid, soak-free deposition techniques, micro-contact printing and spray coating, are also explored. SAM quality is compared for deposition of phenyl phosphonic acid (PPA), F13-octylphosphonic acid (F13OPA), and pentafluorinated benzyl phosphonic acid (F5BnPA) by solution deposition, micro-contact printing and spray coating using PM-IRRAS. In contrast to micro-contact printing and spray coating techniques, 48-168 h solution deposition at both room temperature and 70 °C result in contamination- and surface etch-free close-packed monolayers with good reproducibility. SAMs fabricated by micro-contact printing and spray coating are much less well ordered.

  8. 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. PMID:27873841

  9. 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.

  10. A hydrogen peroxide sensor based on Ag nanoparticles electrodeposited on natural nano-structure attapulgite modified glassy carbon electrode.

    PubMed

    Chen, Huihui; Zhang, Zhe; Cai, Dongqing; Zhang, Shengyi; Zhang, Bailin; Tang, Jilin; Wu, Zhengyan

    2011-10-30

    A novel strategy to fabricate hydrogen peroxide (H(2)O(2)) sensor was developed by electrodepositing Ag nanoparticles (NPs) on a glassy carbon electrode modified with natural nano-structure attapulgite (ATP). The result of electrochemical experiments showed that such constructed sensor had a favorable catalytic ability to reduce H(2)O(2). The good catalytic activity of the sensor was ascribed to the ATP that facilitated the formation and homogenous distribution of small Ag NPs. The resulted sensor achieved 95% of the steady-state current within 2s and had a 2.4 μM detection limit of H(2)O(2).

  11. 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.

  12. 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.

  13. Enhanced ultraviolet photocatalytic activity of Ag/ZnO nanoparticles synthesized by modified polymer-network gel method

    NASA Astrophysics Data System (ADS)

    Lu, Y. H.; Xu, M.; Xu, L. X.; Zhang, C. L.; Zhang, Q. P.; Xu, X. N.; Xu, S.; Ostrikov, K.

    2015-09-01

    Ag/ZnO nanoparticle (NP) heterostructures are synthesized through a modified polymer-network gel method in which glucose is added to the precursor solution to prevent the gel from drastically shrinking during drying of the aqueous solution. Structural and optical properties of the samples are characterized by a range of techniques including XRD, SEM, TEM, XPS, UV-Vis, and PL. The high-quality Ag-ZnO heterostructure is evidenced clearly by high-resolution TEM. The Ag/ZnO heterostructure nanocomposites exhibit a higher photocatalytic activity in the degradation of methyl orange than pure ZnO. Especially, Ag/ZnO NP heterostructures with the Ag/Zn molar ratio of 5:95 (sample ZA-5) show the highest degradation efficiency, which is 11 times higher compared with pure ZnO. The photoluminescence properties of the heterostructures and O defect states are studied to well explain the observed photocatalytic effects. ZA-5 also exhibits competitive photocatalytic activity for the degradation of other pollutant dyes such as Methylene blue and Rhodamine B compared with the recently reported techniques, while showing excellent catalyst photostability as well as offering simplicity and reliability.

  14. Corrosion behavior of Au and Ag modified Cu-Ni-Mn alloys.

    PubMed

    Wright, S R; Cocks, F H; Gettleman, L

    1980-04-01

    The linear electrochemical polarization method was used to provide quantitative in vitro measurements of corrosion rates as a function of exposure time for Cu-Ni-Mn, Cu-Ni-Mn-Au, Cu-Ni-Mn-Ag, and Cu-Ni-Mn-Au-Ag alloys in artificial saliva. Both Au and Ag additives to dental-cast Cu-Ni-Mn alloys lowered the corrosion rate significantly.

  15. 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.

  16. Simultaneous Detection of Cadmium, Copper, and Lead using A Carbon Paste Electrode Modified with Carbamoylphosphonic Acid Self-Assembled Monolayer on Mesoporous Silica (SAMMS)

    SciTech Connect

    Yantasee, Wassana ); Lin, Yuehe ); Fryxell, Glen E. ); Busche, Brad J. )

    2004-01-30

    A new sensor was developed for simultaneous detection of cadmium (Cd2+), copper (Cu2+), and lead (Pb2+), based on the voltammetric response at a carbon paste electrode modified with carbamoylphosphonic acid (acetamide phosphonic acid) self-assembled monolayer on mesoporous silica (Ac-Phos SAMMS). The adsorptive stripping voltammetry technique involves preconcentration of the metal ions onto Ac-Phos SAMMS under an open circuit, then electrolysis of the preconcentrated species, followed by a square wave potential sweep towards positive values. Factors affecting the preconcentration process were investigated. The voltammetric responses increased linearly with the preconcentration time from 1 to 30 minutes or with metal ion concentrations ranging from 10 to 200 ppb. The responses also evolved in the same fashion as adsorption isotherm in the pH range of 2-6. The metal detection limits were 10 ppb after 2 minutes preconcentration and improved to 0.5 ppb after 20 minutes preconcentration.

  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. 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.

  19. Growth of Ag nanoparticles using plasma-modified multi-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Tseng, Chun-Hao; Chen, Chuh-Yung

    2008-01-01

    This study presents a novel method for preparing multi-walled carbon nanotubes (MWNTs) grafted with a poly(2-hydroxyethyl methacrylate) (HEMA)-silver complex (CNTs-HEMA-Ag complex) through plasma-induced grafting polymerization. The characteristics of the MWNTs after being grafted with HEMA polymer are monitored by Fourier transform infrared (FT-IR) spectroscopy. The chelating groups in the HEMA polymer grafted on the surface of the CNTs-HEMA are the coordination sites for chelating silver ions, and are further used as nanotemplates for the growing of Ag nanoparticles (quantum dots). Transmission electron microscopy (TEM) reveals that the particle size of Ag nanoparticles on the CNT surfaces increases with the Ag+ chelating concentration, reaction time, and reaction temperature. Moreover, the crystalline phase of Ag nanoparticles is identified by using x-ray diffraction (XRD). In addition, high-resolution x-ray photoelectron spectroscopy (XPS) is used to characterize the functional groups on the surface of the MWNTs after chemical modification through plasma treatment; it demonstrates that the growing amount of the Ag nanoparticles on the nanotubes increases with the Ag+ chelating concentration due to the blocking effect of the Ag particles forming on the MWNTs.

  20. Enhancement of photocatalytic and photoelectrocatalytic activity of Ag modified Mpg-C3N4 composites

    NASA Astrophysics Data System (ADS)

    He, Qiuchen; Zhou, Feng; Zhan, Su; Yang, Yifan; Liu, Yujun; Tian, Yu; Huang, Naibao

    2017-01-01

    In this study, mpg-C3N4/Ag composites of surface plasmon resonance structures were fabricated to improve the photocatalytic and photoelectrocatalytic activities of g-C3N4 via photo-assisted reduction method, which were characterized by XRD, EDS, XPS, FT-IR, FE-SEM, TEM, DRS and BET. The photocatalytic and photoelectrocatalytic activities were evaluated by the degradation of methylene blue (MB) and the oxygen reduction experiment under visible light. The results showed the photocatalytic and photoelectrocatalytic activities were dependent on the weight ratio of Ag and the optimum photocatalytic activity of mpg-C3N4/Ag at a weight ratio of 3% is almost 3 times as high as that of mpg-C3N4. Additionally, mpg-C3N4/Ag exhibited a significantly enhanced oxygen reduction performance under visible light. The limit current density was increased about 2 times by the modification of Ag nanoparticles, compared with that of pristine mpg-C3N4. Finally, based on the first principle, the enhancement mechanism of the photocatalytic and photoelectrocatalytic activities was discussed by the calculation on the band structure and density of states in the mpg-C3N4/Ag composites. The appropriate amount of Ag modification would cause the surface plasmon resonance effect, which improved the photocatalytic, photoelectrocatalytic, and oxygen reduction activities of mpg-C3N4.

  1. Controlled synthesis of Fe2O3 modified Ag-010BiVO4 heterostructures with enhanced photoelectrochemical activity toward the dye degradation

    NASA Astrophysics Data System (ADS)

    Li, Junqi; Zhou, Jian; Hao, Hongjuan; Li, Weijie

    2017-03-01

    Crystal facet dependence is an important approach for optimizing the performance of photocatalyst. In consideration that there is a close correlation between the photoelectric conversion efficiencies and crystal facet, the monoclinic bismuth vanadate (m-BiVO4) with (010) and (110) crystal facets has drawn attention. We designed the Ag nanoparticles modified the (010) facet of the BiVO4 (Ag-010BiVO4) and then the Ag-010BiVO4 heterogeneous nanostructure was modified by the Fe2O3 nanoparticles. In the Fe2O3 modified Ag-010BiVO4, the (110) facet of the BiVO4 was only modified by the Fe2O3 nano-particles to construct the n-n heterojunction structure. Simultaneously, the Z-scheme system was fabricated on the (010) facet of the BiVO4, where was modified by the Ag and Fe2O3 nano-particles. We investigated its photoelectrochemical (PEC) and photocatalytic activities by the measurement of the electrochemical performance and degradation of methyl orange (MO). The Ag species in the system is only treated as the solid state electron mediator. As was expected, the Fe2O3 modified Ag-010BiVO4 heterojunction structure exhibited the highest photocurrent density and the smallest impedance. Besides, the Fe2O3 modified Ag-010BiVO4 heterojunction structure exhibited excellent redox ability and the MO could be degraded 92% after 150 min. It is worth noting that the outstanding performance should be attributed to the synergistic effect of n-n and Z-scheme system in the different facets, which facilitated the separation of holes and electrons in the opposite direction.

  2. Memristive behavior of Al2O3 film with bottom electrode surface modified by Ag nanoparticles

    NASA Astrophysics Data System (ADS)

    Qin, Shu-Chao; Dong, Rui-Xin; Yan, Xun-Ling

    2014-09-01

    The memristive behavior of Al2O3-based device is significantly improved by introducing Ag nanoparticles (NPs). Inserting Ag NPs can effectively reduce the switching voltages, increase the resistance ratio (about 104) and enhance the sweep endurance (300 cycles). In particular, the stable switching properties are obtained by inserting an Ag NPs layer with an average diameter of 14 nm on the surface of bottom electrode, and the devices show a long retention time (more than 106 s) compared with the devices without Ag NPs. The switching mechanism is related to the oxygen-vacancy-based conducting filaments and the interfacial effect. The local enhancement and nonuniform distribution of electric field have the benefits to promote, induce and modulate the growth of conducting filaments, such as shape, location and orientation, which are responsible for the improvement performance of the devices.

  3. Memristive behavior of Al2O3 film with bottom electrode surface modified by Ag nanoparticles

    NASA Astrophysics Data System (ADS)

    Qin, Shu-Chao; Dong, Rui-Xin; Yan, Xun-Ling

    2015-02-01

    The memristive behavior of Al2O3-based device is significantly improved by introducing Ag nanoparticles (NPs). Inserting Ag NPs can effectively reduce the switching voltages, increase the resistance ratio (about 104) and enhance the sweep endurance (300 cycles). In particular, the stable switching properties are obtained by inserting an Ag NPs layer with an average diameter of 14 nm on the surface of bottom electrode, and the devices show a long retention time (more than 106 s) compared with the devices without Ag NPs. The switching mechanism is related to the oxygen-vacancy-based conducting filaments and the interfacial effect. The local enhancement and nonuniform distribution of electric field have the benefits to promote, induce and modulate the growth of conducting filaments, such as shape, location and orientation, which are responsible for the improvement performance of the devices.

  4. 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.

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

    PubMed

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

    2015-07-07

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

  6. Potential driven deposition of poly(diallyldimethylammonium chloride) onto the surface of 3-mercaptopropionic acid monolayers assembled on gold.

    PubMed

    Sanders, Wesley; Anderson, Mark R

    2008-11-18

    Electrochemical impedance spectroscopy (EIS) and quartz crystal microbalance (QCM) measurements are used to examine the ability of applied potential to drive the ionic self-assembly of poly(diallyldimethylammonium) chloride (PDDA) onto a substrate modified with a monolayer of 3-mercaptopropionic acid (3-MPA). The potential of zero charge (PZC) of the gold electrode modified with a monolayer of 3-MPA was found by differential capacitance measurements to be -0.12 (+/-0.01) V versus Ag-AgCl. Changing the substrate potential to values positive (-0.01 V vs Ag-AgCl) of the PZC induces interfacial conditions that are favorable for the electrostatic deposition of cationic polymers onto the surface of 3-MPA monolayers. This result is also consistent with experimental observations obtained when the 3-MPA-modified substrate is exposed to 0.10 mol L (-1) NaOH solutions. When potentials equal or negative to the PZC are applied to the substrate, no significant accumulation of the PDDA is found by either QCM or EIS measurement. This result is consistent with results obtained when the 3-MPA modified substrate is exposed to 0.10 mol L (-1) HCl solutions where no PDDA adsorption is expected because the monolayer is neutral under these conditions. Changes in the impedance and quartz crystal frequency obtained after potential is applied to the substrate are interpreted in terms of the applied potential creating interfacial conditions that are favorable for the deprotonation of the terminal carboxylic acid groups and the subsequent electrostatic assembly of the polycation onto the negatively charged monolayer.

  7. 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.

  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. Ag-ligand modified tungstovandates and their efficient catalysis degradation properties for methylene blue

    NASA Astrophysics Data System (ADS)

    Zheng, Ran; Zhang, Huixia; Liu, Yunping; Wang, Xiaoxiao; Han, Zhangang

    2017-02-01

    Two polytungstovandates [Ag(mbpy)2][Ag2(mbpy)3][VW5O19]·H2O (1) and [Ag(mbpy)]2[Ag(mbpy)2]4[VW12O40] (2) (mbpy =4,4‧-dimethyl-2,2‧-bipyridyl), had been hydrothermally synthesized and characterized by IR, TG, and single-crystal X-ray diffraction techniques. Single-crystal structural analysis revealed that the polyanionic clusters in two compounds are different: Lindqvist-type in 1 and α-Keggin-type in 2, respectively, while the cationic moieties in them are Ag-mbpy units. The experiments showed that this kind of hybrid crystal materials possesses more efficiently catalytic performance for the degradation of organic dye methylene blue (MB) in water solution under the UV irradiation. The significant degradation rate of MB can reach 89.9%, 94.9% by crystals 1 and 2 (40 mg) in the course of about 5 min.

  10. 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.

  11. Synthesis of beta-cyclodextrin-modified water-dispersible Ag-TiO2 core-shell nanoparticles and their photocatalytic activity.

    PubMed

    Shown, Indrajit; Ujihara, Masaki; Imae, Toyoko

    2011-04-01

    The beta-cyclodextrin-modified Ag-TiO2 core-shell nanoparticles were prepared by sodium borohydrate reduction of AgNO3 and the subsequent hydrolysis of the tetraisopropyl orthotitanate in an aqueous medium. Inversely in the preparation of beta-cyclodextrin-modified TiO2-Ag core-shell nanoparticles, first hydrolysis and then following reduction were carried out. The synthesized spherical core-shell nanoparticles were highly water-dispersible and had an average diameter in the range of 9 to 12 nm. A significant shifting of surface plasmon band was observed for the synthesized Ag-TiO2 and TiO2-Ag core-shell nanoparticles. On a model reaction, namely, the photodegradation of phenol by the UV light irradiation, the photocatalytic property of TiO2 nanoparticles was enhanced, when the Ag nanoparticle was embedded in the core of TiO2 nanoparticles but TiO2 nanoparticles coated by Ag shell decreased the photocatalytic property of TiO2 nanoparticles. The mechanism is ascribed to the surface plasmon characteristics of Ag in the core of the TiO2 nanoparticles under the acceleration by host-guest inclusion characteristics.

  12. 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.

  13. A tris(8-hydroxyquinoline) aluminum-based organic bistable device using ITO surfaces modified by Ag nanoparticles

    NASA Astrophysics Data System (ADS)

    Jiao, Bo; Wu, Zhaoxin; Dong, Hua; Ning, Shuya; Hou, Xun

    2013-11-01

    A tris (8-hydroxyquinoline) aluminum (Alq3)-based organic bistable device (OBD) using Al electrode and ITO electrode modified by Ag nanoparticles (NPs) was reported. The OBD exhibits high ON/OFF switching ratios in the range of 102-103 and long retention time over 104 s. The influence of the Ag NPs densities, as well as the Alq3 film thickness on the switch performance current-voltage (I-V) of the OBDs was studied. Correlation between filament formation mechanism and charge storage mechanism was observed by analysing the I-V characteristics of OBDs with different Alq3 film thickness. As for the Alq3 film with thickness of 300 nm, the trapping effect of Ag NPs leads to both ON and OFF states for OBD; for 100 nm thick Alq3 film, the effect of filamentation dominates in the ON and OFF states of OBD. For the case of 200 nm thick Alq3 film, however, the ON state results from the filamentation effect, while trapping effect is responsible for the OFF state. In addition, the diffusion effect of Al atoms in Alq3 film in the devices was discussed and was expected to explain this thickness-dependence relationship.

  14. Spontaneously adsorbed monolayer films: Fabrication, characterization, and application of monolayers of alkanethiol and sulfur-bearing cyclodestrin derivatives

    SciTech Connect

    Chinkap, Chung.

    1991-03-12

    Monolayers of n-alkanethiols (CH{sub 3}(CH{sub 2}){sub n}SH, n=1--17) and sulfur-bearing cyclodextrin derivatives spontaneously adsorbed on Ag and Au have been studied with a variety of surface characterization methods, such as infrared inflection spectroscopy, contact angle measurements, electro-chemistry, optical ellipsometry, and scanning tunneling microscopy. Long chain n-alkanethiols monolayers on Ag and Au are insulating to electron transfer and have contact angles indicative of well-ordered hydrocarbon terminated structures. Infrared and contact angle data indicate a different orientation of the methyl group with respect to the surface for chains with odd and even numbers of methylene groups. Compared to monolayers on Au, the alkanethiol monolayers on Ag are oriented more towards the surface normal. The observed odd-even effect methyl group orientation for these monolayers on Ag is offset by a methylene group from that on Au. The relationships between the structure and packing of the monolayers on Ag and Au and the composition, roughness, and crystallinity of the substrate are also discussed. Monolayers of sulfur-bearing cyclodextrin derivatives on Au and Ag are fabricated by spontaneous adsorption and characterized by the above techniques. Size-selectively and molecular recognition of the {alpha}- and {beta}- cyclodextrin cavity are shown with our monolayers. Because of molecular recognition, p-nitrophenol is retained preferrentially by the cyclodextrin monolayers over o-nitrophenol. 146 refs., 44 figs., 5 tabs.

  15. 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.

  16. Ultraviolet-visible and surface-enhanced Raman scattering spectroscopy studies on self-assembled metalloporphyrin films on organic monolayer-modified ultra-thin silver substrates.

    PubMed

    Li, Xiaoling; Xu, Weiqing; Jia, Huiying; Wang, Xu; Zhao, Bing; Li, Bofu; Ozaki, Yukihiro

    2004-03-01

    A self-assembled monolayer (SAM) film of 5,10,15,20-tetra-(para-chlorophenyl)-porphyrin terbium (or lutetium) hydroxy compound (TbOH/LuOH) fabricated on a silver substrate premodified with a SAM of 4-mercaptopyridine (PySH) was studied by ultraviolet-visible (UV-Vis) spectroscopy and surface-enhanced Raman scattering (SERS) spectroscopy. PySH can modify the substrate and deliver its pyridyl group pointing out from the silver surface. Thus, we can investigate the effects of the central metals of the metalloporphyrins in the formation of the composite films. For the TbOH-PySH composite film, a new absorption band arising from TbOH appears at 425 nm, and a band at 512 nm due to the PySH-modified silver substrate shifts to a longer wavelength (538 nm). The results suggest that TbOH is successfully assembled on the top of PySH-modified silver film and that there is an interaction between TbOH and PySH in the film. The frequency shifts and relative intensity changes of bands due to PySH in the SERS spectra imply the coordination of the pyridyl group on Tb in the SAM. As for the LuOH-PySH composite film, its SERS spectrum shows bands arising from both the LuOH and PySH moieties, indicating that LuOH is assembled on the PySH-modified silver film. Furthermore, a band at 1221 cm(-1) due to the in-plane C-H bending mode of PySH disappears, implying that the pyridyl moiety of PySH becomes more parallel to the silver surface upon the formation of the LuOH-PySH composite film. Additionally, an absorption band at 515 nm shifts to a longer wavelength (541 nm) and becomes broad upon the formation of the composite film, suggesting an interaction between LuOH and PySH in the film. By comparing the spectral changes between the two self-assembled composite films, we find that the central metal is crucial in the formation of the composite films. The structure and orientation of the composite films depend on the central metal of the metalloporphyrin compounds.

  17. Complete oxidation of methane over Ag- and Cu-modified cerium and zirconium oxides

    NASA Astrophysics Data System (ADS)

    Kundakovic, Ljiljana

    Low temperature oxidation of methane is an area in catalysis that, despite the large number of catalytic systems studied, does not yet have an adequate solution. The exhaust gas from natural gas burning devices (gas turbines and natural gas vehicles), contains unconverted methane which is emitted into the atmosphere (currently unregulated). Methane is the most refractory of all hydrocarbons, and its activation requires temperatures higher than the typical exhaust temperatures (350-400sp°C). In this work, ceria- and zirconia-supported Ag and CuO catalysts were studied for the complete oxidation of methane. Catalysts were typically tested under excess oxygen and high space velocity (72,000 hsp{-1}). The reaction kinetics were measured over selected catalysts. Hsb2- and CHsb4- TPR and oxygen uptake measurements were used to characterize the catalyst reduction properties. XRD, STEM/EDX and HRTEM were used to characterize the catalyst structure. The oxidation state of various active species present was identified by XPS and UV-VIS DR spectrometry. Ceria- and zirconia-supported Ag and CuO catalysts are very active and stable catalysts for the complete oxidation of carbon monoxide and methane. When ceria is used as an active catalyst support, its activity depends strongly on its structure. Nanocrystalline ceria, stabilized by dopants such as La or Zr, is highly reducible and structurally defective. Our results indicate that surface oxygen species present under reaction conditions are the active sites for methane activation. Activity in the complete oxidation of methane is related to ceria crystal size and reducibility of surface oxygen species. The addition of a transition metal (Ag) or a metal oxide (CuO) in low amounts increases the low temperature reducibility of ceria and enhances the catalyst oxidation activity. On the other hand, both Ag and CuO are active catalysts for the complete oxidation of methane. These were studied separately on inert zirconia support. A

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

    SciTech Connect

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

    2006-01-01

    This paper reports on the effects of palladium on the liquidus/solidus temperatures and wetting behavior of a series of Ag-CuOx air braze filler metals. Currently, the maximum operating temperature of the Ag-CuOx system is limited by its eutectic temperature of ~935°C. One strategy to increase the maximum operational temperature of this family of filler metals is to add a higher melting noble alloying element. In the current study, we examined the effects of palladium additions on the melting characteristics of the Ag-CuO materials and the wetting properties of the resulting air braze filler metals with respect to alumina. It was found that while the addition of Pd causes the anticipated increase in the melting temperature, it does so at a sacrifice in wetting properties. The extent of both effects and therefore the opportunity to trade-off the two properties in order to develop an optimized higher temperature air braze depends on concentrations of both the palladium and copper oxide.

  19. AgBr and g-C3N4 co-modified Ag2CO3 photocatalyst: A novel multi-heterostructured photocatalyst with enhanced photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Tang, Hua; Chang, Shufang; Tang, Guogang; Liang, Wei

    2017-01-01

    Novel and highly efficient visible-light-driven g-C3N4/Ag2CO3/AgBr multi-heterostructured photocatalysts are achieved from the surface modification of g-C3N4/Ag2CO3 with AgBr nanoparticles by a facile and efficient ion-exchange method. The as-prepared g-C3N4/Ag2CO3/AgBr photocatalysts were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), scaning electron microscopy (SEM) and UV-vis diffuse reflectance spectrometry (DRS). Compared with g-C3N4/Ag2CO3, g-C3N4/Ag2CO3/AgBr hybrids exhibit enhanced the degradation activity for typical RhB, MB, and MO dyes under visible light excitation (>420 nm). Photoluminescence (PL), photo-induced current and electrochemical impedance spectroscopy (EIS) results demonstrate the g-C3N4/Ag2CO3/AgBr heterojunctions can effectively suppress the recombination of the generated electron-hole pairs. The higher photocatalytical performance of g-C3N4/Ag2CO3/AgBr can be ascribed to the efficient separation of photogenerated electron-hole pairs due to the formation of multi-heterojunctions, in which the Ag nanoparticles acted as the charge transmission bridge. In addition, the possible transferred and separated behavior of electron-hole pairs and photocatalytic mechanisms based on the experimental results are also proposed in detail.

  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. Water treatment with exceptional virus inactivation using activated carbon modified with silver (Ag) and copper oxide (CuO) nanoparticles.

    PubMed

    Shimabuku, Quelen Letícia; Arakawa, Flávia Sayuri; Fernandes Silva, Marcela; Ferri Coldebella, Priscila; Ueda-Nakamura, Tânia; Fagundes-Klen, Márcia Regina; Bergamasco, Rosangela

    2016-10-21

    Continuous flow experiments (450 mL min(-1)) were performed in household filter in order to investigate the removal and/or inactivation of T4 bacteriophage, using granular activated carbon (GAC) modified with silver and/or copper oxide nanoparticles at different concentrations. GAC and modified GAC were characterized by X-ray diffractometry, specific surface area, pore size and volume, pore average diameter, scanning electron microscopy, transmission electron microscopy, zeta potential and atomic absorption spectroscopy. The antiviral activity of the produced porous media was evaluated by passing suspensions of T4 bacteriophage (∼10(5) UFP/mL) through filters. The filtered water was analyzed for the presence of the bacteriophage and the release of silver and copper oxide. The porous media containing silver and copper oxide nanoparticles showed high inactivation capacity, even reaching reductions higher than 3 log. GAC6 (GAC/Ag0.5%Cu1.0%) was effective in the bacteriophage inactivation, reaching 5.53 log reduction. The levels of silver and copper released in filtered water were below the recommended limits (100 ppb for silver and 1000 ppb for copper) in drinking water. From this study, it is possible to conclude that activated carbon modified with silver and copper oxide nanoparticles can be used as a filter for virus removal in the treatment of drinking water.

  2. Quaternary Zn-Ag-In-Se quantum dots for biomedical optical imaging of RGD-modified micelles.

    PubMed

    Deng, Dawei; Qu, Lingzhi; Zhang, Jian; Ma, Yuxiang; Gu, Yueqing

    2013-11-13

    Exploring the synthesis of new biocompatible quantum dots (QDs) helps in overcoming the intrinsic toxicity of the existing QDs composed of highly toxic heavy metals (e.g., Cd, Hg, Pb, etc.) and is particularly interesting for the future practical application of QDs in biomedical imaging. Hence, in this report, a new one-pot approach to oil-soluble (highly toxic heavy metal-free) highly luminescent quaternary Zn-Ag-In-Se (ZAISe) QDs was designed. Their photoluminescence (PL) emission could be systematically tuned from 660 to 800 nm by controlling the Ag/Zn feed ratio, and their highest PL quantum yield is close to 50% after detailed optimization. Next, by using biodegradable RGD peptide (arginine-glycine-aspartic acid)-modified N-succinyl-N'-octyl-chitosan (RGD-SOC) micelles as a water transfer agent, the versatility of these quaternary ZAISe QDs for multiscale bioimaging of micelles (namely, in vitro and in vivo evaluating the tumor targeting of drug carriers) was further explored, as a promising alternative for Cd- and Pb-based QDs.

  3. 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.

  4. Modified carbon surfaces as "organic electrodes" that exhibit conductance switching.

    PubMed

    Solak, Ali Osman; Eichorst, Laura R; Clark, William J; McCreery, Richard L

    2003-01-15

    Glassy carbon (GC) surfaces modified with monolayers of biphenyl and nitrobiphenyl molecules were examined as voltammetric electrodes for ferrocene, benzoquinone, and tetracyanoquinodimethane electrochemistry in acetonitrile. The modified electrodes exhibited slower electron transfer than unmodified GC, by factors that varied with the monolayer and redox system. However, after a negative potential excursion to approximately -2.0 V versus Ag+/Ag, the modified electrodes exhibited much faster electron-transfer kinetics, approaching those observed on unmodified GC. The effect is attributed to an apparently irreversible structural change in the biphenyl or nitrobiphenyl monolayer, which increases the rate of electron tunneling. The transition to the "ON" state is associated with electron injection into the monolayer similar to that observed in previous spectroscopic investigations and causes a significant decrease in the calculated HOMO-LUMO gap for the monolayer molecule. Once the monolayer is switched ON, it supports rapid electron exchange with outer-sphere redox systems, but not with dopamine, which requires adsorption to the GC surface. The increase in electron-transfer rate with electron injection is consistent with an increase in electron tunneling rate through the monolayer, caused by a significant decrease in tunneling barrier height. The ON electrode can reduce biphenyl- or nitrobiphenyldiazonium reagent in solution to permit formation of a second modification layer of biphenyl or nitrobiphenyl molecules. This "double derivatization" procedure was used to prepare tetraphenyl- and nitrotetraphenyl-modified electrodes, which exhibit significantly slower electron transfer than their biphenyl and nitrobiphenyl counterparts. A "switching" electrode may have useful properties for electroanalytical applications and possibly in electrocatalysis. In addition, the ON state represents an "organic electrode" in which electron transfer occurs at an interface between an

  5. Origin of metallicity in atomic Ag wires on Si(557)

    NASA Astrophysics Data System (ADS)

    Krieg, U.; Lichtenstein, T.; Brand, C.; Tegenkamp, C.; Pfnür, H.

    2015-04-01

    We investigated the metallicity of Ag-\\sqrt{3} ordered atomic wires close to one monolayer (ML) coverage, which are formed on Si(557) via self assembly. For this purpose we combined high resolution electron energy loss spectroscopy with tunneling microscopy. By extending the excess Ag coverage up to 0.6 ML on samples annealed at high temperatures where partial desorption occurs, we demonstrate that one-dimensional metallicity in the Ag-\\sqrt{3}× \\sqrt{3} R30° ordered atomic wires on the (111) mini-terraces originates only from Ag atoms in excess of (local) monolayer coverage, which are adsorbed and localized at the highly stepped parts of the Si(557) surface. Thus these Ag atoms act as extrinsic dopants on the atomic scale, causing coverage dependent subband filling and increasing localization as a function of doping concentration. The second layer lattice gas as well as Ag islands on the (111) terraces turn out not to be relevant as dopants. We simulated the peculiar saturation behavior within a modified lattice gas model and give evidence that the preparation dependent saturation of doping is due to changes of average terrace size and step morphology induced by high temperature treatment.

  6. Facile sonochemical synthesis of Ag modified Bi{sub 4}Ti{sub 3}O{sub 12} nanoparticles with enhanced photocatalytic activity under visible light

    SciTech Connect

    Dutta, Dimple P. Tyagi, A.K.

    2016-02-15

    Highlights: • Ag doped/dispersed Bi{sub 4}Ti{sub 3}O{sub 12} nanoparticles synthesized sonochemically. • Undoped Bi{sub 4}Ti{sub 3}O{sub 12} exhibited 100% RhB degradation in 45 min under UV light. • Under visible light 100% RhB degradation occured with Bi{sub 4}Ti{sub 3}O{sub 12} in 150 min. • Improved photodegradation of RhB by Ag doped Bi{sub 4}Ti{sub 3}O{sub 12} in visible light. • The Bi{sub 4}Ti{sub 3}O{sub 12}:Ag(5%) sample photodegrades RhB from wastewater under sunlight. - Abstract: Unmodified and Ag modified Bi{sub 4}Ti{sub 3}O{sub 12}:Ag(x%) (x = 2 and 5) nanoparticles have been synthesized sonochemically and characterized using X-ray diffraction, X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET) surface area analysis, scanning electron microscopy (SEM), energy dispersion X-ray spectrum (EDS) analysis, transmission electron microscopy (TEM) and UV–vis diffuse reflectance spectroscopy. In the presence of unmodified Bi{sub 4}Ti{sub 3}O{sub 12} nanoparticles, complete photocatalytic degradation of Rhodamine B (RhB) was observed under UV light within 45 min. However, the response of this material for photodegradation of RhB under visible light was poor and could be greatly enhanced with Ag modification. A possible mechanism for this observation has been discussed in detail. The reusability of the material has also been tested and it has been found to have favorable recycling capability. Moreover, the Ag- modified Bi{sub 4}Ti{sub 3}O{sub 12} has been tested for RhB degradation from a wastewater sample under sunlight and promising results have been obtained.

  7. Copper pattern on self-assembled monolayer through microcontact printing.

    PubMed

    Liu, Zheng-Chun; Yang, Fei-Peng; Xu, Xiao-Wen; Guo, Can; Liu, Jian-Xin

    2010-05-01

    Cu pattern on 3-mercaptopropyltrimethoxysilane self-assembled monolayers (MPTS-SAMs) modified glass substrate was achieved by a combination of hydrophobic treatment through microcontact printing, activation and electroless plating. The MPTS-SAMs modified glass substrate was selectively deactivated by microcontact printing 1-hexadecanethiol ethanol solution. X-ray photoelectron spectroscopy (XPS) and water contact angle measurements confirmed that a selectively deactivated pattern was obtained, which was attributed to the formation of disulfide linkages between MPTS and 1-hexadecanethiol. The substrate was selectively activated by dipping into Ag colloids solution and then applied for electroless Cu plating. XPS spectra suggested an ideal catalytic pattern on the substrate due to the deposition of Ag particles on the MPTS and the formation of S-Ag bonds. SEM showed that the microstructure of Cu pattern on MPTS-SAMs was in good agreement with the corresponding silicon master with a resolution of 10 microm. The average electrical resistivity was about 1.8 x 10(-6) omegacm, measured by four-point probe technique. The results suggested that microcontact printing deactivating reagents on SAMs is a potential technique for Cu patterns preparation.

  8. 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.

  9. A self-cleaning coating based on commercial grade polyacrylic latex modified by TiO2/Ag-exchanged-zeolite-A nanocomposite

    NASA Astrophysics Data System (ADS)

    Nosrati, Rahimeh; Olad, Ali; Nofouzi, Katayoon

    2015-08-01

    The commercial grade polyacrylic latex was modified in order to prepare a self-cleaning coating. TiO2/Ag-exchanged-zeolite-A nanocomposite was prepared and used as additive in the matrix of polyacrylic latex to achieve a hydrophilic and photocatalytic coating. FTIR and UV-visible spectroscopy, X-ray diffraction patterns and FESEM were used to characterize the composition and structure of the nanocomposites and coatings. The acrylic coatings, were prepared by using of TiO2/Ag-exchanged-zeolite-A additive, had better UV and visible light absorption, hydrophilic, degradation of organic pollutants, stability in water and antimicrobial properties than pristine commercial grade polyacrylic latex coating. According to the results, the modified polyacrylic based coating containing 0.5 wt% of TiO2/Ag-exchanged-zeolite-A nanocomposite additive with TiO2 to Ag-exchanged-zeolite-A ratio of 1:2 was the best coating considering most of useful properties such as small band gap and low water contact angle. The water contact angle for unmodified polyacrylic latex coating was 68° which was decreased to less than 10° in modified coating after 24 h LED lamp illumination.

  10. TiO2 modified with Ag nanoparticles synthesized via ultrasonic atomization-UV reduction and the use of kinetic models to determine the acetic acid photocatalytic degradation

    NASA Astrophysics Data System (ADS)

    Xu, Yingcao; You, Hong

    2014-12-01

    TiO2 surfaces modified with noble metal nanoparticles have been found to effectively reduce the photogenerated carrier recombination rate and significantly extend the light absorption properties of TiO2, thereby greatly increasing its photocatalytic activity. In this paper, highly ordered, double-sided TiO2 nanotube arrays were prepared using an anodic oxidation method in a home-made reactor using glycerol/water (volume ratio 2:1) and NH4F (0.25 mol/L) as the electrolyte, titanium plates (10 cm × 2 cm × 0.5 mm) as the anode and graphite as the cathode at a constant voltage of 25 V. After a 2-h reaction, anatase TiO2 nanotubes were obtained upon calcination at 450 °C for 4 h. The Ag nanoparticles on the surfaces of the TiO2 were prepared via ultrasonic atomization-ultraviolet light reduction. First, a silver nitrate solution was sputtered into small droplets under ultrasonication. Then, the Ag+ droplets were reduced to Ag nanoparticles. The surface morphologies, structures and elemental compositions were characterized using SEM, EDS, XRD and XPS. The photocatalytic activities were determined in acetic acid solutions (40-200 mg/L), and a mathematical model for catalytic degradation was established based on a hyperbolic model. The SEM results showed that the diameters of the as-prepared Ag/TiO2 are approximately 100 nm and that the lengths are approximately 1.8 μm. The XRD crystal structure analysis shows that the anatase phase of the TiO2 does not change during the Ag modification, and there was a peak from Ag (2 2 0). The XPS determined that the Ag atom percentage was 1.11%. The degradation of acetic acid indicated that Ag/TiO2 has a higher photocatalytic activity than the undoped TiO2.

  11. 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.

  12. Photoelectrical properties of Ag2S quantum dot-modified TiO2 nanorod arrays and their application for photovoltaic devices.

    PubMed

    Liu, Bingkun; Wang, Dejun; Zhang, Yu; Fan, Haimei; Lin, Yanhong; Jiang, Tengfei; Xie, Tengfeng

    2013-02-14

    Vertically aligned TiO(2) nanorod arrays (NRAs) modified with Ag(2)S quantum dots (QDs) have been successfully prepared via a successive ionic layer adsorption and reaction (SILAR) process. Ultraviolet-visible (UV-vis) absorption spectra and surface photovoltage (SPV) measurements reveal that the Ag(2)S sensitization extends the range of the photoresponse of the TiO(2) NRAs to the visible region and exhibits higher photovoltage responses. With a polysulfide electrolyte, a maximum conversion efficiency of 0.148% with a superior J(sc) of 1.177 mA cm(-2) are obtained after 6 SILAR cycles under illumination at 100 mW cm(-2). These results indicate that the Ag(2)S QDs/TiO(2) NRAs photoelectrode has a promising application in solar cells.

  13. 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.

  14. 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.

  15. Photoelectrochemical detection of alpha-fetoprotein based on ZnO inverse opals structure electrodes modified by Ag2S nanoparticles.

