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Sample records for assembly organic monolayer

  1. Photoactive self-assembled monolayers for optically switchable organic thin-film transistors

    OpenAIRE

    Salinas, Michael; Halik, Marcus

    2013-01-01

    We investigate the photoconductive and photovoltaic effects in organic thin-film transistors with thin hybrid dielectrics composed of aluminum oxide and self-assembled monolayers (SAMs). By using SAM molecules with an electro-optical functionality tuning of the photoinduced charge transfer at the interface of semiconductor and SAM upon illumination with laser light can be achieved. Control of the threshold voltage by the SAM composition enables the optical operation of the transistors without...

  2. Organic surfaces exposed by self-assembled organothiol monolayers: Preparation, characterization, and application

    Science.gov (United States)

    Kind, Martin; Wöll, Christof

    2009-07-01

    Organic surfaces play a major role in materials science. Most surfaces that we touch in our daily lives are made from organic materials, e.g., vegetables, fruit, skin, wood, and textiles made from natural fibers. In the context of biology, organic surfaces play a prominent role too, proteins docking onto cell surfaces are a good example. To better understand the characteristics of organic surfaces, including physico-chemical properties like wettability or chemical reactivities and physical properties like friction and lubrication, a structurally well-defined model system that can be investigated with numerous analytical techniques is desirable. In the last two decades, one particular system, self-assembled monolayers or SAMs, have demonstrated their suitability for this purpose. In particular, organothiols consisting of an organic molecule with an attached SH-group are well suited to fabricating structurally well-defined adlayers of monolayer thickness on gold substrates using a simple preparation procedure. These ultrathin monolayers expose an organic surface with properties that can be tailored by varying the type of organothiol employed. After a short introduction into the preparation of SAMs, this article provides an overview of the possibilities and limitations of organic surfaces exposed by Au-thiolate SAMs. Applications are as diverse as the metallization of organic surfaces, a fundamental problem in materials science, and the fabrication of surfaces that resist the adsorption of proteins. In addition to a number of different case studies, we will also discuss the most powerful analytical techniques needed to characterize these important model systems.

  3. Room-temperature molecular-resolution characterization of self-assembled organic monolayers on epitaxial graphene.

    Science.gov (United States)

    Wang, Qing Hua; Hersam, Mark C

    2009-06-01

    Graphene, a two-dimensional sheet of carbon atoms, is a promising material for next-generation technology because of its advantageous electronic properties, such as extremely high carrier mobilities. However, chemical functionalization schemes are needed to integrate graphene with the diverse range of materials required for device applications. In this paper, we report self-assembled monolayers of the molecular semiconductor perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) formed on epitaxial graphene grown on the SiC(0001) surface. The molecules possess long-range order with a herringbone arrangement, as shown by ultra-high vacuum scanning tunnelling microscopy at room temperature. The molecular ordering is unperturbed by defects in the epitaxial graphene or atomic steps in the underlying SiC surface. Scanning tunnelling spectra of the PTCDA monolayer show distinct features that are not observed on pristine graphene. The demonstration of robust, uniform organic functionalization of epitaxial graphene presents opportunities for graphene-based molecular electronics and sensors. PMID:21378849

  4. Manipulating the local light emission in organic light-emitting diodes by using patterned self-assembled monolayers

    NARCIS (Netherlands)

    Mathijssen, Simon G. J.; van Hal, Paul A.; van den Biggelaar, Ton J. M.; Smits, Edsger C. P.; de Boer, Bert; Kemerink, Martijn; Janssen, Rene A. J.; de Leeuw, Dago M.

    2008-01-01

    Patterned organic light-emitting diodes are fabricated by using microcontactDrinted self-assembled monolayers on a gold anode (see background figure). Molecules with dipole moments in opposite directions result in an increase or a decrease of the local work function (foreground picture), providing a

  5. Detection of Volatile Organic Compounds by Self-assembled Monolayer Coated Sensor Array with Concentration-independent Fingerprints

    Science.gov (United States)

    Chang, Ye; Tang, Ning; Qu, Hemi; Liu, Jing; Zhang, Daihua; Zhang, Hao; Pang, Wei; Duan, Xuexin

    2016-04-01

    In this paper, we have modeled and analyzed affinities and kinetics of volatile organic compounds (VOCs) adsorption (and desorption) on various surface chemical groups using multiple self-assembled monolayers (SAMs) functionalized film bulk acoustic resonator (FBAR) array. The high-frequency and micro-scale resonator provides improved sensitivity in the detections of VOCs at trace levels. With the study of affinities and kinetics, three concentration-independent intrinsic parameters (monolayer adsorption capacity, adsorption energy constant and desorption rate) of gas-surface interactions are obtained to contribute to a multi-parameter fingerprint library of VOC analytes. Effects of functional group’s properties on gas-surface interactions are also discussed. The proposed sensor array with concentration-independent fingerprint library shows potential as a portable electronic nose (e-nose) system for VOCs discrimination and gas-sensitive materials selections.

  6. Semiconductor monolayer assemblies with oriented crystal faces

    KAUST Repository

    Ma, Guijun

    2012-01-01

    Fabrication of two-dimensional monolayers of crystalline oxide and oxynitride particles was attempted on glass plate substrates. X-Ray diffraction patterns of the assemblies show only specific crystal facets, indicative of the uniform orientation of the particles on the substrate. The selectivity afforded by this immobilization technique enables the organization of randomly distributed polycrystalline powders in a controlled manner.

  7. Novel self-assembled phosphonic acids monolayers applied in N-channel perylene diimide (PDI) organic field effect transistors

    Science.gov (United States)

    Cheng, Heng; Huai, Jinyue; Cao, Li; Li, Zhefeng

    2016-08-01

    Phosphoric acid (PA) self-assembled monolayers (SAMs) have been developed for applications in organic field-effect transistors (OFETs). This efficient interface modification is helpful for semiconductor layer to form crystal thin film during vapor deposition. Results show that the PDI-i8C based OFETs with PA SAMs exhibit field-effect mobilities up to 0.014 cm2 V-1 s-1 (with ODPA as SAMs), which is over 500 times higher than the device without SAMs. Also, transistors with Naph6PA as SAMs show up to 1.5 × 10-3 cm2 V-1 s-1. By studying the morphology of semiconductor layer and SAMs surface, it is found that ODPA bilayer structure plays a key role in inducing PDI-i8C to form orderly crystal thin film.

  8. Enhancement of fill factor in air-processed inverted organic solar cells using self-assembled monolayer of fullerene catechol

    Science.gov (United States)

    Jeon, Il; Ogumi, Keisuke; Nakagawa, Takafumi; Matsuo, Yutaka

    2016-08-01

    [60]Fullerene catechol self-assembled monolayers were prepared and applied to inverted organic solar cells by an immersion method, and their energy conversion properties were measured. By introducing fullerenes at the surface, we improved the hole-blocking capability of electron-transporting metal oxide, as shown by the fill factor enhancement. The fullerene catechol-treated TiO x -containing device gave a power conversion efficiency (PCE) of 2.81% with a fill factor of 0.56 while the non treated device gave a PCE of 2.46% with a fill factor of 0.49. The solar cell efficiency improved by 13% compared with the non treated reference device.

  9. Seeding Atomic Layer Deposition of High-k Dielectrics on Epitaxial Graphene with Organic Self-assembled Monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Alaboson, Justice M. P.; Wang, Qing Hua; Emery, J.D.; Lipson, Albert L; Bedzyk, M.J.; Elam, Jeffrey W.; Pellin, Michael J.; Hersam, Mark C.

    2011-06-28

    The development of high-performance graphene-based nanoelectronics requires the integration of ultrathin and pinhole-free high-k dielectric films with graphene at the wafer scale. Here, we demonstrate that self-assembled monolayers of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) act as effective organic seeding layers for atomic layer deposition (ALD) of HfO₂ and Al₂O₃ on epitaxial graphene on SiC(0001). The PTCDA is deposited via sublimation in ultrahigh vacuum and shown to be highly ordered with low defect density by molecular-resolution scanning tunneling microscopy. Whereas identical ALD conditions lead to incomplete and rough dielectric deposition on bare graphene, the chemical functionality provided by the PTCDA seeding layer yields highly uniform and conformal films. The morphology and chemistry of the dielectric films are characterized by atomic force microscopy, ellipsometry, cross-sectional scanning electron microscopy, and X-ray photoelectron spectroscopy, while high-resolution X-ray reflectivity measurements indicate that the underlying graphene remains intact following ALD. Using the PTCDA seeding layer, metal-oxide-graphene capacitors fabricated with a 3 nm Al₂O₃ and 10 nm HfO₂ dielectric stack show high capacitance values of ~700 nF/cm² and low leakage currents of ~5 × 10{sup –9} A/cm² at 1 V applied bias. These results demonstrate the viability of sublimated organic self-assembled monolayers as seeding layers for high-k dielectric films in graphene-based nanoelectronics.

  10. Seeding atomic layer deposition of high-k dielectrics on epitaxial graphene with organic self-assembled monolayers.

    Science.gov (United States)

    Alaboson, Justice M P; Wang, Qing Hua; Emery, Jonathan D; Lipson, Albert L; Bedzyk, Michael J; Elam, Jeffrey W; Pellin, Michael J; Hersam, Mark C

    2011-06-28

    The development of high-performance graphene-based nanoelectronics requires the integration of ultrathin and pinhole-free high-k dielectric films with graphene at the wafer scale. Here, we demonstrate that self-assembled monolayers of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) act as effective organic seeding layers for atomic layer deposition (ALD) of HfO(2) and Al(2)O(3) on epitaxial graphene on SiC(0001). The PTCDA is deposited via sublimation in ultrahigh vacuum and shown to be highly ordered with low defect density by molecular-resolution scanning tunneling microscopy. Whereas identical ALD conditions lead to incomplete and rough dielectric deposition on bare graphene, the chemical functionality provided by the PTCDA seeding layer yields highly uniform and conformal films. The morphology and chemistry of the dielectric films are characterized by atomic force microscopy, ellipsometry, cross-sectional scanning electron microscopy, and X-ray photoelectron spectroscopy, while high-resolution X-ray reflectivity measurements indicate that the underlying graphene remains intact following ALD. Using the PTCDA seeding layer, metal-oxide-graphene capacitors fabricated with a 3 nm Al(2)O(3) and 10 nm HfO(2) dielectric stack show high capacitance values of ∼700 nF/cm(2) and low leakage currents of ∼5 × 10(-9) A/cm(2) at 1 V applied bias. These results demonstrate the viability of sublimated organic self-assembled monolayers as seeding layers for high-k dielectric films in graphene-based nanoelectronics. PMID:21553842

  11. Multifunctional self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Zawodzinski, T.; Bar, G.; Rubin, S.; Uribe, F. [Los Alamos National Lab., NM (United States); Ferrais, J. [Texas Univ., Dallas, TX (United States)

    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.

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

    OpenAIRE

    Malgorzata Adamkiewicz; David O’Hagan; Georg Hähner

    2014-01-01

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

  13. Preparation of TiO2 thin film by the LPD method on functionalized organic self-assembled monolayers

    Institute of Scientific and Technical Information of China (English)

    HE ZhongLiang; YU ZhiWei; MIAO HongYan; TAN GuoQiang; LIU Yan

    2009-01-01

    In this paper, uniform titania (TiO2) films have been formed at 50℃ on silanol SAMs by the liquid-phase deposition (LPD) method at a temperature below 100℃. OTS (Octadecyltrichloro-Silane) self-assembled monolayers (SAMs) on glass wafers were used as substrates for the deposition of titanium dioxide thin films. This functionalized organic surface has shown to be effective for promoting the growth of films from titanic aqueous solutions by the LPD method at a low temperature below 10012. The crystal phase composition, microstructure and topography of the as-prepared films were characterized by various techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The results indicate that the as-prepared thin films are purely crystallized anatase TiO2 constituted by nanorods after being annealed at 500℃. The pH values, concentration of reactants, and deposition temperatures play important roles in the growth of TiO2 thin films.

  14. Ionically self-assembled monolayers (ISAMs)

    Science.gov (United States)

    Janik, John

    2001-04-01

    Ionically self-assembled monolayers (ISAMs), fabricated by alternate adsorption of cationic and anionic components, yield exceptionally homogeneous thin films with sub-nanometer control of the thickness and relative special location of the component materials. Using organic electrochromic materials such as polyaniline, we report studies of electrochromic responses in ISAM films. Reversible changes in the absorption spectrum are observed with the application of voltages on the order of 1.0 V. Measurements are made using both liquid electrolytes and in all-solid state devices incorporating solid polyelectrolytes such as poly(2-acylamido 2-methyl propane sulfonic acid) (PAMPS).

  15. Organic semiconducting thin film growth on an organic substrate: 3,4,9,10-perylenetetracarboxylic dianhydride on a monolayer of decanethiol self-assembled on Au(111)

    International Nuclear Information System (INIS)

    We use surface x-ray diffraction to study the structure of organic-organic heterojunctions grown by organic molecular-beam deposition. In particular, we study films of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) grown on a decanethiol self-assembled monolayer (SAM) on a Au(111) surface. The deposition of several (≅16) monolayers of PTCDA results in unstrained crystalline films whose (012) lattice planes are rotated 21.6 degree sign with respect to the Au azimuthal direction. This alignment, which is different from that of PTCDA on the bare Au(111) surface, is most likely caused by the corrugation of the SAM surface [with the c(4x2) superlattice of the √(3)x√(3)R30 degree sign unit cell]. The SAM structure was found to be unaltered by the presence of the PTCDA overlayer. In addition, the heterogeneous PTCDA/SAM/Au structure, acting as an x-ray interferometer with the SAM as a spacer, allows for the precise determination of the SAM thickness. (c) 2000 The American Physical Society

  16. Improving the Performance of Organic Thin-Film Transistors by Ion Doping of Ethylene-Glycol-Based Self-Assembled Monolayer Hybrid Dielectrics.

    Science.gov (United States)

    Dietrich, Hanno; Scheiner, Simon; Portilla, Luis; Zahn, Dirk; Halik, Marcus

    2015-12-22

    Tuning the electrostatics of ethylene-glycol-based self-assembled monolayers (SAMs) by doping with ions is shown. Molecular dynamics simulations unravel binding mechanisms and predict dipole strengths of the doped layers. Additionally, by applying such layers as dielectrics in organic thin-film transistors, the incorporated ions are proven to enhance device performance by lowering the threshold voltage and increasing conductivity. PMID:26524344

  17. The Self-Assembly of Nano-Objects Code: Applications to supramolecular organic monolayers adsorbed on metal surfaces

    OpenAIRE

    Roussel, Thomas; Vega, Lourdes F.

    2012-01-01

    The Self-Assembly of Nano-Objects (SANO) code we implemented demonstrates the ability to predict the molecular self-assembly of different structural motifs by tuning the molecular building blocks as well as the metallic substrate. It consists in a two-dimensional Grand Canonical Monte-Carlo (GCMC) approach developed to perform atomistic simulations of thousands of large organic molecules self-assembling on metal surfaces. Computing adsorption isotherms at room temperature and spanning over th...

  18. Self-assembled monolayers formed on AZ31 Mg alloy

    Science.gov (United States)

    Salman, S. A.; Okido, M.

    2012-07-01

    Self-assembled monolayer (SAM) was successfully adsorbed on the AZ31 Mg alloy surface using oleic acid and stearic acid with various organic solvents, such as acetone, ethanol, and hexane. The surface monolayers were characterized using contact angle measurements, X-ray photoelectron spectroscopy (XPS) and anodic polarization test. It was shown that the higher contact angle and the best anti-corrosion property were obtained with treatment in oleic acid with ethanol solution.

  19. Formation of ultrasmooth and highly stable copper surfaces through annealing and self-assembly of organic monolayers.

    Science.gov (United States)

    Platzman, Ilia; Saguy, Cecile; Brener, Reuven; Tannenbaum, Rina; Haick, Hossam

    2010-01-01

    Copper (Cu) has been extensively used as an interconnect material for microelectronic devices because of its high electrical and thermal conductivity and excellent electromigration resistance. However, the formation of relatively rough Cu surfaces ( approximately 5 nm roughness) and Cu-oxide layers upon exposure to air still hinders their reliable application in a wide range of fields. In this article, we show the potential values of highly stable and ultrasmooth polycrystalline bare Cu obtained by simple annealing and chemical modification for a wide range of Cu-based electronic devices. The morphological properties and oxidation behavior of annealed Cu surfaces, before and after coating by self-assembled monolayers of terephthalic acid (TPA), were examined upon exposure to ambient air conditions ( approximately 110 days). Thin films of polycrystalline Cu, deposited on top of an adhesion layer of tantalum nitride (TaN) and annealed for 8 h at 580 degrees C under 2 x 10(-7) Torr, provided ultrasmooth Cu surfaces (R(rms) = 0.15-1.1 nm for fresh samples) and had a stable Cu-oxide layer after 65 days ( approximately 3.5 nm). These observations were perceived to be superior to nonannealed polycrystalline Cu samples. Coating fresh (oxide-free) samples of ultrasmooth Cu with TPA molecules created a closely packed monolayer with a standing-up phase configuration and molecular coverage of approximately 90%. The TPA-coated Cu surface has not shown any detectable oxidation during the first 2 weeks of exposure. The protection efficiency of this layer was found to be superior to those reported earlier on polycrystalline Cu surfaces. The oxidation mechanisms of both annealed and nonannealed Cu surfaces are presented and discussed. PMID:19715329

  20. The Self-Assembly of Nano-Objects Code: Applications to supramolecular organic monolayers adsorbed on metal surfaces

    CERN Document Server

    Roussel, Thomas

    2012-01-01

    The Self-Assembly of Nano-Objects (SANO) code we implemented demonstrates the ability to predict the molecular self-assembly of different structural motifs by tuning the molecular building blocks as well as the metallic substrate. It consists in a two-dimensional Grand Canonical Monte-Carlo (GCMC) approach developed to perform atomistic simulations of thousands of large organic molecules self-assembling on metal surfaces. Computing adsorption isotherms at room temperature and spanning over the characteristic sub-micrometric scales, we confront the robustness of the approach with three different well-known systems: ZnPcCl8 on Ag(111), CuPcF16 on Au(111) and PTBC on Ag(111). We retrieve respectively their square, oblique and hexagonal supramolecular tilling. The code incorporates generalized force fields to describe the molecular interactions, which provides transferability and versatility to many organic building blocks and metal surfaces.

  1. Self-Assembled Monolayers deposition in Supercritical Carbon Dioxide

    OpenAIRE

    Rabbia, Laurent; Perrut, Vincent; Pons, Patrick; Lellouchi, Djemel

    2009-01-01

    Self-Assembled Monolayers of organic molecules have been successfully deposited onto wafer surface in supercritical carbon dioxide. Deposition method and apparatus are described. The layers are characterized by AFM and water droplet contact angle. Interest of this technique compared to liquid and vapor phase is discussed and studied for surface conversion from hydrophilic to hydrophobic for different materials.

  2. Phosphonate self-assembled monolayers as organic linkers in solid-state quantum dot sensetized solar cells

    KAUST Repository

    Ardalan, Pendar

    2010-06-01

    We have employed X-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-vis) spectroscopy, infrared (IR) spectroscopy, water contact angle (WCA) measurements, ellipsometry, and electrical measurements to study the effects of self-assembled monolayers (SAMs) with phosphonic acid headgroups on the bonding and performance of cadmium sulfide (CdS) solid-state quantum dot sensitized solar cells (QDSSCs). ∼2 to ∼6 nm size CdS quantum dots (QDs) were grown on the SAM-passivated TiO2 surfaces by successive ionic layer adsorption and reaction (SILAR). Our results show differences in the bonding of the CdS QDs at the TiO2 surfaces with a SAM linker. Moreover, our data indicate that presence of a SAM increases the CdS uptake on TiO2 as well as the performance of the resulting devices. Importantly, we observe ∼2 times higher power conversion efficiencies in the devices with a SAM compared to those that lack a SAM. © 2010 IEEE.

  3. Probing the initial stages of molecular organization of oligo(p-phenylenevinylene) assemblies with monolayer protected gold nanoparticles.

    Science.gov (United States)

    Kumar, Vattakattu R Rajeev; Sajini, Vadukumpulli; Sreeprasad, Theruvakkattil S; Praveen, Vakayil K; Ajayaghosh, Ayyappanpillai; Pradeep, Thalappil

    2009-06-01

    Thiol-protected gold nanoparticles (GNPs) have been used to probe the initial stages of the molecular organization of oligo(p-phenylenevinylene) (OPV) gelators. The hybrid materials prepared by the self-assembly of OPVs and GNPs are characterized by optical microscopy, fluorescence microscopy, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. GNPs are located preferentially on the sides of the OPV structures, which implies the presence of alkyl chains at the edges, which makes the assemblies hydrophobic. TEM analyses at the early stages of self-assembly show tapes that have a width of 4 nm, which upon further self-assembly, form fibrils through hydrogen bonding. The experiment was performed with GNPs protected with dodecane and octadecane thiols. The existence of tapes, ribbons, fibrils, and fibers were confirmed by nanoparticle marking. Based on the experimental data, we have proposed a hierarchical model for the self-assembly of OPV molecules. The presence of nanoparticles does not alter the morphology or electronic properties of the OPV structures, as revealed by microscopic and spectroscopic studies. PMID:19462383

  4. Site-selective growth of surface-anchored metal-organic frameworks on self-assembled monolayer patterns prepared by AFM nanografting

    Directory of Open Access Journals (Sweden)

    Tatjana Ladnorg

    2013-10-01

    Full Text Available Surface anchored metal-organic frameworks, SURMOFs, are highly porous materials, which can be grown on modified substrates as highly oriented, crystalline coatings by a quasi-epitaxial layer-by-layer method (liquid-phase epitaxy, or LPE. The chemical termination of the supporting substrate is crucial, because the most convenient method for substrate modification is the formation of a suitable self-assembled monolayer. The choice of a particular SAM also allows for control over the orientation of the SURMOF. Here, we demonstrate for the first time the site-selective growth of the SURMOF HKUST-1 on thiol-based self-assembled monolayers patterned by the nanografting technique, with an atomic force microscope as a structuring tool. Two different approaches were applied: The first one is based on 3-mercaptopropionic acid molecules which are grafted in a 1-decanethiolate SAM, which serves as a matrix for this nanolithography. The second approach uses 16-mercaptohexadecanoic acid, which is grafted in a matrix of an 1-octadecanethiolate SAM. In both cases a site-selective growth of the SURMOF is observed. In the latter case the roughness of the HKUST-1 is found to be significantly higher than for the 1-mercaptopropionic acid. The successful grafting process was verified by time-of-flight secondary ion mass spectrometry and atomic force microscopy. The SURMOF structures grown via LPE were investigated and characterized by atomic force microscopy and Fourier-transform infrared microscopy.

  5. Hybrid nanostructures of well-organized arrays of colloidal quantum dots and a self-assembled monolayer of gold nanoparticles for enhanced fluorescence.

    Science.gov (United States)

    Liu, Xiaoying; McBride, Sean P; Jaeger, Heinrich M; Nealey, Paul F

    2016-07-15

    Hybrid nanomaterials comprised of well-organized arrays of colloidal semiconductor quantum dots (QDs) in close proximity to metal nanoparticles (NPs) represent an appealing system for high-performance, spectrum-tunable photon sources with controlled photoluminescence. Experimental realization of such materials requires well-defined QD arrays and precisely controlled QD-metal interspacing. This long-standing challenge is tackled through a strategy that synergistically combines lateral confinement and vertical stacking. Lithographically generated nanoscale patterns with tailored surface chemistry confine the QDs into well-organized arrays with high selectivity through chemical pattern directed assembly, while subsequent coating with a monolayer of close-packed Au NPs introduces the plasmonic component for fluorescence enhancement. The results show uniform fluorescence emission in large-area ordered arrays for the fabricated QD structures and demonstrate five-fold fluorescence amplification for red, yellow, and green QDs in the presence of the Au NP monolayer. Encapsulation of QDs with a silica shell is shown to extend the design space for reliable QD/metal coupling with stronger enhancement of 11 times through the tuning of QD-metal spatial separation. This approach provides new opportunities for designing hybrid nanomaterials with tailored array structures and multiple functionalities for applications such as multiplexed optical coding, color display, and quantum transduction. PMID:27251019

  6. Hybrid nanostructures of well-organized arrays of colloidal quantum dots and a self-assembled monolayer of gold nanoparticles for enhanced fluorescence

    Science.gov (United States)

    Liu, Xiaoying; McBride, Sean P.; Jaeger, Heinrich M.; Nealey, Paul F.

    2016-07-01

    Hybrid nanomaterials comprised of well-organized arrays of colloidal semiconductor quantum dots (QDs) in close proximity to metal nanoparticles (NPs) represent an appealing system for high-performance, spectrum-tunable photon sources with controlled photoluminescence. Experimental realization of such materials requires well-defined QD arrays and precisely controlled QD–metal interspacing. This long-standing challenge is tackled through a strategy that synergistically combines lateral confinement and vertical stacking. Lithographically generated nanoscale patterns with tailored surface chemistry confine the QDs into well-organized arrays with high selectivity through chemical pattern directed assembly, while subsequent coating with a monolayer of close-packed Au NPs introduces the plasmonic component for fluorescence enhancement. The results show uniform fluorescence emission in large-area ordered arrays for the fabricated QD structures and demonstrate five-fold fluorescence amplification for red, yellow, and green QDs in the presence of the Au NP monolayer. Encapsulation of QDs with a silica shell is shown to extend the design space for reliable QD/metal coupling with stronger enhancement of 11 times through the tuning of QD–metal spatial separation. This approach provides new opportunities for designing hybrid nanomaterials with tailored array structures and multiple functionalities for applications such as multiplexed optical coding, color display, and quantum transduction.

  7. Preparation of TiO2 thin film by the LPD method on functionalized organic self-assembled monolayers

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    In this paper, uniform titania (TiO2) films have been formed at 50℃ on silanol SAMs by the liquid-phase deposition (LPD) method at a temperature below 100℃. OTS (Octadecyltrichloro-Silane) selfassembled monolayers (SAMs) on glass wafers were used as substrates for the deposition of titanium dioxide thin films. This functionalized organic surface has shown to be effective for promoting the growth of films from titanic aqueous solutions by the LPD method at a low temperature below 100℃. The crystal phase composition, microstructure and topography of the as-prepared films were characterized by various techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The results indicate that the as-prepared thin films are purely crystallized anatase TiO2 constituted by nanorods after being annealed at 500℃. The pH values, concentration of reactants, and deposition temperatures play important roles in the growth of TiO2 thin films.

  8. Single photon ionisation of self assembled monolayers

    Science.gov (United States)

    King, B. V.; Savina, M. R.; Tripa, C. E.; Calaway, W. F.; Veryovkin, I. V.; Moore, J. F.; Pellin, M. J.

    2002-05-01

    Self assembled monolayers formed from benzenethiol, diphenylsulphide and diphenyldisulphide have been analysed using secondary ion mass spectrometry (SIMS), sputter neutral mass spectrometry (SNMS) and laser desorption photoionisation mass spectrometry (LDPI). The peak corresponding to the parent ion was much stronger in LDPI than with SIMS or SNMS analysis and fragmentation was lower. A useful yield of order 0.5% was obtained for LDPI from diphenyldisulphide.

  9. Single photon ionisation of self assembled monolayers

    International Nuclear Information System (INIS)

    Self assembled monolayers formed from benzenethiol, diphenylsulphide and diphenyldisulphide have been analysed using secondary ion mass spectrometry (SIMS), sputter neutral mass spectrometry (SNMS) and laser desorption photoionisation mass spectrometry (LDPI). The peak corresponding to the parent ion was much stronger in LDPI than with SIMS or SNMS analysis and fragmentation was lower. A useful yield of order 0.5% was obtained for LDPI from diphenyldisulphide

  10. Enhancement of the Luminance Efficiency in Organic Light-Emitting Devices with p-Substituted Phenylphosphonic-Acid Self-Assembled Monolayers.

    Science.gov (United States)

    Kim, Min Sung; Jeon, Young Pyo; Kim, Youngwoo; Noh, Jaegeun; Kim, Tae Whan

    2015-07-01

    Organic light-emitting devices (OLEDs) containing self-assembled monolayers (SAMs) prepared by using p-substituted phenylphosponic acids on indium-tin-oxide electrodes were fabricated and examined to understand the substituent effect of the SAMs on the device performance. OLEDs modified by using (4-methoxyphenyl)phosphonic acid (MOPPA) SAMs or (4-chlorophenyl)phosphonic acid (CPPA) SAMs, both with electron withdrawing groups, had enhanced hole injection, reduced operating voltage, and remarkably increased current density and luminance efficiency compared with those without SAMs. The luminance efficiency which was the ratio of luminous flux to power for OLEDs containing CPPA SAMs and that for the OLEDs containing MOPPA SAMs were enhanced 2.2 and 1.9 times, respectively, in comparison with that of OLEDs without SAMs. CPPA SAMs significantly reduced the operating voltage of OLED by 24.8% compared with OLEDs without SAMs. PMID:26373078

  11. Topographies of Organized Monolayer of α-Amylase Observed by Atomic Force Microscopy

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In this paper, a-amylase organized monolayer was assembled on the surface of the PET-CO2- substrate in different conditions. The different topography of the a-amylase/PET monolayer was obtained by AFM in tapping mode.

  12. Fabrication of self-assembled microsphere monolayers

    Czech Academy of Sciences Publication Activity Database

    Domonkos, Mária; Ižák, Tibor; Kromka, Alexander

    Bratislava: Slovenská vákuová spoločnosť, 2014 - (Michalka, M.; Vincze, A.; Veselý, M.), s. 125-128 ISBN 978-80-971179-4-8. [School of Vacuum Technology /17./. Štrbské Pleso (SK), 02.10.2014-05.10.2014] R&D Projects: GA ČR(CZ) GBP108/12/G108 Institutional support: RVO:68378271 Keywords : self-assembly * monolayer * microspheres * spin-coating Subject RIV: BM - Solid Matter Physics ; Magnetism

  13. Threshold-Voltage Shifts in Organic Transistors Due to Self-Assembled Monolayers at the Dielectric: Evidence for Electronic Coupling and Dipolar Effects.

    Science.gov (United States)

    Aghamohammadi, Mahdieh; Rödel, Reinhold; Zschieschang, Ute; Ocal, Carmen; Boschker, Hans; Weitz, R Thomas; Barrena, Esther; Klauk, Hagen

    2015-10-21

    The mechanisms behind the threshold-voltage shift in organic transistors due to functionalizing of the gate dielectric with self-assembled monolayers (SAMs) are still under debate. We address the mechanisms by which SAMs determine the threshold voltage, by analyzing whether the threshold voltage depends on the gate-dielectric capacitance. We have investigated transistors based on five oxide thicknesses and two SAMs with rather diverse chemical properties, using the benchmark organic semiconductor dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene. Unlike several previous studies, we have found that the dependence of the threshold voltage on the gate-dielectric capacitance is completely different for the two SAMs. In transistors with an alkyl SAM, the threshold voltage does not depend on the gate-dielectric capacitance and is determined mainly by the dipolar character of the SAM, whereas in transistors with a fluoroalkyl SAM the threshold voltages exhibit a linear dependence on the inverse of the gate-dielectric capacitance. Kelvin probe force microscopy measurements indicate this behavior is attributed to an electronic coupling between the fluoroalkyl SAM and the organic semiconductor. PMID:26415103

  14. On the relationship between the structure of self-assembled carboxylic acid monolayers on alumina and the organization and electrical properties of a pentacene thin film

    Science.gov (United States)

    Lang, Philippe; Mottaghi, Daniel; Lacaze, Pierre-Camille

    2016-03-01

    The modification of insulating surfaces by self-assembled monolayers (SAMs) is an elegant way of tailoring the gate dielectric of organic field effect transistors (OFET) to pentacene and is commonly used to improve electrical performance. A SAM based on an alkylcarboxylic acid deposited on a thin layer of alumina, serving as the gate dielectric is considered. The relationship between carrier mobility and (i) the length of the carboxylic acid (CH3(CH2)nCOOH; n = 9, 14, 18), (ii) substrate preparation and (iii) the SAM and pentacene thin film structures is considered. The size and boundaries of pentacene grains are not limiting factors for carrier mobility, and the most relevant parameter, which depends on whether there is a SAM or not, is the organization of the first pentacene layers in contact with the gate dielectric. The variation of the interplanar distance d(0 0 1) of the pentacene layers close to the alumina surface is much greater without SAM than with, and this could explain the lower carrier mobility observed in the case of a bare alumina dielectric. The relationship between the disorder associated with this variation and mobility is discussed.

  15. Patterning Self-Assembled Monolayers on Gold: Green Materials Chemistry in the Teaching Laboratory

    Science.gov (United States)

    McFarland, Adam D.; Huffman, Lauren M.; Parent, Kathryn, E.; Hutchison, James E.; Thompson, John E.

    2004-01-01

    An experiment demonstrating self-assembled monolayer (SAM) chemistry, organic thin-film patterning and the use of molecular functionality to control macroscopic properties is described. Several important green chemistry principles are introduced.

  16. Nonlinear Optically Active Ionically Self-Assembled Monolayer Thin Films of Organic Polymers Intercalated with an Inorganic Hectorite, Laponite RD

    OpenAIRE

    Shah, Smital S

    2002-01-01

    Detailed studies are presented of thin films containing a polycation, a nonlinear optically (NLO) active chromophore, and a synthetic hectorite that self-assemble into the noncentrosymmetric structure required for second order nonlinear optical responses. UV/Vis spectroscopy and ellipsometry were used as probes to monitor film growth for upto 25 deposition cycles. Exceptionally homogeneous films were obtained with regular film growth for up to the 25 cycles deposited. ISAM films self-ass...

  17. Electronic properties of organic monolayers and molecular devices

    Indian Academy of Sciences (India)

    D Vuillaume; S Lenfant; D Guerin; C Delerue; C Petit; G Salace

    2006-07-01

    We review some of our recent experimental results on charge transport in organic nanostructures such as self-assembled monolayer and monolayers of organic semiconductors. We describe a molecular rectifying junction made from a sequential self-assembly on silicon. These devices exhibit a marked current–voltage rectification behavior due to resonant transport between the Si conduction band and the molecule highest occupied molecular orbital of the molecule. We discuss the role of metal Fermi level pinning in the current–voltage behavior of these molecular junctions. We also discuss some recent insights on the inelastic electron tunneling behavior of Si/alkyl chain/metal junctions.

  18. Study of Fused Thiophene Based Organic Semiconductors and Interfacial Self-Assembled Monolayer (SAM) for Thin-Film Transistor (TFT) Application

    Science.gov (United States)

    Youn, Jangdae

    In this thesis, the molecular packing motifs of our newly designed fused thiophenes, benzo[d,d]thieno[3,2-b;4,5-b]dithiophene (BTDT) derivatives, were studied by utilizing grazing incidence wide angle X-ray scattering (GIWAXS). Considering the potential of fused thiophene molecules as an environmentally stable, high performance semiconductor building block, it must be an important groundwork to investigate their thin film structures in relation to molecular structures, single crystal structures, and organic thin-film transistors (OTFT) performances. OTFT device performance is not only determined by semiconductor materials, but also influenced by the interfacial properties. Since there are three major components in TFT structures---electrodes, semiconductors, and dielectrics, two types of major interfaces exist. One is the semiconductor-electrode interface, and the other is the semiconductor-dielectric interface. Both of these interfaces have critical roles for TFT operation. For example, the semiconductor-electrode interface determines the charge injection barrier. Before charge carriers go through the electrode (source)-semiconductor-electrode (drain) pathways, the energy gaps between the work function of the electrodes and the HOMO energy of the semiconductor materials must be overcome for hole injection, or the energy gap between the metal work function of the electrodes and the LUMO energy of the semiconductor materials must be overcome for electron injection. These charge injection barriers are largely determined by the energetic structure of the semiconductor material and work function of the electrode. However, the size of energy gap can be modified by introducing an organic self-assembled monolayer (SAM) on the surface of metal electrode. In addition, the structure of semiconductor films, especially within several monolayers right above the electrode, is greatly influenced by the SAM, and it changes charge injection property of OTFT devices. In this thesis

  19. Applications of self-assembled monolayers in materials chemistry

    Indian Academy of Sciences (India)

    Nirmalya K Chaki; M Aslam; Jadab Sharma; K Vijayamohanan

    2001-10-01

    Self-assembly provides a simple route to organise suitable organic molecules on noble metal and selected nanocluster surfaces by using monolayers of long chain organic molecules with various functionalities like -SH, -COOH, -NH2, silanes etc. These surfaces can be effectively used to build-up interesting nano level architectures. Flexibility with respect to the terminal functionalities of the organic molecules allows the control of the hydrophobicity or hydrophilicity of metal surface, while the selection of length scale can be used to tune the distant-dependent electron transfer behaviour. Organo-inorganic materials tailored in this fashion are extremely important in nanotechnology to construct nanoelctronic devices, sensor arrays, supercapacitors, catalysts, rechargeable power sources etc. by virtue of their size and shape-dependent electrical, optical or magnetic properties. The interesting applications of monolayers and monolayer-protected clusters in materials chemistry are discussed using recent examples of size and shape control of the properties of several metallic and semiconducting nanoparticles. The potential benefits of using these nanostructured systems for molecular electronic components are illustrated using Au and Ag nanoclusters with suitable bifunctional SAMs.

  20. Crossbar nanoarchitectonics of the crosslinked self-assembled monolayer

    OpenAIRE

    Hamoudi, Hicham

    2014-01-01

    A bottom-up approach was devised to build a crossbar device using the crosslinked SAM of the 5,5′-bis (mercaptomethyl)-2,2′-bipyridine-Ni2+ (BPD- Ni2+) on a gold surface. To avoid metal diffusion through the organic film, the author used (i) nanoscale bottom electrodes to reduce the probability of defects on the bottom electrodes and (ii) molecular crosslinked technology to avoid metal diffusion through the SAMs. The properties of the crosslinked self-assembled monolayer were determined by XP...

  1. Selective electroless copper deposition on self-assembled dithiol monolayers.

    Science.gov (United States)

    Aldakov, Dmitry; Bonnassieux, Yvan; Geffroy, Bernard; Palacin, Serge

    2009-03-01

    The paper reports the use of self-assembled monolayers (SAMs) of dithiols to induce electroless copper deposition on a gold substrate. The metallization catalyst, palladium nanoparticles, is bound on the dithiol SAM. The assembly process is followed by IR and X-ray photoelectron spectroscopies to confirm the formation of a monolayer with bound catalyst. Electroless metallization is then carried out with a steady deposition rate of 130 nm/min. Additionally, microcontact printing of the catalyst on the SAM by poly(dimethylsiloxane) stamps is used to localize copper deposits. Resulting metallization is selective and allows for a high resolution. PMID:20355979

  2. Assembly of citrate gold nanoparticles on hydrophilic monolayers

    Science.gov (United States)

    Vikholm-Lundin, Inger; Rosqvist, Emil; Ihalainen, Petri; Munter, Tony; Honkimaa, Anni; Marjomäki, Varpu; Albers, Willem M.; Peltonen, Jouko

    2016-08-01

    Self-assembled monolayers (SAMs) as model surfaces were linked onto planar gold films thorough lipoic acid or disulfide groups. The molecules used were polyethylene glycol (EG-S-S), N-[tris-(hydroxymethyl)methyl]acrylamide polymers with and without lipoic acid (Lipa-pTHMMAA and pTHMMAA) and a lipoic acid triazine derivative (Lipa-MF). All the layers, but Lipa-MF with a primary amino group were hydroxyl terminated. The layers were characterized by contact angle measurements and atomic force microscopy, AFM. Citrate stabilized nanoparticles, AuNPs in water and phosphate buffer were allowed to assemble on the layers for 10 min and the binding was followed in real-time with surface plasmon resonance, SPR. The SPR resonance curves were observed to shift to higher angles and become increasingly damped, while also the peaks strongly broaden when large nanoparticles assembled on the surface. Both the angular shift and the damping of the curve was largest for nanoparticles assembling on the EG-S-S monolayer. High amounts of particles were also assembled on the pTHMMAA layer without the lipoic acid group, but the damping of the curve was considerably lower with a more even distribution of the particles. Topographical images confirmed that the highest number of particles were assembled on the polyethylene glycol monolayer. By increasing the interaction time more particles could be assembled on the surface.

  3. Tribological properties of OTS self-assembled monolayers

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Octadecyltrichlorosilane (OTS) self-assembled monolayers (SAMs)were prepared on the substrates of silicon and glass. The tribological properties were tested with a self-made point-contact pure sliding micro tribometer. The effect of humidity on the tribological properties of both OTS SAMs and the naked substrates were studied. When the substrate is covered by OTS monolayer, the friction coefficient is reduced from 0.5 to 0.1 and the stick-slip phenomenon is weakened. OTS monolayer can keep its friction coefficient steady in a wide range of humidity, because it is highly hydrophobic and thus not sensitive to humidity. In addition, the OTS monolayer has a considerable anti-wear ability.

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

    Science.gov (United States)

    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. PMID:26844645

  5. Template-Directed Self-Assembly of Alkanethiol Monolayers: Selective Growth on Preexisting Monolayer Edges

    NARCIS (Netherlands)

    Sharpe, Ruben B.A.; Burdinski, Dirk; Huskens, Jurriaan; Zandvliet, Harold J.W.; Reinhoudt, David N.; Poelsema, Bene

    2007-01-01

    Self-assembled monolayers were investigated for their suitability as two-dimensional scaffolds for the selective growth of alkanethiol edge structures. Heterostructures with chemical contrast could be grown, whose dimensions were governed by both the initial pattern sizes and the process time. n-Oct

  6. Antifouling Self-assembled Monolayers on Microelectrodes for Patterning Biomolecules

    OpenAIRE

    Noel, John; Teizer, Winfried; Hwang, Wonmuk

    2009-01-01

    We present a procedure for forming a poly(ethylene glycol) (PEG) trimethoxysilane self-assembled monolayer (SAM) on a silicon substrate with gold microelectrodes. The PEG-SAM is formed in a single assembly step and prevents biofouling on silicon and gold surfaces. The SAM is used to coat microelectrodes patterned with standard, positive-tone lithography. Using the microtubule as an example, we apply a DC voltage to induce electrophoretic migration to the SAM-coated electrode in a reversible m...

  7. STRUCTURE DEPENDENT IRRADIATON-INDUCED DESORPTION OF BIPHENYL ALKANETHIOL SELF-ASSEMBLED MONOLAYERS

    OpenAIRE

    Wyczawska, Sabina; Lievens, Peter; Silverans, Roger

    2006-01-01

    1. INTRODUCTION Many nanotechnological applications rely on the patterned functionalization of surfaces with complex organic molecules. In this context, self-assembled monolayers (SAMs) play an important role [ ]. SAMs are spontaneously formed highly ordered and oriented molecular assemblies on a solid substrate. Although most of the insight has been compiled for relatively simple alkanethiol model systems, SAMs containing aromatic structures are gaining much attention lately. They are...

  8. Actinide sequestration using self-assembled monolayers on mesoporous supports.

    Science.gov (United States)

    Fryxell, Glen E; Lin, Yuehe; Fiskum, Sandy; Birnbaum, Jerome C; Wu, Hong; Kemner, Ken; Kelly, Shelley

    2005-03-01

    Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometalate anions, and radionuclides. Details addressing the design, synthesis, and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental cleanup necessary after 40 years of weapons-grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented. PMID:15787373

  9. Self assembled monolayers of octadecyltrichlorosilane for dielectric materials

    Science.gov (United States)

    Kumar, Vijay; Puri, Paridhi; Nain, Shivani; Bhat, K. N.; Sharma, N. N.

    2016-04-01

    Treatment of surfaces to change the interaction of fluids with them is a critical step in constructing useful microfluidics devices, especially those used in biological applications. Selective modification of inorganic materials such as Si, SiO2 and Si3N4 is of great interest in research and technology. We evaluated the chemical formation of OTS self-assembled monolayers on silicon substrates with different dielectric materials. Our investigations were focused on surface modification of formerly used common dielectric materials SiO2, Si3N4 and a-poly. The improvement of wetting behaviour and quality of monolayer films were characterized using Atomic force microscope, Scanning electron microscope, Contact angle goniometer, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) monolayer deposited oxide surface.

  10. Semiconductor nanocrystals covalently bound to solid inorganic surfaces using self-assembled monolayers

    Science.gov (United States)

    Alivisatos, A. Paul; Colvin, Vicki L.

    1998-01-01

    Methods are described for attaching semiconductor nanocrystals to solid inorganic surfaces, using self-assembled bifunctional organic monolayers as bridge compounds. Two different techniques are presented. One relies on the formation of self-assembled monolayers on these surfaces. When exposed to solutions of nanocrystals, these bridge compounds bind the crystals and anchor them to the surface. The second technique attaches nanocrystals already coated with bridge compounds to the surfaces. Analyses indicate the presence of quantum confined clusters on the surfaces at the nanolayer level. These materials allow electron spectroscopies to be completed on condensed phase clusters, and represent a first step towards synthesis of an organized assembly of clusters. These new products are also disclosed.

  11. Microcontact printing of self-assembled monolayers: applications in microfabrication

    Science.gov (United States)

    Wilbur, James L.; Kumar, Amit; Biebuyck, Hans A.; Kim, Enoch; Whitesides, George M.

    1996-12-01

    This paper describes applications in microfabrication using patterned self-assembled monolayers (SAMs) formed by microcontact printing. Microcontact printing 0957-4484/7/4/028/img1 is a flexible new technique that forms patterned SAMs with regions terminated by different chemical functionalities (and thus different physical and chemical properties), in patterns with 0957-4484/7/4/028/img2 dimensions. Patterns of SAM are formed using an alkanethiol as an `ink', and printing the alkanethiol on a metal support with elastomeric `stamp'. We fabricate the stamp by moulding a silicone elastomer using a master prepared by optical or x-ray microlithography or by other techniques. SAMs of long-chain alkanethiolates on gold and other metals can act as nanometer resists by protecting the supporting metal from corrosion by appropriately formulated etchants: the fabrication of microstructures of gold and silicon demonstrates the utility of patterned SAMs (formed by 0957-4484/7/4/028/img3) as nm resists. Patterned SAMs formed by 0957-4484/7/4/028/img3 can also control the wettability of a surface on the 0957-4484/7/4/028/img2 scale. The organization of liquids in patterned arrays with 0957-4484/7/4/028/img2 dimensions, and the patterned deposition of microcrystals and microcrystal arrays illustrate the use of controlled wettability for microfabrication.

  12. Tailoring self-assembled monolayers at the electrochemical interface

    Indian Academy of Sciences (India)

    S Varatharajan; Sheela Berchmans; V Yegnaraman

    2009-09-01

    The main focus of this review is to illustrate the amenability of self-assembled monolayers (SAMs) for functionalisation with different receptors, catalytic materials, biomolecules, enzymes, antigen-antibody, etc for various applications. The review discusses initially about the preparation and characterization of SAMs and tailoring of SAMs by incorporation of suitable recognition elements. A description of how the molecular recognition is achieved through forces like electrostatic, covalent and host-guest interactions is included in the review.

  13. Self Assembled Monolayers for Quartz Crystal Microbalance based Biosensing

    OpenAIRE

    Myrskog, Annica

    2009-01-01

    The work in this thesis has been focused on developing surfaces for use in biosensor systems, especially for quartz crystal microbalances. The surfaces were prepared by adsorption of organosulfur molecules onto gold substrates, so called self assembled monolayers (SAMs). By chemical synthesis these thiols can be specifically tailored to provide surfaces with desired properties. The investigated surfaces were all based on thiols terminated with carboxylic acid groups to render hydrophilic surf...

  14. Permethylated 12-Vertex p-Carborane Self-Assembled Monolayers

    Czech Academy of Sciences Publication Activity Database

    Scholz, F.; Nothofer, H. G.; Wessels, J. M.; Nelles, G.; Wrochem von, F.; Roy, S.; Chen, X.; Michl, Josef

    2011-01-01

    Roč. 115, č. 46 (2011), s. 22998-23007. ISSN 1932-7447 Grant ostatní: National Science Foundation(US) CHE-0848477 Institutional research plan: CEZ:AV0Z40550506 Keywords : p-carbone * monolayer * scanning tunneling microscopy * ultraviolet photoelectron spectroscopy * X-ray photoelectron Subject RIV: CC - Organic Chemistry Impact factor: 4.805, year: 2011

  15. Organic Monolayer Protected Topological Surface State.

    Science.gov (United States)

    Yang, Hung-Hsiang; Chu, Yu-Hsun; Lu, Chun-I; Butler, Christopher John; Sankar, Raman; Chou, Fang-Cheng; Lin, Minn-Tsong

    2015-10-14

    Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA)/Bi2Se3 and Fe/PTCDA/Bi2Se3 heterointerfaces are investigated using scanning tunneling microscopy and spectroscopy. The close-packed self-assembled PTCDA monolayer possesses big molecular band gap and weak molecule-substrate interactions, which leaves the Bi2Se3 topological surface state intact under PTCDA. Formation of Fe-PTCDA hybrids removes interactions between the Fe dopant and the Bi2Se3 surface, such as doping effects and Coulomb scattering. Our findings reveal the functionality of PTCDA to prevent dopant disturbances in the TSS and provide an effective alternative for interface designs of realistic TI devices. PMID:26393876

  16. Self-assembling monolayers of helical oligopeptides with applications in molecular electronics

    International Nuclear Information System (INIS)

    The aim of this project was to develop a generic method of preparing a 'molecular architecture' containing functional groups on a surface at predetermined relative positions several nm apart. This would be of great utility in molecular electronics, chemical sensors and other fields. It was proposed that such an architecture could be prepared on gold using linked, helical oligopeptides that contained the components of interest and sulphur functions able to form monolayers on gold by the self-assembly technique. Towards this ultimate aim Self-Assembled Monolayers (SAMs) of monomeric oligopeptides (13-17 residues) were prepared and characterised. Peptides containing three Met residues spaced in the sequence so that their side-chains lay on the same side of the helix were shown by circular dichroism (CD) to be strongly helical in organic solvents. Their self-assembled films on gold were characterised by Reflection-Absorption Infrared Spectroscopy (RAIRS) which showed the peptides adsorbed with the helix axes parallel to the surface, the orientation expected for self-assembly. However the surface coverage measured by cyclic voltammetry (CV) of the peptides' ferrocenyl derivatives on gold electrodes were less than expected for monolayers. Comparison of the films of ferrocenyl derivatives of Met and Cys showed that the thiolate bound more strongly than the thioether. Accordingly an oligopeptide containing two Cys residues at i, i+3, designed to be 310-helical, was prepared. Transformation of the two (Trt)Cys residues of the resin-bound peptide to the intramolecular disulphide by iodine was achieved in acetonitrile but not in DMF. CD suggested that the conformation of this peptide was a mixture of helix and random coil. Films of the peptide-disulphide and the peptide-dithiol adsorbed from protic solvents were characterised as multilayers by ellipsometry. However CV and ellipsometry showed that a monolayer was successfully prepared from acetonitrile. Future targets for

  17. Lipid dip-pen nanolithography on self-assembled monolayers

    Science.gov (United States)

    Gavutis, Martynas; Navikas, Vytautas; Rakickas, Tomas; Vaitekonis, Šarūnas; Valiokas, Ramūnas

    2016-02-01

    Dip-pen nanolithography (DPN) with lipids as an ink enables functional micro/nanopatterning on different substrates at high process speeds. However, only a few studies have addressed the influence of the physicochemical properties of the surface on the structure and phase behavior of DPN-printed lipid assemblies. Therefore, by combining the scanning probe and optical imaging techniques in this work we have analyzed lipid microdomain formation on the self-assembled monolayers (SAMs) on gold as well-defined model surfaces that displayed hydrophilic (protein-repellent) or hydrophobic (protein-adhesive) characteristics. We have found that on the tri(ethylene glycol)-terminated SAM the lipid ink transfer was fast (~10-1 μm3 s-1), quasi-linear and it yielded unstable, sparsely packed lipid microspots. Contrary to this, on the methyl-terminated SAM the lipid transfer was ~20 times slower, nonlinear, and the obtained stable dots of ~1 μm in diameter consisted of lipid multilayers. Our comparative analysis indicated that the measured lipid transfer was consistent with the previously reported so-called polymer transfer model (Felts et al 2012, Nanotechnology 23 215301). Further on, by employing the observed distinct contrast in the DPN ink behavior we constructed confined lipid microdomains on pre-patterned SAMs, in which the lipids assembled either into monolayer or multilamellar phases. Such microdomains can be further utilized for lipid membrane mimetics in microarray and lab-on-a-chip device formats.

  18. Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers

    Science.gov (United States)

    Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; Kim, Yi-Yeoun; Schenk, Anna S.; Kulak, Alexander N.; Comyn, Timothy P.; Chammas, Oliver; Harder, Ross J.; Duffy, Dorothy M.; Robinson, Ian K.; Meldrum, Fiona C.

    2016-06-01

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates.

  19. Antifouling self-assembled monolayers on microelectrodes for patterning biomolecules.

    Science.gov (United States)

    Noel, John; Teizer, Winfried; Hwang, Wonmuk

    2009-01-01

    We present a procedure for forming a poly(ethylene glycol) (PEG) trimethoxysilane self-assembled monolayer (SAM) on a silicon substrate with gold microelectrodes. The PEG-SAM is formed in a single assembly step and prevents biofouling on silicon and gold surfaces. The SAM is used to coat microelectrodes patterned with standard, positive-tone lithography. Using the microtubule as an example, we apply a DC voltage to induce electrophoretic migration to the SAM-coated electrode in a reversible manner. A flow chamber is used for imaging the electrophoretic migration and microtubule patterning in situ using epifluorescence microscopy. This method is generally applicable to biomolecule patterning, as it employs electrophoresis to immobilize target molecules and thus does not require specific molecular interactions. Further, it avoids problems encountered when attempting to pattern the SAM molecules directly using lithographic techniques. The compatibility with electron beam lithography allows this method to be used to pattern biomolecules at the nanoscale. PMID:19707178

  20. Self-assembly monolayer structures of lipids and macromolecules at interfaces

    CERN Document Server

    Birdi, KS

    2006-01-01

    1. Introduction. 2. Thermodynamics of Liquid Surfaces. 3. Experimental Methods and Procedures for Self-Assembly Monolayers. 4. Lipid Monolayers at Liquid Interfaces. 5. SAMs of Macromolecules (Biopolymers and Synthetic Polymers) at Liquid Interfaces. 6. Kinetics of Adsorption and Desorption at Liquid Interfaces. 7. Lipid-Protein Monolayers (Model Membrane System: Virus-Cell Fusion). 8. SAMs of Membrane Proteins. 9. Adsorption of Monolayers on Solids. 10. Diverse Applications of SAM Films. References. Index.

  1. Self-assembled molecular monolayers as ultrathin gate dielectric in carbon nanotube transistors

    Science.gov (United States)

    Robert, Gaël; Derycke, Vincent; Goffman, Marcelo F.; Lenfant, Stéphane; Vuillaume, Dominique; Bourgoin, Jean-Philippe

    2008-10-01

    We demonstrate the use of a self-assembled monolayer of octadecanethiol on gold as thin gate dielectric for a single-walled carbon nanotube field-effect transistor. P-type transistors display very steep subthreshold slopes, greatly reduced hysteresis, and band-to-band tunneling. The suppression of the gate efficiency for n-type transistors emphasizes the key role of the electrical dipole of the molecular layer in controlling the switching. Combining the versatility of organic dielectrics with the exceptional electronic and mechanical properties of carbon nanotubes opens interesting ways toward the realization of fully organic nanoscale transistors.

  2. Structural Characterization of Self-Assembled Monolayers of Organosilanes Chemically Bonded on Silica Wafers by Dynamical Force Microscopy

    CERN Document Server

    Navarre, S; Bousbaa, J; Bennetau, B; Nony, L; Aimé, J P; Choplin, Franck; Bennetau, Bernard; Nony, Laurent; Aim\\'{e}, Jean-Pierre

    2001-01-01

    In this article, a dynamical force microscopy study of self-assembled monolayers of organosilanes, grafted on a silica support, is reported. Organosilanes, terminated either with a functional group (ethylene glycol) or with a methyl group, were used. The influence of the reaction time and the solvent composition on the grafting was investigated to improve the homogeneity of the self-assembled monolayers. Numerical simulations of approach-retract curves, obtained in the tapping mode, were performed and compared to experimental ones. Informations, such as mechanical response and height of the grafted organic layers, have been obtained.

  3. Modeling disorder in self-assembled monolayers with embedded dipoles

    International Nuclear Information System (INIS)

    Full text: We present a study using several techniques to simulate self assembled monolayers (SAM) on the Au(111) substrate. Accurate quantum mechanical simulations were used to parameterize the charge distribution on the molecules and to estimate the charge transfer to the gold surface caused by the binding of sulfur atoms. The results delivered the inputs for atomistic molecular dynamic simulations carried out with the LAMMPS code. The intermolecular interactions were described by the CHARMM27 force eld, while for the interaction of the molecules and the gold atoms different force fields were tested. The main focus of this work is to provide an accurate description of the morphology of alkylthiols with and without a mid-chain ester functionalization. This particular class of molecules was chosen because the ester group provides an intramolecular electric dipole moment at a certain distance from the surface. We calculated the distribution of dipole orientations from equilibrated structures of monolayers in order to estimate the net-potential shift induced by those dipoles. Also, different surface coverages have been simulated to investigate the thermodynamic mechanisms of SAM islands formation and to quantify the intrinsic structural disorder by computing various order parameters. (author)

  4. Self-assembled monolayers of 1-alkenes on oxidized platinum surfaces as platforms for immobilized enzymes for biosensing

    NARCIS (Netherlands)

    Aznar Alonso, J.M.; Bielen, A.A.M; Olthuis, W.; Kengen, S.W.M; Zuilhof, H.; Franssen, M.

    2016-01-01

    Alkene-based self-assembled monolayers grafted on oxidized Pt surfaces were used as a scaffold to covalently immobilize oxidase enzymes, with the aim to develop an amperometric biosensor platform. NH2-terminated organic layers were functionalized with either aldehyde (CHO) or N-hydroxysuccinimide (N

  5. Self-assembled monolayers of 1-alkenes on oxidized platinum surfaces as platforms for immobilized enzymes for biosensing

    NARCIS (Netherlands)

    Alonso, Jose Maria; Bielen, Abraham A.M.; Olthuis, Wouter; Kengen, Servé W.M.; Zuilhof, Han; Franssen, Maurice C.R.

    2016-01-01

    Alkene-based self-assembled monolayers grafted on oxidized Pt surfaces were used as a scaffold to covalently immobilize oxidase enzymes, with the aim to develop an amperometric biosensor platform. NH2-terminated organic layers were functionalized with either aldehyde (CHO) or N-hydroxy

  6. Special features in self-assembled monolayer revealed by functionalised STM tips

    International Nuclear Information System (INIS)

    Some functional groups in self-assembled monolayers have recently been identified in STM images, due to the chemical modification of gold tips [1]. In those studies, different molecules presenting different functional groups were investigated, resolving several molecular organizations [1-2, 4]. In this paper, we aimed at demonstrating that such chemically modified STM tips can be used to investigate phenomenon routinely observed with standard Pt/Ir tips, such as domain boundary dynamics in hexadecanol SAMs. It also allows transitory features to be identified. Moreover, rarely observed phenomena are also presented below, i.e. bilayers composed of wax esters molecules physisorbed at the phenyloctane/graphite interface

  7. Localized dealloying corrosion mediated by self-assembled monolayers used as an inhibitor system.

    Science.gov (United States)

    Shrestha, B R; Bashir, A; Ankah, G N; Valtiner, M; Renner, F U

    2015-01-01

    The structure and chemistry of thiol or selenol self-assembled organic monolayers have been frequently addressed due to the unique opportunities in functionalization of materials. Such organic films can also act as effective inhibition layers to mitigate oxidation or corrosion. Cu-Au alloy substrates covered by self-assembled monolayers show a different dealloying mechanism compared to bare surfaces. The organic surface layer inhibits dealloying of noble metal alloys by a suppression of surface diffusion at lower potentials but at higher applied potentials dealloying proceeds in localized regions due to passivity breakdown. We present an in situ atomic force microscopy study of a patterned thiol layer applied on Cu-Au alloy surfaces and further explore approaches to change the local composition of the surface layers by exchange of molecules. The pattern for the in situ experiment has been applied by micro-contact printing. This allows the study of corrosion protection with its dependence on different molecule densities at different sites. Low-density thiol areas surrounding the high-density patterns are completely protected and initiation of dealloying proceeds only along the areas with the lowest inhibitor concentration. Dealloying patterns are highly influenced and controlled by molecular thiol to selenol exchange and are also affected by introducing structural defects such as scratches or polishing defects. PMID:25920488

  8. Self-Assembled Monolayers of CdSe Nanocrystals on Doped GaAs Substrates

    DEFF Research Database (Denmark)

    Marx, E.; Ginger, D.S.; Walzer, Karsten; Stokbro, Kurt; Greenham, N.C.

    2002-01-01

    This letter reports the self-assembly and analysis of CdSe nanocrystal monolayers on both p- and a-doped GaAs substrates. The self-assembly was performed using a 1,6-hexanedithiol self-assembled monolayer (SAM) to link CdSe nanocrystals to GaAs substrates. Attenuated total reflection Fourier...... transform infrared spectroscopy (ATR-FTIR), optical ellipsometry, photoluminescence (PL), and scanning tunneling microscopy (STM) measurements were used to confirm stable, disordered, densely packed CdSe nanocrystal monolayers separated from the substrate by a SAM of 1,6-hexanedithiol....

  9. Correlation of Effective Dispersive and Polar Surface Energies in Heterogeneous Self-Assembled Monolayer Coatings

    DEFF Research Database (Denmark)

    Zhuang, Yanxin; Hansen, Ole

    2009-01-01

    We show, theoretically, that the measured effective dispersive and polar surface energies of a heterogeneous Surface are correlated; the correlation, however, differs whether a Cassic or an Israelachvili and Gee model is assumed. Fluorocarbon self-assembled monolayers with varying coverage were...... grown oil oxidized (100) silicon Surfaces in a vapor phase process using five different precursors. Experimentally, effective surface energy components of the fluorocarbon self-assembled monolayers were determined from measured contact angles using the Owens-Wendt-Rabel-Kaelble method. We show that the...... correlation between the effective surface energy components of the heterogeneous Surfaces coated with fluorocarbon self-assembled monolayers is in agreement with the Cassie model....

  10. Chemistry of metal atoms reacting with alkanethiol self-assembled monolayers

    International Nuclear Information System (INIS)

    Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is utilized to investigate the behavior of vapor-deposited K, Au and Ti atoms on several alkanethiol self-assembled monolayers (SAM). The goals are to acquire information about chemical reactions between metal atoms and surface organic functional groups, penetration of metal atoms through the SAMs, growth modes of metal overlayers on top of the SAMs and damage of organic molecules. It is found that appearance of new characteristic peaks and disappearance of initial peaks may indicate chemical reactions or decomposition of organic molecules. The relationship between metal dose and intensity of surface organic functional group-related peaks provides information about penetration or cluster-formation of metal atoms. In addition, removing the metal overlayers by chemical etching and then characterizing samples again is a complementary approach that can reveal valuable information about the location of the metal atoms

  11. A note on the use of ellipsometry for studying the kinetics of formation of self-assembled monolayers

    Indian Academy of Sciences (India)

    Murali Sastry

    2000-06-01

    Ellipsometry is currently one of the most important techniques for characterization of the deposition and growth mode of ultra thin organic films. However, it is well known that for thicknesses normally encountered in organic monolayer films, as would occur for example in self-assembled monolayers, ellipsometry cannot be used to simultaneously determine the thickness and refractive index of the monolayer film. Current practice is to assume a reasonable value for the film refractive index and calculate an effective ‘ellipsometric thickness’. This communication seeks to show that the alternative approach of assuming a thickness for the monolayer (determined by the length of the molecule) and calculating the effective film refractive index lends itself to easier and more meaningful physical interpretation. The Lorentz–Lorenz formula is then used to transform the effective refractive index into a surface coverage and hence to an effective mass coverage. The methodology advanced is applied to the kinetics of formation of a self-assembled monolayer of a well-studied molecule, octadecanethiol on Au.

  12. Investigation of functionalized silicon nanowires by self-assembled monolayer

    Science.gov (United States)

    Hemed, Nofar Mintz; Convertino, Annalisa; Shacham-Diamand, Yosi

    2016-03-01

    The functionalization using self assembled monolayer (SAM) of silicon nanowires (SiNW) fabricated by plasma enhanced chemical vapor deposition (PECVD) is reported here. The SAM is being utilized as the first building block in the functionalization process. The morphology of the SiNW comprises a polycrystalline core wrapped by an hydrogenated amorphous silicon (α-Si:H) shell. Since most of the available methods for SAM verification and characterization are suitable only for flat substrates; therefore, in addition to the SiNW α-Si:H on flat samples were produced in the same system as the SiNWs. First we confirmed the SAM's presence on the flat α-Si:H samples using the following methods: contact angle measurement to determine the change in surface energy; atomic force microscopy (AFM) to determine uniformity and molecular coverage. Spectroscopic ellipsometry and X-ray reflectivity (XRR) were performed to measure SAM layer thickness and density. X-ray photoelectron spectroscopy (XPS) was applied to study the chemical states of the surface. Next, SiNW/SAM were tested by electrochemical impedance spectroscopy (EIS), and the results were compared to α-Si:H/SAM. The SAM electrical coverage on SiNW and α-Si:H was found to be ∼37% and ∼65 ± 3%, respectively. A model, based on transmission line theory for the nanowires is presented to explain the disparity in results between the nanowires and flat surface of the same materials.

  13. Mechanism of UV photoreactivity of alkylsiloxane self-assembled monolayers.

    Science.gov (United States)

    Ye, Tao; McArthur, Eric A; Borguet, Eric

    2005-05-26

    A molecular level understanding of the photoreactivity of self-assembled monolayers (SAMs) becomes increasingly important as the spatial resolution starts to be limited by the size of the resist and the spatial extent of the photochemical reactions in photoresist micropatterning. To this end, a number of surface characterization techniques were combined to understand the reactive agents, reactive sites, kinetics, and reaction pathways in the UV photoreactivity of octadecylsiloxane (ODS) SAMs. Quantitative analysis of our results provides evidence that ground state atomic oxygen is the primary reactive agent for the UV degradation of ODS SAMs. UV degradation, which follows zero-order kinetics, results in the scission of alkyl chains instead of the siloxane headgroups. Our results suggest that the top of the ODS SAMs is the preferential reactive site. Using a novel, highly surface sensitive technique, fluorescence labeling of surface species, we identified the presence of submonolayer quantities chemical functional groups formed by the UV degradation. These groups are intermediates in a proposed mechanism based on hydrogen abstraction. PMID:16852200

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

    Science.gov (United States)

    Smith, Jeremy G; Jain, Prashant K

    2016-08-24

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

  15. Characterization and reactivity of organic monolayers on gold and platinum surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Chien-Ching

    1995-12-06

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

  16. Assembly of oriented zeolite monolayers and thin films on polymeric surfaces via hydrogen bonding.

    Science.gov (United States)

    Zhou, Ming; Liu, Xiufeng; Zhang, Baoquan; Zhu, Huiming

    2008-10-21

    The b-oriented monolayers of microsized silicalite-1 crystals have been manually assembled on glass plate supported poly(ethylene oxide) (PEO), poly(vinyl alcohol) (PVA), chitosan, and poly(methyl methacrylate) (PMMA) thin films via hydrogen bonding with much enhanced binding strength and satisfactory degrees of coverage and close packing. The exerted pressure and rubbing time in the manual assembly do not affect the binding strength of the silicalite-1 monolayer on the glass plate supported polymeric film. This manual assembly has been further applied to fabricate zeolite monolayers on commercially available Plexiglas surfaces and b-oriented multilayered films of silicalite-1 crystals on glass plates. The assembly method established in this study provides a feasible way to produce zeolite monolayers on polymer-modified solid substrates and Plexiglas and to fabricate zeolite-polymer composite membranes by means of the layer-by-layer technique. PMID:18785711

  17. Electro- and photochemical switching of dithienylethene self-assembled monolayers on gold electrodes

    DEFF Research Database (Denmark)

    Browne, W.R.; Kudernac, T.; Katsonis, N.; Areephong, J.; Hjelm, Johan; Feringa, B.L.

    2008-01-01

    The photochemical and electrochemical properties of self-assembled monolayers (SAM) of three structurally distinct hexahydro- and hexafluoro-dithienylcyclopentene-based photochromic switches on gold electrodes are reported. The photochemical and electrochemical switching between the open and closed...

  18. Investigation of Self Assembled Monolayers (SAM) Applied on Si(100) Surfaces by Atomic Force Microscopy

    International Nuclear Information System (INIS)

    Miniaturization of analytical instrumentation in a molecular and nanometer level has technologically significant. The fabrication of nanopatterns with high resolution SPM nanolithograpy may be applied on atomically flat surfaces. Self Assembled-Monolayers (SAMs) are well-ordered two dimensional molecular assemblies formed by a strong adsorption of an active surfactant on a solid surface. In this study, SAM organic thin film method is applied on silicon surfaces. We used various cleaning procedures such as chemical cleaning, ion beam treatment, on p-type Si(1OO) surfaces. SAMs films were produced from bipolar amphiphiles, Octadecylamine ODA-HCl, 1,12-diaminododecane (DAD) and n-tridecylamine (TDA) molecules on Si wafers. Contact mode scanning method and roughness analysis on the scan images were utilized on the SAM coated and uncoated surfaces by Atomic Force Microscopy

  19. Electronic Transport through Self Assembled Thiol Molecules: Effect of Monolayer Order, Dynamics and Temperature

    Science.gov (United States)

    Dholakia, Geetha; Fan, Wendy; Meyyappan, M.

    2005-01-01

    We present the charge transport and tunneling conductance of self assembled organic thiol molecules and discuss the influence of order and dynamics in the monolayer on the transport behavior and the effect of temperature. Conjugated thiol molecular wires and organometals such as terpyridine metal complexes provide a new platform for molecular electronic devices and we study their self assembly on Au(111) substrates by the scanning tunneling microscope. Determining the organization of the molecule and the ability to control the nature of its interface with the substrate is important for reliable performance of the molecular electronic devices. By concurrent scanning tunneling microscopy and spectroscopy studies on SAMs formed from oligo (phenelyne ethynelyne) monolayers with and without molecular order, we show that packing and order determine the response of a self assembled monolayer (SAM) to competing interactions. Molecular resolution STM imaging in vacuum shows that the OPES adopt an imcommensurate SAM structure on Au(111) with a rectangular unit cell. Tunneling spectroscopic measurements were performed on the SAM as a function of junction resistance. STS results show that the I-Vs are non linear and asymmetric due to the inherent asymmetry in the molecular structure, with larger currents at negative sample biases. The asymmetry increases with increasing junction resistance due to the asymmetry in the coupling to the leads. This is brought out clearly in the differential conductance, which also shows a gap at the Fermi level. We also studied the effect of order and dynamics in the monolayer on the charge transport and found that competing forces between the electric field, intermolecular interactions, tip-molecule physisorption and substrate-molecule chemisorption impact the transport measurements and its reliability and that the presence of molecular order is very important for reproducible transport measurements. Thus while developing new electronic platforms

  20. Self-assembled monolayer mechanism for corrosion inhibition of iron by imidazolines

    Energy Technology Data Exchange (ETDEWEB)

    Ramachandran, S.; Tsai, B.L.; Blanco, M.; Goddard, W.A. III [California Inst. of Technology, Pasadena, CA (United States); Chen, H.; Tang, Y. [Chevron Petroleum Technology Company, La Habra, CA (United States)

    1996-12-25

    Some of the most effective corrosion inhibitors for oil field pipeline applications are the oleic imidazoline (OI) class of molecules. However, the mechanism by which the OIs inhibit corrosion is not known. We report atomistic simulations (quantum mechanics and molecular dynamics) designed to elucidate this mechanism. These studies lead to the self-assembled monolayer (SAM) model for corrosion inhibition, which explains the differences in corrosion inhibition efficiency for various OI molecules. The SAM model of OI inhibitors involves the following critical elements: (i) strong bonding of the head group to Lewis acid sites on the iron oxide surface, (ii) self-assembly of the inhibitors on these surfaces to obtain a pattern controlled by the shape of the head group, (iii) self-organization of the tails to form a coherent hydrophobic film that serves as a barrier for migration of water, oxygen, and electrons to the metal surface, and (iv) optimal oil/water partitioning of the inhibitor molecules so that a monolayer can be formed on the surface with only ppm concentration in solution. 25 refs., 13 figs., 3 tabs.

  1. Self-assembled monolayer-modified block copolymers for chemical surface nanopatterning

    International Nuclear Information System (INIS)

    Research highlights: → Self-organizing PS-b-PMMA creates striped nanostructure scaffolds. → These striped nanostructures can be selectively metalized and modified using light. → Metalized stripes can be decorated with SAMs to create functional substrates. → Nanostructured surfaces thus prepared exhibit controlled wetting and recognition. - Abstract: Thin-film poly(styrene-block-methyl methacrylate) diblock copolymer (PS-b-PMMA) is used to create chemically patterned surfaces via metal deposition combined with self-assembled monolayers (SAMs) and UV exposure. We use this method to produce surfaces that are chemically striped on the scale of a few tens of nanometers. Atomic force and transmission electron microscopies are used to verify the spatially localized organization of materials, and contact angle measurements confirm the chemical tunability of these scaffolds. These surfaces may be used for arraying nanoscale objects, such as nanoparticles or biological species, or for electronic, magnetic memory or photovoltaic applications.

  2. Self-assembled monolayers of alpha-cyclodextrin derivatives on gold and their host-guest behavior

    Czech Academy of Sciences Publication Activity Database

    Perl, A.; Kumprecht, Lukáš; Kraus, Tomáš; Armspach, D.; Matt, D.; Reinhoudt, D.N.; Huskens, J.

    2009-01-01

    Roč. 25, č. 3 (2009), s. 1534-1539. ISSN 0743-7463 R&D Projects: GA AV ČR IAA400550810; GA ČR GA203/06/1550; GA MŠk OC 172 Institutional research plan: CEZ:AV0Z40550506 Keywords : cyklodextrins * self-assembled monolayers Subject RIV: CC - Organic Chemistry Impact factor: 3.898, year: 2009

  3. On the lipid head group hydration of floating surface monolayers bound to self-assembled molecular protein layers

    DEFF Research Database (Denmark)

    Lösche, M.; Erdelen, C.; Rump, E.; Ringsdorf, H.; Kjær, K.; Vaknin, D.

    The structure of monomolecular layers of the protein streptavidin, specifically bound to biotin-functionalized lipid monolayers at aqueous surfaces, has been characterized. Neutron and X-ray reflectivity measurements allowed an assessment of the organization of these self-assembled systems with...... molecular resolution. Emphasis here is placed on the hydration of the lipid head groups in the bound state. For three functionalized lipids with spacers of different lengths between the biotin and their chains it was observed that the head groups were dehydrated in monolayers of the pure lipids, which were...... kept at low surface pressure before protein adsorption. The introduction of dipole moments at the interface by the admixture of phospholipids or the application of lateral pressure on the lipid monolayer before protein adsorption were found to impose an extension of the spacer moieties. The biotin...

  4. Micro-patterning of Copper Based on Photolithographed Self-assembly Monolayers

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A new method has been developed for fabrication of copper micro-pattern by selective chemical copper deposition based on photolithographed (3-mercaptopropyl)-trimethoxysilane (MPTS) self-assembly monolayers (SAMs). As confirmed by scanning electron microscopy (SEM), Cu closely replicated the mask features. The present approach makes this technic to be cheap and may be applicable to assembly of microelectronic circuits.

  5. Self-assembly of Carboxyl Functionalized Polystyrene Nanospheres into Close-packed Monolayers via Chemical Adsorption

    Institute of Scientific and Technical Information of China (English)

    LI,Zhi-Wei(李志伟); ZHOU,Jing-Fang(周静芳); ZHANG,Zhi-Jun(张治军); DANG,Hong-Xin(党鸿辛)

    2004-01-01

    The polyacrylic acid functionalized polystyrene nanospheres were synthesized and self-assembled into irregular,densely packed monolayers in non-aqueous media. The polymer nanoparticles were chemically adhered to substrates. The morphologies of the resulting films were investigated. The impact of the volume fraction of alcohol in the mixed solvents on the particle adsorption and fabrication of nanosphere assembled films was examined.

  6. Static and dynamic electronic characterization of organic monolayers grafted on a silicon surface.

    Science.gov (United States)

    Pluchery, O; Zhang, Y; Benbalagh, R; Caillard, L; Gallet, J J; Bournel, F; Lamic-Humblot, A-F; Salmeron, M; Chabal, Y J; Rochet, F

    2016-02-01

    Organic layers chemically grafted on silicon offer excellent interfaces that may open up the way for new organic-inorganic hybrid nanoelectronic devices. However, technological achievements rely on the precise electronic characterization of such organic layers. We have prepared ordered grafted organic monolayers (GOMs) on Si(111), sometimes termed self-assembled monolayers (SAMs), by a hydrosilylation reaction with either a 7-carbon or an 11-carbon alkyl chain, with further modification to obtain amine-terminated surfaces. X-ray photoelectron spectroscopy (XPS) is used to determine the band bending (∼ 0.3 eV), and ultraviolet photoelectron spectroscopy (UPS) to measure the work function (∼ 3.4 eV) and the HOMO edge. Scanning tunneling microscopy (STM) confirms that the GOM surface is clean and smooth. Finally, conductive AFM is used to measure electron transport through the monolayer and to identify transition between the tunneling and the field emission regimes. These organic monolayers offer a promising alternative to silicon dioxide thin films for fabricating metal-insulator-semiconductor (MIS) junctions. We show that gold nanoparticles can be covalently attached to mimic metallic nano-electrodes and that the electrical quality of the GOMs is completely preserved in the process. PMID:26757829

  7. Ultrathin self-assembled polymeric films on solid surfaces. 2. Formation of 11-(n-pentyldithio) undecanoate-bearing polyacrylate monolayers on gold

    Energy Technology Data Exchange (ETDEWEB)

    Sun, F.; Grainger, D.W. (Oregon Graduate Inst. of Science and Technology, Portland, OR (United States)); Castner, D.G. (Univ. of Washington, Seattle, WA (United States))

    1993-11-01

    Polymeric monolayers of poly(methoxyethyl acrylate-co-hydroxyethyl acrylate) copolymers derivatized with 11-(n-pentyldithio)undecanoate side chains on gold surfaces have been fabricated by spontaneous self-assembly from organic solution. Experimental evidence derived from a combination of ellipsometry, polarized reflection infrared spectroscopy, and X-ray photoelectron spectroscopy indicates that two-dimensional polymer films assemble on gold surfaces by multipoint attachment. Further experiments systematically changing polymer composition and solution concentrations for monolayer preparation reveal that polymer assemblies created by adsorption have less structural anisotropy than their corresponding conventional monomeric organic alkyl disulfides. However, these self-assembled polymer films show enhanced thermal stability in wet environments over films of monomeric organic analogs, indicating that polyfunctional polymer anchoring effects greatly improve integral adhesion and binding stabilities of ultrathin polymer assemblies. 29 refs., 10 figs., 5 tabs.

  8. Electrochemical Studies of Glutathione Monolayer Assembled on A Polycrystalline Gold Electrode

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The glutathione (GSH) monolayer and complex monolayer of GSH-metallic ion on polycrys-talline gold electrode were studied by using K3Fe(CN)6 as the redox probe. As for the GSH monolayer, itwas found that the metallic ions could open the ion-gate in the monolayer dramatically in the order La3+>Pb2+>> Ba2+> Ca2+ whereas Zn2+ ion closed the ion-gate. The complexes of GSH-metallic ions were ca-pable of self-assembling the different kind of monolayer. All the differences were related to the structuralconfiguration of the anchored GSH molecule, which changed with the different metallic ions or pH.

  9. Self-assembly and structure of directly imaged inorganic-anion monolayers on a gold nanoparticle.

    Science.gov (United States)

    Wang, Yifeng; Neyman, Alevtina; Arkhangelsky, Elizabeth; Gitis, Vitaly; Meshi, Louisa; Weinstock, Ira A

    2009-12-01

    Cryogenic "trapping" was used to obtain the first TEM images of self-assembled monolayers of inorganic anions on a gold nanoparticle. This unique structural information makes it possible to study the formation of a protecting-ligand shell at an unprecedented level of detail. The protecting ligands are polyoxometalates (POMs; alpha-X(n+)W(12)O(40)((8-n)-), X(n+) = Al(3+) and "2H(+)", and alpha-X(n+)W(11)O(39)((12-n)-), X(n+) = P(5+), Si(4+), and Al(3+)) with large negative charges for association with the gold surface and W atoms (Z = 74) for TEM imaging. The POM-anion shells were obtained by ligand exchange from citrate-protected 13.8 nm gold nanoparticles. Replacement of the organic (citrate) by inorganic (tungsten-oxide) ligand shells results in substantial changes in the surface plasmon resonance (SPR). By correlating cryo-TEM images with changes in the SPR, degrees of surface coverage were reliably quantified by UV-visible spectroscopy. Then, the kinetics and thermodynamics of ligand-shell formation were investigated by systematically varying POM structure and charge. Rates of POM association with the gold surface ("nucleation") are inhibited by the electric-potential barrier of the citrate-stabilized particles, while binding affinities increase linearly with the charges (from 5- to 9-) of structurally different POM anions, suggesting that no single orientation ("lattice matching") is required for monolayer self-assembly. Time-dependent cryo-TEM images reveal that monolayer growth occurs via "islands", a mechanism that points to cation-mediated attraction between bound POMs. Complete ligand shells comprised of 330 molecules of alpha-AlW(11)O(39)(9-) (1) possess small net charges (29e from zeta-potential measurements) and short Debye lengths (kappa(-1) = 1.0 nm), which indicate that approximately 99% of the 2970 K(+) counter cations lie within ca. 1.5 nm (approximately 3 hydrated K(+) ion diameters) from the outer surface of the POM shell. Energetic analysis of

  10. Photoisomerization of azobenzene containing self-assembled monolayers investigated by Kelvin probe work function measurements

    International Nuclear Information System (INIS)

    Photoisomerization of asymmetric azobenzene disulfide self-assembled monolayer (SAM) on gold was characterized by the Kelvin probe work function measurements in ambient atmosphere. The reversible changes in work function between trans and cis azobenzene SAMs are reasonably interpreted by the molecular dipole moments normal to the surface based on the molecular conformational models. The different para-substituents of azobenzene with electron donating and electron-withdrawing properties induce opposite responses in work function against UV-vis photoirradiation, which is a direct evidence of functional SAMs being effective for the energy-level alignment at the organic/electrode interface. The Kelvin probe measurements in atmosphere eventually provide the work function value equivalent to that determined by ultraviolet photoelectron spectroscopy (UPS) in ultrahigh vacuum in our previous study.

  11. Triazolobithiophene Light Absorbing Self-Assembled Monolayers: Synthesis and Mass Spectrometry Applications

    Directory of Open Access Journals (Sweden)

    Denis Séraphin

    2011-10-01

    Full Text Available The synthesis of five light absorbing triazolobithiophenic thiols, which were utilized for producing self-assembled monolayers (SAMs on gold surfaces, is presented. The monolayer formation was monitored by cyclic voltammetry, indicating excellent surface coverage. The new triazolobithiophenic compounds exhibited an absorption maximum around 340 nm, which is close to the emission wavelength of a standard nitrogen laser. Consequently these compounds could be used to aid ionization in laser desorption mass spectrometry (MS.

  12. Femtosecond-laser processing of nitrobiphenylthiol self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Schröter, Anja; Franzka, Steffen [Fakultät für Chemie, Universität Duisburg-Essen, 45117 Essen (Germany); CENIDE – Center for Nanointegration Duisburg-Essen, 47048 Duisburg (Germany); Koch, Jürgen; Chichkov, Boris N. [LZH – Laser Zentrum Hannover e. V., Hollerithallee 8, 30419 Hannover (Germany); Ostendorf, Andreas [Fakultät für Maschinenbau, Ruhruniversität Bochum, Universitätsstr. 150, 44801 Bochum (Germany); Hartmann, Nils, E-mail: nils.hartmann@uni-due.de [Fakultät für Chemie, Universität Duisburg-Essen, 45117 Essen (Germany); CENIDE – Center for Nanointegration Duisburg-Essen, 47048 Duisburg (Germany)

    2013-08-01

    Single-pulse femtosecond laser patterning of nitrobiphenylthiol monolayers on Au-coated Si substrates at λ = 800 nm, τ < 30 fs and ambient conditions has been investigated. After laser processing wet etching experiments are performed. Laser irradiation reduces the chemical resistance of the coating. In particular, the monolayer acts as a positive-tone resist. Burr-free pattern transfer is feasible at laser pulse fluences between 1 and 2.7 J/cm{sup 2}. Minimum structure sizes at a 1/e laser spot diameter of about 1 μm are close to 300 nm, i.e. sub-wavelength processing is demonstrated. Noteworthy, however, no indications for negative-tone resist properties of processed monolayers are evident, that is, cross-linking of the biphenyl moieties, if at all, is marginal. Also, complementary labeling experiments provide no evidence for chemical transformation of the nitro end groups into amine functionalities. Perspectives of resonant fs-laser processing in exploiting the particular prospects of nitrobiphenylthiol monolayers as negative-tone resists and chemically patternable platforms are discussed.

  13. Hybrid plasmonic/semiconductor nanoparticle monolayer assemblies as hyperbolic metamaterials

    DEFF Research Database (Denmark)

    Zhukovsky, Sergei; Ozel, Tuncay; Mutlugun, Evren;

    2014-01-01

    We show that hybrid nanostructures made of alternating colloidal semiconductor quantum dot and metal nanoparticle monolayers can function as multilayer hyperbolic meta-materials. By choosing the thickness of the spacer between the quantum dot and nanoparticle layers, one can achieve the indefinit...

  14. Fabrication of self-assembled oligophenylethynylenethiol monolayer for electrochemical glucose biosensor

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Seul-Ki [Department of Chemical and Biomolecular Engineering, Sogang University, Seoul 121-742 (Korea, Republic of); Namgung, Mi-Ok [Interdisciplinary Program of Integrated Biotechnology, Sogang University, Seoul 121-742 (Korea, Republic of); Oh, Se-Young [Department of Chemical and Biomolecular Engineering, Sogang University, Seoul 121-742 (Korea, Republic of); Interdisciplinary Program of Integrated Biotechnology, Sogang University, Seoul 121-742 (Korea, Republic of); Oh, Byung-Keun, E-mail: bkoh@sogang.ac.kr [Department of Chemical and Biomolecular Engineering, Sogang University, Seoul 121-742 (Korea, Republic of); Interdisciplinary Program of Integrated Biotechnology, Sogang University, Seoul 121-742 (Korea, Republic of)

    2009-07-15

    An electrochemical glucose biosensor was developed using a gold (Au) electrode, which was composed of self-assembled oligophenylethynylenethiol monolayer and glucose oxidase (GOx) structure. Oligophenylethynylenethiol was used as a chemical linker for the immobilization of GOx on Au electrode, which facilitates the transfer of electron produced by enzyme reaction to the Au electrode. The electrical property of self-assembled oligophenylethynylenethiol monolayer was investigated by using cyclic voltammetry (CV). The formation of self-assembled oligophenylethynylenethiol monolayer and GOx layer on Au surface was verified by using atomic force microscopy (AFM) and surface plasmon resonance (SPR). The electrochemical glucose biosensor exhibited a linear relationship between target concentration and oxidation current in the range of 2-30 mM and its detection limit was 2 mM.

  15. Fabrication of self-assembled oligophenylethynylenethiol monolayer for electrochemical glucose biosensor

    International Nuclear Information System (INIS)

    An electrochemical glucose biosensor was developed using a gold (Au) electrode, which was composed of self-assembled oligophenylethynylenethiol monolayer and glucose oxidase (GOx) structure. Oligophenylethynylenethiol was used as a chemical linker for the immobilization of GOx on Au electrode, which facilitates the transfer of electron produced by enzyme reaction to the Au electrode. The electrical property of self-assembled oligophenylethynylenethiol monolayer was investigated by using cyclic voltammetry (CV). The formation of self-assembled oligophenylethynylenethiol monolayer and GOx layer on Au surface was verified by using atomic force microscopy (AFM) and surface plasmon resonance (SPR). The electrochemical glucose biosensor exhibited a linear relationship between target concentration and oxidation current in the range of 2-30 mM and its detection limit was 2 mM.

  16. Trapping dynamics of diindenoperylene (DIP) in self-assembled monolayers using molecular simulation

    KAUST Repository

    Kaushik, Ananth P.

    2011-07-01

    All-atom Molecular Dynamics simulation methods employing a well-tested intermolecular potential model, MM3 (Molecular Mechanics 3), demonstrate the propensity for diindenoperylene (DIP) molecules to insert between molecules of a self-assembled monolayer (SAM) during a deposition process intended to grow a thin film of this organic semiconductor molecule onto the surface of self-assembled monolayers. The tendency to insert between SAM molecules is fairly prevalent at normal growth temperatures and conditions, but is most strongly dependent on the density and the nature of the SAM. We posit the existence of an optimal density to favor surface adsorption over insertion for this system. DIP is less likely to insert in fluorinated SAMs, like FOTS (fluorooctatrichlorosilane), than its unfluorinated analog, OTS (octatrichlorosilane). It is also less likely to insert between shorter SAMs (e.g., less insertion in OTS than ODTS (octadecyltrichlorosilane)). Very short length, surface-coating molecules, like HDMS (hexamethyldisilazane), are more likely to scatter energetic incoming DIP molecules with little insertion on first impact (depending on the incident energy of the DIP molecule). Grazing angles of incidence of the depositing molecules generally favor surface adsorption, at least in the limit of low coverage, but are shown to be dependent on the nature of the SAM. The validity of these predictions is confirmed by comparison of the predicted sticking coefficients of DIP at a variety of incident energies on OTS, ODTS, and FOTS SAMs with results obtained experimentally by Desai et al. (2010) [23]. The simulation predictions of the tendency of DIP to insert can be explained, in large part, in terms of binding energies between SAM and DIP molecules. However, we note that entropic and stochastic events play a role in the deposition outcomes. Preliminary studies of multiple deposition events, emulating growth, show an unexpected diffusion of DIP molecules inserted within the

  17. Electric-Field-Assisted Directed Assembly of Transition Metal Dichalcogenide Monolayer Sheets.

    Science.gov (United States)

    Deng, Donna D; Lin, Zhong; Elías, Ana Laura; Perea-Lopez, Nestor; Li, Jie; Zhou, Chanjing; Zhang, Kehao; Feng, Simin; Terrones, Humberto; Mayer, Jeffrey S; Robinson, Joshua A; Terrones, Mauricio; Mayer, Theresa S

    2016-05-24

    Directed assembly of two-dimensional (2D) layered materials, such as transition metal dichalcogenides, holds great promise for large-scale electronic and optoelectronic applications. Here, we demonstrate controlled placement of solution-suspended monolayer tungsten disulfide (WS2) sheets on a substrate using electric-field-assisted assembly. Micrometer-sized triangular WS2 monolayers are selectively positioned on a lithographically defined interdigitated guiding electrode structure using the dielectrophoretic force induced on the sheets in a nonuniform field. Triangular sheets with sizes comparable to the interelectrode gap assemble with an observed preferential orientation where one side of the triangle spans across the electrode gap. This orientation of the sheets relative to the guiding electrode is confirmed to be the lowest energy configuration using semianalytical calculations. Nearly all sheets assemble without observable physical deformation, and postassembly photoluminescence and Raman spectroscopy characterization of the monolayers reveal that they retain their as-grown crystalline quality. These results show that the field-assisted assembly process may be used for large-area bottom-up integration of 2D monolayer materials for nanodevice applications. PMID:27082162

  18. Self-assembly of tetraalkoxydinaphthophenazines in monolayers on HOPG by scanning tunneling microscopy

    Science.gov (United States)

    Jaroch, Tomasz; Maranda-Niedbala, Agnieszka; Kotwica, Kamil; Wamil, Damian; Bujak, Piotr; Pron, Adam; Nowakowski, Robert

    2015-11-01

    2D supramolecular organization in monolayers of tetraalkoxydinaphthophenazines, a new group of solution processable organic semiconductors obtained by simple functionalization of indanthrone (6,15-dihydrodinaphtho[2,3-a:2‧,3‧-h]phenazine-5,9,14,18-tetraone), an old intractable dye, was investigated by scanning tunneling microscopy (STM). Five derivatives with increasing substituent length from butoxy (P-C4) to dodecyloxy (P-C12) were tested. All derivatives show a strong tendency to form ordered monolayers on HOPG graphite via self-assembly which constitute of rows of molecules oriented in one direction. However, local arrangement in this 2D supramolecular organization is strongly dependent on the substituent length. Two tendencies in the structural evolution are observed. For butoxy (P-C4), hexyloxy (P-C6) and octyloxy (P-C8) derivatives increasing substituent length results in the transformation of the structure governed by the conjugated core interactions to the one in which mutual interactions of the alkoxy groups dominate. As a consequence, for P-C8 a very stable 2D structure is obtained with a nearly rectangular 2D unit cell, as a consequence of the alkoxy group interdigitation in two perpendicular directions. With further increase of the substituent length to decyloxy (P-C10) and dodecyloxy (P-C12) a different effect is observed-a directional expansion of the unit cell along the longitudinal axis of the molecules. This is a consequence of structural nonequivalence of the alkoxy groups attached to the same aromatic ring.

  19. Ozone Oxidation of Self-Assembled Monolayers on SiOx-Coated Zinc Selenide Surfaces

    Science.gov (United States)

    McIntire, T. M.; Ryder, O. S.; Finlayson-Pitts, B. J.

    2008-12-01

    Airborne particles are important for visibility, human health, climate, and atmospheric reactions. Atmospheric particles contain a significant fraction of organics and such compounds present on airborne particles are susceptible to oxidation by atmospheric oxidants, such as OH, ozone, halogen atoms, and nitrogen trioxide. Oxidized organics associated with airborne particles are thought to be polar, hygroscopic species with enhanced cloud-nucleating properties. Oxide layers on silicon, or SiO2-coated substrates, act as models of environmentally relevant surfaces such as dust particles upon which organics adsorb. We have shown previously that ozone oxidation of unsaturated self-assembled monolayers (SAMs) on silicon attenuated total reflectance (ATR) crystals leads to the formation of carbonyl groups and micron-sized, hydrophobic organic aggregates surrounded by carbon depleted substrate that do not have increased water uptake as previously assumed. Reported here are further ATR-FTIR studies of the oxidation of alkene SAMs on ZnSe and SiO2-coated ZnSe. These substrates have the advantage that they transmit below 1500 cm-1, allowing detection of additional product species. These experiments show that the loss of C=C and formation of carbonyl groups is also accompanied by formation of a peak at 1110 cm-1, attributed to the secondary ozonide. Details concerning the products and mechanism of ozonolysis of alkene SAMs on surfaces based on these new data are presented and the implications for the oxidation of alkenes on airborne dust particles are discussed.

  20. Optical constants and self-assembly of phenylene ethynylene oligomer monolayers

    DEFF Research Database (Denmark)

    Marx, E.; Walzer, Karsten; Less, R.J.; Raithby, P.R.; Stokbro, Kurt; Greenham, N.C.

    2004-01-01

    This paper studies the self-assembly on gold surfaces of 1,4-ethynylphenyl-4'-ethynylphenyl-2'-nitro-1-benzenedithiolate (EP2NO(2)), a substituted phenylene ethynylene trimer with applications in molecular electronics. We develop an ellipsometric technique to measure the optical constants of thes...... self-assembled monolayers, and we also use attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and scanning tunneling microscopy (STM) to confirm the structure of the films....

  1. The Effects of Embedded Dipoles in Aromatic Self-Assembled Monolayers

    NARCIS (Netherlands)

    Abu-Husein, Tarek; Schuster, Swen; Egger, David A.; Kind, Martin; Santowski, Tobias; Wiesner, Adrian; Chiechi, Ryan; Zojer, Egbert; Terfort, Andreas; Zharnikov, Michael

    2015-01-01

    Using a representative model system, here electronic and structural properties of aromatic self-assembled monolayers (SAMs) are described that contain an embedded, dipolar group. As polar unit, pyrimidine is used, with its orientation in the molecular backbone and, consequently, the direction of the

  2. Formation of high-quality self-assembled monolayers of conjugated dithiols on gold : Base matters

    NARCIS (Netherlands)

    Valkenier, Hennie; Huisman, Everardus H.; Hal, Paul A. van; de Leeuw, Dagobert; Chiechi, Ryan C.; Hummelen, Jan C.

    2011-01-01

    This Article reports a systematic study on the formation of self-assembled monolayers (SAMs) of conjugated molecules for molecular electronic (ME) devices. We monitored the deprotection reaction of acetyl protected dithiols of oligophenylene ethynylenes (OPEs) in solution using two different bases a

  3. Self-assembled monolayers of azobenzene functionalized 1,3,5-triazine-4,6-dithiols

    International Nuclear Information System (INIS)

    Two novel azobenzene-functionalized 1,3,5-triazine-4,6-dithiols were synthesized and their ultrathin films were prepared by self-assembling (SA) technique. The switching between trans-and cis-forms was observed by measuring the surface potential using the Kelvin probe technique while alternating irradiation the SA monolayer (SAM) with ultraviolet or visible light

  4. Single-Layer Pentacene Field-Effect Transistors Using Electrodes Modified With Self-assembled Monolayers

    NARCIS (Netherlands)

    Asadi, Kamal; Wu, Yu; Gholamrezaie, Fatemeh; Rudolf, Petra; Blom, Paul W. M.

    2009-01-01

    Pentacene field-effect transistor performance can be improved by modifying metal electrodes with self-assembled monolayers. The dominant role in performance is played by pentacene morphology rather than the work function of the modified electrodes. With optimized processing conditions, hysteresis-fr

  5. Large-Ordered Striped Phase of Didodecyl Sulfide Self-Assembled Monolayers on Au(111)

    Energy Technology Data Exchange (ETDEWEB)

    Choi, In Chang; Kang, Hun Gu; Lee, Dong Jin; Noh, Jae Geun [Hanyang University, Seoul (Korea, Republic of)

    2012-02-15

    We demonstrated that the adsorption of DDS molecules on Au(111) at room temperature or 70 .deg. C led to the formation of ordered SAMs with p Χ √3 striped phases. More specifically, DDS SAMs at 70 .deg. C were composed of long-range ordered striped phases with a VI-free structure. The obtained results will be very useful for understanding the self-assembly phenomena and controlling the SAM structure of DDS molecules on gold surfaces. Alkanethiol self-assembled monolayers (SAMs) on metal surfaces are key elements for the fabrication of functional organic layers and devices in the broad fields of nano-technology and biotechnology. However, it was found that alkanethiol SAMs were usually composed of structural defects such as domain boundaries and vacancy islands (VIs), which make them more amenable to oxidation. Compared to alkanethiols, thioethers (RSR') are more robust to oxidation, and their chemical structures with various alkyl chains can be modified readily by a simple synthetic method.

  6. Microelectrode array in mixed alkanethiol self-assembled monolayers: Electrochemical studies

    International Nuclear Information System (INIS)

    We report an efficient alternative to obtain recessed microelectrodes device on gold electrode surface, in which mixed self-assembled monolayer of long and short carbon alkanethiol chains was used for this purpose. Development of the modified electrodes included the chemical adsorption of 11-mercaptoundecanoic acid and 2-mercaptoethanol solution, as well as their mixtures, on gold surface, resulting in the final mixed self-assembled monolayer configuration. For comparison, the electrochemical performance of self-assembled monolayer of 11-mercaptoundecanoic acid, 3-mercaptopropionic acid, 4-mercapto-1-butanol and 6-mercapto-1-hexanol modified electrodes was also investigated. It was verified that, in the mixed self-assembled monolayer, the 11-mercaptoundecanoic acid acts as a barrier for electron transfer while the short alkanethiol chair is deposited in an island-like shape through which electrons can be freely transferred to ions in solution, allowing electrochemical reactions to occur. The performance of the modified electrodes toward microelectrode behavior was investigated via cyclic voltammetry and electrochemical impedance spectroscopy measurements using [Fe(CN)6]3−/4− redox couple as a probe. In this case, sigmoidal voltammetric responses were obtained, very similar to those observed for microelectrodes. Such behavior reinforces the proposition of electron transfer through the short alkanethiol chain layer and surface blockage by the long chain one. Electrochemical impedance results allowed calculated the mean radius value of each microelectrode disks of 3.8 μm with about 22 μm interval between them. The microelectrode environment provided by the mixed self-assembled monolayer can be conveniently used to provide an efficient catalytic conversion in biosensing applications.

  7. Electronic states of titanyl phthalocyanine films on alkanethiolate self-assembled monolayers probed by two-photon photoemission

    Energy Technology Data Exchange (ETDEWEB)

    Ogura, Munehisa [Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan); Shibuta, Masahiro; Eguchi, Toyoaki [Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan); JST-ERATO, Nakajima Designer Nanocluster Assembly Project, 3-2-1 Sakado, Takatsu-ku, Kawasaki 213-0012 (Japan); Nakajima, Atsushi, E-mail: nakajima@chem.keio.ac.jp [Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan); JST-ERATO, Nakajima Designer Nanocluster Assembly Project, 3-2-1 Sakado, Takatsu-ku, Kawasaki 213-0012 (Japan)

    2014-08-15

    We studied both occupied and unoccupied states of titanyl phthalocyanine (TiOPc) films formed on an octanethiolate self-assembled monolayer (SAM) on an Au(1 1 1) surface fabricated in a wet chemical process using two-photon photoemission (2PPE) spectroscopy. A 1.90-nm-thick layer of TiOPc formed an unoccupied state at 2.9 eV above the Fermi level. This state was resonantly enhanced at 4.3–4.4 eV photon energy, suggesting that electrons were excited from the highest occupied molecular orbital of TiOPc. The 2PPE measurements of photon energy dependence and light polarization selectivity revealed that the unoccupied state originates from a charge transfer exciton not observed in organic thin films deposited on bare metallic substrates. The formation of a charge transfer exciton implies that the SAM strongly insulates the molecular monolayer.

  8. Heterointerface Screening Effects between Organic Monolayers and Monolayer Transition Metal Dichalcogenides.

    Science.gov (United States)

    Zheng, Yu Jie; Huang, Yu Li; Chen, Yifeng; Zhao, Weijie; Eda, Goki; Spataru, Catalin D; Zhang, Wenjing; Chang, Yung-Huang; Li, Lain-Jong; Chi, Dongzhi; Quek, Su Ying; Wee, Andrew Thye Shen

    2016-02-23

    The nature and extent of electronic screening at heterointerfaces and their consequences on energy level alignment are of profound importance in numerous applications, such as solar cells, electronics etc. The increasing availability of two-dimensional (2D) transition metal dichalcogenides (TMDs) brings additional opportunities for them to be used as interlayers in "van der Waals (vdW) heterostructures" and organic/inorganic flexible devices. These innovations raise the question of the extent to which the 2D TMDs participate actively in dielectric screening at the interface. Here we study perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) monolayers adsorbed on single-layer tungsten diselenide (WSe2), bare graphite, and Au(111) surfaces, revealing a strong dependence of the PTCDA HOMO-LUMO gap on the electronic screening effects from the substrate. The monolayer WSe2 interlayer provides substantial, but not complete, screening at the organic/inorganic interface. Our results lay a foundation for the exploitation of the complex interfacial properties of hybrid systems based on TMD materials. PMID:26792247

  9. Organization, Structure and Activity of Proteins in Monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Boucher,J.; Trudel, E.; Methot, M.; Desmeules, P.; Salesse, C.

    2007-01-01

    Many different processes take place at the cell membrane interface. Indeed, for instance, ligands bind membrane proteins which in turn activate peripheral membrane proteins, some of which are enzymes whose action is also located at the membrane interface. Native cell membranes are difficult to use to gain information on the activity of individual proteins at the membrane interface because of the large number of different proteins involved in membranous processes. Model membrane systems, such as monolayers at the air-water interface, have thus been extensively used during the last 50 years to reconstitute proteins and to gain information on their organization, structure and activity in membranes. In the present paper, we review the recent work we have performed with membrane and peripheral proteins as well as enzymes in monolayers at the air-water interface. We show that the structure and orientation of gramicidin has been determined by combining different methods. Furthermore, we demonstrate that the secondary structure of rhodopsin and bacteriorhodopsin is indistinguishable from that in native membranes when appropriate conditions are used. We also show that the kinetics and extent of monolayer binding of myristoylated recoverin is much faster than that of the nonmyristoylated form and that this binding is highly favored by the presence polyunsaturated phospholipids. Moreover, we show that the use of fragments of RPE65 allow determine which region of this protein is most likely involved in membrane binding. Monomolecular films were also used to further understand the hydrolysis of organized phospholipids by phospholipases A2 and C.

  10. Crystallization and self-assembly of flowerlike superstructures of calcium carbonate regulated by pepsin Langmuir monolayers

    International Nuclear Information System (INIS)

    Flowerlike superstructures of calcium carbonate were synthesized at air–water interface in the presence of pepsin Langmuir monolayers as the biomimetic template. The phase structure, morphology, and microstructure of the products obtained at various crystallization stages were characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction and high resolution transmission electron microscopy. The structural and morphological evolution processes of the products from monodispersed nanoparticles to nanoparticle aggregates and flowerlike superstructures were investigated. Results indicate that the flowerlike superstructures of calcium carbonate are assembled from amorphous calcium carbonate nanoparticles. The growth and assembly of calcium carbonate minerals are significantly regulated by the pepsin Langmuir monolayers. Namely, the pepsin Langmuir monolayers stabilize amorphous calcium carbonate nanoparticles and direct their transformation to amorphous aggregates via non-oriented aggregation. The present approach presents a feasible way to manipulate the growth of inorganic crystal, which, hopefully, is to help better reveal the role of proteins in mineralization process and understand the mechanism of biomineralization. -- Highlights: ► Pepsin Langmuir monolayer as biomimetic template. ► Flower-like calcite crystals experience a novel assembly and growth process. ► The morphologic evolution and phase transformation were observed. ► The trace of initial nucleation site of CaCO3 at the interface was observed. ► The template directs the crystallization and growth process.

  11. Crystallization and self-assembly of flowerlike superstructures of calcium carbonate regulated by pepsin Langmuir monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Xue, Zhonghui [Key Laboratory for Special Functional Materials of Ministry of Education, Henan University, Kaifeng 475004 (China); School of Physics and Chemistry, Henan Polytechnic University, Jiaozuo 454000 (China); Hu, Binbin; Dai, Shuxi [Key Laboratory for Special Functional Materials of Ministry of Education, Henan University, Kaifeng 475004 (China); Du, Zuliang, E-mail: zld@henu.edu.cn [Key Laboratory for Special Functional Materials of Ministry of Education, Henan University, Kaifeng 475004 (China)

    2012-10-15

    Flowerlike superstructures of calcium carbonate were synthesized at air-water interface in the presence of pepsin Langmuir monolayers as the biomimetic template. The phase structure, morphology, and microstructure of the products obtained at various crystallization stages were characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction and high resolution transmission electron microscopy. The structural and morphological evolution processes of the products from monodispersed nanoparticles to nanoparticle aggregates and flowerlike superstructures were investigated. Results indicate that the flowerlike superstructures of calcium carbonate are assembled from amorphous calcium carbonate nanoparticles. The growth and assembly of calcium carbonate minerals are significantly regulated by the pepsin Langmuir monolayers. Namely, the pepsin Langmuir monolayers stabilize amorphous calcium carbonate nanoparticles and direct their transformation to amorphous aggregates via non-oriented aggregation. The present approach presents a feasible way to manipulate the growth of inorganic crystal, which, hopefully, is to help better reveal the role of proteins in mineralization process and understand the mechanism of biomineralization. -- Highlights: Black-Right-Pointing-Pointer Pepsin Langmuir monolayer as biomimetic template. Black-Right-Pointing-Pointer Flower-like calcite crystals experience a novel assembly and growth process. Black-Right-Pointing-Pointer The morphologic evolution and phase transformation were observed. Black-Right-Pointing-Pointer The trace of initial nucleation site of CaCO{sub 3} at the interface was observed. Black-Right-Pointing-Pointer The template directs the crystallization and growth process.

  12. Characterization of Formation Kinetics of Self-Assembled Thiol Monolayers on Gold by Electrochemical Impedance Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Self-assembled monolayers of octadecanethiol (ODT) on gold have been studied by electrochemical impedance spectroscopy (EIS). The fractional coverage has been examined as a function of immersion time of Au in ODT deposition solution. The fractional coverage exhibits two distinct adsorption steps: an initial rapid step followed by a slow one. The fractional coverage of ODT monolayer increases sharply from zero to more than 99% of its maximum within the first minute. However, it takes a day for the fractional coverage to approach its final value.

  13. Thiolated cyclodextrin self-assembled monolayer-like characterized with secondary ion mass spectrometry

    International Nuclear Information System (INIS)

    In the work the focus is on the preparation of self-assembled monolayer-like films consisting of thiolated cyclodextrin on gold substrate and a characterization by using secondary ion mass spectrometry. The short (1 min) and long (1 h) time preparations of self-assembled monolayer-like films, resulting in submonolayer and monolayer regimes, are investigated, respectively. The observed species of thiolated cyclodextrin (M as molecular ion) self-assembled monolayer-like films are assigned to three groups: AuxHySz clusters, fragments with origin in cyclodextrin molecule associated with Au, and molecular ions. The group of AuxHySz (x = 2-17, y = 0-2, z = 1-5) clusters have higher intensities than other species in the positive and even more in negative mass spectra. Interestingly, the dependence between the number of Au and S atoms shows that with the increasing size of AuxHySz clusters up to 11 Au atoms, the number of associated S atoms is also increasing and then decreasing. Molecular species as (M-S+H)Na+, (M+H)Na+, AuMNa+, (M2-S)Na+, and M2Na+ are determined, and also in cationized forms with K+. The intensities of thiolated cyclodextrin fragments at the long time preparation are approximately 10 times higher than the intensities of the same fragments observed at the short time. The largest observed ions in thiolated cyclodextrin self-assembled monolayer-like films are AuM2 and Au2M. The thiolated cyclodextrin molecular ions are compared with hexadecanethiol molecular ions in the form of AuxMw where the values of x and w are smaller for thiolated cyclodextrin than for hexadecanethiol. This result is supported with larger, more compact, and more stabile thiolated cyclodextrin molecule.

  14. Electrochemical characterization of a 1,8-octanedithiol self-assembled monolayer (ODT-SAM) on a Au(1 1 1) single crystal electrode

    International Nuclear Information System (INIS)

    Recently, it has becoming increasingly important to control the organization of self-assembled monolayers (SAMs) of ω-functionalized thiols for its potential applications in the construction of more complex molecular architectures. In this paper, we report on the spontaneous formation of a SAM of octanedithiol (ODT) as a function of the modification time. Electrochemical techniques such as cyclic voltammetry, double layer capacitance and electrochemical impedance spectroscopy are used for the characterization of this monolayer. The increase in modification time brings about changes in the octanedithiol self-assembled monolayer (ODT-SAM) reductive desorption voltammograms that indicate an evolution toward a more ordered and compact monolayer. This trend has also been found by following the changes in the electron transfer processes of the redox probe K3Fe(CN)6. In fact, the ODT-SAM formed at low-modification time does not significantly perturb the electrochemical response as it is typical of either a low coverage or of the presence of large defects in the layer. Upon increasing the modification time, the voltammograms of the redox probe adopt a sigmoidal shape indicating the existence of pinholes in the monolayer distributed as an array of microelectrodes. The surface coverage as well as the size and distribution of these pinholes have been determined by the impedance technique that gives a more reliable evaluation of these monolayer structural parameters

  15. Electrochemical characterization of a 1,8-octanedithiol self-assembled monolayer (ODT-SAM) on a Au(1 1 1) single crystal electrode

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Raya, Daniel; Madueno, Rafael; Sevilla, Jose Manuel; Blazquez, Manuel [Departamento de Quimica Fisica y Termodinamica Aplicada, Universidad de Cordoba, Campus de Rabanales, Ed. Marie Curie, E-14071 Cordoba (Spain); Pineda, Teresa [Departamento de Quimica Fisica y Termodinamica Aplicada, Universidad de Cordoba, Campus de Rabanales, Ed. Marie Curie, E-14071 Cordoba (Spain)], E-mail: tpineda@uco.es

    2008-11-15

    Recently, it has becoming increasingly important to control the organization of self-assembled monolayers (SAMs) of {omega}-functionalized thiols for its potential applications in the construction of more complex molecular architectures. In this paper, we report on the spontaneous formation of a SAM of octanedithiol (ODT) as a function of the modification time. Electrochemical techniques such as cyclic voltammetry, double layer capacitance and electrochemical impedance spectroscopy are used for the characterization of this monolayer. The increase in modification time brings about changes in the octanedithiol self-assembled monolayer (ODT-SAM) reductive desorption voltammograms that indicate an evolution toward a more ordered and compact monolayer. This trend has also been found by following the changes in the electron transfer processes of the redox probe K{sub 3}Fe(CN){sub 6}. In fact, the ODT-SAM formed at low-modification time does not significantly perturb the electrochemical response as it is typical of either a low coverage or of the presence of large defects in the layer. Upon increasing the modification time, the voltammograms of the redox probe adopt a sigmoidal shape indicating the existence of pinholes in the monolayer distributed as an array of microelectrodes. The surface coverage as well as the size and distribution of these pinholes have been determined by the impedance technique that gives a more reliable evaluation of these monolayer structural parameters.

  16. Electrochemical characterization of a 1,8-octanedithiol self-assembled monolayer (ODT-SAM) on a Au(111) single crystal electrode

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Raya, Daniel; Madueno, Rafael; Sevilla, Jose Manuel; Blazquez, Manuel; Pineda, Teresa [Departamento de Quimica Fisica y Termodinamica Aplicada, Universidad de Cordoba, Campus de Rabanales, Cordoba (Spain)

    2008-11-15

    Recently, it has becoming increasingly important to control the organization of self-assembled monolayers (SAMs) of {omega}-functionalized thiols for its potential applications in the construction of more complex molecular architectures. In this paper, we report on the spontaneous formation of a SAM of octanedithiol (ODT) as a function of the modification time. Electrochemical techniques such as cyclic voltammetry, double layer capacitance and electrochemical impedance spectroscopy are used for the characterization of this monolayer. The increase in modification time brings about changes in the octanedithiol self-assembled monolayer (ODT-SAM) reductive desorption voltammograms that indicate an evolution toward a more ordered and compact monolayer. This trend has also been found by following the changes in the electron transfer processes of the redox probe K{sub 3}Fe(CN){sub 6}. In fact, the ODT-SAM formed at low-modification time does not significantly perturb the electrochemical response as it is typical of either a low coverage or of the presence of large defects in the layer. Upon increasing the modification time, the voltammograms of the redox probe adopt a sigmoidal shape indicating the existence of pinholes in the monolayer distributed as an array of microelectrodes. The surface coverage as well as the size and distribution of these pinholes have been determined by the impedance technique that gives a more reliable evaluation of these monolayer structural parameters. (author)

  17. Distinct self-assembly of dithiol monolayers on Au(1 1 1) in water and hexane

    International Nuclear Information System (INIS)

    Highlights: • The self-assembly of 1,4-benzenedimethanethiol in water and in hexane is studied. • The initial phase of assembly is revealed for each solvent using STM and XPS. • Water stabilizes an ordered lying-down phase. • Hexane coadsorbs with benzenedimethanethiol and promotes standing-up absorption. - Abstract: The self-assembly of 1,4-benzenedimethanethiol on Au(1 1 1), at low concentration in water and in hexane which are respectively polar and non-polar solvent, has been studied by scanning tunneling microscopy (STM). The data reveal that, on clean Au(1 1 1), a complete and ordered self-assembled monolayer (SAM) of lying-down dithiols can form within a few seconds in water. While in hexane the adsorption is initially impeded by the rapid growth of an ordered hexane film that is gradually replaced by disordered domains of dithiol until completion of a saturated monolayer. Complemented by X-ray photoelectron spectroscopy measurements, the STM images resolve the progression of the self-assembly in both these polar and non-polar solvent, and highlight how the self-assembly depends on the trio solvent, dithiol, and substrate

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

    Directory of Open Access Journals (Sweden)

    Guus Rijnders

    2010-03-01

    Full Text Available 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(onates 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.