    PubMed

    Jiang, Yandong; Liu, Dali; Yang, Yudan; Xu, Ru; Zhang, Tianxiang; Sheng, Kuang; Song, Hongwei

    2016-12-06

    In this work, a new photoelectrochemical biosensor based on Ag2S nanoparticles (NPs) modified macroporous ZnO inverse opals structure (IOs) was developed for sensitive and rapid detection of alpha fetal protein (AFP). Small size and uniformly dispersed Ag2S NPs were prepared using the Successive Ionic Layer Adsorption And Reaction (SILAR) method, which were adsorbed on ZnO IOs surface and frame work as matrix for immobilization of AFP. The composite structure of ZnO/Ag2S expanded the scope of light absorption to long wavelength, which can make full use of the light energy. Meanwhile, an effective matching of energy levels between the conduction bands of Ag2S and ZnO are beneficial to the photo-generated electrons transfer. The biosensors based on FTO (fluorine-doped tinoxide) ZnO/Ag2S electrode showed enough sensitivity and a wide linear range from 0.05 ng/mL to 200 ng/mL with a low detection limit of 8 pg/mL for the detection of AFP. It also exhibited high reproducibility, specificity and stability. The proposed method was potentially attractive for achieving excellent photoelectrochemical biosensor for detection of other proteins.

  16. Photoelectrochemical detection of alpha-fetoprotein based on ZnO inverse opals structure electrodes modified by Ag2S nanoparticles

    PubMed Central

    Jiang, Yandong; Liu, Dali; Yang, Yudan; Xu, Ru; Zhang, Tianxiang; Sheng, Kuang; Song, Hongwei

    2016-01-01

    In this work, a new photoelectrochemical biosensor based on Ag2S nanoparticles (NPs) modified macroporous ZnO inverse opals structure (IOs) was developed for sensitive and rapid detection of alpha fetal protein (AFP). Small size and uniformly dispersed Ag2S NPs were prepared using the Successive Ionic Layer Adsorption And Reaction (SILAR) method, which were adsorbed on ZnO IOs surface and frame work as matrix for immobilization of AFP. The composite structure of ZnO/Ag2S expanded the scope of light absorption to long wavelength, which can make full use of the light energy. Meanwhile, an effective matching of energy levels between the conduction bands of Ag2S and ZnO are beneficial to the photo-generated electrons transfer. The biosensors based on FTO (fluorine-doped tinoxide) ZnO/Ag2S electrode showed enough sensitivity and a wide linear range from 0.05 ng/mL to 200 ng/mL with a low detection limit of 8 pg/mL for the detection of AFP. It also exhibited high reproducibility, specificity and stability. The proposed method was potentially attractive for achieving excellent photoelectrochemical biosensor for detection of other proteins. PMID:27922086

  17. Synthesis and characterization of graphene oxide modified AgBr nanocomposites with enhanced photocatalytic activity and stability under visible light

    NASA Astrophysics Data System (ADS)

    Zhang, Du; Tang, Hua; Wang, Yuqi; Wu, Kongqiang; Huang, Hong; Tang, Guogang; Yang, Jin

    2014-11-01

    Novel visible-light-driven graphene oxide (GO)/AgBr nanocomposites were synthesized by a facile solution method. The GO/AgBr nanocomposites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoemission spectroscopy (XPS) analysis, UV-vis diffuse reflectance spectroscopy (DRS), Fourier transform infrared spectra (FTIR), and Raman spectra. The results indicated that AgBr nanoparticles were evenly distributed on the surface of GO and the heterostructures were formed. The photocatalytic activity of the as-prepared nanocomposites was evaluated by using Rhodamine B (RhB), Methylene blue (MB) and Methyl orange (MO) as target organic pollutants. The nanocomposites exhibit excellent photocatalytic activity for all of three dyes. Compared with bare AgBr particles, the GO/AgBr nanocomposites show better photocatalytic properties toward RhB pollutants. Additionally, the radical scavengers experiment indicated that O2rad - radicals was the main reactive species for the RhB degradation under visible light. The increased photocatalytic activity of the GO/AgBr nanocomposites was attributed to the strong coupling between GO and AgBr, which facilitated interfacial charge transfer and inhibited electron-hole recombination. A photocatalytic mechanism of GO/AgBr nanocomposites was also proposed.

  18. TiO2/Ag modified penta-bismuth hepta-oxide nitrate and its adsorption performance for azo dye removal.

    PubMed

    Abdullah, Eshraq Ahmed; Abdullah, Abdul Halim; Zainal, Zulkarnain; Hussein, Mohd Zobir; Ban, Tan Kar

    2012-01-01

    A modified hydrophilic penta-bismuth hepta-oxide nitrate (Bi5O7NO3) surface was synthesized via a precipitation method using TiO2 and Ag as modified agents. The synthesized product was characterized by different analytical techniques. The removal efficiency was evaluated using mono- and di-sulphonated azo dyes as model pollutants. Different kinetic, isotherm and diffusion models were chosen to describe the adsorption process. X-ray photoelectron spectroscopy (XPS) results revealed no noticeable differences in the chemical states of modified adsorbent when compared to pure Bi5O7NO3; however, the presence of hydrophilic centres such as TiO2 and Ag developed positively charged surface groups and improved its adsorption performance to a wide range of azo dyes. Dyes removal was found to be a function of adsorbent dosage, initial dye concentration, solution pH and temperature. The reduction of Langmuir 1,2-mixed order kinetics to the second or first-order kinetics could be successfully used to describe the adsorption of dyes onto the modified adsorbent. Mass transfer can be described by intra-particle diffusion at a certain stage, but it was not the rate limiting step that controlled the adsorption process. Homogenous behavior of adsorbent surface can be explored by applying Langmuir isotherm to fit the adsorption data.

  19. 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.

  20. Highly Wavelength-Selective Enhancement of Responsivity in Ag Nanoparticle-Modified ZnO UV Photodetector.

    PubMed

    Wang, Xiao; Liu, Kewei; Chen, Xing; Li, Binghui; Jiang, Mingming; Zhang, Zhenzhong; Zhao, Haifeng; Shen, Dezhen

    2017-02-15

    We proposed and demonstrated Ag nanoparticles (NPs)-decorated ZnO photodetectors for UV light sensing. After decoration of their surface with random Ag NPs, the dark current density of ZnO UV photodetectors decreases obviously. Moreover, the device exhibits an obvious increase in peak responsivity at around 380 nm, which can be attributed to the narrow-band quadrupole plasmon resonance of Ag NPs in the UV range. Meanwhile, the responsivity at the other wavelengths decreases a lot. As a result, the response peak becomes more significant, and the response of the devices presents an excellent wavelength selectivity after covering with Ag NPs. The detailed mechanism for this phenomenon was explained. We believe that our findings would open a way to harness the high-order plasmon modes in the field of UV optoelectronic devices.

  1. Preparation, characterization and electrochemical application of Ag-ZnO nanoplates for voltammetric determination of glutathione and tryptophan using modified carbon paste electrode.

    PubMed

    Beitollahi, Hadi; Gholami, Abbas; Ganjali, Mohammad Reza

    2015-12-01

    Ag-ZnO nanoplates and 2-chlorobenzoyl ferrocene were synthesized and used to construct a modified carbon paste electrode. The electrooxidation of glutathione at the surface of the modified electrode was studied. Under the optimized conditions, the square wave voltammetric (SWV) peak current of glutathione increased linearly with glutathione concentrations in the range of 5.0 × 10(-8) to 2.0 × 10(-4)M with sensitivity of 0.659 μA μM(-1) and method detection limit of 20.0 nM was obtained for glutathione. The prepared modified electrode exhibits a very good resolution between the voltammetric peaks of glutathione and tryptophan which makes it suitable for the detection of glutathione in the presence of tryptophan in real samples.

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

    PubMed

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

    2015-11-27

    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.

  3. 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.

  4. Modifying γ-Al2O3 surface with Y2Sn2O7 pyrochlore: on monolayer dispersion behaviour of composite oxides.

    PubMed

    Xu, Xianglan; Liu, Fang; Tian, Jinshu; Peng, Honggen; Liu, Wenming; Fang, Xiuzhong; Zhang, Ning; Wang, Xiang

    2017-03-21

    To investigate the dispersion behaviours of composite oxides onto the supports, and to achieve better supports for Pd for CO oxidation, a series of Y2Sn2O7/Al2O3 composite oxides with different Y2Sn2O7 loadings were prepared via deposition-precipitation method. Using XRD and XPS extrapolation methods, it is revealed that similar to single component metal oxides, composite oxides can also disperse spantaneously onto the support surfaces to form a monlayer with a certain capacity. The monolayer dispersion capacity/threshhold for Y2Sn2O7 on γ-Al2O3 surface is 0.109 mmol*100 m-2 γ-Al2O3, equalling to 7.2% Y2Sn2O7 weight loading. It is deserved to mention here that this is the first work to demonstrate the monolayer dispersion phenomenon of a composite oxide on a support. After the combination of Y2Sn2O7 with γ-Al2O3, active oxygen species can be introduced onto the catalyst surfaces. Therefore, the interaction between Pd and the supports can be strengthened, thus improving the Pd dispersion in comparison with the individual Y2Sn2O7 support and inducing synergistic effect between Pd and the composite supports, which is beneficial to the activity of the catalysts. By tuning the γ-Al2O3 surface with different amount of pyrochlore Y2Sn2O7 compound, the CO oxidation activity on the 1%Pd/Y2Sn2O7/Al2O3 has been improved. These findings may put new insights for people to design and prepare competitve supported noble metal catalysts with less amount of noble metals.

  5. 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

  6. Improved Wetting Characteristics in TiO2–Modified Ag-CuO Air Braze Filler Metals

    SciTech Connect

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

    2006-01-04

    A silver-based joining technique referred to as reactive air brazing (RAB) has been recently developed for joining high temperature structural ceramic components of the type used in high-temperature electrochemical devices. In prior work, it was found that additions of CuO to silver have a significant effect on the wettability and joint strength characteristics of the resulting braze on polycrystalline alumina substrates. More recently, it has been found that by adding as little as 0.5 mol % titania to these Ag-CuO brazes, the wettability of the RAB on alumina surfaces is further enhanced. The results of wettabilty measurements of Ag-CuO-TiO2 RAB compositions on alumina will be presented along with the microstructural characterization of Ag-CuO-TiO2 braze joints in alumina.

  7. Design of Ag-Modified TiO2-Based Films with Controlled Optical and Photocatalytic Properties

    NASA Astrophysics Data System (ADS)

    Smirnova, N. P.; Manuilov, E. V.; Korduban, O. M.; Gnatyuk, Yu. I.; Kandyba, V. O.; Eremenko, A. M.; Gorbyk, P. P.; Shpak, A. P.

    TiO2-based functional coatings doped with Ag nanoparticles were prepared via template assisted sol-gel method with an attempt to enhance the decomposition reaction rate of industrial water pollutants. The films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron (XPS), and UV-vis spectroscopies. Catalytic activity in photooxidative organic dyes decomposition remarkably enhances TiO2/ZnO samples with homogeneously distributed noble metal nanoparticles. Ag nanoparticles in TiO2 matrix improve an efficiency of charge separation and charge-transfer processes, acting as traps for photoinduced electrons.

  8. Improved Wetting Characteristics in TiO2–Modified Ag-CuO Air Braze Filler Metals

    SciTech Connect

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

    2006-01-01

    In this paper we report on the results of a series of sessile drop experiments designed to examine the effect of TiO2 on the wetting behavior of Ag-CuO air braze filler metals. It was found that TiO2 concentrations as small as 0.5 mol% can significantly decrease the contact angle of Ag-CuO on alumina over a compositional range of 1 – 34mol% CuO. The effect appears to maximize at a copper oxide concentration of ~4 mol% CuO regardless of the titania content.

  9. 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.

  10. High-efficiency AgInS(2)-modified ZnO nanotube array photoelectrodes for all-solid-state hybrid solar cells.

    PubMed

    Han, Jianhua; Liu, Zhifeng; Guo, Keying; Ya, Jing; Zhao, Yufeng; Zhang, Xueqi; Hong, Tiantian; Liu, Junqi

    2014-10-08

    Highly ordered AgInS2-modified ZnO nanoarrays were fabricated via a low-cost hydrothermal chemical method, and their application as all-solid-state solar cells was also tested. A sensitizer and a buffer layer were developed around the surface of ZnO nanotubes in the preparation process, and this method is easily be manipulated to produce uniform structure. In this structure, the ZnO served as direct electron transport path, the ZnS as the buffer layer, and the ternary sensitizer AgInS2 as absorber and outer shell. The novel all-solid-state hybrid solar cells (ITO/ZnO/ZnS/AgInS2/P3HT/Pt) showed improved short-circuit current density (Jsc) of 7.5 mA/cm(2), open-circuit voltage (Voc) of 512 mV, giving rise to a power conversion efficiency of 2.11%, which is the relatively highest value ever reported for ZnO-based all-solid-state hybrid solar cells. This better result is attributed to the improved absorption spectrum, high speed of photoinduced charge transmission velocity, and appropriate gradient energy gap structure, which implies a promising application in all-solid-state solar cells.

  11. Equilibrium adsorption isotherm studies of Cu (II) and Co (II) in high concentration aqueous solutions on Ag-TiO2-modified kaolinite ceramic adsorbents

    NASA Astrophysics Data System (ADS)

    Ajenifuja, E.; Ajao, J. A.; Ajayi, E. O. B.

    2016-03-01

    Photocatalytic ceramic adsorbents were prepared from locally sourced kaolinite clay minerals for the removal of copper and cobalt ions from high concentration aqueous solutions. The minerals were treated with mild acid before modification using silver nanoparticles sources and titanium-oxide nanoparticles. Batch adsorption experiment was carried out on the targeted ions and the results were analyzed by Langmuir and Freundlich equation at different concentrations (100-1000 mg/l). As-received raw materials do not exhibit any adsorption capacity. However, the adsorption isotherms for modified kaolinite clay ceramic adsorbents could be fitted well by the Langmuir model for Cu2+ and Co2+ with correlation coefficient (R) of up to 0.99705. The highest and lowest monolayer coverage (q max) were 93.023 and 30.497 mg/g for Cu2+ and Co2+, respectively. The separation factor (R L ) was less than one (<1), indicating that the adsorption of metal ions on modified ceramic adsorbent is favorable. The highest adsorbent adsorption capacity (K f ) and intensity (n) constants obtained from Freundlich model are 14.401 (Cu2+ on KLN-T) and 6.057 (Co2+ on KLN-T).

  12. 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.

  13. Thermodynamic properties of Ag2O--B2O3 glasses by a modified scale-transformed energy space sampling Monte Carlo method.

    PubMed

    Nakamura, Hideaki; Aniya, Masaru

    2006-03-01

    The density of states of Ag(2)O--B(2)O(3) glasses has been calculated by using a modified scale-transformed energy space sampling algorithm. This algorithm combines the scale-transformed energy space sampling algorithm and the Wang-Landau method. It is shown how the two algorithms can be combined to improve the efficiency of calculation. The thermodynamic properties, in particular the specific heat C(V), of the above-mentioned glass system is studied. At temperatures above 80 K, the value of specific heat C(v) is close to 22 J/mol/K. At low temperatures, the deviations of C(v) from a T(3) behavior are discernible, that is, C(v)/T(3) exhibits a hump at T = 7 K, which is in good agreement with the reported experimental behavior.

  14. Photochemically controlled electrochemical deposition and dissolution of Ag0 nanoclusters on au electrode surfaces.

    PubMed

    Riskin, Michael; Katz, Eugenii; Gutkin, Vitaly; Willner, Itamar

    2006-12-05

    A photoisomerizable thiolated nitrospiropyran SP, (1a), monolayer is assembled on a Au electrode by the primary deposition of thiolated nitromerocyanine isomer 1b as a monolayer on the electrode, followed by the irradiation of the surface with visible light, lambda > 475 nm. The surface coverage of nitrospiropyran units (1a) on the electrode is 2 x 10-10 mole cm-2. Irradiation of the electrode with UV light, 320 nm < lambda < 360 nm, results in the nitromerocyanine, MR, monolayer on the electrode that binds Ag+ ions to the phenolate units. The Ag+ ions associated with the MR monolayer undergo cyclic reduction to surface-confined Ag0 nanoclusters, and reoxidation and dissolution of the Ag0 nanoclusters to Ag+ ions associated with the monolayer are demonstrated. The electron-transfer rate constants for the reduction of Ag+ to Ag0 and for the dissolution of Ag0 were determined by chronoamperometry and correspond to ketred = 12.7 s-1 and ketox = 10.5 s-1, respectively. The nanoclustering rate was characterized by surface plasmon resonance measurements, and it proceeds on a time scale of 10 min. The size of the Ag0 nanoclusters is in the range of 2 to 20 nm. The electrochemically induced reduction of the MR-Ag+ monolayer to the MR-Ag0 surface and the reoxidation of the MR-Ag0 surface control the hydrophilic-hydrophobic properties of the surface. The advancing contact angle of the MR-Ag0-functionalized surface is 59 degrees , and the contact angle of the MR-Ag+-monolayer-functionalized surface is 74 degrees . Photoisomerization of the Ag0-MR surface to the Ag0-SP state, followed by the oxidation of the Ag0 nanoclusters, results in the dissolution of the Ag+ ions into the electrolyte solution.

  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).

  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.

  17. 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.

  18. 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.

  19. Diamondoid monolayers as electron emitters

    DOEpatents

    Yang, Wanli [El Cerrito, CA; Fabbri, Jason D [San Francisco, CA; Melosh, Nicholas A [Menlo Park, CA; Hussain, Zahid [Orinda, CA; Shen, Zhi-Xun [Stanford, CA

    2012-04-10

    Provided are electron emitters based upon diamondoid monolayers, preferably self-assembled higher diamondoid monolayers. High intensity electron emission has been demonstrated employing such diamondoid monolayers, particularly when the monolayers are comprised of higher diamondoids. The application of such diamondoid monolayers can alter the band structure of substrates, as well as emit monochromatic electrons, and the high intensity electron emissions can also greatly improve the efficiency of field-effect electron emitters as applied to industrial and commercial applications.

  20. Raman spectroscopy and surface wetting of self-assembled monolayer (SAM) of 1-octanethiol and 1,10-decanedithiol

    NASA Astrophysics Data System (ADS)

    Lukose, J.; Kulal, V.; Bankapur, A.; George, S. D.; Chidangil, S.; Sinha, R. K.

    2016-08-01

    We report the preparation of mixed self-assembled monolayer of 1-octanethiol and 1,10-decanedithiol on Au thin film with preferential Au(111) surface and their characterization using Raman spectroscopy of cysteine adsorbed on mixed self-assembled monolayer mediated isolated Ag nanoparticles. The self-assembled monolayer characterization has been also performed through water contact angle measurement. A significant enhancement in water contact angle from 24° to 103° has been observed on Au surface after self-assembled monolayer formation, primarily due to the hydrophobic nature of the methyl group at the terminal end of the 1-octanethiol, which confirms regular self-assembled monolayer formation. Availability of -SH group from 1,10-decanedithiol on the self-assembled monolayer surface and so, the formation of mixed self-assembled monolayer has been ascertained by immobilization of Ag nanoparticles probed via scanning electron microscopy and Raman spectroscopy of cysteine adsorbed on Ag nanoparticles. Raman spectrum of cysteine on self-assembled monolayer mediated Ag nanoparticles in the fingerprint region of 500-1800 cm-1 shows appreciable increase in the band intensity due to surface enhanced Raman scattering as compared to the band intensity on bare Au surface. These results clearly indicate that the mixed self-assembled monolayer with adequate proportion of component molecules can be utilized as a suitable and inexpensive host for surface enhanced Raman scattering substrates.

  1. Temperature dependence of the interaction of prazosin with lipid Langmuir monolayers.

    PubMed

    Gzyl-Malcher, Barbara; Handzlik, Jadwiga; Klekowska, Ewelina

    2013-12-01

    The influence of temperature on membrane-prazosin interactions was studied. Prazosin, a quinazoline derivative of 2-furoylpiperazine, is a classic antihypertensive and antiarrhythmic drug. A mixed cholesterol/phospholipid monolayer at the water/air interface was employed as a simplified biomembrane model. Brewster angle microscopy (BAM) was used to visualize the monolayer morphology. It was found that prazosin penetrates Langmuir monolayers and modifies the interactions between membrane components, causing monolayer fluidization. An increase in temperature facilitates penetration of prazosin into the monolayers. Prazosin interacts preferentially with phosphatidylcholine and modifies the morphology of the condensed phase domains of DPPC. In the presence of prazosin, monolayers collapse at lower surface pressures. The difference between the collapse pressures of monolayers on water with and without prazosin increases with temperature.

  2. Removal of gas phase low-concentration toluene over Mn, Ag and Ce modified HZSM-5 catalysts by periodical operation of adsorption and non-thermal plasma regeneration.

    PubMed

    Wang, Wenzheng; Wang, Honglei; Zhu, Tianle; Fan, Xing

    2015-07-15

    Ag/HZSM-5, Mn/HZSM-5, Ce/HZSM-5, Ag-Mn/HZSM-5 and Ce-Mn/HZSM-5 were prepared by impregnation method. Both their adsorption capacity and catalytic activity were investigated for the removal of gas phase low-concentration toluene by periodical operation of adsorption and non-thermal plasma regeneration. Results show that catalysts loaded with Ag (Ag/HZSM-5 and Ag-Mn/HZSM-5) had larger adsorption capacity for toluene than the other catalysts. And Ag-Mn/HZSM-5 displayed the best catalytic performance for both toluene oxidation by non-thermal plasma and byproducts suppression. On the other hand, the deactivated catalyst can be fully regenerated by calcining in air stream when its adsorption capacity and catalytic activity of the Ag-Mn/HZSM-5 catalyst was found to be decreased after 10 cycles of periodical adsorption and non-thermal regeneration.

  3. 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.

  4. The constitutive creep equation for a eutectic Sn-Ag alloy using the modified theta-projection concept

    NASA Astrophysics Data System (ADS)

    Kariya, Yoshiharu; Otsuka, Masahisa; Plumbridge, William J.

    2003-12-01

    Creep data for a eutectic tin-silver alloy at temperatures between 298 K and 398 K have been analyzed using the modified theta-projection concept, instead of the steady-state creep constitutive equation in the following formula: ɛcr=A {1-exp(-αt)}+B {exp(αt)-1}, where A, B, and α are constants to be experimentally determined. The equation describes well the creep curves of the eutectic tin-silver alloy up to the tertiary stage. All constants exhibited power law relationships with the applied stress. The rate constant, α, has a high stress exponent, which is attributed to dispersion strengthening. The rate constant a and the strain factor B only showed temperature dependence, while the strain factor A was independent of temperature. The activation energy for α was 65 kJ/mol at high stresses and 90 kJ/mol at low stresses. The energies suggest that the dislocation pipe diffusion and the lattice diffusion are predominant at high stresses and low stresses, respectively.

  5. 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.

  6. 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.

  7. Extraordinary optical transmission through metal-coated colloidal monolayers

    NASA Astrophysics Data System (ADS)

    Landström, L.; Brodoceanu, D.; Piglmayer, K.; Bäuerle, D.

    2006-09-01

    Extraordinary optical transmission through metal-coated close-packed monolayers has been observed. The monolayers consist of silica (a-SiO2) or polystyrene microspheres that form two-dimensional close-packed lattices by self-assembly. Metal layers of Ag, Au and Ni with different thicknesses (larger than the skin depth) were evaporated onto such lattices by means of standard techniques. The optical transmission spectra investigated between 300 and 2500 nm show pronounced peaks that scale with the diameter and the optical properties of the composite slabs. The enhanced transmission observed is most likely mediated via plasmons.

  8. 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.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    In this study, we present a theoretical investigation of structural, electronic, and mechanical properties of pentagonal monolayers of carbon (p-graphene), boron nitride (p-B2N4 and p-B4N2), and silver azide (p-AgN3) 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-AgN3 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-B2N4 and p-B4N2 have negative Poisson's ratio values. On the other hand, the p-AgN3 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-B2N4 are stable, but p-AgN3 and p-B4N2 are vulnerable against vibrational excitations.

  11. 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

  12. Adsorption of anionic dyes from aqueous solutions using chemically modified straw.

    PubMed

    Zhang, Wenxuan; Li, Haijiang; Kan, Xiaowei; Dong, Lei; Yan, Han; Jiang, Ziwen; Yang, Hu; Li, Aimin; Cheng, Rongshi

    2012-08-01

    The effective disposal of redundant straw is a significant work for environmental protection and full utilization of resource. In this work, the wheat straw has been modified by etherification to prepare a kind of quaternary ammonium straw adsorbents. The adsorption behaviors of the modified straw for methyl orange (MO) and acid green 25(AG25) were studied in both batch and column systems. The adsorption capacity of the straw for both dyes improved evidently after modification. The maximal MO and AG25 uptakes were more than 300 and 950 mg g(-1), respectively. Furthermore, the adsorption equilibrium, kinetics and column studies all indicated that the adsorption behavior was a monolayer chemical adsorption with an ion-exchange process. In addition, after adsorption of anionic dyes, the used adsorbents were successfully applied to adsorb a cationic dye directly at suitable conditions in the secondary adsorption. This was due to the altered surface structures of the used adsorbents.

  13. Monolayer Contact Doping from a Silicon Oxide Source Substrate.

    PubMed

    Ye, Liang; González-Campo, Arántzazu; Kudernac, Tibor; Núñez, Rosario; de Jong, Michel; van der Wiel, Wilfred G; Huskens, Jurriaan

    2017-04-03

    Monolayer contact doping (MLCD) is a modification of the monolayer doping (MLD) technique that involves monolayer formation of a dopant-containing adsorbate on a source substrate. This source substrate is subsequently brought into contact with the target substrate, upon which the dopant is driven into the target substrate by thermal annealing. Here, we report a modified MLCD process, in which we replace the commonly used Si source substrate by a thermally oxidized substrate with a 100 nm thick silicon oxide layer, functionalized with a monolayer of a dopant-containing silane. The thermal oxide potentially provides a better capping effect and effectively prevents the dopants from diffusing back into the source substrate. The use of easily accessible and processable silane monolayers provides access to a general and modifiable process for the introduction of dopants on the source substrate. As a proof of concept, a boron-rich carboranyl-alkoxysilane was used here to construct the monolayer that delivers the dopant, to boost the doping level in the target substrate. X-ray photoelectron spectroscopy (XPS) showed a successful grafting of the dopant adsorbate onto the SiO2 surface. The achieved doping levels after thermal annealing were similar to the doping levels acessible by MLD as demonstrated by secondary ion mass spectrometry measurements. The method shows good prospects, e.g. for use in the doping of Si nanostructures.

  14. 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.

  15. Visualizing Individual Nitrogen Dopants in Monolayer Graphene

    SciTech Connect

    L Zhao; R He; K Rim; T Schiros; K Kim; H Zhou; C Gutierrez; S Chockalingam; C Arguello; et al.

    2011-12-31

    In monolayer graphene, substitutional doping during growth can be used to alter its electronic properties. We used scanning tunneling microscopy, Raman spectroscopy, x-ray spectroscopy, and first principles calculations to characterize individual nitrogen dopants in monolayer graphene grown on a copper substrate. Individual nitrogen atoms were incorporated as graphitic dopants, and a fraction of the extra electron on each nitrogen atom was delocalized into the graphene lattice. The electronic structure of nitrogen-doped graphene was strongly modified only within a few lattice spacings of the site of the nitrogen dopant. These findings show that chemical doping is a promising route to achieving high-quality graphene films with a large carrier concentration.

  16. Absence of a Dirac cone in silicene on Ag(111): First-principles density functional calculations with a modified effective band structure technique

    NASA Astrophysics Data System (ADS)

    Wang, Yun-Peng; Cheng, Hai-Ping

    2013-06-01

    We investigate the currently debated issue of the existence of the Dirac cone in silicene on an Ag(111) surface, using first-principles calculations based on density functional theory to obtain the band structure. By unfolding the band structure in the Brillouin zone of a supercell to that of a primitive cell, followed by projecting onto Ag and silicene subsystems, we demonstrate that the Dirac cone in silicene on Ag(111) is destroyed. Our results clearly indicate that the linear dispersions observed in both angular-resolved photoemission spectroscopy [P. Vogt , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.108.155501 108, 155501 (2012)] and scanning tunneling spectroscopy [L. Chen , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.109.056804 109, 056804 (2012)] come from the Ag substrate and not from silicene.

  17. Highly efficient heterojunction photocatalyst based on nanoporous g-C3N4 sheets modified by Ag3PO4 nanoparticles: synthesis and enhanced photocatalytic activity.

    PubMed

    Jiang, Deli; Zhu, Jianjun; Chen, Min; Xie, Jimin

    2014-03-01

    Novel visible-light-driven heterojunction photocatalyst composed by Ag3PO4 nanoparticles and nanoporous graphitic carbon nitride sheets (Ag3PO4/p-g-C3N4) was synthesized by a facile and green method. The results showed that photocatalytic activity of Ag3PO4/p-g-C3N4 was much higher than that of pure p-g-C3N4 in the photodegradation of Rhodamine B under visible light irradiation. The kinetic constant of Rhodamine B degradation over Ag3PO4 (33.3 mol%)/p-g-C3N4 was about 5 and 2 times higher than that over pure p-g-C3N4 and Ag3PO4, respectively. The enhanced photocatalytic performance is attributed to the stronger visible light absorption and the heterojunction between Ag3PO4 nanoparticles and p-g-C3N4, which could induce the low recombination rate of photoinduced electron-hole pairs.

  18. 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

  19. Effects of Ge replacement in GeTe by Ag or Sb on the Seebeck coefficient and carrier concentration modified by local electron imbalance

    NASA Astrophysics Data System (ADS)

    Levin, E. M.; Howard, A.; Straszheim, W. E.

    2015-03-01

    XRD, SEM, EDS, 125Te NMR, Seebeck coefficient, and electrical resistivity of AgxGe50-xTe50 and SbxGe50-xTe50 alloys have been studied. Replacement of Ge in GeTe by Sb significantly increases the Seebeck coefficient, while replacement by Ag decreases it. These effects can be attributed to a change in carrier concentration observed via 125Te NMR spin-lattice relaxation measurements and NMR signal position, which mostly depends on the Knight shift. Variation in carrier concentration in AgxGe50-xTe50 and SbxGe50-xTe50 can be attributed to different electron configurations of valence electrons of Ag (4d105s1) and Sb (5s25p3) compared to that of Ge (4s24p2) resulting in local electron imbalances and changing the concentration of charge carrier (holes) generated by Ge vacancies. In contrast, our 125Te NMR and Seebeck coefficient data for Ag2Sb2Ge46Te50 are similar to those observed for GeTe. This shows that effects from Ag and Sb compensate each other and indicates the existence of [Ag +Sb] pairs. The effects of Ge replacement in GeTe by Ag, Sb, or [Ag +Sb] on rhombohedral lattice distortion also have been analyzed. Interplay between the Seebeck coefficient and electrical resistivity in these alloys results in variation of power factor; the value of 45 mW/cm K2, the highest among known tellurides, was found for Sb2Ge48Te50.

  20. Ag modified LaMnO3 nanorods-reduced graphene oxide composite applied in the photocatalytic discoloration of direct green

    NASA Astrophysics Data System (ADS)

    Hu, Jie; Liu, Yuanyuan; Men, Jie; Zhang, Liang; Huang, Hao

    2016-11-01

    A new nanostructure photocatalyst, incorporating Ag and reduced graphene oxide (rGO) with LaMnO3-nanorods have been fabricated via two-step synthetic approaches by using Cetyltrimethyl Ammonium Bromide (CTAB) as a template via a simple hydrothermal reaction and the decoration of Ag nanoparticles is through a traditional silver mirror reaction. The characteristic of the materials are examined by XRD, TEM, FE-SEM and XPS. The results confirm that the LaMnO3 nanorods are perovskite phase and uniform dispersed on the surface of rGO. The Ag nanoparticles is deposited the surface of LaMnO3-nanorods with its metal form. The Ag/LaMnO3-nanorods/rGO exhibit an excellent performance in the photo-degradation of Direct Green BE under the UV-vis irradiation. As an electron capture agent, metal Ag can capture the e- that transported along the LMO-NR, thereby leading to effective separation of the e--h+ pairs and accelerate the transfer of surface charge, which is further demonstrated by the Photoluminescence (PL) spectra, cyclic voltammetry (CV) and AC impedance spectra.

  1. Grafted silane monolayers: reconsideration of growth mechanisms

    NASA Astrophysics Data System (ADS)

    Ivanov, D. A.; Nysten, B.; Jonas, A. M.; Legras, R.

    1998-03-01

    Chemical force microscopy is a new technique devised to image chemical heterogeneities on surfaces. It requires the chemical modification of Atomic Force Microscopy (AFM) tips in order to create chemical probes. In this respect, self-assembled monolayers (SAM) of alkylchlorosilanes are particularly interesting as modifying agents for AFM tips. We report here our results on the kinetics of silanization and on the structure of such SAM's grafted on model surfaces (hydroxylated Si(100) wafers). AFM, contact angle measurements, X-ray reflectivity and X-ray photoelectron spectroscopy were used to characterize SAM's of octadecyltrichlorosilane (OTS) and octadecyldimethylchlorosilane (ODMS) grown from hexadecane and toluene solutions. The mechanism of grafting of OTS follows two stages. The first rapid stage corresponds to the nucleation and growth of island-like monolayer domains. The second slower stage is related to the densification of the monolayer. SAM's of ODMS were found to form thinner layers as compared to OTS, due to their lower grafting density probably resulting in a more disordered state of grafted alkyl chains. We also address the problems concerning the relationships between the quality of final SAM structures and the water content as well as the nature of the solvent used for silanization.

  2. Synthesis and characterization of NaX nanozeolite using stem sweep as silica source and application of Ag-modified nanozeolite in electrocatalytic reduction of H2O2.

    PubMed

    Azizi, Seyed Naser; Ghasemi, Shahram; Kavian, Safura

    2014-12-15

    Nanozeolite is one of the three dimensional nanoporous materials consisting of extremely accessible surface area and shorter diffusion pathways. In this study, NaX nanozeolite is synthesized using the hydrothermal method from natural silica source of stem sweep ash (SSA). The synthesized nanoparticles were characterized using X-ray diffraction, scanning electronic microscopy, Brunauer-Emmett-Teller (BET) and FT-IR techniques. The synthesized nanozeolite is used incorporating Ag (I) ions for preparing modified carbon paste electrode (Ag/X-CPE) as an electrochemical sensor for the reduction of H2O2. Electrochemical results demonstrate that nanozeolite provides a promising platform for the development of electrochemical sensors in biosensing and Ag/X-CPE electrode possesses the remarkable catalytic activity toward the H2O2 reduction. Amprometric results show that this sensor could detect H2O2 in linear ranges of 20 µM to 1.76 mM and 1.76-11.76 mM with a detection limit of 9.1 µM at a signal-to-noise ratio of 3 and a response time of 2s. Furthermore, this sensor exhibited good anti-interference and selectivity.

  3. Dynamical tuning of energy transfer efficiency on a graphene monolayer

    NASA Astrophysics Data System (ADS)

    Karanikolas, Vasilios D.; Marocico, Cristian A.; Bradley, A. Louise

    2015-03-01

    In this contribution we present a theoretical investigation of the energy transfer efficiency between quantum systems placed in proximity of a monolayer of conducting graphene. We calculate the spontaneous emission rate of a quantum system and the energy transfer rate between a donor-acceptor pair, and thus the energy transfer efficiency, using a Green's tensor formalism. The direct interaction between the donor and acceptor dominates when they are close to each other, but is modified from its free-space behavior due to the presence of the graphene monolayer and its interaction with the donor and acceptor. We report on a very large influence of the graphene monolayer on the energy transfer efficiency due to both the Förster mechanism and the propagating graphene plasmon mode. In particular, the Förster radius R0 is modified from its free-space value of 20 nm and can reach values of 120 nm when close to a graphene monolayer. As the donor-acceptor separation is increased, their direct interaction is overshadowed by the interaction via the surface plasmon mode. Due to the large propagation length of the surface plasmon mode on graphene, an energy transfer efficiency as high as 50% can still be achieved for distances as large as 300 nm. The interaction via the surface plasmon mode is tunable via the doping of the graphene monolayer and the surface plasmon channel can also be switched off this way.

  4. Application of disorganized monolayer films on gold electrodes to the prevention of surfactant inhibition of the voltammetric detection of trace metals via anodic stripping of underpotential deposits: detection of copper.

    PubMed

    Herzog, Grégoire; Arrigan, Damien W M

    2003-01-15

    Development of an approach to prevention of electrode surface fouling by surfactants in samples is demonstrated. Spontaneously adsorbed monolayer systems employing short alkyl chains and bulky end groups are used to form porous disorganized monolayers on gold electrodes. Detection of copper by stripping of underpotential deposits formed at electrodes modified with disorganized films of mercaptoethanesulfonate (MES), mercaptopropanesulfonate, mercaptoacetic acid, and mercaptopropanoic acid was possible, and to a much lesser extent at aminoethanethiol and L-cysteine films. Use of short deposition times in conjunction with linear sweep anodic stripping voltammetry allowed detection of Cu2+ ions down to 1 x 10(-6) M in sulfuric acid solution, using underpotential deposition as the deposition step of the procedure. Calibration graphs were linear in the concentration range (1-80) x 10(-6) M Cu2+ using 15-s deposition at 0.00 V versus Ag/AgCl. The surfactants Tween 20, Tween 80, and Triton X-100 were found to have no affect on detection of Cu2+ ions in the calibration curve concentration range using MES-modified gold electrodes, whereas at unmodified gold electrodes very severe attenuation of the detection capability was manifested. The average slope for all calibration curves at the MES-modified electrode in the absence and presence of the surfactants at two different concentration levels was 0.0710 +/- 0.0024 microA microM(-1); in contrast, the slope of the calibration line at uncoated gold electrodes in the presence of surfactant was 0.0268 microA microM(-1). These results indicate the excellent ability of a disorganized, porous monolayer for prevention of fouling of the electrode surface by the surfactants.

  5. Synthesis of one-dimensional silver oxide nanoparticle arrays and silver nanorods templated by Langmuir monolayers.

    PubMed

    Liu, Hong-Guo; Xiao, Fei; Wang, Chang-Wei; Xue, Qingbin; Chen, Xiao; Lee, Yong-Ill; Hao, Jingcheng; Jiang, Jianzhuang

    2007-10-01

    One-dimensional (1D) silver oxide nanoparticle arrays were synthesized by illuminating the composite Langmuir-Blodgett monolayers of porphyrin derivatives/Ag(+) and n-hexadecyl dihydrogen phosphate (n-HDP)/Ag(+) deposited on carbon-coated copper grids with daylight and then exposing them to air. Transmission electron microscopy (TEM) observation shows that the nanoparticle size is around 3 nm, with the separation of about 2-3 nm. High-resolution TEM (HRTEM) investigation indicates that the particles are made up of Ag(2)O. Ag nanorods with the width of 15-35 nm and the length of several hundreds of nanometers were synthesized by irradiating the composite Langmuir monolayers of porphyrin derivatives/Ag(+) and n-HDP/Ag(+) by UV-light directly at the air/water interface at room temperature. HRTEM image and selected-area electron diffraction (SAED) pattern indicate that the nanorods are single crystals with the (110) face of the face-centered cubic (fcc) silver parallel to the air/water interface. The formation of the 1D arrays and the nanorods should be attributed to the templating effect of the linear supramolecules formed by porphyrin derivative or n-HDP molecules in Langmuir monolayers through non-covalent interactions.