  19. Application of the self-assembled monolayer (SAM) model to dithiophosphate and dithiocarbamate engine wear inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Y.; Jiang, S.; Cagin, T.; Yamaguchi, E.S.; Frazier, R.; Ho, A.; Tang, Y.; Goddard, W.A. III

    2000-03-23

    In previous studies of dithiophosphate [TP=S{sub 2}P(OR){sub 2}] wear inhibitors bound to an oxidized iron surface, it was found that the cohesive energy of the self-assembled monolayers (SAM) for DTP molecules with various organic R groups correlate with the wear inhibition observed in full engine experiments. In this paper the calculations are expanded to consider dynamics at 500 K and the SAM model is used to predict new candidates for wear inhibitors. Using molecular dynamics (MD) simulations show that the SAM has one DTP per two surface Fe sites of iron oxide. At this coverage the cohesive energy of the SAM at 500 K is in the sequence 2-alkyl > 1-alkyl > aryl, which again correlates with wear inhibitor performance in engine wear tests. Dithiocarbamates are selected as the best candidate to supplement DTP.A number of possible alkyl substitutions for DTC were considered. The SAM model suggests that iC{sub 5} and nC{sub 3} are the best candidates, followed closely by iC{sub 3}.

  20. Tuning molecular level alignment and work function modification through self-assembled monolayers on noble metals: theoretical perspectives

    International Nuclear Information System (INIS)

    Full text: There is currently significant interest in highly-ordered, self-assembled monolayers (SAMs) on (noble) metal surfaces, inspired both by the emergence of the field of molecular electronics alongside the high potential for SAMs to improve the properties of more conventional device structures. SAMs are also used to control surface reactivity and for chemical sensing applications. In order to tune the interface properties and to endow the self-assembled systems with functionality suitable for use in either macroscopic or nanoscale devices, the use of π-conjugated systems is highly promising and the focus of intense, multidisciplinary research. The goal of the present study is to provide an in-depth description of the electronic structure of the interface between metallic substrates and covalently bound conjugated molecules. In this way, we expect to devise strategies to tune the interaction and thus the properties of the investigated systems and eventually to gain a full understanding of the processes governing the electronics of metal/organic interfaces. Here, we describe a first step in that direction: we study conjugated SAMs consisting of molecules with widely varied molecular ionization potentials, different conjugated backbones with different polarizabilities, and monolayers with varying degrees of coverage. We consider noble metals with varying work functions such as Au, Ag, and Pt, different molecule docking groups and investigate the effects of mechanical stress on the organic system. Using DFT band-structure-type methods, the details of the interface morphology, charge transfer between the metal and the molecules, interface dipoles, molecular layer depolarization, and work function modifications as well as the alignment between metallic and molecular levels are described. Our thorough analysis provides results that are sometimes a priori unexpected, like the finding that by properly tuning the molecular structure, the level alignment between the

  1. On-chip molecular electronic plasmon sources based on self-assembled monolayer tunnel junctions

    Science.gov (United States)

    Du, Wei; Wang, Tao; Chu, Hong-Son; Wu, Lin; Liu, Rongrong; Sun, Song; Phua, Wee Kee; Wang, Lejia; Tomczak, Nikodem; Nijhuis, Christian A.

    2016-04-01

    Molecular electronic control over plasmons offers a promising route for on-chip integrated molecular plasmonic devices for information processing and computing. To move beyond the currently available technologies and to miniaturize plasmonic devices, molecular electronic plasmon sources are required. Here, we report on-chip molecular electronic plasmon sources consisting of tunnel junctions based on self-assembled monolayers sandwiched between two metallic electrodes that excite localized plasmons, and surface plasmon polaritons, with tunnelling electrons. The plasmons originate from single, diffraction-limited spots within the junctions, follow power-law distributed photon statistics, and have well-defined polarization orientations. The structure of the self-assembled monolayer and the applied bias influence the observed polarization. We also show molecular electronic control of the plasmon intensity by changing the chemical structure of the molecules and by bias-selective excitation of plasmons using molecular diodes.

  2. On the Hopping Efficiency of Nanoparticles in the Electron Transfer across Self‐Assembled Monolayers

    DEFF Research Database (Denmark)

    Liu, Feng; Khan, Kamran; Liang, Jing‐Hong;

    2013-01-01

    Redox reactions of solvated molecular species at gold‐electrode surfaces modified by electrochemically inactive self‐assembled molecular monolayers (SAMs) are found to be activated by introducing Au nanoparticles (NPs) covalently bound to the SAM to form a reactive Au–alkanedithiol–NP–molecule hy......Redox reactions of solvated molecular species at gold‐electrode surfaces modified by electrochemically inactive self‐assembled molecular monolayers (SAMs) are found to be activated by introducing Au nanoparticles (NPs) covalently bound to the SAM to form a reactive Au......–alkanedithiol–NP–molecule hybrid entity. The NP appears to relay long‐range electron transfer (ET) so that the rate of the redox reaction may be as efficient as directly on a bare Au electrode, even though the ET distance is increased by several nanometers. In this study, we have employed a fast redox reaction of surface...

  3. A study of calixarene self-assembled monolayers on gold metal surfaces

    Czech Academy of Sciences Publication Activity Database

    Šustrová, Barbora; Mareček, Vladimír; Štulík, Karel

    Ústí nad Labem: BEST servis, 2010 - (Navrátil, T.; Barek, J.), s. 172-176 ISBN 978-80-254-6710-7. [Modern Electroanalytical Methods /30./. Jetřichovice (CZ), 24.05.2010-28.05.2010] R&D Projects: GA AV ČR IAA400400806 Institutional research plan: CEZ:AV0Z40400503 Keywords : calix[4]arene * self-assembled monolayer (SAM) * gold electrode Subject RIV: CG - Electrochemistry

  4. Attachment of tyrosinase on mixed self-assembled monolayers for the construction of electrochemical biosensor

    Institute of Scientific and Technical Information of China (English)

    Xue Ping Ji; Xian Rui Li; Na Wang; Rui Xing Ni; Xiao Hong Liu; Hua Ai Xiong

    2010-01-01

    A mixed self-assembled monolayers(SAMs)of thioctic acid(T-COOH)and thioctic acid amide(T-NH2)were used to immobilize tyrosinase for fabricating biosensor.The results showed that the mixed SAMs prepared from solution at the ratio of 1:4provided an excellent microenvironment for enzymatic reaction between tyrosinase and substrate.The biosensor exhibited a fast response and high sensitivity for sensing substrate.

  5. STM observation of sulfur dimerization in alkanethiol self-assembled monolayers on Au{111}

    OpenAIRE

    O'Dwyer, Colm

    2005-01-01

    We present for the first time, direct microscopical observation by STM of sulfur dimer formation on alkanethiol self-assembled monolayers (SAM) on sputtered Au substrates. The sulfur dimers are observed when imaging at a bias where the tip-molecule interaction occurs, and are formed by displacement of sulfur atoms from their normal three-fold hollow site residence of the (4 × 2) superlattice to nearest-neighbor bridge-site residence between two Au atoms. The displacement is ...

  6. Mass spectrometry assisted lithography for the patterning of cell adhesion ligands on self-assembled monolayers.

    Science.gov (United States)

    Kim, Young-Kwan; Ryoo, Soo-Ryoon; Kwack, Sul-Jin; Min, Dal-Hee

    2009-01-01

    Pattern of events: A simple and flexible method has been developed for patterning cell adhesion ligands. Locally erasing self-assembled monolayers with tri(ethyleneglycol) groups on a gold substrate by using a MALDI-TOF MS nitrogen laser and filling the exposed gold surface with an alkanethiol presenting carboxylic acid groups enables subsequent immobilization of maleimide and a cell adhesion peptide, which can then recognize cells (see scheme). PMID:19347909

  7. Carboranedithiols: Building Blocks for Self-Assembled Monolayers on Copper Surfaces

    Czech Academy of Sciences Publication Activity Database

    Baše, Tomáš; Bastl, Zdeněk; Havránek, Vladimír; Macháček, Jan; Langecker, Jens; Malina, Václav

    2012-01-01

    Roč. 28, č. 34 (2012), s. 12518-12526. ISSN 0743-7463 R&D Projects: GA ČR GAP205/10/0348; GA AV ČR KAN100400702 Institutional support: RVO:61388980 ; RVO:61388955 ; RVO:61389005 ; RVO:67985882 Keywords : copper surfaces * carboranethiols * cluster * chemisorption * self-assembled monolayer Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W) Impact factor: 4.187, year: 2012

  8. Linear hydrogen adsorbate structures on graphite induced by self-assembled molecular monolayers

    DEFF Research Database (Denmark)

    Nilsson, Louis; Sljivancanin, Zeljko; Balog, Richard; Xu, Wei; Linderoth, Trolle René; Lægsgaard, Erik; Stensgaard, Ivan; Hammer, Bjørk; Besenbacher, Flemming; Hornekær, Liv

    2012-01-01

    Combined scanning tunnelling microscopy measurements and density functional theory calculations reveal a method to induce linear structures of hydrogen adsorbates on graphite by covering the surface with a self-assembled molecular monolayer of cyanuric acid and exposing it to atomic hydrogen. The...... method can in principle be applied to obtain nanopatterned hydrogen structures on free standing graphene and graphene laid down on insulating substrates, hereby opening up for the possibility of substrate independent bandgap engineering of graphene....

  9. Reducing Staphylococcus aureus biofilm formation on stainless steel 316L using functionalized self-assembled monolayers

    OpenAIRE

    Kruszewski, Kristen M; Nistico, Laura; Mark J Longwell; Hynes, Matthew J; Maurer, Joshua A; Hall-Stoodley, Luanne; Gawalt, Ellen S.

    2013-01-01

    Stainless steel 316L (SS316L) is a common material used in orthopedic implants. Bacterial colonization of the surface and subsequent biofilm development can lead to refractory infection of the implant. Since the greatest risk of infection occurs perioperatively, strategies that reduce bacterial adhesion during this time are important. As a strategy to limit bacterial adhesion and biofilm formation on SS316L, self-assembled monolayers (SAMs) were used to modify the SS316L surface. SAMs with lo...

  10. Self-assembled monolayer as optical transducers using spiropyran photochromic material

    Science.gov (United States)

    Ortiz Ramírez, Alicia; Delgado Macuil, Raúl; Rojas López, Marlon; López Gayou, Valentin; Orduña Díaz, Abdu

    2011-09-01

    The self assembled monolayers (SAM) have become in the most popular strategy for design and generate surfaces characterizing by specific functional organic groups. The aimed of this work is applied this SAM as optical transducer in biosensors. The techniques, Infrared (in ATR mode) and UV/Vis spectroscopy have been used to study the films generated in each step in the self assembled process. The SAM was generated as follow; first silane group was added to the glass substrate. After that, the substrates were immersed in a solution containing carbomiide group (EDC). Finally the spiropyran 1',3'-Dihydro-8-methoxy-1',3',3'-trimethyl-6-nitrospiro[2H-1-benzopyran-2,2'-(2H)-indole] was attached to functionalized slides. In each process absorbance was analyzed by UV/Vis (270 to 500 nm) and FTIR (650 to 1800 cm-1). In UV, the spectra shows an absorbance band centered at 280 associated to EDC film and a lower intensity band centered at 380 nm associated to spiropyran. In FTIR spectra, the Si-Si and Si-O bond are present below the 1250 cm-1. The EDC film shows very weak bands in the region from 1300 to 1800 cm-1. For the spiropyran film the band associated to the C-N, N-O, C=C, C-H and aromatic ring have a very well defined peaks. Once the transducer bands were detected, it was immersed in glucose solution; the infrared spectral show bands are associated to glucose in the transducer.

  11. A New Organofunctional Ethoxysilane Self-Assembly Monolayer for Promoting Adhesion of Rubber to Aluminum

    Directory of Open Access Journals (Sweden)

    Qian Wang

    2009-10-01

    Full Text Available Practical adhesion of rubber to aluminum is measured for various aluminum silanization treatments. In this study, 6-(3-triethoxysilylpropylamino-1,3,5-triazine-2,4-dithiol (TES was used as the coupling agent for preparing self-assembly monolayers (SAMs on an aluminum surface. The structure and chemical composition of the SAMs were analyzed using Fourier transform infra-red spectroscopy (FT-IR and X-ray photoelectron spectroscopy (XPS. The changes in the surface features of the aluminum surface due to TES treatment were investigated by atomic force microscopy (AFM. The adhesive properties of the silanized aluminum surface and EPDM rubber have been evaluated by a T-peel strength test. The results suggested that the Si-O-Al bonding at aluminum TES interface existed and a TES self-assembly monolayer was formed on the aluminum surface. More than 6.0 KN/m adhesion strength is obtained when the aluminum is silanized with 2.5 mmol/dm3 TES, cured at 160 °C and vulcanized with EPDM rubber at 160 °C for 30 min. It is suggested that the TES self-assembly monolayer is bound to aluminum through its ethoxysilyl functional group, and the thiol function group is strongly crosslinked to EPDM rubber, respectively.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Electrochemical immunosensor for prostate-specific antigen using self-assembled oligophenylethynylenethiol monolayer containing dendrimer

    International Nuclear Information System (INIS)

    Electrochemical immunosensor for prostate-specific antigen (PSA) was fabricated with a self-assembled 4-(2-(4-(acetylthio)phenyl)ethynyl)benzoic acid (APBA) as a bioreceptor. In order to enhance the electrochemical activity of PSA detection, poly(amidoamine) dendrimer was linked on the APBA self-assembled monolayer (SAM). The formation and electrical properties of the SAMs were investigated by surface plasmon resonance and cyclic voltammetry, respectively. The surface morphology of PSA sandwich complex onto the APBA SAM was studied by atomic force microscopy.

  14. Free-Standing Monolayer Two-Dimensional Supramolecular Organic Framework with Good Internal Order.

    Science.gov (United States)

    Pfeffermann, Martin; Dong, Renhao; Graf, Robert; Zajaczkowski, Wojciech; Gorelik, Tatiana; Pisula, Wojciech; Narita, Akimitsu; Müllen, Klaus; Feng, Xinliang

    2015-11-18

    Utilizing dynamic self-assembly and self-sorting to obtain large-area, molecularly precise monolayered structures represents a promising approach toward two-dimensional supramolecular organic frameworks (2D SOF) or 2D supramolecular polymers. So far, related approaches suffer from small domain sizes, fragility and weak long-range internal order. Here we report on the self-assembly of a host-guest enhanced donor-acceptor interaction, consisting of a tris(methoxynaphthyl)-substituted truxene spacer, and a naphthalene diimide substituted with N-methyl viologenyl moieties as donor and acceptor monomers, respectively, in combination with cucurbit[8]uril as host monomer toward monolayers of an unprecedented 2D SOF. Featuring orthogonal solubility, the participating molecules self-assemble at a liquid-liquid interface, yielding exceptionally large-area, insoluble films, which were analyzed by transmission electron microscopy, atomic force microscopy and optical microscopy to be monolayers with a thickness of 1.8 nm, homogeneously covering areas up to 0.25 cm(2), and featuring the ability to be free-standing over holes of 10 μm(2). Characterization with ultraviolet-visible absorption spectroscopy, solid-state nuclear magnetic resonance spectroscopy, infrared spectroscopy, and grazing incidence wide-angle X-ray scattering allowed for confirmation of a successful complexation of all three monomers toward an internal long-range order and gave indications to an expected hexagonal superstructure. Our results extend the existing variety of two-dimensional soft nanomaterials by a versatile supramolecular approach, whereas the possibility of varying the functional monomers is supposed to open adaptability to different applications like membranes, sensors, molecular sieves, and optoelectronics. PMID:26529142

  15. Improved aging performance of vapor phase deposited hydrophobic self-assembled monolayers

    International Nuclear Information System (INIS)

    A hydrophobic self-assembled monolayer (SAM) of fluoro-octyl-trichloro-silane (FOTS) was deposited on silicon using a vapor phase technique. The aging of the hydrophobic layer was examined using water contact angle measurements. It has been found that while such monolayer films suffer from a loss of hydrophobicity with time, pre-immersion nitrogen annealing can significantly improve the aging characteristics of these monolayers. The effect of nitrogen annealing on the improved aging properties of SAM coatings has been investigated by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The hydrolytic stability and the effect of nitrogen annealing were studied by morphological evolution during immersion. A spontaneous formation of silane mounds on the surface of the monolayers was found by AFM. These mounds have been irreversibly transformed from initially uniform hydrophobic surface layers. It is highly probable that the compliance of these mounds can reasonably allow hydrophilic sites to be located around the mounds. Interestingly, the density of these mounds formation is very less on the annealed samples. XPS reveals a higher level of coverage by the N2-annealed film due to agglomeration. A relative abundance of CF3 and CF2 moieties in the annealed film may explain the enhancement of the hydrophobicity as revealed by higher level of water contact angle. This hydrophobicity was found to be significantly stable in water. This novel finding explains the improved hydrophobic stability of FOTS monolayers as primarily a morpho-chemical effect that originates from the densification of the monolayers upon annealing.

  16. Self-assembled monolayers of perfluoroalkylsilane on plasma-hydroxylated silicon substrates

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Lin; Cai, Lu; Liu, Anqi; Wang, Wei; Yuan, Yanhua [College of Textile, Clothing Engineering, Soochow University, Suzhou 215021 (China); National Engineering Laboratory for Modern Silk, Suzhou 215123 (China); Li, Zhanxiong, E-mail: lizhanxiong@suda.edu.cn [College of Textile, Clothing Engineering, Soochow University, Suzhou 215021 (China); State Key Laboratory of Disaster Prevention & Mitigation of Explosion & Impact, Nanjing 210007 (China)

    2015-09-15

    Highlights: • A novel kind of fluoroalkylsilane monomers with different fluoroalkyl chain length was synthesized. • The fluoroalkyl-terminated self-assembled monolayers (SAMs) on silanol-terminated silicon substrates were chemically fabricated using the liquid phase deposition method. • Fluoroalkylsilanes were used for the self-assembly rather than the silane coupling agents and fluorochemicals to fabricate controllable, ordered SAMs. • The angle-dependent XPS study was conducted to investigate the changes of surface structures as well as elemental compositions of the SAMs. • The results indicated that fluoroalkyl groups would migrate from the inner part of the monolayers to the outermost interface after heat treatment, resulting into the microphase separation of the SAMs surface. - Abstract: In this study, a novel kind of fluoroalkylsilane monomers with different fluoroalkyl chain lengths was synthesized via three steps method and characterized by Fourier transform infrared (FT-IR) spectroscopy, {sup 1}H and {sup 19}F nuclear magnetic resonance ({sup 1}H NMR and {sup 19}F NMR), and mass spectra (MS). Fluoroalkyl-terminated self-assembled monolayers (SAMs) on silanol-terminated silicon substrates (O{sub 2} plasma treatment) were chemically fabricated via –Si–O– covalent bonds using the liquid phase deposition method (LPD). The wetabilities of the SAMs were characterized by water contact angles (CA), surface free energies and adhesive force (AF) measurements. 3-(1H,1H,2H,2H-perfluorooctyloxycarbonyl) -propionamidepropyl-triethoxysilane (PFOPT) assembled monolayer was chosen for in-depth investigation as its CA was higher than the others. Attenuated total reflection infrared spectroscopy (ATR-IR) and X-ray photoelectron spectroscopy (XPS) were used to validate the attachment of PFOPT on the silicon substrate, together with the chemical composition and structure of the SAMs. The surface morphologies and roughness of the monolayers were obtained and

  17. Self-assembled monolayers of perfluoroalkylsilane on plasma-hydroxylated silicon substrates

    International Nuclear Information System (INIS)

    Highlights: • A novel kind of fluoroalkylsilane monomers with different fluoroalkyl chain length was synthesized. • The fluoroalkyl-terminated self-assembled monolayers (SAMs) on silanol-terminated silicon substrates were chemically fabricated using the liquid phase deposition method. • Fluoroalkylsilanes were used for the self-assembly rather than the silane coupling agents and fluorochemicals to fabricate controllable, ordered SAMs. • The angle-dependent XPS study was conducted to investigate the changes of surface structures as well as elemental compositions of the SAMs. • The results indicated that fluoroalkyl groups would migrate from the inner part of the monolayers to the outermost interface after heat treatment, resulting into the microphase separation of the SAMs surface. - Abstract: In this study, a novel kind of fluoroalkylsilane monomers with different fluoroalkyl chain lengths was synthesized via three steps method and characterized by Fourier transform infrared (FT-IR) spectroscopy, 1H and 19F nuclear magnetic resonance (1H NMR and 19F NMR), and mass spectra (MS). Fluoroalkyl-terminated self-assembled monolayers (SAMs) on silanol-terminated silicon substrates (O2 plasma treatment) were chemically fabricated via –Si–O– covalent bonds using the liquid phase deposition method (LPD). The wetabilities of the SAMs were characterized by water contact angles (CA), surface free energies and adhesive force (AF) measurements. 3-(1H,1H,2H,2H-perfluorooctyloxycarbonyl) -propionamidepropyl-triethoxysilane (PFOPT) assembled monolayer was chosen for in-depth investigation as its CA was higher than the others. Attenuated total reflection infrared spectroscopy (ATR-IR) and X-ray photoelectron spectroscopy (XPS) were used to validate the attachment of PFOPT on the silicon substrate, together with the chemical composition and structure of the SAMs. The surface morphologies and roughness of the monolayers were obtained and calculated through atomic force

  18. Tracing the 4000 year history of organic thin films: From monolayers on liquids to multilayers on solidsa)

    Science.gov (United States)

    Greene, J. E.

    2015-03-01

    The recorded history of organic monolayer and multilayer thin films spans approximately 4000 years. Fatty-acid-based monolayers were deposited on water by the ancients for applications ranging from fortune telling in King Hammurabi's time (˜1800 BC, Mesopotamia) to stilling choppy waters for sailors and divers as reported by the Roman philosopher Pliny the Elder in ˜78 AD, and then much later (1774) by the peripatetic American statesman and natural philosopher Benjamin Franklin, to Japanese "floating-ink" art (suminagashi) developed ˜1000 years ago. The modern science of organic monolayers began in the late-1800s/early-1900s with experiments by Lord Rayleigh and the important development by Agnes Pockels, followed two decades later by Irving Langmuir, of the tools and technology to measure the surface tension of liquids, the surface pressure of organic monolayers deposited on water, interfacial properties, molecular conformation of the organic layers, and phase transitions which occur upon compressing the monolayers. In 1935, Katherine Blodgett published a landmark paper showing that multilayers can be synthesized on solid substrates, with controlled thickness and composition, using an apparatus now known as the Langmuir-Blodgett (L-B) trough. A disadvantage of LB films for some applications is that they form weak physisorbed bonds to the substrate. In 1946, Bigelow, Pickett, and Zisman demonstrated, in another seminal paper, the growth of organic self-assembled monolayers (SAMs) via spontaneous adsorption from solution, rather than from the water/air interface, onto SiO2 and metal substrates. SAMs are close-packed two-dimensional organic crystals which exhibit strong covalent bonding to the substrate. The first multicomponent adsorbed monolayers and multilayer SAMs were produced in the early 1980s. Langmuir monolayers, L-B multilayers, and self-assembled mono- and multilayers have found an extraordinarily broad range of applications including controlled wetting

  19. Tracing the 4000 year history of organic thin films: From monolayers on liquids to multilayers on solids

    Energy Technology Data Exchange (ETDEWEB)

    Greene, J. E. [University of Illinois, Urbana, Illinois 61801 (United States); Linköping University, 581 83 Linköping (Sweden); National Taiwan University of Science and Technology, Taipei 10607, Taiwan (China)

    2015-03-15

    The recorded history of organic monolayer and multilayer thin films spans approximately 4000 years. Fatty-acid-based monolayers were deposited on water by the ancients for applications ranging from fortune telling in King Hammurabi's time (∼1800 BC, Mesopotamia) to stilling choppy waters for sailors and divers as reported by the Roman philosopher Pliny the Elder in ∼78 AD, and then much later (1774) by the peripatetic American statesman and natural philosopher Benjamin Franklin, to Japanese “floating-ink” art (suminagashi) developed ∼1000 years ago. The modern science of organic monolayers began in the late-1800s/early-1900s with experiments by Lord Rayleigh and the important development by Agnes Pockels, followed two decades later by Irving Langmuir, of the tools and technology to measure the surface tension of liquids, the surface pressure of organic monolayers deposited on water, interfacial properties, molecular conformation of the organic layers, and phase transitions which occur upon compressing the monolayers. In 1935, Katherine Blodgett published a landmark paper showing that multilayers can be synthesized on solid substrates, with controlled thickness and composition, using an apparatus now known as the Langmuir-Blodgett (L-B) trough. A disadvantage of LB films for some applications is that they form weak physisorbed bonds to the substrate. In 1946, Bigelow, Pickett, and Zisman demonstrated, in another seminal paper, the growth of organic self-assembled monolayers (SAMs) via spontaneous adsorption from solution, rather than from the water/air interface, onto SiO{sub 2} and metal substrates. SAMs are close-packed two-dimensional organic crystals which exhibit strong covalent bonding to the substrate. The first multicomponent adsorbed monolayers and multilayer SAMs were produced in the early 1980s. Langmuir monolayers, L-B multilayers, and self-assembled mono- and multilayers have found an extraordinarily broad range of applications including

  20. Tracing the 4000 year history of organic thin films: From monolayers on liquids to multilayers on solids

    International Nuclear Information System (INIS)

    The recorded history of organic monolayer and multilayer thin films spans approximately 4000 years. Fatty-acid-based monolayers were deposited on water by the ancients for applications ranging from fortune telling in King Hammurabi's time (∼1800 BC, Mesopotamia) to stilling choppy waters for sailors and divers as reported by the Roman philosopher Pliny the Elder in ∼78 AD, and then much later (1774) by the peripatetic American statesman and natural philosopher Benjamin Franklin, to Japanese “floating-ink” art (suminagashi) developed ∼1000 years ago. The modern science of organic monolayers began in the late-1800s/early-1900s with experiments by Lord Rayleigh and the important development by Agnes Pockels, followed two decades later by Irving Langmuir, of the tools and technology to measure the surface tension of liquids, the surface pressure of organic monolayers deposited on water, interfacial properties, molecular conformation of the organic layers, and phase transitions which occur upon compressing the monolayers. In 1935, Katherine Blodgett published a landmark paper showing that multilayers can be synthesized on solid substrates, with controlled thickness and composition, using an apparatus now known as the Langmuir-Blodgett (L-B) trough. A disadvantage of LB films for some applications is that they form weak physisorbed bonds to the substrate. In 1946, Bigelow, Pickett, and Zisman demonstrated, in another seminal paper, the growth of organic self-assembled monolayers (SAMs) via spontaneous adsorption from solution, rather than from the water/air interface, onto SiO2 and metal substrates. SAMs are close-packed two-dimensional organic crystals which exhibit strong covalent bonding to the substrate. The first multicomponent adsorbed monolayers and multilayer SAMs were produced in the early 1980s. Langmuir monolayers, L-B multilayers, and self-assembled mono- and multilayers have found an extraordinarily broad range of applications including

  1. Self-assembled monolayers on mosoporous supports (SAMMS) for RCRA metal removal

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Xiangdong; Liu, Jun; Fryxell, G. [Pacific Northwest National Lab., Richland, WA (United States)

    1997-10-01

    The Mixed Waste Focus Area has declared mercury removal and stabilization as the first and fourth priorities among 30 prioritized deficiencies. Resource Conservation and Recovery Act (RCRA) metal and mercury removal has also been identified as a high priority at DOE sites such as Albuquerque, Idaho Falls, Oak Ridge, Hanford, Rocky Flats, and Savannah River. Under this task, a proprietary new technology, Self-Assembled Monolayers on Mesoporous Supports (SAMMS), for RCRA metal ion removal from aqueous wastewater and mercury removal from organic wastes such as vacuum pump oils is being developed at Pacific Northwest National Laboratory (PNNL). The six key features of the SAMMS technology are (1) large surface area (>900 m{sup 2}/g) of the mesoporous oxides (SiO{sub 2}, ZrO{sub 2}, TiO{sub 2}) ensures high capacity for metal loading (more than 1 g Hg/g SAMMS); (2) molecular recognition of the interfacial functional groups ensures the high affinity and selectivity for heavy metals without interference from other abundant cations (such as calcium and iron) in wastewater; (3) suitability for removal of mercury from both aqueous wastes and organic wastes; (4) the Hg-laden SAMMS not only pass TCLP tests, but also have good long-term durability as a waste form because the covalent binding between mercury and SAMMS has good resistance to ion exchange, oxidation, and hydrolysis; (5) the uniform and small pore size (2 to 40 nm) of the mesoporous silica prevents bacteria (>2000 nm) from solubilizing the bound mercury; and (6) SAMMS can also be used for RCRA metal removal from gaseous mercury waste, sludge, sediment, and soil.

  2. Effect of density and structure on dynamics within self-assembled monolayers

    Science.gov (United States)

    Stevens, Derrick; Scott, Mary; Bochinski, Jason; Clarke, Laura

    2009-03-01

    Previously, we have observed interacting dynamics within self-assembled alkylsiloxane monolayers, and characterized this motion via sensitive dielectric spectroscopy (along with more traditional techniques such as ellipsometry, contact angle, and force microscopy). In these monolayers, molecules are covalently bound to the surface and thus cannot spontaneously change density, as in an adsorbate system. We identified this relaxation as akin to the polyethylene-like glass transition observed in polymers with phase-segregated alkyl side chains [1]. As a next step, we deliberately manipulated the physical structure of the monolayers (via different film growth procedures and/or post-deposition heat treating) and the monolayer density (from ˜10% to full coverage), and observed the resultant changes in dynamics. This experimental system may prove a useful model for more complex materials, such as glassy polymers or traditional molecular glasses, where density cannot be explicitly tuned. As density increases, the steepness index increases, indicating a more complex or fragile relaxation. At low densities, the motion has an almost-Arrhenius dependence on temperature. [1] M.C. Scott, D.R. Stevens, J.R. Bochinski, L.I. Clarke, ACS Nano. DOI: 10.1021/nn800543j.

  3. Molecular junctions of self-assembled monolayers with conducting polymer contacts.

    Science.gov (United States)

    Neuhausen, Alexander B; Hosseini, Ali; Sulpizio, Joseph A; Chidsey, Christopher E D; Goldhaber-Gordon, David

    2012-11-27

    We present a method to fabricate individually addressable junctions of self-assembled monolayers (SAMs) that builds on previous studies which have shown that soft conductive polymer top contacts virtually eliminate shorts through the SAMs. We demonstrate devices with nanoscale lateral dimensions, representing an order of magnitude reduction in device area, with high yield and relatively low device-to-device variation, improving several features of previous soft contact devices. The devices are formed in pores in an inorganic dielectric layer with features defined by e-beam lithography and dry etching. We replace the aqueous PEDOT:PSS conductive polymer used in prior devices with Aedotron P, a low-viscosity, amphiphilic polymer, allowing incorporation of self-assembled monolayers with either hydrophobic or hydrophilic termination with the same junction geometry and materials. We demonstrate the adaptability of this new design by presenting transport measurements on SAMs composed of alkanethiols with methyl, thiol, carboxyl, and azide terminations. We establish that the observed room-temperature tunnel barrier is primarily a function of monolayer thickness, independent of the terminal group's hydrophilicity. Finally, we investigate the temperature dependence of transport and show that the low-temperature behavior is based on the energy distribution of sites from which carriers can tunnel between the polymer and gold contacts, as described by a model of variable-range hopping transport in a disordered conductor. PMID:23035989

  4. Oxidation protection of copper surfaces using self-assembled monolayers of octadecanethiol

    International Nuclear Information System (INIS)

    Self-assembled monolayers (SAMs) of alkanethiols adsorbed onto clean surfaces of face centred cubic (fcc) metals have been studied extensively for their ability to control the chemical functionality of the surface and as a means of preventing the oxidation and corrosion of the substrate metal. However, in many cases it has been found that on reactive substrates such as copper, it is difficult to prepare SAMs without the incorporation of some oxygen into the structure. In this work, self-assembled monolayers of octadecanethiol (ODT) were formed on copper foil substrates using a series of etching treatments to remove the native oxide layer prior to deposition of the ODT coating from a modified solution. X-ray photoelectron spectroscopy was used to analyse the SAMs and showed that monolayers with no detectable oxygen content could be produced. The effect of exposing the samples to air at different temperatures was monitored to examine the rate of the oxidation process, which was found to vary strongly with temperature. Samples stored at room temperature were found to oxidise relatively quickly, while those kept in a refrigerator were slower. Storing samples in a freezer dramatically reduced the oxidation of the copper, such that samples kept for 10 weeks still did not show any clear evidence of oxygen incorporation

  5. Advancing atomic nanolithography: cold atomic Cs beam exposure of alkanethiol self-assembled monolayers

    International Nuclear Information System (INIS)

    We report the results of a study into the quality of functionalized surfaces for nanolithographic imaging. Self-assembled monolayer (SAM) coverage, subsequent post-etch pattern definition and minimum feature size all depend on the quality of the Au substrate used in atomic nanolithographic experiments. We find sputtered Au substrates yield much smoother surfaces and a higher density of {111} oriented grains than evaporated Au surfaces. A detailed study of the self-assembly mechanism using molecular resolution AFM and STM has shown that the monolayer is composed of domains with sizes typically of 5-25 nm, and multiple molecular domains can exist within one Au grain. Exposure of the SAM to an optically-cooled atomic Cs beam traversing a two-dimensional array of submicron material masks and also standing wave optical masks allowed determination of the minimum average Cs dose (2 Cs atoms per SAM molecule) and the realization of < 50 nm structures. The SAM monolayer contains many non-uniformities such as pin-holes, domain boundaries and monoatomic depressions which are present in the Au surface prior to SAM adsorption. These imperfections limit the use of alkanethiols as a resist in atomic nanolithography experiments. These studies have allowed us to realize an Atom Pencil suitable for deposition of precision quantities of material at the microand nanoscale to an active surface

  6. Protection of iron corrosion by stearic acid and stearic imidazoline self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Liu Xiuyu [Department of Chemistry, Shandong University, Jinan 250100 (China); Chen Shenhao [Department of Chemistry, Shandong University, Jinan 250100 (China) and State Key laboratory for Corrosion and Protection, Shenyang 110015 (China)]. E-mail: shchen@sdu.edu.cn; Ma Houyi [Department of Chemistry, Shandong University, Jinan 250100 (China); Liu Guangzeng [Department of Chemistry, Shandong University, Jinan 250100 (China); Shen Lixia [Department of Chemistry, Shandong University, Jinan 250100 (China)

    2006-11-15

    A type of stearic imidazoline (IM) inhibitor was prepared using stearic acid (SA) and diethylenetriamine (DETA) as raw materials. The monolayers of IM and SA were assembled on the iron surface. The electrochemical characterization of stearic acid (SA) and stearic imidazoline (IM) on an oxide free iron surface had been studied. The monolayers of IM inhibitor were characterized by electrochemical impedance spectroscopy (EIS), electrochemical polarization curves, double layer capacitance, X-ray photoelectron spectroscopy (XPS) and molecular simulation. The results of electrochemical studies had illustrated that the inhibition efficiency of IM was higher than SA. XPS showed that the IM molecules adsorbed on the iron surface. The molecular simulation calculations showed that the IM molecules were tilted at an angle on the iron surface.

  7. Preparation and characterization of 3-(triethoxysilyl) propyl isocyanate self-assembled monolayer on surface of chip

    Institute of Scientific and Technical Information of China (English)

    XIE Yao; GENG LiNa; QU Feng; LUO AiQin; QU Feng; DENG YuLin

    2009-01-01

    Monolayer of 3-(triethoxysilyl) propyl isocyanate was prepared on the slide by self-assembled tech-nique. X-ray photoelectron spectroscopy (XPS) was employed to analyze the elementary composition of the film. Contact angle of distilled water was measured to characterize the surface state. It was shown that 3-(triethoxysilyl) propyl isocyanate had been successfully assembled on the slide. The in-crease of contact angle to 80 demonstrated that the hydrophobicity of the surface of chip was in-creased significantly. Moreover, further self-assembly of bovine serum albumin (BSA) on 3-(trietho-xysilyl) propyl isocyanate was also carried out with the advantages such as simple and convenient preparation. Therefore, the potential of broader applications in the modification of micro-channel in the μ-TAS system, the immobilization of protein or peptide and the surface modification of materials are all expectative.

  8. Spontaneous phase separation during self-assembly in bi-dispersed spherical iron oxide nanoparticle monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Stanley, Jacob; Boucheron, Leandra; Shpyrko, Oleg, E-mail: lin@cars.uchicago.edu, E-mail: oshpyrko@physics.ucsd.edu [Department of Physics, University of California, San Diego, La Jolla, California 92093 (United States); Lin, Binhua, E-mail: lin@cars.uchicago.edu, E-mail: oshpyrko@physics.ucsd.edu; Meron, Mati [Center for Advanced Radiation Sources (CARS), University of Chicago, Chicago, Illinois 60637 (United States)

    2015-04-20

    Recent developments in the synthesis of iron oxide nanoparticles have resulted in the ability to fabricate roughly spherical particles with extremely high size uniformity (low polydispersity). These particles can form self-assembled monolayer films at an air-water interface. When the polydispersity of the particles is low, these monolayers can be well-ordered over a length scale dozens of times the particle size. The van der Waals force between the particles is what drives this self-assembly. Through the use of Grazing Incidence X-Ray Diffraction we demonstrate that, when these films are formed at the liquid surface from bi-dispersed solutions containing 10 and 20 nm spherical particles suspended in chloroform, the particles phase separate into well-ordered patches during the self-assembly process. Furthermore, the domain sizes of these phase separated regions are at most 2–3 times smaller than that of a film comprising only mono-dispersed particles and their degree of disorder is comparable. This is shown for multiple solutions with differing ratios of 10 and 20 nm particles.

  9. Spontaneous phase separation during self-assembly in bi-dispersed spherical iron oxide nanoparticle monolayers

    International Nuclear Information System (INIS)

    Recent developments in the synthesis of iron oxide nanoparticles have resulted in the ability to fabricate roughly spherical particles with extremely high size uniformity (low polydispersity). These particles can form self-assembled monolayer films at an air-water interface. When the polydispersity of the particles is low, these monolayers can be well-ordered over a length scale dozens of times the particle size. The van der Waals force between the particles is what drives this self-assembly. Through the use of Grazing Incidence X-Ray Diffraction we demonstrate that, when these films are formed at the liquid surface from bi-dispersed solutions containing 10 and 20 nm spherical particles suspended in chloroform, the particles phase separate into well-ordered patches during the self-assembly process. Furthermore, the domain sizes of these phase separated regions are at most 2–3 times smaller than that of a film comprising only mono-dispersed particles and their degree of disorder is comparable. This is shown for multiple solutions with differing ratios of 10 and 20 nm particles

  10. Vapor Phase Self-assembled Monolayers for Anti-stiction Applications in MEMS

    DEFF Research Database (Denmark)

    Zhuang, Yanxin; Hansen, Ole; Knieling, Thomas;

    2007-01-01

    We have investigated the anti-stiction performance of self-assembled monolayers (SAMs) that were grown in vapor phase from six different organosilane precursors: CF3(CF2)5(CH2)2SiCl3 (FOTS), CF3(CF2)5(CH2)2Si(OC2H5)3 (FOTES), CF3(CF2)5(CH2)2Si(CH3)Cl2 (FOMDS), CF3(CF2)5(CH2)2Si(CH3)2Cl (FOMMS), C...

  11. Towards strain gauges based on a self-assembled nanoparticle monolayer-SAXS study

    International Nuclear Information System (INIS)

    An in situ small-angle x-ray scattering study of the nanoparticle displacement in a self-assembled monolayer as a function of a supporting membrane strain is presented. The average nanoparticle spacing is 6.7 nm in the unstrained state and increases in the applied force direction, following linearly the membrane strain which reaches the maximum value of 11%. The experimental results suggest a continuous mutual shift of the nanoparticles and their gradual separation with the growing stress rather than nanoparticle islands formation. No measurable shift of the nanoparticles was observed in the direction perpendicular to the applied stress.

  12. Concentration dependence of nanoparticle surface coverage for ionic self-assembled monolayers

    Science.gov (United States)

    Kim, Vincent; Simpson, Brian; Seredinski, Andrew; Schwen, Eric; Mazilu, Dan; Mazilu, Irina

    2014-03-01

    We investigate the concentration dependence of the surface coverage of thin films that consist of silica nanoparticles deposited on the substrates via the ISAM (ionically self-assembled monolayers) technique. Several experiments were conducted in order to investigate the factors that affected the quality of the coatings and one significant factor observed was the concentration of the colloidal silica solution. Using SEM micrographs, we analyzed the surface coverage and compared it to the analytical results obtained using a cooperative sequential adsorption model. The results we obtained matched the linear relation between particle density and the inverse of the concentration predicted by the theory.

  13. Experimental Study of the Temperature Dependence of Substrate Coverage in Ionic Self-Assembled Monolayers

    Science.gov (United States)

    Simpson, Brian; Abudayyeh, Mohammad; Ali, Md; Hamrick, Alena; Mazilu, Dan; Mazilu, Irina

    2014-03-01

    We investigate the temperature dependence of the surface coverage of thin films consisting of silica nanoparticles deposited on glass substrates via the ISAM (ionically self-assembled monolayers) technique. Variables such as the concentration and pH of the silica colloidal suspension and polyelectrolyte solution, dipping time, and particle size among others are controlled, and the thin films are deposited on substrates under a range of temperature values. The samples are analyzed using scanning electron microscopy. The surface coverage is estimated by employing a pixel-count comparison of grayscale values in the SEM micrographs and compared to analytical results obtained using a cooperative sequential adsorption model. Presentor.

  14. Crystalline self-assembly into monolayers of folded oligomers at the air-water interface

    DEFF Research Database (Denmark)

    Lederer, K.; Godt, A.; Howes, P.B.; Kjær, K.; Als-Nielsen, J.; Lahav, M.; Wegner, G.; Leiserowitz, L.; Weissbuch, I.

    2000-01-01

    Insertion of the 115-bis(ethynylene)benzene unit as a rigid spacer into a linear alkyl chain, thus separating the two resulting stems by 9 Angstrom, induces chain folding at the air-water interface. These folded molecules self-assemble into crystalline monolayers at this interface, with the plane...... the number and position of the hydrophilic groups in the molecule. The molecules form ribbons with a higher crystal coherence in the direction of stacking between the molecular ribbons, and a lower coherence along the ribbon direction. A similar molecule, but with a spacer unit that imposes a 5...

  15. Specific ion effects on the hydrophobic interaction of benzene self-assembled monolayers

    DEFF Research Database (Denmark)

    Dobberschütz, Sören; Pedersen, Morten Rimmen; Hassenkam, Tue;

    2015-01-01

    interaction of benzene self-assembled monolayers. Using the jump to contact phenomenon of an atomic force microscope (AFM) tip as an indicator of attractive forces between the surfaces of a sample and the tip, we discovered lower frequencies in the snap in as well as narrower distributions for the snap....... Bridging capillaries, i.e. nanometre scale gas bubbles, are some of the factors contributing to the long range hydrophobic interaction. The results demonstrate how ions influence the attraction of hydrophobic entities in aqueous solutions....

  16. Self-assembly monolayer of mercaptopropyltrimethoxysilane for electroless deposition of Ag

    International Nuclear Information System (INIS)

    Mercaptopropyltrimethoxysilane (MPTS) was used to form self-assembly monolayers (SAMs) on glass slides, which was verified by using X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES). Electroless plating of Ag was performed on the SAMs-modified glass slide. XPS study showed that Ag colloids formed in solution were successfully and hard anchored on SAMs through chemical bonds. Scanning electron microscopy (SEM) analysis illustrated that Ag film on the SAMs-modified glass showed more predominant in durability of temperature than that on conventionally modified glass

  17. Functionalization of SnO₂ crystals with a covalently-assembled porphyrin monolayer.

    Science.gov (United States)

    Cristaldi, Domenico A; Gulino, Antonino

    2013-06-01

    The functionalization of micro- and nano-sized metal-oxide powders offers many advantages because of their large surface areas and, therefore, the large number of functional molecules that can be grafted onto the grain surfaces. Porphyrin molecules on large band-gap semiconducting metal oxides represent key materials for many different optical and electronic applications. Herein, we have proposed a general two-step procedure for the functionalization of metal-oxide crystals with dye-sensitizers. In particular, we functionalized SnO₂ nanoparticles with a monolayer of the bifunctional trichloro[4-(chloromethyl)phenyl]silane. Then, a monolayer of 5,10,15,20-tetrakis(4-hydroxyphenyl)-21H,23H-porphyne was covalently bound to the silanized SnO₂ grains. IR, UV/Vis, and luminescence measurements were used for optical characterization. The measured footprint of the grafted porphyrin molecules indicated total surface coverage of the grains. The surface electronic characterization was performed by using X-ray photoelectron spectroscopy. Emission measurements revealed two strong bands at 664.1 and 721.0 nm that were attributed to the porphyrin monolayer assembled on the surface of the SnO₂ crystals. PMID:23610085

  18. A DNA self-assembled monolayer for the specific attachment of unmodified double- or single-stranded DNA.

    OpenAIRE

    Bamdad, C

    1998-01-01

    A novel method for DNA surface immobilization and a paradigm for the attachment of unmodified DNA of any length or sequence are described herein. The development of a DNA self-assembled monolayer (DNA-SAM) that incorporates a DNA-thiol into a monolayer of inert alkane thiolates is reported. This DNA-SAM specifically hybridized complementary oligonucleotides while resisting the nonspecific adsorption of noncomplementary DNA and irrelevant proteins. Duplex DNA, having a single-stranded "capture...

  19. High-Efficiency Colloidal Quantum Dot Photovoltaics via Robust Self-Assembled Monolayers

    KAUST Repository

    Kim, Gi-Hwan

    2015-11-11

    © 2015 American Chemical Society. The optoelectronic tunability offered by colloidal quantum dots (CQDs) is attractive for photovoltaic applications but demands proper band alignment at electrodes for efficient charge extraction at minimal cost to voltage. With this goal in mind, self-assembled monolayers (SAMs) can be used to modify interface energy levels locally. However, to be effective SAMs must be made robust to treatment using the various solvents and ligands required for to fabricate high quality CQD solids. We report robust self-assembled monolayers (R-SAMs) that enable us to increase the efficiency of CQD photovoltaics. Only by developing a process for secure anchoring of aromatic SAMs, aided by deposition of the SAMs in a water-free deposition environment, were we able to provide an interface modification that was robust against the ensuing chemical treatments needed in the fabrication of CQD solids. The energy alignment at the rectifying interface was tailored by tuning the R-SAM for optimal alignment relative to the CQD quantum-confined electron energy levels. This resulted in a CQD PV record power conversion efficiency (PCE) of 10.7% with enhanced reproducibility relative to controls.

  20. Electrochemical and Photoelectrochemical Study of Self-assembled Monolayer of Phytic Acid on Brass

    Institute of Scientific and Technical Information of China (English)

    XU Qun-Jie; WAN Zong-Yue; ZHOU Guo-Ding; YIN Ren-He; CAO Wei-Min; LIN Chang-Jian

    2008-01-01

    Phytic acid is an environment-friendly reagent for processing metals.The anticorrosion and inhibiting mechanism for phytic acid monolayers self-assembled on a brass (HSn70-1) electrode has been investigated by using electrochemical and photocurrent response methods.The electrochemical measurements indicate that phytic acid is liable to form surface complexes on the brass electrode,and the self-assembled monolayers (SAM) change the structure of the electric double-layer and shift the potential of zero charge positively.The photochemical measurement indicates that the brass electrode shows a p-type photoresponse owing to the formation of a Cu2O layer on its surface,and the presence of SAM weakens significantly the photoresponse,suggesting an excellent effect on anticorrosion,which is consistent with the EIS and polarization curve measurements.Adsorption of phytic acid was found to be typical of chemisorption,which can be reasonably described on the basis of the Langmuir isotherm.

  1. Gold electrode modified by self-assembled monolayers of thiols to determine DNA sequences hybridization

    Indian Academy of Sciences (India)

    Mízia M S Silva; Igor T Cavalcanti; M Fátima Barroso; M Goreti F Sales; Rosa Fireman Dutra

    2010-11-01

    The process of immobilization of biological molecules is one of the most important steps in the construction of a biosensor. In the case of DNA, the way it exposes its bases can result in electrochemical signals to acceptable levels. The use of self-assembled monolayer that allows a connection to the gold thiol group and DNA binding to an aldehydic ligand resulted in the possibility of determining DNA hybridization. Immobilized single strand of DNA (ssDNA) from calf thymus pre-formed from alkanethiol film was formed by incubating a solution of 2-aminoethanothiol (Cys) followed by glutaraldehyde (Glu). Cyclic voltammetry (CV) was used to characterize the self-assembled monolayer on the gold electrode and, also, to study the immobilization of ssDNA probe and hybridization with the complementary sequence (target ssDNA). The ssDNA probe presents a well-defined oxidation peak at +0.158 V. When the hybridization occurs, this peak disappears which confirms the efficacy of the annealing and the DNA double helix performing without the presence of electroactive indicators. The use of SAM resulted in a stable immobilization of the ssDNA probe, enabling the hybridization detection without labels. This study represents a promising approach for molecular biosensor with sensible and reproducible results.

  2. Protection of beryllium metal against microbial influenced corrosion using silane self-assembled monolayers

    Science.gov (United States)

    Vaidya, Rajendra U.; Deshpande, Alina; Hersman, Larry; Brozik, Susan M.; Butt, Darryl

    1999-08-01

    The effectiveness of a self-assembled silane monolayer as protection for beryllium against microbiologically influenced corrosion (MIC) was demonstrated. Four-point bend tests on coated and uncoated beryllium samples were conducted after microbiological exposures, and the effectiveness of these coatings as MIC protection was reported through mechanical property evaluations. Application of the silane monolayer to the beryllium surfaces was found to prevent degradation of the failure strength and displacement-to-failure of beryllium in bending. In contrast, the uncoated beryllium samples exhibited a severe reduction in these mechanical properties in the presence of the marine Pseudomonas bacteria. The potentiodynamic measurements showed that both the uncoated and coated samples pitted at the open-circuit potential. However, the size and distribution of the corrosion pits formed on the surface of the beryllium samples were significantly different for the various cases (coated vs uncoated samples exposed to control vs inoculated medium). This study demonstrates the following: (1) the deleterious effects of MIC on the mechanical properties of beryllium and (2) the potential for developing fast, easy, and cost-effective MIC protection for beryllium metal using silane self-assemblies.

  3. Understanding the Phase Diagram of Self-Assembled Monolayers of Alkanethiolates on Gold

    Science.gov (United States)

    2016-01-01

    Alkanethiolate monolayers on gold are important both for applications in nanoscience as well as fundamental studies of adsorption and self-assembly at metal surfaces. While considerable experimental effort has been put into understanding the phase diagram of these systems, theoretical work based on density functional theory (DFT) has long been hampered by the inability of conventional exchange-correlation functionals to describe dispersive interactions. In this work, we combine dispersion-corrected DFT calculations using the new vdW-DF-CX functional with the ab initio thermodynamics method to study the stability of dense standing-up and low-coverage lying-down phases on Au(111). We demonstrate that the lying-down phase has a thermodynamic region of stability starting from thiolates with alkyl chains consisting of n ≈ 3 methylene units. This phase emerges as a consequence of a competition between dispersive chain–chain and chain–substrate interactions, where the strength of the latter varies more strongly with n. A phase diagram is derived under ultrahigh-vacuum conditions, detailing the phase transition temperatures of the system as a function of the chain length. The present work illustrates that accurate ab initio modeling of dispersive interactions is both feasible and essential for describing self-assembled monolayers. PMID:27313813

  4. Studies of the structure and properties of organic monolayers, multilayers and superlattices

    International Nuclear Information System (INIS)

    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. 20 refs., 11 figs

  5. Photocatalytic oxidation of the organic monolayers on TiO{sub 2} surface investigated by in-situ sum frequency generation spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Tong, Yujin; Peng, Qiling; Ma, Tongsen; Nishida, Takuma; Ye, Shen, E-mail: ye@cat.hokudai.ac.jp [Catalysis Research Center, Hokkaido University, Sapporo 060-0811 (Japan)

    2015-10-01

    In-situ vibrational sum frequency generation (SFG) spectroscopy has been employed to investigate the photocatalytic oxidation of two types of well-ordered organic monolayers, namely, an arachidic acid (AA) monolayer prepared by the Langmuir-Blodgett method and an octadecyltrichlorosilane (OTS) monolayer prepared by the self-assembling method, on a TiO{sub 2} surface under ultraviolet (UV) irradiation. The extremely high sensitivity and unique selectivity of the SFG spectroscopy enabled us to directly probe the structural changes in these monolayers during the surface photocatalytic oxidation and further elucidate their reaction mechanisms at a molecular level. It was revealed that the ordering of the monolayers during the photocatalytic reaction is strongly dependent on their interaction with the substrate; the AA monolayer maintains its ordered conformation until the final oxidation stage, while the OTS monolayer shows a large increase in disordering during the initial oxidation stage, indicating a different photocatalytic reaction mechanism of the two monolayers on the TiO{sub 2} surface.

  6. Photocatalytic oxidation of the organic monolayers on TiO2 surface investigated by in-situ sum frequency generation spectroscopy

    Directory of Open Access Journals (Sweden)

    Yujin Tong

    2015-10-01

    Full Text Available In-situ vibrational sum frequency generation (SFG spectroscopy has been employed to investigate the photocatalytic oxidation of two types of well-ordered organic monolayers, namely, an arachidic acid (AA monolayer prepared by the Langmuir-Blodgett method and an octadecyltrichlorosilane (OTS monolayer prepared by the self-assembling method, on a TiO2 surface under ultraviolet (UV irradiation. The extremely high sensitivity and unique selectivity of the SFG spectroscopy enabled us to directly probe the structural changes in these monolayers during the surface photocatalytic oxidation and further elucidate their reaction mechanisms at a molecular level. It was revealed that the ordering of the monolayers during the photocatalytic reaction is strongly dependent on their interaction with the substrate; the AA monolayer maintains its ordered conformation until the final oxidation stage, while the OTS monolayer shows a large increase in disordering during the initial oxidation stage, indicating a different photocatalytic reaction mechanism of the two monolayers on the TiO2 surface.

  7. Fabrication of a Mono-Domain Alignment Ferroelectric Liquid Crystal Device Using a Polar Self-Assembled Monolayer

    Institute of Scientific and Technical Information of China (English)

    ZOU Zhong-Fei; YAO Li-Shuang; TANG Xian-Zhu; JI Xin-Jian; XUAN Li

    2008-01-01

    A mono-domain ferroelectric liquid crystal device (FLCD) is fabricated using a novel method. The cell used in this method is an asymmetric cell, typically the combination of a polar self-assembled monolayer (SAM) for one substrate and a rubbed polyimide for the other substrate. A defect-free alignment of ferroelectric liquid crystal is fabricated without applying a dc voltage to remove degeneracy in the layer structure. The contact angles of self-assembled monolayer and PI-2942 are measured and the polarity of SAM is higher than the PI alignment. It is found that the polarity of self-assembled monolayer is a key factor in the formation of mono-domain alignment of FLC.

  8. Patterning of self-assembled monolayers by phase-shifting mask and its applications in large-scale assembly of nanowires

    International Nuclear Information System (INIS)

    A nonselective micropatterning method of self-assembled monolayers (SAMs) based on laser and phase-shifting mask (PSM) is demonstrated. Laser beam is spatially modulated by a PSM, and periodic SAM patterns are generated sequentially through thermal desorption. Patterned wettability is achieved with alternating hydrophilic/hydrophobic stripes on octadecyltrichlorosilane monolayers. The substrate is then used to assemble CdS semiconductor nanowires (NWs) from a solution, obtaining well-aligned NWs in one step. Our results show valuably the application potential of this technique in engineering SAMs for integration of functional devices

  9. Kinetic studies on the interactions between glycolipid biosurfactant assembled monolayers and various classes of immunoglobulins using surface plasmon resonance.

    Science.gov (United States)

    Ito, Seya; Imura, Tomohiro; Fukuoka, Tokuma; Morita, Tomotake; Sakai, Hideki; Abe, Masahiko; Kitamoto, Dai

    2007-08-01

    Kinetic studies on the interactions between self-assembled monolayers of mannosylerythritol lipids (MELs), which are glycolipid biosurfactants abundantly produced by microorganisms, and various classes of immunoglobulins including human IgG, IgA, and IgM were performed using surface plasmon resonance (SPR). The effect of the MEL structure on the binding behavior of HIgG was examined. Assembled monolayers of MEL-A having two acetyl groups on the headgroup gave a high affinity (K(d)=1.7x10(-6)M) toward HIgG, while those of MEL-B or MEL-C having only one acetyl group at C-6' or C-4' position gave little affinity. Our kinetic analysis revealed that the binding manner of HIgG, HIgA (K(d)=2.4x10(-7)M), and HIgM (K(d)=2.2x10(-7)M) to the assembled monolayers of MEL-A is not the monovalent mode but the bivalent mode, and both the first and second rate association constants (k(a1), k(a2)) increase with an increase in the number of antibody binding sites, while those for dissociation (k(d1), k(d2)) changed little. Moreover, we succeeded in directly observing great amounts of HIgG, HIgA, and HIgM bound to MEL-A monolayers using atomic force microscopy (AFM). Finally, we found that MEL-A assembled monolayer binds toward various IgG derived from mouse, pig, rabbit, horse, goat, rat, and bovine as well as human IgG (HIgG), and the only exception was sheep IgG. These results clearly demonstrate that MEL-A assembled monolayers would be useful as noble affinity ligand system for various immunoglobulins. PMID:17428643

  10. Self-assembly and charge carrier transport of solution-processed conjugated polymer monolayers on dielectric surfaces with controlled sub-nanometer roughness

    Science.gov (United States)

    Li, Mengmeng; Hinkel, Felix; Müllen, Klaus; Pisula, Wojciech

    2016-04-01

    In recent years organic field-effect transistors have received extensive attention, however, it is still a great challenge to fabricate monolayer-based devices of conjugated polymers. In this study, one single layer of poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) is directly dip-coated, and its self-assembly is precisely tuned from nanofibers to granular aggregates by controlling the dielectric roughness on a sub-nanometer scale. The charge carrier transport of the monolayer transistor exhibits a strong dependence on the dielectric roughness, which is attributed to the roughness-induced effects of higher densities of grain boundaries and charge trapping sites as well as surface scattering. These results mark a great advance in the bottom-up fabrication of organic electronics.In recent years organic field-effect transistors have received extensive attention, however, it is still a great challenge to fabricate monolayer-based devices of conjugated polymers. In this study, one single layer of poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) is directly dip-coated, and its self-assembly is precisely tuned from nanofibers to granular aggregates by controlling the dielectric roughness on a sub-nanometer scale. The charge carrier transport of the monolayer transistor exhibits a strong dependence on the dielectric roughness, which is attributed to the roughness-induced effects of higher densities of grain boundaries and charge trapping sites as well as surface scattering. These results mark a great advance in the bottom-up fabrication of organic electronics. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01082b

  11. Polymer blend lithography: A versatile method to fabricate nanopatterned self-assembled monolayers

    Directory of Open Access Journals (Sweden)

    Cheng Huang

    2012-09-01

    Full Text Available A rapid and cost-effective lithographic method, polymer blend lithography (PBL, is reported to produce patterned self-assembled monolayers (SAM on solid substrates featuring two or three different chemical functionalities. For the pattern generation we use the phase separation of two immiscible polymers in a blend solution during a spin-coating process. By controlling the spin-coating parameters and conditions, including the ambient atmosphere (humidity, the molar mass of the polystyrene (PS and poly(methyl methacrylate (PMMA, and the mass ratio between the two polymers in the blend solution, the formation of a purely lateral morphology (PS islands standing on the substrate while isolated in the PMMA matrix can be reproducibly induced. Either of the formed phases (PS or PMMA can be selectively dissolved afterwards, and the remaining phase can be used as a lift-off mask for the formation of a nanopatterned functional silane monolayer. This “monolayer copy” of the polymer phase morphology has a topographic contrast of about 1.3 nm. A demonstration of tuning of the PS island diameter is given by changing the molar mass of PS. Moreover, polymer blend lithography can provide the possibility of fabricating a surface with three different chemical components: This is demonstrated by inducing breath figures (evaporated condensed entity at higher humidity during the spin-coating process. Here we demonstrate the formation of a lateral pattern consisting of regions covered with 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS and (3-aminopropyltriethoxysilane (APTES, and at the same time featuring regions of bare SiOx. The patterning process could be applied even on meter-sized substrates with various functional SAM molecules, making this process suitable for the rapid preparation of quasi two-dimensional nanopatterned functional substrates, e.g., for the template-controlled growth of ZnO nanostructures.

  12. Interfacial structures of self-assembled monolayers of 2-pyridinethiol on Au(111) studied by in situ scanning tunneling microscopy

    International Nuclear Information System (INIS)

    In situ Scanning Tunneling Microscopy (STM) operating under electrochemical condition was used to study self-assembled monolayers of 2-pyridinethiol (2-PySH) on Au(111) in perchloric acid solution. Each molecule appeared as two spots, presumably originated from adsorption through S and N atoms of 2-pyridinethiolate with a vertical orientation on the Au(111) surface. The ordered 2-pyridinethiolate monolayers exhibited a p(4 x √7R-40.9deg) structure, which was constructed by alternative arrangements of two types of molecular rows with differently rotated molecules. In situ STM also revealed that the monolayer consisted of molecularly ordered domains with the p(4 x √7R-40.9deg) structure, its mirror structure defined as a p(4 x √7R-19.1deg), and their rotational structures. Detailed interfacial structures and molecularly ordered domains of the 2-pyridinethiolate monolayer have been elucidated by in situ STM imaging in aqueous solution. (author)

  13. Hematite nanoparticle monolayers on mica preparation by controlled self-assembly.

    Science.gov (United States)

    Oćwieja, Magdalena; Adamczyk, Zbigniew; Morga, Maria; Bielańska, Elżbieta; Węgrzynowicz, Adam

    2012-11-15

    A stable suspension of α-Fe(2)O(3) (hematite) was synthesized according to the method of Matijevic and Scheiner by an acidic hydrolysis of ferric chloride. The average size of the particles was determined by dynamic light scattering (DLS) and atomic force microscopy (AFM) and was 22 nm. The electrophoretic mobility and zeta potential of particles were determined as a function of ionic strength and pH. The zeta potential of the hematite particles was positive for pHAFM and SEM imaging. Particle deposition was diffusion controlled, with the initial rate proportional to the bulk concentration of particles. On the other hand, for long times, the saturation coverage was attained, increasing systematically with ionic strength. The deposition kinetic runs were adequately reflected by the random sequential adsorption (RSA) model. Additionally, particle desorption kinetics, from previously formed monolayers, were studied using the AFM and SEM methods. It was confirmed that hematite particle desorption was practically negligible within the time period of 60 h. Our experimental data proved, therefore, that it is feasible to produce uniform and stable hematite particle monolayers of desired coverage in self-assembly processes controlled by the bulk suspension concentration and the ionic strength. PMID:22909964

  14. Simultaneous nanoindentation and electron tunneling through alkanethiol self-assembled monolayers.

    Science.gov (United States)

    Engelkes, Vincent B; Frisbie, C Daniel

    2006-05-25

    Electrical tunnel junctions consisting of alkanethiol molecules self-assembled on Au-coated Si substrates and contacted with Au-coated atomic force microscopy tips were characterized under varying junction loads in a conducting-probe atomic force microscopy configuration. Junction load was cycled in the fashion of a standard nanoindentation experiment; however, junction conductance rather than probe depth was measured directly. The junction conductance data have been analyzed with typical contact mechanics (Derjaguin-Müller-Toporov) and tunneling equations to extract the monolayer modulus (approximately 50 GPa), the contact transmission (approximately 2 x 10(-6)), contact area, and probe depth as a function of load. The monolayers are shown to undergo significant plastic deformation under compression, yielding indentations approximately 7 Angstroms deep for maximum junction loads of approximately 50 nN. Comparison of mechanical properties for different chain lengths was also performed. The film modulus decreased with the number of carbons in the molecular chain for shorter-chain films. This trend abruptly reversed once 12 carbons were present along the backbone. PMID:16706460

  15. Metamaterial Absorbers for Infrared Detection of Molecular Self-Assembled Monolayers

    Science.gov (United States)

    Ishikawa, Atsushi; Tanaka, Takuo

    2015-07-01

    The emerging field of plasmonic metamaterials has introduced new degree of freedom to manipulate optical field from nano to macroscopic scale, offering an attractive platform for sensing applications. So far, metamaterial sensor concepts, however, have focused on hot-spot engineering to improve the near-field enhancement, rather than fully exploiting tailored material properties. Here, we present a novel spectroscopic technique based on the metamaterial infrared (IR) absorber allowing for a low-background detection scheme as well as significant plasmonic enhancement. Specifically, we experimentally demonstrate the resonant coupling of plasmonic modes of a metamaterial absorber and IR vibrational modes of a molecular self-assembled monolayer. The metamaterial consisting of an array of Au/MgF2/Au structures exhibits an anomalous absorption at ~3000 cm-1, which spectrally overlaps with C-H stretching vibrational modes. Symmetric/asymmetric C-H stretching modes of a 16-Mercaptohexadecanoic acid monolayer are clearly observed as Fano-like anti-resonance peaks within a broad plasmonic absorption of the metamaterial. Spectral analysis using Fano line-shape fitting reveals the underlying resonant interference in plasmon-molecular coupled systems. Our metamaterial approach achieves the attomole sensitivity with a large signal-to-noise ratio in the far-field measurement, thus may open up new avenues for realizing ultrasensitive IR inspection technologies.

  16. Self-Assembly of Protein Monolayers Engineered for Improved Monoclonal Immunoglobulin G Binding

    Directory of Open Access Journals (Sweden)

    Jeremy H. Lakey

    2011-08-01

    Full Text Available Bacterial outer membrane proteins, along with a filling lipid molecule can be modified to form stable self-assembled monolayers on gold. The transmembrane domain of Escherichia coli outer membrane protein A has been engineered to create a scaffold protein to which functional motifs can be fused. In earlier work we described the assembly and structure of an antibody-binding array where the Z domain of Staphylococcus aureus protein A was fused to the scaffold protein. Whilst the binding of rabbit polyclonal immunoglobulin G (IgG to the array is very strong, mouse monoclonal IgG dissociates from the array easily. This is a problem since many immunodiagnostic tests rely upon the use of mouse monoclonal antibodies. Here we describe a strategy to develop an antibody-binding array that will bind mouse monoclonal IgG with lowered dissociation from the array. A novel protein consisting of the scaffold protein fused to two pairs of Z domains separated by a long flexible linker was manufactured. Using surface plasmon resonance the self-assembly of the new protein on gold and the improved binding of mouse monoclonal IgG were demonstrated.

  17. Self-assembly of human plasma fibrinogens on binary organosilane monolayers with micro domains

    International Nuclear Information System (INIS)

    The adsorption behavior and self-assembly of human plasma fibrinogen (HPF) on binary methyl- and amino-terminated self-assembled monolayers (SAMs) were investigated by atomic force microscopy (AFM). The binary SAMs were fabricated through self-assembly mechanism of organosilane molecules. The height of domains is the domain height is 0.8 ± 0.2 nm from the AFM topographic image. It corresponds to the domain height is 0.8 ± 0.2 nm from the AFM topographic image. It corresponds to the difference between the length of the alkyl chain of octadecyltrichlorosilane (OTS) and that of n-(6-aminohexyl)aminopropyltrimethoxysilane (AHAPS). The fibrinogen solution used ultrapure water as the solvent and its pH was adjusted at 3 and 10. From the AFM results at pH 3, HPF only formed network structures on the OTS domains of the binary SAM at early immersion times, and then the network structures expanded and connected between OTS domains through the AHAPS surface at long immersion times. In this case, a few HPFs are discretely adsorbed on the AHAPS surface. However, HPF is uniformly adsorbed on the binary SAM under the other conditions of pH.

  18. Formation and Characterization of Self-Assembled Phenylboronic Acid Derivative Monolayers toward Developing Monosaccaride Sensing-Interface

    Directory of Open Access Journals (Sweden)

    Kwangnak Koh

    2007-08-01

    Full Text Available We designed and synthesized phenylboronic acid as a molecular recognitionmodel system for saccharide detection. The phenylboronic acid derivatives that haveboronic acid moiety are well known to interact with saccharides in aqueous solution; thus,they can be applied to a functional interface of saccharide sensing through the formation ofself-assembled monolayer (SAM. In this study, self-assembled phenylboronic acidderivative monolayers were formed on Au surface and carefully characterized by atomicforce microscopy (AFM, Fourier transform infrared reflection absorption spectroscopy(FTIR-RAS, surface enhanced Raman spectroscopy (SERS, and surface electrochemicalmeasurements. The saccharide sensing application was investigated using surface plasmonresonance (SPR spectroscopy. The phenylboronic acid monolayers showed goodsensitivity of monosaccharide sensing even at the low concentration range (1.0 × 10-12 M.The SPR angle shift derived from interaction between phenylboronic acid andmonosaccharide was increased with increasing the alkyl spacer length of synthesizedphenylboronic acid derivatives.

  19. Determination of surface recombination velocities of organic monolayers on silicon through Kelvin probe

    OpenAIRE

    Alderman, Nicholas; Adib Ibrahim, Mohd; Danos, Lefteris; Martin C. Grossel; Markvart, Tom

    2013-01-01

    We report the determination of the surface recombination velocity of electron-hole pairs for silicon samples passivated with organic monolayers using the Kelvin probe. The recombination velocity was determined from the surface photovoltage and incident photon flux. By scanning of the Kelvin probe tip over the sample, the change in surface recombination velocity can be measured allowing recombination lifetime mapping. Organic monolayers with different chain lengths and exhibiting various recom...

  20. Electrostatic adsorption of hematite nanoparticles on self-assembled monolayer surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lau, Boris L. T., E-mail: borislau@engin.umass.edu; Huang, Rixiang [Baylor University, Department of Geology (United States); Madden, Andrew S. [University of Oklahoma, School of Geology and Geophysics (United States)

    2013-08-15

    Deposition of nanoparticles (NPs) on different environmental surfaces has important implication on their fate and transport in aquatic systems. This study quantitatively and kinetically analyzed the adsorption of hematite ({alpha}-Fe{sub 2}O{sub 3}) NPs (HNPs) onto self-assembled monolayer modified surfaces using QCM, AFM, and SEM. Experiments were conducted to study the immobilization of two different sizes of HNPs onto gold substrate and surfaces modified with 1-mercapto-11-undecanoic acid and cysteine. It is shown that the extent and rate of HNPs adsorption onto substrate surfaces can be modulated electrostatically. Control over the surface coverage of the adsorbed HNPs has been demonstrated by pH variation. Size-dependent adsorption kinetics was observed, with the 79 nm HNPs adsorbed 2-3 times faster than the 116 nm HNPs.

  1. Antifouling properties of oligo(lactose)-based self-assembled monolayers.

    Science.gov (United States)

    Nugraha, Roni; Finlay, John A; Hill, Sophie; Fyrner, Timmy; Yandi, Wetra; Callow, Maureen E; Callow, James A; Ederth, Thomas

    2015-01-01

    The antifouling (AF) properties of oligo(lactose)-based self-assembled monolayers (SAMs), using four different proteins, zoospores of the green alga Ulva linza and cells of the diatom Navicula incerta, were investigated. The SAM-forming alkylthiols, which contained 1, 2 or 3 lactose units, showed significant variation in AF properties, with no differences in wettability. Non-specific adsorption of albumin and pepsin was low on all surfaces. Adsorption of lysozyme and fibrinogen decreased with increasing number of lactose units in the SAM, in agreement with the generally observed phenomenon that thicker hydrated layers provide higher barriers to protein adsorption. Settlement of spores of U. linza followed an opposite trend, being greater on the bulkier, more hydrated SAMs. These SAMs are more ordered for the larger saccharide units, and it is therefore hypothesized that the degree of order, and differences in crystallinity or stiffness between the surfaces, is an important parameter regulating spore settlement on these surfaces. PMID:25629533

  2. Crystalline self-assembly into monolayers of folded oligomers at the air-water interface

    DEFF Research Database (Denmark)

    Lederer, K.; Godt, A.; Howes, P.B.; Kjær, K.; Als-Nielsen, J.; Lahav, M.; Wegner, G.; Leiserowitz, L.; Weissbuch, I.

    2000-01-01

    Insertion of the 115-bis(ethynylene)benzene unit as a rigid spacer into a linear alkyl chain, thus separating the two resulting stems by 9 Angstrom, induces chain folding at the air-water interface. These folded molecules self-assemble into crystalline monolayers at this interface, with the plane...... of the folding unit almost perpendicular to the water surface, as determined by synchrotron grazing-incidence X-ray diffraction. Three distinct molecular shapes, of the types U, inverted U, and M, were obtained in the two-dimensional crystalline state, depending upon the number of spacer units, and...... the number and position of the hydrophilic groups in the molecule. The molecules form ribbons with a higher crystal coherence in the direction of stacking between the molecular ribbons, and a lower coherence along the ribbon direction. A similar molecule, but with a spacer unit that imposes a 5...

  3. Multiple-trapping in pentacene field-effect transistors with a nanoparticles self-assembled monolayer

    Directory of Open Access Journals (Sweden)

    Keanchuan Lee

    2012-06-01

    Full Text Available A silver nanoparticles self-assembled monolayer (SAM was incorporated in pentacene field-effect transistor and its effects on the carrier injection and transport were investigated using the current-voltage (I − V and impedance spectroscopy (IS measurements. The I − V results showed that there was a significant negative shift of the threshold voltage, indicating the hole trapping inside the devices with about two orders higher in the contact resistance and an order lower in the effective mobility when a SAM was introduced. The IS measurements with the simulation using a Maxwell-Wagner equivalent circuit model revealed the existence of multiple trapping states for the devices with NPs, while the devices without NPs exhibited only a single trap state.

  4. Suppression of the coffee-ring effect by self-assembling graphene oxide and monolayer titania

    International Nuclear Information System (INIS)

    The in situ self-assembly of two types of typical two-dimensional (2D) nanomaterials (i.e., graphene oxide (GO) and monolayer titania (TO)) is realized using a simple drop-casting method. Within the as-prepared hybrid films, the GO and TO nanosheets arrange alternately into a lamellar structure. Notably, the hybridization of GO and TO suppresses the formation of coffee-rings when drop-cast, which is attributed to the strong interactions between the GO and TO nanosheets. Finally, the mechanism for the in situ hybridization of these two types of nanosheets into heterogeneous lamellar films and the suppression of the coffee-ring effect are discussed. These results demonstrate the potential applications of drop-cast hybrid films for high-quality membrane deposition from liquid phases. (paper)

  5. Creating periodic local strain in monolayer graphene with nanopillars patterned by self-assembled block copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Mi, Hongyi; Mikael, Solomon; Seo, Jung-Hun; Gui, Gui; Ma, Alice L.; Ma, Zhenqiang, E-mail: nealey@uchicago.edu, E-mail: mazq@engr.wisc.edu [Department of Electrical and Computer Engineering, University of Wisconsin–Madison, Madison, Wisconsin 53706 (United States); Liu, Chi-Chun; Nealey, Paul F., E-mail: nealey@uchicago.edu, E-mail: mazq@engr.wisc.edu [Department of Chemical and Biological Engineering, University of Wisconsin–Madison, Madison, Wisconsin 53706 (United States)

    2015-10-05

    A simple and viable method was developed to produce biaxial strain in monolayer graphene on an array of SiO{sub 2} nanopillars. The array of SiO{sub 2} nanopillars (1 cm{sup 2} in area, 80 nm in height, and 40 nm in pitch) was fabricated by employing self-assembled block copolymer through simple dry etching and deposition processes. According to high resolution micro-Raman spectroscopy and atomic force microscopy analyses, 0.9% of maximum biaxial tensile strain and 0.17% of averaged biaxial tensile strain in graphene were created. This technique provides a simple and viable method to form biaxial tensile strain in graphene and offers a practical platform for future studies in graphene strain engineering.

  6. Self assembled monolayer based liquid crystal biosensor for free cholesterol detection

    International Nuclear Information System (INIS)

    A unique cholesterol oxidase (ChOx) liquid crystal (LC) biosensor, based on the disruption of orientation in LCs, is developed for cholesterol detection. A self-assembled monolayer (SAM) of Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (DMOAP) and (3-Aminopropyl)trimethoxy-silane (APTMS) is prepared on a glass plate by adsorption. The enzyme (ChOx) is immobilized on SAM surface for 12 h before utilizing the film for biosensing purpose. LC based biosensing study is conducted on SAM/ChOx/LC (5CB) cells for cholesterol concentrations ranging from 10 mg/dl to 250 mg/dl. The sensing mechanism has been verified through polarizing optical microscopy, scanning electron microscopy, and spectrometric techniques

  7. Surface reconstitution of glucose oxidase onto a norbornylogous bridge self-assembled monolayer

    International Nuclear Information System (INIS)

    An electrode construct was fabricated in which a self-assembled monolayer containing a novel norbornylogous bridge was covalently attached to flavin adenine dinucleotide (FAD), the redox active centre of several oxidase enzymes. The electrochemistry of the construct was investigated before and after the reconstitution of glucose oxidase around the surface bound FAD. Rapid rates of electron transfer were observed both before and after the reconstitution of biocatalytically active enzyme. However, no biocatalytic activity was observed under anaerobic conditions suggesting the a lack of enzyme turnover through direct electron transfer. It is proposed that a decrease in the electronic coupling between the redox active FAD and the electrode following reconstitution of the glucose oxidase - a probable consequence of the FAD being immersed in a protein environment - was responsible for the inability of the enzyme to be turned over under anaerobic conditions

  8. Patterning of self-assembled monolayers based on differences in molecular conductance

    International Nuclear Information System (INIS)

    Scanning tunneling microscopy (STM) is used for replacement patterning of self-assembled monolayers (SAMs) of thiols on a sub-10 nm scale. Contrasting other schemes of scanning probe patterning of SAMs, the exchange of molecules relies on differences in conductance and, thus, occurs under tunneling conditions where the resolution of the tip is maintained. Exchange takes place at the boundary between different thiols but only when the tip moves from areas of lower to higher conductance. In combination with SAMs which exhibit excellent structural quality, patterns with a contour definition of ± 1 molecule, lines as thin as 2.5 nm and islands with an area of less than 20 nm2 are straightforwardly produced. It is suggested that the shear force exerted onto the molecules with the lower conductance triggers displacement of the one with higher conductance.

  9. Microdroplet Protein Sensors on a Gold Surface with a Self-assembled Monolayer Treatment

    Directory of Open Access Journals (Sweden)

    Tzu-Chun Liao

    2012-03-01

    Full Text Available A new kind of microdroplet-based biological protein sensor is presented. The sensor was made by placing silicon oil on gold film with a self-assembled monolayer (SAM. The surface tension dominates the sensitivity of the sensor. Using mercaptoundecanoic acid (11-MUA as the sensor’s SAM layer, the sensor can detect 0.5 mg/ml, 20 μg/ml, and 0.4 μg/ml bovine serum albumin (BSA protein solutions in a control volume of 0.5ml. The sensor’s reaction time for concentrations of 0.5 mg/ml, 20 μg/ml, and 0.4μg/ml protein solutions was 15, 60 and 120 minutes, respectively. As the size of microdroplet decreased, the change of contact angle increased.

  10. Interaction of bovine serum albumin protein with self assembled monolayer of mercaptoundecanoic acid

    Science.gov (United States)

    Poonia, Monika; Agarwal, Hitesh; Manjuladevi, V.; Gupta, R. K.

    2016-05-01

    Detection of proteins and other biomolecules in liquid phase is the essence for the design of a biosensor. The sensitivity of a sensor can be enhanced by the appropriate functionalization of the sensing area so as to establish the molecular specific interaction. In the present work, we have studied the interaction of bovine serum albumin (BSA) protein with a chemically functionalized surface using a quartz crystal microbalance (QCM). The gold-coated quartz crystals (AT-cut/5 MHz) were functionalized by forming self-assembled monolayer (SAM) of 11-Mercaptoundecanoic acid (MUA). The adsorption characteristics of BSA onto SAM of MUA on quartz crystal are reported. BSA showed the highest affinity for SAM of MUA as compared to pure gold surface. The SAM of MUA provides carboxylated surface which enhances not only the adsorption of the BSA protein but also a very stable BSA-MUA complex in the liquid phase.

  11. Thickness dependence of second-harmonic generation in thin films fabricated from ionically self-assembled monolayers

    OpenAIRE

    Heflin, James R.; Figura, C.; Marciu, D.; Liu, Y.; Claus, Richard O.

    1999-01-01

    An ionically self-assembled monolayer (ISAM) technique for thin-film deposition has been employed to fabricate materials possessing the noncentrosymmetry that is requisite for a second-order, chi((2)), nonlinear optical response. As a result of the ionic attraction between successive layers, the ISAM chi((2)) films self-assemble into a noncentrosymmetric structure that has exhibited no measurable decay of chi((2)) at room temperature over a period of more than one year. The second-harmonic in...

  12. Biomimetic synthesis of enamel-like hydroxyapatite on self-assembled monolayers

    International Nuclear Information System (INIS)

    Hydroxyapatite (HAp) crystals mimicking tooth enamel in chemical composition and morphology were formed on sulfonic-terminated self-assembled monolayer (SAM) in 1.5SBF with F- at 50 oC for 7 days. F- ions showed a marked effect on the composition and morphology of deposited HAp crystals. In the absence of F- ions, HAp containing CO32- were formed on SAM, and worm-like crystals of 200-300 nm in length aggregated to form a spherical morphology. When F- was added, HAp crystals containing both CO32- and F- were formed on SAM. Needle-shaped crystals of high aspect ratio and 1-2 μm in length grew elongated along the c-axial direction. In addition, these needle-shaped crystals grew in bundles, mimicking HAp crystals in tooth enamel. After the process of ripening, the needles in bundle grew to large size of up to 10 μm in length, and still kept no crystal-crystal fusion like enamel HAp crystals. The formation of enamel-like HAp can be attributed to the substitute of F- for OH- by disturbing the normal progress of HAp formation on SAM. The results suggest potential applications in preparing a novel dental material by a simple method. -- Graphical abstract: Hydroxyapatite (HAp) crystals mimicking tooth enamel in chemical composition and morphology were formed on self-assembled monolayer (SAM) by a biomimetic process. The needle-shaped crystals grew in bundles, mimicking HAp crystals in tooth enamel. Display Omitted

  13. Biomimetic synthesis of enamel-like hydroxyapatite on self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Li Hong [Department of Materials Science and Engineering, Jinan University, Guangzhou, 510632 (China); Huang Weiya [Department of Chemistry, Jinan University, Guangzhou, 510632 (China); Zhang Yuanming [Department of Chemistry, Jinan University, Guangzhou, 510632 (China)]. E-mail: tzhangym@jnu.edu.cn; Zhong Mei [Department of Stomatology, Affiliated Hospital of Jinan University, Guangzhou, 510632 (China)

    2007-05-16

    Hydroxyapatite (HAp) crystals mimicking tooth enamel in chemical composition and morphology were formed on sulfonic-terminated self-assembled monolayer (SAM) in 1.5SBF with F{sup -} at 50 {sup o}C for 7 days. F{sup -} ions showed a marked effect on the composition and morphology of deposited HAp crystals. In the absence of F{sup -} ions, HAp containing CO{sub 3} {sup 2-} were formed on SAM, and worm-like crystals of 200-300 nm in length aggregated to form a spherical morphology. When F{sup -} was added, HAp crystals containing both CO{sub 3} {sup 2-} and F{sup -} were formed on SAM. Needle-shaped crystals of high aspect ratio and 1-2 {mu}m in length grew elongated along the c-axial direction. In addition, these needle-shaped crystals grew in bundles, mimicking HAp crystals in tooth enamel. After the process of ripening, the needles in bundle grew to large size of up to 10 {mu}m in length, and still kept no crystal-crystal fusion like enamel HAp crystals. The formation of enamel-like HAp can be attributed to the substitute of F{sup -} for OH{sup -} by disturbing the normal progress of HAp formation on SAM. The results suggest potential applications in preparing a novel dental material by a simple method. -- Graphical abstract: Hydroxyapatite (HAp) crystals mimicking tooth enamel in chemical composition and morphology were formed on self-assembled monolayer (SAM) by a biomimetic process. The needle-shaped crystals grew in bundles, mimicking HAp crystals in tooth enamel. Display Omitted.

  14. Directly Addressable Sub-3 nm Gold Nanogaps Fabricated by Nanoskiving Using Self-Assembled Monolayers as Templates

    NARCIS (Netherlands)

    Pourhossein, Parisa; Chiechi, Ryan C.

    2012-01-01

    This paper describes the fabrication of electrically addressable, high-aspect-ratio (>10000:1) nanowires of gold with square cross sections of 100 nm on each side that are separated by gaps of 1.7-2.2 nm which were defined using self-assembled monolayers (SAMs) as templates. We fabricated these nano

  15. Fast Electron Transfer Exchange at Self-Assembled Monolayers of Organometallic Ruthenium(II) σ-Arylacetylide Complexes.

    Science.gov (United States)

    Mulas, Andrea; Hervault, Yves-Marie; He, Xiaoyan; Di Piazza, Emmanuel; Norel, Lucie; Rigaut, Stéphane; Lagrost, Corinne

    2015-06-30

    A new series of ruthenium organometallic carbon-rich complexes, exhibiting fast electron transfer kinetics combined to a low oxidation potential, was synthesized for self-assembled monolayer (SAM) formation on gold surfaces. The molecules consist of highly conjugated ruthenium(II) mono(σ-arylacetylide) or bis(σ-arylacetylide) complexes functionalized with different bridge units with specific (protected) anchoring groups that possess high affinity for gold, such as thiol, carbodithioate, and isocyanide. Single component and mixed SAMs were prepared and fully characterized by wettability studies, infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS), and electrochemical analyses. By applying the Laviron's formalism, fast electron transfer kinetics (≈10(4) s(-1)) were found at the derived self-assemblies while no significant effect could have been evidenced with variation of the bridging unit and of the anchoring moiety. Interestingly, a hexyl aliphatic spacer in the bridging unit with a thiol group and dilution with suitable nonelectroactive thiols lead to better SAM organization and packing, in comparison with undiluted complexes with shorter spacers. Such features make these compounds suitable alternatives to the widely used ferrocene center as redox-active building blocks for reversible charge storage devices. PMID:26053314

  16. Ordered Self-assembled Alkane Monolayer on Graphite and Graphene Surface

    Science.gov (United States)

    Su, Yudan; Han, Huiling; Wang, Feng; Cai, Qun; Tian, Chuanshan; Shen, Y. R.

    2015-03-01

    The 2D self-assembly of long chain alkane molecule on graphite and graphene had been studied with phase-sensitive sum-frequency vibrational spectroscopy (PS-SFVS) and scanning tunneling microscopy (STM). The spectrum of Imχs(2) (ωIR) which directly characterizes the surface resonances, shows 10-cm-1 red-shift of the symmetric-stretch frequency of the CH2 groups pointing towards graphite (or graphene) surface indicating Van der Waals interaction in between. The Gibbs adsorption energy of polyethylene (PE, n ~ 140) on graphite from chloroform solution was determined to be -42kJ/mol per molecule or -0.6 kJ/mol per CH2 unit. This large adsorption energy drives the long alkane chain to form an ordered self-assembled monolayer on graphite (or graphene). The sum frequency spectra suggest the orientation of carbon skeleton plane of alkane is predominately perpendicular to the graphite/graphene surface. Our STM result also provides clear evidence for the proposed molecular adsorption model. These results explain the large amount residual of long chain alkane on polystyrene (PS) or poly(methyl methacrylate) (PMMA) transferred graphene, and facilitate a better way to fabricate cleaner large-size graphene.

  17. Computer organization and assembly language programming

    CERN Document Server

    Peterson, James L

    2014-01-01

    Computer Organization and Assembly Language Programming deals with lower level computer programming-machine or assembly language, and how these are used in the typical computer system. The book explains the operations of the computer at the machine language level. The text reviews basic computer operations, organization, and deals primarily with the MIX computer system. The book describes assembly language programming techniques, such as defining appropriate data structures, determining the information for input or output, and the flow of control within the program. The text explains basic I/O

  18. Intermixed Adatom and Surface‐Bound Adsorbates in Regular Self‐Assembled Monolayers of Racemic 2‐Butanethiol on Au(111)

    DEFF Research Database (Denmark)

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

    2015-01-01

    RSAuSR adatom‐bound motifs plus two RS species bound directly to face‐centered‐cubic and hexagonally close‐packed sites. This is the first time that these competing head‐group arrangements have been observed in the same ordered SAM. Such unusual packing is favored as it facilitates SAMs with......In situ scanning tunneling microscopy combined with density functional theory molecular dynamics simulations reveal a complex structure for the self‐assembled monolayer (SAM) of racemic 2‐butanethiol on Au(111) in aqueous solution. Six adsorbate molecules occupy a (10×√3)R30° cell organized as two...

  19. Self Assembly of Mixed Monolayers of Mercaptoundecylferrocene and Undecanethiol studied by STM

    International Nuclear Information System (INIS)

    Mixed monolayers of mercaptoundecylferrocene and undecanethiol were deposited from solution by coadsorption and by a two-step insertion method, using the alkanethiol monolayer as insulating matrix. The resulting layers were characterized by UHV-STM, showing molecular resolution. For insertion-processed samples, a mesh-like surface structure of ferrocenes was observed, due to the preferential incorporation of molecules along domain boundaries and defect sites of the alkanethiol monolayer. For monolayers in the intermediate coverage regime, a crystalline phase was observed

  20. Processing follows function: pushing the formation of self-assembled monolayers to high-throughput compatible time scales.

    Science.gov (United States)

    Alt, Milan; Schinke, Janusz; Hillebrandt, Sabina; Hänsel, Marc; Hernandez-Sosa, Gerardo; Mechau, Norman; Glaser, Tobias; Mankel, Eric; Hamburger, Manuel; Deing, Kaja; Jaegermann, Wolfram; Pucci, Annemarie; Kowalsky, Wolfgang; Lemmer, Uli; Lovrincic, Robert

    2014-11-26

    Self-assembled monolayers (SAMs) of organic molecules can be used to tune interface energetics and thereby improve charge carrier injection at metal-semiconductor contacts. We investigate the compatibility of SAM formation with high-throughput processing techniques. Therefore, we examine the quality of SAMs, in terms of work function shift and chemical composition as measured with photoelectron and infrared spectroscopy and in dependency on molecular exposure during SAM formation. The functionality of the SAMs is determined by the performance increase of organic field-effect transistors upon SAM treatment of the source/drain contacts. This combined analytical and device-based approach enables us to minimize the necessary formation times via an optimization of the deposition conditions. Our findings demonstrate that SAMs composed of partially fluorinated alkanethiols can be prepared in ambient atmosphere from ethanol solution using immersion times as short as 5 s and still exhibit almost full charge injection functionality if process parameters are chosen carefully. This renders solution-processed SAMs compatible with high-throughput solution-based deposition techniques. PMID:25323064

  1. Modified fabrication process of protein chips using a short-chain self-assembled monolayer.

    Science.gov (United States)

    Jang, Ling-Sheng; Keng, Hao-Kai

    2008-04-01

    In previous work a short chain SAM, 4,4-Dithiodibutyric Acid (DTBA) was found to be a thin monolayer in protein chips. However, obtaining uniform fluorescent intensity remains difficult because water-soluble carbodiimides (EDC) in an aqueous system cause the hydrolysis of N-hydroxysuccinimide ester (NHS esters). The hydrolysis of NHS esters reduces coupling yields and therefore reduces the fluorescent intensity of protein chips. The NHS can increase the stability of active intermediate resulting from the reaction of EDC and NHS, but the ratio of the concentration of EDC to that of NHS strongly affects this stability. The effects of the solvents used in the washing step are studied to solve this problem. The results reveal that PBST (PBS + 5% Tween20) is more effective in reducing the hydrolysis of NHS esters than deionized water. Additionally, the effects of 3:1 and 5:2 EDC/NHS ratios on the chips are examined. The 3:1 EDC/NHS ratio yields a higher fluorescent intensity than the 5:2 ratio. The effects on the chips of dissolving EDC in DI water, DI water + 0.1 M MES and alcohol are also investigated. The results show that alcohol provides higher fluorescent intensity than other solvents and the reaction time of 4 h yields a high fluorescent intensity with 3:1 EDC/NHS ratio. A modified fabrication process of protein chips using 4,4-DTBA is developed. In this work, 160 mM 4,4-DTBA is used as a self-assembled monolayer in the fabrication of protein chips. Experiments to characterize 4,4-DTBA are performed by contact angle goniometry and Fourier transform infrared spectroscopy (FTIR). Furthermore, the immobilized protein A-FITC (fluorescein isothiocyanate) is adopted in fluorescent assays. PMID:17849186

  2. Investigation of cellular and protein interactions with model self-assembled monolayer surfaces

    Science.gov (United States)

    Tegoulia, Vassiliki Apostolou

    Self-assembled monolayers (SAMs) of alkanethiolates on gold have been used to investigate the effect of substrate surface properties on bacterial and blood cell adhesion in the presence and absence of blood proteins. Protein adsorption and binding strength on SAMs as well as complement activation by these model surfaces were also studied. It is hoped that information gained, regarding factors that influence biological processes, will lead to strategies for designing materials and surfaces that specifically inhibit cell adhesion and protein adsorption. Single component SAMs of the general formula HS(CH2) 10X, where X = CH3, CH2OH. COOH and CH2(OCH 2CH2)3OH, and two component mixed SAMs created from binary solutions of HS(CH2), OCH3 and HS(CH 2)10CH2OH, were used. Adhesion was investigated under well-defined flow conditions. Adhesion was found to be higher for the hydrophobic methyl and minimal for the tri(ethyleneoxide) terminated SAM. Preincubation of the SAMs with fibrinogen led to an increase in cell adhesion for bacteria and a decrease for leukocyte adhesion. The effect of surface chemistry on protein adsorption was studied for three blood proteins, fibrinogen, fibronectin and albumin. Adsorption was found to be higher on the hydrophobic CH3 surface and lower but comparable for the other surfaces while proteins adsorbed strongly on all surfaces. SAMs were also used to evaluate complement activation by foreign surfaces. The hydroxyl rich SAMs were found to activate complement more significantly than the anionic carboxyl and the hydrophobic methyl terminated SAMs. A surface modification was introduced to incorporate a zwitterionic phosphorylcholine (PC) group on a hydroxyl monolayer in an effort to create a biomimetic surface that could minimize cell adhesion and protein adsorption. The good antifouling properties of the phosphorylcholine modified surface led to the synthesis of a novel phosphorylcholine functionalized thiol. Single component and two component

  3. A study of the inhibiton of copper corrosion by triethyl phosphate and triphenyl phosphate self-assembled monolayers

    Directory of Open Access Journals (Sweden)

    HOUYI MA

    2006-02-01

    Full Text Available Two kinds of phosphates, triethyl phosphate (TEP and triphenyl phosphate (TPP, were used to form self-assembled monolayers for the inhibition of the corrosion of copper in 0.2 mol dm–3 NaCl solution. Electrochemical impedance spectroscopy (EIS was applied to investigate the inhibition effects. The results showed that their inhibition ability first increased with increasing immersion time in ethanolic solutions of the corresponding compounds. However, when the immersion time was increased over some critical point, the inhibition effect decreased. For the same immersion time, the inhibition effect of the TPP monolayer was more pronounced than that of the TEP monolayer. Thus, ab initio calculations were used to interpret the relationship between the inhibition effects and the structures of the compounds.

  4. Effect of processing methods on drug release profiles of anti-restenotic self-assembled monolayers

    International Nuclear Information System (INIS)

    The use of anti-restenotic self-assembled monolayers (ARSAMs) has been previously demonstrated for delivering drugs from stents without polymeric carriers. ARSAMs have been prepared by coating an anti-restenotic drug (paclitaxel - PAT) on -COOH terminated phosphonic acid self-assembled monolayers (SAMs) coated Co-Cr alloy specimens. This study investigates the effect of different processing methods on the percentage of drug release from ARSAMs. The different methods that were used in this study to process ARSAMs include room temperature (RT) treatment, heat treatment (HT), cold treatment (CT) and quenching. The changes in polymorphism, chemical structure, morphology, and distribution of PAT on SAMs coated specimens were investigated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and atomic force microscopy (AFM), respectively. DSC showed dihydrate, dehydrated dihydrate, semi-crystalline, and mixed (amorphous and dihydrate) forms of PAT for RT, HT, CT, and quenched specimens, respectively. FTIR showed that the chemical structure of PAT was unaltered in all the specimens processed by various methods employed in this study. SEM showed a mixture of spherical, ovoid, and bean-shaped morphologies of PAT on RT, HT, and CT while particle-like and needle-shaped morphologies of PAT were observed on quenched specimens. AFM showed PAT was uniformly distributed on RT, HT and CT specimens while particle-like PAT was well distributed and needle-shaped PAT was sparsely distributed on quenched specimens. CT specimens showed greater density of PAT crystals when compared to other methods. Thus, this study demonstrated that processing methods have significant influence on the polymorphism, morphology, and distribution of PAT on SAMs coated Co-Cr alloy specimens. The in vitro drug elution studies for up to 56 days showed sustained release for all the different groups of specimens. CT showed lesser

  5. Effect of processing methods on drug release profiles of anti-restenotic self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Stoebner, Susan E. [Biomedical Engineering Program, University of South Dakota, Sioux Falls, SD 57107 (United States); Mani, Gopinath, E-mail: Gopinath.Mani@usd.edu [Biomedical Engineering Program, University of South Dakota, Sioux Falls, SD 57107 (United States)

    2012-04-01

    The use of anti-restenotic self-assembled monolayers (ARSAMs) has been previously demonstrated for delivering drugs from stents without polymeric carriers. ARSAMs have been prepared by coating an anti-restenotic drug (paclitaxel - PAT) on -COOH terminated phosphonic acid self-assembled monolayers (SAMs) coated Co-Cr alloy specimens. This study investigates the effect of different processing methods on the percentage of drug release from ARSAMs. The different methods that were used in this study to process ARSAMs include room temperature (RT) treatment, heat treatment (HT), cold treatment (CT) and quenching. The changes in polymorphism, chemical structure, morphology, and distribution of PAT on SAMs coated specimens were investigated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and atomic force microscopy (AFM), respectively. DSC showed dihydrate, dehydrated dihydrate, semi-crystalline, and mixed (amorphous and dihydrate) forms of PAT for RT, HT, CT, and quenched specimens, respectively. FTIR showed that the chemical structure of PAT was unaltered in all the specimens processed by various methods employed in this study. SEM showed a mixture of spherical, ovoid, and bean-shaped morphologies of PAT on RT, HT, and CT while particle-like and needle-shaped morphologies of PAT were observed on quenched specimens. AFM showed PAT was uniformly distributed on RT, HT and CT specimens while particle-like PAT was well distributed and needle-shaped PAT was sparsely distributed on quenched specimens. CT specimens showed greater density of PAT crystals when compared to other methods. Thus, this study demonstrated that processing methods have significant influence on the polymorphism, morphology, and distribution of PAT on SAMs coated Co-Cr alloy specimens. The in vitro drug elution studies for up to 56 days showed sustained release for all the different groups of specimens. CT showed lesser

  6. Surface structure and stereochemical properties of self-assembled monolayer materials. Final Report

    International Nuclear Information System (INIS)

    This document reports the progress the authors have made in support of their proposal to generate well-characterized, well-ordered organic surfaces and to impinge upon the array of oriented organic molecules a well-collimated beam of radical atoms at a well-defined angle of incidence. Using the intensity of helium atom diffraction from the organic surface as a measure of the number of unreacted molecules at the surface, the authors will measure the rate of the reaction. They will then vary the angle of incidence of the reactive atom beam and repeat the measurement. In this manner they plan to map out the reactivity of the molecules on the surface as a function of the angle of incidence of the reactive moiety. To carry out this experiment requires that two fields of research be brought together: (1) molecular beam technology and (2) the science/art of growing well-ordered organic surfaces. The first half of this report describes recent helium diffraction results from molecular beam deposited organic monolayers (structural layer characterization work). The second half reports progress in constructing and characterizing the reactive atom (oxygen) beam source.

  7. Enhanced performance of polymer solar cells with a monolayer of assembled gold nanoparticle films fabricated by Langmuir-Blodgett technique

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Xiaoqiang; Yang, Xi; Fu, Weifei; Xu, Mingsheng [State Key Lab of Silicon Materials, MOE Key Laboratory of Macromolecular Synthesis and Functionalization, and Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Chen, Hongzheng, E-mail: hzchen@zju.edu.cn [State Key Lab of Silicon Materials, MOE Key Laboratory of Macromolecular Synthesis and Functionalization, and Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027 (China)

    2013-01-01

    Highlights: Black-Right-Pointing-Pointer Au NP monolayers are incorporated into ITO/anodic buffer layer by LB method. Black-Right-Pointing-Pointer Au NP monolayers are surface oxidized by UV/O{sub 3} treatment. Black-Right-Pointing-Pointer The effects of packing density and particle size on device performance were investigated. Black-Right-Pointing-Pointer Both short-circuit current and open-circuit voltage are improved with Au NP layer. - Abstract: We reported the enhanced performance of polymer solar cells with the blend of poly (2-methoxy-5(2 Prime -ethylhexyloxy)-1,4-phenylene-vinylene) (MEH-PPV) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) as active layer by incorporation of an assembled gold nanoparticle (Au NP) monolayer. The dense Au NP monolayer has been fabricated by Langmuir-Blodgett (LB) assembly and positioned between the transparent electrode ITO and the anode-modification PEDOT:PSS [poly (3,4-ethylenedioxythiophene):poly(styrene sulfonate)] layer, resulting in the device architecture of ITO/Au/PEDOT:PSS/MEH-PPV:PCBM/Al. We attribute the performance improvement to the localized surface plasmon resonance (LSPR) effect of Au NP films, which could lead to the increased absorption of the active layer. The parameters (nanoparticle size and interparticle distance) that govern this SPR effect have been optimized by selecting various sizes of Au NPs and controlling the LB assembly conditions. We observed {approx}10-20% enhancement in power conversion efficiency for all the devices with the Au NP monolayer.

  8. Utilizing self-assembled-monolayer-based gate dielectrics to fabricate molybdenum disulfide field-effect transistors

    Science.gov (United States)

    Kawanago, Takamasa; Oda, Shunri

    2016-01-01

    In this study, we apply self-assembled-monolayer (SAM)-based gate dielectrics to the fabrication of molybdenum disulfide (MoS2) field-effect transistors. A simple fabrication process involving the selective formation of a SAM on metal oxides in conjunction with the dry transfer of MoS2 flakes was established. A subthreshold slope (SS) of 69 mV/dec and no hysteresis were demonstrated with the ultrathin SAM-based gate dielectrics accompanied by a low gate leakage current. The small SS and no hysteresis indicate the superior interfacial properties of the MoS2/SAM structure. Cross-sectional transmission electron microscopy revealed a sharp and abrupt interface of the MoS2/SAM structure. The SAM-based gate dielectrics are found to be applicable to the fabrication of low-voltage MoS2 field-effect transistors and can also be extended to various layered semiconductor materials. This study opens up intriguing possibilities of SAM-based gate dielectrics in functional electronic devices.

  9. Direct, Noncovalent Coating of a Gold Surface with Polymeric Self-Assembled Monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hojae; Hong, Daewha; Jon, Sangyong; Choi, Insung S. [KAIST, Daejeon (Korea, Republic of)

    2013-12-15

    We demonstrated a simple but rather unexpected method for coating a gold surface with the random copolymer presenting a long alkyl chain. The poly(ethylene glycol) group in the polymer effectively minimized the unwanted adsorption of proteins onto the surface, and the N-hydroxysuccinimide group was utilized for covalent immobilization of the antibody. The successful generation of IgG/anti-IgG showed that the long alkyl chain-mediated coating of the gold surface led to the stable formation of the polymeric self-assembled monolayers at least in water and phosphate-buffered saline. We think that more detailed studies on the stability of the pSAMs on gold are needed for the practical applications of the method described in this work to the bioanalytical analysis, which is our next research thrust. The spatio-selective immobilization of biomolecules, such as DNAs, antibodies, or aptamers, onto a solid surface is required for the development of bioanalytical and biomedical devices that interface the immobilized probe with the target biospecifically.

  10. Comparative Study of Electroless Copper Film on Different Self-Assembled Monolayers Modified ABS Substrate

    Directory of Open Access Journals (Sweden)

    Jiushuai Xu

    2014-04-01

    Full Text Available Copper films were grown on (3-Mercaptopropyltrimethoxysilane (MPTMS, (3-Aminopropyltriethoxysilane (APTES and 6-(3-(triethoxysilylpropylamino-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.

  11. Self-assembled monolayers based spintronics: from ferromagnetic surface functionalization to spin-dependent transport

    Science.gov (United States)

    Tatay, Sergio; Galbiati, Marta; Delprat, Sophie; Barraud, Clément; Bouzehouane, Karim; Collin, Sophie; Deranlot, Cyrile; Jacquet, Eric; Seneor, Pierre; Mattana, Richard; Petroff, Frédéric

    2016-03-01

    Chemically functionalized surfaces are studied for a wide range of applications going from medicine to electronics. Whereas non-magnetic surfaces have been widely studied, functionalization of magnetic surfaces is much less common and has almost never been used for spintronics applications. In this article we present the functionalization of La2/3Sr1/3MnO3, a ferromagnetic oxide, with self-assembled monolayers for spintronics. La2/3Sr1/3MnO3 is the prototypical half-metallic manganite used in spintronics studies. First, we show that La2/3Sr1/3MnO3 can be functionalized by alkylphosphonic acid molecules. We then emphasize the use of these functionalized surfaces in spintronics devices such as magnetic tunnel junctions fabricated using a nano-indentation based lithography technique. The observed exponential increase of tunnel resistance as a function of alkyl chain length is a direct proof of the successful connection of molecules to ferromagnetic electrodes. For all alkyl chains studied we obtain stable and robust tunnel magnetoresistance, with effects ranging from a few tens to 10 000%. These results show that functionalized electrodes can be integrated in spintronics devices and open the door to a molecular engineering of spintronics.

  12. Passivation of copper surfaces for selective-area ALD using a thiol self-assembled monolayer

    Science.gov (United States)

    Färm, Elina; Vehkamäki, Marko; Ritala, Mikko; Leskelä, Markku

    2012-07-01

    Self-assembled monolayers (SAMs) of 1-dodecanethiol (CH3(CH2)11SH) were prepared from the vapor phase and used as a passivation layer for selective-area ALD. Thiol SAMs have commonly been prepared by immersing the substrates into a solution containing alkyl thiols. Formation of SAMs from the vapor phase, however, has advantages compared to liquid phase preparation. Passivation of surface can be done as a part of the ALD process forming a SAM first and then continuing with the common ALD process. SAMs can also be applied to three-dimensional structures relying on chemical selectivity of the thiol SAM formation. For example in the copper damascene process the thiol SAMs should form only on the copper surface but not on the insulators. In this study, the SAMs were prepared by placing the substrate and the alkylthiol to the reaction chamber and heating the system to the temperature of 73 °C. Preparation time varied from 0.5 to 24 h. Passivation properties of SAMs were tested with ALD iridium and polyimide processes. Iridium was deposited at 250  ° C for 500 cycles and polyimide at 160  ° C for 20 cycles.

  13. Frictional properties of two alkanethiol self assembled monolayers in sliding contact: Odd-even effects

    Science.gov (United States)

    Ramin, Leyla; Jabbarzadeh, Ahmad

    2012-11-01

    Using molecular dynamics simulation, we have investigated the structural effects on the frictional properties of self assembled monolayers (SAM) of n-alkanethiols [CH3(CH2)n-1SH, n = 12-15] in SAM-SAM contacts attached on Au (111) substrates. We have observed an odd-even effect where friction coefficient for SAM-SAM contacts with n = odd showed consistently higher values than those with n = even. This odd-even effect is independent of the sliding velocity and the relative tilt directions of the SAMs, and persists over a much higher pressure range than that reported before for SAM-Au contacts [L. Ramin and A. Jabbarzadeh, Langmuir 28, 4102-4112 (2012), 10.1021/la204701z]. For odd systems higher gauche defects were shown to be the possible source of high friction coefficient. Under the same load and shear rates (comparable sliding velocities), SAM-SAM contacts show mostly higher friction compared to SAM-Au contacts. For SAM-SAM contacts, a more significant increase of friction occurs at higher shear rates due to a shift in the tilt orientation angle. We show SAM-SAM contacts with misaligned relative tilt orientation angle (˜45°-90°) have considerably lower friction compared with those whose tilt orientation angles are almost aligned in the opposite directions and parallel to the shear.

  14. Self-Cleaning Features of Plasma-Treated Surfaces with Self-Assembled Monolayer Coating

    Science.gov (United States)

    Lee, Sang‑Joon; Paik, Bu‑Geun; Kim, Guk‑Bae; Jang, Young‑Gil

    2006-02-01

    A biomimic surface was coated onto a poly(tetrafluoroethylene) (PTFE) substrate. The coated PTFE surface was found to have nanoscale roughness and high hydrophobicity. In the first preparation step, the PTFE surface was modified by plasma etching. A self-assembled monolayer (SAM) of octadecyltrichlorosilane (ODTS) was then deposited onto the modified surface with a thickness of a 2-3 nm. This surface was found to have self-cleaning features similar to those of a lotus leaf. The self-cleaning features were confirmed by comparing the contact and sliding angles of the original PTFE surface, a PTFE surface plasma treated, and a PTFE surface plasma treated and SAM coated. The PTFE surface treated with plasma and SAM coated had an increased contact angle and a decreased sliding angle compared with the other surfaces. It also exhibited increased stability and slow aging. The quantity of oxygen-containing groups that can be greatly influenced by plasma treatment, SAM coating, and aging, seems to play an important role in surface modification.

  15. Surface plasmon resonance immunosensor for human cardiac troponin T based on self-assembled monolayer.

    Science.gov (United States)

    Dutra, Rosa Fireman; Mendes, Renata Kelly; Lins da Silva, Valdinete; Kubota, Lauro Tatsuo

    2007-04-11

    The cardiac troponin T (cTnT) is specific biomarker important for trials of acute myocardial infarctions (AMI). In this paper, a SPR sensor in real time to detect the biomarker was developed on a commercially available surface plasmon resonance AUTOLAB SPIRIT. The cTnT receptor molecule was covalently immobilized on a gold substrate via a self-assembled monolayer (SAM) of thiols by using cysteamine-coupling chemistry. This biosensor presented a linear response range for cTnT between 0.05 and 4.5 ng/mL (r=0.997, p<0.01) with a good reproducibility (CV=4.4%). The effect of the cysteamine (CYS) concentrations on the SAM coated gold sensor was studied as a function of the amount of the immobilized cTnT monoclonal antibodies. Analysis using serum samples undiluted was carried out at room temperature showing a well agreement with the ECLIA methods and the sensor surface could be regenerated by using a solution of 1% (w/v) sodium dodecyl sulphate (SDS) without losing the sensor immunoreactivity. These studies open new perspectives of using SAM to develop regenerable immunosensor with a good reproducibility allowing its use in the clinical applications. PMID:17254730

  16. Immobilization and release strategies for DNA delivery using carbon nanofiber arrays and self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Peckys, Diana B [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6030 (United States); Melechko, Anatoli V [Department of Materials Science and Engineering, North Carolina State University, Raleigh, NC 27695 (United States); Simpson, Michael L [University of Tennessee in Knoxville, Knoxville, TN 37996-2200 (United States); McKnight, Timothy E [Measurement Science and Systems Engineering Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6006 (United States)], E-mail: peckysdb@ornl.gov

    2009-04-08

    We report a strategy for immobilizing dsDNA (double-stranded DNA) onto vertically aligned carbon nanofibers and subsequently releasing this dsDNA following penetration and residence of these high aspect ratio structures within cells. Gold-coated nanofiber arrays were modified with self-assembled monolayers (SAM) to which reporter dsDNA was covalently and end-specifically bound with or without a cleavable linker. The DNA-modified nanofiber arrays were then used to impale, and thereby transfect, Chinese hamster lung epithelial cells. This mechanical approach enables the transport of bound ligands directly into the cell nucleus and consequently bypasses extracellular and cytosolic degradation. Statistically significant differences were observed between the expression levels from immobilized and releasable DNA, and these are discussed in relation to the distinct accessibility and mode of action of glutathione, an intracellular reducing agent responsible for releasing the bound dsDNA. These results prove for the first time that an end-specifically and covalently SAM-bound DNA can be expressed in cells. They further demonstrate how the choice of immobilization and release methods can impact expression of nanoparticle delivered DNA.

  17. Voltammetry of Vitamin B12 on a thin self-assembled monolayer modified electrode

    International Nuclear Information System (INIS)

    Vitamin B12 showed three reduction waves at a thin self-assembled monolayer of mercaptoacetic acid modified gold electrode at 0.21, 0.16, -0.41 V in a 0.01 mol l-1 HCl solution at a scan rate of 100 mV s-1. The overall electrode reaction followed an ECE mechanism, leading to a total two-electron exchange. The predominant Co(III) form was reduced directly at 0.21 V by a one-electron transfer accomplished by CN- cleavage into the cyanocob(II)alamin. The latter species then equilibrated with the base-off B12r, which was immediately reduced into B12s at 0.16 V. The wave at -0.41 V might be a catalytic hydrogen wave. The cathodic peak currents at 0.21 V were controlled by the diffusion of Vitamin B12. On the base of its diffusion behavior, the semi-derivate voltammetric method for the detection of Vitamin B12 was presented. The semi-derivate voltammetric peak current of the wave at 0.21 V was linear with the content of Vitamin B12 in the range of 4.0 x 10-9 to 4.0 x 10-5 mol l-1. The detection limit was 1.0 x 10-9 mol l-1. The proposed method was applied successfully to determine the content of Vitamin B12 in pharmaceutical preparations

  18. Immobilization and release strategies for DNA delivery using carbon nanofiber arrays and self-assembled monolayers

    International Nuclear Information System (INIS)

    We report a strategy for immobilizing dsDNA (double-stranded DNA) onto vertically aligned carbon nanofibers and subsequently releasing this dsDNA following penetration and residence of these high aspect ratio structures within cells. Gold-coated nanofiber arrays were modified with self-assembled monolayers (SAM) to which reporter dsDNA was covalently and end-specifically bound with or without a cleavable linker. The DNA-modified nanofiber arrays were then used to impale, and thereby transfect, Chinese hamster lung epithelial cells. This mechanical approach enables the transport of bound ligands directly into the cell nucleus and consequently bypasses extracellular and cytosolic degradation. Statistically significant differences were observed between the expression levels from immobilized and releasable DNA, and these are discussed in relation to the distinct accessibility and mode of action of glutathione, an intracellular reducing agent responsible for releasing the bound dsDNA. These results prove for the first time that an end-specifically and covalently SAM-bound DNA can be expressed in cells. They further demonstrate how the choice of immobilization and release methods can impact expression of nanoparticle delivered DNA.

  19. Nanoscale patterning of a self-assembled monolayer by modification of the molecule–substrate bond

    Directory of Open Access Journals (Sweden)

    Cai Shen

    2014-03-01

    Full Text Available The intercalation of Cu at the interface of a self-assembled monolayer (SAM and a Au(111/mica substrate by underpotential deposition (UPD is studied as a means of high resolution patterning. A SAM of 2-(4'-methylbiphenyl-4-ylethanethiol (BP2 prepared in a structural phase that renders the Au substrate completely passive against Cu-UPD, is patterned by modification with the tip of a scanning tunneling microscope. The tip-induced defects act as nucleation sites for Cu-UPD. The lateral diffusion of the metal at the SAM–substrate interface and, thus, the pattern dimensions are controlled by the deposition time. Patterning down to the sub-20 nm range is demonstrated. The difference in strength between the S–Au and S–Cu bond is harnessed to develop the latent Cu-UPD image into a patterned binary SAM. Demonstrated by the exchange of BP2 by adamantanethiol (AdSH this is accomplished by a sequence of reductive desorption of BP2 in Cu free areas followed by adsorption of AdSH. The appearance of Au adatom islands upon the thiol exchange suggests that the interfacial structures of BP2 and AdSH SAMs are different.

  20. Fabrication of a molecularly imprinted polymer sensor by self-assembling monolayer/mediator system

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Po-Yen; Nien, Po-Chin; Wu, Cheng-Tar [Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan (China); Wu, Tsing-Hua; Lin, Chii-Wann [Institute of Biomedical Engineering, National Taiwan University, Taipei 10617, Taiwan (China); Ho, Kuo-Chuan, E-mail: kcho@ntu.edu.tw [Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan (China); Institute of Polymer Science and Engineering, National Taiwan University, Taipei 10617, Taiwan (China)

    2009-06-08

    Detection of dopamine (DA) by using a molecularly imprinted polymer (MIP) which fabricated by the self-assembling monolayer (SAM)/mediator system was studied. The SAM was made by attaching thioglycolic acid (TGA) on a gold electrode and quercetin (Q) was selected as an electron transfer mediator in this system. Methyl methacrylate (MMA) was polymerized by photopolymerization with the addition of dopamine to form a MIP electrode. The MIP and non-MIP (NMIP) modified electrodes were identified by FTIR and scanning electrochemical microscopy (SECM) approach curves. DA was detected by an amperometric method at a constant potential of 0.45 V and obtained a sensitivity of 0.445 mA cm{sup -2} M{sup -1}. The imprinting efficiency approaches infinity due to a non-reactive surface of NMIP. In the interference test, ascorbic acid contributed less than 12% of current response in the coexistence solution with DA and the performance is highly related to the concentration of template added during the fabrication process.