  6. 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.

  7. Chemical trends of the magnetocrystalline anisotropy of magnetic monolayers

    NASA Astrophysics Data System (ADS)

    Nie, X.; Wei, Su-Huai; Blügel, Stefan

    2001-03-01

    The in-plane and out-of-plane magnetocrystalline anisotropy energies of 3d, 4d, and 5d magnetic monolayers are calculated using the self-consistent density functional theory in the local spin density approximation (LSDA) and the generalized gradient approximation (GGA), as implemented by the film and bulk FLAPW code FLEUR. The spin-orbit interaction is included using a second variation method. The magnetic monolayers are treated as free-standing or strained coherently on various substrates [e.g., Cu(100), Ag(100)]. To monitor the chemical trend of the magnetocrystalline anisotropy, orbital and spin moment, the nuclear number Z of the atom was varied artificially in steps of Δ Z = 0.1. This approach is better than the simple band filling arguments since it includes the change of the electronic structure due to the change of the atomic potentials. We find that the magnetic anisotropy and the anisotropy of the orbital moment is a rapidly oscillating function between in-plane and out-of-plane easy axis across the transition-metal series. The anisotropy energy increases rapidly when the atomic number of the atom increases in a row. Monolayers grown on Cu(100) and Ag(100) substrate show a very similar trend. The trend of the anisotropy energy is explained in terms evolution of the band structures. The relation between the anisotropy energy and the orbital moment is discussed.

  8. Morphology and mechanical properties of nanocrystalline Cu/Ag alloy

    NASA Astrophysics Data System (ADS)

    Li, Ao; Szlufarska, Izabela

    2017-04-01

    Hybrid Monte Carlo (MC)/molecular dynamics (MD) simulations are conducted to study the microstructures of nanocrystalline (nc) Cu/Ag alloys with various Ag concentrations. When the Ag concentration is below 50 Ag atoms/nm!, an increase in Ag concentration leads to a gradual growth of monolayer grain boundary (GB) complexions into nanolayer complexions. Above the concentration of 50 Ag atoms/nm!, wetting layers with a bulk crystalline phase are observed. The effects of Ag on mechanical properties and deformation mechanisms of nc Cu/Ag alloys are investigated in MD simulations of uniaxial tension. GB sliding resistance is found to first increase and then decrease with an increase in Ag concentration. Surprisingly, we also find that the dislocation density decreases monotonically with an increase in Ag concentration, which suggests that the grain interiors are softened by the introduction of Ag dopants at GBs. In addition, there is a critical Ag concentration that maximizes flow stress of nc Cu/Ag alloys. The flow stress, GB sliding resistance, and the intragranular dislocation densities become less sensitive to Ag dopants when the grain diameter increases from 5nm to 40nm.

  9. Plasmon enhanced photoelectrochemical sensing of mercury (II) ions in human serum based on Au@Ag nanorods modified TiO₂ nanosheets film.

    PubMed

    Zhang, Yong; Shoaib, Anwer; Li, Jiaojiao; Ji, Muwei; Liu, Jiajia; Xu, Meng; Tong, Bin; Zhang, Jiatao; Wei, Qin

    2016-05-15

    Taking advantages of the monodisperse TiO2 nanosheets (NSs) with high active crystal face exposure and the tunable localized surface plasmon resonance (LSPR) properties of Au@Ag nanorods (NRs), this study demonstrated that TiO2 NSs film with trace amount of Au@Ag NRs modification possess a strong enhancement of photocurrent response, which was remarkably inhibited with the addition of mercury (II) ions (Hg(2+)). Based on the selective decrease of photocurrent with the addition of Hg(2+), a simple photoelectrochemical (PEC) sensor has been assembled. The PEC sensor exhibits wide linear range (0.01-10nM), low detection limit (2.5 pM), satisfying selectivity, reproducibility and acceptable stability for Hg(2+) detection. The feasibility of this method for practical application in human serum has been evaluated and the result was satisfactory. This PEC sensing method would provide a potential application for Hg(2+) detection in clinical diagnosis.

  10. 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.

  11. Self-Assembled Monolayers: a Molecular Resolution STM Study

    NASA Astrophysics Data System (ADS)

    Dhirani, Al-Amin

    Building on studies of self-assembled monolayers (SAMs) based on the (CH_3(CH _2)_{rm n{-}1}SH) + Au(111) prototype, we have designed and constructed a high impedance STM to consider the formation and properties of new SAM systems with molecular resolution. On Au-, Ag-, and Pt-(111), the monolayer structures of n-decanethiol were found to be (1) ordered on gold and silver but not platinum (2) strongly correlated with the structures formed by simpler sulfur components. In addition the potential formation and properties of new molecular classes of ordered SAMs were considered by studying monolayers of H(C _6H_4Cequiv C)_{rm n}C _6H_4SH (n = 0 - 2) (1a - c) on Au(111). An increase in order with chain length as well as the formation of an ordered SAM by 1c were observed. Finally, current-voltage (I-V) measurements of 1 monolayers displayed an increasing nonlinearity with chain length and an asymmetry for 1c. The electrical behavior is consistent with a model based on a semi-classical tunneling formalism using the barrier height and molecular polarizability of 1.

  12. 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.

  13. 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.

  14. Structure and function evolution of thiolate monolayers on gold

    SciTech Connect

    Edwards, Grant Alvin

    2006-01-01

    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 (infrared 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.

  15. Structure and Function Evolution of Thiolate Monolayers on Gold

    SciTech Connect

    Edwards, Grant Alvin

    2006-01-01

    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.

  16. Surface-segregated monolayers: a new type of ordered monolayer for surface modification of organic semiconductors.

    PubMed

    Wei, Qingshuo; Tajima, Keisuke; Tong, Yujin; Ye, Shen; Hashimoto, Kazuhito

    2009-12-09

    We report a new type of ordered monolayer for the surface modification of organic semiconductors. Fullerene derivatives with fluorocarbon chains ([6,6]-phenyl-C(61)-buryric acid 1H,1H-perfluoro-1-alkyl ester or FC(n)) spontaneously segregated as a monolayer on the surface of a [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) film during a spin-coating process from the mixture solutions, as confirmed by X-ray photoelectron spectroscopy (XPS). Ultraviolet photoelectron spectroscopy (UPS) showed the shift of ionization potentials (IPs) depending on the fluorocarbon chain length, indicating the formation of surface dipole moments. Surface-sensitive vibrational spectroscopy, sum frequency generation (SFG) revealed the ordered molecular orientations of the C(60) moiety in the surface FC(n) layers. The intensity of the SFG signals from FC(n) on the surface showed a clear odd-even effect when the length of the fluorocarbon chain was changed. This new concept of the surface-segregated monolayer provides a facile and versatile approach to modifying the surface of organic semiconductors and is applicable to various organic optoelectronic devices.

  17. 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

    2014-09-07

    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.

  18. Studies of Monolayers of Cyclodextrin and Flavin Derivatives

    DTIC Science & Technology

    2007-11-02

    formation has been continued. These flavins are modified in the N-10 position with a methylthiopropyl group or other alkyl groups and can have electron ...the reduction potentials for the 7- carboxyl (-0.36 V) and 7-trifluoromethyl (-0.25 V) vs. Ag|AgCl show the versatility of this approach. Electron ...for polishing silver foil and electrochemical roughening have been investigated and practiced by the PI. (3) An automated surface tensiometer has

  19. 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.

  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. Tuning Oleophobicity of Silicon Oxide Surfaces with Mixed Monolayers of Aliphatic and Fluorinated Alcohols.

    PubMed

    Lee, Austin W H; Gates, Byron D

    2016-12-13

    We demonstrate the formation of mixed monolayers derived from a microwave-assisted reaction of alcohols with silicon oxide surfaces in order to tune their surface oleophobicity. This simple, rapid method provides an opportunity to precisely tune the constituents of the monolayers. As a demonstration, we sought fluorinated alcohols and aliphatic alcohols as reagents to form monolayers from two distinct constituents for tuning the surface oleophobicity. The first aspect of this study sought to identify a fluorinated alcohol that formed monolayers with a relatively high surface coverage. It was determined that 1H,1H,2H,2H-perfluoro-1-octanol yielded high quality monolayers with a water contact angle (WCA) value of ∼110° and contact angle values of ∼80° with toluene and hexadecane exhibiting both an excellent hydrophobicity and oleophobicity. Tuning of the oleophobicity of the modified silicon oxide surfaces was achieved by controlling the molar ratio of 1H,1H,2H,2H-perfluoro-1-octanol within the reaction mixtures. Surface oleophobicity progressively decreased with a decrease in the fluorinated alcohol content while the monolayers maintained their hydrophobicity with WCA values of ∼110°. The simple and reliable approach to preparing monolayers of a tuned composition that is described in this article can be utilized to control the fluorocarbon content of the hydrophobic monolayers on silicon oxide surfaces.

  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. Electrodeposition of a Pt monolayer film: using kinetic limitations for atomic layer epitaxy.

    PubMed

    Brimaud, Sylvain; Behm, R Jürgen

    2013-08-14

    A new and facile one-step method to prepare a smooth Pt monolayer film on a metallic substrate in the absence of underpotential deposition-type stabilizations is presented as a general approach and applied to the growth of Pt monolayer films on Au. The strongly modified electronic properties of these films were demonstrated by in situ IR spectroscopy at the electrified solid-liquid interface with adsorbed carbon monoxide serving as a probe molecule. The Pt monolayer on Au is kinetically stabilized by adsorbed CO, inhibiting further Pt deposition in higher layers.

  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. 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.

  7. In Situ Surface X-Ray Crystallography of Electrochemically Deposited BI on AG (111): Structure, Compressibility, and Anisotropy

    DTIC Science & Technology

    1991-01-29

    underpotentially deposited monolayer of Bi on Ag(lll). The Bi forms a two-dimensional nearly centered rectangular structure that is uniaxially...measurements on an underpotentially deposited monolayer of Bi on Ag(l 11). The Bi forms a two-dimensional nearly centered rectangular structure that is... deposited at a potential positive of the Nernst potential for bulk deposition . This is termed underpotential deposition (UPD) (1). Then atthe Nernst

  8. Stability and Electronic properties of Ultra-thin Metallic nanowires on MoS2 monolayer

    NASA Astrophysics Data System (ADS)

    Kumar, Ashok; Zhong, Xiaoliang; Gupta, Sanjeev K.; Ahluwalia, P. K.; Karna, Shashi P.; Pandey, Ravindra

    2014-03-01

    MoS2 has emerged as a promising 2D nanomaterial for several technological applications. It has recently been shown that the highly capacitive Au nanoparticles raised the effective gate voltage for the MoS2 based device by an order of magnitude (Nano Lett. 13, 4434-41, 2013). In this talk, we examine stability and electronic properties of commensurable ultra-thin noble-metal nanowires (Cu, Ag, Au, Pt) on MoS2 monolayer. Results based on density functional theory will be presented to determine the preferred configuration for nanowires on the monolayer together with the enhancement in the conductivity of the composite system considered.

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

    DTIC Science & Technology

    1991-01-29

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

  10. Platinum Monolayer Electrocatalysts for O2 Reduction: Pt Monolayer on Carbon-Supported PdIr Nanoparticles

    SciTech Connect

    Vukmirovic, M.B.; Knupp, S.L. Haldar, P.; Herron, J.A.: Mavrikakis, M.; Adzic, R.R.

    2010-11-01

    The kinetics of oxygen reduction was investigated in acid solutions on Pt monolayers deposited on modified carbon-supported PdIr nanoparticles using the rotating disk-electrode technique. Iridium is introduced into the Pd substrate in order to fine-tune the Pt-Pd interactions and to improve Pd stability under operating conditions of the fuel cell. The kinetics of the oxygen reduction reaction shows enhancement with the Pt monolayer on the PdIr nanoparticle surfaces in comparison with the reaction on Pt/C and Pt monolayer on Pd/C nanoparticles. The electrochemical measurements suggest that reduced oxidation of Pt monolayer on PdIr/C compared to Pt/C and Pt monolayer on Pd/C is the cause of enhanced activity. Besides a ligand effect induced to the Pt surface by the presence of PdIr in the second sublayer of the nanoparticle, as suggested by our density functional theory analysis, Ir also leads to a Pd skin contraction, so the Pt monolayer on PdIr/C is compressed more than on Pd/C. Both effects lead to further weakening of the Pt-OH interaction, thus increasing the ORR activity. The Pt-specific activity for Pt{sub ML}PdIr/C is three times and 25% higher than that of Pt/C and Pt{sub ML}Pd/C respectively; the Pt-mass activity of Pt{sub ML}PdIr/C is more than 20 times and 25% higher than that of Pt/C and Pt{sub ML}Pd/C, respectively.

  11. Thermal Decomposition Based Synthesis of Ag-In-S/ZnS Quantum Dots and Their Chlorotoxin-Modified Micelles for Brain Tumor Cell Targeting.

    PubMed

    Chen, Siqi; Ahmadiantehrani, Mojtaba; Publicover, Nelson G; Hunter, Kenneth W; Zhu, Xiaoshan

    Cadmium-free silver-indium-sulfide (Ag-In-S or AIS) chalcopyrite quantum dots (QDs) as well as their core-shell structures (AIS/ZnS QDs) are being paid significant attention in biomedical applications because of their low toxicity and excellent optical properties. Here we report a simple and safe synthetic system to prepare high quality AIS and AIS/ZnS QDs using thermal decomposition. The synthetic system simply involves heating a mixture of silver acetate, indium acetate, and oleic acid in dodecanethiol at 170 °C to produce AIS QDs with a 13% quantum yield (QY). After ZnS shell growth, the produced AIS/ZnS QDs achieve a 41% QY. To facilitate phase transfer and bioconjugation of AIS/ZnS QDs for cellular imaging, these QDs were loaded into the core of PLGA-PEG (5k:5k) based micelles to form AIS/ZnS QD-micelles. Cellular imaging studies showed that chlorotoxin-conjugated QD-micelles can be specifically internalized into U-87 brain tumor cells. This work discloses that the scalable synthesis of AIS/ZnS QDs and the facile surface/interface chemistry for phase transfer and bioconjugation of these QDs may open an avenue for the produced QD-micelles to be applied to the detection of endogenous targets expressed on brain tumor cells, or more broadly to cell- or tissue-based diagnosis and therapy.

  12. 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

  13. Critical island size for Ag thin film growth on ZnO (0 0 0 1 bar)

    NASA Astrophysics Data System (ADS)

    Lloyd, Adam L.; Smith, Roger; Kenny, Steven D.

    2017-02-01

    Island growth of Ag on ZnO is investigated with the development of a new technique to approximate critical island sizes. Ag is shown to attach in one of three highly symmetric sites on the ZnO surface or initial monolayers of grown Ag. Due to this, a lattice based adaptive kinetic Monte Carlo (LatAKMC) method is used to investigate initial growth phases. As island formation is commonly reported in the literature, the critical island sizes of Ag islands on a perfect polar ZnO surface and a first monolayer of grown Ag on the ZnO surface are considered. A mean rate approach is used to calculate the average time for an Ag ad-atom to drop off an island and this is then compared to deposition rates on the same island. Results suggest that Ag on ZnO (0 0 0 1 bar) will exhibit Stranski-Krastanov (layer plus island) growth.

  14. Physicochemical properties of the anion-modified surfaces of silver nanostructures

    NASA Astrophysics Data System (ADS)

    Sibbald, Morgan Scot

    Nano-sized structures of silver were prepared, characterized, and then chemically-modified with the adsorption of molecules and ions on the metal surface. Nanostructures prepared as aqueous colloids were found to have highly regular polyhedral shapes by transmission electron microscopy. Electron diffraction techniques indicated that isolated Ag structures were composed of a single crystalline phase or were multiply-twinned, both having a lattice constant of 4.05 A. Adsorption of iodide and bromide ions on the silver surface was monitored by surface-enhanced Raman spectroscopy. A characteristic halide-metal stretching vibration was observed at 112 cmsp{-1} for Isp- and at 156 cmsp{-1} for Brsp-. Extinction spectra of the halide-modified Ag colloids showed a frequency-shift and damping of the surface plasmon resonance band assigned to particle aggregation. This was confirmed using two dimensional arrays of particles in which the surface-modifier caused only damping with no change in the plasmon frequency. Addition of cytochrome c to the halide-modified colloid resulted in the reduction of the protein. Competitive binding of Isp- ions between cytochrome c and the metal necessitated the use of a redox active indophenol dye for quantitative measurements of reduction efficiencies. Two distinct processes were identified: reduction at iodide coverages up to one monolayer on the Ag surface and reduction in the presence of excess Isp- in solution. The latter was characterized by Isp- reacting with silver in a 1:1 stoichiometry to form molecular AgI. The former, which resulted in only 5% reduction of the electron acceptors, was a consequence of partial charge transfer from Isp- to the metal, producing a unique iodide-Ag surface complex different than molecular AgI. Raman spectra of the complex excited at 413 nm and at temperatures less than 150 K contained a strong vibrational progression with a fundamental band at 123 cmsp{-1} and up to six overtones. An excitation profile

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

    DOE PAGES

    Song, Wentao; Leung, Kevin; Shao, Qian; ...

    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

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

    SciTech Connect

    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 phase 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.

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

    NASA Astrophysics Data System (ADS)

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

    2000-04-01

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

  18. Atomistic simulation of the electronic states of adatoms in monolayer MoS{sub 2}

    SciTech Connect

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

    2014-04-07

    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 (MoS{sub 2}). 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 MoS{sub 2} are examined as starting points to search for the most energetically stable configuration for each adatom-monolayer MoS{sub 2} 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.

  19. 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.

  20. Specific effects of monovalent counterions on the structural and interfacial properties of dodecyl sulfate monolayers.

    PubMed

    Allen, Daniel T; Saaka, Yussif; Pardo, Luis Carlos; Lawrence, M Jayne; Lorenz, Christian D

    2016-11-09

    A series of molecular dynamics simulations have been conducted in order to study the specific ion effects of Li(+), Na(+), Cs(+) and NH4(+) cations on dodecyl sulfate (DS(-)) monolayers. Varying the counterion had no appreciable effect on the structure of the surfactant molecules within the different monolayers. However, the different counterions have a significant effect on the interfacial properties of the monolayer. In particular, we have investigated to what extent each of the counterions is dehydrated when interacting with the DS(-) headgroup, the specific interactions between the counterions and the headgroup and the salt bridging of the headgroups caused by each counterion. The NH4(+) ions are found to directly compete with water molecules to form hydrogen bonds with the DS(-) headgroup and as a result the ammonium dodecyl sulfate monolayer is the least hydrated of any of those studied. The Cs(+) ions are strongly bound to the headgroup and weakly hydrated, such that they would prefer to displace water in the DS(-) hydration shell to interact with the headgroups. In the case of the Li(+) ions, they interact almost as strongly with the DS(-) headgroups as the Na(+) ions, but are generally less hydrated than the Na(+) ions and consequently the lithium dodecyl sulfate monolayers are less hydrated than the sodium dodecyl sulfate monolayers. Therefore, by changing the counterion, one can modify the interfacial properties of the surfactant monolayer, and thus affect their ability to encapsulate poorly water soluble drug molecules, which we discuss further in the manuscript.

  1. Quantifying Plasmon-Enhanced Light Absorption in Monolayer WS2 Films.

    PubMed

    Butun, Serkan; Palacios, Edgar; Cain, Jeffrey D; Liu, Zizhuo; Dravid, Vinayak P; Aydin, Koray

    2017-04-10

    Transition metal dichalcogenide semiconductors hold great promise in photonic and optoelectronic applications such as flexible solar cells and ultrafast photodetectors due to their direct band-gap and few-atom thicknesses. However, it is crucial to understand and improve the absorption characteristics of these monolayer semiconducting materials. In this paper, we performed a systematic numerical and experimental investigation to demonstrate and quantify absorption enhancement in WS2 monolayer films, in the presence of silver plasmonic nanodisk arrays. Our analysis combining full-field electromagnetic simulations and optical absorption spectroscopy measurements indicate a 4-fold enhancement in the absorption of WS2 film near its band edge, close to the plasmonic resonance wavelength of Ag nanodisk arrays. Proposed Ag/WS2 heterostructure exhibited 2.5-fold enhancement in calculated short circuit current. Such hybrid plasmonic/2D materials with enhanced absorption pave the way towards practical realization of 2D optoelectronic devices including ultrafast photodetectors and solar cells.

  2. Metal monolayer deposition by replacement of metal adlayers on electrode surfaces

    NASA Astrophysics Data System (ADS)

    Brankovic, S. R.; Wang, J. X.; Adžić, R. R.

    2001-03-01

    A new metal deposition method is demonstrated by deposition of a submonolayer of Pt, a monolayer of Pd and a bilayer of Ag on Au(1 1 1) surfaces by using a Cu adlayer as a template. The deposition of these metals occurs as a spontaneous irreversible redox process in which a Cu adlayer, obtained by underpotential deposition, is oxidized by more noble metal cations, which are reduced and simultaneously deposited. The Pt deposit is a two-dimensional submonolayer consisting of partially interconnected nano-clusters of monoatomic height. Pd forms a uniform, but textured monolayer, while Ag forms a bilayer. The deposit of each metal uniformly covers the entire gold surface without preferential deposition along the step edges. This method provides surface adlayer-controlled growth, as compared to the current distribution controlled growth in conventional electrodeposition.

  3. 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.

  4. Pinholes and Defects in Octadecylmercaptan Monolayers on Gold.

    NASA Astrophysics Data System (ADS)

    Snider, Daniel Aaron

    Alkylmercaptan monolayers on gold electrodes have been actively studied since they have potential use as modified electrodes. The amazing thing about these electrodes, is that they survive the electrochemical experiment and are extremely blocking to redox couples in solution. Early attempts to model blocked electrode behavior in terms of electron tunnelling failed. The approximate shape of a Tafel plot at low overpotentials should obey Butler-Volmer kinetics with a slope of 1 order of magnitude current per 120 mV of overpotential. Typical alkylmercaptan-coated electrodes result in Tafel plots with depressed slopes. This phenomena was interpreted in terms of imperfections in the monolayer which allow redox couples to approach the gold surface closer than the full length of the monolayer would allow. We assess imperfections in octadecylmercaptan -coated (OM) gold electrodes by passivating and blocking the pinholes. We passivate pinholes to an inner-sphere redox couple with an adsorbed layer of iodine. We block pinholes with the self-passivating polymer polyphenylene oxide to an outer sphere redox couple. To determine the size and distribution of pinholes in the OM monlayer we study the system with oxide stripping, liner scan voltammetry and AC Impedance Spectroscopy. We have determined that imperfections can be classified as pinholes and defects. Pinholes are areas where a redox couple has direct access to the gold surface. Defects are areas where a redox couple can come closer than the full length of the monolayer but not in direct contact with the monolayer. Both, pinholes and defects result in larger faradaic currents and more non-ideal Tafel plots than would be seen with electron tunnelling. We have determined that pinholes, typically, have radii that are micron size with pinhole separation tens of microns. Additionally, Oxide Stripping experiments are the most damaging way to assess pinhole coverage, with AC impedance spectroscopy providing the most useful

  5. 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.

  6. 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.

  7. Modeling Stimuli-Responsive Nanoparticle Monolayer

    NASA Astrophysics Data System (ADS)

    Yong, Xin

    2015-03-01

    Using dissipative particle dynamics (DPD), we model a monolayer formed at the water-oil interface, which comprises stimuli-responsive nanoparticles. The solid core of the nanoparticle encompasses beads arranged in an fcc lattice structure and its surface is uniformly grafted with stimuli-responsive polymer chains. The surface-active nanoparticles adsorb to the interface from the suspension to minimize total energy of the system and create a monolayer covering the interface. We investigate the monolayer formation by characterizing the detailed adsorption kinetics. We explore the microstructure of the monolayer at different surface coverage, including the particle crowding and ordering, and elucidate the response of monolayer to external stimuli. The collective behavior of the particles within the monolayer is demonstrated quantitatively by vector-vector autocorrelation functions. This study provides a fundamental understanding of the interfacial behavior of stimuli-responsive nanoparticles.

  8. 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.

  9. Equilibrating Nanoparticle Monolayers Using Wetting Films

    SciTech Connect

    Pontoni, D.; Alvine, K; Checco, A; Gang, O; Ocko, B; Pershan, P

    2009-01-01

    Monolayers of bimodal gold nanoparticles on silicon are investigated by a combination of microscopy (dry monolayers) and x-ray diffraction (dry and wet monolayers). In the presence of an excess of small particles, the nanoscale packing structure closely resembles the small-particle-rich scenario of the structural crossover transition that has been predicted and also observed with micron-scale hard-sphere colloids. Structural morphology is monitored in situ during monolayer dissolution and reassembly within the thin liquid wetting film. This approach allows investigation of size and solvent effects on nanoparticles in quasi-two-dimensional confinement.

  10. Dewetting of a solid monolayer.

    PubMed

    Pierre-Louis, O; Chame, Anna; Saito, Yukio

    2007-09-28

    We report on the dewetting of a monolayer on a solid substrate, where mass transport occurs via surface diffusion. For a wide range of parameters, a labyrinthine pattern of bilayer islands is formed. An irreversible regime and a thermodynamic regime are identified. In both regimes, the velocity of a dewetting front, the wavelength of the bilayer island pattern, and the rate of nucleation of dewetted zones are obtained. We also point out the existence of a scaling behavior, which is analyzed by means of a geometrical model.

  11. 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.

  12. 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.

  13. Strain tuning of the charge density wave in monolayer and bilayer 1T-TaS2.

    PubMed

    Gan, Li-Yong; Zhang, Li-Hong; Zhang, Qingyun; Guo, Chun-Sheng; Schwingenschlögl, Udo; Zhao, Yong

    2016-01-28

    Using first-principles calculations, we investigate the strain effects on the charge density wave states of monolayer and bilayer 1T-TaS2. The modified stability of the charge density wave in the monolayer is understood in terms of the strain dependent electron localization, which determines the distortion amplitude. On the other hand, in the bilayer, the effect of strain on the interlayer interaction is also crucial. The rich phase diagram under strain opens new venues for applications of 1T-TaS2. We interpret the experimentally observed insulating state of bulk 1T-TaS2 as inherited from the monolayer by effective interlayer decoupling.

  14. Surface activity coefficients of spread monolayers of behenic acid salts at air-water interface.

    PubMed

    Chattoraj, D K; Halder, E; Das, K P; Mitra, A

    2006-11-16

    The pressure-area isotherms of ionized monolayers of behenic acid at air-water interface at pH 12.0 have been obtained from the Langmuir film balance experiments under various physico-chemical conditions. The value of the measured surface pressure at a given area per molecule is equal to the sum of the ideal pressure, cohesive pressure and electrical pressure. The electrical pressure term is regarded as the sum of the pressure originating from the Gouy-Chapman double layer including discrete ion effect, ion binding and monolayer hydration effect. At a given area, the deviation of the measured surface pressure from its ideal value has been calculated in terms of the apparent surface compressibility coefficients, surface fugacity coefficients for gaseous monolayer and surface activity coefficients of solute forming two-dimensional solutions in the monolayer phase respectively. Values of all these coefficients have been calculated for different compositions of the monolayer using non-ideal gas model and Raoult's and Henry's laws modified for two-dimensional non-ideal solutions respectively. Values of these coefficients may be higher or lower than unity depending upon ionic strengths and nature of inorganic salts present in the sub-phase. Using these values of surface activity coefficients, the standard free energies of formation, of spread monolayers of salts of behenic acid have been calculated at different standard states of reference.

  15. Mixed multilayered vertical heterostructures utilizing strained monolayer WS2

    NASA Astrophysics Data System (ADS)

    Sheng, Yuewen; Xu, Wenshuo; Wang, Xiaochen; He, Zhengyu; Rong, Youmin; Warner, Jamie H.

    2016-01-01

    Creating alternating layers of 2D materials forms vertical heterostructures with diverse electronic and opto-electronic properties. Monolayer WS2 grown by chemical vapour deposition can have inherent strain due to interactions with the substrate. The strain modifies the band structure and properties of monolayer WS2 and can be exploited in a wide range of applications. We demonstrate a non-aqueous transfer method for creating vertical stacks of mixed 2D layers containing a strained monolayer of WS2, with Boron Nitride and Graphene. The 2D materials are all grown by CVD, enabling large area vertical heterostructures to be formed. WS2 monolayers grown by CVD directly on Si substrates with SiO2 surface are easily washed off by water and this makes aqueous based transfer methods challenging for creating vertical stacks on the growth substrate. 2D hexagonal Boron Nitride films are used to provide an insulating layer that limits interactions with a top graphene layer and preserve the strong photoluminescence from the WS2. This transfer method is suitable for layer by layer control of 2D material vertical stacks and is shown to be possible for all CVD grown samples, which opens up pathways for the rapid large scale fabrication of vertical heterostructure systems with atomic thickness depth control and large area coverage.Creating alternating layers of 2D materials forms vertical heterostructures with diverse electronic and opto-electronic properties. Monolayer WS2 grown by chemical vapour deposition can have inherent strain due to interactions with the substrate. The strain modifies the band structure and properties of monolayer WS2 and can be exploited in a wide range of applications. We demonstrate a non-aqueous transfer method for creating vertical stacks of mixed 2D layers containing a strained monolayer of WS2, with Boron Nitride and Graphene. The 2D materials are all grown by CVD, enabling large area vertical heterostructures to be formed. WS2 monolayers grown by

  16. Ozone decomposition on Ag/SiO2 and Ag/clinoptilolite catalysts at ambient temperature.

    PubMed

    Nikolov, Penko; Genov, Krassimir; Konova, Petya; Milenova, Katya; Batakliev, Todor; Georgiev, Vladimir; Kumar, Narendra; Sarker, Dipak K; Pishev, Dimitar; Rakovsky, Slavcho

    2010-12-15

    Silver modified zeolite (Bulgarian natural clinoptilolite) and Ag/silica catalysts were synthesized by ion exchange and incipient wet impregnation method respectively and characterized by different techniques. DC arc-AES was used for Ag detection. XRD spectra show that Ag is loaded over the surface of the SiO(2) sample and that after the ion-exchange process the HEU type structure of clinoptilolite is retained. UV-VIS (specific reflection at 310 nm) and IR (band at 695 cm(-1)) spectroscopy analysis proved that silver is loaded as a T-atom into zeolite channels as Ag(+), instead of Na(+), Ca(2+), or K(+) ions, existing in the natural clinoptilolite form. The samples Ag/SiO(2) and Ag-clinoptilolite were tested as catalysts for decomposition of gas phase ozone. Very high catalytic activity (up to 99%) was observed and at the same time the catalysts remained active over time at room temperature.

  17. 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…

  18. 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.

  19. Nonlinear light scattering by a dipole monolayer

    NASA Astrophysics Data System (ADS)

    Averbukh, B. B.; Averbukh, I. B.

    2013-08-01

    Scattering of a strong p-polarized monochromatic field by a dipole monolayer is considered. It is shown that a triplet should be observed at incident angles (between the wave vector of the incident wave and the normal to the monolayer surface) not too close to π/2 in the spectrum of the scattered radiation. For grazing incidence of a strong field on the monolayer, waves with frequencies of the strong field and the high-frequency component of the triplet scatter forward and backward. In this case, radiation with frequency of the low-frequency component of the triplet propagates in the form of two inhomogeneous waves along the monolayer on both sides of it, exponentially decaying with distance from the monolayer.

  20. Coulomb excitations of monolayer germanene

    NASA Astrophysics Data System (ADS)

    Shih, Po-Hsin; Chiu, Yu-Huang; Wu, Jhao-Ying; Shyu, Feng-Lin; Lin, Ming-Fa

    2017-01-01

    The feature-rich electronic excitations of monolayer germanene lie in the significant spin-orbit coupling and the buckled structure. The collective and single-particle excitations are diversified by the magnitude and direction of transferred momentum, the Fermi energy and the gate voltage. There are four kinds of plasmon modes, according to the unique frequency- and momentum-dependent phase diagrams. They behave as two-dimensional acoustic modes at long wavelength. However, for the larger momenta, they might change into another kind of undamped plasmons, become the seriously suppressed modes in the heavy intraband e–h excitations, keep the same undamped plasmons, or decline and then vanish in the strong interband e–h excitations. Germanene, silicene and graphene are quite different from one another in the main features of the diverse plasmon modes.

  1. Coulomb excitations of monolayer germanene

    PubMed Central

    Shih, Po-Hsin; Chiu, Yu-Huang; Wu, Jhao-Ying; Shyu, Feng-Lin; Lin, Ming-Fa

    2017-01-01

    The feature-rich electronic excitations of monolayer germanene lie in the significant spin-orbit coupling and the buckled structure. The collective and single-particle excitations are diversified by the magnitude and direction of transferred momentum, the Fermi energy and the gate voltage. There are four kinds of plasmon modes, according to the unique frequency- and momentum-dependent phase diagrams. They behave as two-dimensional acoustic modes at long wavelength. However, for the larger momenta, they might change into another kind of undamped plasmons, become the seriously suppressed modes in the heavy intraband e–h excitations, keep the same undamped plasmons, or decline and then vanish in the strong interband e–h excitations. Germanene, silicene and graphene are quite different from one another in the main features of the diverse plasmon modes. PMID:28091555

  2. Thermoelectric transport in monolayer phosphorene

    NASA Astrophysics Data System (ADS)

    Zare, Moslem; Rameshti, Babak Zare; Ghamsari, Farnood G.; Asgari, Reza

    2017-01-01

    We apply the generalized Boltzmann theory to describe thermoelectric transport properties of monolayer phosphorene in the presence of short- and long-range charged impurity interactions. First, we propose a low-energy Hamiltonian to explore the accurate electronic band structure of phosphorene in comparison with those results obtained by density-functional simulations. We explain the effect of the coupling between the conduction and valence bands on the thermoelectric properties. We show that the electric conductivity of phosphorene is highly anisotropic, while the Seebeck coefficient and figure of merit, without being influenced via either the presence or absence of the coupling term, are nearly isotropic. Furthermore, we demonstrate that the conductivity for the n type of doping is more influenced by the coupling term than that of the p type. Along with thermopower sign change, profound thermoelectric effects can be achieved.

  3. Electronic versus phononic contributions to sliding friction: Xe on Ag

    NASA Astrophysics Data System (ADS)

    Liebsch, Ansgar; Gonçalves, Sebastian; Kiwi, Miguel

    1998-03-01

    The microscopic origin of the sliding friction of one or more monolayers of adsorbed films on metal surfaces has recently attracted considerable interest. Dynamical response time--dependent density functional calculations suggest that, for Xe on Ag, the excitation of electron--hole pairs contributes significantly to η_allel, the damping of the parallel motion of the Xe overlayer. To compare η_allel with η_phon, the contribution due to phonons excited in the Xe layer, we have performed molecular dynamics calculations for various coverages. The effective friction coefficient turns out to be sensitive to the surface corrugation potential. In particular, for an incommensurate Xe monolayer on Ag, we find η_allel and η_phon to be of the same order of magnitude in a large region of parameter space.

  4. A convenient phase transfer route for Ag nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhao, Shi-Yong; Chen, Shen-Hao; Li, De-Gang; Yang, Xue-Geng; Ma, Hou-Yi

    2004-06-01

    Generally, phase transfer of metal nanoparticles between aqueous phase and organic phase need two reagents at last. One is stabilizer of nanoparticles, the other is phase-transfer agent (Chem. Lett. 21 (1992) 1527; J. Colloid Interface Sci. 161 (1993) 471; J. Phys. Chem B 101 (1997) 9876; Chem. Commun. (1997) 537; Langmuir 14 (1998) 602; J. Phys. Chem B 103 (1999) 7238; Chem. Mater. 13 (2001) 4692; Langmuir 17 (2001) 733; Langmuir 16 (2000) 9775; Langmuir 18 (2002) 3364; J. Am. Chem. Soc. 123 (2001) 11148). In this paper, Ag nanoparticle prepared by tannic acid reduction of AgNO 3 in aqueous medium were transferred to chloroform solution via a remarkably simple one-step route under the effect of phase-transfer inducer dimethyldioctadecylammonium chloride (DDAC), where no special stabilizer was required. Monolayer of Ag nanoparticles is obtained on carbon film by self-assembly using chloroform organosol. The effect of the inducer DDAC concentration is checked, and it was found that 5×10 -3 mol dm -3 of DDAC was the optimum concentration for phase transfer of Ag nanoparticles. The organosol, Ag nanoparticle self-assembled monolayer and phase transfer were characterized by UV-vis spectra, TEM, ED and TF-IR.

  5. The effects of substituent grafting on the interaction of pH-responsive polymers with phospholipid monolayers.

    PubMed

    Zhang, Shengwen; Nelson, Andrew; Coldrick, Zachary; Chen, Rongjun

    2011-07-05

    pH-responsive amphiphilic polymers with suitable graftings have demonstrated highly efficient cell membrane activity and hence are promising applicants for drug-delivery. Grafting the hydrophobic amino acid l-phenylalanine and the hydrophilic methoxy poly(ethylene glycol) amine onto the pendant carboxylic acid moieties of a linear polyamide, poly(l-lysine isophthalamide), can effectively modify the amphiphilicity and conformation of the amphiphilic polymers. Here, the interactions of these polymers with phospholipid monolayers adsorbed on mercury (Hg) electrodes have been studied. AC voltammetry (ACV), rapid cyclic voltammetry (RCV), and electrochemical impedance spectroscopy (EIS) have been applied to monitor phospholipid monolayer associations with different polymer concentrations under different pH values. The polymers interact reversibly with the monolayer shown by altering the monolayer capacitance and inhibiting the phospholipid reorientation in electric field. Polymer grafting enhances the pH-mediated conformational change of the polymers which in turn increases their phospholipid monolayer activity. The most significant monolayer interactions have been observed with the polymer grafted with hydrophobic l-phenylalanine. A low level of PEGylation of the backbone also increases the monolayer activity. The polymer/DOPC interactions have been represented with an impedance model, which takes account of the interaction giving rise to an increase in monolayer capacitance and inhomogeneity and a Debye type dielectric relaxation. The extent of penetration of the polymers into the monolayer is inversely related to the electrical resistance they give rise to during the Debye relaxation. The cell membrane activities of these amphiphilic polymers have been successfully mirrored in this supported DOPC monolayer system, isolating the key parameters for biomembrane activities and giving insight into the mechanism of the interactions. The conclusions from this study provide

  6. Highly doped silicon nanowires by monolayer doping.

    PubMed

    Veerbeek, Janneke; Ye, Liang; Vijselaar, Wouter; Kudernac, Tibor; van der Wiel, Wilfred G; Huskens, Jurriaan

    2017-02-23

    Controlling the doping concentration of silicon nanostructures is challenging. Here, we investigated three different monolayer doping techniques to obtain silicon nanowires with a high doping dose. These routes were based on conventional monolayer doping, starting from covalently bound dopant-containing molecules, or on monolayer contact doping, in which a source substrate coated with a monolayer of a carborane silane was the dopant source. As a third route, both techniques were combined to retain the benefits of conformal monolayer formation and the use of an external capping layer. These routes were used for doping fragile porous nanowires fabricated by metal-assisted chemical etching. Differences in porosity were used to tune the total doping dose inside the nanowires, as measured by X-ray photoelectron spectroscopy and secondary ion mass spectrometry measurements. The higher the porosity, the higher was the surface available for dopant-containing molecules, which in turn led to a higher doping dose. Slightly porous nanowires could be doped via all three routes, which resulted in highly doped nanowires with (projected areal) doping doses of 10(14)-10(15) boron atoms per cm(2) compared to 10(12) atoms per cm(2) for a non-porous planar sample. Highly porous nanowires were not compatible with the conventional monolayer doping technique, but monolayer contact doping and the combined route resulted for these highly porous nanowires in tremendously high doping doses up to 10(17) boron atoms per cm(2).