  1. Water-repellent coating: formation of polymeric self-assembled monolayers on nanostructured surfaces

    International Nuclear Information System (INIS)

    In this paper, we suggest a facile and effective method for water-repellent coating of oxide surfaces. As a coating material, we synthesized a new random copolymer, referred to as poly(TMSMA-r-fluoroMA), by the radical polymerization of 3-(trimethoxysilyl)propyl methacrylate (TMSMA) and a fluoromonomer'' (registered) bearing methacrylate moiety (fluoroMA). The random copolymer was designed to consist of a 'surface-reactive part' (trimethoxysilyl group) for anchoring onto oxide-based surfaces and a 'functional part' (perfluoro group) for water repellency. The polymeric self-assembled monolayers (pSAMs) of poly(TMSMA-r-fluoroMA) were constructed on three different aluminum oxide substrates, such as flat, concave-textured, and nanoporous plates, and the static water contact angle of each surface before and after the formation of pSAMs was measured. The formation of pSAMs resulted in significantly enhanced hydrophobicity compared with the corresponding bare surfaces. In particular, among three poly(TMSMA-r-fluoroMA)-coated surfaces, the nanoporous plate showed the highest water-repellent property, with a static contact angle of ∼163 deg., which is indicative of superhydrophobic surfaces

  2. Utilizing self-assembled-monolayer-based gate dielectrics to fabricate molybdenum disulfide field-effect transistors

    Energy Technology Data Exchange (ETDEWEB)

    Kawanago, Takamasa, E-mail: kawanago.t.ab@m.titech.ac.jp; Oda, Shunri [Quantum Nanoelectronics Research Center (QNERC), Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo, 152-8550 (Japan)

    2016-01-25

    In this study, we apply self-assembled-monolayer (SAM)-based gate dielectrics to the fabrication of molybdenum disulfide (MoS{sub 2}) field-effect transistors. A simple fabrication process involving the selective formation of a SAM on metal oxides in conjunction with the dry transfer of MoS{sub 2} flakes was established. A subthreshold slope (SS) of 69 mV/dec and no hysteresis were demonstrated with the ultrathin SAM-based gate dielectrics accompanied by a low gate leakage current. The small SS and no hysteresis indicate the superior interfacial properties of the MoS{sub 2}/SAM structure. Cross-sectional transmission electron microscopy revealed a sharp and abrupt interface of the MoS{sub 2}/SAM structure. The SAM-based gate dielectrics are found to be applicable to the fabrication of low-voltage MoS{sub 2} field-effect transistors and can also be extended to various layered semiconductor materials. This study opens up intriguing possibilities of SAM-based gate dielectrics in functional electronic devices.

  3. Fabrication of a molecularly imprinted polymer sensor by self-assembling monolayer/mediator system

    International Nuclear Information System (INIS)

    Detection of dopamine (DA) by using a molecularly imprinted polymer (MIP) which fabricated by the self-assembling monolayer (SAM)/mediator system was studied. The SAM was made by attaching thioglycolic acid (TGA) on a gold electrode and quercetin (Q) was selected as an electron transfer mediator in this system. Methyl methacrylate (MMA) was polymerized by photopolymerization with the addition of dopamine to form a MIP electrode. The MIP and non-MIP (NMIP) modified electrodes were identified by FTIR and scanning electrochemical microscopy (SECM) approach curves. DA was detected by an amperometric method at a constant potential of 0.45 V and obtained a sensitivity of 0.445 mA cm-2 M-1. The imprinting efficiency approaches infinity due to a non-reactive surface of NMIP. In the interference test, ascorbic acid contributed less than 12% of current response in the coexistence solution with DA and the performance is highly related to the concentration of template added during the fabrication process.

  4. An Investigation of the Effects of Self-Assembled Monolayers on Protein Crystallisation

    Directory of Open Access Journals (Sweden)

    Da-Chuan Yin

    2013-06-01

    Full Text Available Most protein crystallisation begins from heterogeneous nucleation; in practice, crystallisation typically occurs in the presence of a solid surface in the solution. The solid surface provides a nucleation site such that the energy barrier for nucleation is lower on the surface than in the bulk solution. Different types of solid surfaces exhibit different surface energies, and the nucleation barriers depend on the characteristics of the solid surfaces. Therefore, treatment of the solid surface may alter the surface properties to increase the chance to obtain protein crystals. In this paper, we propose a method to modify the glass cover slip using a self-assembled monolayer (SAM of functional groups (methyl, sulfydryl and amino, and we investigated the effect of each SAM on protein crystallisation. The results indicated that both crystallisation success rate in a reproducibility study, and crystallisation hits in a crystallisation screening study, were increased using the SAMs, among which, the methyl-modified SAM demonstrated the most significant improvement. These results illustrated that directly modifying the crystallisation plates or glass cover slips to create surfaces that favour heterogeneous nucleation can be potentially useful in practical protein crystallisation, and the utilisation of a SAM containing a functional group can be considered a promising technique for the treatment of the surfaces that will directly contact the crystallisation solution.

  5. Chemical stability of nonwetting, low adhesion self-assembled monolayer films formed by perfluoroalkylsilanization of copper

    Science.gov (United States)

    Hoque, E.; DeRose, J. A.; Hoffmann, P.; Bhushan, B.; Mathieu, H. J.

    2007-03-01

    A self-assembled monolayer (SAM) has been produced by reaction of 1H,1H,2H,2H-perfluorodecyldimethylchlorosilane (PFMS) with an oxidized copper (Cu) substrate and investigated by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), friction force microscopy (FFM), a derivative of AFM, and contact angle measurement. FFM showed a significant reduction in the adhesive force and friction coefficient of PFMS modified Cu (PFMS/Cu) compared to unmodified Cu. The perfluoroalkyl SAM on Cu is found to be extremely hydrophobic, yielding sessile drop static contact angles of more than 130° for pure water and a "surface energy" (which is proportional to the Zisman critical surface tension for a Cu surface with 0rms roughness) of 14.5mJ/m2(nM/m). Treatment by exposure to harsh conditions showed that PFMS/Cu SAM can withstand boiling nitric acid (pH=1.8), boiling water, and warm sodium hydroxide (pH =12, 60°C) solutions for at least 30min. Furthermore, no SAM degradation was observed when PFMS/Cu was exposed to warm nitric acid solution for up to 70min at 60°C or 50min at 80°C. Extremely hydrophobic (low surface energy) and stable PFMS/Cu SAMs could be useful as corrosion inhibitors in micro/nanoelectronic devices and/or as promoters for antiwetting, low adhesion surfaces or dropwise condensation on heat exchange surfaces.

  6. Utilizing self-assembled-monolayer-based gate dielectrics to fabricate molybdenum disulfide field-effect transistors

    International Nuclear Information System (INIS)

    In this study, we apply self-assembled-monolayer (SAM)-based gate dielectrics to the fabrication of molybdenum disulfide (MoS2) field-effect transistors. A simple fabrication process involving the selective formation of a SAM on metal oxides in conjunction with the dry transfer of MoS2 flakes was established. A subthreshold slope (SS) of 69 mV/dec and no hysteresis were demonstrated with the ultrathin SAM-based gate dielectrics accompanied by a low gate leakage current. The small SS and no hysteresis indicate the superior interfacial properties of the MoS2/SAM structure. Cross-sectional transmission electron microscopy revealed a sharp and abrupt interface of the MoS2/SAM structure. The SAM-based gate dielectrics are found to be applicable to the fabrication of low-voltage MoS2 field-effect transistors and can also be extended to various layered semiconductor materials. This study opens up intriguing possibilities of SAM-based gate dielectrics in functional electronic devices

  7. Selective atomic layer deposition with electron-beam patterned self-assembled monolayers

    International Nuclear Information System (INIS)

    The authors selectively deposited nanolines of titanium oxide (TiO2) through atomic layer deposition (ALD) using an octadecyltrichlorosilane (OTS) self-assembled monolayer (SAM) as a nucleation inhibition layer. Electron-beam (e-beam) patterning is used to prepare nanoline patterns in the OTS SAM on SiO2/Si substrates suitable for selective ALD. The authors have investigated the effect of an e-beam dose on the pattern width of the selectively deposited TiO2 lines. A high dose (e.g., 20 nC/cm) causes broadening of the linewidth possibly due to scattering, while a low dose (e.g., 5 nC/cm) results in a low TiO2 deposition rate because of incomplete exposure of the OTS SAMs. The authors have confirmed that sub-30 nm isolated TiO2 lines can be achieved by selective ALD combined with OTS patterned by EBL at an accelerating voltage of 2 kV and line dose of 10 nC/cm. This research offers a new approach for patterned gate dielectric layer fabrication, as well as potential applications for nanosensors and solar cells.

  8. Spatially defined silver mirror reaction on a micropatterned aldehyde-terminated self-assembled monolayer

    International Nuclear Information System (INIS)

    A simple microfabrication technique for silver (Ag) based on spatially defined silver mirror reaction using a photolithographically micropatterned aldehyde (CHO)-terminated self-assembled monolayer (SAM) is proposed. First, both a Si substrate covered with native oxide and a quartz glass plate were exposed to a vapor of triethoxysilylundecanal (TESUD) diluted with absolute toluene for 3 h at 403 K. This vapor phase treatment produced a 1.2-nm-thick TESUD-SAM with a flat, homogeneous surface. Several samples were then photolithographically micropatterned using an excimer lamp radiating 172 nm vacuum ultraviolet light, and subsequently employed as templates for area-selective electroless Ag plating. Optical microscopy, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) confirmed that Ag metal was preferentially deposited on the CHO-terminated regions, resulting in the formation of well-ordered Ag microstructures composed of rectangular 5 μm x 25 μm features. The CHO terminal groups of the TESUD-SAM were found to be effective in reducing Ag ionic species at the solid/liquid interface

  9. Employing X-ray Photoelectron Spectroscopy for Determining Layer Homogeneity in Mixed Polar Self-Assembled Monolayers

    Science.gov (United States)

    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

  10. Employing X-ray Photoelectron Spectroscopy for Determining Layer Homogeneity in Mixed Polar Self-Assembled Monolayers.

    Science.gov (United States)

    Hehn, Iris; Schuster, Swen; Wächter, Tobias; Abu-Husein, Tarek; Terfort, Andreas; Zharnikov, Michael; Zojer, Egbert

    2016-08-01

    Self-assembled monolayers (SAMs) containing embedded dipolar groups offer the particular advantage of changing the electronic properties of a surface without affecting the SAM-ambient interface. Here we show that such systems can also be used for continuously tuning metal work functions by growing mixed monolayers consisting of molecules with different orientations of the embedded dipolar groups. To avoid injection hot-spots when using the SAM-modified electrodes in devices, a homogeneous mixing of the two components is crucial. We show that a combination of high-resolution X-ray photoelectron spectroscopy with state-of-the-art simulations is an ideal tool for probing the electrostatic homogeneity of the layers and thus for determining phase separation processes in polar adsorbate assemblies down to inhomogeneities at the molecular level. PMID:27429041

  11. Study of the ability of self-assembled N-vinylcarbazole monolayers to protect copper against corrosion

    Directory of Open Access Journals (Sweden)

    NAI-XING WANG

    2002-10-01

    Full Text Available N-Vinylcarbazole (NVC monolayers were self-assembled on copper surfaces. The electrochemical properties of the copper surfaces modified by NVC self-assembled monolayers (SAMs were investigated using polarization and electrochemical impedance spectroscopic (EIS methods. The polarization measurements indicated that the NVC SAMs could reduce the rates of the anodic and cathodic reaction on the surface of copper electrodes in 0.5 mol dm-3 NaCl solution. The EIS results showed the NVC formed a closely packed film that was able to inhibit copper corrosion. X-Ray photoelectron spectroscopy (XPS analysis of the copper samples and atomic adsorption analysis of the solution showed that the copper surfaces were covered by NVC SAMs, and the adsorption of NVC on the copper surfaces was accompanied with dissolution of Cu into the solution.

  12. Nanocomposite of ZrO2/Polymer Thin-Film Coatings by The Ionically Self-Assembled Monolayer Technique

    OpenAIRE

    Rosidian, Aprillya

    1998-01-01

    Nanocomposites of multilayer structures of zirconia/polymer thin-film coatings have been fabricated on quartz and single-crystal silicon substrates by the Ionically Self-Assembled Monolayer (ISAM) technique. Particle size distribution was measured to calculate the grain diameter of the zirconia particles. UV/Vis spectroscopy and ellipsometry were used to characterize the ISAM technique. SEM and AFM were used to observe the microscopic structure of the multilayer structures. Some mechanical pr...

  13. A Study of the Modification of the Gold Electrode Surface with a Calix[4]arene Self-Assembled Monolayer

    Czech Academy of Sciences Publication Activity Database

    Šustrová, Barbora; Štulík, Karel; Mareček, Vladimír; Janda, Pavel

    2010-01-01

    Roč. 22, 17-18 (2010), s. 2051-2057. ISSN 1040-0397. [International Conference on Modern Electroanalytical Methods. Prague, 09.12.2009-14.12.2009] R&D Projects: GA AV ČR IAA400400806 Institutional research plan: CEZ:AV0Z40400503 Keywords : Calix[4]arene * Self-assembled monolayer (SAM) * ionophores Subject RIV: CG - Electrochemistry Impact factor: 2.721, year: 2010

  14. Electrochemistry of nucleic acids and proteins. 2. Self-assembled monolayers of thiolated DNA at mercury electrodes

    Czech Academy of Sciences Publication Activity Database

    Paleček, Emil

    Lańsk-Olsztyn, 2009. s. 1. [III Summer School. 06.09.2009-18.09.2009, Lańsk-Olsztyn] R&D Projects: GA AV ČR(CZ) KAN400310651; GA MŠk(CZ) LC06035 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040507 Keywords : thiolated DNA electroactivity * self-assembled monolayers Subject RIV: BO - Biophysics

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

    OpenAIRE

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

    2009-01-01

    Bioactive glass (BG) can directly bond to living bone without fibrous tissue encapsulation. Key mechanistic steps of BG’s activity are attributed to calcium phosphate formation, surface hydroxylation and fibronectin (FN) adsorption. In the present study, self-assembled monolayers (SAMs) of alkanesilanes with different surface chemistry (OH, NH2, and COOH) were used as a model system to mimic BG’s surface activity. Calcium phosphate (Ca-P) was formed on SAMs by immersion in a solution which si...

  16. Interactions of gaseous HNO3 and water with individual and mixed alkyl self-assembled monolayers at room temperature.

    Science.gov (United States)

    Nishino, Noriko; Hollingsworth, Scott A; Stern, Abraham C; Roeselová, Martina; Tobias, Douglas J; Finlayson-Pitts, Barbara J

    2014-02-14

    The major removal processes for gaseous nitric acid (HNO3) in the atmosphere are dry and wet deposition onto various surfaces. The surface in the boundary layer is often covered with organic films, but the interaction of gaseous HNO3 with them is not well understood. To better understand the factors controlling the uptake of gaseous nitric acid and its dissociation in organic films, studies were carried out using single component and mixtures of C8 and C18 alkyl self-assembled monolayers (SAMs) attached to a germanium (Ge) attenuated total reflectance (ATR) crystal upon which a thin layer of SiOx had been deposited. For comparison, diffuse reflectance infrared Fourier transform spectrometry (DRIFTS) studies were also carried out using a C18 SAM attached to the native oxide layer on the surface of silicon powder. These studies show that the alkyl chain length and order/disorder of the SAMs does not significantly affect the uptake or dissociation/recombination of molecular HNO3. Thus, independent of the nature of the SAM, molecular HNO3 is observed up to 70-90% relative humidity. After dissociation, molecular HNO3 is regenerated on all SAM surfaces when water is removed. Results of molecular dynamics simulations are consistent with experiments and show that defects and pores on the surfaces control the uptake, dissociation and recombination of molecular HNO3. Organic films on surfaces in the boundary layer will certainly be more irregular and less ordered than SAMs studied here, therefore undissociated HNO3 may be present on surfaces in the boundary layer to a greater extent than previously thought. The combination of this observation with the results of recent studies showing enhanced photolysis of nitric acid on surfaces suggests that renoxification of deposited nitric acid may need to be taken into account in atmospheric models. PMID:24352159

  17. Label-free and reagentless electrochemical detection of PCR fragments using self-assembled quinone derivative monolayer: Application to Mycobacterium tuberculosis

    DEFF Research Database (Denmark)

    Zhang, Q D; March, G; Noel, V;

    2012-01-01

    We report a signal-on, label-free and reagentless electrochemical DNA biosensor, based on a mixed self-assembled monolayer of thiolated hydroxynaphthoquinone and thiolated oligonucleotide. Electrochemical changes resulting from hybridization were evidenced with oligonucleotide targets (as models...

  18. Self-assembled monolayers of pyridylthio-functionalized carbon nanotubes used as a support to immobilize cytochrome c

    OpenAIRE

    Sun, Qing; Liu, Jiang; Huang, Hong-Xiang; Chen, Meng; Qian, Dong-Jin

    2013-01-01

    Self-assembled monolayers (SAMs) of pyridylthio-functionalized multiwalled carbon nanotubes (pythio-MWNTs) have been constructed on the gold substrate surface, which were used as a support to immobilize cytochrome c (Cyt c). The assembly processes of the SAMs and adsorption of Cyt c were monitored by using quartz crystal microbalance (QCM). Based on the frequency change of the QCM resonator, the surface coverage for the SAMs of pythio-MWNTs was estimated to be about 5.2 μg/cm2, and that of th...

  19. Self-Assembly of Tetraphenyldibenzoperiflanthene (DBP) Films on Ag(111) in the Monolayer Regime.

    Science.gov (United States)

    Kirchhuebel, Tino; Gruenewald, Marco; Sojka, Falko; Kera, Satoshi; Bussolotti, Fabio; Ueba, Takahiro; Ueno, Nobuo; Rouillé, Gaël; Forker, Roman; Fritz, Torsten

    2016-03-01

    Tetraphenyldibenzoperiflanthene (DBP) is a promising candidate as a component of highly efficient organic photovoltaic cells and organic light-emitting diodes. The structural properties of thin films of this particular lander-type molecule on Ag(111) were investigated by complementary techniques. Highly ordered structures were obtained, and their mutual alignment was characterized by means of low-energy electron diffraction (LEED). Scanning tunneling microscopy (STM) images reveal two slightly different arrangements within the first monolayer (ML), both describable as specific herringbone patterns with two molecules per unit cell whose dibenzoperiflanthene framework is parallel to the surface. In contrast, single DBP molecules in the second ML were imaged with much higher intramolecular resolution, resembling the shape of the frontier orbitals in the gas phase as calculated by means of density functional theory (DFT). Further deposition leads to the growth of highly ordered bilayer islands on top of the first ML with identical unit cell dimensions and orientation but slightly inclined molecules. This suggests that the first ML acts as a template for the epitaxial growth of further layers. Simultaneously, a significant number of second-layer molecules mainly located at step edges or scattered over narrow terraces do not form highly ordered aggregates. PMID:26844381

  20. Corrosion protection ability of self-assembled monolayer of 3-amino-5-mercapto-1,2,4-triazole on copper electrode

    International Nuclear Information System (INIS)

    The self-assembled monolayer (SAM) of 3-amino-5-mercapto-1,2,4-triazole (AMTa) was formed on a copper surface and characterized using cyclic voltammetry, Fourier Transform Infra-red spectroscopy and scanning electron microscopy. Quantum chemical calculations suggested the stronger interaction between AMTa and copper. The protection ability of SAM has been evaluated using electrochemical impedance spectroscopy and potentiodynamic polarization measurements. The formed monolayer showed significant protection ability in 1% NaCl medium. The enhanced corrosion protection ability could be due to the compact film structure which blocks the electron transfer from the solution to AMTa monolayer modified copper substrate. - Highlights: • Self-assembled monolayer (SAM) of AMTa has been achieved on copper surface. • Monolayer formed has been duly characterized. • SAM of AMTa has been shown to offer significant protection to copper in NaCl medium

  1. Unfolding of cytochrome c immobilized on self-assembled monolayers. An electrochemical study

    International Nuclear Information System (INIS)

    Highlights: → Denaturation involves intermediate and partially unfolded forms. → An unfolded species displaying the haem with Fe coordinated by two His is observed. → Under unfolding conditions the nature of the SAM influences conformation of protein. → Concentration of the unfolding agent affects redox properties of immobilized protein. - Abstract: The electron transfer (ET) process of progressively unfolded bovine cytochrome c immobilized on different self-assembled monolayers (SAMs) was investigated. Insight is gained on the role of the SAM surface on the functionality of the partially unfolded and non-native forms of the adsorbed protein. Direct electrochemical measurements were performed on cytochrome c adsorbed on mercaptopyridine (MP) and mixed 11-mercapto-1-undecanoic acid/11-mercapto-1-undecanol (MUA/MU) at varying temperature, in the presence of urea as unfolding agent. Under strongly unfolding conditions, a non-native form of cytochrome c, in which the methionine ligand is replaced by a histidine, was observed on both MP and MUA/MU SAMs. The Eo' of the native form, in which the haem is axially coordinated by methionine and histidine, slightly shifts to negative values upon increasing urea concentration. However, the non-native bis-histidinate species shows a much lower Eo' value (by approximately 0.4 V) which is by far enthalpic in origin and largely determined by axial ligand swapping. Analysis of the reduction enthalpies and entropies and of the ET rate constants indicate that the nature of the SAM (hydrophilic or anionic) results in changes in the conformational rearrangement of the cytochrome c under unfolding conditions.

  2. Unfolding of cytochrome c immobilized on self-assembled monolayers. An electrochemical study

    Energy Technology Data Exchange (ETDEWEB)

    Monari, Stefano; Ranieri, Antonio; Bortolotti, Carlo Augusto; Peressini, Silvia [Department of Chemistry, University of Modena and Reggio Emilia, via Campi 183, 41125 Modena (Italy); Tavagnacco, Claudio [Department of Chemistry, University of Trieste, via Giorgieri 1, 34127 Trieste (Italy); Borsari, Marco, E-mail: marco.borsari@unimore.it [Department of Chemistry, University of Modena and Reggio Emilia, via Campi 183, 41125 Modena (Italy)

    2011-08-01

    Highlights: > Denaturation involves intermediate and partially unfolded forms. > An unfolded species displaying the haem with Fe coordinated by two His is observed. > Under unfolding conditions the nature of the SAM influences conformation of protein. > Concentration of the unfolding agent affects redox properties of immobilized protein. - Abstract: The electron transfer (ET) process of progressively unfolded bovine cytochrome c immobilized on different self-assembled monolayers (SAMs) was investigated. Insight is gained on the role of the SAM surface on the functionality of the partially unfolded and non-native forms of the adsorbed protein. Direct electrochemical measurements were performed on cytochrome c adsorbed on mercaptopyridine (MP) and mixed 11-mercapto-1-undecanoic acid/11-mercapto-1-undecanol (MUA/MU) at varying temperature, in the presence of urea as unfolding agent. Under strongly unfolding conditions, a non-native form of cytochrome c, in which the methionine ligand is replaced by a histidine, was observed on both MP and MUA/MU SAMs. The E{sup o}' of the native form, in which the haem is axially coordinated by methionine and histidine, slightly shifts to negative values upon increasing urea concentration. However, the non-native bis-histidinate species shows a much lower E{sup o}' value (by approximately 0.4 V) which is by far enthalpic in origin and largely determined by axial ligand swapping. Analysis of the reduction enthalpies and entropies and of the ET rate constants indicate that the nature of the SAM (hydrophilic or anionic) results in changes in the conformational rearrangement of the cytochrome c under unfolding conditions.

  3. Equivalent circuits of a self-assembled monolayer-based tunnel junction determined by impedance spectroscopy.

    Science.gov (United States)

    Sangeeth, C S Suchand; Wan, Albert; Nijhuis, Christian A

    2014-08-01

    The electrical characteristics of molecular tunnel junctions are normally determined by DC methods. Using these methods it is difficult to discriminate the contribution of each component of the junctions, e.g., the molecule-electrode contacts, protective layer (if present), or the SAM, to the electrical characteristics of the junctions. Here we show that frequency-dependent AC measurements, impedance spectroscopy, make it possible to separate the contribution of each component from each other. We studied junctions that consist of self-assembled monolayers (SAMs) of n-alkanethiolates (S(CH2)(n-1)CH3 ≡ SC(n) with n = 8, 10, 12, or 14) of the form Ag(TS)-SC(n)//GaO(x)/EGaIn (a protective thin (~0.7 nm) layer of GaO(x) forms spontaneously on the surface of EGaIn). The impedance data were fitted to an equivalent circuit consisting of a series resistor (R(S), which includes the SAM-electrode contact resistance), the capacitance of the SAM (C(SAM)), and the resistance of the SAM (R(SAM)). A plot of R(SAM) vs n(C) yielded a tunneling decay constant β of 1.03 ± 0.04 n(C)(-1), which is similar to values determined by DC methods. The value of C(SAM) is similar to previously reported values, and R(S) (2.9-3.6 × 10(-2) Ω·cm(2)) is dominated by the SAM-top contact resistance (and not by the conductive layer of GaO(x)) and independent of n(C). Using the values of R(SAM), we estimated the resistance per molecule r as a function of n(C), which are similar to values obtained by single molecule experiments. Thus, impedance measurements give detailed information regarding the electrical characteristics of the individual components of SAM-based junctions. PMID:25036915

  4. Self-assembled monolayer cleaning methods: Towards fabrication of clean high-temperature superconductor nanostructures

    International Nuclear Information System (INIS)

    Although extensive amounts of research have been carried out on superconductor-normal metal-superconductor (SNS) electronic devices, the fabrication of superconductor SNS devices still remains difficult. Surface modification of high-temperature superconductors could be a way to control the interface of SNS electronic device fabrication. Here, we developed a cleaning method for thin films of high-temperature superconductor surface based on self-assembled monolayers. High-quality c-axis orientated YBa2Cu3O7-δ (i.e., YBCO) and Y0.6Ca0.4Ba1.6La0.4Cu3O7-δ (i.e., TX-YBCO) thin films were deposited by standard laser ablation methods. YBCO/Au/YBCO and TX-YBCO/Au/TX-YBCO planar type junctions were fabricated by photolithography, focused-ion-beam milling, and ex situ sputter depositions. A 40-50 nm nanotrench was ion milled on the thin film by FIB, and a thin gold layer was deposited by an ex situ method on the nanotrench to connect the two separated high-temperature superconductor electrodes. SEM, AFM, and R vs T resistivity measurements were used to compare the corrosion layer formed in the interface of the SNS junctions with the SAM cleaned SNS junction. Evidence here suggests that the SAM cleaning method can be used to remove the degradation layer on the surface of cuprate superconductors. The obtained contact resistivity value (10-8 Ω cm2) for a SNS junction with SAM treatment is comparable with that of SNS junctions fabricated by the in situ methods

  5. Ultrafast shock compression of self-assembled monolayers: a molecular picture.

    Science.gov (United States)

    Patterson, James E; Dlott, Dana D

    2005-03-24

    Simulations of self-assembled monolayers (SAMs) are performed to interpret experimental measurements of ultrafast approximately 1 GPa (volume compression deltaV approximately 0.1) planar shock compression dynamics probed by vibrational sum-frequency generation (SFG) spectroscopy (Lagutchev, A. S.; Patterson, J. E.; Huang, W.; Dlott, D. D. J. Phys. Chem. B 2005, 109, XXXX). The SAMs investigated are octadecanethiol (ODT) and pentadecanethiol (PDT) on Au(111) and Ag(111) substrates, and benzyl mercaptan (BMT) on Au(111). In the alkane SAMs, SFG is sensitive to the instantaneous orientation of the terminal methyl; in BMT it is sensitive to the phenyl orientation. Computed structures of alkane SAMs are in good agreement with experiment. In alkanes, the energies of gauche defects increase with increasing number and depth below the methyl plane, with the exception of ODT/Au where both single and double gauche defects at the two uppermost dihedrals have similar energies. Simulations of isothermal uniaxial compression of SAM lattices show that chain and methyl tilting is predominant in PDT/Au, ODT/Ag and PDT/Ag, whereas single and double gauche defect formation is predominant in ODT/Au. Time-resolved shock data showing transient SFG signal loss of ODT/Au and PDT/Au are fit by calculations of the terminal group orientations as a function of deltaV and their contributions to the SFG hyperpolarizability. The highly elastic response of PDT/Au results from shock-generated methyl and chain tilting. The viscoelastic response of ODT/Au results from shock generation of single and double gauche defects. Isothermal compression simulations help explain and fit the time dependence of shock spectra but generally underestimate the magnitude of SFG signal loss because they do not include effects of high-strain-rate dynamics and shock front and surface irregularities. PMID:16863164

  6. Charge Retention of Soft-Landed Phosphotungstate Keggin Anions on Self-Assembled Monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Gunaratne, Kalupathirannehelage Don D.; Prabhakaran, Venkateshkumar; Andersen, Amity; Johnson, Grant E.; Laskin, Julia

    2016-04-07

    Soft landing of mass-selected ions onto surfaces often results in partial loss of charge that may affect the structure and reactivity of deposited species. In this study, Keggin phosphotungstate anions in two selected charge states, PW12O403- (WPOM3-) and PW12O402- (WPOM2-), were soft-landed onto different self-assembled monolayer (SAM) surfaces and examined using in situ infrared reflection absorption spectroscopy (IRRAS) and density functional theory (DFT) calculations. Partial retention of the 3- charge was observed when WPOM3- was soft-landed onto the fluorinated SAM (FSAM), while the charge state distribution was dominated by the 2- charge after both WPOM3- and WPOM2- were deposited onto a hydrophilic alkylthiol SAM terminated with cationic NH3+ functional groups (NH3+SAM). We found that during the course of the soft landing of WPOM3-, the relative abundance of WPOM3- on FSAM decreased while that of WPOM2- increased. We propose that the higher stability of immobilized WPOM2- in comparison with WPOM3- makes it the preferred charge state of WPOM on both the FSAM and NH3+SAM. We also observe weaker binding of WPOM anions to SAMs in comparison with phosphomolybdate ions (MoPOM) reported previously (J. Phys. Chem. C 2014, 118, 27611–27622). The weaker binding of WPOM to SAMs is attributed to the lower reactivity of WPOM reported in the literature. This study demonstrates that both the charge retention and the reactivity of deposited anionic POM clusters on surfaces are determined by the type of addenda metal atoms in the cluster.

  7. Reducing Staphylococcus aureus biofilm formation on stainless steel 316L using functionalized self-assembled monolayers

    International Nuclear Information System (INIS)

    Stainless steel 316L (SS316L) is a common material used in orthopedic implants. Bacterial colonization of the surface and subsequent biofilm development can lead to refractory infection of the implant. Since the greatest risk of infection occurs perioperatively, strategies that reduce bacterial adhesion during this time are important. As a strategy to limit bacterial adhesion and biofilm formation on SS316L, self-assembled monolayers (SAMs) were used to modify the SS316L surface. SAMs with long alkyl chains terminated with hydrophobic (− CH3) or hydrophilic (oligoethylene glycol) tail groups were used to form coatings and in an orthogonal approach, SAMs were used to immobilize gentamicin or vancomycin on SS316L for the first time to form an “active” antimicrobial coating to inhibit early biofilm development. Modified SS316L surfaces were characterized using surface infrared spectroscopy, contact angles, MALDI-TOF mass spectrometry and atomic force microscopy. The ability of SAM-modified SS316L to retard biofilm development by Staphylococcus aureus was functionally tested using confocal scanning laser microscopy with COMSTAT image analysis, scanning electron microscopy and colony forming unit analysis. Neither hydrophobic nor hydrophilic SAMs reduced biofilm development. However, gentamicin-linked and vancomycin-linked SAMs significantly reduced S. aureus biofilm formation for up to 24 and 48 h, respectively. - Highlights: ► SS316L was modified with glycol terminated SAMs in order to reduce biofilm growth. ► Antibiotics gentamicin and vancomycin were immobilized on SS316L via SAMs. ► Only the antibiotic modifications reduced biofilm development on SS316L

  8. Reducing Staphylococcus aureus biofilm formation on stainless steel 316L using functionalized self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Kruszewski, Kristen M., E-mail: kruszewskik@duq.edu [Duquesne University, Department of Chemistry and Biochemistry, 600 Forbes Avenue, Pittsburgh, PA 15282 (United States); Nistico, Laura, E-mail: lnistico@wpahs.org [Allegheny General Hospital, Center for Genomic Sciences, Allegheny-Singer Research Institute, 320 East North Avenue, 11th floor, South Tower, Pittsburgh, PA 15212 (United States); Longwell, Mark J., E-mail: mlongwel@wpahs.org [Allegheny General Hospital, Center for Genomic Sciences, Allegheny-Singer Research Institute, 320 East North Avenue, 11th floor, South Tower, Pittsburgh, PA 15212 (United States); Hynes, Matthew J., E-mail: mjhynes@go.wustl.edu [Washington University in St. Louis, Department of Chemistry, One Brookings Drive, St. Louis, MO 63130 (United States); Maurer, Joshua A., E-mail: maurer@wustl.edu [Washington University in St. Louis, Department of Chemistry, One Brookings Drive, St. Louis, MO 63130 (United States); Hall-Stoodley, Luanne, E-mail: L.Hall-Stoodley@soton.ac.uk [Southampton Wellcome Trust Clinical Research Facility/NIHR Respiratory BRU, University of Southampton Faculty of Medicine, Southampton General Hospital, Tremona Road, Southampton, Hampshire SO16 6YD (United Kingdom); Gawalt, Ellen S., E-mail: gawalte@duq.edu [Duquesne University, Department of Chemistry and Biochemistry, McGowan Institute for Regenerative Medicine, 600 Forbes Avenue, Pittsburgh, PA 15282 (United States)

    2013-05-01

    Stainless steel 316L (SS316L) is a common material used in orthopedic implants. Bacterial colonization of the surface and subsequent biofilm development can lead to refractory infection of the implant. Since the greatest risk of infection occurs perioperatively, strategies that reduce bacterial adhesion during this time are important. As a strategy to limit bacterial adhesion and biofilm formation on SS316L, self-assembled monolayers (SAMs) were used to modify the SS316L surface. SAMs with long alkyl chains terminated with hydrophobic (− CH{sub 3}) or hydrophilic (oligoethylene glycol) tail groups were used to form coatings and in an orthogonal approach, SAMs were used to immobilize gentamicin or vancomycin on SS316L for the first time to form an “active” antimicrobial coating to inhibit early biofilm development. Modified SS316L surfaces were characterized using surface infrared spectroscopy, contact angles, MALDI-TOF mass spectrometry and atomic force microscopy. The ability of SAM-modified SS316L to retard biofilm development by Staphylococcus aureus was functionally tested using confocal scanning laser microscopy with COMSTAT image analysis, scanning electron microscopy and colony forming unit analysis. Neither hydrophobic nor hydrophilic SAMs reduced biofilm development. However, gentamicin-linked and vancomycin-linked SAMs significantly reduced S. aureus biofilm formation for up to 24 and 48 h, respectively. - Highlights: ► SS316L was modified with glycol terminated SAMs in order to reduce biofilm growth. ► Antibiotics gentamicin and vancomycin were immobilized on SS316L via SAMs. ► Only the antibiotic modifications reduced biofilm development on SS316L.

  9. Reflection and extinction of light by self-assembled monolayers of a quinque-thiophene derivative: A coherent scattering approach

    Science.gov (United States)

    Gholamrezaie, Fatemeh; de Leeuw, Dago M.; Meskers, Stefan C. J.

    2016-06-01

    Scattering matrix theory is used to describe resonant optical properties of molecular monolayers. Three types of coupling are included: exciton-exciton, exciton-photon, and exciton-phonon coupling. We use the K-matrix formalism, developed originally to describe neutron scattering spectra in nuclear physics to compute the scattering of polaritons by phonons. This perturbation approach takes into account the three couplings and allows one to go beyond molecular exciton theory without the need of introducing additional boundary conditions for the polariton. We demonstrate that reflection, absorption, and extinction of light by 2D self-assembled monolayers of molecules containing quinque-thiophene chromophoric groups can be calculated. The extracted coherence length of the Frenkel exciton is discussed.

  10. Organized monolayers of biological macromolecules on Au(111) surfaces

    DEFF Research Database (Denmark)

    Zhang, Jingdong; Chi, Qijin; Nielsen, Jens Ulrik;

    2002-01-01

    now been applied comprehensively to proteins and other biomolecules in recent studies, discussed in this report. Focus is on three systems. The first one is a pair of amino acids, cysteine and cystine. These are strongly adsorbed via thiolate and disulfide, respectively, with identical reductive...... the protein is linked via its surface disulfide group. This orients the copper center away from the electrode surface. The other mode is by hydrophobic interactions with variable-length alkanethiols self-assembled on Au(I 11). In this mode the copper center is directed towards the surface. Adsorption...

  11. Self-assembled monolayers of alkylsiloxanes on SrTiO3 substrates

    OpenAIRE

    Kropman, Boike L.; Blank, Dave H. A.; Rogalla, Horst

    1997-01-01

    The formation and structure of alkyltrichlorosilanes on several types of SrTiO3 substrates have been studied. The silanes adsorb spontaneously from a hexadecane solution and form monolayers on all the substrates used. Characterization has been performed by atomic force microscopy, wettability, angle resolved X-ray photoelectron spectroscopy, reflection absorption infrared spectroscopy, and spectroscopic ellipsometry. It was found that highly ordered and densely packed monolayers were formed b...

  12. PM-IRRAS Determination of Molecular Orientation of Phosphonic Acid Self-Assembled Monolayers on Indium Zinc Oxide.

    Science.gov (United States)

    Sang, Lingzi; Mudalige, Anoma; Sigdel, Ajaya K; Giordano, Anthony J; Marder, Seth R; Berry, Joseph J; Pemberton, Jeanne E

    2015-05-26

    Self-assembled monolayers (SAMs) of phosphonic acids (PAs) on transparent conductive oxide (TCO) surfaces can facilitate improvement in TCO/organic semiconductor interface properties. When ordered PA SAMs are formed on oxide substrates, interface dipole and electronic structure are affected by the functional group properties, orientation, and binding modes of the modifiers. Choosing octylphosphonic acid (OPA), F13-octylphosphonic acid (F13OPA), pentafluorophenyl phosphonic acid (F5PPA), benzyl phosphonic acid (BnPA), and pentafluorobenzyl phosphonic acid (F5BnPA) as a representative group of modifiers, we report polarization modulation-infrared reflection-absorption spectroscopy (PM-IRRAS) of binding and molecular orientation on indium-doped zinc oxide (IZO) substrates. Considerable variability in molecular orientation and binding type is observed with changes in PA functional group. OPA exhibits partially disordered alkyl chains but on average the chain axis is tilted ∼57° from the surface normal. F13OPA tilts 26° with mostly tridentate binding. The F5PPA ring is tilted 23° from the surface normal with a mixture of bidentate and tridentate binding; the BnPA ring tilts 31° from normal with a mixture of bidentate and tridentate binding, and the F5BnPA ring tilts 58° from normal with a majority of bidentate with some tridenate binding. These trends are consistent with what has been observed previously for the effects of fluorination on orientation of phosphonic acid modifiers. These results from PM-IRRAS are correlated with recent results on similar systems from near-edge X-ray absorption fine structure (NEXAFS) and density functional theory (DFT) calculations. Overall, these results indicate that both surface binding geometry and intermolecular interactions play important roles in dictating the orientation of PA modifiers on TCO surfaces. This work also establishes PM-IRRAS as a routine method for SAM orientation determination on complex oxide substrates

  13. Molecular dynamics simulations of peptide adsorption on self-assembled monolayers

    Science.gov (United States)

    Xie, Yun; Liu, Meifeng; Zhou, Jian

    2012-08-01

    All-atom molecular dynamics simulations are performed to investigate the neuromedin-B peptide adsorption on the self-assembled monolayers (SAMs) of SH(CH2)10N+(CH3)2CH2CH(OH)CH2SO3- (SBT), SH(CH2)10OH and SH(CH2)10CH3. The force-distance profiles show that the surface resistance to peptide adsorption is mainly generated by the water molecules tightly bound to surfaces via hydrogen bonds (hydration water molecules); but surfaces themselves may also set an energy barrier for the approaching peptide. For the SBT-SAM, the surface first exerts a relatively high repulsive force and then a rather week attractive force on the approaching peptide; meanwhile the hydration water molecules exert a strong repulsive force on the peptide. Therefore, SBT-SAM has an excellent performance on resisting protein adsorption. For the OH-SAM and CH3-SAM, surfaces show low or little energy barrier but strong affinity to the peptide; and the hydration water molecules apply merely a repulsive force within a much narrower range and with lower intensity compared with the case for the SBT-SAM. The analysis of structural and dynamical properties of the peptide, surface and water indicates that possible factors contributing to surface resistance include the hydrogen-bond formation capability of surfaces, mobility of water molecules near surfaces, surface packing density and chain flexibility of SAMs. There are a large number of hydrogen bonds formed between the hydration water molecules and the functional groups of the SBT-SAM, which greatly lowers the mobility of water molecules near the surface. This tightly-bound water layer effectively reduces the direct contact between the surface and the peptide. Furthermore, the SBT-SAM also has a high flexibility and a low surface packing density, which allows water molecules to penetrate into the surface to form tightly-bound networks and therefore reduces the affinity between the peptide and the surface. The results show that the protein

  14. Effect of substrate composition on atomic layer deposition using self-assembled monolayers as blocking layers

    International Nuclear Information System (INIS)

    The authors have examined the effect of two molecules that form self-assembled monolayers (SAMs) on the subsequent growth of TaNx by atomic layer deposition (ALD) on two substrate surfaces, SiO2 and Cu. The SAMs that the authors have investigated include two vapor phase deposited, fluorinated alkyl silanes: Cl3Si(CH2)2(CF2)5CF3 (FOTS) and (C2H5O)3Si(CH2)2(CF2)7CF3 (HDFTEOS). Both the SAMs themselves and the TaNx thin films, grown using Ta[N(CH3)2]5 and NH3, were analyzed ex situ using contact angle, spectroscopic ellipsometry, x-ray photoelectron spectroscopy (XPS), and low energy ion-scattering spectroscopy (LEISS). First, the authors find that both SAMs on SiO2 are nominally stable at Ts ∼ 300 °C, the substrate temperature used for ALD, while on Cu, the authors find that HDFTEOS thermally desorbs, while FOTS is retained on the surface. The latter result reflects the difference in the head groups of these two molecules. The authors find that both SAMs strongly attenuate the ALD growth of TaNx on SiO2, by about a factor of 10, while on Cu, the SAMs have no effect on ALD growth. Results from LEISS and XPS are decisive in determining the nature of the mechanism of growth of TaNx on all surfaces. Growth on SiO2 is 2D and approximately layer-by-layer, while on the surfaces terminated by the SAMs, it nucleates at defect sites, is islanded, and is 3D. In the latter case, our results support growth of the TaNx thin film over the SAM, with a considerable delay in formation of a continuous thin film. Growth on Cu, with or without the SAMs, is also 3D and islanded, and there is also a delay in the formation of a continuous thin film as compared to growth on SiO2. These results highlight the power of coupling measurements from both LEISS and XPS in examinations of ultrathin films formed by ALD

  15. The Effect of Hydrophobic Pockets in Human Serum Albumin Adsorption to Self-Assembled Monolayers

    Science.gov (United States)

    Choi, Eugene J.; Jia, Shijin; Petrash, Stanislaw; Foster, Mark D.

    2001-04-01

    Molecular properties of proteins and their interactions with surfaces have an effect on protein adsorption, which is one of the first and most important events that occurs when a biological fluid contacts a surface. For biomaterials applications, blood reaction to foreign objects can cause thrombosis. To understand thrombosis, it is necessary to understand the mechanism of adsorption of blood proteins onto artificial surfaces. Such interactions as hydrophobicity^1,2, electrostatics^3 and specific binding^4 have been found to be driving forces for protein adsorption. Self-assembled monolayers (SAMs) provide an ideal surface for which protein adsorption behavior can be studied.^1 SAMs provide chemical homogeneity, robustness, and variable surface functionality. The hydrophobicity of SAMs has been of great interest in studying surface interactions with proteins.^1, 2 The packing density of alkyl chains of SAMs can also be varied in order to obtain different surface properties. The most abundant protein in the blood is human serum albumin (HSA). Because HSA acts as a fatty acid transporter, it has six binding sites for fatty acids. Pitt and Cooper^4 have shown that alkylation of surfaces increases the initial adsorption rate of delipidized (fatty acid free) HSA. Petrash et al.^5 have shown that delipidized HSA binds more tenaciously to less densely packed alkyl SAMs than to densely packed alkyl SAMs when desorbed by sodium dodecyl sulfate. Using X-ray reflectivity to study the adsorbed protein layer thickness, lipidized HSA (fatty acid bound) adsorption and desorption studies showed that specific binding of HSA is one of the main factors in binding tenacity between HSA and less densely packed alkyl SAMs. Atomic force microscopy was used as a complementary technique to confirm these results, and neutron reflectivity and spectroscopy techniques will also be used to study the adsorption behaviors of HSA and other blood proteins in future work. 1. Prime, K. L.; Whitesides

  16. Effect of substrate composition on atomic layer deposition using self-assembled monolayers as blocking layers

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Wenyu; Engstrom, James R., E-mail: jre7@cornell.edu [School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, New York 14853 (United States)

    2016-01-15

    The authors have examined the effect of two molecules that form self-assembled monolayers (SAMs) on the subsequent growth of TaN{sub x} by atomic layer deposition (ALD) on two substrate surfaces, SiO{sub 2} and Cu. The SAMs that the authors have investigated include two vapor phase deposited, fluorinated alkyl silanes: Cl{sub 3}Si(CH{sub 2}){sub 2}(CF{sub 2}){sub 5}CF{sub 3} (FOTS) and (C{sub 2}H{sub 5}O){sub 3}Si(CH{sub 2}){sub 2}(CF{sub 2}){sub 7}CF{sub 3} (HDFTEOS). Both the SAMs themselves and the TaN{sub x} thin films, grown using Ta[N(CH{sub 3}){sub 2}]{sub 5} and NH{sub 3}, were analyzed ex situ using contact angle, spectroscopic ellipsometry, x-ray photoelectron spectroscopy (XPS), and low energy ion-scattering spectroscopy (LEISS). First, the authors find that both SAMs on SiO{sub 2} are nominally stable at T{sub s} ∼ 300 °C, the substrate temperature used for ALD, while on Cu, the authors find that HDFTEOS thermally desorbs, while FOTS is retained on the surface. The latter result reflects the difference in the head groups of these two molecules. The authors find that both SAMs strongly attenuate the ALD growth of TaN{sub x} on SiO{sub 2}, by about a factor of 10, while on Cu, the SAMs have no effect on ALD growth. Results from LEISS and XPS are decisive in determining the nature of the mechanism of growth of TaN{sub x} on all surfaces. Growth on SiO{sub 2} is 2D and approximately layer-by-layer, while on the surfaces terminated by the SAMs, it nucleates at defect sites, is islanded, and is 3D. In the latter case, our results support growth of the TaN{sub x} thin film over the SAM, with a considerable delay in formation of a continuous thin film. Growth on Cu, with or without the SAMs, is also 3D and islanded, and there is also a delay in the formation of a continuous thin film as compared to growth on SiO{sub 2}. These results highlight the power of coupling measurements from both LEISS and XPS in examinations of ultrathin films formed by ALD.

  17. Molecular dynamics simulations of peptide adsorption on self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Xie Yun; Liu Meifeng [School of Chemistry and Chemical Engineering, Guangdong Provincial Key Lab for Green Chemical Product Technology, South China University of Technology, Guangzhou, Guangdong Province, 510640 (China); Zhou Jian, E-mail: jianzhou@scut.edu.cn [School of Chemistry and Chemical Engineering, Guangdong Provincial Key Lab for Green Chemical Product Technology, South China University of Technology, Guangzhou, Guangdong Province, 510640 (China)

    2012-08-01

    All-atom molecular dynamics simulations are performed to investigate the neuromedin-B peptide adsorption on the self-assembled monolayers (SAMs) of SH(CH{sub 2}){sub 10}N{sup +}(CH{sub 3}){sub 2}CH{sub 2}CH(OH)CH{sub 2}SO{sub 3}{sup -} (SBT), SH(CH{sub 2}){sub 10}OH and SH(CH{sub 2}){sub 10}CH{sub 3}. The force-distance profiles show that the surface resistance to peptide adsorption is mainly generated by the water molecules tightly bound to surfaces via hydrogen bonds (hydration water molecules); but surfaces themselves may also set an energy barrier for the approaching peptide. For the SBT-SAM, the surface first exerts a relatively high repulsive force and then a rather week attractive force on the approaching peptide; meanwhile the hydration water molecules exert a strong repulsive force on the peptide. Therefore, SBT-SAM has an excellent performance on resisting protein adsorption. For the OH-SAM and CH{sub 3}-SAM, surfaces show low or little energy barrier but strong affinity to the peptide; and the hydration water molecules apply merely a repulsive force within a much narrower range and with lower intensity compared with the case for the SBT-SAM. The analysis of structural and dynamical properties of the peptide, surface and water indicates that possible factors contributing to surface resistance include the hydrogen-bond formation capability of surfaces, mobility of water molecules near surfaces, surface packing density and chain flexibility of SAMs. There are a large number of hydrogen bonds formed between the hydration water molecules and the functional groups of the SBT-SAM, which greatly lowers the mobility of water molecules near the surface. This tightly-bound water layer effectively reduces the direct contact between the surface and the peptide. Furthermore, the SBT-SAM also has a high flexibility and a low surface packing density, which allows water molecules to penetrate into the surface to form tightly-bound networks and therefore reduces the

  18. Study of fibrinogen adsorption on self-assembled monolayers on Au(1 1 1) by atomic force microscopy

    International Nuclear Information System (INIS)

    The adsorption of plasma protein fibrinogen on the self-assembled monolayers (SAMs) of n-hexadecyl mercaptan and citrate was investigated with atomic force microscopy (AFM). On the basis of the preparation of these two flat SAMs on Au(1 1 1), high-resolution AFM images of bovine fibrinogen were obtained with different protein concentrations. The results indicated that the surface chemical composition significantly affected the adsorption behavior of fibrinogen. Since fibrinogen plays a key role in the regulation of both haemostasis and thrombosis, high-resolution AFM imaging on SAMs is expected to be an effective approach to study the haemocompatibility of materials with different surface chemistry

  19. Surface passivation of (100) GaSb using self-assembled monolayers of long-chain octadecanethiol

    Science.gov (United States)

    Papis-Polakowska, E.; Kaniewski, J.; Jurenczyk, J.; Jasik, A.; Czuba, K.; Walkiewicz, A. E.; Szade, J.

    2016-05-01

    The passivation of (100) GaSb surface was investigated by means of the long-chain octadecanethiol (ODT) self-assembled monolayer (SAM). The properties of ODT SAM on (100) GaSb were characterized by the atomic force microscopy using Kelvin probe force microscopy mode and X-ray photoelectron spectroscopy. The chemical treatment of 10mM ODT-C2H5OH has been applied to the passivation of a type-II superlattice InAs/GaSb photodetector. The electrical measurements indicate that the current density was reduced by one order of magnitude as compared to an unpassivated photodetector.

  20. Surface passivation of (100 GaSb using self-assembled monolayers of long-chain octadecanethiol

    Directory of Open Access Journals (Sweden)

    E. Papis-Polakowska

    2016-05-01

    Full Text Available The passivation of (100 GaSb surface was investigated by means of the long-chain octadecanethiol (ODT self-assembled monolayer (SAM. The properties of ODT SAM on (100 GaSb were characterized by the atomic force microscopy using Kelvin probe force microscopy mode and X-ray photoelectron spectroscopy. The chemical treatment of 10mM ODT-C2H5OH has been applied to the passivation of a type-II superlattice InAs/GaSb photodetector. The electrical measurements indicate that the current density was reduced by one order of magnitude as compared to an unpassivated photodetector.

  1. Capacitance Characterization of the Effect of pH Value on the Self-assembled Monolayers of Octadecanethiol

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    In this paper, the membrane capacitance (Cm), which was obtained from the electro- chemical impedance spectroscopy (EIS) method, was used to characterize the effect of pH value on the self-assembled monolayers (SAMs) of octadecanethiol(18SH) for the first time. The results not only strongly proved that inorganic ions could penetrate the SAMs of 18SH, but also ascertained that SAMs of 18SH were not an absolute of free of ion-penetration. Verifying the existence of pin-holes in the octadecanethiol SAMs was the main contribution of this paper, which coincided with the former conjecture very well.

  2. Study of Alkylthiolate Self-assembled Monolayers on Au(111) Using a Semilocal meta-GGA Density Functional

    DEFF Research Database (Denmark)

    Ferrighi, Lara; Pan, Yun-xiang; Grönbeck, Henrik;

    2012-01-01

    We present a density functional theory study of the structure and stability of self-assembled monolayers (SAMs) of alkylthiolate on Au(111) as a function of the alkyl chain length. The most favorable structure of the SAMs involves an RS–Au–SR complex (S being sulfur, R being an alkyl chain) formed...... particular, the use of M06-L yields an increased stability of the SAMs with increasing alkyl chain length and an increased attractive interaction between RS–Au–SR complexes at shorter distances....

  3. Spectroscopic analysis of a nanostructure roughness of plasma-deposited Au films using organic monolayer

    International Nuclear Information System (INIS)

    The morphology and roughness of nanostructure of Au film are discussed using an atomic-force microscope (AFM) and a laser Raman spectroscopy. The Au films are deposited on mica and Si substrate by means of a dc plasma sputtering technique, and a self-assembled monolayer (SAM) of benzene-thiol is formed on the Au films. The cluster size and roughness on the surface increase with substrate annealing during the deposition on mica substrate, while they decrease on Si substrate. Raman spectra show a surface-enhanced Raman scattering (SERS) occurs at the optimum roughness RA∼0.3 of the substrate.

  4. Self-assembled monolayer of 3-aminopropyltrimethoxysilane for improved adhesion between aluminum alloy substrate and polyurethane coating

    International Nuclear Information System (INIS)

    A good adhesion between a polymer coating and a metal or metal alloy substrate such as Al 2024-T3 plays a critical role in corrosion protection of metal substrates. In our study, a self-assembled monolayer film of 3-aminopropyltrimethoxysilane was formed on Al 2024-T3 substrate by covalent bonding. The adhesion property of a self-priming polyurethane coating was evaluated by pull-off adhesion test, wet tape test and thermal cycling test. All the testing results indicate that both dry and wet adhesion properties of the polyurethane coating were improved significantly after APS treatment of Al 2024-T3 in polar solvents such as methanol and acetone. In nonpolar solvents such as hexane, the APS treatment led to inconsistent improvement or sometime decreased adhesion of polyurethane coating. X-ray photoelectron spectroscopic study revealed that while a monolayer film was formed on the aluminum alloy surface after treating the substrate with APS in methanol and acetone, a multilayer film was formed on the substrate surface when the treatment was conducted in hexane. The APS monolayer film served as a covalent bond linkage between polymer coating and aluminum alloy substrates, which led to the increased adhesion property of polymer coating and corrosion resistance of the metal alloy substrate

  5. Optical modulation of nano-gap tunnelling junctions comprising self-assembled monolayers of hemicyanine dyes

    Science.gov (United States)

    Pourhossein, Parisa; Vijayaraghavan, Ratheesh K.; Meskers, Stefan C. J.; Chiechi, Ryan C.

    2016-06-01

    Light-driven conductance switching in molecular tunnelling junctions that relies on photoisomerization is constrained by the limitations of kinetic traps and either by the sterics of rearranging atoms in a densely packed monolayer or the small absorbance of individual molecules. Here we demonstrate light-driven conductance gating; devices comprising monolayers of hemicyanine dyes trapped between two metallic nanowires exhibit higher conductance under irradiation than in the dark. The modulation of the tunnelling current occurs faster than the timescale of the measurement (~1 min). We propose a mechanism in which a fraction of molecules enters an excited state that brings the conjugated portion of the monolayer into resonance with the electrodes. This mechanism is supported by calculations showing the delocalization of molecular orbitals near the Fermi energy in the excited and cationic states, but not the ground state and a reasonable change in conductance with respect to the effective barrier width.

  6. Optical modulation of nano-gap tunnelling junctions comprising self-assembled monolayers of hemicyanine dyes.

    Science.gov (United States)

    Pourhossein, Parisa; Vijayaraghavan, Ratheesh K; Meskers, Stefan C J; Chiechi, Ryan C

    2016-01-01

    Light-driven conductance switching in molecular tunnelling junctions that relies on photoisomerization is constrained by the limitations of kinetic traps and either by the sterics of rearranging atoms in a densely packed monolayer or the small absorbance of individual molecules. Here we demonstrate light-driven conductance gating; devices comprising monolayers of hemicyanine dyes trapped between two metallic nanowires exhibit higher conductance under irradiation than in the dark. The modulation of the tunnelling current occurs faster than the timescale of the measurement (∼1 min). We propose a mechanism in which a fraction of molecules enters an excited state that brings the conjugated portion of the monolayer into resonance with the electrodes. This mechanism is supported by calculations showing the delocalization of molecular orbitals near the Fermi energy in the excited and cationic states, but not the ground state and a reasonable change in conductance with respect to the effective barrier width. PMID:27272394

  7. Chiral hierarchical self-assembly in Langmuir monolayers of diacetylenic lipids

    KAUST Repository

    Basnet, Prem B.

    2013-01-01

    When compressed in the intermediate temperature range below the chain-melting transition yet in the low-pressure liquid phase, Langmuir monolayers made of chiral lipid molecules form hierarchical structures. Using Brewster angle microscopy to reveal this structure, we found that as the liquid monolayer is compressed, an optically anisotropic condensed phase nucleates in the form of long, thin claws. These claws pack closely to form stripes. This appears to be a new mechanism for forming stripes in Langmuir monolayers. In the lower temperature range, these stripes arrange into spirals within overall circular domains, while near the chain-melting transition, the stripes arrange into target patterns. We attributed this transition to a change in boundary conditions at the core of the largest-scale circular domains. © 2013 The Royal Society of Chemistry.

  8. Structure of self-assembled monolayer of NPAN on Au(111) electrode

    Institute of Scientific and Technical Information of China (English)

    YANG Guangzheng; ZENG Qingdao; WAN Lijun; BAI Chunli

    2003-01-01

    Adsorption of 4-(4-nitrophenylazo)-1-naphthol (NPAN), an azobenzene derivative, on Au(111) has been investigated in aqueous HClO4 solution by using the cyclic voltammetry and scanning tunneling microscopy (STM). The molecule is found to form a stable monolayer on the electrode with a (6×4) structure relative to the underlying Au(111) lattice. Cyclic voltammograms show that the redox reactions occurring on the electrode are retarded by the formation of the monolayer. A structural model is proposed for the two-dimensional adlayer.

  9. The structure and dynamics of self-assembling colloidal monolayers in oscillating magnetic fields

    CERN Document Server

    Koser, Alison E; Arratia, Paulo E

    2013-01-01

    Many fascinating phenomena such as large-scale collective flows, enhanced fluid mixing and pattern formation have been observed in so-called active fluids, which are composed of particles that can absorb energy and dissipate it into the fluid medium. For active particles immersed in liquids, fluid-mediated viscous stresses can play an important role on the emergence of collective behavior. Here, we experimentally investigate their role in the dynamics of self-assembling magnetically-driven colloidal particles which can rapidly form organized hexagonal structures. We find that viscous stresses reduce hexagonal ordering, generate smaller clusters, and significantly decrease the rate of cluster formation, all while holding the system at constant number density. Furthermore, we show that time and length scales of cluster formation depend on the Mason number (Mn), or ratio of viscous to magnetic forces, scaling as t / Mn and L / Mn^(1/2). Our results suggest that viscous stresses hinder collective behavior in a se...

  10. Insights into eisosome assembly and organization

    Indian Academy of Sciences (India)

    Murphy Er; Kim Kt

    2012-06-01

    Eisosomes, large protein complexes that are predominantly composed of BAR-domain-containing proteins Pil1 and its homologs, are situated under the plasma membrane of ascomycetes. A successful targeting of Pil1 onto the future site of eisosome accompanies maturation of eisosome. During or after recruitment, Pil1 undergoes self-assembly into filaments that can serve as scaffolds to induce membrane furrows or invaginations. Although a consequence of the invagination is likely to redistribute particular proteins and lipids to a different location, the precise physiological role of membrane invagination and eisosome assembly awaits further investigation. The present review summarizes recent research findings within the field regarding the detailed structural and functional significance of Pil1 on eisosome organization.

  11. Phase behaviour of self-assembled monolayers controlled by tuning physisorbed and chemisorbed states: A lattice-model view

    Science.gov (United States)

    Fortuna, Sara; Cheung, David L.; Johnston, Karen

    2016-04-01

    The self-assembly of molecules on surfaces into 2D structures is important for the bottom-up fabrication of functional nanomaterials, and the self-assembled structure depends on the interplay between molecule-molecule interactions and molecule-surface interactions. Halogenated benzene derivatives on platinum have been shown to have two distinct adsorption states: a physisorbed state and a chemisorbed state, and the interplay between the two can be expected to have a profound effect on the self-assembly and phase behaviour of these systems. We developed a lattice model that explicitly includes both adsorption states, with representative interactions parameterised using density functional theory calculations. This model was used in Monte Carlo simulations to investigate pattern formation of hexahalogenated benzene molecules on the platinum surface. Molecules that prefer the physisorbed state were found to self-assemble with ease, depending on the interactions between physisorbed molecules. In contrast, molecules that preferentially chemisorb tend to get arrested in disordered phases. However, changing the interactions between chemisorbed and physisorbed molecules affects the phase behaviour. We propose functionalising molecules in order to tune their adsorption states, as an innovative way to control monolayer structure, leading to a promising avenue for directed assembly of novel 2D structures.

  12. Fabrication of controllable and stable In2O3 nanowire transistors using an octadecylphosphonic acid self-assembled monolayer

    International Nuclear Information System (INIS)

    The controllability and stability of nanowire transistor characteristics are essential for the development of low-noise and fast-switching nano-electronic devices. In this study, the positive shift of threshold voltage and the improvement of interface quality on In2O3 nanowire transistors were simultaneously achieved by using octadecylphosphonic acid (OD-PA) self-assembly. Following the chemical bond of OD-PA molecules on the surface of In2O3 nanowires, the threshold voltage was positively shifted to 2.95 V, and the noise amplitude decreased to approximately 87.5%. The results suggest that an OD-PA self-assembled monolayer can be used to manipulate and stabilize the transistor characteristics of nanowire-based memory and display devices that require high-sensitivity, low-noise, and fast-response. (paper)

  13. Density Functional Theory with Modified Dispersion Correction for Metals Applied to Self-Assembled Monolayers of Thiols on Au(111

    Directory of Open Access Journals (Sweden)

    M. P. Andersson

    2013-01-01

    Full Text Available Using sound physical principles we modify the DFT-D2 atom pairwise semiempirical dispersion correction to density functional theory to work for metallic systems and in particular self-assembled monolayers of thiols on gold surfaces. We test our approximation for two functionals PBE-D and revPBE-D for lattice parameters and cohesive energies for Ni, Pd, Pt, Cu, Ag, and Au, adsorption energies of CO on (111 surfaces of Pd, Pt, Cu, Ag, and Au, and adsorption energy of benzene on Ag(111 and Au(111. Agreement with experimental data is substantially improved. We apply the method to self-assembled monolayers of alkanethiols on Au(111 and find reasonable agreement for PBE-D and revPBE-D for both physisorption of n-alkanethiols as well as dissociative chemisorption of dimethyl disulfide as an Au-adatom-dithiolate complex. By modifying the C6 coefficient for Au, we obtain quantitative agreement for physisorption and chemisorption for both PBE-D and revPBE-D using the same set of parameters. Our results confirm that inclusion of dispersion forces is crucial for any quantitative analysis of the thiol and thiolate bonds to the gold surface using quantum chemical calculations.

  14. Electron transfer kinetics of cytochrome c immobilized on a phenolic terminated thiol self assembled monolayer determined by scanning electrochemical microscopy

    International Nuclear Information System (INIS)

    Highlights: → Preparing a thiolated phenolic self-assembled monolayer surface (SAM). → Application of this SAM to immobilize cytochrome C. → Scanning electrochemical microscopy used for these studies. → Determination of both tunneling electron transfer and bimolecular rate constants between the immobilized protein-substrate and probe. - Abstract: In the present manuscript, the electrochemical behavior of cytochrome c (cyt-c) immobilized onto a phenolic terminated self assembled monolayer (SAM) on a gold electrode is investigated using cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM). The tunneling electron transfer (ET) rate constant between the immobilized protein and the underlying electrode surface, and also the bimolecular ET rate constant between the immobilized protein and a probe has been obtained using approach curves that were obtained by SECM. The approach curves were recorded at different substrate overpotentials in the presence of various concentrations of ferrocyanide as a probe and various surface concentrations of cyt-c; then the standard tunneling ET and bimolecular rate constants are obtained as 3.4 ± 0.3 s-1 and (2.0 ± 0.5) x 107 cm3 mol-1 s-1, respectively.

  15. On the influence of the aliphatic linker on fabrication of highly ordered and orientated self-assembled monolayers of aromatic selenols on AU(111)

    KAUST Repository

    Azzam, Waleed

    2014-03-06

    Self-assembled monolayers (SAMs) formed by adsorption of 1,2-dibenzyldiselenide (DPMSe) and 1,2-diphenyldiselenide (DBSe) on Au(111) substrates at room temperature have been characterized using scanning tunnelling microscopy, X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and low-energy electron diffraction. Upon adsorption, the Se-Se bonds in DPMSe and DBSe were cleaved on the gold surface to form phenylmethaneselenolate (PMSe) and benzeneselenolate (BSe) species, respectively. Although both PMSe and BSe molecular entities only differ in their structure (an additional methyl group in PMSe), the resulting monolayer films revealed noteworthy dissimilarities regarding their adlayer SAM structure and surface morphology. The molecular adlayer structure and orientation of PMSe and BSe species were found to vary significantly with the immersion time (IT). The resulting PMSe films were poorly organized, and the structure was described by a (4√3 × 2) rectangular unit cell for the SAMs prepared with 24 h of IT. Moreover, the PMSe-SAMs were found to be unstable upon exposure to air for a long time. Our results showed that exposure to air for 48 h results in the formation of small bright ad-islands, which have a height corresponding to that of a single atomic step on the Au(111). Contrary, BSe-SAMs exhibited densely packed and well-ordered monolayers, and two different structural phases were resolved at short and long ITs. The most densely packed structure was obtained for SAMs prepared with very short ITs (10 min). Upon increasing the IT, the SAMs exhibited structural changes to a lower density of molecular packing structure. The spectroscopic data also confirmed this structural transformation by suggesting an upright orientation for BSe-SAMs prepared after short ITs and strongly inclined adsorption geometry for SAMs prepared after long ITs. © 2014 American Chemical Society.

  16. Investigation of Tribological Behavior of Lanthanum-Based Thin Films Deposited on Sulfonated Self-Assembled Monolayer

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    3-mercaptopropyl trimethoxysilane (MPTS) was prepared on glass substrate so as to form a two-dimensional self-assembled monolayer (SAM), and the terminal -SH group in the film was in situ oxidized to -SO3H group to confer good chemisorption ability to the film. Thus, lanthanum-based thin films were deposited on oxidized MPTS-SAM, making use of the chemisorption ability of -SO3H group. Atomic force microscopy (AFM) and X-ray photoelectron spectrometry (XPS) and contact angle measurements were used to characterize the thin films. The tribological properties of the as-prepared thin films sliding against a steel ball were evaluated on a friction and wear tester. Tribological experiment shows that the friction coefficient of glass substrate decreases from 0.8 to 0.08 after the rare earth (RE) self-assembled films (SAMs) are formed on its surface. And the RE self-assembled films have longer wear life (500 sliding passes). It is demonstrated that RE self-assembled film exhibits good wear-resistant property. The marked decrease in friction and the longer wear life of RE films are attributed to the excellent adhesion of the film to the substrate and to the special characteristics of the RE elements. The frictional behaviors of RE thin-films-coated silicon surface were sensitive to the applied load and the sliding velocity of the steel ball.

  17. A surface enhanced Raman spectroscopy study of aminothiophenol and aminothiophenol-C{sub 60} self-assembled monolayers: Evolution of Raman modes with experimental parameters

    Energy Technology Data Exchange (ETDEWEB)

    Delafosse, G.; Patrone, L. [CNRS, IM2NP (UMR 7334), Faculte des Sciences et Techniques, Avenue Escadrille Normandie Niemen - Case 142, 13397 Marseille Cedex 20 (France); Aix-Marseille Universite, IM2NP, Campus de Saint-Jerome - Case 142, F-13397 Marseille Cedex 20 (France); Institut Superieur de l' Electronique et du Numerique, IM2NP, Maison des Technologies, Place Georges Pompidou, F-83000 Toulon (France); Merlen, A. [CNRS, IM2NP (UMR 7334), Faculte des Sciences et Techniques, Avenue Escadrille Normandie Niemen - Case 142, 13397 Marseille Cedex 20 (France); Universite du Sud Toulon-Var, IM2NP, Batiment R, BP 132, F-83957 La Garde Cedex (France); Clair, S. [CNRS, IM2NP (UMR 7334), Faculte des Sciences et Techniques, Avenue Escadrille Normandie Niemen - Case 142, 13397 Marseille Cedex 20 (France); Aix-Marseille Universite, IM2NP, Campus de Saint-Jerome - Case 142, F-13397 Marseille Cedex 20 (France)

    2012-05-21

    P-aminothiophenol (PATP) is a well-known molecule for the preparation of self-assembled monolayers on gold via its thiol functional group. After adsorption, it has been demonstrated that this molecule is anchored to gold through its thiol group, and standing nearly upright at the surface with the amino functional group on top. This molecule has been extensively studied by surface enhanced Raman spectroscopy but its exact SERS spectrum remains unclear. Here, we demonstrate that it can be strongly affected by at least two experimental parameters: laser power and layer density. Those features are discussed in terms of a dimerization of the PATP molecules. The free amino group affords the adsorption of other molecules such as C{sub 60}. In this case, a complex multilayer system is formed and the question of its precise characterisation remains a key point. In this article, we demonstrate that surface enhanced Raman spectroscopy combined with x ray photoelectron spectroscopy can bring very important information about the organization of such a self-assembled multilayer on gold. In our study, the strong evolution of Raman modes after C{sub 60} adsorption suggests a change in the organization of aminothiophenol molecules during C{sub 60} adsorption. These changes, also observed when the aminothiophenol layer is annealed in toluene, do not prevent the adsorption of C{sub 60} molecules.

  18. Self-assembling monolayers of helical oligopeptides with applications in molecular electronics

    CERN Document Server

    Strong, A E

    1997-01-01

    prepared. Transformation of the two (Trt)Cys residues of the resin-bound peptide to the intramolecular disulphide by iodine was achieved in acetonitrile but not in DMF. CD suggested that the conformation of this peptide was a mixture of helix and random coil. Films of the peptide-disulphide and the peptide-dithiol adsorbed from protic solvents were characterised as multilayers by ellipsometry. However CV and ellipsometry showed that a monolayer was successfully prepared from acetonitrile. Future targets for improving and extending this method to form monolayers of linked disulphides are presented. The aim of this project was to develop a generic method of preparing a 'molecular architecture' containing functional groups on a surface at predetermined relative positions several nm apart. This would be of great utility in molecular electronics, chemical sensors and other fields. It was proposed that such an architecture could be prepared on gold using linked, helical oligopeptides that contained the components o...

  19. Motor-mediated cortical versus astral microtubule organization in lipid-monolayered droplets.

    Science.gov (United States)

    Baumann, Hella; Surrey, Thomas

    2014-08-01

    The correct spatial organization of microtubules is of crucial importance for determining the internal architecture of eukaryotic cells. Microtubules are arranged in space by a multitude of biochemical activities and by spatial constraints imposed by the cell boundary. The principles underlying the establishment of distinct intracellular architectures are only poorly understood. Here, we studied the effect of spatial confinement on the self-organization of purified motors and microtubules that are encapsulated in lipid-monolayered droplets in oil, varying in diameter from 5-100 μm, which covers the size range of typical cell bodies. We found that droplet size alone had a major organizing influence. The presence of a microtubule-crosslinking motor protein decreased the number of accessible types of microtubule organizations. Depending on the degree of spatial confinement, the presence of the motor caused either the formation of a cortical array of bent microtubule bundles or the generation of single microtubule asters in the droplets. These are two of the most prominent forms of microtubule arrangements in plant and metazoan cells. Our results provide insights into the combined organizing influence of spatial constraints and cross-linking motor activities determining distinct microtubule architectures in a minimal biomimetic system. In the future, this simple lipid-monolayered droplet system characterized here can be expanded readily to include further biochemical activities or used as the starting point for the investigation of motor-mediated microtubule organization inside liposomes surrounded by a deformable lipid bilayer. PMID:24966327

  20. Electrical characteristics of conjugated self-assembled monolayers in large-area molecular junctions

    OpenAIRE

    A. J. Kronemeijer; Huisman, E. H.; Akkerman, H. B.; Goossens, A. M.; Katsouras, I.; Hal, P.A. van; Geuns, T. C. T.; van der Molen, S. J.; Blom, P. W. M.; de Leeuw, D. M.

    2010-01-01

    We have studied the electrical characteristics of close-packed monolayers of conjugated para-phenylene oligomers as a function of molecular length in large-area molecular junctions. An exponential increase in resistance with molecular length is observed, R proportional to exp(beta L), with beta = 0.26 +/- 0.04 angstrom(-1) and beta = 0.20 +/- 0.06 angstrom(-1) for dithiol and monothiol derivatives, respectively. The decay coefficients are lower than previously determined experimentally using ...

  1. Single-step DNA immobilization on antifouling self-assembled monolayers covalently bound to silicon (111).

    Science.gov (United States)

    Böcking, Till; Kilian, Kristopher A; Gaus, Katharina; Gooding, J Justin

    2006-04-11

    Hydrosilylation of alkenes with epoxide-terminated tri(ethylene oxide) moieties on Si-H surfaces yields homogeneous monolayers for the efficient coupling of biomolecules. The wetting properties of the epoxide-functionalized surface allow for the spotting of solutions of biomolecules, making the surface amenable to microarraying. Immobilization of thiolated DNA was achieved in a single step to fabricate biorecognition interfaces showing the hybridization of complementary DNA at low concentrations and negligible binding of noncomplementary DNA. PMID:16584219

  2. Self-assembly, self-organization and division of labour

    OpenAIRE

    Sendova-Franks, A. B.

    1999-01-01

    The prospect of generic principles of biological organization being uncovered through the increasingly broad use of the concepts of 'self-assembly' and 'self-organization' in biology will only be fulfilled if students of different levels of biological organization use the same terms with the same meanings. We consider the different ways the terms 'self-assembly' and 'self-organization' have been used, from studies of molecules to studies of animal societies. By linking 'self-assembly' and 'se...

  3. EXAFS in total reflection (reflEXAFS) for the study of organometallic Pd(II) thiol complexes based self-assembled monolayers on gold

    International Nuclear Information System (INIS)

    Graphical abstract: The molecular structure and organization of organometallic Pd(II) thiolates SAMs and multilayers on Au/Si(1 1 1) were investigated by reflEXAFS. For SAMs, S-Au bond lengths, Pd-S-Au bond angles and molecular orientations were assessed. Research highlights: → Organometallic Pt(II) thiolates deposited as SAMs and multilayers on gold. → Molecular structure and organization of SAMs and multilayers studied by reflEXAFS. → SAMs S-Au bond lengths, Pd-S-Au bond angles and molecular orientations are assessed. - Abstract: The molecular structure and organization of self-assembled monolayers (SAMs) and multilayer films grafted onto Au/Si(1 1 1) surfaces of mononuclear transition metal dialkynyl bridged Pd(II) complexes trans-[HS-Pd(PBu3)2-SH] (1), trans-[HS-Pd(PBu3)2(-C≡C-C6H5)] (2) and of the binuclear complex trans, trans-[HS-Pd(PBu3)2(-C≡C-C6H4-C6H4-C≡C-Pd(PBu3)2-SH] (3), have been investigated by extended X-ray absorption fine structure spectroscopy in total reflection conditions (reflEXAFS). ReflEXAFS analysis of the data lead to determine the local structure around Pd atoms, assessing the square-planar geometry around the transition metal in the multilayers case, preserved in the monolayer regime. The investigation on the SAMs also provided the assessment of the S-Au bond length and Pd-S-Au bond angle and on the molecular orientation on the gold substrate of the complexes, confirmed by quantum chemical calculations.

  4. Characterization of Functionalized Self-Assembled Monolayers and Surface-Attached Interlocking Molecules Using Near-Edge X-ray Absorption Fine Structure Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Willey, T; Willey, T

    2004-03-24

    Quantitative knowledge of the fundamental structure and substrate binding, as well as the direct measurement of conformational changes, are essential to the development of self-assembled monolayers (SAMs) and surface-attached interlocking molecules, catenanes and rotaxanes. These monolayers are vital to development of nano-mechanical, molecular electronic, and biological/chemical sensor applications. This dissertation investigates properties of functionalized SAMs in sulfur-gold based adsorbed molecular monolayers using quantitative spectroscopic techniques including near-edge x-ray absorption fine structure spectroscopy (NEXAFS) and x-ray photoelectron spectroscopy (XPS). The stability of the gold-thiolate interface is addressed. A simple model SAM consisting of dodecanethiol adsorbed on Au(111) degrades significantly in less than 24 hours under ambient laboratory air. S 2p and O 1s XPS show the gold-bound thiolates oxidize to sulfinates and sulfonates. A reduction of organic material on the surface and a decrease in order are observed as the layer degrades. The effect of the carboxyl vs. carboxylate functionalization on SAM structure is investigated. Carboxyl-terminated layers consisting of long alkyl-chain thiols vs. thioctic acid with short, sterically separated, alkyl groups are compared and contrasted. NEXAFS shows a conformational change, or chemical switchability, with carboxyl groups tilted over and carboxylate endgroups more upright. Surface-attached loops and simple surface-attached rotaxanes are quantitatively characterized, and preparation conditions that lead to desired films are outlined. A dithiol is often insufficient to form a molecular species bound at each end to the substrate, while a structurally related disulfide-containing polymer yields surface-attached loops. Similarly, spectroscopic techniques show the successful production of a simple, surface-attached rotaxane that requires a ''molecular riveting'' step to hold the

  5. Reversible switching in self-assembled monolayers of azobenzene thiolates on Au (111) probed by threshold photoemission

    International Nuclear Information System (INIS)

    Highlights: ► Photoelectron spectroscopy of liquid phase prepared SAMs of azobenzene derivative. ► Photo-induced reversible switching in densely packed SAM is monitored. ► Maximum density of switched molecules in SAM is derived from photoemission data. ► Switching reaction only enabled at defects sites within the molecular layer. - Abstract: The reversible photo- and thermally activated isomerization of the molecular switch 3-(4-(4-Hexyl-phenylazo)-phenoxy)-propane-1-thiol (ABT, short for AzoBenzeneThiol) deposited by self-assembly from solution on Au (111) was studied using laser-based photoelectron spectroscopy. Differences in the molecular dipole moment characteristic for the trans and the cis isomer of ABT were monitored via changes in the sample work function, accessible by detection of the threshold energy for photoemission. A quantitative analysis of our data shows that the fraction of molecules within the densely packed monolayer that undergoes a switching process is of the order of 1%. This result indicates the relevance of substrate and film defects required to overcome the steric or electronic hindrance of the isomerization reaction in a densely packed monolayer.

  6. Stability of phosphonic self assembled monolayers (SAMs) on cobalt chromium (Co-Cr) alloy under oxidative conditions

    International Nuclear Information System (INIS)

    Cobalt chromium (Co-Cr) alloys have been widely used in the biomedical arena for cardiovascular, orthopedic and dental applications. Surface modification of the alloy allows us to tailor the interfacial properties to address critical challenges of Co-Cr alloy in medical applications. Self assembled monolayers (SAMs) of Octadecylphosphonic acid (ODPA) have been used to form thin films on the oxide layer of the Co-Cr alloy surface by solution deposition technique. The SAMs formed were investigated for their stability to oxidative conditions of ambient laboratory environment over periods of 1, 3, 7 and 14 days. The samples were then characterized for their stability using X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and contact angle measurements. Detailed high energy XPS elemental scans confirmed the presence of the phosphonic monolayer after oxidative exposure which suggested that the SAMs were firmly attached to the oxide layer of Co-Cr alloy. AFM images gave topographical data of the surface and showed islands of SAMs on Co-Cr alloy surface, before and after SAM formation and also over the duration of the oxidative exposure. Contact angle measurements confirmed the hydrophobicity of the surface over 14 days. Thus the SAMs were found to be stable for the duration of the study. These SAMs could be subsequently tailored by modifying the terminal functional groups and could be used for various potential biomedical applications such as drug delivery, biocompatibility and tissue integration.

  7. Use of Self-Assembling Monolayers to Control Interface Bonding in a Model Study of Interfacial Fracture

    Energy Technology Data Exchange (ETDEWEB)

    Kent, M.S.; Matheson, A.; Reedy, E.D.; Yim, H.

    1999-03-05

    The relationships between the extent of interfacial bonding, energy dissipation mechanisms, and fracture toughness in a glassy adhesive/inorganic solid joint are not well understood. We address this subject with a model system involving an epoxy adhesive on a polished silicon wafer containing its native oxide. The extent of interfacial bonding, and the wetting behavior of the epoxy, is varied continuously using self-assembling monolayers (SAMs) of octadecyltrichlorosilane (ODTS). The epoxy interacts strongly with the bare silicon oxide surface, but forms only a very weak interface with the methylated tails of the ODTS monolayer. We examine the fracture behavior of such joints as a function of the coverage of ODTS in the napkin-ring geometry. Various characterization methods are applied to the ODTS-coated surface before application of the epoxy, and to both surfaces after fracture. The fracture data are discussed with respect to the wetting of the liquid epoxy on the ODTS-coated substrates, the locus of failure, and the energy dissipation mechanisms. Our goal is to understand how energy is dissipated during fracture as a function of interface strength.

  8. Stability of phosphonic self assembled monolayers (SAMs) on cobalt chromium (Co-Cr) alloy under oxidative conditions

    Science.gov (United States)

    Bhure, Rahul; Abdel-Fattah, Tarek M.; Bonner, Carl; Hall, Felicia; Mahapatro, Anil

    2011-04-01

    Cobalt chromium (Co-Cr) alloys have been widely used in the biomedical arena for cardiovascular, orthopedic and dental applications. Surface modification of the alloy allows us to tailor the interfacial properties to address critical challenges of Co-Cr alloy in medical applications. Self assembled monolayers (SAMs) of Octadecylphosphonic acid (ODPA) have been used to form thin films on the oxide layer of the Co-Cr alloy surface by solution deposition technique. The SAMs formed were investigated for their stability to oxidative conditions of ambient laboratory environment over periods of 1, 3, 7 and 14 days. The samples were then characterized for their stability using X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and contact angle measurements. Detailed high energy XPS elemental scans confirmed the presence of the phosphonic monolayer after oxidative exposure which suggested that the SAMs were firmly attached to the oxide layer of Co-Cr alloy. AFM images gave topographical data of the surface and showed islands of SAMs on Co-Cr alloy surface, before and after SAM formation and also over the duration of the oxidative exposure. Contact angle measurements confirmed the hydrophobicity of the surface over 14 days. Thus the SAMs were found to be stable for the duration of the study. These SAMs could be subsequently tailored by modifying the terminal functional groups and could be used for various potential biomedical applications such as drug delivery, biocompatibility and tissue integration.

  9. Self-assembled monolayer and multilayer formation using redox-active Ru complex with phosphonic acids on silicon oxide surface

    International Nuclear Information System (INIS)

    The formation of self-assembled monolayer and multilayer using redox-active Ru complex molecules with phosphonic acids on SiO2 surface has been examined using X-ray photoelectron spectroscopy (XPS), ellipsometry, and time of flight secondary mass-ion spectroscopy (TOF-SIMS). We found that an introduction of a Zr adlayer leads to higher surface molecular density of Ru complex SAMs on the SiO2 surface, compared to that of obtained from the direct adsorption of Ru complex monolayer on the SiO2 surface. We further tried to fabricate a multilayer film using this molecule with Zr(IV) ion acting as a chemical glue by a successive immersion process. The XPS data revealed that the molecular densities of the multilayers were also higher for the immobilization with Zr adlayer between Ru complex and SiO2 surface than those without the Zr adlayer, suggesting that Zr adlayer is effective in forming highly packed molecular layer of phosphonic acids on SiO2 surface. We found the film growth reached a saturation point after 6 layers on the SiO2 surface. The film growth saturation can be explained by a molecular domain boundary effect encountered due to the large tilt angle of the molecular layer.

  10. Tribological properties of self-assembled monolayers of catecholic imidazolium and the spin-coated films of ionic liquids.

    Science.gov (United States)

    Liu, Jianxi; Li, Jinlong; Yu, Bo; Ma, Baodong; Zhu, Yangwen; Song, Xinwang; Cao, Xulong; Yang, Wu; Zhou, Feng

    2011-09-20

    A novel compound of an imidazolium type of ionic liquid (IL) containing a biomimetic catecholic functional group normally seen in mussel adhesive proteins was synthesized. The IL can be immobilized on a silicon surface and a variety of other engineering material surfaces via the catecholic anchor, allowing the tribological protection of these substrates for engineering applications. The surface wetting and adhesive properties and the tribological property of the synthesized self-assembled monolayers (SAMs) are successfully modulated by altering the counteranions. The chemical composition and wettability of the IL SAMs were characterized by means of X-ray photoelectron spectroscopy (XPS) and contact angle (CA) measurements. The adhesive and friction forces were measured with an atomic force microscope (AFM) on the nanometer scale. IL composite films were prepared by spin coating thin IL films on top of the SAMs. The macrotribological properties of these IL composite films were investigated with a pin-on-disk tribometer. The results indicate that the presence of IL SAMs on a surface can improve the wettability of spin-coated ionic liquids and thus the film quality and the tribological properties. These films registered a reduced friction coefficient and a significantly enhanced durability and load-carrying capacity. The tribological properties of the composite films are better than those of pure IL films because the presence of the monolayers improves the adhesion and compatibility of spin-coated IL films with substrates. PMID:21834561

  11. Electron-beam patterned self-assembled monolayers as templates for Cu electrodeposition and lift-off

    Directory of Open Access Journals (Sweden)

    Zhe She

    2012-02-01

    Full Text Available Self-assembled monolayers (SAMs of 4'-methylbiphenyl-4-thiol (MBP0 adsorbed on polycrystalline gold substrates served as templates to control electrochemical deposition of Cu structures from acidic solution, and enabled the subsequent lift-off of the metal structures by attachment to epoxy glue. By exploiting the negative-resist behaviour of MBP0, the SAM was patterned by means of electron-beam lithography. For high deposition contrast a two-step procedure was employed involving a nucleation phase around −0.7 V versus Cu2+/Cu and a growth phase at around −0.35 V versus Cu2+/Cu. Structures with features down to 100 nm were deposited and transferred with high fidelity. By using substrates with different surface morphologies, AFM measurements revealed that the roughness of the substrate is a crucial factor but not the only one determining the roughness of the copper surface that is exposed after lift-off.

  12. Support-Free Transfer of Ultrasmooth Graphene Films Facilitated by Self-Assembled Monolayers for Electronic Devices and Patterns.

    Science.gov (United States)

    Wang, Bin; Huang, Ming; Tao, Li; Lee, Sun Hwa; Jang, A-Rang; Li, Bao-Wen; Shin, Hyeon Suk; Akinwande, Deji; Ruoff, Rodney S

    2016-01-26

    We explored a support-free method for transferring large area graphene films grown by chemical vapor deposition to various fluoric self-assembled monolayer (F-SAM) modified substrates including SiO2/Si wafers, polyethylene terephthalate films, and glass. This method yields clean, ultrasmooth, and high-quality graphene films for promising applications such as transparent, conductive, and flexible films due to the absence of residues and limited structural defects such as cracks. The F-SAM introduced in the transfer process can also lead to graphene transistors with enhanced field-effect mobility (up to 10,663 cm(2)/Vs) and resistance modulation (up to 12×) on a standard silicon dioxide dielectric. Clean graphene patterns can be realized by transfer of graphene onto only the F-SAM modified surfaces. PMID:26701198

  13. Self-assembled monolayers of a bis(pyrazol-1-yl)pyridine-substituted thiol on Au(111).

    Science.gov (United States)

    Shen, Cai; Haryono, Marco; Grohmann, Andreas; Buck, Manfred; Weidner, Tobias; Ballav, Nirmalya; Zharnikov, Michael

    2008-11-18

    Self-assembled monolayers (SAMs) of a bis(pyrazol-1-yl)pyridine-substituted thiol (bpp-SH) on Au (111)/mica were studied with scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). Using substrates precoated with perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA), preparation at elevated temperatures yields highly ordered layers whose structure is described by a rectangular (5 x radical3) unit cell containing one molecule. The bis(pyrazol-1-yl)pyridine (bpp) units exhibit pi-stacking along the 112 direction, and they are tilted significantly. We conclude the three imine nitrogen atoms in the bpp headgroup adopt a trans,trans arrangement. PMID:18950209

  14. Electrocatalytic oxidation of thiocyanate, L -cysteine and 2-mercaptoethanol by self-assembled monolayer of cobalt tetraethoxy thiophene phthalocyanine

    International Nuclear Information System (INIS)

    Catalytic activity of a self-assembled monolayer (SAM) of cobalt tetra ethoxythiophene phthalocyanine (CoTEThPc-SAM) complex towards oxidation of thiocyanate (SCN-), L -cysteine (CYS) and 2-mercaptoethanol (2-ME) is reported. The oxidation of thiocyanate occurs via a two electron transfer, whereas L-cysteine and 2-ME require 1 electron. The oxidation of thiocyanate is catalysed by ring based processes, while L-cysteine is catalysed by both CoIII/CoII process and by ring based processes. 2-ME is catalysed by CoIII/CoII process. The oxidation of thiocyanate on CoTEThPc was performed in acid media instead of basic media commonly employed. The reaction order was found to be unity for all the analytes, showing that only one molecule of analyte interacts with one molecule of the catalyst during the rate determining step

  15. Fabrication of uniform and high resolution copper nanowire using intermediate self-assembled monolayers through direct AFM lithography

    International Nuclear Information System (INIS)

    Electrochemical AFM lithography was used to directly fabricate copper nanowires. The copper ions were strongly reduced by a negative sample bias at the point where the AFM tip was localized, and copper metal wires were successfully fabricated following the direction of the electrical field of the bias. A TDA⋅HCl self-assembled monolayer (SAM) was found to play an important role as an intermediate layer for enhancing the capability of high resolution and complete development after the AFM lithographic process. The physical and electrical properties of the wires were analyzed by AFM, EFM, SEM, TEM and I–V measurement. The fabricated copper has promising potential for applications such as masks and interconnectors for nanoelectronic devices. (paper)

  16. Cyclic voltammetry on n-alkylphosphonic acid self-assembled monolayer modified large area indium tin oxide electrodes

    International Nuclear Information System (INIS)

    We show stable bonding of n-alkylphosphonic acid self-assembled monolayers (SAMs) to indium tin oxide electrodes and their direct electrical characterization by cyclic voltammetry (CV). The functional coatings were investigated with regards to the addressability and stability of the electrodes, which are related to small changes in molecular layer thickness. The response of a redox active compound in solution to the faradic current is indirectly proportional to the molecular chain length of the SAMs. We observed a decrease of the electrode sensitivity with enhanced surface protection and slow long term degradation of the SAM under electrochemical stress by CV, and therefore conclude a trade-off optimum for molecules with the C10 chain.

  17. Simple, Reversible, and Fast Modulation in Superwettability, Gradient, and Adsorption by Counterion Exchange on Self-Assembled Monolayer.

    Science.gov (United States)

    Osicka, Josef; Ilčiková, Marketa; Popelka, Anton; Filip, Jaroslav; Bertok, Tomas; Tkac, Jan; Kasak, Peter

    2016-06-01

    A simple fabrication method for preparation of surfaces able to switch from superhydrophobic to superhydrophilic state in a reversible and fast way is described. A self-assembled monolayer (SAM) consisting of quaternary ammonium group with aliphatic tail bearing terminal thiol functionality was created on gold nano/microstructured and gold planar surfaces, respectively. A rough nano/microstructured surface was prepared by galvanic reaction on a silicon wafer. The reversible counterion exchange on the rough surface resulted in a switchable contact angle between superhydrophobic to superhydrophilic can be formed on the modified rough gold surface in a robust and simple way by passive incubation of the substrate in a counterion solution and controlled by ionic strength. Furthermore, adsorption of gold nanoparticles to modified plain gold surface can be controlled to a high extent by counterions present on the SAM layer. PMID:27181793

  18. Influence of a self-assembled monolayer on indium-zinc-oxide semiconductor thin-film transistors

    International Nuclear Information System (INIS)

    The fabrication of an active-matrix liquid-crystal display by using printing processes offers the potential to reduce the number of photolithography steps and the manufacturing costs. In this study, we prepare the indium-zinc-oxide (IZO) thin-film transistors (TFTs) by using non-vacuum processes such as inkjet printing. The self-assembled monolayers of hexadecanethiol (HDT) on the surface of the oxide semiconductor prior to the inkjet printing of Ag were employed to modify the electric barrier between the IZO and the printed Ag. The field-effect mobility of the IZO TFTs with 0.5-mM HDT treatments and with the inkjet-printed Ag electrodes that were investigated by using their current-voltage characteristics was approximately 0.36 cm2/Vs.

  19. Self-assembled monolayers of stearic imidazoline on copper electrodes detected using electrochemical measurements, XPS, molecular simulation and FTIR

    Institute of Scientific and Technical Information of China (English)

    LIU XiuYu; MA HouYi; MIAO Shuai; ZHOU Min

    2009-01-01

    A type of imidazoline inhibitor was synthesized using stearic acid and diethylenetriamine (DETA) as raw materials. Self-assembled monolayers (SAMs) of stearic imidazoline (IM) were prepared on copper surface. The copper electrode modified by IM was detected by electrochemical impedance spectros-copy (EIS), Tafel polarization curves, X-ray photoelectron spectroscopy (XPS) and Fourial transform reflection spectroscopy (FTIR). The biggest inhibition efficiency for copper corrosion of IM was 99% in NaCI solution according to EIS results. The XPS results provided evidence that the IM was adsorbed on copper surface. The theoretical calculations of molecular simulation supported the experimental re-sults and showed that the IM molecules were tilted at an angle to the copper surface.

  20. Morse potential-based model for contacting composite rough surfaces: Application to self-assembled monolayer junctions

    Science.gov (United States)

    Sierra-Suarez, Jonatan A.; Majumdar, Shubhaditya; McGaughey, Alan J. H.; Malen, Jonathan A.; Higgs, C. Fred

    2016-04-01

    This work formulates a rough surface contact model that accounts for adhesion through a Morse potential and plasticity through the Kogut-Etsion finite element-based approximation. Compared to the commonly used Lennard-Jones (LJ) potential, the Morse potential provides a more accurate and generalized description for modeling covalent materials and surface interactions. An extension of this contact model to describe composite layered surfaces is presented and implemented to study a self-assembled monolayer (SAM) grown on a gold substrate placed in contact with a second gold substrate. Based on a comparison with prior experimental measurements of the thermal conductance of this SAM junction [Majumdar et al., Nano Lett. 15, 2985-2991 (2015)], the more general Morse potential-based contact model provides a better prediction of the percentage contact area than an equivalent LJ potential-based model.

  1. Vascular endothelial growth factor attachment to hydroxyapatite via self-assembled monolayers promotes angiogenic activity of endothelial cells

    International Nuclear Information System (INIS)

    Currently, tissue engineered constructs for critical sized bone defects are non-vascularized. There are many strategies used in order to promote vascularization, including delivery of growth factors such as vascular endothelial growth factor (VEGF). In this study, hydroxyapatite (HA) was coated with self-assembled monolayers (SAMs). The SAMs were in turn used to covalently bind VEGF to the surface of HA. The different SAM chain length ratios (phosphonoundecanoic acid (11-PUDA):16-phosphonohexadecanoic acid (16-PHDA) utilized in this study were 0:100, 25:75, 50:50, 75:25, and 100:0. Surfaces were characterized by contact angle (CA) and atomic force microscopy, and an in vitro VEGF release study was performed. It was observed that CA and root-mean-squared roughness were not significantly affected by the addition of SAMs, but that CA was significantly lowered with the addition of VEGF. VEGF release profiles of bound VEGF groups all demonstrated less initial burst release than adsorbed control, indicating that VEGF was retained on the HA surface when bound by SAMs. An in vitro study using human aortic endothelial cells (HAECs) demonstrated that bound VEGF increased metabolic activity and caused sustained production of angiopoietin-2, an angiogenic marker, over 28 days. In conclusion, SAMs provide a feasible option for growth factor delivery from HA surfaces, enhancing angiogenic activity of HAECs in vitro. - Highlights: • Vascular endothelial growth factor (VEGF) is attached to hydroxyapatite (HA). • Self-assembled monolayers (SAMs) delay the release of VEGF from hydroxyapatite. • SAM chain length ratio affects the total mass of VEGF released. • VEGF on HA up-regulates proliferation and angiogenic activity of endothelial cells

  2. Preparation of Sm2S3 thin films by liquid phase deposition method with self-assembled monolayers

    International Nuclear Information System (INIS)

    Highlights: ► Sm2S3 thin films with orientation growth along (1 0 3) direction. ► The influence of the precursor solution pH value. ► Liquid phase deposition method on self-assembled monolayers. ► Red photoluminescence properties. - Abstract: Sm2S3 thin films were prepared on Si(1 0 0) substrates using SmCl3 and Na2S2O3 as source material by liquid phase deposition method on self-assembled monolayers. The influence of the precursor solution pH value on the phase composition, surface morphology and optical properties of the as-deposited films were investigated. The as-deposited Sm2S3 thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), ultraviolet–visible (UV–Vis) and photoluminescence spectrum (PL). Results show that it is important to control the solution pH value during the deposition process and monophase Sm2S3 thin films with orientation growth along (1 0 3) direction can be achieved when pH 3.0, using citrate as a template agent. The as-deposited thin films exhibit a dense and crystalline surface morphology. Good transmittance in the visible spectrum and excellent absorbency of ultraviolet light of the thin films are observed, and the band gap of the thin films first decrease and then increase with the increase of the pH value. The as-deposited thin films also exhibit red photoluminescence properties under visible light excitation. With the increase of the solution pH value, the PL properties of Sm2S3 thin films are obviously improved.

  3. Vascular endothelial growth factor attachment to hydroxyapatite via self-assembled monolayers promotes angiogenic activity of endothelial cells

    Energy Technology Data Exchange (ETDEWEB)

    Solomon, Kimberly D., E-mail: solomonk@livemail.uthscsa.edu [Department of Biomedical Engineering, University of Texas at San Antonio, San Antonio, TX (United States); UTSA-UTHSCSA Joint Graduate Program in Biomedical Engineering, San Antonio, TX (United States); Ong, Joo L., E-mail: anson.ong@utsa.edu [Department of Biomedical Engineering, University of Texas at San Antonio, San Antonio, TX (United States); UTSA-UTHSCSA Joint Graduate Program in Biomedical Engineering, San Antonio, TX (United States)

    2013-06-30

    Currently, tissue engineered constructs for critical sized bone defects are non-vascularized. There are many strategies used in order to promote vascularization, including delivery of growth factors such as vascular endothelial growth factor (VEGF). In this study, hydroxyapatite (HA) was coated with self-assembled monolayers (SAMs). The SAMs were in turn used to covalently bind VEGF to the surface of HA. The different SAM chain length ratios (phosphonoundecanoic acid (11-PUDA):16-phosphonohexadecanoic acid (16-PHDA) utilized in this study were 0:100, 25:75, 50:50, 75:25, and 100:0. Surfaces were characterized by contact angle (CA) and atomic force microscopy, and an in vitro VEGF release study was performed. It was observed that CA and root-mean-squared roughness were not significantly affected by the addition of SAMs, but that CA was significantly lowered with the addition of VEGF. VEGF release profiles of bound VEGF groups all demonstrated less initial burst release than adsorbed control, indicating that VEGF was retained on the HA surface when bound by SAMs. An in vitro study using human aortic endothelial cells (HAECs) demonstrated that bound VEGF increased metabolic activity and caused sustained production of angiopoietin-2, an angiogenic marker, over 28 days. In conclusion, SAMs provide a feasible option for growth factor delivery from HA surfaces, enhancing angiogenic activity of HAECs in vitro. - Highlights: • Vascular endothelial growth factor (VEGF) is attached to hydroxyapatite (HA). • Self-assembled monolayers (SAMs) delay the release of VEGF from hydroxyapatite. • SAM chain length ratio affects the total mass of VEGF released. • VEGF on HA up-regulates proliferation and angiogenic activity of endothelial cells.

  4. Building a Low-Cost, Six-Electrode Instrument to Measure Electrical Properties of Self-Assembled Monolayers of Gold Nanoparticles

    Science.gov (United States)

    Gerber, Ralph W.; Oliver-Hoyo, Maria

    2007-01-01

    The development of a new low-cost, six-electrode instrument for measuring the electrical properties of the self-assembled monolayers of gold particles is being described. The system can also be used to measure conductive liquids, except for those that contain aqua region.

  5. Self-assembly of mildly reduced graphene oxide monolayer for enhanced Raman scattering

    Science.gov (United States)

    Yin, Fenping; Wu, Shang; Wang, Yanbin; Wu, Lan; Yuan, Peilin; Wang, Xia

    2016-05-01

    Graphene-enhanced Raman scattering (GERS) has attracted much attention recently. In present study, monolayer of chemically reduced graphene oxide (RGO) nanosheets was chemically bonded on Si substrates and their possible applications in Raman scattering were investigated. In comparison with the mechanically exfoliated graphene, mildly reduced graphene oxide (MR-GO) monolayer is a better substrate to quench the fluorescence (FL) signals and simultaneously enhance the Raman signals of adsorbed Rhodamin 6G (R6G) molecules. Raman and X-ray photoelectron spectra indicate that π-π stacking and the residual polarized oxygen groups on MRGO surface, which can produce a strong local electric field under laser excitation, are mainly responsible for the excellent GERS effect of MR-GO substrate, while the charge transfer between R6G and MR-GO has a relatively low contribution for GERS effect. Our results not only provide a new approach to realize sensitive GERS substrate, but also are helpful for improving the fundamental understanding of GERS effect on RGO substrate.

  6. Photonic properties of organic molecular assemblies

    Science.gov (United States)

    Huggins, Kevin Edward

    1997-12-01

    This work attempts to characterize various photonic properties of spontaneously created organic molecular objects. A novel diacetylene monomer was synthesized and found to polymerize forming two-dimensional supramolecular assemblies. The two-dimensional structure self assembles when UV light generates polydiacetylene comb polymers. The material forms blue solid thin films which have been characterized by x-ray diffraction, infrared spectroscopy and Raman scattering. The photopolymerization rate of the monomer was followed by Raman scattering and was shown to be of second order. A reaction rate threshold was observed between 300 and 400mW of incident 647.1nm laser radiation where the reaction rate increased substantially. The material generates high third order nonlinear optical signals and have remarkable photochemical stability to 1064nm radiation from a Q-switched Nd:YAG laser. Upon heating to 62oC, the material turns bright red reversibly while maintaining its two-dimensional structure, characterized by differential scanning calorimetry. Heating to 180oC results in an irreversible color change to bright orange characterized by UV-Vis-NIR spectrophotometry. Variable temperature sum frequency generation experiments show that the third harmonic generation signals retain much of their original intensity through the thermochromic transitions. A system of novel rodcoil materials self assembles into mushroom-shaped supramolecular objects. These nanophase separated aggregates form oblique-plane superlattices exhibiting long-range order. The superlattice is composed of isolated crystallized rod domains surrounded by amorphous coil which form from simple solvent casting techniques. Second harmonic generation was used to confirm the polar head-to-tail stacking of the aggregates and to determine the average physical tilt of (5/pm 5)o of the aggregates relative to the film plane. A novel chiral oligomer synthesized in our group gave rise to interesting phase behavior

  7. SELFORGANIZING ASSEMBLY MODELING BASED ON RELATIONAL CONSTRAINTS

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    On the research of assembly modeling of mechanical products, current CAD systems can only support the design process of componettoassembly. It is difficult to realize the design process of assemblyto component. The theory of selforganizing assembly modeling based on relational constraints is proposed, which implements the product design of assembly to component commencing with conceptual design and supporting abstract design and sepnice refinement design.

  8. Tuning the self-assembled monolayer formation on nanoparticle surfaces with different curvatures: investigations on spherical silica particles and plane-crystal-shaped zirconia particles.

    Science.gov (United States)

    Feichtenschlager, Bernhard; Lomoschitz, Christoph J; Kickelbick, Guido

    2011-08-01

    The ordering of dodecyl-chain self-assembled monolayers (SAM) on different nanoscopic surfaces was investigated by FT-IR studies. As model systems plane-crystal-shaped ZrO(2) nanoparticles and spherical SiO(2) nanoparticles were examined. The type of capping agent was chosen dependent on the substrate, therefore dodecylphosphonic acid and octadecylphosphonic acid were used for ZrO(2) and dodecyltrimethoxysilane for SiO(2) samples. The plane ZrO(2) nanocrystals yielded more ordered alkyl-chain structures whereas spherical SiO(2) nanoparticles showed significantly lower alkyl-chain ordering. Submicron-sized silica spheres revealed a significantly higher alkyl chain ordering, comparable to an analogously prepared SAM on a non-curved plane oxidized Si-wafer. In the case of ZrO(2) nanocrystals an intense alkyl-chain alignment could be disturbed by decreasing the grafting density from the maximum of 2.1 molecules/nm(2) through the variation of coupling agent concentration to lower values. Furthermore, the co-adsorption of a different coupling agent, such as phenylphosphonic acid for ZrO(2) and phenyltrimethoxysilane for SiO(2), resulted in a significantly lower alkyl-chain ordering for ZrO(2) plane crystals and for large SiO(2) spherical particles at high grafting density. An increasing amount of order-disturbing molecules leads to a gradual decrease in alkyl-chain alignment on the surface of the inorganic nanoparticles. In the case of the ZrO(2) nanoparticle system it is shown via dynamic light scattering (DLS) that the mixed monolayer formation on the particle surface impacts the dispersion quality in organic solvents such as n-hexane. PMID:21549385

  9. Characterization of self-assembled monolayers (SAMs) on silicon substrate comparative with polymer substrate for Escherichia coli O157:H7 detection

    International Nuclear Information System (INIS)

    This article presents the characterization of two substrates, silicon and polymer coated with gold, that are functionalized by mixed self-assembled monolayers (SAMs) in order to efficiently immobilize the anti-Escherichia coli O157:H7 polyclonal purified antibody. A biosurface functionalized by SAMs (self-assembled monolayers) technique has been developed. Immobilization of goat anti-E. coli O157:H7 antibody was performed by covalently bonding of thiolate mixed self-assembled monolayers (SAMs) realized on two substrates: polymer coated with gold and silicon coated with gold. The F(ab')2 fragments of the antibodies have been used for eliminating nonspecific bindings between the Fc portions of antibodies and the Fc receptor on cells. The properties of the monolayers and the biofilm formatted with attached antibody molecules were analyzed at each step using infrared spectroscopy (FTIR-ATR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and cyclic voltammetry (CV). In our study the gold-coated silicon substrates approach yielded the best results. These experimental results revealed the necessity to investigate each stage of the immobilization process taking into account in the same time the factors that influence the chemistry of the surface and the further interactions as well and also provide a solid basis for further studies aiming at elaborating sensitive and specific immunosensor or a microarray for the detection of E. coli O157:H7.

  10. Characterization of self-assembled monolayers (SAMs) on silicon substrate comparative with polymer substrate for Escherichia coli O157:H7 detection

    Science.gov (United States)

    Moldovan, Carmen; Mihailescu, Carmen; Stan, Dana; Ruta, Lavinia; Iosub, Rodica; Gavrila, Raluca; Purica, Munizer; Vasilica, Schiopu

    2009-08-01

    This article presents the characterization of two substrates, silicon and polymer coated with gold, that are functionalized by mixed self-assembled monolayers (SAMs) in order to efficiently immobilize the anti- Escherichia coli O157:H7 polyclonal purified antibody. A biosurface functionalized by SAMs (self-assembled monolayers) technique has been developed. Immobilization of goat anti- E. coli O157:H7 antibody was performed by covalently bonding of thiolate mixed self-assembled monolayers (SAMs) realized on two substrates: polymer coated with gold and silicon coated with gold. The F(ab') 2 fragments of the antibodies have been used for eliminating nonspecific bindings between the Fc portions of antibodies and the Fc receptor on cells. The properties of the monolayers and the biofilm formatted with attached antibody molecules were analyzed at each step using infrared spectroscopy (FTIR-ATR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and cyclic voltammetry (CV). In our study the gold-coated silicon substrates approach yielded the best results. These experimental results revealed the necessity to investigate each stage of the immobilization process taking into account in the same time the factors that influence the chemistry of the surface and the further interactions as well and also provide a solid basis for further studies aiming at elaborating sensitive and specific immunosensor or a microarray for the detection of E. coli O157:H7.

  11. Characterization of self-assembled monolayers (SAMs) on silicon substrate comparative with polymer substrate for Escherichia coli O157:H7 detection

    Energy Technology Data Exchange (ETDEWEB)

    Moldovan, Carmen, E-mail: carmen.moldovan@imt.ro [National Institute for R and D in Microtechnologies, IMT-Bucharest, 126A Erou Iancu Nicolae, 077190 Bucharest (Romania); Mihailescu, Carmen, E-mail: carmen_mihail28@yahoo.com [University of Bucharest, 90-92 Sos Panduri, Bucharest (Romania); Stan, Dana, E-mail: dana_stan2005@yahoo.com [DDS Diagnostic, 1 Segovia Street, Bucharest (Romania); Ruta, Lavinia, E-mail: laviniacoco@yahoo.com [University of Bucharest, 90-92 Sos Panduri, Bucharest (Romania); Iosub, Rodica, E-mail: rodica.iosub@imt.ro [National Institute for R and D in Microtechnologies, IMT-Bucharest, 126A Erou Iancu Nicolae, 077190 Bucharest (Romania); Gavrila, Raluca, E-mail: raluca.gavrila@imt.ro [National Institute for R and D in Microtechnologies, IMT-Bucharest, 126A Erou Iancu Nicolae, 077190 Bucharest (Romania); Purica, Munizer, E-mail: munizer.purica@imt.ro [National Institute for R and D in Microtechnologies, IMT-Bucharest, 126A Erou Iancu Nicolae, 077190 Bucharest (Romania); Vasilica, Schiopu, E-mail: vasilica.schiopu@imt.ro [National Institute for R and D in Microtechnologies, IMT-Bucharest, 126A Erou Iancu Nicolae, 077190 Bucharest (Romania)

    2009-08-30

    This article presents the characterization of two substrates, silicon and polymer coated with gold, that are functionalized by mixed self-assembled monolayers (SAMs) in order to efficiently immobilize the anti-Escherichia coli O157:H7 polyclonal purified antibody. A biosurface functionalized by SAMs (self-assembled monolayers) technique has been developed. Immobilization of goat anti-E. coli O157:H7 antibody was performed by covalently bonding of thiolate mixed self-assembled monolayers (SAMs) realized on two substrates: polymer coated with gold and silicon coated with gold. The F(ab'){sub 2} fragments of the antibodies have been used for eliminating nonspecific bindings between the Fc portions of antibodies and the Fc receptor on cells. The properties of the monolayers and the biofilm formatted with attached antibody molecules were analyzed at each step using infrared spectroscopy (FTIR-ATR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and cyclic voltammetry (CV). In our study the gold-coated silicon substrates approach yielded the best results. These experimental results revealed the necessity to investigate each stage of the immobilization process taking into account in the same time the factors that influence the chemistry of the surface and the further interactions as well and also provide a solid basis for further studies aiming at elaborating sensitive and specific immunosensor or a microarray for the detection of E. coli O157:H7.

  12. Manipulation of Work Function and Surface Free Energy of Tungsten Oxide Hole Injection Layer Modified with a Self-Assembled Monolayer

    Science.gov (United States)

    Kim, Seong-Ho; Otsuka, Hanae; Shin, Hyea-Weon; Tanaka, Kuniaki; Advincula, Rigoberto C.; Usui, Hiroaki

    2011-01-01

    As a hole injection layer for organic devices, a tungsten oxide (WOx) thin film was vapor-deposited on an indium-tin oxide (ITO) substrate, on which a self-assembled monolayer (SAM) of either 3-aminopropyltrimethoxysilane (APS), phenyltrimethoxysilane (PTMS), or octadecyltrimethoxysilane (ODS) was prepared to modify the surface characteristics. The deposition of WOx substantially increased the ionization potential (Ip) of the substrate surface, which was effective in enhancing hole injection. The formation of SAM on WOx reduced Ip, but enabled the control of the surface free energy so as to modify the growth morphology of an organic film deposited on its surface. A hole-only device was prepared using a hole transport material of N,N '-diphenyl-N,N '-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD). In the space-charge-limited region, a high current was drawn by using an anode that has a high Ip. At low driving voltages, however, the current flow was considerably influenced by the surface free energy. It was found that the PTMS-SAM on WOx gives a satisfactory accommodation of both the work function and the surface energy.

  13. Impact of chain length, temperature, and humidity on the growth of long alkyltrichlorosilane self-assembled monolayers.

    Science.gov (United States)

    Desbief, Simon; Patrone, Lionel; Goguenheim, Didier; Guérin, David; Vuillaume, Dominique

    2011-02-21

    In this work, we have studied the growth of self-assembled monolayers (SAMs) on silicon dioxide (SiO(2)) made of various long alkyltrichlorosilane chains (16, 18, 20, 24, and 30 carbon atoms in the alkyl chain), at several values of temperature (11 and 20 °C in most cases) and relative humidity (18 and 45% RH). Using atomic force microscopy analysis, thickness measurements by ellipsometry, and contact angle measurements, we have built a model of growth behaviour of SAMs of those molecules according to the deposition conditions and the chain length. Particularly, this work brings not only a better knowledge of the less studied growth of triacontyltrichlorosilane (C(30)H(61)SiCl(3)) SAMs but also new results on SAMs of tetracosyltrichlorosilane (C(24)H(49)SiCl(3)) that have not already been studied to our knowledge. We have shown that the SAM growth behaviour of triacontyltrichlorosilane at 20 °C and 45% RH is similar to that obtained at 11 °C and 45% RH for shorter molecules of hexadecyltrichlorosilane (C(16)H(33)SiCl(3)), octadecyltrichlorosilane (C(18)H(37)SiCl(3)), eicosyltrichlorosilane (C(20)H(41)SiCl(3)) and tetracosyltrichlorosilane (C(24)H(49)SiCl(3)). We have also observed that the monolayers grow faster at 45% than at 18% RH, and surprisingly slower at 20 °C than at 11 °C. Another important result is that the growth time constant decreases with the number of carbon atoms in the alkyl chain except for C(24)H(49)SiCl(3) at 11 °C and 18% RH, and for C(30)H(61)SiCl(3). To our knowledge, such a chain length dependence of the growth time constant has never been reported. The latter and all the other results are interpreted by adapting a diffusion limited aggregation growth model. PMID:21161113

  14. 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

    Science.gov (United States)

    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

  15. Fibronectin Binding to the Treponema pallidum Adhesin Protein Fragment rTp0483 on Functionalized Self-Assembled Monolayers

    Science.gov (United States)

    Dickerson, Matthew T.; Abney, Morgan B.; Cameron, Caroline E.; Knecht, Marc; Bachas, Leonidas G.; Anderson, Kimberly W.