  7. 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.

  8. Squish and CuAAC: Additive-Free Covalent Monolayers of Discrete Molecules in Seconds

    PubMed Central

    Pellow, Matthew A.

    2013-01-01

    A terminal alkyne is immobilized rapidly into a full monolayer by squishing a small volume of a solution of the alkyne between an azide-modified surface and a copper plate. The monolayer is covalently attached to the surface through a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction, and the coverages of the immobilized electroactive alkyne species are quantified by cyclic voltammetry. A reaction time of less than twenty seconds is possible with no other reagents required. The procedure is effective in aerobic conditions using either an aqueous or aprotic organic solution of the alkyne (1–100 mM). PMID:23551032

  9. Silicene: from monolayer to multilayer — A concise review

    NASA Astrophysics Data System (ADS)

    Li, Hui; Hui-Xia, Fu; Meng, Sheng

    2015-08-01

    Silicene, a newly isolated silicon allotrope with a two-dimensional (2D) honeycomb lattice structure, is predicted to have electronic properties similar to those of graphene, including the existence of signature Dirac fermions. Furthermore, the strong spin-orbit interaction of Si atoms potentially makes silicene an experimentally accessible 2D topological insulator. Since 2012, silicene films have been experimentally synthesized on Ag (111) and other substrates, motivating a burst of research on silicene. We and collaborators have employed STM investigations and first principles calculations to intensively study the structure and electronic properties of silicene films on Ag (111), including monolayer, bilayer, and multilayer silicenes, as well as hydrogenation of silicene. Project supported by the National Natural Science Foundation of China (Grant Nos. 11334011, 11222431, and 11322431), the National Basic Research Program of China (Grant Nos. 2012CB921403, 2013CBA01600, and 2012CB921703), the “Strategic Priority Research Program” of the Chinese Academy of Sciences, and the Hundred Talents Program of Institute of Physics, Chinese Academy of Sciences.

  10. DNA-embedded Au-Ag core-shell nanoparticles assembled on silicon slides as a reliable SERS substrate.

    PubMed

    Zhang, Zhong; Zhang, Sha; Lin, Mengshi

    2014-05-07

    This study aimed at developing a sensitive and reliable SERS substrate by assembling DNA-embedded Au-Ag core-shell nanoparticles (NPs) on silicon slides. First, a monolayer of well separated DNA-functionalized Au NPs (40 nm) was decorated on (3-aminopropyl)triethoxysilane modified silicon slides. The DNA-embedded Au-Ag core-shell NPs were assembled on the 40 nm Au-DNA NPs to form a core-satellite structure through DNA hybridization. Using 4-MBA as a Raman dye, the SERS performance of the substrates was evaluated after being cleaned by low oxygen and argon plasma. The Raman intensity of the assembly using DNA-embedded Au-Ag core-shell NPs was 8-10 times higher than the intensity of the assembly using Au NPs as satellites. In addition, the signal-to-noise ratio of the assembly was 2.6 times higher than that of a commercial substrate (Klarite™) when a 785 nm laser was used. The SERS enhancements of the assembled substrates were 2.2 to 2.8 times higher than the Klarite when an acquisition time of 5 s was used at an excitation wavelength of 633 nm. The assembled substrates also show a good spot-to-spot and substrate-to-substrate reproducibility at the excitation wavelengths of 633 and 785 nm. These results demonstrate that the fabrication process is simple and cost-effective for assembling DNA-embedded Au-Ag core-shell NPs on silicon slides that can be used as a reliable SERS substrate.

  11. 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.

  12. Monolayer coated gold nanoparticles for delivery applications

    PubMed Central

    Rana, Subinoy; Bajaj, Avinash; Mout, Rubul; Rotello, Vincent M.

    2011-01-01

    Gold nanoparticles (AuNPs) provide attractive vehicles for delivery of drugs, genetic materials, proteins, and small molecules. AuNPs feature low core toxicity coupled with the ability to parametrically control particle size and surface properties. In this review, we focus on engineering of the AuNP surface monolayer, highlighting recent advances in tuning monolayer structures for efficient delivery of drugs and biomolecules. This review covers two broad categories of particle functionalization, organic monolayers and biomolecule coatings, and discusses their applications in drug, DNA/RNA, protein and small molecule delivery. PMID:21925556

  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. 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

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

    DOE PAGES

    Sun, Jifeng; Shi, Hongliang; Siegrist, Theo; ...

    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

  16. Microwave-assisted formation of organic monolayers from 1-alkenes on silicon carbide.

    PubMed

    van den Berg, Sebastiaan A; Alonso, Jose Maria; Wadhwa, Kuldeep; Franssen, Maurice C R; Wennekes, Tom; Zuilhof, Han

    2014-09-09

    The rate of formation of covalently linked organic monolayers on HF-etched silicon carbide (SiC) is greatly increased by microwave irradiation. Upon microwave treatment for 60 min at 100 °C (60 W), 1-alkenes yield densely packed, covalently attached monolayers on flat SiC surfaces, a process that typically takes 16 h at 130 °C under thermal conditions. This approach was extended to SiC microparticles. The monolayers were characterized by X-ray photoelectron spectroscopy and static water contact angle measurements. The microwave-assisted reaction is compatible with terminal functionalities such as alkenes that enable subsequent versatile "click" chemistry reactions, further broadening the range and applicability of chemically modified SiC surfaces.

  17. A monolayer of hierarchical silver hemi-mesoparticles with tunable surface topographies for highly sensitive surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhu, Shuangmei; Fan, Chunzhen; Mao, Yanchao; Wang, Junqiao; He, Jinna; Liang, Erjun; Chao, Mingju

    2016-02-01

    We proposed a facile green synthesis system to synthesize large-scale Ag hemi-mesoparticles monolayer on Cu foil. Ag hemi-mesoparticles have different surface morphologies on their surfaces, including ridge-like, meatball-like, and fluffy-like shapes. In the reaction, silver nitrate was reduced by copper at room temperature in dimethyl sulfoxide via the galvanic displacement reaction. The different surface morphologies of the Ag hemi-mesoparticles were adjusted by changing the reaction time, and the hemi-mesoparticle surface formed fluffy-spherical nanoprotrusions at longer reaction time. At the same time, we explored the growth mechanism of silver hemi-mesoparticles with different surface morphologies. With 4-mercaptobenzoic acid as Raman probe molecules, the fluffy-like silver hemi-mesoparticles monolayer with the best activity of surface enhanced Raman scattering (SERS), the enhancement factor is up to 7.33 × 107 and the detection limit can reach 10-10M. SERS measurements demonstrate that these Ag hemi-mesoparticles can serve as sensitive SERS substrates. At the same time, using finite element method, the distribution of the localized electromagnetic field near the particle surface was simulated to verify the enhanced mechanism. This study helps us to understand the relationship between morphology Ag hemi-mesoparicles and the properties of SERS.

  18. 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.

  19. 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)

  20. Method to synthesize metal chalcogenide monolayer nanomaterials

    SciTech Connect

    Hernandez-Sanchez, Bernadette A.; Boyle, Timothy J.

    2016-12-13

    Metal chalcogenide monolayer nanomaterials can be synthesized from metal alkoxide precursors by solution precipitation or solvothermal processing. The synthesis routes are more scalable, less complex and easier to implement than other synthesis routes.

  1. C60 fullerene promotes lung monolayer collapse

    PubMed Central

    Barnoud, Jonathan; Urbini, Laura; Monticelli, Luca

    2015-01-01

    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. PMID:25589571

  2. 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.

  3. 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.

  4. Scanning tunneling microscopy studies of corrosion passivation and nanometer-scale lithography with self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Zamborini, Francis Patrick

    The research in this dissertation examines the possible applications of organomercaptan self-assembled monolayers (SAMs) for corrosion passivation and nanometer-scale lithography. We examined linear-chain n-alkanethiol and aromatic SAMs in these studies and used scanning tunneling microscopy (STM) as the main tool for surface characterization. The corrosion passivation properties of n-alkanethiol SAMs were studied on Au in aqueous CN- and Br - solutions and on underpotentially deposited Cu on Au (Au/Cu-UPD) in aqueous HClO4. All SAMs suppress corrosion and shift the potential for corrosion to more positive potentials compared to that on the unmodified metals. We found that corrosion of n-alkanethiol SAM-modified Au begins at defects in the monolayer and the surface morphology depends on the functional end group of the SAM. Corrosion on the unpassivated metal surface begins at high energy sites such as step edges and pits. The chain length and functional end group of SAMs were varied to determine which factors were most important for the best protection against corrosion. We found that corrosion passivation improves with increasing chain length and more hydrophilic functional end groups like OH and COOH protect better than hydrophobic end groups like CH3. The passivation properties of linear-chain SAMs was compared with aromatic SAMs and we found that if they are equally thick and contain the same functional end group, the aromatic SAMs are superior. One goal of this research was to improve the barrier properties of SAMs. We found that depositing a single layer of Cu onto Au before adsorbing the SAM improved its barrier properties dramatically compared to when the SAM was adsorbed directly to the Au. In summary, the corrosion-related studies in this dissertation discuss the corrosion mechanism of SAM-modified metal surfaces, the important factors that determine the passivation properties of SAMs, and a strategy for dramatically improving the barrier properties of

  5. The preparation and antibacterial effects of dopa-cotton/AgNPs

    NASA Astrophysics Data System (ADS)

    Xu, Hong; Shi, Xue; Ma, Hui; Lv, Yihang; Zhang, Linping; Mao, Zhiping

    2011-05-01

    Silver nanoparticles (AgNPs) have been known to have powerful antibacterial activity. In this paper, in situ generation of AgNPs on the surface of dopamine modified cotton fabrics (dopa-cotton/AgNPs) in aqueous solution under room temperature is presented. X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscope (FE-SEM) were used to analyze the surface chemical composition and the morphology of the modified cotton fabrics, respectively. The results indicated that the surface of cotton fabrics was successfully coated with polydopamine and AgNPs. The cotton fabrics with AgNPs showed durable antibacterial activity.

  6. Phosphonate-anchored monolayers for antibody binding to magnetic nanoparticles.

    PubMed

    Benbenishty-Shamir, Helly; Gilert, Roni; Gotman, Irena; Gutmanas, Elazar Y; Sukenik, Chaim N

    2011-10-04

    Targeted delivery of magnetic iron oxide nanoparticles (IONPs) to a specific tissue can be achieved by conjugation with particular biological ligands on an appropriately functionalized IONP surface. To take best advantage of the unique magnetic properties of IONPs and to maximize their blood half-life, thin, strongly bonded, functionalized coatings are required. The work reported herein demonstrates the successful application of phosphonate-anchored self-assembled monolayers (SAMs) as ultrathin coatings for such particles. It also describes a new chemical approach to the anchoring of antibodies on the surface of SAM-coated IONPs (using nucleophilic aromatic substitution). This anchoring strategy results in stable, nonhydrolyzable, covalent attachment and allows the reactivity of the particles toward antibody binding to be activated in situ, such that prior to the activation the modified surface is stable for long-term storage. While the SAMs do not have the well-packed crystallinity of other such monolayers, their structure was studied using smooth model substrates based on an iron oxide layer on a double-side polished silicon wafer. In this way, atomic force microscopy, ellipsometry, and contact angle goniometry (tools that could not be applied to the nanoparticles' surfaces) could contribute to the determination of their monomolecular thickness and uniformity. Finally, the successful conjugation of IgG antibodies to the SAM-coated IONPs such that the antibodies retain their biological activity is verified by their complexation to a secondary fluorescent antibody.

  7. 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.

  8. 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.

  9. Underpotential deposition of Cd on Ag(1 1 1): an in situ STM study

    NASA Astrophysics Data System (ADS)

    García, S. G.; Salinas, D. R.; Staikov, G.

    2005-02-01

    The kinetics and mechanism of Cd underpotential deposition (UPD) and involved surface alloy formation processes in the system Ag(1 1 1)/Cd 2+, SO42-, are studied by means of combined electrochemical measurements and in situ scanning tunneling microscopy (STM). The results show that the UPD process starts with a formation of an expanded (diluted) adlayer with a superlattice structure Ag(1 1 1)- (√{3}×√{19})R23.4°. In the underpotential range 50 mV < Δ E < 80 mV this adlayer transforms to a condensed close packed Cd monolayer via a first order phase transition. At long polarization times the condensed monolayer undergoes structural changes involving place exchange processes between Cd atoms and surface Ag atoms. A formation of a second Cd monolayer and a significant Ag-Cd surface alloying take place at lower underpotentials (Δ E < 50 mV). The kinetics of surface alloying are analyzed on the basis of a recently proposed diffusion model including a relatively fast initial formation of a very thin surface alloy film and a subsequent slow alloy growth controlled by solid state diffusion. The anodic dealloying results in an appearance of monatomically deep pits, which disappear quickly at relatively high underpotentials (Δ E > 550 mV) indicating a high mobility of surface Ag atoms.

  10. Phase-Specific Diffusivity of DPPG Monolayers

    NASA Astrophysics Data System (ADS)

    Dewitt, Joel; Thapa, Prem; Flanders, Bret

    2004-03-01

    The primary role of lung surfactant is to reduce the alveolar surface tension during exhalation in a reversible manner. Failure to do so results in respiratory distress syndrome. Model lung surfactants provide simplified systems for studying the mechanisms that underlie this essential role of alveolar surfactant. Dipalmitoyl-phosphatidylglycerol (DPPG) monolayers exhibit reversible folding when compressed to a critical surface tension. This process may exemplify how the compression-expansion cycle attains reversibility and, thus, requires penetrating study. The buckling theory for reversible collapse provides a promising though untested description of this process, but poor knowledge of domain boundary widths in DPPG monolayers impedes the evaluation of this theory as a model for the observed behavior. In turn, the measurement of the domain boundary widths requires knowledge of the phase-specific viscosities of the monolayer. In this study, multi-particle tracking has been used to determine the phase-specific diffusion coefficients of polystyrene spheres embedded in DPPG monolayers. By invoking a Stokes-Einstein relationship that is appropriate for spheres diffusing in a viscous surfactant, the phase specific viscosities of the monolayers have been estimated. The rationale for this work is that this knowledge will promote the quantitative evaluation of buckling as a model for reversible folding and, thus, promote growth in understanding of the folding mechanism in model lung surfactants.

  11. Nanoparticle interaction with model lung surfactant monolayers

    PubMed Central

    Harishchandra, Rakesh Kumar; Saleem, Mohammed; Galla, Hans-Joachim

    2010-01-01

    One of the most important functions of the lung surfactant monolayer is to form the first line of defence against inhaled aerosols such as nanoparticles (NPs), which remains largely unexplored. We report here, for the first time, the interaction of polyorganosiloxane NPs (AmorSil20: 22 nm in diameter) with lipid monolayers characteristic of alveolar surfactant. To enable a better understanding, the current knowledge about an established model surface film that mimics the surface properties of the lung is reviewed and major results originating from our group are summarized. The pure lipid components dipalmitoylphosphatidylcholine and dipalmitoylphosphatidylglycerol have been used to study the biophysical behaviour of their monolayer films spread at the air–water interface in the presence of NPs. Film balance measurements combined with video-enhanced fluorescence microscopy have been used to investigate the formation of domain structures and the changes in the surface pattern induced by NPs. We are able to show that NPs are incorporated into lipid monolayers with a clear preference for defect structures at the fluid–crystalline interface leading to a considerable monolayer expansion and fluidization. NPs remain at the air–water interface probably by coating themselves with lipids in a self-assembly process, thereby exhibiting hydrophobic surface properties. We also show that the domain structure in lipid layers containing surfactant protein C, which is potentially responsible for the proper functioning of surfactant material, is considerably affected by NPs. PMID:19846443

  12. Giant piezoelectricity of monolayer group IV monochalcogenides

    NASA Astrophysics Data System (ADS)

    Fei, Ruixiang; Li, Wenbin; Li, Ju; Yang, Li

    We predict enormous, anisotropic piezoelectric effects in intrinsic monolayer group IV monochalcogenides (MX, M =Sn or Ge, X =Se or S), including SnSe, SnS, GeSe, and GeS. Using first-principle simulations based on the modern theory of polarization, we find that their piezoelectric coefficients are about one to two orders of magnitude larger than those of other 2D materials, such as MoS2 and GaSe, and bulk quartz and AlN which are widely used in industry. This enhancement is a result of the unique ``puckered'' C2v symmetry and electronic structure of monolayer group IV monochalcogenides. Given the achieved experimental advances in the fabrication of monolayers, their flexible character, and ability to withstand enormous strain, these 2D structures with giant piezoelectric effects may be promising for a broad range of applications such as nano-sized sensors, piezotronics, and energy harvesting in portable electronic devices.

  13. Edge plasmons in monolayer black phosphorus

    NASA Astrophysics Data System (ADS)

    Bao, Zhi-Wei; Wu, Hong-Wei; Zhou, Yu

    2016-12-01

    In this paper, we numerically investigate the edge plasmons in monolayer black phosphorus. It is found that the complex effective indexes of these modes depend on the molecular configuration of the edge. We have calculated the ratio of the real over the imaginary part of the mode effective index, and the results indicate that such edge modes indeed possess outstanding propagation performances in the mid-infrared. In the case of black phosphorus nanoribbon, it seems that only the anti-symmetric modes have low losses, and may be of use in applications. Compared with those at the edge of monolayer black phosphorus, the propagation performances can be further enhanced due to the mode coupling between the two edges. In the end, the effects of substrates are discussed. Our study shows that monolayer black phosphorus may be regarded as a promising candidate for plasmonic applications in the mid-infrared.

  14. Magneto photoluminescence measurements of tungsten disulphide monolayers

    NASA Astrophysics Data System (ADS)

    Kuhnert, Jan; Rahimi-Iman, Arash; Heimbrodt, Wolfram

    2017-03-01

    Layered transition-metal dichalcogenides have attracted great interest in the last few years. Thinned down to the monolayer limit they change from an indirect band structure to a direct band gap in the visible region. Due to the monolayer thickness the inversion symmetry of the crystal is broken and spin and valley are coupled to each other. The degeneracy between the two equivalent valleys, K and K‧, respectively, can be lifted by applying an external magnetic field. Here, we present photoluminescence measurements of CVD-grown tungsten disulphide (WS2) monolayers at temperatures of 2 K. By applying magnetic fields up to 7 T in Faraday geometry, a splitting of the photoluminescence peaks can be observed. The magnetic field dependence of the A-exciton, the trion and three bound exciton states is discussed and the corresponding g-factors are determined.

  15. 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.

  16. 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.

  17. Stiffness of lipid monolayers with phase coexistence.

    PubMed

    Caruso, Benjamín; Mangiarotti, Agustín; Wilke, Natalia

    2013-08-27

    The surface dilational modulus--or compressibility modulus--has been previously studied for monolayers composed of pure materials, where a jump in this modulus was related with the onset of percolation as a result of the establishment of a connected structure at the molecular level. In this work, we focused on monolayers composed of two components of low lateral miscibility. Our aim was to investigate the compressibility of mixed monolayers at pressures and compositions in the two-phase region of the phase diagram, in order to analyze the effect of the mechanical properties of each phase on the stiffness of the composite. In nine different systems with distinct molecular dipoles and charges, the stiffness of each phase and the texture at the plane of the monolayer were studied. In this way, we were able to analyze the general compressibility of two-phase lipid monolayers, regardless of the properties of their constituent parts. The results are discussed in the light of the following two hypotheses: first, the stiffness of the composite could be dominated by the stiffness of each phase as a weighted sum according to the percentage of each phase area, regardless of the distribution of the phases in the plane of the monolayer. Alternatively, the stiffness of the composite could be dominated by the mechanical properties of the continuous phase. Our results were better explained by this latter proposal, as in all the analyzed mixtures it was found that the mechanical properties of the percolating phase were the determining factors. The value of the compression modulus was closer to the value of the connected phase than to that of the dispersed phase, indicating that the bidimensional composites displayed mechanical properties that were related to the properties of each phases in a rather complex manner.

  18. Adsorption isotherm studies of Cu (II) and Co (II) in high concentration aqueous solutions on photocatalytically modified diatomaceous ceramic adsorbents

    NASA Astrophysics Data System (ADS)

    Ajenifuja, E.; Ajao, J. A.; Ajayi, E. O. B.

    2017-01-01

    Photocatalytically modified ceramic adsorbents were synthesized for the removal of high concentration Cu (II) and Co (II) ions from their aqueous solutions. The raw material, diatomaceous aluminosilicate mineral was modified using silver and anatase titanium oxide nanoparticles. Batch adsorption experiment was carried out on the targeted metal ions and the results were analyzed by the Langmuir and Freundlich equation at different concentrations (100-1000 mg/l) and the characteristic parameters for each adsorption isotherm were determined. As-received raw materials do not exhibit any sorption capacity for high concentration Cu2+ and Co2+ adsorbates. However, the adsorption isotherms for modified diatomaceous ceramic adsorbents could be fitted well by the Langmuir model for both Cu2+ and Co2+ with correlation coefficient (R) of up to 0.99953. The highest and lowest monolayer coverage (q max) were 121.803 and 31.289 mg/g for Cu2+ and Co2+, respectively. The separation factor (R L) in the experiment was less than one (<1), indicating that the adsorption of metal ions on the Ag-TiO2-modified ceramic adsorbent is favorable. The highest adsorption capacity (K f) and intensity (n) constants obtained from Freundlich model are 38.832 (Cu2+ on ZEO-T) and 5.801 (Co2+ on STOX-Z).

  19. Resistance of Ag-silicene-Ag junctions: A combined nonequilibrium Green's function and Boltzmann transport study

    NASA Astrophysics Data System (ADS)

    Wang, Yun-Peng; Fry, J. N.; Cheng, Hai-Ping

    2013-09-01

    For several years the electronic structure properties of the two-dimensional system silicene have been studied extensively. Electron transport across metal-silicene junctions, however, remains relatively unexplored. To address this issue, we developed and implemented a theoretical framework that utilizes the tight-binding Fisher-Lee relation to span nonequilibrium Green's function (NEGF) techniques, the scattering method, and semiclassical Boltzmann transport theory. Within this hybrid quantum-classical, two-scale framework, we calculated transmission and reflection coefficients of monolayer and bilayer Ag-silicene-Ag junctions using the NEGF method in conjunction with density functional theory; derived and calculated the group velocities; and computed resistance using the semiclassical Boltzmann equation. We found that resistances of these junctions are ˜0.08fΩm2 for monolayer silicene junctions and ˜0.3fΩm2 for bilayer ones; factors of ˜8 and ˜2, respectively, smaller than Sharvin resistances estimated via the Landauer formalism.

  20. 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.

  1. 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.

  2. Monochromatic Electron Photoemission from DiamondoidMonolayers

    SciTech Connect

    Yang, W.L.

    2010-04-15

    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 68% 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 flat-panel displays.

  3. 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.

  4. A flexible transparent Ag-NC@PE film as a cut-and-paste SERS substrate for rapid in situ detection of organic pollutants.

    PubMed

    Zhou, Ningning; Meng, Guowen; Huang, Zhulin; Ke, Yan; Zhou, Qitao; Hu, Xiaoye

    2016-10-21

    This report presents a simple and inexpensive fabrication approach to a flexible transparent composite film as a "cut-and-paste" surface-enhanced Raman scattering (SERS) substrate for in situ detection of organic pollutants. First, a self-assembled monolayer of Ag-nanocubes (Ag-NCs) is obtained at the air/water interface. Then, the Ag-NC monolayer is retrieved onto a flexible transparent polyethylene (PE) film to achieve an Ag-NC@PE composite film as a flexible SERS substrate. As the Ag-NCs in the monolayer are closely and uniformly packed on the PE film, the Ag-NC@PE composite film shows high SERS-activity with good signal homogeneity and reproducibility. Furthermore, the flexible transparent Ag-NC@PE composite film is "cut into" small pieces and directly "pasted" onto contaminated fruits for in situ SERS detection, as a result 10 nM thiram, 1 μM 4-polychlorinated biphenyl and 10 nM methyl parathion contaminants on oranges are detected, respectively. Therefore the Ag-NC@PE composite film is an inexpensive and effective SERS substrate for rapid in situ detection of organic pollutants in aqueous solutions, on fruits and other solid objects.

  5. Using specific synthetic peptide (p176) derived AgB 8/1-kDa accompanied by modified patient's sera: a novel hypothesis to follow-up of Cystic echinococcosis after surgery.

    PubMed

    Rouhani, Soheila; Parvizi, Parviz; Spotin, Adel

    2013-10-01

    Cystic echinococcosis (CE) is caused by the larval stage of the tapeworm Echinococcus granulosus. Until now, CE does not have an effective follow-up after surgery. To date, CE follow-up is conducted based on either antibody or antigen detection assays by double antibody sandwich ELISA. Unlike antigen detection, antibodies to imply exposure to an Echinococcus infection while their titration could remain for a longer period (1-10years) after surgery. Likewise, antibody respond may be related to the location of a mature hydatid cyst. Antigen detection shows presence of CE infection, it is extremely important and necessary in follow-up of CE after surgery. The circulating antigen (CAg) titration decrease faster than circulating antibody (during 1-3weeks) after operation. Location of hydatid cyst in detecting antigen is affected less than antibody also. Regarding this subject, antigen detection has several limitations that lead to be used less in CE follow-up. Although, AgB 8/1-kDa subunit is considered as a principle and immunogenic CAg but sensitivity of CAg detection compared to with antibody has variable range, between 33% and 85% which owing to formation of circulating immune complexes (CICs) in result of antigen - antibody complex. The another problem is non using specific CAg (AgB 8/1-kDa subunit) for production of specific paratopes (rabbit hyper immune antiserum) against AgB 8/1-kDa which is used as capture (primary) antibody in double antibody sandwich ELISA assay. The designation of synthetic peptides from conserved regions of AgB 8/1-kDa can help to this problem. These regions (motifs) should be selected for allelic, dominant, immunogenic and conserved without any genetic variation. The first part of this hypothesis suggests which patient's sera should be treated with acidic buffers such as boric acid, acetic acid, glycine/HCl, polyethylene glycol (PEG) or combination of each of them accompanied by boiling patient's sera which causes breaking Ag-Ab complexes

  6. Confirmation of a de novo structure prediction for an atomically precise monolayer-coated silver nanoparticle

    PubMed Central

    Conn, Brian E.; Atnagulov, Aydar; Yoon, Bokwon; Barnett, Robert N.; Landman, Uzi; Bigioni, Terry P.

    2016-01-01

    Fathoming the principles underpinning the structures of monolayer-coated molecular metal nanoparticles remains an enduring challenge. Notwithstanding recent x-ray determinations, coveted veritable de novo structural predictions are scarce. Building on recent syntheses and de novo structure predictions of M3AuxAg17−x(TBBT)12, where M is a countercation, x = 0 or 1, and TBBT is 4-tert-butylbenzenethiol, we report an x-ray–determined structure that authenticates an a priori prediction and, in conjunction with first-principles theoretical analysis, lends force to the underlying forecasting methodology. The predicted and verified Ag(SR)3 monomer, together with the recently discovered Ag2(SR)5 dimer and Ag3(SR)6 trimer, establishes a family of unique mount motifs for silver thiolate nanoparticles, expanding knowledge beyond the earlier-known Au-S staples in thiol-capped gold nanoclusters. These findings demonstrate key principles underlying ligand-shell anchoring to the metal core, as well as unique T-like benzene dimer and cyclic benzene trimer ligand bundling configurations, opening vistas for rational design of metal and alloy nanoparticles. PMID:28138537

  7. A new HBsAg screening assay designed for sensitive detection of HBsAg subtypes and variants.

    PubMed

    van Roosmalen, M H; de Jong, J J; Haenen, W; Jacobs, T; Couwenberg, F; Ahlers-de Boer, G J C M; Hellings, J A

    2006-01-01

    The design of a new HBsAg screening assay, the Hepanostika HBsAg Ultra is based on the use of monoclonal antibodies raised against native wild-type HBsAg and reactive with HBsAg in which the common 'a'-determinant is modified by site-directed mutagenesis of four of the cysteine moieties. The design was checked using the same cysteine variants and samples from patients known to be infected with HBsAg variants. The results found were compared with other state-of-the-art commercial screening assays. The design of the Hepanostika HBsAg Ultra enabled detection of all variant HBsAg-positive samples in contrast to the other commercial assays. An additional 980 samples were tested to assess the specificity and sensitivity of the Hepanostika HBsAg Ultra. Screening of presumed negative serum and plasma samples resulted in a specificity of 100%. This makes the Hepanostika HBsAg Ultra the first screening assay with a design able to detect HBsAg variants with high sensitivity and specificity.

  8. 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

  9. Compressibility study of quaternary phospholipid blend monolayers.

    PubMed

    Cavalcanti, Leide P; Tho, Ingunn; Konovalov, Oleg; Fossheim, Sigrid; Brandl, Martin

    2011-07-01

    The mechanical properties of liposome membranes are strongly dependent on type and ratio of lipid compounds, which can have important role in drug targeting and release processes when liposome is used as drug carrier. In this work we have used Brewster's angle microscopy to monitor the lateral compression process of lipid monolayers containing as helper lipids either distearoyl phosphatidylethanolamine (DSPE) or dioleoyl phophatidylethanolamine (DOPE) molecules on the Langmuir trough. The compressibility coefficient was determined for lipid blend monolayers containing the helper lipids above, cholesterol, distearoyl phosphatidylcholine (DSPC) and pegylated-DSPE at room temperature. Two variables, the cholesterol fraction and the ratio ρ between the helper lipid (either DSPE or DOPE) and the reference lipid DSPC, were studied by multivariate analysis to evaluate their impact on the compressibility coefficient of the monolayers. The cholesterol level was found to be the most significant variable for DSPE blends while the ratio ρ was the most significant one for DOPE blend monolayers. It was also found that these two variables can exhibit positive interaction and the same compressibility value can be obtained with different blend compositions.

  10. Adsorption of Ions at Uncharged Insoluble Monolayers.

    PubMed

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

    2016-09-06

    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.

  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. 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.

  13. Modulation of dipalmitoylphosphatidylcholine monolayers by dimethyl sulfoxide.

    PubMed

    Dabkowska, Aleksandra P; Collins, Louise E; Barlow, David J; Barker, Robert; McLain, Sylvia E; Lawrence, M Jayne; Lorenz, Christian D

    2014-07-29

    The action of the penetration-enhancing agent, dimethyl sulfoxide (DMSO), on phospholipid monolayers was investigated at the air-water interface using a combination of experimental techniques and molecular dynamics simulations. Brewster angle microscopy revealed that DPPC monolayers remained laterally homogeneous at subphase concentrations up to a mole fraction of 0.1 DMSO. Neutron reflectometry of the monolayers in combination with isotopic substitution enabled the determination of solvent profiles as a function of distance perpendicular to the interface for the different DMSO subphase concentrations. These experimental results were compared to those obtained from molecular dynamic (MD) simulations of the corresponding monolayer systems. There was excellent agreement found between the MD-derived reflectivity curves and the measured data for all of the H/D contrast variations investigated. The MD provide a detailed description of the distribution of water and DMSO molecules around the phosphatidylcholine headgroup, and how this distribution changes with increasing DMSO concentrations. Significantly, the measurements and simulations that are reported here support the hypothesis that DMSO acts by dehydrating the phosphatidylcholine headgroup, and as such provide the first direct evidence that it does so primarily by displacing water molecules bound to the choline group.

  14. Phospholipid lateral diffusion in phosphatidylcholine-sphingomyelin-cholesterol monolayers; effects of oxidatively truncated phosphatidylcholines.

    PubMed

    Parkkila, Petteri; Stefl, Martin; Olżyńska, Agnieszka; Hof, Martin; Kinnunen, Paavo K J

    2015-01-01

    Oxidative stress is involved in a number of pathological conditions and the generated oxidatively modified lipids influence membrane properties and functions, including lipid-protein interactions and cellular signaling. Brewster angle microscopy demonstrated oxidatively truncated phosphatidylcholines to promote phase separation in monolayers of 1-palmitoyl-2-oleoyl-sn-glycerol-3-phosphocholine (POPC), sphingomyelin (SM) and cholesterol (Chol). More specifically, 1-palmitoyl-2-azelaoyl-sn-glycero-3-phosphocholine (PazePC), was found to increase the miscibility transition pressure of the SM/Chol-phase. Lateral diffusion of lipids is influenced by a variety of membrane properties, thus making it a sensitive parameter to observe the coexistence of different lipid phases, for instance. The dependence on lipid lateral packing of the lateral diffusion of fluorophore-containing phospholipid analogs was investigated in Langmuir monolayers composed of POPC, SM, and Chol and additionally containing oxidatively truncated phosphatidylcholines, using fluorescence correlation spectroscopy (FCS). To our knowledge, these are the first FCS results on miscibility transition in ternary lipid monolayers, confirming previous results obtained using Brewster angle microscopy on such lipid monolayers. Wide-field fluorescence microscopy was additionally employed to verify the transition, i.e. the loss and reformation of SM/Chol domains.

  15. Thioaromatic DNA monolayers for target-amplification-free electrochemical sensing of environmental pathogenic bacteria.

    PubMed

    Miranda-Castro, Rebeca; Sánchez-Salcedo, Raquel; Suárez-Álvarez, Beatriz; de-Los-Santos-Álvarez, Noemí; Miranda-Ordieres, Arturo J; Jesús Lobo-Castañón, María

    2017-06-15

    Genosensing technology has mostly based on mixed self-assembled monolayers (SAMs) of thiol-modified oligonucleotides and alkanethiols on gold surfaces. However, the typical backfilling approach, which incorporates the alkanethiol in a second step, gives rise to a heterogeneous distribution of oligonucleotide probes on the surface, negatively affecting to both hybridization efficiency and surface stability. Despite aromatic thiols present a remarkably different behavior from alkanethiols, with higher rigidity and stronger intermolecular interactions, they have been scarcely explored for the fabrication of DNA sensing platforms. We have investigated different approaches involving SAMs of aromatic thiols, namely p-mercaptobenzoic acid (p-MBA) and p-aminothiophenol (p-ATP), to yield DNA sensing layers for sequence-specific detection of target oligonucleotides. The studied monolayers were evaluated by DNA surface coverage and further information was obtained by determining their functionality in a sandwich hybridization assay with enzymatic amplification of the electrochemical read-out. The insertion of thiol-oligonucleotides into p-ATP monolayers previously oxidized, and the covalent binding of amino-oligonucleotides to pure p-MBA monolayers give rise to increased storage stability and better analytical performance. The quantification of RNA from Legionella pneumophila cellular lysates was successfully performed, illustrating the usefulness of these sensing architectures for detecting pathogenic bacteria.

  16. 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.

  17. Incoherent Ag islands growth on Ni(100)

    NASA Astrophysics Data System (ADS)

    Marie, J. B.; Braems, I.; Bellec, A.; Chacon, C.; Creuze, J.; Girard, Y.; Gueddani, S.; Lagoute, J.; Repain, V.; Rousset, S.

    2017-02-01

    Growth of two-dimensional superstructure and island morphologies of silver atoms evaporated on a nickel (100) surface are studied by scanning tunneling microscopy. Near-equilibrium islands form at moderate annealing temperature (lower than 500 K) and present two kinds of morphologies. While they share a common monolayer c(2×8) superstructure, two distinct populations of islands coexist: rounded islands grown on the surface and spindle-shaped islands grown inside the Ni surface. The latter present a clear saturation of their density with increasing coverage. These shapes are mostly dominated by boundary energies as confirmed by a simple two-dimensional Wulff model whose parameters are derived using molecular statics simulations. Further annealing to 700 K leads to long Ag strips decorating the Ni step edges.

  18. 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

    2016-03-02

    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.

  19. Surface modification of silicon oxide with trialkoxysilanes toward close-packed monolayer formation.

    PubMed

    Tanaka, Mutsuo; Sawaguchi, Takahiro; Kuwahara, Masashi; Niwa, Osamu

    2013-05-28

    In order to scrutinize potential of trialkoxysilanes to form close-packed monolayer, surface modification of silicon oxide was carried out with the trialkoxysilanes bearing a ferrocene moiety for analysis by electrochemical methods. As it was found that hydrogen-terminated silicon reacts with trialkoxysilane through natural oxidation in organic solvents, where the silicon oxide layer is thin enough to afford conductivity for electrochemical analysis, hydrogen-terminated silicon wafer was immersed in trialkoxysilane solution for surface modification without oxidation treatment. Cyclic voltammetry measurements to determine surface concentrations of the immobilized ferrocene-silane on silicon surface were carried out with various temperature, concentration, solvent, and molecular structure, while the blocking effect in the cyclic voltammogram was investigated to obtain insight into density leading to the close-packed layer. The results suggested that a monolayer modification tended to occur under milder conditions when the ferrocene-silane had a longer alkyl chain, and formation of a close-packed layer to show significant blocking effect was observed. However, the surface modification proceeded even when surface concentration of the immobilized ferrocene-silane was greater than that expected for the monolayer. On the basis of these tendencies, the surface of silicon oxide modified with trialkoxysilane is considered to be a partial multilayer rather than monolayer although a close-packed layer is formed. This result is supported by the comparison with carbon surface modified with ferrocene-diazonium, in which a significant blocking effect was observed when surface concentrations of the immobilized ferrocene moiety are lower than that for silicon oxide modified with ferrocene-silane.

  20. An Ab Initio Study of the Low-Lying Doublet States of AgO and AgS

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R.

    1990-01-01

    Spectroscopic constants (D(sub o), r(sub e), mu(sub e), T(sub e)) are determined for the doublet states of AgO and AgS below approx. = 30000/cm. Large valence basis sets are employed in conjunction with relativistic effective core potentials (RECPs). Electron correlation is included using the modified coupled-pair functional (MCPF) and multireference configuration interaction (MRCI) methods. The A(sup 2)Sigma(sup +) - X(sup 2)Pi band system is found to occur in the near infrared (approx. = 9000/cm) and to be relatively weak with a radiative lifetime of 900 microns for A(sup 2)Sigma(sup +) (upsilon = 0). The weakly bound C(sup 2)Pi state (our notation), the upper state of the blue system, is found to require high levels of theoretical treatment to determine a quantitatively accurate potential. The red system is assigned as a transition from the C(sup 2)Pi state to the previously unobserved A(sup 2)Sigma(sup +) state. Several additional transitions are identified that should be detectable experimentally. A more limited study is performed for the vertical excitation spectrum of AgS. In addition, a detailed all-electron study of the X(sup 2)Pi and A(sup 2)Sigma(sup +) states of AgO is carried out using large atomic natural orbital (ANO) basis sets. Our best calculated D(sub o) value for AgO is significantly less than the experimental value, which suggests that there may be some systematic error in the experimental determination.