    2012-01-01

    Past work has shown that Treponema pallidum, the causative agent of syphilis, binds host fibronectin (FN). FN and other host proteins are believed to bind to rare outer membrane proteins (OMPs) of T. pallidum, and it is postulated that this interaction may facilitate cell attachment and mask antigenic targets on the surface. This research seeks to prepare a surface capable of mimicking the FN binding ability of T. pallidum in order to investigate the impact of FN binding with adsorbed Tp0483 on the host response to the surface. By understanding this interaction it may be possible to develop more effective treatments for infection and possibly mimic the stealth properties of the bacteria. Functionalized self-assembled monolayers (SAMs) on0 gold were used to investigate rTp0483 and FN adsorption. Using a quartz crystal microbalance (QCM) rTp0483 adsorption and subsequent FN adsorption onto rTp0483 was determined to be higher on negatively charged carboxylate-terminated self-assembled monolayers (−COO− SAMs) compared to the other surfaces analyzed. Kinetic analysis of rTp0483 adsorption using surface plasmon resonance (SPR) supported this finding. Kinetic analysis of FN adsorption using SPR revealed a multi-step event, where the concentration of immobilized rTp0483 plays a role in FN binding. An examination of relative QCM dissipation energy compared to the shift in frequency showed a correlation between the physical properties of adsorbed rTp0483 and SAM surface chemistry. In addition, AFM images of rTp0483 on selected SAMs illustrated a preference of rTp0483 to bind as aggregates. Adsorption on −COO− SAMs was more uniform across the surface, which may help further explain why FN bound more strongly. rTp0483 antibody studies suggested the involvement of amino acids 274–289 and 316–333 in binding between rTp0483 to FN, while a peptide blocking study only showed inhibition of binding with amino acids 316–333. Finally, surface adsorbed rTp0483 with FN

  16. Highly organized crystalline monolayer of a semi-fluorinated alkane on a solid substrate obtained by spin-coating

    International Nuclear Information System (INIS)

    We have obtained a 40 nm parameter crystalline monolayer of a semifluorinated alkane on a silicon wafer using the spin-coating technique. Its structure, analyzed by atomic force microscopy (AFM), is identical to that recently observed at the air-water interface, showing the existence of hexagonal nanodomains, organized on a long range order hexagonal lattice of a few tens of nanometers lateral parameter. Considering AFM images published on films transferred by the usual Langmuir-Blodgett method, one can note that the monolayers form locally ordered rounded domains. With our procedure, the original highly organized large crystalline structure is recovered.

  17. Diamondoid monolayers as electron emitters

    Science.gov (United States)

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

    2012-04-10

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

  18. Towards the hybrid organic semiconductor fet (hosfet) : electrical and electrochemical characterization of functionalized and unfunctionalized, covalently bound organic monolayers on silicon surfaces

    OpenAIRE

    Faber, Erik Jouwert

    2006-01-01

    Since their introduction in 1993 the class of covalently bound organic monolayers on oxide free silicon surfaces have found their way to multiple application fields such as passivation layers in solar cells, masking layers in lithographic processing, insulating films in hybrid moleculesilicon electronics, and memory devices. Furthermore, these monolayers can easily be functionalized with a large variety of receptor groups or sensing moieties, thereby forming a new promising material for incor...

  19. Electrochemical and surface plasmon resonance characterization of β-cyclodextrin-based self-assembled monolayers and evaluation of their inclusion complexes with glucocorticoids

    International Nuclear Information System (INIS)

    This paper describes the characterization of a self-assembled β-cyclodextrin (β-CD)-derivative monolayer (β-CD-SAM) on a gold surface and the study of their inclusion complexes with glucocorticoids. To this aim the arrangement of a self-assembled β-cyclodextrin-derivative monolayer on a gold surface was monitored in situ by means of surface plasmon resonance (SPR) spectroscopy and double-layer capacitance measurements. Film thickness and dielectric constant were evaluated for a monolayer of β-CD using one-color-approach SPR. The selectivity of the β-CD host surface was verified by using electroactive species permeable and impermeable in the β-CD cavity. The redox probe was selected according to its capacity to permeate the β-CD monolayer and its electrochemical behavior. In order to evaluate the feasibility of an inclusion complex between β-CD-SAM with some steroids such as cortisol and cortisone, voltammetric experiments in the presence of the redox probes as molecules competitive with the steroids have been performed. The formation constant of the surface host-guest by β-CD-SAM and the steroids under study was calculated.

  20. Comparison of Genotoxic Damage in Monolayer Cell and Three-Dimensional Tissue-Like Cell Assemblies

    Science.gov (United States)

    Behravesh, E.; Emami, K.; Wu, H.; Gonda, S.

    Risk assessment for the biological effects of high-energy charged particles, ranging from protons to iron nuclei, encountered in space is essential for the success of long-term space exploration. While prokaryotic and eukaryotic cell models, developed in our lab and others, have advanced our understanding of many aspects of genotoxicity, there is a need for in vitro models to assess the risk to humans from space radiation insults that are representative of the cellular interactions present in tissues and capable of quantifying genotoxic damage. Toward this overall goal, the objective of this study is to examine the effect of the localized microenvironment of cells, either cultured as 2-dimensional monolayers (2D) or 3-dimensional aggregates (3D), on the rate and type of genotoxic damage, and to examine those effects after the normal cell repair processes. Rodent transgenic cell lines containing 50-70 copies of a transgene were utilized to provide the enhanced sensitivity required to enable the identification and quantification of the types of mutational events incurred from exposure to iron charged particles which makes up a significant portion of Space radiation. Although the LacI target of this system is ~1000 bps, each copy of the entire construct is over 45 kbps. The utilization of this system allows for the quantification of mutational frequency and type for the LacI target as well as assessment of DNA damage for the entire 45 kbp construct. The samples were exposed to high-LET iron charged particles at Brookhaven National Laboratory's AGS/NSRL facilities for a total dose of 0, 0.1, 0.25, 0.5, 1.0, and 2.0 Gy and recovered after 0, 1, and 7 days of tissue culture post-irradiation. The mutational frequency was found to be greater for the 3D samples when compared to the 2D samples at all doses. In addition, there was increased mutational frequency with 7 days culture post irradiation when compared to samples analyzed immediately after exposure. DNA sequencing of

  1. Electrochemical impedance spectroscopy investigations on the L-cysteine-thiolate self-assembled monolayers formed at p-GaAs(100) electrodes

    International Nuclear Information System (INIS)

    Electrochemical impedance spectroscopy investigations carried out in solutions with different pH brought evidence that the monolayers of L-cysteine-thiolate self-assembled on GaAs (hkl) electrodes exert a complex molecular control over their electrochemical behavior. The analysis of the impedance spectra coupled with that of the XPS data and the AFM images taken before and after the EIS measurements reveled that both pH and applied potential brings significant changes at the electrified interface. The most important effect of pH is the conformational change of the L-cysteine-thiolate molecule observed at pH 11 that allows the interaction of the carboxyl group with the substrate atoms. A similar conformational change occurs at pH 5.5 but only under the applied potential control, being just a consequence of another major effect of the applied electric field. This is the H+ transfer inside the L-cysteine-thiolate film, an electric field driven process but pH dependent, which results in significant charge diminution both in the organic overlayer and in the semiconductor depletion region

  2. Selective formation of monodisperse CdSe nanoparticles on functionalized self-assembled monolayers using chemical bath deposition

    International Nuclear Information System (INIS)

    Using CdSe chemical bath deposition (CBD) we demonstrate the selective growth and deposition of monodisperse nanoparticles on functionalized self-assembled monolayers (SAMs) using time-of-flight secondary ion mass spectrometry and scanning electron microscopy. We show that the deposition mechanism involves both ion-by-ion growth and cluster-by-cluster deposition. On -COOH terminated SAMs strongly adherent CdSe nanoparticles form via a mixed ion-by-ion and cluster-by-cluster mechanism. Initially, Cd2+ ions form complexes with the terminal carboxylate groups. The Cd2+-carboxylate complexes then act as the nucleation sites for the ion-by-ion growth of CdSe. After a sufficient concentration of Se2- has formed in solution via the hydrolysis of selenosulfate ions, the deposition mechanism switches to cluster-by-cluster deposition. On -OH and -CH3 terminated SAMs monodisperse CdSe nanoparticles are deposited via cluster-by-cluster deposition and they do not bind strongly to the surface. Finally, under the appropriate experimental conditions we demonstrate the selective deposition of CdSe nanoparticles on patterned -CH3/-COOH SAMs.

  3. Surface conductivity of InAs/GaSb superlattice infrared detectors treated with thiolated self assembled monolayers

    Science.gov (United States)

    Henry, Nathan C.; Brown, Alexander; Knorr, Daniel B.; Baril, Neil; Nallon, Eric; Lenhart, Joseph L.; Tidrow, Meimei; Bandara, Sumith

    2016-01-01

    The surface conductivity of InAs/GaSb based type II superlattice (T2SL) long wavelength infrared material following the deposition of thiolated self-assembled monolayers (SAMs) of cysteamine, octadecanethiol, dodecanethiol, and hexanethiol are reported. Quantitative mobility spectrum analysis (QMSA) was employed to study the mobility and to isolate and identify surface carriers following SAM treatments on planar samples. QMSA data collected following the deposition of the SAMs on InAs/GaSb material correlates well with dark current measurements, demonstrating the usefulness of QMSA as a tool for evaluating surface conductivity and predicting device performance. All samples displayed a reduction in surface conductivity and dark current density following thiol treatment. Dark current densities were reduced to 1.1 × 10-5, 1.3 × 10-5, 1.6 × 10-5, and 5 × 10-6 A/cm2 for hexanethiol, dodecanethiol, octadecanethiol, and cysteamine, respectively, from 5.7 × 10-4 A cm2 for unpassivated devices.

  4. Atmospheric corrosion of Cu, Zn, and Cu-Zn alloys protected by self-assembled monolayers of alkanethiols

    Science.gov (United States)

    Hosseinpour, Saman; Forslund, Mattias; Johnson, C. Magnus; Pan, Jinshan; Leygraf, Christofer

    2016-06-01

    In this article results from earlier studies have been compiled in order to compare the protection efficiency of self-assembled monolayers (SAM) of alkanethiols for copper, zinc, and copper-zinc alloys exposed to accelerated indoor atmospheric corrosion conditions. The results are based on a combination of surface spectroscopy and microscopy techniques. The protection efficiency of investigated SAMs increases with chain length which is attributed to transport hindrance of the corrosion stimulators in the atmospheric environment, water, oxygen and formic acid, towards the copper surface. The transport hindrance is selective and results in different corrosion products on bare and on protected copper. Initially the molecular structure of SAMs on copper is well ordered, but the ordering is reduced with exposure time. Octadecanethiol (ODT), the longest alkanethiol investigated, protects copper significantly better than zinc, which may be attributed to the higher bond strength of Cu-S than of Zn-S. Despite these differences, the corrosion protection efficiency of ODT for the single phase Cu20Zn brass alloy is equally efficient as for copper, but significantly less for the heterogeneous double phase Cu40Zn brass alloy.

  5. TOF-SIMS structural characterization of self-assembly monolayer of cytochrome b5 onto gold substrate

    CERN Document Server

    Aoyagi, Satoka; Boireau, Wilfrid; 10.1016/j.apsusc.2008.05.086

    2010-01-01

    Orientation and three-dimensional structure of immobilized proteins on bio-devices are very important to assure their high performance. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is able to analyze upper surface of one layer of molecules. Orientation of immobilized proteins can be evaluated based on determination of a partial structure, representing ensemble of amino acids, on the surface part. In this study, a monolayer of cytochrome b5 was reconstituted onto gold substrate and investigated by surface plasmon resonance (SPR). After freeze-drying, the resulted protein self-assembly was evaluated using TOF-SIMS with the bismuth cluster ion source, and then TOF-SIMS spectra were analyzed to select peaks specific to cytochrome b5 and identify their chemical formula and ensembles of amino acids. The results from TOF-SIMS spectra analysis were compared to the amino acid sequence of the modified cytochrome b5 and three-dimensional structure of cytochrome b5 registered in the protein data bank. Finall...

  6. Nano-tribological characteristics of TiO2 films on 3-mercaptopropyl trimethoxysilane sulfonated self-assembled monolayer

    Indian Academy of Sciences (India)

    J Li; X H Sheng

    2009-10-01

    Silane coupling reagent (3-mercaptopropyl trimethoxysilane (MPTS)) was used to prepare twodimensional self-assembled monolayer (SAM) on silicon substrate. The terminal –SH group was in situ oxidized to –SO3H group to endow the film with good chemisorption ability. Then TiO2 thin films were deposited on the oxidized MPTS–SAM to form composite thin films, making use of the chemisorption ability of the –SO3H group. Atomic force microscope (AFM) and contact angle measurements were used to characterize TiO2 films. Adhesive force and friction force of TiO2 thin films and silicon substrate were measured under various applied normal loads and scanning speed of AFM tip. Results showed that the friction force increased with applied normal loads and scanning speed of AFM tip. In order to study the effect of capillary force, tests were performed in various relative humidities. Results showed that the adhesive force of silicon substrate increases with relative humidities and the adhesive force of TiO2 thin films only increases slightly with relative humidity. Research showed that surfaces with more hydrophobic property revealed the lower adhesive and friction forces.

  7. Self-assembled monolayers of alendronate on Ti6Al4V alloy surfaces enhance osteogenesis in mesenchymal stem cells

    Science.gov (United States)

    Rojo, Luis; Gharibi, Borzo; McLister, Robert; Meenan, Brian J.; Deb, Sanjukta

    2016-07-01

    Phosphonates have emerged as an alternative for functionalization of titanium surfaces by the formation of homogeneous self-assembled monolayers (SAMs) via Ti-O-P linkages. This study presents results from an investigation of the modification of Ti6Al4V alloy by chemisorption of osseoinductive alendronate using a simple, effective and clean methodology. The modified surfaces showed a tailored topography and surface chemistry as determined by SEM microscopy and RAMAN spectroscopy. X-ray photoelectron spectroscopy revealed that an effective mode of bonding is created between the metal oxide surface and the phosphate residue of alendronate, leading to formation of homogenous drug distribution along the surface. In-vitro studies showed that alendronate SAMs induce differentiation of hMSC to a bone cell phenotype and promote bone formation on modified surfaces. Here we show that this novel method for the preparation of functional coatings on titanium-based medical devices provides osseoinductive bioactive molecules to promote enhanced integration at the site of implantation.

  8. Photoactive, covalent attachment of deoxyribonucleic acid on gold with double-strand specificity using self-assembled monolayers containing psoralen

    International Nuclear Information System (INIS)

    Taking advantages of psoralen photochemistry, we have developed a new method of immobilizing DNA on gold substrate surfaces. A psoralen derivative having an alkylamine function was synthesized, and was self-assembled on gold substrate surfaces in a combined use of a thiol-derivatized molecule, 3,3'-dithiobis(succinimidyl propionate) forming amide bonds on the surface. We found that by irradiating with long wavelength ultraviolet light (320-400 nm), DNA molecules added in the solution phase were covalently immobilized on the monolayer surface through the photoadduct formation of the psoralen molecules with the DNA nucleobases. The present method has its advantage that is applicable to native DNAs, no chemically modifying DNAs, in spite of its covalent immobilization principle. We have examined 12 mer synthetic oligonucleotide immobilizations and have found that the surface concentration thus attained was to be 20 pmol cm-2, which is consistent with saturated surface coverage. Interestingly, the immobilization occurred double-stranded-DNA-preferentially; no immobilization for single-stranded DNAs. Characterization of the immobilization chemistry has been achieved using atomic force microscopic imaging, infrared absorption, X-ray photoelectron spectroscopy, electrochemistry, and quartz-crystal microbalance and their results were described

  9. Partial ion yield and NEXAFS of 2-(perfluorooctyl)ethanethiol self-assembled monolayer: Comparison with PTFE results

    CERN Document Server

    Setoyama, H; Murase, T; Imamura, M; Mase, K; Okudaira, K K; Hara, M; Ueno, N

    2003-01-01

    Partial-ion-yield (PIY) spectra using ion time-of-flight (TOF) method and near-edge absorption fine structure (NEXAFS) spectra were measured for 2-(perfluorooctyl)ethanethiol [CF sub 3 (CF sub 2) sub 7 (CH sub 2) sub 2 SH] self-assembled monolayer (F8-SAM) on Au(1 1 1) near carbon K-edge. The PIY spectra of the F8-SAM at the magic angle, where -CF sub 3 groups exist at the surface were compared with those of the rubbed polytetrafluoroethylene (PTFE) thin film. The F sup + intensity from the F8-SAM at the photon energy of the sharp peak of the NEXAFS, which originates from the excitation of C1s electron to sigma sup * (C-F) states at -CF sub 2 - chain, was extremely smaller than that from the rubbed PTFE film. This result clearly indicates that the ions observed by PIY do not originate from the film inside but from the surface. This was confirmed by changes in ion-TOF mass spectra during soft X-ray induced etching of the F8-SAM. The NEXAFS peaks of the F8-SAM were also assigned by considering PIY results.

  10. First Observation of Charge Reduction and Desorption Kinetics of Multiply Protonated Peptides Soft Landed onto Self-Assembled Monolayer Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Hadjar, Omar; Futrell, Jean H.; Laskin, Julia

    2007-12-13

    The kinetics of charge reduction and desorption of different species produced by soft-landing of mass-selected ions was studied using in situ secondary ion mass spectrometry (SIMS) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). The improved SIMS capability described in this work utilizes an in-line 8 keV Cs+ ion gun and allows us to interrogate the surface both during the ion deposition and after the deposition is terminated. As a model system doubly protonated ions of Gramicidin S were deposited onto a fluorinated self-assembled monolayer (FSAM) surface. Our results demonstrate for the first time that various peptide-related peaks in FT-ICR SIMS spectra follow very different kinetics. We obtained unique kinetics signatures for doubly protonated, singly protonated and neutral peptides retained on the surface and followed their evolution as a function of time. The experimental results are in excellent agreement with a kinetic model that takes into account charge reduction and thermal desorption of different species from the surface.

  11. Surface plasmon Raman scattering studies of liquid crystal anchoring on liquid-crystal-based self-assembled monolayers.

    Science.gov (United States)

    Critchley, Kevin; Cheadle, Edward M; Zhang, Hao-Li; Baldwin, Kurt J; Liu, Quanying; Cheng, Yaling; Fukushima, Hitoshi; Tamaki, Takashi; Batchelder, David N; Bushby, Richard J; Evans, Stephen D

    2009-11-26

    We studied the anchoring of 6CB on a series of self-assembled monolayers (SAMs) with a functional group that mimics that of the nematic liquid crystal (LC). The SAMs were first characterized by wetting, Fourier-transform infrared spectroscopy, and surface potential measurements. We found that, in two of these SAMs, the end group dipoles were oriented close to the normal of the surface and that these promoted homeotropic anchoring. In the case of the other SAM, the dipole was oriented parallel to the surface, and planar anchoring was obtained. Raman scattering by adsorbates on thin metal films is enhanced by the electromagnetic fields of surface plasmon polaritons (SPPs). Despite the inherent polarization of SPPs, there have been few reports in which SPP Raman scattering has been used to study molecular orientation. We have developed optical instrumentation to provide efficient excitation and collection of SPP Raman scattered light using attenuated total reflection geometry. The Kretschmann prism coupling configuration was used to excite SPPs on thin (500 A) gold films with adsorbed SAMs of alkanethiols in contact with thin films (50 microm) of the nematic liquid crystal 4'-hexylbiphenyl-4-carbonitrile (6CB, Merck). The anchoring and orientational wetting of the LC 6CB at the interface with omega-functionalized SAMs was studied using this arrangement. In agreement with the results of previous studies, a high-energy surface (-COOH) was found to promote planar anchoring, whereas a low-energy surface (-CF(3)) was found to induce homeotropic anchoring. PMID:19921953

  12. Development and characterization of a pressure-sensitive luminescent coating based on Pt(II)-porphyrin self-assembled monolayers

    Science.gov (United States)

    Sakamura, Y.; Suzuki, T.; Kawabata, S.

    2015-06-01

    A pressure-sensitive luminescent coating (PSLC) applicable to the visualization of pressure distributions in micro-scale flow devices was developed. Pt(II)-porphyrin was synthesized and covalently attached to the surface of indium tin oxide (ITO) glass plates by a self-assembled monolayer (SAM) process. The UV-visible absorption spectrum, pressure and temperature sensitivities and photostability of the PSLC were then measured to characterize the developed PSLC. It was found that (a) the chemisorption of the porphyrin did not greatly perturb the molecular orbitals of the porphyrin responsible for its photophysics, (b) the pressure dependency of the luminescent intensity of the PSLC obeyed a power function curve and the pressure sensitivities at 273, 293, 313 and 333 K were obtained in the pressure range from 5 to 120 kPa, (c) the luminescent intensity of the PSLC almost linearly decreased with temperature and the temperature sensitivities at 5, 40, 100 and 120 kPa evaluated in the temperature range from 273 to 333 K were -0.67, -0.72, -0.75 and -0.78%/K, respectively and (d) the decrease in the luminescent intensity of the PSLC after a 30 min exposure to an excitation light was 1.23% of its initial intensity and much smaller than that of Pt(II)-porphyrin absorbed on a TLC (thin-layer chromatography) sheet.

  13. A yeast glycolipid biosurfactant, mannosylerythritol lipid, shows high binding affinity towards lectins on a self-assembled monolayer system.

    Science.gov (United States)

    Konishi, Masaaki; Imura, Tomohiro; Fukuoka, Tokuma; Morita, Tomotake; Kitamoto, Dai

    2007-03-01

    Mannosylerythritol lipids (MEL), which are glycolipid biosurfactants secreted by the Pseudozyma yeasts, show not only excellent surface-active properties but also versatile biochemical actions including antitumor and cell-differentiation activities. In order to address the biochemical actions, interactions between MEL-A, the major component of MEL, and different lectins were investigated using the surface plasmon resonance spectroscopy. The monolayer of MEL-A showed high binding affinity to concanavalin A (ConA) and Maackia amurensis lectin-I (MAL-I). The observed affinity constants for ConA and MAL-I were estimated to be 9.48 +/- 1.31 x 10(6) and 3.13 +/- 0.274 x 10(6) M(-1), respectively; the value was comparable to that of Manalpha1-6(Manalpha1-3)Man, which is one of the most specific probe to ConA. Significantly, alpha-methyl-D-mannopyranoside (1 mM) exhibited no binding inhibition between MEL-A and ConA. MEL-A is thus likely to self-assemble to give a high affinity surface, where ConA binds to the hydrophilic headgroup in a different manner from that generally observed in lectin-saccharide interactions. The binding manner should be related with the biochemical actions of MEL toward mammalian cells via protein-carbohydrate interactions. PMID:17205206

  14. Effects of Self-Assembled Monolayers on Solid-State CdS Quantum Dot Sensitized Solar Cells

    KAUST Repository

    Ardalan, Pendar

    2011-02-22

    Quantum dot sensitized solar cells (QDSSCs) are of interest for solar energy conversion because of their tunable band gap and promise of stable, low-cost performance. We have investigated the effects of self-assembled monolayers (SAMs) with phosphonic acid headgroups on the bonding and performance of cadmium sulfide (CdS) solid-state QDSSCs. CdS quantum dots ∼2 to ∼6 nm in diameter were grown on SAM-passivated planar or nanostructured TiO 2 surfaces by successive ionic layer adsorption and reaction (SILAR), and photovoltaic devices were fabricated with spiro-OMeTAD as the solid-state hole conductor. X-ray photoelectron spectroscopy, Auger electron spectroscopy, ultraviolet-visible spectroscopy, scanning electron microscopy, transmission electron microscopy, water contact angle measurements, ellipsometry, and electrical measurements were employed to characterize the materials and the resulting device performance. The data indicate that the nature of the SAM tailgroup does not significantly affect the uptake of CdS quantum dots on TiO2 nor their optical properties, but the presence of the SAM does have a significant effect on the photovoltaic device performance. Interestingly, we observe up to ∼3 times higher power conversion efficiencies in devices with a SAM compared to those without the SAM. © 2011 American Chemical Society.

  15. Application of Self-Assembled Monolayers to the Electroless Metallization of High Aspect Ratio Vias for Microelectronics

    Science.gov (United States)

    Bernasconi, R.; Molazemhosseini, A.; Cervati, M.; Armini, S.; Magagnin, L.

    2016-07-01

    All-wet electroless metallization of through-silicon vias (TSVs) with a width of 5 μm and a 1:10 aspect ratio was carried out. Immersion in a n-(2-aminoethyl) 3-aminopropyl-trimethoxysilane (AEAPTMS) self-assembled monolayer (SAM) was used to enhance the adhesion between the metal film and substrate. Contact angle variation and atomic force microscopy were used to verify the formation of a SAM layer. A PdCl2 solution was later used to activate the silanized substrates, exploiting the affinity of the -NH3 functional group of AEAPTMS to palladium. A nickel-phosphorus-boron electroless bath was employed to deposit the first barrier layer onto silicon. The NiPB growth rate was evaluated on flat silicon wafers, while the structure of the coating obtained was investigated via glow discharge optical emission spectroscopy. Cross-sectional scanning electron microscope observations were carried out on metallized TSVs to characterize the NiPB seed, the Cu seed layer deposited with a second electroless step, and the Cu superfilling obtained with a commercial solution. Complete filling of TSV was achieved.

  16. Near-field photochemical and radiation-induced chemical fabrication of nanopatterns of a self-assembled silane monolayer

    Directory of Open Access Journals (Sweden)

    Ulrich C. Fischer

    2014-09-01

    Full Text Available A general concept for parallel near-field photochemical and radiation-induced chemical processes for the fabrication of nanopatterns of a self-assembled monolayer (SAM of (3-aminopropyltriethoxysilane (APTES is explored with three different processes: 1 a near-field photochemical process by photochemical bleaching of a monomolecular layer of dye molecules chemically bound to an APTES SAM, 2 a chemical process induced by oxygen plasma etching as well as 3 a combined near-field UV-photochemical and ozone-induced chemical process, which is applied directly to an APTES SAM. All approaches employ a sandwich configuration of the surface-supported SAM, and a lithographic mask in form of gold nanostructures fabricated through colloidal sphere lithography (CL, which is either exposed to visible light, oxygen plasma or an UV–ozone atmosphere. The gold mask has the function to inhibit the photochemical reactions by highly localized near-field interactions between metal mask and SAM and to inhibit the radiation-induced chemical reactions by casting a highly localized shadow. The removal of the gold mask reveals the SAM nanopattern.

  17. Study on surface acid-base property of carboxylic acid-terminated self-assembled monolayers by cyclic voltammetry and electro-chemical impedance spectroscopy

    Institute of Scientific and Technical Information of China (English)

    罗立强; 程志亮; 杨秀荣; 汪尔康

    2000-01-01

    Cyclic voltammetry and electrochemical impedance spectroscopy were used to study the surface acid-base property of carboxylic acid-terminated self-assembled monolayers (SAMs). A carboxylic acid-terminated thiol, such as thioctic acid (1,2-dithiolane-3-pentanoic acid), was self-assembled on gold electrodes. Electron transfer between the bulk solution and the SAM modified electrode was studied at different pH using Fe(CN)63 as a probe. The surface pK. of thioctic acid was determined by cyclic voltammetry and electrochemical impedance spectroscopy to be 5.6±0.1 and 5.8±0.1, respectively. The method is compared with other methods of monolayer pK.measurement.

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

    NARCIS (Netherlands)

    Bonifacio, A.; Sneppen, van der L.; Gooijer, C.; Zwan, van der G.

    2004-01-01

    A new citrate-reduced silver hydrosol coated with omega-mercaptoalkanoic acids (mercaptopropionic and mercaptoundecanoic acids) self-assembled monolayers was prepared and characterized with surface-enhanced Raman spectroscopy. The structure and the quality of the coating monolayers are discussed and

  19. Hydrogen-plasma-induced magnetocrystalline anisotropy ordering in self-assembled magnetic nanoparticle monolayers

    Directory of Open Access Journals (Sweden)

    Alexander Weddemann

    2013-03-01

    Full Text Available Self-assembled two-dimensional arrays of either 14 nm hcp-Co or 6 nm ε-Co particle components were treated by hydrogen plasma for various exposure times. A change of hysteretic sample behavior depending on the treatment duration is reported, which can be divided in two time scales: oxygen reduction increases the particle magnetization during the first 20 min, which is followed by an alteration of the magnetic response shape. The latter depends on the respective particle species. Based on the Landau–Lifshitz equations for a discrete set of magnetic moments, we propose a model that relates the change of the hysteresis loops to a dipole-driven ordering of the magnetocrystalline easy axes within the particle plane due to the high spatial aspect ratio of the system.

  20. Oriented crystalline monolayers and bilayers of 2 x 2 silver(1) grid architectures at the air-solution interface: Their assembly and crystal structure elucidation

    DEFF Research Database (Denmark)

    Weissbuch, J.; Baxter, P.N.W.; Kuzmenko, I.; Cohen, H.; Cohen, S.; Kjær, K.; Howes, P.B.; Als-Nielsen, J.; Lehn, J.M.; Leiserowitz, L.; Lahav, M.

    2000-01-01

    Oriented crystalline monolayers, similar to 14 Angstrom thick, of a 2 x 2 Ag+ grid complex, self-assembled at the air-solution interface starting from an water-insoluble ligand 3,6-bis[2-(6-phenylpyridine)]pyridazine spread on silver-ion-containing solutions,were examined by grazing-incidence X....... Such a phase transition is of relevance to the understanding of crystal nucleation....

  1. Laterally Mobile, Functionalized Self-Assembled Monolayers at the Fluorous-Aqueous Interface in a Plug-Based Microfluidic System: Characterization and Testing with Membrane Protein Crystallization

    OpenAIRE

    Kreutz, Jason E.; Li, Liang; Roach, L. Spencer; Hatakeyama, Takuji; Ismagilov, Rustem F.

    2009-01-01

    This paper describes a method to generate functionalizable, mobile self-assembled monolayers (SAMs) in plug-based microfluidics. Control of interfaces is advancing studies of biological interfaces, heterogeneous reactions, and nanotechnology. SAMs have been useful for such studies, but they are not laterally mobile. Lipid-based methods, though mobile, are not easily amenable to setting up the hundreds of experiments necessary for crystallization screening. Here we demonstrate a method, comple...

  2. Self-assembly of monolayers of aromatic carboxylic acid molecules on silver and copper modified gold surfaces at the liquid-solid interface

    OpenAIRE

    Aitchison, Hannah

    2015-01-01

    Exploiting coordination bonding of aromatic carboxylic acids at metal surfaces, this thesis explores new directions in the design and application of self-assembled monolayers (SAMs). The SAMs are investigated using a multi-technique approach comprising of a complementary combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. In addition, the X-ray standing wave technique (XSW) was used to ...

  3. Investigation of Bovine Serum Albumin (BSA) Attachment onto Self-Assembled Monolayers (SAMs) Using Combinatorial Quartz Crystal Microbalance with Dissipation (QCM-D) and Spectroscopic Ellipsometry (SE)

    OpenAIRE

    Phan, Hanh T. M.; Bartelt-Hunt, Shannon; Keith B Rodenhausen; Schubert, Mathias; Bartz, Jason C.

    2015-01-01

    Understanding protein adsorption kinetics to surfaces is of importance for various environmental and biomedical applications. Adsorption of bovine serum albumin to various self-assembled monolayer surfaces including neutral and charged hydrophilic and hydrophobic surfaces was investigated using in-situ combinatorial quartz crystal microbalance with dissipation and spectroscopic ellipsometry. Adsorption of bovine serum albumin varied as a function of surface properties, bovine serum albumin co...

  4. Experimental Investigation Of Microbially Induced Corrosion Of Test Samples And Effect Of Self-assembled Hydrophobic Monolayers. Exposure Of Test Samples To Continuous Microbial Cultures, Chemical Analysis, And Biochemical Studies

    CERN Document Server

    Laurinavichius, K S

    1998-01-01

    Experimental Investigation Of Microbially Induced Corrosion Of Test Samples And Effect Of Self-assembled Hydrophobic Monolayers. Exposure Of Test Samples To Continuous Microbial Cultures, Chemical Analysis, And Biochemical Studies

  5. Atomic MoS2 monolayers synthesized from a metal-organic complex by chemical vapor deposition

    Science.gov (United States)

    Liu, Lina; Qiu, Hailong; Wang, Jingyi; Xu, Guanchen; Jiao, Liying

    2016-02-01

    The controllable synthesis of MoS2 monolayers is the key challenge for their practical applications. Here we report the chemical vapor deposition (CVD) growth of single layered MoS2 by utilizing a bifunctional precursor. This precursor is a metal-organic complex which supplies both Mo sources and organic seeding promoters for the efficient CVD growth of MoS2 monolayers. The successful growth of high quality MoS2 flakes indicates that the rational design of bifunctional precursors will open up a new way for the controllable CVD growth of two-dimensional (2D) transition metal dichalcogenides (TMDCs).The controllable synthesis of MoS2 monolayers is the key challenge for their practical applications. Here we report the chemical vapor deposition (CVD) growth of single layered MoS2 by utilizing a bifunctional precursor. This precursor is a metal-organic complex which supplies both Mo sources and organic seeding promoters for the efficient CVD growth of MoS2 monolayers. The successful growth of high quality MoS2 flakes indicates that the rational design of bifunctional precursors will open up a new way for the controllable CVD growth of two-dimensional (2D) transition metal dichalcogenides (TMDCs). Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr09089j

  6. Microscopic wetting of mixed self-assembled monolayers: A molecular dynamics study

    Czech Academy of Sciences Publication Activity Database

    Szöri, Milan; Tobias, D. J.; Roeselová, Martina

    2009-01-01

    Roč. 113, č. 13 (2009), s. 4161-4169. ISSN 1520-6106 R&D Projects: GA ČR GA203/06/1488; GA MŠk LC512 Grant ostatní: NSF(US) CHE-0431312 Institutional research plan: CEZ:AV0Z40550506 Keywords : model organic aerosol surfaces * hydrophobic * hydrophilic Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.471, year: 2009

  7. Nanodimentional Aggregates In Organic Monolayers Studied With Atomic Force Microscopy (AFM) And Fluorescence Lifetime Imaging Microscopy (FLIM)

    Science.gov (United States)

    Ivanov, George R.; Burov, Julian

    2007-04-01

    Organic monolayers from a fluorescently labeled phospholipid (DPPE-NBD) were deposited on solid supports under special conditions that form stable nanometer wide bilayers cylinders that protrude from the monolayer. This molecule was frequently used in sensor applications due to its sensitivity to environment changes. The proposed configuration should provide both fast response times (ultra thin film) and increased sensitivity (greatly increased surface area). AFM can clearly distinguish between the different phases. The height difference between the solid-expanded and the liquid-expanded phase was measured to be 1.4 nm while the bilayer thickness was 5.6 nm. The solid domains show a 20 % decrease in fluorescence lifetime in comparison to the monolayer as measured by FLIM. This difference in lifetimes is explained in the model of fluorescence self quenching in the solid phase due to the molecules being closer to each other.

  8. Direct imaging by atomic force microscopy of surface-localized self-assembled monolayers on a cuprate superconductor and surface X-ray scattering analysis of analogous monolayers on the surface of water

    International Nuclear Information System (INIS)

    A self-assembled monolayer of CF3(CF2)3(CH2)11NH2 atop the (001) surface of the high-temperature superconductor YBa2Cu3O7-x was imaged by atomic force microscopy (AFM). The AFM images provide direct 2D-structural evidence for the epitaxial 5.5 A square √2 x √2R45o unit cell previously predicted for alkyl amines by molecular modeling [J.E. Ritchie, C.A. Wells, J.-P. Zhou, J. Zhao, J.T. McDevitt, C.R. Ankrum, L. Jean, D.R. Kanis, J. Am. Chem. Soc. 120 (1998) 2733]. Additionally, the 3D structure of an analogous Langmuir monolayer of CF3(CF2)9(CH2)11NH2 on water was studied by grazing-incidence X-ray diffraction and specular X-ray reflectivity. Structural differences and similarities between the water-supported and superconductor-localized monolayers are discussed

  9. Direct imaging by atomic force microscopy of surface-localized self-assembled monolayers on a cuprate superconductor and surface X-ray scattering analysis of analogous monolayers on the surface of water

    DEFF Research Database (Denmark)

    Schougaard, Steen B.; Reitzel, Niels; Bjørnholm, Thomas;

    2007-01-01

    cell previously predicted for alkyl amines by molecular modeling [J.E. Ritchie, C.A. Wells, J.-P. Zhou, J. Zhao, J.T. McDevitt, C.R. Ankrum, L. Jean, D.R. Kanis, J. Am. Chem. Soc. 120 (1998) 2733]. Additionally, the 3D structure of an analogous Langmuir monolayer of CF3(CF2)9(CH2)(11)NH2 on water was......A self-assembled monolayer of CF3(CF2)(3)(CH2)(11)NH2 atop the (001) surface of the high-temperature superconductor YBa2Cu3O7-x was imaged by atomic force microscopy (AFM). The AFM images provide direct 2D-structural evidence for the epitaxial 5.5 angstrom square root 2 x root 2R45 degrees unit...... studied by grazing-incidence X-ray diffraction and specular X-ray reflectivity. Structural differences and similarities between the water-supported and superconductor-localized monolayers are discussed....

  10. Controlling coordination reactions and assembly on a Cu(111) supported boron nitride monolayer.

    Science.gov (United States)

    Urgel, José I; Schwarz, Martin; Garnica, Manuela; Stassen, Daphné; Bonifazi, Davide; Ecija, David; Barth, Johannes V; Auwärter, Willi

    2015-02-25

    We report the formation of a metal-organic network on a BN/Cu(111) template by codeposition of carbonitrile-functionalized porphyrin derivatives (2H-TPCN) with Co atoms in an ultrahigh vacuum environment. The resulting metallo-supramolecular structure explored by scanning tunneling microscopy and spectroscopy features a distinct 4-fold coordination motif. Furthermore, we demonstrate an in situ metalation of the tetrapyrrole macrocycles with deposited Co atoms yielding Co-TPCN directly on the BN sheet. Our results provide perspectives for the formation of coordination networks on BN and related systems featuring structural, electronic, and magnetic properties unachievable on metallic supports. PMID:25689599

  11. Self-Assembled Large-Scale Monolayer of Au Nanoparticles at the Air/Water Interface Used as a SERS Substrate.

    Science.gov (United States)

    Guo, Qinghua; Xu, Minmin; Yuan, Yaxian; Gu, Renao; Yao, Jianlin

    2016-05-10

    Self-assembly of metal nanoparticles has attracted considerable attention because of its unique applications in technologies such as plasmonics, surface-enhanced optics, sensors, and catalysts. However, fabrication of ordered nanoparticle structures remains a significant challenge. Thus, developing an efficient approach for the assembly of large-scale Au nanoparticles films for theoretical studies and for various applications is highly desired. In this paper, a facial approach for fabricating a monolayer film of Au nanoparticles was developed successfully. Using the surfactant polyvinylpyrrolidone (PVP), a large-scale monolayer film of well-ordered, uniform-sized Au nanoparticles was fabricated at the air/water interface. The film exhibited a two-dimensional (2D) hexagonal close-packed (HCP) structure having interparticle gaps smaller than 2 nm. These gaps generated numerous uniform "hot spots" for surface-enhanced Raman scattering (SERS) activity. The as-prepared monolayer film could be transferred to a solid substrate for use as a suitable SERS substrate with high activity, high uniformity, and high stability. The low spot-to-spot and substrate-to-substrate variations of intensity (film onto a glassy carbon electrode produced an Au electrode with clean, well-defined nanostructure suitable for electrochemical SERS measurements. The adsorption process of ionic liquids on the electrode with the monolayer film is similar to that on bulk metal electrodes. The present strategy provides an effective way for self-assembly of Au nanoparticles into well-defined nanostructures that may form optimal reproducible SERS substrates for quantitative analysis. It also provides an electrode with clean, well-defined nanostructure for electrochemical investigations. PMID:27101361

  12. Effect of chain length on the adhesion behaviour of n-alkanethiol self-assembled monolayers on Au(1 1 1): An atomic force microscopy study

    Indian Academy of Sciences (India)

    S Subramanian; S Sampath

    2005-10-01

    The effect of chain length on the adhesion behaviour of n-alkanethiols CH3(CH2) SH, where = 5, 6, 7, 9, 10, 11, 14 and 15 has been followed by carrying out pull-off force measurement using atomic force microscopy (AFM). The self-assembled monolayers on Au(111) surface has been characterized by reflection absorption infra-red spectroscopy (RAIRS) and contact mode AFM. It is observed that the work of adhesion is independent of thiol chain length though the standard deviation is high for short chain length thiol-based monolayers. This may be attributed to the relatively more deformable nature of the short chain thiol films due to their heterogeneity in the monolayer structure than the long chain ones. This, in turn, increases the contact area/volume between the AFM tip and the monolayer, and hence the force of adhesion. However, in the presence of water, the force of adhesion is lower than that observed in air reflecting the effects of capillary forces/polar components associated with the surface energy.

  13. Molecular self-assembly approaches for supramolecular electronic and organic electronic devices

    Science.gov (United States)

    Yip, Hin-Lap

    Molecular self-assembly represents an efficient bottom-up strategy to generate structurally well-defined aggregates of semiconducting pi-conjugated materials. The capability of tuning the chemical structures, intermolecular interactions and nanostructures through molecular engineering and novel materials processing renders it possible to tailor a large number of unprecedented properties such as charge transport, energy transfer and light harvesting. This approach does not only benefit traditional electronic devices based on bulk materials, but also generate a new research area so called "supramolecular electronics" in which electronic devices are built up with individual supramolecular nanostructures with size in the sub-hundred nanometers range. My work combined molecular self-assembly together with several novel materials processing techniques to control the nucleation and growth of organic semiconducting nanostructures from different type of pi-conjugated materials. By tailoring the interactions between the molecules using hydrogen bonds and pi-pi stacking, semiconducting nanoplatelets and nanowires with tunable sizes can be fabricated in solution. These supramolecular nanostructures were further patterned and aligned on solid substrates through printing and chemical templating methods. The capability to control the different hierarchies of organization on surface provides an important platform to study their structural-induced electronic properties. In addition to using molecular self-assembly to create different organic nanostructures, functional self-assembled monolayer (SAM) formed by spontaneous chemisorption on surfaces was used to tune the interfacial property in organic solar cells. Devices showed dramatically improved performance when appropriate SAMs were applied to optimize the contact property for efficiency charge collection.

  14. Formation of organic monolayers on hydrogen-terminated silicon surfaces via silicon-carbon bond: effect of terminal groups on stability

    International Nuclear Information System (INIS)

    Full text: Functionalization of hydrogen-terminated silicon surfaces with stable and dense aryl-terminated alkyl self-assembled monolayers (SAMs) provides opportunities for the development of low cost organic field effect transistors. In this paper we present results for one such σ-π SAMs, 3-phenylpropyl (C6H5(CH2)3-) SAMs on porous silicon, and compare its stability with octyl (CH3(CH2)7-) SAMs on Si(100). The SAMs were prepared using the Grignard reagent method and characterized using X-ray photoelectron and FT-infrared spectroscopies and contact angle measurements Our results show the 3-phenylpropyl SAMs are not as susceptible to oxidation as the octyl SAMs, and we attribute the increased stability in the former to be due to its more dense structure arising from the π-π stacking of the phenyl rings. Copyright (2005) Australian Institute of Physics

  15. Assembly of cells and vesicles for organ engineering

    International Nuclear Information System (INIS)

    The development of materials and technologies for the assembly of cells and/or vesicles is a key for the next generation of tissue engineering. Since the introduction of the tissue engineering concept in 1993, various types of scaffolds have been developed for the regeneration of connective tissues in vitro and in vivo. Cartilage, bone and skin have been successfully regenerated in vitro, and these regenerated tissues have been applied clinically. However, organs such as the liver and pancreas constitute numerous cell types, contain small amounts of extracellular matrix, and are highly vascularized. Therefore, organ engineering will require the assembly of cells and/or vesicles. In particular, adhesion between cells/vesicles will be required for regeneration of organs in vitro. This review introduces and discusses the key technologies and materials for the assembly of cells/vesicles for organ regeneration. (topical review)

  16. Assembly of cells and vesicles for organ engineering

    Directory of Open Access Journals (Sweden)

    Tetsushi Taguchi

    2011-01-01

    Full Text Available The development of materials and technologies for the assembly of cells and/or vesicles is a key for the next generation of tissue engineering. Since the introduction of the tissue engineering concept in 1993, various types of scaffolds have been developed for the regeneration of connective tissues in vitro and in vivo. Cartilage, bone and skin have been successfully regenerated in vitro, and these regenerated tissues have been applied clinically. However, organs such as the liver and pancreas constitute numerous cell types, contain small amounts of extracellular matrix, and are highly vascularized. Therefore, organ engineering will require the assembly of cells and/or vesicles. In particular, adhesion between cells/vesicles will be required for regeneration of organs in vitro. This review introduces and discusses the key technologies and materials for the assembly of cells/vesicles for organ regeneration.

  17. Assembly of cells and vesicles for organ engineering

    Energy Technology Data Exchange (ETDEWEB)

    Taguchi, Tetsushi, E-mail: taguchi.tetsushi@nims.go.jp [Biofunctional Materials Unit, Nano-Bio Field, Materials Nanoarchitectonics (MANA), National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)

    2011-12-15

    The development of materials and technologies for the assembly of cells and/or vesicles is a key for the next generation of tissue engineering. Since the introduction of the tissue engineering concept in 1993, various types of scaffolds have been developed for the regeneration of connective tissues in vitro and in vivo. Cartilage, bone and skin have been successfully regenerated in vitro, and these regenerated tissues have been applied clinically. However, organs such as the liver and pancreas constitute numerous cell types, contain small amounts of extracellular matrix, and are highly vascularized. Therefore, organ engineering will require the assembly of cells and/or vesicles. In particular, adhesion between cells/vesicles will be required for regeneration of organs in vitro. This review introduces and discusses the key technologies and materials for the assembly of cells/vesicles for organ regeneration. (topical review)

  18. Assembly of cells and vesicles for organ engineering

    Science.gov (United States)

    Taguchi, Tetsushi

    2011-12-01

    The development of materials and technologies for the assembly of cells and/or vesicles is a key for the next generation of tissue engineering. Since the introduction of the tissue engineering concept in 1993, various types of scaffolds have been developed for the regeneration of connective tissues in vitro and in vivo. Cartilage, bone and skin have been successfully regenerated in vitro, and these regenerated tissues have been applied clinically. However, organs such as the liver and pancreas constitute numerous cell types, contain small amounts of extracellular matrix, and are highly vascularized. Therefore, organ engineering will require the assembly of cells and/or vesicles. In particular, adhesion between cells/vesicles will be required for regeneration of organs in vitro. This review introduces and discusses the key technologies and materials for the assembly of cells/vesicles for organ regeneration.

  19. Electrochemical and SERS spectroscopic investigations of 4-methyl-4H-1,2,4-triazole-3-thiol monolayers self-assembled on copper surface

    International Nuclear Information System (INIS)

    Electrochemically anticorrosive behaviors of 4-methyl-4H-1,2,4-triazole-3-thiol (4-MTTL) monolayers self-assembled on copper surface have been investigated by electrochemical impedance spectroscopy (EIS), electrochemical polarization measurement and surface-enhanced Raman scattering (SERS) spectroscopy. The EIS mechanism of the copper surface adsorbed with 4-MTTL monolayers was fitted with the mode of R(QR)(QR)(CR). The electrochemical polarization experimental results indicated the high inhibitive efficiency of about 81.1%. Potential dependent SERS result suggests that 4-MTTL molecule was anchored at the copper surface via S6 and N2 atoms with a tilted orientation, which resulting in a strong interaction between the 4-MTTL molecule and copper surface. The molecule tended to experience a transition state of the adsorption at the copper surface via S6 atom only as the potential applied at -0.5 V vs. SCE.

  20. Parallel- and serial-contact electrochemical metallization of monolayer nanopatterns: A versatile synthetic tool en route to bottom-up assembly of electric nanocircuits

    Directory of Open Access Journals (Sweden)

    Jonathan Berson

    2012-02-01

    Full Text Available Contact electrochemical transfer of silver from a metal-film stamp (parallel process or a metal-coated scanning probe (serial process is demonstrated to allow site-selective metallization of monolayer template patterns of any desired shape and size created by constructive nanolithography. The precise nanoscale control of metal delivery to predefined surface sites, achieved as a result of the selective affinity of the monolayer template for electrochemically generated metal ions, provides a versatile synthetic tool en route to the bottom-up assembly of electric nanocircuits. These findings offer direct experimental support to the view that, in electrochemical metal deposition, charge is carried across the electrode–solution interface by ion migration to the electrode rather than by electron transfer to hydrated ions in solution.

  1. Cyclic voltammetry and scanning electrochemical microscopy studies of methylene blue immobilized on the self-assembled monolayer of n-dodecanethiol

    International Nuclear Information System (INIS)

    Electron transfer (ET) kinetics through n-dodecanethiol (C12SH) self-assembled monolayer on gold electrode was studied using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS). An SECM model for compensating pinhole contribution, was used to measure the ET kinetics of solution-phase probes of ferrocyanide/ferricyanide (Fe(CN)64-/3-) and ferrocenemethanol/ferrociniummethanol (FMC0/+) through the C12SH monolayer yielding standard tunneling rate constant (kET0) of (4 ± 1) x 10-11 and (3 ± 1) x 10-10 cm s-1 for Fe(CN)64-/3- and FMC0/+ respectively. Decay tunneling constants (β) of 0.97 and 0.96 A-1 for saturated alkane thiol chains were obtained using Fe(CN)64- and FMC respectively. Also, it was found that methylene blue (MB) molecules are effectively immobilized on the C12SH monolayer and can mediate the ET between the solution-phase probes and underlying gold substrate. SECM-mediated model was used to simultaneously measure the bimolecular ET between the solution-phase probes and the monolayer-immobilized MB molecules, as well as tunneling ET between the monolayer-immobilized MB molecules and the underlying gold electrode, allowing the measurement of kBI = (5 ± 1) x 106 and (4 ± 2) x 107 cm3 mol-1 s-1 for the bimolecular ET and kET/MB0=(1±0.3)x10-3 and (7 ± 3) x 10-2 s-1 for the standard tunneling rate constant of ET using Fe(CN)64-/3- and FMC0/+ probes respectively.

  2. Molecular organization of antifungal antibiotic amphotericin B in lipid monolayers studied by means of Fluorescence Lifetime Imaging Microscopy

    OpenAIRE

    Gruszecki, Wieslaw I.; Luchowski, Rafał; Gagoś, Mariusz; Arczewska, Marta; Sarkar, Pabak; Hereć, Monika; Myśliwa-Kurdziel, Beata; Strzałka, Kazimierz; Gryczynski, Ignacy; Gryczynski, Zygmunt

    2009-01-01

    Abstract Amphotericin B (AmB) is a life-saving polyene antibiotic used to treat deep-seated mycotic infections. Both the mode of therapeutic action as well as toxic side effects are directly dependent on molecular organization of the drug. Binding of AmB to lipid monolayers formed with dipalmitoylphosphatidylcholine, pure and containing 40 mol% cholesterol or ergosterol, the sterols of human and fungi respectively, has been examined by means of Fluorescence Lifetime Imaging Microsc...

  3. On the stability of silicon field effect capacitors with phosphate buffered saline electrolytic gate and self assembled monolayer gate insulator

    International Nuclear Information System (INIS)

    We herein report on the stability of Electrolyte/Insulator/Semiconductor (EIS) devices with Self-Assembled Monolayer (SAM) gate insulator layers, i.e. Electrolyte/SAM/Semiconductor (ESS) devices. ESS devices can be functionalized creating highly specific sensors that can be integrated on standard silicon platform. However, biosensors by their nature are in contact with biological solutions that contain ions and molecules that may affect the device characteristics and cause electrical instability. In this paper we present a list of potential hazards to ESS devices and a study of the device stability under common testing conditions analyzing possible causes for the instabilities. ESS capacitors under open circuit conditions (i.e. open circuit bias of ∼0.6 V vs. Ag/AgCl reference electrode) were periodically characterized. We measured the complex impedance of the capacitors versus bias and extracted the effective capacitance vs. voltage (C–V) curves using two methods. We observed a parallel shift of the C–V curves toward negative bias; showing an effective accumulation of positive charge. The quantitative analysis of the drift vs. time was found to depend on the effective capacitance evaluation method. This effect is discussed and a best-known method is proposed. The devices surface composition was tested before and after the stress experiment by X-ray Photoelectron Spectroscopy (XPS) and sodium accumulation was observed. To further explore the flat-band voltage drift effect and to challenge the assumption that alkali ions are involved in the drift we conceived a novel alkali-free phosphate buffer saline (AF-PBS) where the sodium and potassium ions are replaced by ammonium ion and tested the capacitor under similar conditions to standard PBS. We found that the drift of the AF-PBS solution was much less at the first hour but was similar to that of the conventional PBS for longer stress times; hence, AF-PBS does not solve the long-term instability problem

  4. Binary Mixtures of SH- and CH3-Terminated Self-Assembled Monolayers to Control the Average Spacing Between Aligned Gold Nanoparticles

    Directory of Open Access Journals (Sweden)

    Pavelka Laura

    2009-01-01

    Full Text Available Abstract This paper presents a method to control the average spacing between organometallic chemical vapor deposition (OMCVD grown gold nanoparticles (Au NPs in a line. Focused ion beam patterned CH3-terminated self-assembled monolayers are refilled systematically with different mixtures of SH- and CH3-terminated silanes. The average spacing between OMCVD Au NPs is demonstrated systematically to decrease by increasing the v/v% ratio of the thiols in the binary silane mixtures with SH- and CH3-terminated groups.

  5. Tuning the self-assembled monolayer formation on nanoparticle surfaces with different curvatures: Investigations on spherical silica particles and plane-crystal-shaped zirconia particles

    OpenAIRE

    Feichtenschlager, Bernhard; Lomoschitz, Christoph J.; Kickelbick, Guido

    2011-01-01

    The ordering of dodecyl-chain self-assembled monolayers (SAM) on different nanoscopic surfaces was investigated by FT-IR studies. As model systems plane-crystal-shaped ZrO2 nanoparticles and spherical SiO2 nanoparticles were examined. The type of capping agent was chosen dependent on the substrate, therefore dodecylphosphonic acid and octadecylphosphonic acid were used for ZrO2 and dodecyltrimethoxysilane for SiO2 samples. The plane ZrO2 nanocrystals yielded more ordered alkyl-chain structure...

  6. Studies of metal ion binding by apo-metallothioneins attached onto preformed self-assembled monolayers using a highly sensitive surface plasmon resonance spectrometer

    OpenAIRE

    Zhang, Yintang; Xu, Maotian; Wang, Yanju; Toledo, Freddy; Zhou, Feimeng

    2007-01-01

    The use of a flow-injection surface plasmon resonance (FI-SPR) spectrometer equipped with a bicell detector or a position-sensitive device for determining coordination of heavy metal ions (Cd2+ and Hg2+) by surface-confined apo-metallothionein (apo-MT) molecules is described. To facilitate the formation of a compact MT adsorbate layer with a uniform surface orientation, MT molecules were attached onto a preformed alkanethiol self-assembled monolayer. The method resorts to the generation of ap...

  7. A study of the electron transfer inhibition on a charged self-assembled monolayer modified gold electrode by odd random phase multisine electrochemical impedance spectroscopy

    International Nuclear Information System (INIS)

    The interest of self-assembled monolayers (SAM) comes from their wide range of very specific technological applications. The SAMs having a terminal charged group are of great importance as model surfaces for electron transfer studies. The electron transfer for highly charged electroactive ions at a SAM modified electrode involves an electrostatic interaction. The present work studies a negatively charged SAM of 2-mercaptobenzimidazole-5-sulfonate (MBIS). The adsorption of the molecule on polycrystalline gold is described by X-ray photoelectron spectroscopy (XPS) and the reductive desorption of MBIS. The behavior of the MBIS monolayer towards the electron transfer of the ferri/ferrocyanide reaction is investigated by cyclic voltammetry and odd random phase multisine electrochemical impedance spectroscopy (ORP-EIS). This technique ensures reliable experiments and enables a statistically founded modeling. The combined electrochemical and surface study allows the investigation of the characteristics and electrochemical properties of the MBIS monolayer formed on polycrystalline gold to provide a quantitative modeling, which is physically and statistically validated. The major contribution of this work is the use of ORP-EIS and XPS to understand how the interaction between a charged SAM and electroactive ions affects the electron transfer

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

    Science.gov (United States)

    Asav, Engin; Akyilmaz, Erol

    2010-01-15

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

  9. Functionalisation of bolaamphiphiles with mononuclear bis(2,2 '-bipyridyl)ruthenium(II) complexes for application in self assembled monolayers

    NARCIS (Netherlands)

    Killeen, JS; Browne, WR; Skupin, M; Fuhrhop, JH; Vos, JG

    2003-01-01

    A novel ruthenium(II) polypyridyl complex connected covalently to a bolaamphiphile, containing amide linkages to provide rigidity via hydrogen bonding in the monolayer, has been prepared. The ruthenium( II) complexes of this ligand and of the intermediates in the synthesis were prepared by modi. cat

  10. Si-C Linked Organic Monolayers on Crystalline Silicon Surfaces as Alternative Gate Insulators

    NARCIS (Netherlands)

    Faber, Erik J.; Smet, de Louis C.P.M.; Olthuis, Wouter; Zuilhof, Han; Sudhölter, Ernst J.R.; Bergveld, Piet; Berg, van den Albert

    2005-01-01

    Herein, the influence of silicon surface modification via Si-CnH2n+1 (n=10,12,16,22) monolayer-based devices on p-type (100) and n-type (100) silicon is studied by forming MIS (metal–insulator–semiconductor) diodes using a mercury probe. From current density–voltage (J–V) and capacitance–voltage (C–

  11. Long-range order of organized oligonucleotide monolayers on Au(111) electrodes

    DEFF Research Database (Denmark)

    Wackerbarth, Hainer; Grubb, Mikala; Zhang, Jingdong;

    2004-01-01

    -S bond. The coverage is high and in keeping with dense monolayers of adsorbed HS-10A and HS-10AT in an upright or tilted orientation, with the oligonucleotide backbone repelled from the strongly negatively charged electrode surface. Adsorbed thiol-free 10A only gives aAu(111)-reconstruction peak, while...

  12. Gradients of Rectification: Tuning Molecular Electronic Devices by the Controlled Use of Different-Sized Diluents in Heterogeneous Self-Assembled Monolayers.