  1. 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.

  2. 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.

  3. Grazing incidence X-ray diffraction studies of condensed double-chain phospholipid monolayers formed at the soft air/water interface.

    PubMed

    Stefaniu, Cristina; Brezesinski, Gerald

    2014-05-01

    The use of highly brilliant synchrotron light sources in the middle of the 1980s for X-ray diffraction has revolutionized the research of condensed monolayers. Since then, monolayers gained popularity as convenient quasi two-dimensional model systems widely used in biophysics and material science. This review focuses on structures observed in one-component phospholipid monolayers used as simplified two-dimensional models of biological membranes. In a monolayer system the phase transitions can be easily triggered at constant temperature by increasing the packing density of the lipids by compression. Simultaneously the monolayer structure changes are followed in situ by grazing incidence X-ray diffraction. Competing interactions between the different parts of the molecule are responsible for the different monolayer structures. These forces can be modified by chemical variations of the hydrophobic chain region, of the hydrophilic head group region or of the interfacial region between chains and head groups. Modifications of monolayer structures triggered by changes of the chemical structure of double-chain phospholipids are highlighted in this paper.

  4. 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.

  5. Orientation dynamics of azobenzene-based self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Fang, Guanjiu

    2007-12-01

    Self-assembled monolayers (SAMs) synthesized on glass and incorporating azobenzene are illuminated with actinic light to study the effect of photo-isomerization on in-plane molecular orientation. Measurements of the monolayer birefringence show that the SAM orientation dynamics are non-first-order kinetics, characterized by an exponential relaxation with a distribution of relaxation times. The orientational birefringence decays as a power law with an exponent that decreases with increasing initial writing intensity, indicative of orientational trapping wells with a distribution of depths. The distribution of trapping well depths, resulting from the distribution of free volumes among the SAM molecules, is modified by exposure to light. This depth modification indicates that photoisomerization is a collective process depending on neighboring molecules. Increasing the light intensity enhances the collective effect so that the orientation dynamics are changed from fractal to normal diffusion. With a further increase in light intensity, the collective effect does not change any more so that the mean width of the trapping well depth distribution, characterized by the power law exponent, becomes constant. The liquid crystal alignment in a photo-buffed SAM/rubbed nylon twisted nematic cell is very stable at room temperature, but it is lost upon cooling if the liquid crystal is heated into the isotropic phase, which is attributed to the thermal orientational relaxation of the SAM molecules. The liquid crystal response to reorienting the SAM with polarized light depends on the initial SAM writing time: the harder the initial writing, the slower subsequent reorientation, which is similar to the behavior of bare SAMs. The reorientation of the liquid crystals shows hysteresis compared with that of bare SAMs, with a larger dose required at higher intensity.

  6. 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

  7. 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.

  8. 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.

  9. Realization of continuous Zachariasen carbon monolayer.

    PubMed

    Joo, Won-Jae; Lee, Jae-Hyun; Jang, Yamujin; Kang, Seog-Gyun; Kwon, Young-Nam; Chung, Jaegwan; Lee, Sangyeob; Kim, Changhyun; Kim, Tae-Hoon; Yang, Cheol-Woong; Kim, Un Jeong; Choi, Byoung Lyong; Whang, Dongmok; Hwang, Sung-Woo

    2017-02-01

    Rapid progress in two-dimensional (2D) crystalline materials has recently enabled a range of device possibilities. These possibilities may be further expanded through the development of advanced 2D glass materials. Zachariasen carbon monolayer, a novel amorphous 2D carbon allotrope, was successfully synthesized on germanium surface. The one-atom-thick continuous amorphous layer, in which the in-plane carbon network was fully sp(2)-hybridized, was achieved at high temperatures (>900°C) and a controlled growth rate. We verified that the charge carriers within the Zachariasen carbon monolayer are strongly localized to display Anderson insulating behavior and a large negative magnetoresistance. This new 2D glass also exhibited a unique ability as an atom-thick interface layer, allowing the deposition of an atomically flat dielectric film. It can be adopted in conventional semiconductor and display processing or used in the fabrication of flexible devices consisting of thin inorganic layers.

  10. Ground state structures in ferrofluid monolayers.

    PubMed

    Prokopieva, Taisia A; Danilov, Victor A; Kantorovich, Sofia S; Holm, Christian

    2009-09-01

    A combination of analytical calculations and Monte Carlo simulations is used to find the ground state structures in monodisperse ferrofluid monolayers. Taking into account the magnetic dipole-dipole interaction between all particles in the system we observe different topological structures that are likely to exist at low temperatures. The most energetically favored structures we find are rings, embedded rings, and rings side by side, and we are able to derive analytical expressions for the total energy of these structures. A detailed analysis of embedded rings and rings side by side shows that the interring interactions are negligible. We furthermore find that a single ideal ring is the ground state structure for a ferrofluid monolayer. We compared our theoretical predictions to the results of simulated annealing data and found them to be in excellent agreement.

  11. Piezoelectric monolayers as nonlinear energy harvesters.

    PubMed

    López-Suárez, Miquel; Pruneda, Miguel; Abadal, Gabriel; Rurali, Riccardo

    2014-05-02

    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.

  12. Collective cell motion in endothelial monolayers

    PubMed Central

    Szabó, A.; Ünnep, R.; Méhes, E.; Twal, W. O.; Argraves, S. W.; Cao, Y.; Czirók, A.

    2011-01-01

    Collective cell motility is an important aspect of several developmental and pathophysiological processes. Despite its importance, the mechanisms that allow cells to be both motile and adhere to one another are poorly understood. In this study we establish statistical properties of the random streaming behavior of endothelial monolayer cultures. To understand the reported empirical findings, we expand the widely used cellular Potts model to include active cell motility. For spontaneous directed motility we assume a positive feedback between cell displacements and cell polarity. The resulting model is studied with computer simulations, and is shown to exhibit behavior compatible with experimental findings. In particular, in monolayer cultures both the speed and persistence of cell motion decreases, transient cell chains move together as groups, and velocity correlations extend over several cell diameters. As active cell motility is ubiquitous both in vitro and in vivo, our model is expected to be a generally applicable representation of cellular behavior. PMID:21076204

  13. Fracture characteristics of monolayer CVD-graphene.

    PubMed

    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

    2014-03-24

    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.

  14. Fracture Characteristics of Monolayer CVD-Graphene

    NASA Astrophysics Data System (ADS)

    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

    2014-03-01

    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.

  15. Realization of continuous Zachariasen carbon monolayer

    PubMed Central

    Joo, Won-Jae; Lee, Jae-Hyun; Jang, Yamujin; Kang, Seog-Gyun; Kwon, Young-Nam; Chung, Jaegwan; Lee, Sangyeob; Kim, Changhyun; Kim, Tae-Hoon; Yang, Cheol-Woong; Kim, Un Jeong; Choi, Byoung Lyong; Whang, Dongmok; Hwang, Sung-Woo

    2017-01-01

    Rapid progress in two-dimensional (2D) crystalline materials has recently enabled a range of device possibilities. These possibilities may be further expanded through the development of advanced 2D glass materials. Zachariasen carbon monolayer, a novel amorphous 2D carbon allotrope, was successfully synthesized on germanium surface. The one-atom-thick continuous amorphous layer, in which the in-plane carbon network was fully sp2-hybridized, was achieved at high temperatures (>900°C) and a controlled growth rate. We verified that the charge carriers within the Zachariasen carbon monolayer are strongly localized to display Anderson insulating behavior and a large negative magnetoresistance. This new 2D glass also exhibited a unique ability as an atom-thick interface layer, allowing the deposition of an atomically flat dielectric film. It can be adopted in conventional semiconductor and display processing or used in the fabrication of flexible devices consisting of thin inorganic layers. PMID:28246635

  16. 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

  17. Selective degradation of chemical bonds: from single-source molecular precursors to metallic Ag and semiconducting Ag2S nanocrystals via instant thermal activation.

    PubMed

    Tang, Qun; Yoon, Seok Min; Yang, Hyun Jin; Lee, Yoonmi; Song, Hyun Jae; Byon, Hye Ryung; Choi, Hee Cheul

    2006-03-14

    Selective formation of metallic Ag and semiconducting Ag(2)S nanocrystals has been achieved via a modified hot-injection process from a single-source precursor molecule, Ag(SCOPh), which can potentially generate both [Ag] and [AgS] fragments simultaneously. When the precursor molecules are injected into a preheated reaction system at 160 degrees C, spherical Ag(2)S nanocrystals are directly obtained even without a molecular activator, such as alkylamines. Mixtures of Ag and Ag(2)S or pure metallic Ag nanocrystals are obtained if the precursor molecules are injected at lower than 160 degrees C or room temperature. These results are attributed to the direct transfer of thermal energies to precursor molecules, which are enough to dissociate S-C as well as Ag-S bonds simultaneously. Detailed characterizations about the produced nanocrystals have been performed using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), as well as energy-dispersive X-ray (EDX) spectrum.

  18. 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

  19. 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.

  20. Phase transitions of monolayers on graphene

    NASA Astrophysics Data System (ADS)

    Kahn, Joshua; Dzyubenko, Boris; Vilches, Oscar; Cobden, David

    We have studied physisorbed layers of monatomic and diatomic gases on graphene. We used devices in which few-layer graphene, ranging from monolayer to trilayer, is suspended across a trench between two platinum contacts and are cleaned by thermal and current annealing. We found that the density of adsorbates is revealed by the conductance, similar to the case with nanotubes. The conductance change for a monolayer can be large. On trilayer graphene the adsorbed gases can be seen to exhibit transitions between two-dimensional phases identical to those on bulk graphite, including incommensurate and commensurate solid, fluid and vapor and multiple layers. New features appear in the conductance at the boundaries of the commensurate phase of Kr. We are able to measure single-particle binding energies very accurately and see how it depends on thickness; investigate the effects of changing disorder by gradually current annealing; and search for new phases in the case of monolayer graphene where atoms adsorbed on both sides can interact. We can map out the 2d phase diagrams very quickly by ohmic heating, which gives nearly instantaneous control of the temperature.

  1. Biocompatible Ferromagnetic Cr-Trihalide Monolayers

    NASA Astrophysics Data System (ADS)

    Sun, Qiang

    Cr with an electronic configuration of 3d54s1 possesses the largest atomic magnetic moment (6µB) of all elements in the 3d transition metal series. Furthermore, the trivalent chromium (Cr3+) is biocompatible and is widely found in food and supplements. Here using first principles calculations combined with Monte Carlo simulations based on Ising model, we systematically study a class of 2D ferromagnetic monolayers CrX3 (X = Cl, Br, I). The feasibility of exfoliation from their layered bulk phase is confirmed by the small cleavage energy and high in-plane stiffness. Spin-polarized calculations, combined with self consistently determined Hubbard U that accounts for strong correlation energy, demonstrate that CrX3 (X =Cl, Br, I) monolayers are ferromagnetic and Cr is trivalent and carries a magnetic moment of 3µB, the resulting Cr3+ ions are biocompatible. The corresponding Curie temperatures for CrCl3 CrBr3 CrI3 are are found to 66, 86, and 107 K, respectively, which can be increased to 323, 314, 293 K by hole doping. The biocompatibility and ferromagnetism render these Cr-containing trichalcogenide monolayers unique for applications.

  2. @AuAg nanostructures

    NASA Astrophysics Data System (ADS)

    Singh, Rina; Soni, R. K.

    2014-09-01

    Bimetallic and trimetallic nanoparticles have attracted significant attention in recent times due to their enhanced electrochemical and catalytic properties compared to monometallic nanoparticles. The numerical calculations using Mie theory has been carried out for three-layered metal nanoshell dielectric-metal-metal (DMM) system consisting of a particle with a dielectric core (Al@Al2O3), a middle metal Ag (Au) layer and an outer metal Au (Ag) shell. The results have been interpreted using plasmon hybridization theory. We have also prepared Al@Al2O3@Ag@Au and Al@Al2O3@AgAu triple-layered core-shell or alloy nanostructure by two-step laser ablation method and compared with calculated results. The synthesis involves temporal separations of Al, Ag, and Au deposition for step-by-step formation of triple-layered core-shell structure. To form Al@Ag nanoparticles, we ablated silver for 40 min in aluminium nanoparticle colloidal solution. As aluminium oxidizes easily in water to form alumina, the resulting structure is core-shell Al@Al2O3. The Al@Al2O3 particle acts as a seed for the incoming energetic silver particles for multilayered Al@Al2O3@Ag nanoparticles is formed. The silver target was then replaced by gold target and ablation was carried out for different ablation time using different laser energy for generation of Al@Al2O3@Ag@Au core-shell or Al@Al2O3@AgAu alloy. The formation of core-shell and alloy nanostructure was confirmed by UV-visible spectroscopy. The absorption spectra show shift in plasmon resonance peak of silver to gold in the range 400-520 nm with increasing ablation time suggesting formation of Ag-Au alloy in the presence of alumina particles in the solution.

  3. Preparation and characterization of pure and mixed monolayers of poly(ethylene glycol) brushes chemically adsorbed to silica surfaces.

    PubMed

    McNamee, Cathy E; Yamamoto, Shinpei; Higashitani, Ko

    2007-04-10

    We prepared pure and mixed monolayers of methoxy-terminated poly(ethylene glycol)s (m-PEG's) chemically attached to silica surfaces by using m-PEG silane coupling agents of three different molecular weights. These films were subsequently characterized in water by atomic force microscopy (AFM). Images of pure m-PEG monolayers showed the formation of polymer brushes on silica. Force curves between two modified surfaces suggested that an increase in the number of oxyethylene (OE) groups from 6 (PEG6 surface) to 43 (PEG43 surface) to 113 (PEG113 surface) decreased the flexibility of the m-PEG chains in the m-PEG brushes. Frictional force measurements also showed that the friction increased in the order PEG6 < PEG43 monolayers of PEG6 and PEG113 were prepared using various fractions of PEG6 and PEG113. Images of mixed PEG6 and PEG113 monolayers showed that the size of the PEG113 islands in the film decreased as the fraction of PEG113 decreased. The force curves between two modified surfaces suggested that the flexibility of the mixed monolayers decreased as the fraction of PEG113 increased. Frictional force measurements also showed that the friction decreased as the fraction of PEG6 in the PEG6-PEG113 mixed film increased. Entanglements were therefore thought to decrease as the fraction of PEG113 in the mixed monolayer decreased.

  4. 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.

  5. 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.

  6. Anion Binding in Self-Assembled Monolayers in Mesoporous Supports (SAMMS)

    SciTech Connect

    Mattigod, Shas V.; Fryxell, Glen E.; Parker, Kent E.

    2007-02-19

    The binding of various anions to cationic transition metal complexes lining the pores of mesoporous silica is characterized and correlated to anion basicity. By lining the pore surfaces of mesoporous silica with self-assembled monolayer of organosilanes terminated with chemically selective ligands, a powerful new class of heavy metal sorbents has been realized, called self-assembled monolayers on mesoporous supports (SAMMS) [1-18]. When this interfacial functionality is composed of cationic transition metal complexes, a valuable new class of anion exchange material came into being [19]. Yoshitake and co-workers, have extended this concept to include other transition metal cations in similar cationic complexes inside mesoporous silica [20-23]. Other amine-based ligands (including polymer-based systems) were also explored, and the highest binding capacity was found with the diethylenetriamine ligand [20]. This synthetic strategy allows the chemist to easily modify both the metal center and ligand field, thereby tailoring chemical selectivity at multiple levels.

  7. Variable temperature STM study of Co deposition on a dodecanethiol self assembled monolayer

    NASA Astrophysics Data System (ADS)

    Breitwieser, Romain; Campiglio, Paolo; Chacon, Cyril; Repain, Vincent; Nemausat, Ruidy; Girard, Yann; Lagoute, Jérôme; Rousset, Sylvie

    2012-02-01

    The present scanning tunneling microscopy study reports on the growth processes of Co vapor-deposited on a dodecanethiol (DDT) self-assembled monolayer (SAM)/Au(111). We observe strongly modified surface and depth diffusions of Co adatoms depending on the growth temperature. Co deposited at 300 K shows an extremely incomplete regime of condensation on the organic layer. Besides, Co penetrates the DDT monolayer and resides at the DDT/Au(111) interface as 2D clusters. This phenomenon takes place through defects in the SAM which are transient channels. In contrast, Co deposited at 50 K shows a complete condensation and nucleates on defects of the SAM layer as 3D islands sitting most likely on top of the DDTs. These results are of interest in the growing field of organic spintronics where the quality of the organic/ferromagnetic interface is a key issue.

  8. Change of cobalt magnetic anisotropy and spin polarization with alkanethiolates self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Campiglio, Paolo; Breitwieser, Romain; Repain, Vincent; Guitteny, Solène; Chacon, Cyril; Bellec, Amandine; Lagoute, Jérôme; Girard, Yann; Rousset, Sylvie; Sassella, Adele; Imam, Mighfar; Narasimhan, Shobhana

    2015-06-01

    We demonstrate that the deposition of a self-assembled monolayer of alkanethiolates on a 1 nm thick cobalt ultrathin film grown on Au(111) induces a spin reorientation transition from in-plane to out-of-plane magnetization. Using ab initio calculations, we show that a methanethiolate layer changes slightly both the magnetocrystalline and shape anisotropy, both effects almost cancelling each other out for a 1 nm Co film. Finally, the change in hysteresis cycles upon alkanethiolate adsorption could be assigned to a molecular-induced roughening of the Co layer, as shown by STM. In addition, we calculate how a methanethiolate layer modifies the spin density of states of the Co layer and we show that the spin polarization at the Fermi level through the organic layer is reversed as compared to the uncovered Co. These results give new theoretical and experimental insights for the use of thiol-based self-assembled monolayers in spintronic devices.

  9. Superlattice of resonators on monolayer graphene created by intercalated gold nanoclusters

    NASA Astrophysics Data System (ADS)

    Cranney, M.; Vonau, F.; Pillai, P. B.; Denys, E.; Aubel, D.; De Souza, M. M.; Bena, C.; Simon, L.

    2010-09-01

    Here we report on a "new" type of ordering which allows to modify the electronic structure of a graphene monolayer (ML). We have intercalated small gold clusters between the top monolayer graphene and the buffer layer of epitaxial graphene. We show that these clusters perturb the quasiparticles on the ML graphene, acting as quantum dots creating a superlattice of resonators on the graphene ML, as revealed by a strong pattern of standing waves. A detailed analysis of the standing-wave pattern using Fourier Transform Scanning Tunneling Spectroscopy strongly indicates that this phenomenon can arise from a strong modification of the band structure of graphene and (or) from Charge Density Waves (CDW) where a large extension of Van Hove singularities is involved.

  10. Scanning tunneling microscope observation of the phosphatidylserine domains in the phosphatidylcholine monolayer.

    PubMed

    Matsunaga, Soichiro; Yamada, Taro; Kobayashi, Toshihide; Kawai, Maki

    2015-05-19

    A mixed monolayer of 1,2-dihexanoyl-sn-glycero-3-phospho-l-serine (DHPS) and 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) on an 1-octanethiol-modified gold substrate was visualized on the nanometer scale using in situ scanning tunneling microscopy (STM) in aqueous solution. DHPS clusters were evident as spotty domains. STM enabled us to distinguish DHPS molecules from DHPC molecules depending on their electronic structures. The signal of the DHPS domains was abolished by neutralization with Ca(2+). The addition of the PS + Ca(2+)-binding protein of annexin V to the Ca(2+)-treated monolayer gave a number of spots corresponding to a single annexin V molecule.

  11. Formation of the BiAg2 surface alloy on lattice-mismatched interfaces

    NASA Astrophysics Data System (ADS)

    Abd El-Fattah, Z. M.; Lutz, P.; Piquero-Zulaica, I.; Lobo-Checa, J.; Schiller, F.; Bentmann, H.; Ortega, J. E.; Reinert, F.

    2016-10-01

    We report on the growth of a monolayer-thick BiAg2 surface alloy on thin Ag films grown on Pt(111) and Cu(111). Using low energy electron diffraction (LEED), angle resolved photoemission spectroscopy (ARPES), and scanning tunneling microscopy (STM) we show that the surface structure of the 1/3 ML Bi/x -ML Ag/Pt(111) system (x ≥2 ) is strongly affected by the annealing temperature required to form the alloy. As judged from the characteristic (√{3 }×√{3 } )R 30∘ LEED pattern, the BiAg2 alloy is partially formed at room temperature. A gentle, gradual increase in the annealing temperatures successively results in the formation of a pure BiAg2 phase, a combination of that phase with a (2 ×2 ) superstructure, and finally the pure (2 ×2 ) phase, which persists at higher annealing temperatures. These results complement recent work reporting the (2 ×2 ) as a predominant phase, and attributing the absence of BiAg2 alloy to the strained Ag/Pt interface. Likewise, we show that the growth of the BiAg2 alloy on similarly lattice-mismatched 1 and 2 ML Ag-Cu(111) interfaces also requires a low annealing temperature, whilst higher temperatures result in BiAg2 clustering and the formation of a BiCu2 alloy. The demonstration that the BiAg2 alloy can be formed on thin Ag films on different substrates presenting a strained interface has the prospect of serving as bases for technologically relevant systems, such as Rashba alloys interfaced with magnetic and semiconductor substrates.

  12. Tribology and stability of organic monolayers on CrN: a comparison among silane, phosphonate, alkene, and alkyne chemistries.

    PubMed

    Pujari, Sidharam P; Li, Yan; Regeling, Remco; Zuilhof, Han

    2013-08-20

    The fabrication of chemically and mechanically stable monolayers on the surfaces of various inorganic hard materials is crucial to the development of biomedical/electronic devices. In this Article, monolayers based on the reactivity of silane, phosphonate, 1-alkene, and 1-alkyne moieties were obtained on the hydroxyl-terminated chromium nitride surface. Their chemical stability and tribology were systematically investigated. The chemical stability of the modified CrN surfaces was tested in aqueous media at 60 °C at pH 3, 7, and 11 and monitored by static water contact angle measurements, X-ray photoelectron spectroscopy (XPS), ellipsometry, and Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS). The tribological properties of the resulting organic monolayers with different end groups (fluorinated or nonfluorinated) were studied using atomic force microscopy (AFM). It was found that the fluorinated monolayers exhibit a dramatic reduction of adhesion and friction force as well as excellent wear resistance compared to those of nonfluorinated coatings and bare CrN substrates. The combination of remarkable chemical stability and superior tribological properties makes these fluorinated monolayers promising candidates for the development of robust high-performance devices.

  13. Enzyme immobilization on Ag nanoparticles/polyaniline nanocomposites.

    PubMed

    Crespilho, Frank N; Iost, Rodrigo M; Travain, Silmar A; Oliveira, Osvaldo N; Zucolotto, Valtencir

    2009-06-15

    We show a simple strategy to obtain an efficient enzymatic bioelectrochemical device, in which urease was immobilized on electroactive nanostructured membranes (ENMs) made with polyaniline and silver nanoparticles (AgNP) stabilized in polyvinyl alcohol (PAni/PVA-AgNP). Fabrication of the modified electrodes comprised the chemical deposition of polyaniline followed by drop-coating of PVA-AgNP and urease, resulting in a final ITO/PAni/PVA-AgNP/urease electrode configuration. For comparison, the electrochemical performance of ITO/PAni/urease electrodes (without Ag nanoparticles) was also studied. The performance of the modified electrodes toward urea hydrolysis was investigated via amperometric measurements, revealing a fast increase in cathodic current with a well-defined peak upon addition of urea to the electrolytic solution. The cathodic currents for the ITO/PAni/PVA-AgNP/urease electrodes were significantly higher than for the ITO/PAni/urease electrodes. The friendly environment provided by the ITO/PAni/PVA-AgNP electrode to the immobilized enzyme promoted efficient catalytic conversion of urea into ammonium and bicarbonate ions. Using the Michaelis-Menten kinetics equation, a K(M)(app) of 2.7 mmol L(-1) was obtained, indicating that the electrode architecture employed may be advantageous for fabrication of enzymatic devices with improved biocatalytic properties.

  14. Improved prediction of bilayer and monolayer properties using a refined BMW-MARTINI force field.

    PubMed

    Miguel, Virginia; Perillo, Maria A; Villarreal, Marcos A

    2016-11-01

    Coarse-grained (CG) models allow enlarging the size and time scales that are reachable by atomistic molecular dynamics simulations. A CG force field (FF) for lipids and amino acids that possesses a polarizable water model has been developed following the MARTINI parametrization strategy, the BMW-MARTINI [1]. We tested the BMW-MARTINI FF capability to describe some structural and thermodynamical properties of lipid monolayers and bilayers. We found that, since the surface tension values of oil/water interfaces calculated with the model are not correct, compression isotherms of lipid monolayers present artifacts. Also, this FF predicts DPPC and DAPC bilayers to remain in the Lα phase at temperatures as low as 283K, contrary to the expected from their experimental Tm values. Finally, simulations at constant temperature of bilayers of saturated lipids belonging to PC homologous, showed an increase in the mean molecular area (Mma) upon increasing the chain length, inversely to the experimental observation. We refined BMW-MARTINI FF by modifying as few parameters as possible in order to bring simulated and experimental measurements closer. We have also modified structural parameters of the lipid geometry that do not have direct influence in global properties of the bilayer membranes or monolayers, but serve to approach the obtained CG geometry to atomistic reference values. The refined FF is able to better reproduce phase transition temperatures and Mma for saturated PC bilayers than BMW-MARTINI and MARTINI FF. Finally, the simulated surface pressure-Mma isotherms of PC monolayers resemble the experimental ones and eliminate serious artifacts of previous models.

  15. High-temperature magnetization anomaly in Co/Ag/Si(1 1 1) ultrathin films

    NASA Astrophysics Data System (ADS)

    Lin, J. Y.; Tsay, J. S.; Liou, Y.; Yao, Y. D.; Lee, S. F.; Yang, C. S.

    2000-01-01

    High-temperature magnetic properties of ultrathin Co/Ag/Si(1 1 1) films were studied by surface magneto-optic Kerr effect (SMOKE) in an ultra-high vacuum (UHV) chamber with a background pressure less than 1×10 -10 Torr. A 6 mono-layer (ML) Co layer was deposited on Si(1 1 1) surface with Ag as a buffer layer with the thickness being varied between 0 and 5.6 ML. Both polar and longitudinal MOKE (P- and LMOKE) were studied as a function of temperature between 300 and 550 K. It is interesting to note that the Kerr intensity of LMOKE for Co/Ag/Si(1 1 1) thin film with Ag thickness of 2.8 and 5.6 ML decreases with increasing temperature and vanishes near 475 K; it shows up again in the opposite direction above 475 K before vanishing again at 550 K. This was not observed for samples with Ag thickness less than 2.8 ML. This indicates that the Ag buffer layer is playing an important role in the variation of magnetization of Co at high temperature; in other words, stress or small Co/Co-Ag clusters formed by the diffusion between Ag and Co layer at high temperature may cause the magnetization anomaly.

  16. Morphology Effect of Ni-Ag/CARBON Nanomaterials on Their Electrocatalytic Activity for Glucose Oxidation

    NASA Astrophysics Data System (ADS)

    Ouyang, Ruizhuo; Li, Weiwei; Yang, Yang; Zhang, Wangyao; Feng, Kai; Zong, Tianyu; An, Yarui; Zhou, Shuang; Miao, Yuqing

    2016-06-01

    We presented here three carbon-nanomaterials-based modified glassy carbon electrodes (GCE) with Ni-Ag nanohybrid nanoparticles (NPs) deposited upon, including single-wall carbon nanotubes (SWCNTs), multi-wall carbon nanotubes (MWCNTs) and the mesoporous carbons (MPCs), and compared their morphology effects on both Ni-Ag deposition quality and electrocatalytic performances toward Glu oxidation. After being deposited with Ni-Ag NPs, a homogenous surface with very small Ni-Ag NPs was obtained for Ni-Ag/SWCNTs/GCE, while heterogeneous, coarse surfaces with obvious embedment with large Ni-Ag particles were observed for both Ni-Ag/MWCNTs/GCE and Ni-Ag/MPC/GCE. All three modified electrodes were well characterized in terms of surface morphology, electron transfer rate, hydrophilicity, interference resistance, stability, electrocatalytic behaviors as well as practicability in real samples, based on which Ni-Ag/SWCNTs/GCE was always proved to be more advantageous over other two composite electrodes. Such advantage of Ni-Ag/SWCNTs/GCE was attributed to its desirable surface morphology good for Ni-Ag deposition and exposure of as many active sites as possible to Glu oxidation, leading to the extraordinary electrocatalytic performance.

  17. Direct observation of enhanced magnetic moments in Fe/Ag(100)

    NASA Astrophysics Data System (ADS)

    Wooten, C. L.; Chen, J.; Mulhollan, G. A.; Erskine, J. L.; Markert, J. T.

    1994-04-01

    The magnetic properties of ultrathin (1-5 monolayer) Fe films on Ag(100) substrates were investigated using SQUID magnetometry. Films were grown in pairs (one bulklike, the other thin), and characterized in situ by low-energy electron diffraction, Auger spectroscopy, and the surface magneto-optic Kerr effect. The films were than capped with Au and studied with a SQUID magnetometer over the temperature range 2-340 K. We report here a direct observation of enhanced magnetic moments for Fe on Ag(100), with interface moments enhanced as much as 29%.

  18. 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

    2010-11-09

    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.

  19. Influence of bioregulators on the phospholipid Langmuir monolayers.

    PubMed

    Mogilevich, A S; Mogilevich, S E; Luik, A L

    1997-01-01

    Influence of bioregulators on the phospholipid Langmuir monolayers made of distearoylphosphatidylcholine and its equimolar mixture with dimitrystoylphosphatidylcholine was investigated. The results obtained allow concluding that the presence of physiologically active compounds in the subphase weakens the lipid-lipid interaction and increases the free energy change of air-liquid interface in the case of pure distearoylphosphatidylcholine monolayers, but in the case of mixed monolayers it leads both to the increase and decrease of these parameters. Presence of the dimirystoylphosphatidylcholine molecules with the short fatty acyl chains in the monolayer destabilizes it. This effect is partially compensated by the interaction between lipid and subphase molecules.

  20. AgSTAR Partners

    EPA Pesticide Factsheets

    AgSTAR’s Partner Program builds stronger relationships with state and non-governmental stakeholders to support all phases of anaerobic digester projects: planning, deployment, and long-term success.

  1. 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

  2. One-pot synthesis of visible-light-driven Ag/Ag3PO4 photocatalyst immobilized on exfoliated montmorillonite by clay-mediated in situ reduction

    NASA Astrophysics Data System (ADS)

    Liu, Chang; Zhang, Xiaoyuan; Wu, Jianning; Meng, Guihua; Guo, Xuhong; Liu, Zhiyong

    2016-11-01

    In order to find efficient photocatalytic materials and convenient preparation method, a well-designed Ag/Ag3PO4-OMMT (organically modified montmorillonite) plasmonic photocatalyst was synthesized via the "one-pot" process without any reducing species. Ag+ could be reduced by Si-OH moiety on the surface of OMMT. The resulting samples were thoroughly studied by using X-ray diffraction, X-ray photoelectron spectra, transmission electron microscopy, scanning electron microscope, energy-dispersive X-ray spectroscopy, UV-Vis diffuse reflectance spectra, and so on. The as-prepared Ag/Ag3PO4-OMMT photocatalyst exhibited efficient, stable photocatalytic activity and recyclability for the degradation of Rhodamine B (RhB) under visible light radiation ( λ > 420 nm). The optimum synergetic effect of Ag3PO4/OMMT was found at a weight ratio of 50 %. The degradation efficiency of RhB over Ag/Ag3PO4-OMMT (1:1) was about 92.9 %, and photocatalytic activity remained stable after three cycles. The results show that the designed photocatalyst is feasible and effective. The proposed photocatalysis mechanism is probably attributed to surface plasmon resonance of metallic Ag nanoparticles (NPs) and also attributed to negatively charged exfoliated montmorillonite. The Ag/Ag3PO4-OMMT composites showed highly visible light photocatalytic activity, which makes them promising nanomaterials for further applications in water treatment.

  3. 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.

  4. Ag-Al-Ca

    NASA Astrophysics Data System (ADS)

    Carow-Watamura, U.; Louzguine, D. V.; Takeuchi, A.

    This document is part of Part 1 http://dx.doi.org/10.1007/97.etType="URL"/> 'Systems from Ag-Al-Ca to Au-Pd-Si' of Subvolume B 'Physical Properties of Ternary Amorphous Alloys' of Volume 37 'Phase Diagrams and Physical Properties of Nonequilibrium Alloys' of Landolt-Börnstein - Group III 'Condensed Matter'. It contains the Chapter 'Ag-Al-Ca' with the content:

  5. Determination of low levels of cadmium ions by the under potential deposition on a self-assembled monolayer on gold electrode.

    PubMed

    Noyhouzer, Tomer; Mandler, Daniel

    2011-01-17

    The electrochemical determination of low levels of Cd using a self-assembled monolayer (SAM) modified Au electrode is reported. Determination was based on the stripping of Cd, which was deposited by under potential deposition (UPD). A series of short alkanethiol SAMs bearing different end groups, i.e., sulfonate, carboxylate and ammonium, were examined. Lowest level of detection (ca. 50 ngL(-1)) was achieved with a 3-mercaptopropionic acid (MPA) monolayer using subtractive anodic square wave voltammetry (SASV). Additional surface methods, namely, reductive desorption and X-ray photoelectron spectroscopy, were applied to determine the interfacial structure of the electrodeposited Cd on the modified electrodes. We conclude that the deposited Cd forms a monoatomic layer, which bridges between the gold surface and the alkanethiol monolayer associating with both the gold and the sulfur atoms.

  6. Chiral solidification of a phospholipid monolayer

    NASA Technical Reports Server (NTRS)

    Langer, J. S.

    1985-01-01

    The formation of chiral solidlike domains observed by Weiss and McConnell (1984) in monolayers of depalmitoylphosphatidylcholine (DPPC) floating on an air-water interface is investigated theoretically. It is proposed that the diffusion tensor for the two-dimensional fluidlike phase of the DPPC molecules has a chiral component acting perpendicular to the concentration gradient and coupled to the rotational motion of a pinwheellike molecule by the viscous forces. Diagrams are provided, and numerical estimates of the forces involved are shown to be in agreement with the observed behavior of the structures.

  7. 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.

  8. Fluidization of a horizontally driven granular monolayer.

    PubMed

    Heckel, Michael; Sack, Achim; Kollmer, Jonathan E; Pöschel, Thorsten

    2015-06-01

    We consider the transition of a horizontally vibrated monodisperse granular monolayer between its condensed state and its three-dimensional gaseous state as a function of the vibration parameters, amplitude, and frequency as well as particle number density. The transition is characterized by an abrupt change of the dynamical state which leaves its fingerprints in several measurable quantities including dissipation rate, sound emission, and a gap size which characterizes the sloshing motion of the material. The transition and its pronounced hysteresis is explained through the energy due to the collective motion of the particles relative to the container.

  9. Transcription by eucaryotic and procaryotic RNA polymerases of DNA modified at a d(GG) or a d(AG) site by the antitumor drug cis-diamminedichloroplatinum (II)

    SciTech Connect

    Corda, Y.; Job, C.; Job, D. ); Anin, M-F.; Leng, M. )

    1991-01-01

    The authors have investigated whether DNA modifed at a d(GG) or a d(AG) site by the chemotherapeutic drug cis-diamminedichloroplatinum(II) (cis-DDP) can be used as template by wheat germ RNA polymerase II. The templates used in the present study were obtained by ligation of double-helical oligodeoxyribonucleotides, containing 18 pyrimidine bases and 2 central dG, or dA and dG, bases on one strand and 18 purine bases and 2 central dC, or dT and dC, bases on the complementary strand. Therefore, the cis-DDP adducts are only present on one strand of each of the two templates and are regularly spaced by 18 pyrimidine bases. These constructs allowed the authors to investigate the effect of cis-DDP on transcription of the platinated strand and of the complementary unplatinated sequence. Transcription experiments were carried out in the presence of dinucleotide primers and either a single triphosphate substrate (abortive elongation) or the full set of triphosphate substrates dictated by the template sequence (productive elongation). The results show taht the eucraryotic RNA polymerase can catalyze dinucleotide-primed reactions on platinated DNA. However, the eurcaryotic enzyme behaved very differently depending on which strand was transcribed. Thus, transcription elongation was completely blocked on the strand carrying the metal complex, whereas transcription elongation was not blocked on the complementary template strand. Similar results were obtained in transcription of the platinated templates by Escherichia coli RNA polymerase, suggesting that the cis-DDP-induced effect is associated with modifications of the basic catalytic properties of the transcriptases.

  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. Structural Transformations in Chemically Modified Graphene

    DTIC Science & Technology

    2012-07-16

    nanomaterials (CNMs), there remains interest in randomly assembled CNM films for commer- cial development and fundamental research. For example, in 2003...produce a material that is highly conducting or insulating , transparent or opaque, or very stiff or soft. We attempt to exploit this flexible carbon...on- insulator (SOI) substrates using a modified spin-casting technique (Fig. 1a) [9]. The thinnest con- tinuous films are approximately 1–4 monolayers

  12. Growth of Atomically Flat Ultra-Thin Ag Films on Si(111) by Introducing a √3 × √3-Ga Buffer Layer

    NASA Astrophysics Data System (ADS)

    He, Jie-Hui; Jiang, Li-Qun; Qiu, Jing-Lan; Chen, Lan; Wu, Ke-Hui

    2014-12-01

    It is known that, when Ag is deposited on Si(111)-7×7 substrates in a conventional growth procedure at room temperature, no atomically flat Ag film could be obtained. We use scanning tunneling microscopy and low-energy electron diffraction to investigate the growth of ultra-thin Ag films on the Si(111) substrates at room temperature. Our study reveals that, upon introducing a Si(111)-√3 × √3-Ga buffer layer, atomically flat Ag films can easily grow on Si(111) with a critical thickness of two monolayers. Moreover, Ag film growth follows a layer-by-layer mode with further deposition. This novel growth behavior of Ag can be explained in terms of a free electron model (i.e., particle in a box) and kinetic Monte Carlo simulations.

  13. 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

  14. 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

  15. 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.

  16. 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

  17. Self-assembled matrix monolayer for UV-MALDI mass spectrometry

    SciTech Connect

    Mouradian, S.; Nelson, C.M.; Smith, L.M.

    1996-09-11

    Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry has in recent years significantly advanced the field of polymer analysis. However. the mechanisms of the desorption and ionization processes, and in particular the critical role played by the matrix, remain unclear. In the present work, the usual matrix is replaced with a self-assembled monolayer consisting of a UV absorbing matrix-like compound covalently linked to a gold surface. Analytes such as proteins or oligonucleotides are directly deposited on the covalently modified probe tips and mass analyzed by laser desorption time of flight (TOF) mass spectrometry. Several types of monolayers were investigated and tested for their ability to produce positive and negative analyte ions. Molecular ion signals were obtained for dT{sub 10} oligonucleotides and proteins as large as cytochrome C on monolayers of methyl N-(4-mercaptophenyl)carbamate (MMPC). The amenability of this model system to characterization with established physical and chemical methods should help investigate the processes involved in MALDI. 85 refs., 5 figs., 2 tabs.

  18. 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.

  19. 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.

  20. Glycosylated Self-Assembled Monolayers for Arrays and Surface Analysis

    PubMed Central

    Cheng, Fang; Ratner, Daniel M.

    2013-01-01

    Over the past few decades, carbohydrates (glycans) have received growing attention for their many roles in biological systems, including pathogenesis, receptor-ligand interactions, and cell signaling. To unravel the biology of this important category of biomolecules, a host of new tools have been developed for glycomics investigation. At the forefront is the carbohydrate microarray, developed to immobilize functional glycans on a solid substrate to rapidly screen a variety of potential binding partners (carbohydrates, proteins, nucleic acids, cells, and viruses). The essential role played by surface modification on glycan microarray performance requires new methods to rigorously characterize glycan surface chemistries. Due to their highly reproducible nature and well-studied properties, self-assembled monolayers (SAMs) on gold are powerful models for presenting glycans on a solid substrate, engineering biomimetic microenvironments and exploring the bioactivity of immobilized carbohydrates via surface plasmon resonance (SPR). However, it can be challenging to prepare high quality glycosylated SAMs (glyco-SAMs) that retain their biological function following surface immobilization. Herein, a selection of versatile methods for the preparation of glyco-SAMs using natural and chemically modified glycans is described. This chapter will highlight the following three immobilization techniques: (1) direct self assembly using thiolated glycosides onto gold, (2) tethering aminated glycosides onto amine-reactive SAMs, and (3) conjugating natural glycan onto divinyl sulfone-activated SAMs. PMID:22057519

  1. Modified cyanobacteria

    SciTech Connect

    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.

  2. 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.

  3. Electrochemical detection of aqueous Ag+ based on Ag+-assisted ligation reaction

    NASA Astrophysics Data System (ADS)

    Miao, Peng; Han, Kun; Wang, Bidou; Luo, Gangyin; Wang, Peng; Chen, Mingli; Tang, Yuguo

    2015-03-01

    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.

  4. Electrochemical detection of aqueous Ag+ based on Ag+-assisted ligation reaction.

    PubMed

    Miao, Peng; Han, Kun; Wang, Bidou; Luo, Gangyin; Wang, Peng; Chen, Mingli; Tang, Yuguo

    2015-03-17

    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.

  5. Plasmon resonances of Ag(001) and Ag(111) studied by power density absorption and photoyield

    NASA Astrophysics Data System (ADS)

    Raseev, Georges

    2013-09-01

    This paper models the surface and bulk plasmon resonances in photoabsorption and photoelectron spectra (PES) of the Ag(001) and the Ag(111) surfaces in the region of 2.8-10 eV excited with a p or transverse magnetic linearly polarized laser incident at 45°. Using the recently developed vector potential from electron density-coupled integro-differential equations (VPED-CIDE, [1,2]) model, we calculate the electron escaping probability from the power density absorption, Feibelman's parameter d⊥, the reflectance and the Fermi PE cross section. In the PES experiment the work function is lowered from 4.5 to 2.8 eV by adsorption of sodium. In our model, this lowering is introduced by adding a phenomenological term to the DFT-LDA model potential of Chulkov et al. [3]. For both Ag(001) and Ag(111), the calculated observables display two plasmon resonances, the multipole surface at 3.70 eV and the bulk at 3.90 eV, in fair agreement with the experimental PES of Barman et al. [4,5] and the reflectance. Except for the Fermi PE cross section of Ag(001) which does not display the multipole surface plasmon resonance at 3.70 eV. This poor result is probably due to a poor calculation of the conduction band wave functions obtained from the Schrödinger equation using the modified DFT-LDA model potential of Chulkov et al.

  6. Pulsed Electrodeposition of Two-Dimensional Ag Nanostructures on Au(111)

    NASA Astrophysics Data System (ADS)

    Borissov, D.; Tsekov, R.; Freyland, W.

    2006-07-01

    One-step pulsed potential electrodeposition of Ag on Au(111) in the underpotential deposition (UPD) region has been studied in 0.5 mM Ag2SO4 + 0.1 M H2SO4 aqueous electrolyte at various pulse durations from 0.2 to 500 ms. Evolution of the deposited Ag nanostructures was followed by in situ scanning tunneling microscopy (STM) and by measurement of the respective current transients. At short pulse durations a relatively high number density (4 × 10^11 cm-2) of two-dimensional Ag clusters with a narrow size and distance distribution is observed. They exhibit a remarkably high stability characterized by a dissolution potential which lies about 200 mV more anodically than the typical potential of Ag-(1 × 1) monolayer dissolution. To elucidate the underlying nucleation and growth mechanism, two models have been considered: two-dimensional lattice incorporation and a newly developed coupled diffusion-adsorption model. The first one yields a qualitative description of the current transients, whereas the second one is in nearly quantitative agreement with the experimental data. In this model the transformation of a Ag-(3 × 3) into a Ag-(1 × 1) structure indicated in the cyclic voltammogram (peaks at 520 vs 20 mV) is taken into account.

  7. 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.

  8. Comparative investigation of underpotential deposition of Ag from aqueous and ionic electrolytes: An electrochemical and in situ STM study.

    PubMed

    Borissov, D; Aravinda, C L; Freyland, W

    2005-06-16

    Underpotential deposition (UPD) of Ag on Au(111) has been studied with two different electrolytes: aqueous 0.1 M H2SO4 solution in comparison with the ionic liquid 1-butyl-3-methylimidazolium chloride BMICl + AlCl3. Of particular interest is the distinct behavior of 2D phase formation at both interfaces, which has been investigated by cyclic and linear sweep voltammetry in combination with in situ electrochemical scanning tunneling microscopy (STM). It is found that one monolayer (ML) of Ag is formed in the UPD region in both electrolytes. In aqueous solution, atomically resolved STM images at 500 mV versus Ag/Ag+ show a (3 x 3) adlayer of Ag, whereas after sweeping the potential just before the commencement of the bulk Ag deposition, a transition from expanded (3 x 3) to pseudomorphic ML of Ag on Au(111) occurs. In BMICl-AlCl3, the first UPD process of Ag exhibits two peaks at 410 and 230 mV indicating that two distinct processes on the surface take place. For the first time, STM images with atomic resolution reveal a transition from an inhomogeneous to an ordered phase with a (square root of 3 x square root of 3)R30 degrees structure and an adsorption of AlCl4- anions having a superlattice of (1.65 x square root of 3)R30 degrees preceding the deposition of Ag.

  9. 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.

  10. Abscisic acid-lipid interactions: a phospholipid monolayer study.

    PubMed

    Bürner, H; Benz, R; Gimmler, H; Hartung, W; Stillwell, W

    1993-08-15

    Lipid monolayer studies were performed on a Langmuir trough in the absence and in the presence of the plant hormone abscisic acid (ABA). The ABA-induced effects on the lipid monolayers can be summarized as follows: (i) ABA as the free acid (pH below 5.3) increased the molecular area and slightly decreased the surface pressure in the collapse points of monolayers made of saturated, unsaturated and of mixed lipids; ABA as the anion showed only minor effects. (ii) The ABA-induced area increase of the lipid monolayers decreased when the surface pressure increased, but some ABA remained in the monolayers made of unsaturated phospholipids even at collapse pressure. (iii) The incorporation of ABA into the monolayers could be inhibited by adding the plant sterol beta-sitosterol to the monolayer forming phospholipids. (iv) There was no substantial difference of ABA action on plant phospholipids as compared with other phospholipids. (v) ABA had a much stronger influence on unsaturated phospholipids than on saturated ones. (vi) ABA decreased the phase-transition temperature of saturated phospholipids. These results, which agree with those obtained from phospholipid vesicle studies, indicate that the physical state of the lipid is important for the ability of ABA penetrating into the lipid monolayer. Finally, a possible relevance of these results is discussed in terms of the action of ABA on guard cell membranes of plants.

  11. Synthesis of copper monolayer and particles at aqueous organic interface

    NASA Astrophysics Data System (ADS)

    Yang, Jian-guang; Yang, Sheng-hai; Okamoto, Takeshi; Bessho, Takeshi; Satake, Shigeru; Ichino, Ryoichi; Okido, Masazumi

    2006-12-01

    Using aqueous-organic interface (water-oleic acid) reduction of Cu 2+ by ascorbic acid, hydrophobic copper monolayer and copper particles have been prepared and characterized. The resultant monolayer could be transferred from the interface onto solid substrate or be dissolved to yield an organosol and copper nanoparticles.

  12. 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

  13. Topological, Valleytronic, and Optical Properties of Monolayer PbS.

    PubMed

    Wan, Wenhui; Yao, Yugui; Sun, Liangfeng; Liu, Cheng-Cheng; Zhang, Fan

    2017-03-01

    A PbS monolayer is demonstrated to be a novel platform for topological, valleytronic, and optical phenomena. Compressive strain can turn the trivial monolayer into a topological insulator. Optical pumping can facilitate charge, spin, and valley Hall effects tunable by external strain and light ellipticity. Similar results apply to other IV-VI semiconductors.

  14. 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.

  15. Modification of degenerative photoluminescence in aged monolayer WS2 by PC61BM surface processing.

    PubMed

    Liu, Yu; Zheng, Xin; Li, Han; Xu, Zhongjie; Jiang, Tian

    2017-02-01

    Owing to their unique physical properties, monolayer transition metal dichalcogenides (TMDCs) have been widely used in applications of light-emitting diodes (LEDs). However, monolayers of TMDCs undergo dramatic aging effects, including intense degradation in optical behavior, extensive cracking, and severe quenching of the direct gap photoluminescence (PL), seriously limiting the device performance. In this work, we show that monolayer WS2 stored for three months even in the glovebox exhibits obvious degenerative PL with changed peak position that can be attributed to the presence of a large number of trions induced by the aging effect. PC61BM surface processing was used to modify the surface of the aged monolayer WS2. As expected, higher uniformity in the PL spectrum was obtained. Besides, the PL peak wavelength was modified to be the same as that of the nonaged one and did not change even at higher excitation power. This strategy is shown to successfully suppress the formation of the trion by transferring the excess electrons from WS2 to PC61BM. The results demonstrate the feasibility of applying PC61BM surface modification to improve the performance of the LED based on monolayer WS2.

  16. 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.

  17. Reorientation of a dipolar monolayer and dipolar solvent.

    PubMed

    Yi, Taeil; Lichter, Seth

    2014-06-01

    The reliable persistence of an adhered monolayer film on a substrate is critical for film function. The process by which monolayers degrade or disperse remains unclear. Our study investigates the properties and dynamics of a solute of dipolar molecules initially adhered as a monolayer on a substrate in a water-like Stockmayer solvent. We find that for a rigid solute, both the solute and solvent show qualitatively different dynamics than for a flexible solute and its solvent. For the rigid solute, spreading is hindered and solvent orientation is more pronounced. We formulate a simple kinetic model that shows qualitatively similar results to the molecular dynamics simulations of the time evolution of the monolayer. Simple kinetics of molecules on substrates is a starting point for understanding important industrial monolayer applications and complex interactions on membranes.

  18. Heterostructured Ag3PO4/AgBr/Ag plasmonic photocatalyst with enhanced photocatalytic activity and stability under visible light

    NASA Astrophysics Data System (ADS)

    Wang, Wan-Sheng; Du, Hong; Wang, Rui-Xia; Wen, Tao; Xu, An-Wu

    2013-03-01

    A heterostructured Ag3PO4/AgBr/Ag plasmonic photocatalyst was prepared by a rational in situ ion exchange reaction between Ag3PO4 micro-cubes and Br- in aqueous solution followed by photoreduction. The photocatalytic activities of obtained photocatalysts were measured by the degradation of methyl orange (MO) and methylene blue (MB) under visible light irradiation (λ >= 400 nm). Compared to AgBr/Ag, Ag3PO4/AgBr heterocrystals and pure Ag3PO4 crystals, the heterostructured Ag3PO4/AgBr/Ag plasmonic photocatalysts exhibit much higher photocatalytic activity and stability. This enhanced photocatalytic activity suggests that the synergetic effects of the heterostructured Ag3PO4/AgBr/Ag and the strong SPR of Ag NPs on the surface result in the high efficiencies of the photocatalytic activity and the improved stability. With the assistance of Ag3PO4/AgBr/Ag heterostructures, only 8 min and 12 min are taken to completely decompose MO and MB molecules under visible-light irradiation, respectively. Furthermore, the photodegradation rate does not show an obvious decrease during ten successive cycles, indicating that our heterostructured Ag3PO4/AgBr/Ag plasmonic photocatalysts are extremely stable under visible-light irradiation.A heterostructured Ag3PO4/AgBr/Ag plasmonic photocatalyst was prepared by a rational in situ ion exchange reaction between Ag3PO4 micro-cubes and Br- in aqueous solution followed by photoreduction. The photocatalytic activities of obtained photocatalysts were measured by the degradation of methyl orange (MO) and methylene blue (MB) under visible light irradiation (λ >= 400 nm). Compared to AgBr/Ag, Ag3PO4/AgBr heterocrystals and pure Ag3PO4 crystals, the heterostructured Ag3PO4/AgBr/Ag plasmonic photocatalysts exhibit much higher photocatalytic activity and stability. This enhanced photocatalytic activity suggests that the synergetic effects of the heterostructured Ag3PO4/AgBr/Ag and the strong SPR of Ag NPs on the surface result in the high

  19. 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

    2015-11-07

    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.

  20. 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

  1. Enhancement of stability of N-doped TiO2 photocatalysts with Ag loading

    NASA Astrophysics Data System (ADS)

    Gao, Yuanpeng; Fang, Pengfei; Chen, Feitai; Liu, Yang; Liu, Zhi; Wang, Dahai; Dai, Yiqun

    2013-01-01

    Various contents of Ag nanoparticles were successfully introduced into the N-doped TiO2 photocatalysts via a hydrothermal procedure in the silver-ammonia solutions with different Ag concentrations. Effects of Ag loading on the structure and properties of N-doped TiO2 photocatalysts were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, fluorescence spectroscopy (FL), UV-vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and N2 physical adsorption analysis. The relationship between the stability of N dopants in TiO2 lattice and the Ag loading content was investigated for the first time. The results confirm that Ag nanoparticles loading on TiO2 surfaces significantly restrain the escape of the N dopants from the oxide during the hydrothermal process, and the escape rate of N dopants decreased gradually with the increase of Ag loading amount. The dependence of photocatalytic activity on Ag content was also investigated through degradation of rhodamine B (RhB) under visible light irradiation. It was found that the photocatalytic activity increases gradually with increasing Ag content first, and then decreases after exceeding the optimal Ag content. Therefore, the photocatalytic activity of Ag/N co-modified TiO2 photocatalysts can be adjusted by the Ag content.

  2. Valley depolarization in monolayer WSe2

    PubMed Central

    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

  3. Ultrafast response of monolayer molybdenum disulfide photodetectors

    PubMed Central

    Wang, Haining; Zhang, Changjian; Chan, Weimin; Tiwari, Sandip; Rana, Farhan

    2015-01-01

    The strong light emission and absorption exhibited by single atomic layer transitional metal dichalcogenides in the visible to near-infrared wavelength range make them attractive for optoelectronic applications. In this work, using two-pulse photovoltage correlation technique, we show that monolayer molybdenum disulfide photodetector can have intrinsic response times as short as 3 ps implying photodetection bandwidths as wide as 300 GHz. The fast photodetector response is a result of the short electron–hole and exciton lifetimes in this material. Recombination of photoexcited carriers in most two-dimensional metal dichalcogenides is dominated by nonradiative processes, most notable among which is Auger scattering. The fast response time, and the ease of fabrication of these devices, make them interesting for low-cost ultrafast optical communication links. PMID:26572726

  4. Phospholipid monolayers between fluid and solid states.

    PubMed Central

    Helm, C A; Möhwald, H; Kjaer, K; Als-Nielsen, J

    1987-01-01

    Monolayers of the phospholipid dimyristoyl phosphatidic acid on the surface of water have been studied by a combination of the new techniques of synchrotron x-ray diffraction and fluorescence microscopy with classical surface pressure data. The pressure vs. area isotherm changes slope at the surface pressures pi c and pi s. The optical technique demonstrates that between pi c and pi s the fluid phase coexists with a denser "gel" phase. Electron diffraction data have shown that the gel phase has bond orientational order over tens of micrometers. However, the x-ray data demonstrate that positional correlations extend only over tens of angstroms. Thus, the gel phase is not crystalline. Above pi s a solid phase is formed with a positional correlation range that is eight times longer for the chemically purest films. Images FIGURE 1 FIGURE 2 PMID:3651557

  5. 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

  6. 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

    2015-04-02

    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.

  7. Anomalous thermal conductivity of monolayer boron nitride

    NASA Astrophysics Data System (ADS)

    Tabarraei, Alireza; Wang, Xiaonan

    2016-05-01

    In this paper, we use nonequilibrium molecular dynamics modeling to investigate the thermal properties of monolayer hexagonal boron nitride nanoribbons under uniaxial strain along their longitudinal axis. Our simulations predict that hexagonal boron nitride shows an anomalous thermal response to the applied uniaxial strain. Contrary to three dimensional materials, under uniaxial stretching, the thermal conductivity of boron nitride nanoribbons first increases rather than decreasing until it reaches its peak value and then starts decreasing. Under compressive strain, the thermal conductivity of monolayer boron nitride ribbons monolithically reduces rather than increasing. We use phonon spectrum and dispersion curves to investigate the mechanism responsible for the unexpected behavior. Our molecular dynamics modeling and density functional theory results show that application of longitudinal tensile strain leads to the reduction of the group velocities of longitudinal and transverse acoustic modes. Such a phonon softening mechanism acts to reduce the thermal conductivity of the nanoribbons. On the other hand, a significant increase in the group velocity (stiffening) of the flexural acoustic modes is observed, which counteracts the phonon softening effects of the longitudinal and transverse modes. The total thermal conductivity of the ribbons is a result of competition between these two mechanisms. At low tensile strain, the stiffening mechanism overcomes the softening mechanism which leads to an increase in the thermal conductivity. At higher tensile strain, the softening mechanism supersedes the stiffening and the thermal conductivity slightly reduces. Our simulations show that the decrease in the thermal conductivity under compressive strain is attributed to the formation of buckling defects which reduces the phonon mean free path.

  8. 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.

  9. Monolayer semiconductor nanocavity lasers with ultralow thresholds

    DOE PAGES

    Wu, Sanfeng; Buckley, Sonia; Schaibley, John R.; ...

    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

  10. 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.

  11. Adhesion of human leukocytes to biomaterials: an in vitro study using alkanethiolate monolayers with different chemically functionalized surfaces.

    PubMed

    Barbosa, Judite N; Barbosa, Mário A; Aguas, Artur P

    2003-06-15

    The adhesion of human leukocytes to self-assembled monolayers of well-defined surface chemistry was investigated in vitro. Polymorphonuclear (PMN) and mononuclear leukocytes were isolated from human blood by centrifugation techniques. The effect on adhesion of cell activation produced by pre-incubation of leukocytes with phytohemagglutinin (PHA) and phorbol 12-myristate 13-acetate (PMA) was also studied. Gold substrates were modified by treatment with alkanethiols with three different terminal chemical groups: COOH, OH, and CH(3). After incubation with the two subpopulations of leukocytes, the monolayers were washed, treated with fixative, stained with a Giemsa method, and observed by light microscopy to quantify the number of attached leukocytes. Comparative quantification of the density of leukocyte adhesion to the three types of self-assembled monolayers was determined. The hydrophobic surface expressing CH(3) was found to be the one that induced the highest adhesion density of leukocytes, both of PMN and mononuclear cells. In vitro activation of both mononuclear and PMN leukocytes further increased cell adhesion to the chemically defined monolayers that were used. This enhancement was higher for PHA-activated than for PMA-stimulated mononuclear cells, whereas PMA treatment of neutrophils resulted in a higher rate of adhesion of these cells than PHA stimulation.

  12. Surface-enhanced infrared absorption spectroscopy (SEIRAS) to probe monolayers of membrane proteins.

    PubMed

    Ataka, Kenichi; Stripp, Sven Timo; Heberle, Joachim

    2013-10-01

    Surface-enhanced infrared absorption spectroscopy (SEIRAS) represents a variation of conventional infrared spectroscopy and exploits the signal enhancement exerted by the plasmon resonance of nano-structured metal thin films. The surface enhancement decays in about 10nm with the distance from the surface and is, thus, perfectly suited to selectively probe monolayers of biomembranes. Peculiar to membrane proteins is their vectorial functionality, the probing of which requires proper orientation within the membrane. To this end, the metal surface used in SEIRAS is chemically modified to generate an oriented membrane protein film. Monolayers of uniformly oriented membrane proteins are formed by tethering His-tagged proteins to a nickel nitrilo-triacetic acid (Ni-NTA) modified gold surface and SEIRAS commands molecular sensitivity to probe each step of surface modification. The solid surface used as plasmonic substrate for SEIRAS, can also be employed as an electrode to investigate systems where electron transfer reactions are relevant, like e.g. cytochrome c oxidase or plant-type photosystems. Furthermore, the interaction of these membrane proteins with water-soluble proteins, like cytochrome c or hydrogenase, is studied on the molecular level by SEIRAS. The impact of the membrane potential on protein functionality is verified by monitoring light-dark difference spectra of a monolayer of sensory rhodopsin (SRII) at different applied potentials. It is demonstrated that the interpretations of all of these experiments critically depend on the orientation of the solid-supported membrane protein. Finally, future directions of SEIRAS including cellular systems are discussed. This article is part of a Special Issue entitled: FTIR in membrane proteins and peptide studies.

  13. Translational Diffusion in Phospholipid Monolayers Measured by Fluorescence Microphotolysis

    NASA Astrophysics Data System (ADS)

    Peters, Reiner; Beck, Konrad

    1983-12-01

    A method is described that eliminates surface flow in monolayers at the air-water interface and makes possible diffusion measurements by fluorescence microphotolysis (``photobleaching''). In contrast to previous studies that did not account for surface flow, lipid probe diffusion has been found to be similar in densely packed monolayers and in related bilayers. Furthermore, it seems that lipid diffusion is based on the same molecular mechanism in monolayers, bilayers, and potentially also cell membranes. In monolayers of L-α -dilauroylphosphatidylcholine (Lau2-PtdCho) the translational diffusion coefficient D of the fluorescent lipid probe N-4-nitrobenzo-2-oxa-1,3 diazole egg phosphatidylethanolamine decreased from 110 μ m2/s at a surface pressure Pi =1 mN/m to 15 μ m2/s at Pi =38 mN/m (T = 21-22 degrees C). Data could be fitted by the ``free volume model.'' In monolayers of L-α -dipalmitoylphosphatidylcholine (Pam2-PtdCho) D decreased by >3 orders of magnitude upon increasing Pi at constant temperature, thus indicating a fluid-to-crystalline phase transition. In Lau2-PtdCho/Pam2-PtdCho monolayers phase separation has been visualized in the fluorescence microscope and the effect on D measured. These results suggest that monolayers are a promising model system for studying the molecular mobility of lipids and other cell membrane components.

  14. Optically Reconfigurable Monolayer of Azobenzene Donor Molecules on Oxide Surfaces.

    PubMed

    McElhinny, Kyle M; Huang, Peishen; Joo, Yongho; Kanimozhi, Catherine; Lakkham, Arunee; Sakurai, Kenji; Evans, Paul G; Gopalan, Padma

    2017-03-07

    The structural configuration of molecules assembled at organic-inorganic interfaces within electronic materials strongly influences the functional electronic and vibrational properties relevant to applications ranging from energy storage to photovoltaics. Controlling and characterizing the structural state of an interface and its evolution under external stimuli is crucial both for the fundamental understanding of the factors influenced by molecular structure and for the development of methods for material synthesis. It has been challenging to create complete molecular monolayers that exhibit external reversible control of the structure and electronic configuration. We report a monolayer/inorganic interface consisting of an organic monolayer assembled on an oxide surface, exhibiting structural and electronic reconfiguration under ultraviolet illumination. The molecular monolayer is linked to the surface through a carboxylate link, with the backbone bearing an azobenzene functional group and the head group consisting of a rhenium-bipyridine group. Optical spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and X-ray reflectivity show that closely packed monolayers are formed from these molecules via the Langmuir-Blodgett technique. Reversible photoisomerization is observed in solution and in monolayers assembled on Si and quartz substrates. The reconfiguration of these monolayers provides additional means to control excitation and charge transfer processes that are important in applications in catalysis, molecular electronics, and solar energy conversion.

  15. 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.

  16. EXCESS FIBRINOGEN ADSORPTION TO MONOLAYERS OF MIXED LIPIDS

    PubMed Central

    Deshmukh, V.; Britt, D.W.; Hlady, V.

    2010-01-01

    Adsorption of fibrinogen to the monolayers of mixed lipids, dipalmitoyl phosphatidyl choline (DPPC) and eicosylamine (EA) was measured at a surface pressure of 20 mN/m by an in situ surface plasmon resonance technique. Pressure-area isotherms of DPPC+EA mixtures on water and buffer subphases indicated good lipid miscibility and some contraction of the monolayers at intermediate and higher surface pressures. Surface electric potential of the DPPC+EA monolayers showed excess values for intermediate DPPC:EA ratios. Fibrinogen adsorption and its adsorption rates from a dilute solution (0.03 mg/ml) were proportional to the fraction of EA in the monolayer indicating that protein binding was primarily driven by electrostatic interactions between positive EA charges in the monolayer and a net negative protein charge. At a higher protein concentration (0.06 mg/ml) both the fibrinogen adsorbed amount and its maximum adsorption rate showed excess values relative to the pure EA for 1:1, 2:1 and 3:1 DPPC+EA monolayers. This excess adsorption could be explained, in part, by the contraction of the monolayers with intermediate DPPC:EA ratios which resulted in an excess surface electric potential. PMID:20829000

  17. Dynamics of a monolayer of microspheres on an elastic substrate

    NASA Astrophysics Data System (ADS)

    Wallen, S. P.; Maznev, A. A.; Boechler, N.

    2015-11-01

    We present a model for wave propagation in a monolayer of spheres on an elastic substrate. The model, which considers sagittally polarized waves, includes: horizontal, vertical, and rotational degrees of freedom; normal and shear coupling between the spheres and substrate, as well as between adjacent spheres; and the effects of wave propagation in the elastic substrate. For a monolayer of interacting spheres, we find three contact resonances, whose frequencies are given by simple closed-form expressions. For a monolayer of isolated spheres, only two resonances are present. The contact resonances couple to surface acoustic waves in the substrate, leading to mode hybridization and "avoided crossing" phenomena. We present dispersion curves for a monolayer of silica microspheres on a silica substrate, assuming adhesive Hertzian interactions, and compare calculations using an effective medium approximation (including elasticity of the substrate) to a discrete model of a monolayer on a rigid substrate. While the effective medium model does not describe discrete lattice effects occurring at short wavelengths, we find that it is well suited for describing the interaction between the monolayer and substrate in the long wavelength limit. We suggest that a complete picture of the dynamics of a monolayer adhered to an elastic substrate can be found by combining the dispersion curves generated with the effective medium model for the elastic substrate and the discrete model for the rigid substrate. This model is potentially scalable for use with nano- to macroscale systems, and offers the prospect of experimentally extracting contact stiffnesses from measurements of acoustic dispersion.

  18. Unveiling the origin of the linear dispersion in silicene/Ag(111)

    NASA Astrophysics Data System (ADS)

    Chen, Mingxing; Weinert, Michael

    2014-03-01

    The band structure of the recently synthesized (3 ×3) silicene monolayer on (4 ×4) Ag(111) is investigated using density functional theory. To compare to recent angle-resolved photoemission spectroscopy (ARPES) experiments [Phys. Rev. Lett. 108, 155501 (2012)], including the photon energy (k⊥) dependence of the spectra, we use a k-projection technique to unfold the supercell bands of both silicene and the substrate onto the corresponding primitive cells. Our calculations reproduce the observed linear dispersion across the K point of (1 ×1) silicene observed, but demonstrate that this is not a Dirac state, but rather originates from the Ag(111) substrate, thus resolving the controversy concerning the origin of the linear dispersion in silicene/Ag(111).

  19. 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.

  20. 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.

  1. Assessment of in vitro cellular responses of monocytes and keratinocytes to tannic acid modified silver nanoparticles.

    PubMed

    Orlowski, Piotr; Krzyzowska, Malgorzata; Zdanowski, Robert; Winnicka, Anna; Nowakowska, Julita; Stankiewicz, Wanda; Tomaszewska, Emilia; Celichowski, Grzegorz; Grobelny, Jaroslaw

    2013-09-01

    Hydrolyzable tannins are known to exhibit diverse biological effects, which can be used in combination with silver nanoparticles (AgNPs). In this study, we tested toxic and inflammatory properties of tannic-acid modified 13, 33, 46 nm and unmodified 10-65 nm AgNPs using murine 291.03C keratinocyte and RAW 264.7 monocyte cell lines. Both cell lines exposed for 24h to 1-10 μg/ml of 13 nm, 33 nm, 46 nm and unmodified AgNPs showed dose-dependent toxicity and decreased cell proliferation. Only small-sized AgNPs induced production of ROS by monocytes, but not keratinocytes. Monocytes internalized large aggregates of 33, 46 nm and 10-65 nm AgNPs in cytoplasmic vacuoles, whereas keratinocytes accumulated less particles. AgNPs of 13 nm were localized ubiquitously within both cell types. The tested AgNPs strongly down-regulated production of tumor necrosis factor-α (TNF-α) by monocytes, whereas keratinocytes exposed to AgNPs showed an opposite effect. Unmodified but not tannic acid-modified AgNPs increased production of the pro-inflammatory MCP-1 by monocytes and keratinocytes. In summary, low inflammatory potential and lack of ROS production by tannic-acid modified AgNPs sized above 30 nm suggests that tannic acid modification of large silver nanoparticles may help to increase AgNPs biosafety.

  2. Ag2S/g-C3N4 composite photocatalysts for efficient Pt-free hydrogen production. The co-catalyst function of Ag/Ag2S formed by simultaneous photodeposition.

    PubMed

    Jiang, Deli; Chen, Linlin; Xie, Jimin; Chen, Min

    2014-03-28

    Without Pt as cocatalyst, the photocatalytic hydrogen evolution activity of graphitic carbon nitride (g-C3N4) or even its composite is normally rather low (<1 μmol h(-1)). Exploring Pt-free cocatalysts to substitute precious Pt is of great importance in the photocatalytic field. In the present work, Ag2S-modified g-C3N4 (Ag2S/g-C3N4) composite photocatalysts were prepared via a simple precipitation method. The results demonstrated that the photocatalytic H2-production activity of g-C3N4 can be remarkably increased by the combination of Ag2S. The optimal Ag2S loading was found to be 5 wt%, giving a H2 production of 10 μmol h(-1), around 100 times that of pure g-C3N4. The enhanced photocatalytic activity can be mainly attributed to the effective charge transfer between g-C3N4 and Ag/Ag2S, of which the latter is formed by simultaneous photodeposition in the photocatalytic H2 evolution reaction and acts as an efficient co-catalyst for the g-C3N4. This work showed the possibility for utilization of Ag2S or Ag/Ag2S as a substitute for Pt in the photocatalytic production of H2 using g-C3N4.

  3. Preparation of melamine sponge decorated with silver nanoparticles-modified graphene for water disinfection.

    PubMed

    Deng, Can-Hui; Gong, Ji-Lai; Zhang, Peng; Zeng, Guang-Ming; Song, Biao; Liu, Hong-Yu

    2017-02-15

    This paper reports the fabrication of melamine sponge decorated with silver nanoparticles-modified graphene (G/AgNPs-MS) for water disinfection. The G/AgNPs-MS composites with the high porosity and elasticity were used in an antibacterial process in which the composite was first immersed in bacterial suspension, and subsequently squeezed via hand compression. G/AgNPs-MS exhibited more excellent bactericidal activity against Escherichia coli and Staphylococcus aureus bacteria compared with melamine sponge (MS), melamine sponge decorated with graphene (G-MS), and melamine sponge decorated with silver nanoparticles (AgNPs-MS). The superior antibacterial effect was possibly ascribed to the coordination of graphene oxide (GO) and silver nanoparticles (Ag NPs). Compared to AgNPs-MS, G/AgNPs-MS displayed better stability with fewer Ag(+) release. G/AgNPs-MS composites were highly reusable with no significant differences in the loss of bacterial viability over 12 operational cycles. The possible antibacterial mechanism of G/AgNPs-MS was also investigated. It was found that the destruction of bacterial membrane by G/AgNPs-MS played an important role in the bactericidal activity. The generation of intercellular ROS and scavenging assays confirmed the involvement of Ag(+) and ROS in the antibacterial process of G/AgNPs-MS. All the results demonstrated that the prepared G/AgNPs-MS composites, as innovative antibacterial materials, showed a great potential for water disinfection.

  4. Ordered Porous Pd Octahedra Covered with Monolayer Ru Atoms.

    PubMed

    Ge, Jingjie; He, Dongsheng; Bai, Lei; You, Rui; Lu, Haiyuan; Lin, Yue; Tan, Chaoliang; Kang, Yan-Biao; Xiao, Bin; Wu, Yuen; Deng, Zhaoxiang; Huang, Weixin; Zhang, Hua; Hong, Xun; Li, Yadong

    2015-11-25

    Monolayer Ru atoms covered highly ordered porous Pd octahedra have been synthesized via the underpotential deposition and thermodynamic control. Shape evolution from concave nanocube to octahedron with six hollow cavities was observed. Using aberration-corrected high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy, we provide quantitative evidence to prove that only a monolayer of Ru atoms was deposited on the surface of porous Pd octahedra. The as-prepared monolayer Ru atoms covered Pd nanostructures exhibited excellent catalytic property in terms of semihydrogenation of alkynes.

  5. Optical Control of Spin Polarization in Monolayer Transition Metal Dichalcogenides.

    PubMed

    Chen, Xi; Yan, Tengfei; Zhu, Bairen; Yang, Siyuan; Cui, Xiaodong

    2017-02-28

    Optical excitation could generate electrons' spin polarization in some semiconductors with the control of the field polarization. In this article, we report a series of spin-resolved photocurrent experiments on monolayer tungsten disulfide. The experiments demonstrate that the optical excitations with the same helicity could generate opposite spin polarization around the Fermi level by tuning the excitation energy. The mechanism lies in the valley-dependent optical selection rules, the giant spin-orbit coupling, and spin-valley locking in monolayer transition metal dichalcogenides (TMDs). These exotic features make monolayer TMDs promising candidates for conceptual semiconductor-based spintronics.

  6. 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.

  7. 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.

  8. 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.

  9. STM-assisted manipulation of Ag nanoparticles

    NASA Astrophysics Data System (ADS)

    Radojkovic, P.; Schwartzkopff, M.; Gabriel, T.; Hartmann, E.

    We report scanning tunneling microscope (STM) investigations of inert-gas-evaporated Ag nanoparticles deposited on atomically flat, H-terminated Si(111) surfaces, to which they weakly stick. For the present purpose, nanoparticles having an average size of 3 nm are fabricated and the particle coverage on the substrate fluctuates between one and three monolayers. The weakly coupling particle network can repeatedly be imaged with the STM without inadvertently manipulating the fundamental building blocks. When the STM is operated in the field-emission regime and the tunnel current is kept between 50 pA and 39 μA, the temperature of the nanoparticles rises, thus stimulating local manipulation processes. Depending on the power density dissipated in the particles, we distinguish between a local sintering process leading to the formation of narrow necks to the nearest neighbors, while the original granular nature of the particle layer is maintained, and a complete fusion. In the latter case, stable nanometer-scale structures are fabricated which strongly interconnect with the underlying substrate. In combining nanoparticle-inherent properties with existing theory, we roughly estimate the temperature rise of the nanoparticles and confirm the possibility of particle liquefaction for the highest power densities generated.

  10. 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.

  11. Thiophene-based monolayer OFETs prepared by Langmuir techniques

    NASA Astrophysics Data System (ADS)

    Agina, Elena V.; Sizov, Alexey S.; Anisimov, Daniil S.; Trul, Askold A.; Borshchev, Oleg V.; Paraschuk, Dmitry Y.; Shcherbina, Maxim A.; Chvalun, Sergey N.; Ponomarenko, Sergey A.

    2015-08-01

    A novel fast, easily processible and highly reproducible approach to thiophene-based monolayer OFETs fabrication by Langmuir-Blodgett or Langmuir-Schaefer techniques was developed and successfully applied. It is based on selfassembly of organosilicon derivatives of oligothiophenes or benzothienobenzothiophene on the water-air interface. Influence of the conjugation length and the anchor group chemistry of the self-assembling molecules on the monolayer structure and electric performance of monolayer OFETs was systematically investigated. The efficient monolayer OFETs with the charge carrier mobilities up to 0.01 cm2/Vs and on/off ratio up to 106 were fabricated, and their functionality in integrated circuits under normal air conditions was demonstrated.

  12. 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.

  13. The Formation and Stability of Alkylthiol Monolayers on Carbon Substrates

    PubMed Central

    Lockett, Matthew R.; Smith, Lloyd M.

    2010-01-01

    The formation and stability of alkylthiol monolayers on amorphous carbon thin films are investigated. Alkylthiol monolayers were prepared via a two-step, wet chemical process in which the carbon surface was first halogenated and then incubated with (4-(trifluoromethyl)phenyl)methanethiol (4tBM). The 4tBM covalently attaches to the surface in a substitution reaction in which the 4tBM thiol replaces the surface halogen. Studies of the substitution mechanism showed that monolayer formation is affected by the nature of the surface-bound halogen as well as the concentration and nucleophilicity of the 4tBM sulfur atom, consistent with a bimolecular (SN2) substitution reaction mechanism. The alkylthiol monolayers are stable over a wide range of solvent, pH, and temperature conditions. PMID:20706614

  14. 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.

  15. Optical emission and vibrational modes of uniform pentacene monolayers (*)

    NASA Astrophysics Data System (ADS)

    He, Rui; Tassi, Nancy; Blanchet, Graciela; Pinczuk, Aron

    2006-03-01

    Pentacene monolayers are probed by photoluminescence and resonant Raman spectroscopies below 10K. Monolayers grown on polymeric substrate of poly-alpha-methyl-styrene (PAMS) exhibit high uniformity within micron size clusters. These films show sharp exciton luminescence bands, and the energy of the exciton optical emission displays a red-shift as the average film thickness increases. The large resonance enhancements of Raman scattering intensities enable the measurements of low-lying (40- 200cm-1) optical lattice vibrations from these monolayers. These experiments demonstrate that luminescence and resonant Raman scattering from single pentacene monolayers are venues for probing 2D properties, studies of interface effects, and thin film characterization. (*) Supported primarily by the Nanoscale Science and Engineering Initiative of the National Science Foundation under NSF Award No. CHE-0117752 and by the New York State Office of Science, Technology, and Academic Research (NYSTAR), and by a research grant of the W. M. Keck Foundation.

  16. Recognition of Salmonella typhimurium by immobilized phage P22 monolayers

    NASA Astrophysics Data System (ADS)

    Handa, Hitesh; Gurczynski, Stephen; Jackson, Matthew P.; Auner, Gregory; Walker, Jeremy; Mao, Guangzhao

    2008-04-01

    Phages are promising alternatives to antibodies as the biorecognition element in a variety of biosensing applications. In this study, a monolayer of bacteriophage P22 whose tailspike proteins specifically recognize Salmonella serotypes was covalently bound to glass substrates through a bifunctional cross linker 3-aminopropyltrimethoxysilane. The specific binding of Salmonella typhimurium to the phage monolayer was studied by enzyme-linked immunosorbent assay and atomic force microscopy. Escherichia coli and a Gram-positive bacterium Listeria monocytogenes were also studied as control bacteria. The P22 particles show strong binding affinity to S. typhimurium. In addition, the dried P22 monolayer maintained 50% binding capacity to S. typhimurium after a one-week storage time. This is a promising method to prepare phage monolayer coatings on surface plasmon resonance and acoustic biosensor substrates in order to utilize the nascent phage display technology.

  17. 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.

  18. Monolayers of hard rods on planar substrates. I. Equilibrium

    NASA Astrophysics Data System (ADS)

    Oettel, M.; Klopotek, M.; Dixit, M.; Empting, E.; Schilling, T.; Hansen-Goos, H.

    2016-08-01

    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.

  19. Unsupported single-atom-thick copper oxide monolayers

    NASA Astrophysics Data System (ADS)

    Yin, Kuibo; Zhang, Yu-Yang; Zhou, Yilong; Sun, Litao; Chisholm, Matthew F.; Pantelides, Sokrates T.; Zhou, Wu

    2017-03-01

    Oxide monolayers may present unique opportunities because of the great diversity of properties of these materials in bulk form. However, reports on oxide monolayers are still limited. Here we report the formation of single-atom-thick copper oxide layers with a square lattice both in graphene pores and on graphene substrates using aberration-corrected scanning transmission electron microscopy. First-principles calculations find that CuO is energetically stable and its calculated lattice spacing matches well with the measured value. Furthermore, free-standing copper oxide monolayers are predicted to be semiconductors with band gaps ∼3 eV. The new wide-bandgap single-atom-thick copper oxide monolayers usher a new frontier to study the highly diverse family of two-dimensional oxides and explore their properties and their potential for new applications.

  20. 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

    2016-11-05

    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.

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

    PubMed

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

    2014-04-21

    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.

  2. Scaling laws for buckling instability in monolayer networks

    NASA Technical Reports Server (NTRS)

    Noever, David A.

    1992-01-01

    In this comment a power law is argued to govern the thickening of cell widths relative to their lengths in buckling monolayer networks. A scaling relation is derived for general instabilities in cellular networks, and a reply is given that questions the use of the amplitude of the buckling undulation in an already buckled wall in the Euler relation. Both treatments provided shed light on the stability/instability of wavelengths for buckling monolayer networks.

  3. 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.

  4. Colloidal polycrystalline monolayers under oscillatory shear

    NASA Astrophysics Data System (ADS)

    Buttinoni, Ivo; Steinacher, Mathias; Spanke, Hendrik Th.; Pokki, Juho; Bahmann, Severin; Nelson, Bradley; Foffi, Giuseppe; Isa, Lucio

    2017-01-01

    In this paper we probe the structural response to oscillatory shear deformations of polycrystalline monolayers of soft repulsive colloids with varying area fraction over a broad range of frequencies and amplitudes. The particles are confined at a fluid interface, sheared using a magnetic microdisk, and imaged through optical microscopy. The structural and mechanical response of soft materials is highly dependent on their microstructure. If crystals are well understood and deform through the creation and mobilization of specific defects, the situation is much more complex for disordered jammed materials, where identifying structural motifs defining plastically rearranging regions remains an elusive task. Our materials fall between these two classes and allow the identification of clear pathways for structural evolution. In particular, we demonstrate that large enough strains are able to fluidize the system, identifying critical strains that fulfill a local Lindemann criterion. Conversely, smaller strains lead to localized and erratic irreversible particle rearrangements due to the motion of structural defects. In this regime, oscillatory shear promotes defect annealing and leads to the growth of large crystalline domains. Numerical simulations help identify the population of rearranging particles with those exhibiting the largest deviatoric stresses and indicate that structural evolution proceeds towards the minimization of the stress stored in the system. The particles showing high deviatoric stresses are localized around grain boundaries and defects, providing a simple criterion to spot regions likely to rearrange plastically under oscillatory shear.

  5. Hopping magnetoresistance in ion irradiated monolayer graphene

    NASA Astrophysics Data System (ADS)

    Shlimak, I.; Zion, E.; Butenko, A. V.; Wolfson, L.; Richter, V.; Kaganovskii, Yu.; Sharoni, A.; Haran, A.; Naveh, D.; Kogan, E.; Kaveh, M.

    2016-02-01

    Magnetoresistance (MR) of ion irradiated monolayer graphene samples with a variable-range hopping (VRH) mechanism of conductivity was measured at temperatures down to T=1.8 K in magnetic fields up to B=8 T. It was observed that in perpendicular magnetic fields, hopping resistivity R decreases, which corresponds to negative MR (NMR), while parallel magnetic field results in positive MR (PMR) at low temperatures. NMR is explained on the basis of the "orbital" model in which perpendicular magnetic field suppresses the destructive interference of many paths through the intermediate sites in the total probability of the long-distance tunneling in the VRH regime. At low fields, a quadratic dependence (| ΔR / R | ∼ B2) of NMR is observed, while at B > B*, the quadratic dependence is replaced by the linear one. It was found that all NMR curves for different samples and different temperatures could be merged into common dependence when plotted as a function of B/B*. It is shown that B* ∼ T1/2 in agreement with predictions of the "orbital" model. The obtained values of B* also allowed us to estimate the localization radius ξ of charge carriers for samples with a different degree of disorder. PMR in parallel magnetic fields is explained by suppression of hopping transitions via double occupied states due to alignment of electron spins.

  6. Photogalvanic effect in monolayer black phosphorus

    NASA Astrophysics Data System (ADS)

    Xie, Yiqun; Zhang, Lei; Zhu, Yu; Liu, Lei; Guo, Hong

    2015-11-01

    We report a first-principles theoretical approach for analyzing linear and circular photogalvanic effects (PGEs) based on density functional theory within the nonequilibrium Green’s function formalism. Using this approach we investigate the PGE phenomena in monolayer black phosphorus (MBP) doped with sulfur atoms. The impurity doping breaks the space inversion symmetry of pristine MBP, leading to a C s symmetry with a mirror reflection plane normal to the zigzag direction of the MBP lattice. Governed by this symmetry, a linear PGE is induced in both zigzag and armchair directions, and a circular PGE is induced along the zigzag direction. A robust broadband photoresponse is found from the near-infrared to the visible range for the MBP device. There is a strong anisotropy in PGE: photoresponse in the zigzag direction can be larger by an order of magnitude than that in the armchair direction. We identify the origin of the observed PGE as the inter-band transitions from the impurity and valence bands to the conduction bands, which involves a transfer of angular momentum from photons to electrons.

  7. Photogalvanic effect in monolayer black phosphorus.

    PubMed

    Xie, Yiqun; Zhang, Lei; Zhu, Yu; Liu, Lei; Guo, Hong

    2015-11-13

    We report a first-principles theoretical approach for analyzing linear and circular photogalvanic effects (PGEs) based on density functional theory within the nonequilibrium Green's function formalism. Using this approach we investigate the PGE phenomena in monolayer black phosphorus (MBP) doped with sulfur atoms. The impurity doping breaks the space inversion symmetry of pristine MBP, leading to a C s symmetry with a mirror reflection plane normal to the zigzag direction of the MBP lattice. Governed by this symmetry, a linear PGE is induced in both zigzag and armchair directions, and a circular PGE is induced along the zigzag direction. A robust broadband photoresponse is found from the near-infrared to the visible range for the MBP device. There is a strong anisotropy in PGE: photoresponse in the zigzag direction can be larger by an order of magnitude than that in the armchair direction. We identify the origin of the observed PGE as the inter-band transitions from the impurity and valence bands to the conduction bands, which involves a transfer of angular momentum from photons to electrons.

  8. Properties of Langmuir monolayers from semifluorinated alkanes

    NASA Astrophysics Data System (ADS)

    Broniatowski, M.; Macho, I. Sandez; Miñones, J.; Dynarowicz-Łątka, P.

    2005-06-01

    The aim of this study was to characterize several semifluorinated alkanes (SFA), of the general formula F(CF 2) m(CH 2) nH (in short F mH n), containing 25 carbon atoms in total (pentacosanes) differing in the m/ n ratio, as Langmuir monolayers at the free water surface. The following compounds have been studied: F6H19, F8H17, F10H15 and F12H13. Surface pressure ( π) and electric surface potential (Δ V) isotherms were recorded in addition to quantitative Brewster angle microscopy results. The negative sign of Δ V evidenced for the orientation of all the investigated semifluorinated pentacosanes, regardless the length of the hydrogenated segment, with their perfluorinated parts directed towards the air. As inferred from apparent dipole moment values and relative reflectivity results, the fluorinated pentacosanes with shorter perfluorinated fragment (F6H19 and F8H17) were found to be vertically oriented at the air/water interface, while those with longer perfluorinated moiety (F10H15 and F12H13) remain titled even in the vicinity of the film collapse.

  9. 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.

  10. Induction of homochirality in achiral enantiomorphous monolayers.

    PubMed

    Parschau, Manfred; Romer, Sara; Ernst, Karl-Heinz

    2004-12-01

    We report the induction of homochirality in enantiomorphous layers of achiral succinic acid on a Cu(110) surface after doping with tartaric acid (TA) enantiomers. Succinic acid becomes chiral upon adsorption due to symmetry-breaking interactions with the Cu(110) surface. The doubly deprotonated bisuccinate forms mirror domains on the surface, which leads to a superposition of (11,-90) and (90,-11) patterns observed by low-energy electron diffraction (LEED). On average, however, the surface layer is racemic. An amount of 2 mol % of (R,R)- or (S,S)-tartaric acid in the monolayer, corresponding to an absolute coverage of 0.001 tartaric acid molecule per surface copper atom, is sufficient to make the LEED spots of one enantiomorphous lattice disappear. After thermally induced desorption of TA, the succinic acid lattice turns racemic again. In analogy to the "sergeants-and-soldiers" principle described for helical polymers, this effect is explained by a lateral cooperative interaction within the two-dimensional lattice.

  11. 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.

  12. 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.

  13. 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.

  14. Thermoelectric properties of SnSe2 monolayer

    NASA Astrophysics Data System (ADS)

    Li, Guanpeng; Ding, Guangqian; Gao, Guoying

    2017-01-01

    The 2H (MoS2-type) phase of 2D transition metal dichalcogenides (TMDCs) has been extensively studied and exhibits excellent electronic and optoelectronic properties, but the high phonon thermal conductivity is detrimental to the thermoelectric performances. Here, we use first-principles methods combined with Boltzmann transport theory to calculate the electronic and phononic transport properties of 1T (CdI2-type) SnSe2 monolayer, a recently realized 2D metal dichalcogenide semiconductor. The calculated band gap is 0.85 eV, which is a little larger than the bulk value. Lower phonon thermal conductivity and higher power factor are obtained in 1T-SnSe2 monolayer compared to 2H-TMDCs monolayers. The low phonon thermal conductivity (3.27 W mK-1 at room temperature) is mainly due to the low phonon frequency of acoustic modes and the coupling of acoustic modes with optical modes. We also find that the p-type has better thermoelectric performance than the n-type, and the figure of merit within p-type can reach 0.94 at 600 K for 1T-SnSe2 monolayer, which is higher than those of most 2H-TMDCs monolayers, making 1T-SnSe2 monolayer a promising candidate for thermoelectric applications.

  15. Using self-assembled monolayers to model the extracellular matrix.

    PubMed

    Mrksich, Milan

    2009-03-01

    The extracellular matrix is an insoluble aggregate of large proteins and glycosoaminoglycans that comprises the microenvironment of cells in tissue. The matrix displays a host of ligands that interact with cell-surface receptors to mediate the attachment and spreading of cells and regulate signaling processes. Studies of cell-matrix interactions and downstream signaling processes commonly employ substrates having an adsorbed layer of protein and are challenged by the difficulty in controlling the structure and activity of the immobilized protein. Significant effort has been directed towards the development of model substrates that present adhesion ligands in defined densities, orientations and environments. Among these approaches, self-assembled monolayers of alkanethiolates on gold offer a high level of control over the molecular structure of the surface and are well-suited to studies of cell adhesion. This review describes the design and use of monolayers for applications in cell biology, including the use of monolayers to evaluate the roles of peptide and protein ligands in cell-matrix interactions, the development of methods to pattern ligands on monolayers and applications to cell biology, the development of dynamic monolayers that can switch the activities of ligands presented to an adherent cell, and the rewiring of interactions between a cell and its substrate. These examples illustrate the flexibility inherent to monolayers for applications in cell biology.

  16. 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

  17. Growth of calcium oxalate monohydrate at phospholipid Langmuir monolayers

    NASA Astrophysics Data System (ADS)

    Whipps, Scott; Khan, Saeed R.; Jeffrey O'Palko, F.; Backov, Rénal; Talham, Daniel R.

    1998-08-01

    Calcium oxalate monohydrate crystals have been nucleated from metastable solutions at Langmuir monolayers of the phospholipids dipalmitoylphosphatidylglycerol (DPPG), dipalmitoylphosphatidylserine and dipalmitoylphosphatidylcholine and the fatty acid arachidic acid. The phospholipid monolayers were used as model systems for domains of pure lipid in cellular media as part of investigations of their potential role in the nucleation of calcium oxalate in the urinary tract. Crystal formation was monitored at the air/water interface using Brewster angle microscopy and in transferred films using SEM and TEM. For each Langmuir monolayer, it was observed that nucleation is heterogeneous and is selective with respect to the orientation and morphology of the precipitated crystals with up to 90% of crystals growing with the ( 1 0 1¯) face oriented towards the monolayer interface. The selectivity is attributed to calcium binding at the lipid monolayer favoring formation of the calcium-rich ( 1 0 1¯) face. The behavior at each monolayer was similar, although a higher rate of crystal formation was observed at the anionic DPPG interface.

  18. 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

  19. 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

    2016-08-04

    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.

  20. 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...

  1. Nanostructure formation by self-assembled monolayers: influence of the isomerization state of azobenzene ligands on monolayer formation

    NASA Astrophysics Data System (ADS)

    Vogel, Florian; Bretthauer, Frauke; Siemeling, Ulrich; Träger, Frank

    2011-03-01

    The monolayer formation of photoswitchable self-assembled monolayers of azobenzene-functionalized molecules was studied in situ and in real time by optical second-harmonic generation. Especially the influence of the isomerization state during the adsorption process was measured in our experiments. As will be shown, the isomerization state has a significant influence on the adsorption process of the investigated molecules. Based on the results of the second-harmonic generation experiments the kinetics of the adsorption process was determined.

  2. Low-magnification image analysis of Giemsa stained, electroporation and bleomycin treated endothelial monolayers provides reliable monolayer integrity data.

    PubMed

    Meulenberg, Cécil J W; Cemazar, Maja

    2014-06-01

    The aim of this study was to develop an in vitro cell model for studying the in vivo observed vascular effect, induced by exposing blood vessels to changing electric field strengths. Human microvascular endothelial cells (HMEC-1) were cultured as monolayers on 8 chamber glass slides as a model of capillary wall. Exposed to electric pulses alone, or in the presence of bleomycin (electrochemotherapy), monolayers were incubated with culture medium, fixed with methanol, stained with Giemsa, and photographed. Images of high-contrast low-magnification monolayers made under identical optimal light exposure were converted to greyscale, and the use of a threshold tool yielded a binary distribution, from which we determined two parameters of monolayer integrity: the covered surface area and the number of cells. We show that this low-magnification image analysis method for attached endothelial cells provides reliable control parameters of monolayer integrity, representing capillary wall. Besides, already within 2h post-treatment the data show distinct effects in the monolayer integrity parameters for electric pulses alone, or in the presence of bleomycin. The present method can be readily introduced to short and long-term toxicity assays with a variety of treatment conditions.

  3. Second harmonic generation of chiral-modified silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Tao, Yue

    Chiral molecules, which exist under enantiomers with non-mirror-symmetrical structures, have been the subject of intense research for their linear and nonlinear optical activities. Cysteine is such a chiral amino acid found as a building block of proteins throughout human bodies. Second harmonic generation (SHG) has been considered to investigate chiral molecules. SHG from metallic nanoparticles is promising for nanoplasmonics and photonic nanodevice applications. Therefore, it's desirable to combine and study nonlinear properties due to both chirality and metallic nanoparticles, and help developing an alternatively optical diagnostic of chiral molecules. Our experiments are carried out with the FemtoFiber Scientific FFS laser system. SHG of silver nanoparticles (Ag NPs) modified by either L-Cysteine (L-C) or D-Cysteine (D-C) is observed, where L-Cysteine and D-Cysteine are a pair of enantiomers. Ag NPs are deposited through Vacuum Thermal Evaporation, controlled under different deposition thicknesses. UV-Vis/IR spectra and AFM are used to characterize Ag NPs under different conditions. Transmitted SHG measurements dependent on incidence are recorded with standard lock-in techniques. Deposition thickness of vacuum thermal evaporation plays an important role in forming diverse Ag NPs, which strongly imparts the intensity of SHG. Second harmonic intensity as a function of the incident angle presents similar results for Ag NPs with or without L-Cysteine or D-Cysteine modification, in the output of p- and s-polarization. However, we monitor reversed rotation difference in second harmonic intensities at linearly +45° and -45° polarization for L-C/Ag NPs and D-C/Ag NPs, while there's no difference at linearly +45° and -45° polarization for Ag NPs alone. This optical rotation difference in SHG is termed as SHG-ORD. Also, for second harmonic light fixed at p-polarization, L-C/Ag NPs and D-C/Ag NPs exhibit a reversely net difference for SHG excited by right and left

  4. Nucleic-acid-programmed Ag-nanoclusters as a generic platform for visualization of latent fingerprints and exogenous substances.

    PubMed

    Ran, Xiang; Wang, Zhenzhen; Zhang, Zhijun; Pu, Fang; Ren, Jinsong; Qu, Xiaogang

    2016-01-11

    We display a nucleic acid controlled AgNC platform for latent fingerprint visualization. The versatile emission of aptamer-modified AgNCs was regulated by the nearby DNA regions. Multi-color images for simultaneous visualization of fingerprints and exogenous components were successfully obtained. A quantitative detection strategy for exogenous substances in fingerprints was also established.

  5. Monte Carlo studies of model Langmuir monolayers.

    PubMed

    Opps, S B; Yang, B; Gray, C G; Sullivan, D E

    2001-04-01

    This paper examines some of the basic properties of a model Langmuir monolayer, consisting of surfactant molecules deposited onto a water subphase. The surfactants are modeled as rigid rods composed of a head and tail segment of diameters sigma(hh) and sigma(tt), respectively. The tails consist of n(t) approximately 4-7 effective monomers representing methylene groups. These rigid rods interact via site-site Lennard-Jones potentials with different interaction parameters for the tail-tail, head-tail, and head-head interactions. In a previous paper, we studied the ground-state properties of this system using a Landau approach. In the present paper, Monte Carlo simulations were performed in the canonical ensemble to elucidate the finite-temperature behavior of this system. Simulation techniques, incorporating a system of dynamic filters, allow us to decrease CPU time with negligible statistical error. This paper focuses on several of the key parameters, such as density, head-tail diameter mismatch, and chain length, responsible for driving transitions from uniformly tilted to untilted phases and between different tilt-ordered phases. Upon varying the density of the system, with sigma(hh)=sigma(tt), we observe a transition from a tilted (NNN)-condensed phase to an untilted-liquid phase and, upon comparison with recent experiments with fatty acid-alcohol and fatty acid-ester mixtures [M. C. Shih, M. K. Durbin, A. Malik, P. Zschack, and P. Dutta, J. Chem. Phys. 101, 9132 (1994); E. Teer, C. M. Knobler, C. Lautz, S. Wurlitzer, J. Kildae, and T. M. Fischer, J. Chem. Phys. 106, 1913 (1997)], we identify this as the L'(2)/Ov-L1 phase boundary. By varying the head-tail diameter ratio, we observe a decrease in T(c) with increasing mismatch. However, as the chain length was increased we observed that the transition temperatures increased and differences in T(c) due to head-tail diameter mismatch were diminished. In most of the present research, the water was treated as a hard

  6. Monte Carlo studies of model Langmuir monolayers

    NASA Astrophysics Data System (ADS)

    Opps, S. B.; Yang, B.; Gray, C. G.; Sullivan, D. E.

    2001-04-01

    This paper examines some of the basic properties of a model Langmuir monolayer, consisting of surfactant molecules deposited onto a water subphase. The surfactants are modeled as rigid rods composed of a head and tail segment of diameters σhh and σtt, respectively. The tails consist of nt~4-7 effective monomers representing methylene groups. These rigid rods interact via site-site Lennard-Jones potentials with different interaction parameters for the tail-tail, head-tail, and head-head interactions. In a previous paper, we studied the ground-state properties of this system using a Landau approach. In the present paper, Monte Carlo simulations were performed in the canonical ensemble to elucidate the finite-temperature behavior of this system. Simulation techniques, incorporating a system of dynamic filters, allow us to decrease CPU time with negligible statistical error. This paper focuses on several of the key parameters, such as density, head-tail diameter mismatch, and chain length, responsible for driving transitions from uniformly tilted to untilted phases and between different tilt-ordered phases. Upon varying the density of the system, with σhh=σtt, we observe a transition from a tilted (NNN)-condensed phase to an untilted-liquid phase and, upon comparison with recent experiments with fatty acid-alcohol and fatty acid-ester mixtures [M. C. Shih, M. K. Durbin, A. Malik, P. Zschack, and P. Dutta, J. Chem. Phys. 101, 9132 (1994); E. Teer, C. M. Knobler, C. Lautz, S. Wurlitzer, J. Kildae, and T. M. Fischer, J. Chem. Phys. 106, 1913 (1997)], we identify this as the L'2/Ov-L1 phase boundary. By varying the head-tail diameter ratio, we observe a decrease in Tc with increasing mismatch. However, as the chain length was increased we observed that the transition temperatures increased and differences in Tc due to head-tail diameter mismatch were diminished. In most of the present research, the water was treated as a hard surface, whereby the surfactants are only

  7. UV/vis and NIR light-responsive spiropyran self-assembled monolayers.

    PubMed

    Ivashenko, Oleksii; van Herpt, Jochem T; Feringa, Ben L; Rudolf, Petra; Browne, Wesley R

    2013-04-02

    Self-assembled monolayers of a 6-nitro BIPS spiropyran (SP) modified with a disulfide-terminated aliphatic chain were prepared on polycrystalline gold surfaces and characterized by UV/vis absorption, surface-enhanced Raman scattering (SERS), and X-ray photoelectron spectroscopies (XPS). The SAMs obtained are composed of the ring-closed form (i.e., spiropyran) only. Irradiation with UV light results in conversion of the monolayer to the merocyanine form (MC), manifested in the appearance of an N(+) contribution in the N 1s region of the XPS spectrum of the SAMs, the characteristic absorption band of the MC form in the visible region at 555 nm, and the C-O stretching band in the SERS spectrum. Recovery of the initial state of the monolayer was observed both thermally and after irradiation with visible light. Several switching cycles were performed and monitored by SERS spectroscopy, demonstrating the stability of the SAMs during repeated switching between SP and MC states. A key finding in the present study is that ring-opening of the surface-immobilized spiropyrans can be induced by irradiation with continuous wave NIR (785 nm) light as well as by irradiation with UV light. We demonstrate that ring-opening by irradiation at 785 nm proceeds by a two-photon absorption pathway both in the SAMs and in the solid state. Hence, spiropyran SAMs on gold can undergo reversible photochemical switching from the SP to the MC form with both UV and NIR and the reverse reaction induced by irradiation with visible light or heating. Furthermore, the observation of NIR-induced switching with a continuous wave source holds important consequences in the study of photochromic switches on surfaces using SERS and emphasizes the importance of the use of multiple complementary techniques in characterizing photoresponsive SAMs.

  8. Collectively Induced Quantum-Confined Stark Effect in Monolayers of Molecules Consisting of Polar Repeating Units

    PubMed Central

    2011-01-01

    The electronic structure of terpyrimidinethiols is investigated by means of density-functional theory calculations for isolated molecules and monolayers. In the transition from molecule to self-assembled monolayer (SAM), we observe that the band gap is substantially reduced, frontier states increasingly localize on opposite sides of the SAM, and this polarization in several instances is in the direction opposite to the polarization of the overall charge density. This behavior can be analyzed by analogy to inorganic semiconductor quantum-wells, which, as the SAMs studied here, can be regarded as semiperiodic systems. There, similar observations are made under the influence of a, typically external, electric field and are known as the quantum-confined Stark effect. Without any external perturbation, in oligopyrimidine SAMs one encounters an energy gradient that is generated by the dipole moments of the pyrimidine repeat units. It is particularly strong, reaching values of about 1.6 eV/nm, which corresponds to a substantial electric field of 1.6 × 107 V/cm. Close-lying σ- and π-states turn out to be a particular complication for a reliable description of the present systems, as their order is influenced not only by the docking groups and bonding to the metal, but also by the chosen computational approach. In the latter context we demonstrate that deliberately picking a hybrid functional allows avoiding pitfalls due to the infamous self-interaction error. Our results show that when aiming to build a monolayer with a specific electronic structure one can not only resort to the traditional technique of modifying the molecular structure of the constituents, but also try to exploit collective electronic effects. PMID:21955058

  9. The melting of pulmonary surfactant monolayers.

    PubMed

    Yan, Wenfei; Biswas, Samares C; Laderas, Ted G; Hall, Stephen B

    2007-05-01

    Monomolecular films of phospholipids in the liquid-expanded (LE) phase after supercompression to high surface pressures (pi), well above the equilibrium surface pressure (pi(e)) at which fluid films collapse from the interface to form a three-dimensional bulk phase, and in the tilted-condensed (TC) phase both replicate the resistance to collapse that is characteristic of alveolar films in the lungs. To provide the basis for determining which film is present in the alveolus, we measured the melting characteristics of monolayers containing TC dipalmitoyl phosphatidylcholine (DPPC), as well as supercompressed 1-palmitoyl-2-oleoyl phosphatidylcholine and calf lung surfactant extract (CLSE). Films generated by appropriate manipulations on a captive bubble were heated from < or =27 degrees C to > or =60 degrees C at different constant pi above pi(e). DPPC showed the abrupt expansion expected for the TC-LE phase transition, followed by the contraction produced by collapse. Supercompressed CLSE showed no evidence of the TC-LE expansion, arguing that supercompression did not simply convert the mixed lipid film to TC DPPC. For both DPPC and CLSE, the melting point, taken as the temperature at which collapse began, increased at higher pi, in contrast to 1-palmitoyl-2-oleoyl phosphatidylcholine, for which higher pi produced collapse at lower temperatures. For pi between 50 and 65 mN/m, DPPC melted at 48-55 degrees C, well above the main transition for bilayers at 41 degrees C. At each pi, CLSE melted at temperatures >10 degrees C lower. The distinct melting points for TC DPPC and supercompressed CLSE provide the basis by which the nature of the alveolar film might be determined from the temperature-dependence of pulmonary mechanics.

  10. Clustering in vibrated monolayers of granular rods.

    PubMed

    González-Pinto, M; Borondo, F; Martínez-Ratón, Y; Velasco, E

    2017-04-05

    We investigate the ordering properties of vertically-vibrated monolayers of granular cylinders in a circular container at high packing fraction. In line with previous works by other groups, we identify liquid-crystalline ordering behaviour similar to that of two-dimensional hard rectangular particles subject to thermal equilibrium fluctuations. However, due to dissipation, there is a much stronger tendency for particles to cluster into parallel arrangements in the granular system. These clusters behave as a polydisperse mixture of long life-time 'superparticles', and some aspects of the system behaviour can be understood by applying mean-field theories for equilibrium hard rectangles, based on two-body correlations, to these 'superparticles'. Many other features of the granular system are different: (i) for small particle length-to-breadth ratio κ, we identify tetratic ordering at moderate packing fractions and smectic fluctuations at higher packing fractions, with no sharp transition between the two states. Both types of ordering can be explained in terms of clustering. (ii) For large κ, strong clustering precludes the stabilisation of a uniaxial nematic state, and the system exhibits a mixture of randomly-oriented clusters which, as packing fraction is increased, develops into states with smectic fluctuations, again through a diffuse transition. (iii) Vorticity excitations of the velocity field compete with smectic ordering, causing dynamic fluctuations and the absence of steady states at high densities; the tetratic state, by contrast, is very stiff against vorticity, and long-standing steady states, spatially and orientationally homogeneous except for four symmetrical defects located close to the wall, can be observed.

  11. 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.

  12. The melting of pulmonary surfactant monolayers

    PubMed Central

    Yan, Wenfei; Biswas, Samares C.; Laderas, Ted G.; Hall, Stephen B.

    2012-01-01

    Monomolecular films of phospholipids in the liquid-expanded (LE) phase after supercompression to high surface pressures (π), well above the equilibrium surface pressure (πe) at which fluid films collapse from the interface to form a three-dimensional bulk phase, and in the tilted-condensed (TC) phase both replicate the resistance to collapse that is characteristic of alveolar films in the lungs. To provide the basis for determining which film is present in the alveolus, we measured the melting characteristics of monolayers containing TC dipalmitoyl phosphatidylcholine (DPPC), as well as supercompressed 1-palmitoyl-2-oleoyl phosphatidylcholine and calf lung surfactant extract (CLSE). Films generated by appropriate manipulations on a captive bubble were heated from ≤27°C to ≥60°C at different constant π above πe. DPPC showed the abrupt expansion expected for the TC-LE phase transition, followed by the contraction produced by collapse. Supercompressed CLSE showed no evidence of the TC-LE expansion, arguing that supercompression did not simply convert the mixed lipid film to TC DPPC. For both DPPC and CLSE, the melting point, taken as the temperature at which collapse began, increased at higher π, in contrast to 1-palmitoyl-2-oleoyl phosphatidylcholine, for which higher π produced collapse at lower temperatures. For π between 50 and 65 mN/m, DPPC melted at 48–55°C, well above the main transition for bilayers at 41°C. At each π, CLSE melted at temperatures >10°C lower. The distinct melting points for TC DPPC and supercompressed CLSE provide the basis by which the nature of the alveolar film might be determined from the temperature-dependence of pulmonary mechanics. PMID:17194731

  13. 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.

  14. 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.

  15. The Catalytic Behaviour of NanoAg@montmorillonite Composite Materials

    NASA Astrophysics Data System (ADS)

    Karlíková, Martina; Kvítek, Libor; Prucek, Robert; Panáček, Aleš; Filip, Jan; Pechoušek, Jiří; Adegboyega, Nathaniel F.

    The preparation of nanoAg@montmorillonite composite materials and their catalytic activity is reported in this article. The nanoAg@montmorillonite composite materials were prepared by the adsorption of silver NPs, with an average size about 30 nm, from their aqueous dispersion onto two types of montmorillonite with different chemical composition. Silver NPs were prepared via modified Tollens process, which involves the reduction of [Ag(NH3)2]+ complex cation by maltose. The amount of silver NPs anchored onto the MMT surfaces was determined by UV-VIS spectroscopy; the decrease in absorbance of the dispersion after the adsorption was monitored. Prepared nanocomposite materials were subsequently characterized by means of transmission electron microscopy (TEM) and powder X-ray diffraction (XRD). The reduction of 4-nitrophenol by sodium borohydride was chosen to examine the catalytic properties of the synthesized silver nanocomposite materials.

  16. Ag/AgCl reference electrode in thionyl chloride electrolytes

    NASA Astrophysics Data System (ADS)

    Delnick, F. M.; Cieslak, W. R.

    1985-07-01

    Thionyl chloride is the active cathode and electrolyte solvent in Li/SOCl2 primary battery systems. To evaluate charge-transfer reactions in this solvent system, a reference electrode is required. This report describes the fabrication and characterization of Ag/AgCl microreference electrodes that can be used in SOCl2 battery electrolytes.

  17. SEIRA Spectroscopy on a Membrane Receptor Monolayer Using Lipoprotein Particles as Carriers

    PubMed Central

    Zaitseva, Ekaterina; Saavedra, Marcia; Banerjee, Sourabh; Sakmar, Thomas P.; Vogel, Reiner

    2010-01-01

    Surface-enhanced infrared absorption (SEIRA) difference spectroscopy can probe reactions in a protein monolayer tethered to a nanostructured gold surface. SEIRA studies of membrane proteins, however, remain challenging due to sample stability, effects of the metal surface on function, and the need for a membrane-mimicking environment. Here we demonstrate and characterize a model system for membrane receptor investigations using SEIRA spectroscopy. The system employs nanoscale apolipoprotein bound bilayer (NABB) particles, similar to discoidal high-density lipoprotein particles, as soluble carriers for the G-protein-coupled receptor rhodopsin. The His-tag of the engineered apolipoprotein allows for selective binding of the NABBs to a Ni-NTA modified surface, while the lipid environment of the particle ensures stability and protection of the embedded receptor. Using SEIRA spectroscopy, we followed specific binding of rhodopsin-loaded NABB particles to the surface and formation of a membrane protein monolayer. Functionality of the photoreceptor in the immobilized NABBs was probed by SEIRA difference spectroscopy confirming protein conformational changes associated with photoactivation. Orientation of the immobilized NABB particles was assessed by comparing SEIRA data with polarized attenuated total reflection-Fourier-transform infrared spectroscopy. Thus, SEIRA difference spectroscopy supported by the NABB technology provides a promising approach for further functional studies of transmembrane receptors. PMID:20923668

  18. Structural and configurational properties of nanoconfined monolayer ice from first principles

    PubMed Central

    Corsetti, Fabiano; Matthews, Paul; Artacho, Emilio

    2016-01-01

    Understanding the structural tendencies of nanoconfined water is of great interest for nanoscience and biology, where nano/micro-sized objects may be separated by very few layers of water. Here we investigate the properties of ice confined to a quasi-2D monolayer by a featureless, chemically neutral potential, in order to characterize its intrinsic behaviour. We use density-functional theory simulations with a non-local van der Waals density functional. An ab initio random structure search reveals all the energetically competitive monolayer configurations to belong to only two of the previously-identified families, characterized by a square or honeycomb hydrogen-bonding network, respectively. We discuss the modified ice rules needed for each network, and propose a simple point dipole 2D lattice model that successfully explains the energetics of the square configurations. All identified stable phases for both networks are found to be non-polar (but with a topologically non-trivial texture for the square) and, hence, non-ferroelectric, in contrast to previous predictions from a five-site empirical force-field model. Our results are in good agreement with very recently reported experimental observations. PMID:26728125

  19. Monolayer-directed assembly and magnetic properties of FePt nanoparticles on patterned aluminum oxide.

    PubMed

    Yildirim, Oktay; Gang, Tian; Kinge, Sachin; Reinhoudt, David N; Blank, Dave H; van der Wiel, Wilfred G; Rijnders, Guus; Huskens, Jurriaan

    2010-03-19

    FePt nanoparticles (NPs) were assembled on aluminum oxide substrates, and their ferromagnetic properties were studied before and after thermal annealing. For the first time, phosph(on)ates were used as an adsorbate to form self-assembled monolayers (SAMs) on alumina to direct the assembly of NPs onto the surface. The Al(2)O(3) substrates were functionalized with aminobutylphosphonic acid (ABP) or phosphonoundecanoic acid (PNDA) SAMs or with poly(ethyleneimine) (PEI) as a reference. FePt NPs assembled on all of these monolayers, but much less on unmodified Al(2)O(3), which shows that ligand exchange at the NPs is the most likely mechanism of attachment. Proper modification of the Al(2)O(3) surface and controlling the immersion time of the modified Al(2)O(3) substrates into the FePt NP solution resulted in FePt NPs assembly with controlled NP density. Alumina substrates were patterned by microcontact printing using aminobutylphosphonic acid as the ink, allowing local NP assembly. Thermal annealing under reducing conditions (96%N(2)/4%H(2)) led to a phase change of the FePt NPs from the disordered FCC phase to the ordered FCT phase. This resulted in ferromagnetic behavior at room temperature. Such a process can potentially be applied in the fabrication of spintronic devices.

  20. Heterogeneous nanotribological response of polymorphic self-assembled monolayers arising from domain and phase dependent friction.

    PubMed

    Paradinas, Markos; Munuera, Carmen; Silien, Christophe; Buck, Manfred; Ocal, Carmen

    2013-01-28

    Micro-/nanoelectromechanical systems demand robust ultrathin films for lubrication. As they can drastically modify the frictional properties of surfaces, few nanometers thick self-assembled monolayers (SAMs) constitute accepted candidates as boundary lubricants. Their high stability and easy preparation make them attractive also for low cost applications. Given their high order, organosulfur SAMs have been archetypal systems for structural investigations, but few efforts have been devoted to analyze the influence of lateral inhomogeneities on their surface properties. The impact on the frictional response of the surface due to the existence of crystalline domains with lateral dimension in the sub-micrometer range is considered here. To this end, two polymorphic structures of self-assembled monolayers of ω-(4'-methylbiphenyl-4-yl) butane-1-thiol coexisting on Au(111) are investigated by scanning tunneling and force microscopy. Described by rectangular 5√5 × 3 (α-phase) and oblique 6√3 × 2√3 (β-phase) unit cells, they exhibit pronouncedly different frictional responses. The lateral nano-tribological heterogeneity of the surface is further influenced by the azimuthal orientation dependence of friction for each phase. In particular, this phenomenon is exploited in the less densely packed β-phase for which the separate analysis of forward and backward lateral force scans is used to differentiate domains rotated 180°. The results demonstrate the level of structural control required in the design of SAMs for nano-tribology applications.

  1. Quantum dot monolayer for surface plasmon resonance signal enhancement and DNA hybridization detection.

    PubMed

    Ghrera, Aditya Sharma; Pandey, Manoj Kumar; Malhotra, Bansi Dhar

    2016-06-15

    We report results of studies relating to the fabrication of a surface plasmon resonance (SPR)-based nucleic acid sensor for quantification of DNA sequence specific to chronic myelogeneous leukemia (CML). The SPR disk surface has been modified with octadecanethiol self-assembled monolayer followed by deposition of the tri-n-octylphosphine oxide capped cadmium selenide quantum dots (QD) Langmuir monolayer. The deposition is performed via Langmuir-Blodgett (LB) technique. For the sensor chip preparation, covalent immobilization of the thiol-terminated DNA probe sequence (pDNA) using displacement reaction is accomplished. This integrated SPR chip has been used to detect target complementary DNA concentration by monitoring the change in coupling angle via hybridization. It is revealed that this biosensor exhibits high sensitivity (0.7859 m(0)pM(-1)) towards complementary DNA and can be used to detect it in the concentration range, 180 pM to 5 pM with detection limit as 4.21 pM. The results of kinetic studies yield the values of hybridization and dissociation rate constants as 9.6 × 10(4) M(-1) s(-1) and 2.3 × 10(-2) s(-1), respectively, with the equilibrium constant for hybridization as 4.2 × 10(6) M(-1).

  2. 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.

  3. Structural and configurational properties of nanoconfined monolayer ice from first principles

    NASA Astrophysics Data System (ADS)

    Corsetti, Fabiano; Matthews, Paul; Artacho, Emilio

    2016-01-01

    Understanding the structural tendencies of nanoconfined water is of great interest for nanoscience and biology, where nano/micro-sized objects may be separated by very few layers of water. Here we investigate the properties of ice confined to a quasi-2D monolayer by a featureless, chemically neutral potential, in order to characterize its intrinsic behaviour. We use density-functional theory simulations with a non-local van der Waals density functional. An ab initio random structure search reveals all the energetically competitive monolayer configurations to belong to only two of the previously-identified families, characterized by a square or honeycomb hydrogen-bonding network, respectively. We discuss the modified ice rules needed for each network, and propose a simple point dipole 2D lattice model that successfully explains the energetics of the square configurations. All identified stable phases for both networks are found to be non-polar (but with a topologically non-trivial texture for the square) and, hence, non-ferroelectric, in contrast to previous predictions from a five-site empirical force-field model. Our results are in good agreement with very recently reported experimental observations.

  4. Monolayer-directed Assembly and Magnetic Properties of FePt Nanoparticles on Patterned Aluminum Oxide

    PubMed Central

    Yildirim, Oktay; Gang, Tian; Kinge, Sachin; Reinhoudt, David N.; Blank, Dave H.A.; van der Wiel, Wilfred G.; Rijnders, Guus; Huskens, Jurriaan

    2010-01-01

    FePt nanoparticles (NPs) were assembled on aluminum oxide substrates, and their ferromagnetic properties were studied before and after thermal annealing. For the first time, phosph(on)ates were used as an adsorbate to form self-assembled monolayers (SAMs) on alumina to direct the assembly of NPs onto the surface. The Al2O3 substrates were functionalized with aminobutylphosphonic acid (ABP) or phosphonoundecanoic acid (PNDA) SAMs or with poly(ethyleneimine) (PEI) as a reference. FePt NPs assembled on all of these monolayers, but much less on unmodified Al2O3, which shows that ligand exchange at the NPs is the most likely mechanism of attachment. Proper modification of the Al2O3 surface and controlling the immersion time of the modified Al2O3 substrates into the FePt NP solution resulted in FePt NPs assembly with controlled NP density. Alumina substrates were patterned by microcontact printing using aminobutylphosphonic acid as the ink, allowing local NP assembly. Thermal annealing under reducing conditions (96%N2/4%H2) led to a phase change of the FePt NPs from the disordered FCC phase to the ordered FCT phase. This resulted in ferromagnetic behavior at room temperature. Such a process can potentially be applied in the fabrication of spintronic devices. PMID:20480007

  5. 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.

  6. Construction of Ag/AgCl nanostructures from Ag nanoparticles as high-performance visible-light photocatalysts

    NASA Astrophysics Data System (ADS)

    Yang, Fan; Liu, Dongzhi; Wang, Tianyang; Li, Wei; Hu, Wenping; Zhou, Xueqin

    2016-11-01

    A combined strategy of in situ oxidation and assembly is developed to prepare Ag/AgCl nanospheres and nanocubes from Ag nanoparticles under room temperature. It is a new facile way to fabricate Ag/AgCl with small sizes and defined morphologies. Ag/AgCl nanospheres with an average size of 80 nm were achieved without any surfactants, while Ag/AgCl nanocubes with a mean edge length of 150 nm were obtained by introduction of N-dodecyl- N, N-dimethyl-2-ammonio-acetate. The possible formation mechanism involves the self-assembly of AgCl nanoparticles, Ostwald ripening and photoreduction of Ag+ into Ag0 by the room light. The as-prepared Ag/AgCl nanospheres and nanocubes exhibit excellent photocatalytic activity and stability toward degradation of organic pollutants under visible-light irradiation. It is demonstrated that Ag/AgCl nanocubes display enhanced photocatalytic activity in comparison with Ag/AgCl nanospheres due to the more efficient charge transfer. This work may pave an avenue to construct various functional materials via the assembly strategy using nanoparticles as versatile building blocks.

  7. Impurity Decoration for Crystal Shape Control: C60 on Ag(111)

    NASA Astrophysics Data System (ADS)

    Stasevich, T. J.; Tao, C. G.; Cullen, W. G.; Williams, E. D.; Einstein, T. L.

    2008-03-01

    The decoration of hexagonal Ag/Ag(111) monolayer islands by chains of C60, observed via STM at 300K, dramatically changes their shape and fluctuations. We tune coverage so that a single C60 chain fully decorates each Ag island boundary.ootnotetextC.G. Tao et al., PRB 73, 125436 (2006); Nano Letters 7, 1495 (2007). The C60-induced rounding appears due to competing energetic and entropic effects.ootnotetextT.J. Stasevich & TLE, (SIAM) Multiscale Model. Simul. 6, 90 (2007) We estimate the Ag - C60 and C60 - C60 attractions as ˜0.13 eV and ˜0.04 eV, respectively.ootnotetextT.J. Stasevich et al., submitted. The edge fluctuations are remarkable: 1) C60 decoration does not notably impede the step-edge diffusion (SED) and 2) while the bare-island fluctuations are driven by SED, the decorated island has the signature of non-conserved dynamics, even though the C60s remain at the island edge. We suggest that rapidly diffusing Ag atoms randomly attracting the nearby C60s. Generalizations of our model show that both spherical and rectangular decorating molecules will similarly lower the energy of highly-kinked boundaries, leading to similar island shape changes.

  8. Roughening in electronic growth of Ag on Si(111)-(7×7) surfaces.

    PubMed

    Pal, Arindam; Mahato, J C; Dev, B N; Goswami, D K

    2013-10-09

    Roughening in the electronic growth of Ag films on Si(111)-(7×7) surfaces for a film thickness ranging from 1 to 30 monolayers is reported. Ag films exhibit the growth of flat-top plateaus of preferential heights due quantum electronic effect. We have observed roughening of the film growth due to instability with linear diffusion characterized by the ln(θ)(1/2) dependence of the local surface slope, where θ is the Ag coverage. The roughening of the surface morphology has been characterized by scaling exponents α, β and 1/z, which are determined using scanning tunneling microscopy. Increased value of α = 0.67 ± 0.04 at the early stage of the electronic growth with two atomic layer height flat-top isolated Ag mounds to 0.77 ± 0.06 at the later stage of the growth when isolated mounds coalesce and form percolated structures maintaining preferential heights of an even number of atomic layers in the Ag mounds indicates the instability in the electronic growth. As a result, interface width W increases as a power law of coverage (θ), W ∼ θ(β), with growth exponent β = 0.33 ± 0.03, and lateral correlation length ξ grows as ξ ∼ θ(1/z) with 1/z = 0.27 ± 0.05.

  9. Oxidation Resistance of Monolayer Group-IV Monochalcogenides.

    PubMed

    Guo, Yu; Zhou, Si; Bai, Yizhen; Zhao, Jijun

    2017-03-21

    Ridged, orthorhombic two-dimensional (2D) group-V elemental and group IV-VI compound analogues of phosphorene provide a versatile platform for nanoelectronics, optoelectronics, and clean energy. However, phosphorene is vulnerable to oxygen in ambient air, which is a major obstacle for its applications. Regarding this issue, here we explore the oxidation behavior of monolayer group-IV monochalcogenides (GeS, GeSe, SnS, and SnSe), in comparison to that of phosphorene and arsenene by first-principles calculations. We find superior oxidation resistance of the monolayer group-IV monochalcogenides, with activation energies for the chemisorption of O2 on the 2D sheets in the range of 1.26-1.60 eV, about twice of the values of phosphorene and arsenene. The distinct oxidation behaviors of monolayer group-IV monochalcogenides and group-V phosphorene analogues originate from their different bond natures. Moreover, the chemisorption of a moderate amount of oxygen atoms does not severely deteriorate the electronic band structures of the monolayer group-IV monochalcogenides. These results shine light on the utilization of the monolayer group-IV monochalcogenides for next-generation 2D electronics and optoelectronics with high performance and stability.

  10. Fluorescently labeled pulmonary surfactant protein C in spread phospholipid monolayers.

    PubMed Central

    Nag, K; Perez-Gil, J; Cruz, A; Keough, K M

    1996-01-01

    Pulmonary surfactant, a lipid-protein complex, secreted into the fluid lining of lungs prevents alveolar collapse at low lung volumes. Pulmonary surfactant protein C (SP-C), an acylated, hydrophobic, alpha-helical peptide, enhances the surface activity of pulmonary surfactant lipids. Fluorescein-labeled SP-C (F-SP-C) (3, 6, 12 wt%) in dipalmitoylphosphatidylcholine (DPPC), and DPPC:dipalmitoylphosphatidylglycerol (DPPG) [DPPC:DPPG 7:3 mol/mol] in spread monolayers was studied by epifluorescence microscopy. Mass spectometry of F-SP-C indicated that the protein is partially deacylated and labeled with 1 mol fluorescein/1 mol protein. The protein partitioned into the fluid, or liquid expanded, phase. Increasing amounts of F-SP-C in DPPC or DPPC:DPPG monolayers decreased the size and total amounts of the condensed phase at all surface pressures. Calcium (1.6 mM) increased the amount of the condensed phase in monolayers of DPPC:DPPG but not of DPPC alone, and such monolayers were also perturbed by F-SP-C. The study indicates that SP-C perturbs the packing of neutral and anionic phospholipid monolayers even when the latter systems are condensed by calcium, indicating that interactions between SP-C and the lipids are predominantly hydrophobic in nature. Images FIGURE 2 FIGURE 4 FIGURE 7 PMID:8804608

  11. Influence of vitamin C on alcohol binding to phospholipid monolayers.

    PubMed

    Weis, M; Kopáni, M

    2008-07-01

    The simple model of the biological membrane is provided by well-controlled lipid monolayers at the air-water interface. The Maxwell displacement current technique (MDC) provides novel approach to conformation study of the membrane models. The effect of alcohols is interaction with membrane molecules, mainly with the lipid head group and consequent changes in physical-chemical properties of the membrane. The aim of study is to detect changes in structural, electrical and mechanical properties of dipalmitoyl-phosphatidylcholine (DPPC) monolayer on the subphase of methanol-water and ethanol-water mixtures before and after addition of antioxidant agent, vitamin C. Monolayers properties are investigated by a surface pressure analysis (including mechanical properties evaluation) and the Maxwell displacement current measurement, the dipole moment projection calculation. Surface pressure-area isotherms show similar behaviour of the DPPC monolayer on alcohol-water mixtures independently on presence of vitamin C. Binding/adsorption process induces change of electron density distribution across monolayer and thus the molecular dipole moment. We observe small or negligible binding of methanol molecules on oxygen bonds of DPPC. Thus the antioxidant, vitamin C, has no significant effect. For ethanol-water mixtures is observed recovery of electrical properties in presence of antioxidant agent. We suppose that vitamin C regulates DPPC-ethanol molecules interaction.

  12. Diffusion and Partitioning of Fluorescent Lipid Probes in Phospholipid Monolayers

    PubMed Central

    Gudmand, M.; Fidorra, Matthias; Bjørnholm, T.; Heimburg, T.

    2009-01-01

    The pressure-dependent diffusion and partitioning of single lipid fluorophores in DMPC and DPPC monolayers were investigated with the use of a custom-made monolayer trough mounted on a combined fluorescence correlation spectroscopy (FCS) and wide-field microscopy setup. It is shown that lipid diffusion, which is essential for the function of biological membranes, is heavily influenced by the lateral pressure and phase of the lipid structure. Both of these may change dynamically during, e.g., protein adsorption and desorption processes. Using FCS, we measured lipid diffusion coefficients over a wide range of lateral pressures in DMPC monolayers and fitted them to a free-area model as well as the direct experimental observable mean molecular area. FCS measurements on DPPC monolayers were also performed below the onset of the phase transition (Π < 5 mN/m). At higher pressures, FCS was not applicable for measuring diffusion coefficients in DPPC monolayers. Single-molecule fluorescence microscopy and differential scanning calorimetry clearly showed that this was due to heterogeneous partitioning of the lipid fluorophores in condensed phases. The results were compared with dye partitioning in giant lipid vesicles. These findings are significant in relation to the application of lipid fluorophores to study diffusion in both model systems and biological systems. PMID:19486682

  13. The crystalline structures of carboxylic acid monolayers adsorbed on graphite.

    PubMed

    Bickerstaffe, A K; Cheah, N P; Clarke, S M; Parker, J E; Perdigon, A; Messe, L; Inaba, A

    2006-03-23

    X-ray and neutron diffraction have been used to investigate the formation of solid crystalline monolayers of all of the linear carboxylic acids from C(6) to C(14) at submonolayer coverage and from C(8) to C(14) at multilayer coverages, and to characterize their structures. X-rays and neutrons highlight different aspects of the monolayer structures, and their combination is therefore important in structural determination. For all of the acids with an odd number of carbon atoms, the unit cell is rectangular of plane group pgg containing four molecules. The members of the homologous series with an even number of carbon atoms have an oblique unit cell with two molecules per unit cell and plane group p2. This odd-even variation in crystal structure provides an explanation for the odd-even variation observed in monolayer melting points and mixing behavior. In all cases, the molecules are arranged in strongly hydrogen-bonded dimers with their extended axes parallel to the surface and the plane of the carbon skeleton essentially parallel to the graphite surface. The monolayer crystal structures have unit cell dimensions similar to certain close-packed planes of the bulk crystals, but the molecular arrangements are different. There is a 1-3% compression on increasing the coverage over a monolayer.

  14. Controlling enantiomeric populations in fluctuating Brownian monolayers of chiral colloids.

    PubMed

    Rossi, L; Mason, T G

    2015-03-28

    An ideal parallelogram platelet, although achiral in 3D, has an identifiable chirality when confined in a 2D monolayer. We lithographically fabricate microscale parallelogram platelets, disperse them in an aqueous surfactant solution, and allow them to settle towards a lower glass wall. To reduce the thermal-gravitational height, we add polystyrene nanospheres as a depletion agent to create a depletion attraction between the parallelograms and the wall. Surprisingly, by increasing the volume fraction of the depletion agent, we show that a nearly enantiopure monolayer can be created. We explain this by developing a model of 2D monolayer formation based on anisotropic facial attractions; one face of a platelet is more strongly attracted to the wall than the other as a consequence of an anisotropy introduced by the lithographic process. We study enantiopure Brownian systems of parallelograms as a function of particle area fraction and show that oblique chiral crystals form at high densities. By mixing parallelogram platelets printed in opposite senses, we also dictate the chiral ratio in the monolayer over the entire possible range. This approach is not limited to parallelograms and provides a means for tuning the chiral ratio in fluctuating 2D monolayers composed of a wide variety of chiral shapes.

  15. 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.

  16. Chemical imaging of monolayers on metal surfaces: applications in corrosion, catalysis, and self-assembled monolayers.

    PubMed

    Baldelli, Steven

    2008-11-10

    In situ techniques are indispensable to understanding many topics in surface chemistry. As a consequence, several spectroscopic methods have been developed to provide molecular-level information that only spectroscopy can supply. However, as important as this information is, it is just as critical to realize that nearly all surfaces under investigation have spatial heterogeneities of the order of nanometers to millimeters; thus, spatial analysis is very important to the overall interpretation. This Minireview focuses on a few of the recent developments in spectroscopic techniques that can provide spatial, spectroscopic, and in situ information. These techniques include photo-electron microscopy, infrared and Raman imaging, and nonlinear optical imaging vibrational spectroscopy as applied to topics in corrosion, catalysis and self-assembled monolayers.

  17. Surface structural, morphological, and catalytic studies of homogeneously dispersed anisotropic Ag nanostructures within mesoporous silica

    NASA Astrophysics Data System (ADS)

    Sareen, Shweta; Mutreja, Vishal; Pal, Bonamali; Singh, Satnam

    2016-11-01

    Highly dispersed anisotropic Ag nanostructures were synthesized within the channels of 3-aminopropyltrimethoxysilane (APTMS)-modified mesoporous SBA-15 for catalyzing the reduction of p-dinitrobenzene, p-nitrophenol, and p-nitroacetophenone, respectively. A green templating process without involving any reducing agent, by varying the amount (1-10 wt.%) of Ag loading followed by calcination at 350 °C under H2 led to change in the morphology of Ag nanoparticles from nanospheres ( 7-8 nm) to nanorods (aspect ratio 12-30 nm) without any deformation in mesoporous sieves. In comparison to white bare SBA-15, gray-colored samples were formed with Ag impregnation exhibiting absorption bands at 484 and 840 nm indicating the formation of anisotropic Ag nanostructures within mesoporous matrix. TEM and FE-SEM micrographs confirmed the presence of evenly dispersed Ag nanostructures within as well as on the surface of mesoporous matrix. AFM studies indicated a small decrease in the average roughness of SBA-15 from 20.59 to 19.21 nm for 4 wt.% Ag/m-SBA-15, illustrating the encapsulation of majority of Ag nanoparticles in the siliceous matrix and presence of small amount of Ag nanoparticles on the mesoporous support. Moreover, due to plugging of mesopores with Ag, a significant decrease in surface area from 680 m2/g of SBA-15 to 385 m2/g was observed. The Ag-impregnated SBA-15 catalyst displayed superior catalytic activity than did bare SBA-15 with 4 wt.% Ag-loaded catalyst exhibiting optimum activity for selective reduction of p-nitrophenol to p-aminophenol (100 %), p-nitroacetophenone to p-aminoacetophenone (100 %), and p-dinitrobenzene to p-nitroaniline (87 %), with a small amount of p-phenylenediamine formation.

  18. 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.

  19. 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.

  20. What Is Ag-Ed?

    ERIC Educational Resources Information Center

    Lindley, Judy

    Ag-Ed is an agricultural education project aimed at upper primary students, held in conjunction with the Toowoomba Show (similar to a county fair) in Queensland, Australia. The program achieves its purpose of helping children understand the impact and relevance that agriculture has on their everyday lives through two components, an Ag-Ed day and a…

  1. 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.

  2. DNA/Ag Nanoparticles as Antibacterial Agents against Gram-Negative Bacteria

    PubMed Central

    Takeshima, Tomomi; Tada, Yuya; Sakaguchi, Norihito; Watari, Fumio; Fugetsu, Bunshi

    2015-01-01

    Silver (Ag) nanoparticles were produced using DNA extracted from salmon milt as templates. Particles spherical in shape with an average diameter smaller than 10 nm were obtained. The nanoparticles consisted of Ag as the core with an outermost thin layer of DNA. The DNA/Ag hybrid nanoparticles were immobilized over the surface of cotton based fabrics and their antibacterial efficiency was evaluated using E. coli as the typical Gram-negative bacteria. The antibacterial experiments were performed according to the Antibacterial Standard of Japanese Association for the Functional Evaluation of Textiles. The fabrics modified with DNA/Ag nanoparticles showed a high enough inhibitory and killing efficiency against E. coli at a concentration of Ag ≥ 10 ppm. PMID:28347012

  3. A General Method for Solvent Exchange of Plasmonic Nanoparticles and Self-Assembly into SERS-Active Monolayers

    PubMed Central

    2015-01-01

    We present a general route for the transfer of Au and Ag nanoparticles of different shapes and sizes, from water into various organic solvents. The experimental conditions for each type of nanoparticles were optimized by using a combination of thiolated poly(ethylene glycol) and a hydrophobic capping agent, such as dodecanethiol. The functionalized nanoparticles were readily transferred into organic dispersions with long-term stability (months). Such organic dispersions efficiently spread out on water, leading to self-assembly at the air/liquid interface into extended nanoparticle arrays which could in turn be transferred onto solid substrates. The dense close packing in the obtained nanoparticle monolayers results in extensive plasmon coupling, rendering them efficient substrates for surface-enhanced Raman scattering spectroscopy. PMID:26258732

  4. Magnesium carbide monolayer: A novel quasi-planar semiconductor

    NASA Astrophysics Data System (ADS)

    Naseri, Mosayeb

    2017-02-01

    By using the first principles calculations in the framework of the density functional theory, a new quasi-planer semiconductor material, namely Magnesium Carbide Monolayer (Mg2C) is predicted. The stability of the proposed structure is confirmed by cohesive energy calculation. According to our simulation, Mg2C monolayer is a semiconductor material with an indirect band gap of 0.68 eV, which is tunable under external biaxial stress. Optical properties calculation indicates considerable sharp absorption peaks in ultra violet (UV) energy range. As a semiconductor with an indirect tunable band gap, Mg2C monolayer is a promising 2D material for application in future optoelectronic technology especially in designing ultraviolet (UV) light filters.

  5. Control of Exciton Valley Coherence in Transition Metal Dichalcogenide Monolayers

    NASA Astrophysics Data System (ADS)

    Wang, G.; Marie, X.; Liu, B. L.; Amand, T.; Robert, C.; Cadiz, F.; Renucci, P.; Urbaszek, B.

    2016-10-01

    The direct gap interband transitions in transition metal dichalcogenide monolayers are governed by chiral optical selection rules. Determined by laser helicity, optical transitions in either the K+ or K- valley in momentum space are induced. Linearly polarized laser excitation prepares a coherent superposition of valley states. Here, we demonstrate the control of the exciton valley coherence in monolayer WSe2 by tuning the applied magnetic field perpendicular to the monolayer plane. We show rotation of this coherent superposition of valley states by angles as large as 30° in applied fields up to 9 T. This exciton valley coherence control on the ps time scale could be an important step towards complete control of qubits based on the valley degree of freedom.

  6. Structural and electronic properties of arsenic nitrogen monolayer

    NASA Astrophysics Data System (ADS)

    Liu, Pei; Nie, Yao-zhuang; Xia, Qing-lin; Guo, Guang-hua

    2017-03-01

    We present our first-principles calculations of a new two-dimensional material, arsenic nitrogen monolayer. The structural, electronic, and mechanical properties are investigated in detail by means of density functional theory computations. The calculated binding energy and the phonon spectra demonstrate that the AsN can form stable monolayer in puckered honeycomb structure. It is a semiconductor with indirect band gap of 0.73 eV, and displays highly anisotropic mechanical properties. Strain has obvious influence on the electronic properties of AsN monolayer. It is found that in the armchair direction, a moderate compression strain (-12%) can trigger an indirect to direct band gap transition and a tensile strain of 18% can make the AsN becoming a stable metal. In the zigzag direction, a rather smaller strain than armchair direction (12% for compression and 8% for stretch) can induce the indirect band gap to metal transition.

  7. Manipulating interface states in monolayer-bilayer graphene planar junctions.

    PubMed

    Zhao, Fang; Xu, Lei; Zhang, Jun

    2016-05-11

    We report on transport properties of monolayer-bilayer graphene planar junctions in a magnetic field. Due to its unique geometry, the edge and interface states can be independently manipulated by either interlayer potential or Zeeman field, and the conductance exhibits interesting quantized behaviors. In the hybrid graphene junction, the quantum Hall (QH) conductance is no longer antisymmetric with respect to the charge neutrality point. When the Zeeman field is considered, a quantum spin Hall (QSH) phase is found in the monolayer region while the weak-QSH phase stays in the bilayer region. In the presence of both interlayer potential and Zeeman field, the bilayer region hosts a QSH phase, whereas the monolayer region is still in a QH phase, leading to a spin-polarized current in the interface. In particular, the QSH phase remains robust against the disorder.

  8. Manipulating interface states in monolayer-bilayer graphene planar junctions

    NASA Astrophysics Data System (ADS)

    Zhao, Fang; Xu, Lei; Zhang, Jun

    2016-05-01

    We report on transport properties of monolayer-bilayer graphene planar junctions in a magnetic field. Due to its unique geometry, the edge and interface states can be independently manipulated by either interlayer potential or Zeeman field, and the conductance exhibits interesting quantized behaviors. In the hybrid graphene junction, the quantum Hall (QH) conductance is no longer antisymmetric with respect to the charge neutrality point. When the Zeeman field is considered, a quantum spin Hall (QSH) phase is found in the monolayer region while the weak-QSH phase stays in the bilayer region. In the presence of both interlayer potential and Zeeman field, the bilayer region hosts a QSH phase, whereas the monolayer region is still in a QH phase, leading to a spin-polarized current in the interface. In particular, the QSH phase remains robust against the disorder.

  9. Controlled electrodeposition of Au monolayer film on ionic liquid

    NASA Astrophysics Data System (ADS)

    Ma, Qiang; Pang, Liuqing; Li, Man; Zhang, Yunxia; Ren, Xianpei; Liu, Shengzhong Frank

    2016-05-01

    Gold (Au) nanoparticles have been attractive for centuries for their vibrant appearance enhanced by their interaction with sunlight. Nowadays, there have been tremendous research efforts to develop them for high-tech applications including therapeutic agents, sensors, organic photovoltaics, medical applications, electronics and catalysis. However, there remains to be a challenge to fabricate a monolayer Au coating with complete coverage in controlled fashion. Here we present a facile method to deposit a uniform Au monolayer (ML) film on the [BMIM][PF6] ionic liquid substrate using an electrochemical deposition process. It demonstrates that it is feasible to prepare a solid phase coating on the liquid-based substrate. Moreover, the thickness of the monolayer coating can be controlled to a layer-by-layer accuracy.

  10. Computational prediction of the diversity of monolayer boron phosphide allotropes

    NASA Astrophysics Data System (ADS)

    Zhu, Zhili; Cai, Xiaolin; Niu, Chunyao; Wang, Chongze; Jia, Yu

    2016-10-01

    We propose previously unrecognized allotropes of monolayer boron phosphorus (BP) based on ab initio density functional calculations. In addition to the hexagonal structure of h-BP, four types of boron phosphide compounds were predicted to be stable as monolayers. They can form sp2 hybridized planar structures composed of 6-membered rings, and buckled geometries including 4-8 or 3-9 membered rings with sp3 like bonding for P atoms. The calculated Bader charges illustrate their ionic characters with the charge transfers from B to P atoms. The competing between the electrostatic energy and the bonding energy of sp2 and sp3 hybridizations reflected in P atoms results in multiple structures of BP. These 2D BP structures can be semiconducting or metallic depending on their geometric structures. Our findings significantly broaden the diversity of monolayer BP allotropes and provide valuable guidance to other 2D group-III-V allotropes.

  11. Band structures in silicene on monolayer gallium phosphide substrate

    NASA Astrophysics Data System (ADS)

    Ren, Miaojuan; Li, Mingming; Zhang, Changwen; Yuan, Min; Li, Ping; Li, Feng; Ji, Weixiao; Chen, Xinlian

    2016-07-01

    Opening a sizable band gap in the zero-gap silicene is a key issue for its application in nanoelectronics. We design new 2D silicene and GaP heterobilayer (Si/GaP HBL) composed of silicene and monolayer (ML) GaP. Based on first-principles calculations, we find that the interaction energies are in the range of -295.5 to -297.5 meV per unit cell, indicating a weak interaction between silicene and gallium phosphide (GaP) monolayer. The band gap changes ranging from 0.06 to 0.44 eV in hybrid HBLs. An unexpected indirect-direct band gap crossover is also observed in HBLs, dependent on the stacking pattern. These provide a possible way to design effective FETs out of silicene on GaP monolayer.

  12. Modification of ferromagnetism in semiconductors by molecular monolayers

    NASA Astrophysics Data System (ADS)

    Carmeli, Itai; Kreutz, Ted; Naaman, Ron; Gossard, Art

    2005-03-01

    We report that adsorption of monolayers of organic molecules onto ferromagnetic semiconductor heterostructures can produce large changes in magnetic properties [1]. The digital-alloy heterostructures studied have 1/2 monolayer MnAs planes embedded in GaAs. We investigate effects on magnetic properties of self- assembly of various organic molecules onto the heterostructure surface. Depending on the molecular structure, the monolayers can either strengthen or suppress ferromagnetism. We attribute this chemical modulation of magnetic properties to electronic changes brought about by molecular binding to the semiconductor surface. [1] T.C. Kreutz, R. Artzi, E.G. Gwinn, R. Naaman, H. Pizem, C.N. Sukenik and A.C. Gossard, Applied Physics Letters 83, 4211(2003).

  13. Effect of ammonia plasma treatment on graphene oxide LB monolayers

    SciTech Connect

    Singh, Gulbagh; Botcha, V. Divakar; Narayanam, Pavan K.; Sutar, D. S.; Talwar, S. S.; Major, S. S.; Srinivasa, R. S.

    2013-02-05

    Graphene oxide monolayer sheets were transferred on Si and SiO{sub 2}/Si substrates by Langmuir-Blodgett technique and were exposed to ammonia plasma at room temperature. The monolayer character of both graphene oxide and plasma treated graphene oxide sheets were ascertained by atomic force microscopy. X-ray photoelectron spectroscopy and Raman spectroscopy revealed that ammonia plasma treatment results in enhancement of graphitic carbon content along with the incorporation of nitrogen. The conductivity of graphene oxide monolayers, which was in the range of 10{sup -6}-10{sup -7} S/cm, increased to 10{sup -2}-10{sup -3} S/cm after the ammonia plasma treatment. These results indicate that the graphene oxide was simultaneously reduced and N-doped during ammonia plasma treatment, without affecting the morphological stability of sheets.

  14. Graphene-modulated photo-absorption in adsorbed azobenzene monolayers.

    PubMed

    Fu, Qiang; Cocchi, Caterina; Nabok, Dmitrii; Gulans, Andris; Draxl, Claudia

    2017-02-22

    The impact of graphene on the photo-absorption properties of trans- and cis-azobenzene monolayers is studied in the framework of density-functional theory and many-body perturbation theory. We find that, despite the weak hybridization between the electronic bands of graphene and those of the azobenzene monolayers, graphene remarkably modulates the absorption spectra of the adsorbates. The excitation energies are affected via two counteracting mechanisms: substrate polarization reduces the band-gap of azobenzene, and enhanced dielectric screening weakens the attractive interaction between electrons and holes. The competition between these two effects gives rise to an overall blueshift of peaks stemming from intramolecular excitations, and a redshift of peaks from intermolecular ones. Even more interesting is that excitations corresponding to intermolecular electron-hole pairs, which are dark in the isolated monolayers, are activated by the graphene substrate. Our results demonstrate that the photoisomerization process of weakly adsorbed azobenzene undergoes notable changes on a carbon-based substrate.

  15. Frictional transition from superlubric islands to pinned monolayers

    NASA Astrophysics Data System (ADS)

    Pierno, Matteo; Bruschi, Lorenzo; Mistura, Giampaolo; Paolicelli, Guido; di Bona, Alessandro; Valeri, Sergio; Guerra, Roberto; Vanossi, Andrea; Tosatti, Erio

    2015-08-01

    The inertial sliding of physisorbed submonolayer islands on crystal surfaces contains unexpected information on the exceptionally smooth sliding state associated with incommensurate superlubricity and on the mechanisms of its disappearance. Here, in a joint quartz crystal microbalance and molecular dynamics simulation case study of Xe on Cu(111), we show how superlubricity emerges in the large size limit of naturally incommensurate Xe islands. As coverage approaches a full monolayer, theory also predicts an abrupt adhesion-driven two-dimensional density compression on the order of several per cent, implying a hysteretic jump from superlubric free islands to a pressurized commensurate immobile monolayer. This scenario is fully supported by the quartz crystal microbalance data, which show remarkably large slip times with increasing submonolayer coverage, signalling superlubricity, followed by a dramatic drop to zero for the dense commensurate monolayer. Careful analysis of this variety of island sliding phenomena will be essential in future applications of friction at crystal/adsorbate interfaces.

  16. Frictional transition from superlubric islands to pinned monolayers.

    PubMed

    Pierno, Matteo; Bruschi, Lorenzo; Mistura, Giampaolo; Paolicelli, Guido; di Bona, Alessandro; Valeri, Sergio; Guerra, Roberto; Vanossi, Andrea; Tosatti, Erio

    2015-08-01

    The inertial sliding of physisorbed submonolayer islands on crystal surfaces contains unexpected information on the exceptionally smooth sliding state associated with incommensurate superlubricity and on the mechanisms of its disappearance. Here, in a joint quartz crystal microbalance and molecular dynamics simulation case study of Xe on Cu(111), we show how superlubricity emerges in the large size limit of naturally incommensurate Xe islands. As coverage approaches a full monolayer, theory also predicts an abrupt adhesion-driven two-dimensional density compression on the order of several per cent, implying a hysteretic jump from superlubric free islands to a pressurized commensurate immobile monolayer. This scenario is fully supported by the quartz crystal microbalance data, which show remarkably large slip times with increasing submonolayer coverage, signalling superlubricity, followed by a dramatic drop to zero for the dense commensurate monolayer. Careful analysis of this variety of island sliding phenomena will be essential in future applications of friction at crystal/adsorbate interfaces.

  17. Assembly of designed protein scaffolds into monolayers for nanoparticle patterning.

    PubMed

    Mejias, Sara H; Couleaud, Pierre; Casado, Santiago; Granados, Daniel; Garcia, Miguel Angel; Abad, Jose M; Cortajarena, Aitziber L

    2016-05-01

    The controlled assembly of building blocks to achieve new nanostructured materials with defined properties at different length scales through rational design is the basis and future of bottom-up nanofabrication. This work describes the assembly of the idealized protein building block, the consensus tetratricopeptide repeat (CTPR), into monolayers by oriented immobilization of the blocks. The selectivity of thiol-gold interaction for an oriented immobilization has been verified by comparing a non-thiolated protein building block. The physical properties of the CTPR protein thin biomolecular films including topography, thickness, and viscoelasticity, are characterized. Finally, the ability of these scaffolds to act as templates for inorganic nanostructures has been demonstrated by the formation of well-packed gold nanoparticles (GNPs) monolayer patterned by the CTPR monolayer.

  18. Thermodynamic aspects of cholesterol effect on properties of phospholipid monolayers: Langmuir and Langmuir-Blodgett monolayer study.

    PubMed

    Jurak, Małgorzata

    2013-04-04

    Cholesterol is an important component of lipid rafts in mammalian cell membranes. Studies of phospholipid monolayers containing cholesterol provide insight into the role of cholesterol in regulating the properties of animal cells, raft stability, and organization. In this contribution, a study of the characteristics of binary Langmuir monolayers consisting of phospholipids, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), 2-oleoyl-1-palmitoyl-sn-glycero-3-phosphocholine (POPC), 1,2-dipalmitoyl-sn-glycero-3-phospho-rac-(1-glycerol) (DPPG), and cholesterol (Chol), was conducted on the basis of the surface pressure-area per molecule (π-A) isotherms. Analysis of the results obtained provided information on the mean molecular area, the excess Gibbs energy of mixing, and condensation in the monolayer. The mixed monolayers were also deposited onto the mica plates and investigated by the contact angle measurements of water, formamide, and diiodomethane. The contact angles allowed calculating surface free energy of the films from the van Oss et al. approach. It was found that cholesterol determines the molecular packing and ordering of the monolayers closely connected with the kind of phospholipid. This is reflected in the values of surface free energy of the model membranes. From the thermodynamic analysis of phospholipid/cholesterol/liquid interactions, one may draw conclusions about the most favorable composition (stoichiometry) of the binary film which is especially important in view of the lipid rafts formation.

  19. Surface-modification of poly(dimethylsiloxane) membrane with self-assembled monolayers for alcohol permselective pervaporation.

    PubMed

    Li, Jie; Ji, Shulan; Zhang, Guojun; Guo, Hongxia

    2013-06-25

    The use of self-assembled monolayers (SAMs) has recently been recognized as an effective way to tailor the surface properties of films used in various applications. However, application of SAMs in the preparation of separation membranes remains unexplored. In the present study, surface-modified poly(dimethylsiloxane) (PDMS) membranes were prepared using SAMs to fabricate a membrane for use in pervaporation separation of ethanol/water mixtures. A cross-linked PDMS/polysulfone (PSf) composite membrane was transformed by introducing hydroxyl functionalities on the PDMS surface through a UV/ozone conversion process. (Tridecafluoroctyl)triethoxysilane was allowed to be adsorbed on the resulting Si-OH substrate to increase the hydrophobicity of the membrane. Results from Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectrometry, atomic force microscopy, and contact angle analyses suggest that the fluoroalkylsilane monolayer was successfully formed on the modified PDMS/PSf membrane treated by 60 min UV/ozone exposure. The newly SAM-modified membrane exhibited a separation factor of 13.1 and a permeate flux of 412.9 g/(m(2) h), which are higher than those obtained from PDMS membranes.

  20. Plasmonic Ag2MoO4/AgBr/Ag composite: Excellent photocatalytic performance and possible photocatalytic mechanism

    NASA Astrophysics Data System (ADS)

    Wang, Zhongliao; Zhang, Jinfeng; Lv, Jiali; Dai, Kai; Liang, Changhao

    2017-02-01

    Plasmonic Ag2MoO4/AgBr/Ag composite is fabricated by in-situ ion exchange and reduction methods at room temperature. The samples are characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance (DRS), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscope (SEM) and photoluminescence (PL) measurements. The results show that butterfly-like Ag2MoO4 nanosheets served as the precursor, and Ag2MoO4/AgBr/Ag is formed in phase transformation with MoO42- displaced by Br-. The ternary Ag2MoO4/AgBr/Ag composite photocatalysts show greatly enhanced photocatalytic activity in photodegrading methylene blue (MB) under visible light irradiation compared with AgBr and Ag2MoO4. The pseudo-first-order rate constant kapp of Ag2MoO4/AgBr/Ag is 0.602 min-1, which is 11.6 and 18.3 times as high as that of AgBr and Ag2MoO4, respectively. Meanwhile, the efficiency of degradation still kept 90% after ten times cyclic experiments. Eventually, possible photocatalytic mechanism was proposed.