    Science.gov (United States)

    Kong, Gyu Don; Kim, Miso; Cho, Soo Jin; Yoon, Hyo Jae

    2016-08-22

    Molecular electronics has received significant attention in the last decades. To hone performance of devices, eliminating structural defects in molecular components inside devices is usually needed. We herein demonstrate this problem can be turned into a strength for modulating the performance of devices. We show the systematic dilution of a monolayer of an organic rectifier (2,2'-bipyridine-terminated n-undecanethiolate) with electronically inactive diluents (n-alkanethiolates of different lengths), gives remarkable gradients of rectification. Rectification is finely tunable in a range of approximately two orders of magnitude, retaining its polarity. Trends of rectification against the length of the diluent indicate the gradient of rectification is extremely sensitive to the molecular structure of the diluent. Further studies reveal that noncovalent intermolecular interactions within monolayers likely leads to gradients of structural defect and rectification. PMID:27443577

  13. Monolayer FePt nanocrystal self-assembly embedded into atomic-layer-deposited Al2O3 films for nonvolatile memory applications

    International Nuclear Information System (INIS)

    Highlights: • Memory cells containing chemically-synthesized FePt nanocrystals are fabricated. • A hexagonal arrangement monolayer is self-assembled on alumina by dip-coating. • The core–shell structure is formed with alloy core and amorphous iron oxide shell. • The MOS capacitors are electrically measured exhibiting obvious memory effects. -- Abstract: A simple approach is developed to fabricate oxide/FePt nanocrystals/oxide composite films by a combination of chemically-synthesized FePt nanocrystals’ self-assembly and atomic layer deposition for ultrahigh-density nonvolatile memory applications. A hexagonally arranged monolayer of well-monodispersed FePt nanocrystals with a grain size of 4.5 nm has been assembled onto atomic-layer-deposited Al2O3 oxide by solution-based dip-coating. The lattice constant of this two-dimensional pattern is about 8 nm with the high density of 1.8 × 1012/cm2. A fraction of the Fe is oxidized during annealing at 500 °C for 5 min in O2 atmosphere, and the core–shell structure is formed with fcc-Fe0.75Pt nanocrystal core and amorphous Fe2O3 shell. The metal–oxide–Si capacitors with unannealed and annealed FePt nanocrystals embedded into Al2O3 films are electrically measured, and exhibit obvious memory effects with a hysteresis memory window of 4.1 and 8.1 V at the sweeping gate voltage of ±8 V, respectively. The enhanced memory window of samples with annealed FePt nanocrystals can be attributed to the existence of the Fe2O3 shell, which introduces additional interface and provides more trap sites for charge trapping storage

  14. Assembly of gold composite thin films by spontaneous reduction of subphase chloroaurate anions beneath vitamin E Langmuir monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, L. [School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Department of Chemistry-Biology, Suzhou College, Suzhou 234000 (China); Shen, Y.H. [School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China)], E-mail: s_yuhua@163.com; Xie, A.J.; Li, S.K.; Qiu, L.G.; Li, Y.M. [School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China)

    2007-09-15

    Gold composite thin films were generated by the spontaneous reduction of chloroaurate (AuCl{sub 4}{sup -}) ions beneath vitamin E (VE) Langmuir monolayer. The monolayer and gold nanocomposite LB films were then characterized by surface pressure-area ({pi}-A) isotherms, ultraviolet-visible spectroscopy (UV-vis), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction analysis (XRD), respectively. The results showed that the limiting area/VE molecule on the HAuCl{sub 4} solution subphase was larger than that on the pure water subphase, and it increased with reaction time. The morphologies of Au particles such as spherical-like, triangular and multiply-twinned particles (MTPs) could be observed. The XRD pattern indicated that the gold particles in LB films were face-centered cubic (fcc) polycrystalline. The plasmon absorption intensities of gold composite LB films increased with the film thickness, which suggested that the monolayer containing gold particles could be transferred successfully onto the substrates.

  15. Si-C linked organic monolayers on crystalline silicon surfaces as alternative gate insulators

    NARCIS (Netherlands)

    Faber, E.J.; Smet, de L.C.P.M.; Olthuis, W.; Zuilhof, H.; Sudhölter, E.J.R.; Bergveld, P.; Berg, van den A.

    2005-01-01

    Herein, the influence of silicon surface modification via SiCnH2n+1 (n=10,12,16,22) monolayer-based devices on p-type 100 and n-type 100 silicon is studied by forming MIS (metal-insulator-semiconductor) diodes using a mercury probe. From current density-voltage (J-V) and capacitance-voltage (C-V) me

  16. Monolayer Co3 O4 Inverse Opals as Multifunctional Sensors for Volatile Organic Compounds.

    Science.gov (United States)

    Lee, Chul-Soon; Dai, Zhengfei; Jeong, Seong-Yong; Kwak, Chang-Hoon; Kim, Bo-Young; Kim, Do Hong; Jang, Ho Won; Park, Joon-Shik; Lee, Jong-Heun

    2016-05-17

    Monolayers of periodic porous Co3 O4 inverse opal (IO) thin films for gas-sensor applications were prepared by transferring cobalt-solution-dipped polystyrene (PS) monolayers onto sensor substrates and subsequent removal of the PS template by heat treatment. Monolayer Co3 O4 IO thin films having periodic pores (d≈500 nm) showed a high response of 112.9 to 5 ppm C2 H5 OH at 200 °C with low cross-responses to other interfering gases. Moreover, the selective detection of xylene and methyl benzenes (xylene+toluene) could be achieved simply by tuning the sensor temperature to 250 and 275 °C, respectively, so that multiple gases can be detected with a single chemiresistor. Unprecedentedly high ethanol response and temperature-modulated control of selectivity with respect to ethanol, xylene, and methyl benzenes were attributed to the highly chemiresistive IO nanoarchitecture and to the tuned catalytic promotion of different gas-sensing reactions, respectively. These well-ordered porous nanostructures could have potential in the field of high-performance gas sensors based on p-type oxide semiconductors. PMID:27125495

  17. Effects of ambient conditions on adsorbed surfactant and polymer monolayers

    International Nuclear Information System (INIS)

    The physical properties of surfactant-coated and polyelectrolyte-coated surfaces in adhesive contact in air have been studied using the surface forces apparatus technique. Various physisorbed monolayers with different head groups and chains (or polymer segments) were prepared both by adsorption form solution (self-assembly) and by the Langmuir-Blodgett deposition technique. The results show that many monolayer properties depend on the atmospheric conditions such as the relative humidity or presence of organic vapors and that these properties can further change when two monolayer-coated surfaces are brought into contact. These properties include monolayer composition and structure, thickness and compressibility, fluidity and phase state (i.e., whether solid, gel, or liquid), and the adhesion between two monolayer-coated surfaces. In addition, we find that both out-of-plane and in-plane (lateral) phase transitions can be induced in certain adsorbed monolayers when they are subjected to a compressive stress. The results provide new insights into molecular ordering and dynamics in physisorbed monolayers and how monolayers are affected when they are exposed to vapors or when they interact with other surfaces. 18 refs., 13 figs., 4 tabs

  18. Bottom-up organic integrated circuits

    OpenAIRE

    Smits, Edsger C. P; Mathijssen, Simon G. J.; van Hal, Paul A.; Setayesh, Sepas; Geuns, Thomas C. T.; Mutsaers, Kees A. H. A.; Cantatore, Eugenio; Wondergem, Harry J.; Werzer, Oliver; Resel, Roland; Kemerink, Martijn; Kirchmeyer, Stephan; Muzafarov, Aziz M.; Ponomarenko, Sergei A.; de Boer, Bert

    2008-01-01

    Self- assembly - the autonomous organization of components into patterns and structures(1) - is a promising technology for the mass production of organic electronics. Making integrated circuits using a bottom- up approach involving self- assembling molecules was proposed(2) in the 1970s. The basic building block of such an integrated circuit is the self- assembled- monolayer field- effect transistor ( SAMFET), where the semiconductor is a monolayer spontaneously formed on the gate dielectric....

  19. Use of self assembled monolayers at variable coverage to control interface bonding in a model study of interfacial fracture: Pure shear loading

    Energy Technology Data Exchange (ETDEWEB)

    KENT,MICHAEL S.; YIM,HYUN; MATHESON,AARON J.; COGDILL,C.; NELSON,GERALD C.; REEDY JR.,EARL DAVID

    2000-05-16

    The relationships between fundamental interfacial interactions, energy dissipation mechanisms, and fracture stress or fracture toughness in a glassy thermoset/inorganic solid joint are not well understood. This subject is addressed with a model system involving an epoxy adhesive on a polished silicon wafer containing its native oxide. The proportions of physical and chemical interactions at the interface, and the in-plane distribution, are varied using self-assembling monolayers of octadecyltrichlorosilane (ODTS). The epoxy interacts strongly with the bare silicon oxide surface, but forms only a very weak interface with the methylated tails of the ODTS monolayer. The fracture stress is examined as a function of ODTS coverage in the napkin-ring (pure shear) loading geometry. The relationship between fracture stress and ODTS coverage is catastrophic, with a large change in fracture stress occurring over a narrow range of ODTS coverage. This transition in fracture stress does not correspond to a wetting transition of the epoxy. Rather, the transition in fracture stress corresponds to the onset of deformation in the epoxy, or the transition from brittle to ductile fracture. The authors postulate that the transition in fracture stress occurs when the local stress that the interface can support becomes comparable to the yield stress of the epoxy. The fracture results are independent of whether the ODTS deposition occurs by island growth (T{sub dep} = 10 C) or by homogeneous growth (T{sub dep} = 24 C).

  20. Selective anion sensing by a tris-amide CTV derivative: 1H NMR titration, self-assembled monolayers, and impedance spectroscopy.

    Science.gov (United States)

    Zhang, Sheng; Echegoyen, Luis

    2005-02-16

    A hydrogen-bond forming tris(amide) receptor based on cyclotriveratrylene (CTV) was prepared. Self-assembled monolayers (SAMs) of the receptor were formed on gold surfaces. Desorption experiments show a surface coverage of 2.26 x 10(-10) mol/cm(2). (1)H NMR and UV measurements confirm that the receptor exhibits the highest affinity for acetate ions among the anions studied. Electrochemical impedance was used to investigate anion sensing by the SAMs and proved to be an efficient and convenient technique for detecting anions in aqueous solutions. Upon binding acetate anions, the monolayer-modified gold electrodes show a drastic increase of the R(ct) values when Fe(CN)(6)(3-/4-) is used as the redox probe. When the probe was changed to a positively charged one, Ru(NH3)(6)(3+/2+), the R(ct) values decreased monotonically as the acetate concentration was increased, thus confirming the accumulation of negative surface charge upon anion binding. H(2)PO(4-) shows some interference when sensing AcO-. Other monovalent anions such as Cl-, Br-, NO3(-) and HSO4(-) do not bind to the CTV receptor either in solution or on the surfaces. PMID:15701037

  1. Polarized total-reflection x-ray absorption fine structure for self-assembled monolayer of zinc porphyrin at air-water interface

    International Nuclear Information System (INIS)

    A new x-ray absorption fine structure (XAFS) method is applied to the air-solution interface. Under the total reflection condition, the XAFS method becomes surface sensitive, enabling the self-assembled monolayer of a metal complex at the solution surface to analyze in situ. Furthermore the introduction of two types of linearly polarized x rays allows us to determine the selective orientation of a planar metal complex at the surface. We obtain spectra for a square planar complex, 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrinato zinc(II) (ZnTPPC) adsorbed on the aqueous solution surface forming a monolayer with two polarized x rays and compared them with spectra of the same compound in a bulk solution and in solid powder. The polarized XAFS spectra exhibit different features leading to the unambiguous conclusion that the plane of the ZnTPPC molecule is oriented parallel to the air-water interface and that there is no coordination to the axial sites of the zinc atom

  2. Influence of molecular ordering on electrical and friction properties of omega-(trans-4-stilbene)alkylthiol self-assembled monolayers on Au (111)

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Yabing; Liu, Xiaosong; Hendriksen, B.L.M.; Navarro, V.; Park, Jeong Y.; Ratera, Imma; Klopp, J.M.; Edder, C.; Himpsel, Franz J.; Frechet, J.M.J.; Haller, Eugene E.; Salmeron, Miquel

    2010-04-21

    The electrical and friction properties of omega-(trans-4-stilbene)alkylthiol self-assembled monolayers (SAMs) on Au(111) were investigated using atomic force microscopy (AFM) and near edge x-ray absorption fine structure spectroscopy (NEXAFS). The sample surface was uniformly covered with a molecular film consisting of very small grains. Well-ordered and flat monolayer islands were formed after the sample was heated in nitrogen at 120 oC for 1 h. While lattice resolved AFM images revealed a crystalline phase in the islands, the area between islands showed no order. The islands exhibit substantial reduction (50percent) in friction, supporting the existence of good ordering. NEXAFS measurements revealed an average upright molecular orientation in the film, both before and after heating, with a narrower tilt-angle distribution for the heated fim. Conductance-AFM measurements revealed a two orders of magnitude higher conductivity on the ordered islands than on the disordered phase. We propose that the conductance enhancement is a result of a better pi-pi stacking between the trans-stilbene molecular units as a result of improved ordering in islands.

  3. Kinetic studies of attachment and re-orientation of octyltriethoxysilane for formation of self-assembled monolayer on a silica substrate.

    Science.gov (United States)

    Hasan, Abshar; Pandey, Lalit M

    2016-11-01

    The present study deals with kinetic studies of the chemical modification for synthesizing a hydrophobic silica surface. Surface silanization (modification) via formation of Self-Assembled Monolayer (SAM) using a short chain triethoxyoctylsilane (TEOS) was carried out under inert atmosphere at room temperature. Fourier transmission infrared (FTIR) spectroscopy, water contact angle (WCA) and atomic force microscopy (AFM) were employed to investigate surface modification. FTIR analysis in the range from 900-1200cm(-1) and 2850-3000cm(-1) confirmed surface modification and re-orientation of the attached molecules. Kinetic studies of TEOS SAM formation were fitted by Exponential Association function. Kinetic fitting of FTIR data in the range from 900-1200cm(-1) revealed a very fast attachment of TEOS molecules resulting in total surface coverage within 16min whereas re-orientation rate was slow and continued till 512min. Further, change in orientation from lying-down to standing-up state was supported by contact angle analysis. AFM images initially showed small islands of ~20nm, which in-fill with time indicating formation of a smooth monolayer. Our findings indicate that formation of octyl SAM is fast process and completes within 8.5h in contrary to reported 24h in conventional SAM formation protocols. The kinetic fitting data can be explored to design a nanopatterned surface for a specific application. PMID:27524037

  4. Etching of Crystalline ZnO Surfaces upon Phosphonic Acid Adsorption: Guidelines for the Realization of Well-Engineered Functional Self-Assembled Monolayers.

    Science.gov (United States)

    Ostapenko, Alexandra; Klöffel, Tobias; Eußner, Jens; Harms, Klaus; Dehnen, Stefanie; Meyer, Bernd; Witte, Gregor

    2016-06-01

    Functionalization of metal oxides by means of covalently bound self-assembled monolayers (SAMs) offers a tailoring of surface electronic properties such as their work function and, in combination with its large charge carrier mobility, renders ZnO a promising conductive oxide for use as transparent electrode material in optoelectronic devices. In this study, we show that the formation of phosphonic acid-anchored SAMs on ZnO competes with an unwanted chemical side reaction, leading to the formation of surface precipitates and severe surface damage at prolonged immersion times of several days. Combining atomic force microscopy (AFM), X-ray diffraction (XRD), and thermal desorption spectroscopy (TDS), the stability and structure of the aggregates formed upon immersion of ZnO single crystal surfaces of different orientations [(0001̅), (0001), and (101̅0)] in phenylphosphonic acid (PPA) solution were studied. By intentionally increasing the immersion time to more than 1 week, large crystalline precipitates are formed, which are identified as zinc phosphonate. Moreover, the energetics and the reaction pathway of this transformation have been evaluated using density functional theory (DFT), showing that zinc phosphonate is thermodynamically more favorable than phosphonic acid SAMs on ZnO. Precipitation is also found for phosphonic acids with fluorinated aromatic backbones, while less precipitation occurs upon formation of SAMs with phenylphosphinic anchoring units. By contrast, no precipitates are formed when PPA monolayer films are prepared by sublimation under vacuum conditions, yielding smooth surfaces without noticeable etching. PMID:27159837

  5. Enhancement of electron injection into a light-emitting polymer from an aluminum oxide cathode modified by a self-assembled monolayer

    Science.gov (United States)

    Vaynzof, Yana; Dennes, T. Joseph; Schwartz, Jeffrey; Kahn, Antoine

    2008-09-01

    A self-assembled monolayer (SAM) of octylphosphonate was deposited on an AlOx electrode using the tethering by aggregation and growth (T-BAG) procedure. Ultraviolet photoemission spectroscopy (UPS) measurements showed a decrease in the substrate work function from 3.8to3.3eV. Poly[9,9'-dioctylfluorene-co-bis-N ,N'-(4-butylphenyl)-diphenylamine] (TFB) films spin coated on the bare and the SAM-modified oxide surfaces were investigated by UPS. A shift in molecular levels, corresponding to a reduction in the electron injection barrier, was observed for the SAM-modified electrode. This barrier lowering was confirmed by current-voltage measurements showing a corresponding increase in electron current through the TFB/SAM/AlOx device.

  6. Improved microstructure and performance of PbS thin films via in-situ thermal decomposition of lead xanthate precursors using self-assembling monolayer

    Science.gov (United States)

    Wang, Jingni; Yao, Kai; Jia, Zhenrong; Wang, Xiaofeng; Li, Fan

    2016-09-01

    Microstructure control is critical to achieve thin film-based devices with high performance. The surface properties of the substrates on which thin films grow are expected to greatly influence the morphology and the resulting performance. Generally, homogeneous, dense and highly crystalline films are required. However, "island" like structures are usually obtained mainly due to the non-uniform nucleation. In this article, the self-assembling monolayer (SAM) strategy was applied to efficiently realize the uniform nucleation and modulate the microstructure of lead sulfide (PbS) thin films, which were fabricated on the modified ZnO-coated substrates with 3-mercaptopropionic acid (MPA) SAM via in-situ thermal decomposition of lead xanthate precursors. The results showed that PbS thin films with reduced pin-holes and uniform crystalline grains were fabricated with the incorporation of MPA SAM. More importantly, PbS thin films modulated by MPA showed better photoelectric response.

  7. FET immunosensor for hemoglobin A1c using a gold nanofilm grown by a seed-mediated technique and covered with mixed self-assembled monolayers

    International Nuclear Information System (INIS)

    A micro FET-based immunosensor was developed for the determination of hemoglobin-A1c (HbA1c). The HbA1c/hemoglobin ratio is an important index in diabetes control. The sensor was fabricated by Complementary Metal-Oxide-Semiconductor Transistor (CMOS) and Micro Electronic Mechanical System (MEMS) techniques. The antibodies were immobilized via mixed self-assembled monolayers (SAMs) on a gold nanofilm. The nanofilm was deposited on a gold electrode by seed-mediated growth and gave a uniform and well distributed coverage. Nonspecific sites and interferences by noise were eliminated by covering the AuNPs with mixed SAMs. Compared to the immunosensor fabricated via the mixed SAMs method without gold nanofilm, the immunosensor displays a more than 2-fold sensitivity. The immunosensor is capable of detecting HbA1c and hemoglobin in hemolyzed and diluted whole blood, and results showed good agreement with the established clinical method. (author)

  8. Effects of interface modification with self-assembled monolayers on the photovoltaic performance of CdS quantum dots sensitized solar cells

    International Nuclear Information System (INIS)

    We employ 3-PPA, BPA and APPA as self-assembled monolayers (SAMs), who owns the same phosphonic acid headgroup but different tail group, to modify the surface of ZnO nanorods. Their effects on the photovoltaic performance of quantum dots sensitized soar cells are systematically investigated. The results indicate that the deposition of SAMs not only passivates the surface defects of ZnO nanorods, but also tunes their surface work function to adjust the band alignment of solar cells. In particular, the 3-PPA modification exhibits the best passivation effect and makes the surface work function of ZnO decreases by 1.04 eV to realize a better band alignment due to its electron-withdrawing tailgroup, which results in an enhancement in photovoltaic conversion efficiency of solar cells

  9. Water-COOH Composite Structure with Enhanced Hydrophobicity Formed by Water Molecules Embedded into Carboxyl-Terminated Self-Assembled Monolayers.

    Science.gov (United States)

    Guo, Pan; Tu, Yusong; Yang, Jinrong; Wang, Chunlei; Sheng, Nan; Fang, Haiping

    2015-10-30

    By combining molecular dynamics simulations and quantum mechanics calculations, we show the formation of a composite structure composed of embedded water molecules and the COOH matrix on carboxyl-terminated self-assembled monolayers (COOH SAMs) with appropriate packing densities. This composite structure with an integrated hydrogen bond network inside reduces the hydrogen bonds with the water above. This explains the seeming contradiction on the stability of the surface water on COOH SAMs observed in experiments. The existence of the composite structure at appropriate packing densities results in the two-step distribution of contact angles of water droplets on COOH SAMs, around 0° and 35°, which compares favorably to the experimental measurements of contact angles collected from forty research articles over the past 25 years. These findings provide a molecular-level understanding of water on surfaces (including surfaces on biomolecules) with hydrophilic functional groups. PMID:26565476

  10. Direct patterning of negative nanostructures on self-assembled monolayers of 16-mercaptohexadecanoic acid on Au(111) substrate via dip-pen nanolithography

    International Nuclear Information System (INIS)

    Both bare and self-assembled monolayer (SAM) protected gold substrate could be etched by allyl bromide according to atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometric (ICPMS) analysis results. With this allyl bromide ink material, negative nanopatterns could be fabricated directly by dip-pen nanolithography (DPN) on SAMs of 16-mercaptohexadecanoic acid (MHA) on Au(111) substrate. A tip-promoted etching mechanism was proposed where the gold-reactive ink could penetrate the MHA resist film through tip-induced defects resulting in local corrosive removal of the gold substrate. The fabrication mechanism was also confirmed by electrochemical characterization, energy dispersive spectroscopy (EDS) analysis and fabrication of positive nanopatterns via a used DPN tip

  11. Monolayers assembled from a glycolipid biosurfactant from Pseudozyma (Candida) antarctica serve as a high-affinity ligand system for immunoglobulin G and M.

    Science.gov (United States)

    Imura, Tomohiro; Ito, Seya; Azumi, Reiko; Yanagishita, Hiroshi; Sakai, Hideki; Abe, Masahiko; Kitamoto, Dai

    2007-06-01

    A carbohydrate ligand system has been developed which is composed of self-assembled monolayers (SAMs) of mannosylerythritol lipid-A (MEL-A) from Pseudozyma antarctica, serving for human immunoglobulin G and M (HIgG and HIgM). The estimated binding constants from surface plasmon resonance (SPR) measurement were Ka = 9.4 x 10(6) M(-1) for HIgG and 5.4 x 10(6) M(-1) for HIgM, respectively. The binding site was not in the Fc region of immunoglobulin but in the Fab region. Large amounts of HIgG and HIgM bound to MEL-A SAMs were directly observed by atomic force microscopy. PMID:17342348

  12. Role of Self-Assembled Monolayers on Improved Electrical Stability of Amorphous In-Ga-Zn-O Thin-Film Transistors

    CERN Document Server

    Du, Xiaosong; Motley, Joshua R; Stickle, William F; Bluhm, Hendrik; Herman, Gregory S

    2014-01-01

    Self-assembled monolayers (SAMs) have been used to improve both the positive and negative bias-stress stability of amorphous indium gallium zinc oxide (IGZO) bottom gate thin film transistors (TFTs). N-hexylphosphonic acid (HPA) and fluorinated hexylphosphonic acid (FPA) SAMs adsorbed on IGZO back channel surfaces were shown to significantly reduce bias stress turn-on voltage shifts compared to IGZO back channel surfaces with no SAMs. FPA was found to have a lower surface energy and lower packing density than HPA, as well as lower bias stress turn-on voltage shifts. The improved stability of IGZO TFTs with SAMs can be primarily attributed to a reduction in molecular adsorption of contaminants on the IGZO back channel surface and minimal trapping states present with phosphonic acid binding to the IGZO surface.

  13. Evaluating the surface density and heterogeneity of a dithiobis (succinimidylpropionate) self-assembled monolayer on gold and its coupling with DNA embedded within a matrix

    International Nuclear Information System (INIS)

    The homogeneity of a self-assembled monolayer (SAM) on a surface is an important parameter which affects the ability of a SAM to fulfill its intended function. As an example, SAMs formed from octanethiols can form an impermeable surface, while SAMs based on a bifunctional coupling reagent can form a surface with uniform reactivity. Exposure of gold nanoparticles or gold surfaces to solutions of dithiobis (succinimidylpropionate) (DSP) gives rise to a surface which can react with DNA. Atomic force microscopy, UV-vis and gel electrophoresis experiments indicate that a self-assembled monolayer of DSP on gold nanoparticles can attenuate aggregation, inhibit the 'lying down' of covalently-bound single-stranded (ss) DNA and promote more efficient hybridization. The determination of the point of aggregation after reacting DSP with colloidal gold yields 2.86 x 10-10 mol/cm2 or 42% of the value determined from molecular modeling. Cyclic voltammetry experiments validate that DSP on a gold quartz crystal (6.3 x 10-10 mol/cm2) forms a fairly uniform SAM that is within 94% of maximum coverage when compared with results obtained from molecular modeling (6.67 x 10-10 mol/cm2). Surface plasmon resonance experiments indicate that the reaction of a DSP coated gold surface with (ss) DNA yields 2.4 x 10-12 mol/cm2 or reaction with about 1% of the available surface area. Subsequent reactions of the DSP surface with the filler, n-boc-1,4-phenylene diamine (n-boc), yield a total surface coverage of 1.8 x 10-11 mol/cm2. The surrounded (ss) DNA yields a surface with 97% hybridization efficiency toward the complement.

  14. Quantum Hall effect of self-organized graphene monolayers on the C-face of 6H-SiC

    International Nuclear Information System (INIS)

    We review some of the electric properties of self-organized graphene monolayers on the carbon face of SiC. From sparse surface defects acting as nucleation centres, isolated graphene layers grow in the shape of triangles or ribbons on the step bunched SiC surface. Using e-beam lithography, standard Hall bars have been made. At low magnetic fields, conductance fluctuations, weak localization, electron–electron interactions are usually observed. At higher magnetic fields, the anomalous quantum Hall (QHE) effect typical of monolayer graphene is also observed. In this regime, the breakdown of the QHE appears at moderate currents, which we attribute to the persistence of impurities in the vicinity of the graphene layer. Moderate heating (150 °C) is not sufficient to overcome this issue, and moreover, the carrier concentration cannot be controlled. In order to control the carrier concentration, bottom-gated samples are also presented. In these devices, the carrier concentration can be modulated, but the breakdown current remains very small. (paper)

  15. On the valve nature of a monolayer of aligned molecular magnets in tunneling spin-polarized electrons: Towards organic molecular spintronics

    International Nuclear Information System (INIS)

    We form a monolayer of magnetic organic molecules and immobilize their moments pointing either upwards or downwards with respect to the substrate through an electrostatic-binding process. Such a monolayer is probed with a scanning tunneling microscope tip, which is also magnetized with the magnetization vector pointing towards (or away from) apex of the tip. From spin-polarized tunneling current, we show that the current was higher when magnetization vectors of the tip and molecules were parallel as compared to that when they were anti-parallel. We show that for tunneling of spin-polarized electrons, aligned organic molecular magnets can act as a valve

  16. Surface sealing using self-assembled monolayers and its effect on metal diffusion in porous low-k dielectrics studied using monoenergetic positron beams

    Science.gov (United States)

    Uedono, Akira; Armini, Silvia; Zhang, Yu; Kakizaki, Takeaki; Krause-Rehberg, Reinhard; Anwand, Wolfgang; Wagner, Andreas

    2016-04-01

    Surface sealing effects on the diffusion of metal atoms in porous organosilicate glass (OSG) films were studied by monoenergetic positron beams. For a Cu(5 nm)/MnN(3 nm)/OSG(130 nm) sample fabricated with pore stuffing, C4F8 plasma etch, unstuffing, and a self-assembled monolayer (SAM) sealing process, it was found that pores with cubic pore side lengths of 1.1 and 3.1 nm coexisted in the OSG film. For the sample without the SAM sealing process, metal (Cu and Mn) atoms diffused from the top Cu/MnN layer into the OSG film and were trapped by the pores. As a result, almost all pore interiors were covered with those metals. For the sample damaged by an Ar/C4F8 plasma etch treatment before the SAM sealing process, SAMs diffused into the OSG film, and they were preferentially trapped by larger pores. The cubic pore side length in these pores containing self-assembled molecules was estimated to be 0.7 nm. Through this work, we have demonstrated that monoenergetic positron beams are a powerful tool for characterizing capped porous films and the trapping of atoms and molecules by pores.

  17. DL-valine Self-Assembled Monolayers on Copper Electrode%自组装DL-缬氨酸铜电极的电化学研究

    Institute of Scientific and Technical Information of China (English)

    文泽东

    2011-01-01

    The self-assembly method was used to process DL-valine monolayer modified copper electrode. Compact degree of the DL-Valine film on copper electrode at different times was investigated by using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (AC).The results show that spatial conformation of DL-valine in the copper surface has changed. According to the experiment,when the assembly time is 8 h, the packing density is best.%利用自组装的方法制得了DL-缬氨酸修饰铜电极,采用循环伏安法(CV)和交流阻抗谱(AC)探讨了在铜电极上DL-缬氨酸自组装膜在不同组装时间的致密程度.结果表明,DL-缬氨酸在铜表面的空间构象发生变化.并由实验可知,组装时间为8 h时,膜的致密性最好.

  18. Moiré pattern induced by the electronic coupling between 1-octanol self-assembled monolayers and graphite surface

    OpenAIRE

    Silly, Fabien

    2012-01-01

    Two-dimensional self-assembly of 1-octanol molecules on a graphite surface is investigated using scanning tunneling microscopy (STM) at the solid/liquid interface. STM images reveal that this molecule self-assembles into a compact hydrogen-bonded herringbone nanoarchitecture. Molecules are preferentially arranged in a head-to-head and tail-to-tail fashion. A Moir'e pattern appears in the STM images when the 1-octanol layer is covering the graphite surface. The large Moir'e stripes are perpend...

  19. Self-assembled monolayers of radical molecules physisorbed on HOPG(0 0 0 1) substrate studied by scanning tunnelling microscopy and electron paramagnetic resonance techniques

    International Nuclear Information System (INIS)

    In this paper, we present a combined STM and EPR study on the adsorption and self-organization of monolayers formed from 2-(14-Carboxytetradecyl)-2-ethyl-4,4-dimethyl-3-oxazolidinyloxy (16DS) and 4',4'-Dimethylspiro(5α-cholestane-3,2'-oxazolidin)-3'-yloxy (CSL) adsorbed on a highly oriented pyrolitic graphite HOPG(0 0 0 1) substrate. Both 16DS and CSL molecules are persistent free radicals containing a paramagnetic doxyl group. The STM measurements of 16DS on HOPG(0 0 0 1) were performed at the liquid-solid interface while the studies of CSL on HOPG(0 0 0 1) were carried out under ultrahigh vacuum conditions. It was found that the 16DS molecules on the HOPG(0 0 0 1) surface form a highly-ordered monolayer with a domain structure. The high-resolution STM images show structural details of 16DS molecules on HOPG(0 0 0 1) revealing the paramagnetic doxyl group. In contrast, CSL molecules on HOPG(0 0 0 1) form a well-ordered monolayer without domain structure. The EPR results indicate that both compounds deposited on HOPG(0 0 0 1) substrate are not reduced and retain their paramagnetic character. We believe that the molecular systems described can be used in single spin detection experiments using an electron spin noise-scanning tunnelling microscopy (ESN-STM) technique. In particular, the possibility of obtaining contrast spin signals from the paramagnetic and diamagnetic parts of molecules increases the significance of our results.

  20. Self-assembled hierarchically structured organic-inorganic composite systems.

    Science.gov (United States)

    Tritschler, Ulrich; Cölfen, Helmut

    2016-01-01

    Designing bio-inspired, multifunctional organic-inorganic composite materials is one of the most popular current research objectives. Due to the high complexity of biocomposite structures found in nacre and bone, for example, a one-pot scalable and versatile synthesis approach addressing structural key features of biominerals and affording bio-inspired, multifunctional organic-inorganic composites with advanced physical properties is highly challenging. This article reviews recent progress in synthesizing organic-inorganic composite materials via various self-assembly techniques and in this context highlights a recently developed bio-inspired synthesis concept for the fabrication of hierarchically structured, organic-inorganic composite materials. This one-step self-organization concept based on simultaneous liquid crystal formation of anisotropic inorganic nanoparticles and a functional liquid crystalline polymer turned out to be simple, fast, scalable and versatile, leading to various (multi-)functional composite materials, which exhibit hierarchical structuring over several length scales. Consequently, this synthesis approach is relevant for further progress and scientific breakthrough in the research field of bio-inspired and biomimetic materials. PMID:27175790

  1. Perforated monolayers

    Energy Technology Data Exchange (ETDEWEB)

    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.

  2. Second-Order Nonlinear Optical Characteristics of Nanoscale Self-Assembled Multilayer Organic Films

    OpenAIRE

    Neyman, Patrick J.

    2004-01-01

    Ionically self-assembled monolayer (ISAM) films are typically an assemblage of oppositely charged polymers built layer by layer through Coulombic attraction utilizing an environmentally friendly process to form ordered structures that are uniform, molecularly smooth and physically robust. ISAM films have been shown to be capable of the noncentrosymmetric order requisite for a second-order nonlinear optical response with excellent temporal and thermal stability. However, such films fabricate...

  3. Change in surface states of Ag(111) thin films upon adsorption of a monolayer of PTCDA organic molecules

    International Nuclear Information System (INIS)

    The change in the electronic structure of silver thin films of different thicknesses with the Ag( 111) orientation due to the interaction with an adsorbed monolayer of ordered organic molecules of 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) has been investigated in terms of density functional theory. It has been shown that one of the two surface states of the pure films transforms into an unocc upied interface state due to the interaction so that all the main features of the initial state are retained. The relation of the resulting state to the unoccupied state experimentally observed in the PTCDA/Ag( 111 ) system by scanning tunneling and two-photon photoemission spectroscopy has been discussed.

  4. Molecular Dynamics Simulation of the Binding Interaction between Hormone Glucagon Protein and Self-Assembled Monolayer Molecules

    Institute of Scientific and Technical Information of China (English)

    WANG,Yeng-Tseng; CHENG,Cheng-Lung; SHIH,Yu-Ching; KAN,Heng-Chuan; CHEN,Chang-Hung; HU,Jeu-Jiun; SU,Zhi-Yuan

    2007-01-01

    Restrained molecular dynamics simulations were performed to study the binding affinity of the peptide with alkanethiols of different tail-groups, S(CH2)7CH3, S(CH2)7OH and S(CH2)7COOH, which self-assembled on Au(111)surface in the presence of water molecules. The curves of binding affinity were calculated by fixing the center of mass of the peptide at various distances from the assembling surface. Simulation results show that the binding affinity is in the order as COOH-SAMs>OH-SAMs>CH3-SAMs, while 100% COOH-SAMs>5% COOH-SAMs in concentration. The effects on binding affinity by different tail-groups were also studied. Results show that the binding affinity between COOH-SAMs and the peptide is bigger than those of the others and increasing the acidity of COOH-SAMs will result in stronger attractive power.

  5. Determination of Parathion and Carbaryl Pesticides in Water and Food Samples Using a Self Assembled Monolayer/Acetylcholinesterase Electrochemical Biosensor

    OpenAIRE

    Mauro Bertotti; Sergio A. S. Machado; Josiane Caetano; Pedrosa, Valber A.

    2008-01-01

    An acetylcholinesterase (AchE) based amperometric biosensor was developed by immobilisation of the enzyme onto a self assembled modified gold electrode. Cyclic voltammetric experiments performed with the SAM-AchE biosensor in phosphate buffer solutions (pH = 7.2) containing acetylthiocholine confirmed the formation of thiocholine and its electrochemical oxidation at Ep = 0.28 V vs Ag/AgCl. An indirect methodology involving the inhibition effect of parathion and carbaryl on the enzymatic react...

  6. Sensing Escherichia coli O157:H7 via frequency shift through a self-assembled monolayer based QCM immunosensor

    Institute of Scientific and Technical Information of China (English)

    Li-jiang WANG; Chun-sheng WU; Zhao-ying HU; Yuan-fan ZHANG; Rong LI; Ping WANG

    2008-01-01

    By means of the specific immuno-recognition and ultra-sensitive mass detection, a quartz crystal microbalance (QCM) biosensor for Escherichia coli O157:H7 detection was developed in this work. As a suitable surfactant, 16-mercaptohexadecanoic acid (MHDA) was introduced onto the Au surface of QCM, and then self-assembled with N-hydroxysuccinimide (NHS) raster as a reactive intermediate to provide an active interface for the specific antibody immobilization. The binding of target bacteria with the immobilized antibodies decreased the sensor's resonant frequency, and the frequency shift was correlated to the bacterial concentration. The stepwise assembly of the immunosensor was characterized by means of the electrochemical techniques. Using the immersion-dry-immersion procedure, this QCM biosensor could detect 2.0×102 colony forming units (CFU)/ml E. coli O157:H7. In order to reduce the fabrication time, a polyelectrolyte layer-by-layer self-assembly (LBL-SA) method was adopted for fast construction. Finally, the reproducibility of this biosensor was discussed.

  7. Approaching charge balance in organic light-emitting diodes by tuning charge injection barriers with mixed monolayers.

    Science.gov (United States)

    Yu, Szu-Yen; Huang, Ding-Chi; Chen, Yi-Ling; Wu, Kun-Yang; Tao, Yu-Tai

    2012-01-10

    Self-assembled monolayers (SAMs) of binary mixtures of 1-butylphosphonic acid and the trifluoromethyl-terminated analogue (4,4,4-trifluoro-1-butylphosphonic acid) were formed on ITO surfaces to tune the work function of ITO over a range of 5.0 to 5.75 eV by varying the mixing ratio of the two adsorbents. The mixed SAM-modified ITO surfaces were used as the anode in the fabrication of OLED devices with a configuration of ITO/SAM/HTL/Alq3/MX/Al, where HTL was the NPB or BPAPF hole-transporting layer and MX was the LiF or Cs(2)CO(3) injection layer. It was shown that, depending on the HTL or MX used, the maximum device current and the maximum luminance efficiency occurred with anodes of different modifications because of a shift in the point of hole/electron carrier balance. This provides information on the charge balance in the device and points to the direction to improve the performance. PMID:22103763

  8. Atom beam triangulation of organic layers at 100 meV normal energy: self-assembled perylene on Ag(110) at room temperature

    CERN Document Server

    Kalashnyk, Nataliya

    2015-01-01

    The controlled growth of organic layer on surface is still awaiting for an on-line reliable monitoring that would allow improvement of its quality. We show here that the self-assembly of the perylene monolayer deposited on Ag(110) at room temperature can be tracked with low energy atoms in a regime where the energy perpendicular to the layer is less than 0.1 eV preventing damage to the layer. The image processing required for this triangulation technique with atoms is described in details.

  9. Photoelectron spectroscopy of self-assembled monolayers of molecular switches on noble metal surfaces; Photoelektronenspektroskopie selbstorganisierter Adsorbatschichten aus molekularen Schaltern auf Edelmetalloberflaechen

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, Nils

    2012-09-12

    Self-assembled monolayers (SAMs) of butanethiolate (C4) on single crystalline Au(111) surfaces were prepared by adsorption from solution. The thermally activated desorption behaviour of the C4 molecules from the gold substrate was examined by qualitative thermal desorption measurements (TDM), through this a desorption temperature T{sub Des}=473 K could be determined. With this knowledge, it was possible to produce samples of very good surface quality, by thermal treatment T{sub Sample}assembly from solution on Au(111), was examined using laser-based photoelectron spectroscopy. Differences in the molecular dipole moment characteristic for the trans and the cis isomer of ABT were observed via changes in the sample work function, accessible by detection of the threshold energy for photoemission. A quantitative

  10. Comparison of Genotoxic Damage in Monolayer Cell Cultures and Three-Dimensional Tissue-Like Cell Assemblies

    Science.gov (United States)

    Behravesh, E.; Emami, K.; Wu, H.; Gonda, S.

    2004-01-01

    Assessing the biological risks associated with exposure to the high-energy charged particles encountered in space is essential for the success of long-term space exploration. Although prokaryotic and eukaryotic cell models developed in our laboratory and others have advanced our understanding of many aspects of genotoxicity, in vitro models are needed to assess the risk to humans from space radiation insults. Such models must be representative of the cellular interactions present in tissues and capable of quantifying I genotoxic damage. Toward this overall goal, the objectives of this study were to examine the effect of the localized microenvironment of cells, cultured as either 2-dimensional (2D) monolayers or 3-dimensional (3D) aggregates, on the rate and type of genotoxic damage resulting from exposure to iron charged particles, a significant portion of space radiation. We used rodent transgenic cell lines containing 50-70 copies of a LacI transgene to provide the enhanced sensitivity required to quantify mutational frequency and type in the 1,100-bp LacI target as well as assessment of DNA,damage to the entire 45-kbp construct. Cultured cells were exposed to high-enerir on charged particles at Brookhaven National Laboratory s Alternating Gradient Synchrotron facility for a total dose of 0, 0.1, 0.25,0.5, 1.0, or 2.0 Gy and allowed to recover for 0, 1, or 7 days, after which mutational type and frequency were evaluated. The mutational frequency was found to be higher in 3D samples than in 2D samples at all radiation doses. Mutational frequency also was higher at 7 days after irradiation than immediately after exposure. DNA sequencing of the mutant targets revealed that deletional mutations contributed an increasingly high percentage (up to 27%) of all mutations in cells as the dose was increased from 0.5 to 2 Gy. Several mutants also showed large and complex deletions in multiple locations within the Lac1 target. However, no differences in mutational type were

  11. A friendly detergent for H2 oxidation by Aquifex aeolicus membrane-bound hydrogenase immobilized on graphite and Self-Assembled-Monolayer-modified gold electrodes

    International Nuclear Information System (INIS)

    Immobilization of membrane bound enzymes onto electrodes is of great interest for studying physiological electron transfer processes and for biotechnological devices. Hydrogenases are the key enzymes for hydrogen metabolism in many microorganisms. Due to the high efficiency and specificity they develop for H2 oxidation, research in the last 5 years has aimed towards their use as biocatalysts for H2/O2 biofuel cells to replace platinum-based bioanodes. We demonstrate in this work that the O2-, CO- and T°-resistant membrane-bound [NiFe] hydrogenase purified from the hyperthermophilic bacterium Aquifex aeolicus can be efficiently immobilized onto electrodes. Both pyrolytic graphite (PG) and hydrophobic Self-Assembled-Monolayers (SAMs) on gold electrodes are used for hydrogenase immobilization. According to the chemistry and structure of the electrochemical interface, a different process for H2 oxidation is observed, from direct to mediated electron transfer process. To gain new insight in the catalytic process, a quantification of the remaining detergent surrounding the membrane protein is performed. Adsorption isotherms of hydrogenase are determined as a function of the electrode material and the amount of detergent. Competitive adsorption of free detergent and hydrogenase is demonstrated coupling electrochemistry and Polarization Modulation Infrared Reflexion Adsorption Spectroscopy (PM-IRRAS). The efficiency of the enzymatic process is then analyzed according to the tiny interaction between the lipophilic redox mediator (methylene blue), the detergent, the enzyme and the electrochemical interface.

  12. Work-function modification of the (1 1 1) gold surface upon deposition of self-assembled monolayers based on alkanethiol derivatives

    International Nuclear Information System (INIS)

    Highlights: •We model the electronic properties of SAM/gold interfaces at a theoretical DFT level. •We examine changes in the metal work-function upon SAM deposition. •Modulation of the work-function can be achieved by changing the anchoring groups. •Intermolecular interactions between electroactive substituents can drastically affect the molecular packing. -- Abstract: The modification in the work-function of the (1 1 1) gold surface upon deposition of self-assembled monolayers (SAMs) based on alkanethiol derivatives has been characterized at the Density Functional Theory level when introducing chemical derivatizations. Chemical derivatizations have been introduced by: (i) replacing thiol as anchoring group by selenol or isocyanide functionalities; and (ii) introducing terminal electroactive substituents varying by their electron donor versus acceptor character. Changes in the anchoring group have shown that substitution of S by Se has no significant impact on the total work-function shift. Consideration of various terminal substituents has also pointed to the key role played by internal restructuration of the SAM geometry on the work-function. These results contribute in establishing guidelines toward a fine control of interface engineering in opto-electronic devices

  13. First-Principles Surface Stress Calculations and Multiscale Deformation Analysis of a Self-Assembled Monolayer Adsorbed on a Micro-Cantilever

    Directory of Open Access Journals (Sweden)

    Yu-Ching Shih

    2014-04-01

    Full Text Available Micro-cantilever sensors are widely used to detect biomolecules, chemical gases, and ionic species. However, the theoretical descriptions and predictive modeling of these devices are not well developed, and lag behind advances in fabrication and applications. In this paper, we present a novel multiscale simulation framework for nanomechanical sensors. This framework, combining density functional theory (DFT calculations and finite element method (FEM analysis, is capable of analyzing molecular adsorption-induced deformation and stress fields in the sensors from the molecular scale to the device scale. Adsorption of alkanethiolate self-assembled monolayer (SAM on the Au(111 surface of the micro-cantilever sensor is studied in detail to demonstrate the applicability of this framework. DFT calculations are employed to investigate the molecular adsorption-induced surface stress upon the gold surface. The 3D shell elements with initial stresses obtained from the DFT calculations serve as SAM domains in the adsorption layer, while FEM is employed to analyze the deformation and stress of the sensor devices. We find that the micro-cantilever tip deflection has a linear relationship with the coverage of the SAM domains. With full coverage, the tip deflection decreases as the molecular chain length increases. The multiscale simulation framework provides a quantitative analysis of the displacement and stress fields, and can be used to predict the response of nanomechanical sensors subjected to complex molecular adsorption.

  14. Binary self-assembled monolayers of alkanethiols on gold: deposition from solution versus microcontact printing and the study of surface nanobubbles.

    Science.gov (United States)

    Bayat, Haider; Tranchida, Davide; Song, Bo; Walczyk, Wiktoria; Sperotto, Elena; Schönherr, Holger

    2011-02-15

    The coadsorption of alkanethiols on noble metals has been recognized for a long time as a suitable means of affording surfaces with systematically varied wettability and other properties. In this article, we report on a comparative study of the composition of the mixed self-assembled monolayers (SAMs) obtained (i) by the coadsorption of octadecanethiol (ODT) and 16-mercaptohexadecanoic acid (MHDA) from ethanol and chloroform onto gold substrates and (ii) by microcontact printing using poly(dimethyl siloxane) (PDMS) stamps. SAMs prepared by coadsorption from solution showed a preferential adsorption of ODT for both solvents, but this trend was reversed in microcontact-printed SAMs when using chloroform as a solvent, as evidenced by contact angle and Fourier transform infrared (FTIR) spectroscopy measurements. An approximately linear relationship between the static contact angle and the degree of swelling with different solvents was observed, which suggests that the surface composition can be controlled by the interaction of the solvent and the PDMS elastomer. The altered preference is attributed to the different partitioning of the two thiols into solvent-swelled PDMS, as shown by (1)H NMR spectroscopy. Finally, molecularly mixed binary SAMs on ODT and MHDA on template-stripped gold were applied to study the effect of surface nanobubbles on wettability by atomic force microscopy (AFM). With a decreasing macroscopic contact angle measured through water, the nanoscopic contact angle was found to decrease as well. PMID:21117682

  15. Laterally Mobile, Functionalized Self-Assembled Monolayers at the Fluorous−Aqueous Interface in a Plug-Based Microfluidic System: Characterization and Testing with Membrane Protein Crystallization

    Energy Technology Data Exchange (ETDEWEB)

    Kreutz, Jason E.; Li, Liang; Roach, L. Spencer; Hatakeyama, Takuji; Ismagilov, Rustem F.; (UC)

    2009-11-04

    This paper describes a method to generate functionalizable, mobile self-assembled monolayers (SAMs) in plug-based microfluidics. Control of interfaces is advancing studies of biological interfaces, heterogeneous reactions, and nanotechnology. SAMs have been useful for such studies, but they are not laterally mobile. Lipid-based methods, though mobile, are not easily amenable to setting up the hundreds of experiments necessary for crystallization screening. Here we demonstrate a method, complementary to current SAM and lipid methods, for rapidly generating mobile, functionalized SAMs. This method relies on plugs, droplets surrounded by a fluorous carrier fluid, to rapidly explore chemical space. Specifically, we implemented his-tag binding chemistry to design a new fluorinated amphiphile, RfNTA, using an improved one-step synthesis of RfOEG under Mitsunobu conditions. RfNTA introduces specific binding of protein at the fluorous-aqueous interface, which concentrates and orients proteins at the interface, even in the presence of other surfactants. We then applied this approach to the crystallization of a his-tagged membrane protein, Reaction Center from Rhodobacter sphaeroides, performed 2400 crystallization trials, and showed that this approach can increase the range of crystal-producing conditions, the success rate at a given condition, the rate of nucleation, and the quality of the crystal formed.

  16. Synthesis and characterization of aromatic self-assembled monolayers containing methylene and ethyleneglycol entities by means of sum-frequency generation spectroscopy

    International Nuclear Information System (INIS)

    We use infrared-visible sum-frequency generation (SFG) spectroscopy in order to investigate the adsorption properties on Pt(111) of molecules having CH3-C6H4-(O-CH2-CH2) n-O-(CH2) m-SH as general chemical formula. We synthesized three molecules defined by the values m = 5 n = 4, m = 11 n = 4, m = 11 n = 8 and characterized them by Nuclear Magnetic Resonance spectroscopy. Thanks to spectroscopic measurements, we show that these molecules build self-assembled monolayers on Pt(111). First, the weak SFG signals arising from the ad-layer indicate low order and surface coverage of the substrate by these molecules. Next, the vibrational fingerprints of the aforementioned molecules are determined between 2825 and 3125 cm-1 and the observed SFG spectral features are ascribed on the basis of the analysis of shorter and simpler molecules (1-dodecanethiol, 4-methylbenzenethiol and CH3-C6H4-O-(CH2)11-SH) also adsorbed on Pt(111). The occurrence of methylene vibration modes indicates a significant amount of chain defects whatever the n and m numbers are. Finally, the identification of a particular vibration mode, characteristic of the aromatic ring, enables us to qualitatively discuss the effect of the number of methylene and ethylene glycol entities on its orientation. More precisely, higher these numbers, more tilted (with respect to the substrate normal) the aromatic ring plane is

  17. Interfacial engineering of self-assembled monolayer modified semi-roll-to-roll planar heterojunction perovskite solar cells on flexible substrates

    DEFF Research Database (Denmark)

    Gu, Zhuowei; Zuo, Lijian; Larsen-Olsen, Thue Trofod;

    2015-01-01

    The morphologies of the perovskite (e.g. CH3NH3PbI3) layer are demonstrated to be critically important for highly efficient perovskite solar cells. This work applies 3-aminopropanoic acid as a self-assembled monolayer (C3-SAM) on a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT......:PSS) hole transport layer (HTL) to modify the crystallinity and coverage of the CH3NH3PbI3 Cl-x(x) film, resulting in a much smoother perovskite surface morphology together with a PCE increase from 9.7% to 11.6%. Since all fabrication steps of these inverted structure devices are carried out under low...... temperature conditions (processing temperature <120 degrees C), it is possible to employ this method on flexible polymer substrates using roll-coating for the layer deposition. The roll-coated perovskite film on C3-SAM modified PEDOT:PSS presents a similar trend of improvement and results in enhanced PCE from...

  18. Hydroxamation of gold surface via in-situ layer-by-layer functionalization of cysteamine self-assembled monolayer: Preparation and electrochemical characterization

    International Nuclear Information System (INIS)

    A new, simple, and easy method for introducing hydroxamic acid group onto the surface of polycrystalline gold electrode by means of in-situ layer-by-layer functionalization is described. The fabrication was performed in a four-step method: (i) modification of gold by cysteamine self-assembled monolayer, Au-CA SAM, (ii) activation of nitrilotriacetic acid (NTA) by 1-ethyl-3(3-(dimethylamino)propyl)carbodiimide (EDC) and N-hydroxysuccinimide (NHS), (iii) immobilization of activated NTA onto Au-CA to form Au-CA-NTA, and (iv) conversion of the remaining activated carboxylic acid groups of Au-CA-NTA (terminals) to hydroxamic acid groups by using hydroxylamine hydrochloride (HAH) to form Au-CA-NDHA modified electrode. The resulting modified electrode was successfully tested for accumulation of zirconium ion (Zr(IV)) from an aqueous acidic solution. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were used to trace the events in each step, characterize the surface, determine the surface pKas, and find the affinity of the prepared electrode towards the Zr(IV). Surface pKas equal to 6.5 and 5.5 were estimated for Au-CA-NTA, and Au-CA-NDHA SAM electrodes, respectively. These values allowed estimating the charge-state of the surface at any pHs. The modified surface showed a large affinity for selective accumulation of Zr(IV) from acidic solution

  19. Impediment to heterogeneous electron transfer reactions of redox-active species by alkanedithiol self-assembled monolayers with and without an adlayer of Au nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Minli Yang; Zhanjun Zhang [Chinese Academy of Sciences, Beijing (China). Graduate School, Department of Chemistry

    2004-11-01

    The impediment of heterogeneous electron transfer (ET) reactions of several electroactive species by alkanedithiol self-assembled monolayers (SAMs) and those covered with Au nanoparticles was investigated. It was found that, when densely packed 1,6-hexanedithiol and 1,9-nonanedithiol SAMs were formed with and without adsorbed gold nanoparticles, Fe(CN){sub 6}{sup 3-} reduction became extremely sluggish. The attachment of Au nanoparticles does not appear to improve the electronic communication between the solution species and the underlying Au electrode surface. On the other hand, Ru(NH{sub 3}){sub 6}{sup 3+} and ferrocenecarboxylic acid both exhibited quasi-reversible redox waves at these surfaces. The variation of impediment were attributed to the different electron transfer mechanisms for these redox species. The adsorption of Au nanoparticles onto alkanedithiol SAMs was estimated by flow injection quartz crystal microbalance (FI-QCM), showing a rapid adsorption process. Amounts of Au nanoparticles did not vary between the two different alkanedithiols. Finally, we quantified the adsorption of Au nanoparticles at the QCM crystal modified with a 1,9-nonanedithiol SAM in air. A surface coverage of 2.56% was obtained. (author)

  20. Impediment to heterogeneous electron transfer reactions of redox-active species by alkanedithiol self-assembled monolayers with and without an adlayer of Au nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Yang Minli [Department of Chemistry, Graduate School, Chinese Academy of Sciences, Beijing 100039 (China); Zhang Zhanjun [Department of Chemistry, Graduate School, Chinese Academy of Sciences, Beijing 100039 (China)]. E-mail: zhangzj@gscas.ac.cn

    2004-11-01

    The impediment of heterogeneous electron transfer (ET) reactions of several electroactive species by alkanedithiol self-assembled monolayers (SAMs) and those covered with Au nanoparticles was investigated. It was found that, when densely packed 1,6-hexanedithiol and 1,9-nonanedithiol SAMs were formed with and without adsorbed gold nanoparticles, Fe(CN){sub 6}{sup 3-} reduction became extremely sluggish. The attachment of Au nanoparticles does not appear to improve the electronic communication between the solution species and the underlying Au electrode surface. On the other hand, Ru(NH{sub 3}){sub 6}{sup 3+} and ferrocenecarboxylic acid both exhibited quasi-reversible redox waves at these surfaces. The variation of impediment were attributed to the different electron transfer mechanisms for these redox species. The adsorption of Au nanoparticles onto alkanedithiol SAMs was estimated by flow injection quartz crystal microbalance (FI-QCM), showing a rapid adsorption process. Amounts of Au nanoparticles did not vary between the two different alkanedithiols. Finally, we quantified the adsorption of Au nanoparticles at the QCM crystal modified with a 1,9-nonanedithiol SAM in air. A surface coverage of 2.56% was obtained.

  1. A Single-Level Tunnel Model to Account for Electrical Transport through Single Molecule- and Self-Assembled Monolayer-based Junctions

    Science.gov (United States)

    Garrigues, Alvar R.; Yuan, Li; Wang, Lejia; Mucciolo, Eduardo R.; Thompon, Damien; Del Barco, Enrique; Nijhuis, Christian A.

    2016-05-01

    We present a theoretical analysis aimed at understanding electrical conduction in molecular tunnel junctions. We focus on discussing the validity of coherent versus incoherent theoretical formulations for single-level tunneling to explain experimental results obtained under a wide range of experimental conditions, including measurements in individual molecules connecting the leads of electromigrated single-electron transistors and junctions of self-assembled monolayers (SAM) of molecules sandwiched between two macroscopic contacts. We show that the restriction of transport through a single level in solid state junctions (no solvent) makes coherent and incoherent tunneling formalisms indistinguishable when only one level participates in transport. Similar to Marcus relaxation processes in wet electrochemistry, the thermal broadening of the Fermi distribution describing the electronic occupation energies in the electrodes accounts for the exponential dependence of the tunneling current on temperature. We demonstrate that a single-level tunnel model satisfactorily explains experimental results obtained in three different molecular junctions (both single-molecule and SAM-based) formed by ferrocene-based molecules. Among other things, we use the model to map the electrostatic potential profile in EGaIn-based SAM junctions in which the ferrocene unit is placed at different positions within the molecule, and we find that electrical screening gives rise to a strongly non-linear profile across the junction.

  2. Synthesis and characterization of a fatty acid self-assembled monolayer on CeO2 nanoparticles: to explore solution-state property of a SAM

    International Nuclear Information System (INIS)

    Decanoic acid self-assembled monolayer (SAM) in the quasi-crystalline state was prepared on the surface of the cubic CeO2 nanoparticles (6.5 ± 1.1 nm) by hydrothermal synthesis. The purification method to obtain quasi-crystalline SAM without residual (free) decanoic acid was developed. The SAM was carefully washed (purified) and characterized carefully by FT-IR, TG, DSC, and NMR. The obtained results showed that good agreement with the property of the dry state SAM. The solution state properties of the SAM were also examined by the CeO2 nanoparticles. It turned out that the quasi-crystalline SAM could be swollen by its good solvents, cyclohexane, and chloroform; however, the quasi-crystalline SAM showed that a size exclusion effect to the solvent, trans-decalin. In addition, it turned out that the molecular motion of the decanoic acids in the SAM was highly restricted even in the swollen state depending on the distance from the grafting point to the CeO2 surface. The strong osmosis was also observed. The solvent molecules were not easily released from the SAM even after the solvent molecules outside of the SAM were frozen.

  3. Nanostructured materials based on the integration of ferrocenyl-tethered dendrimer and redox proteins on self-assembled monolayers: an efficient biosensor interface

    Energy Technology Data Exchange (ETDEWEB)

    Frasconi, Marco; Deriu, Daniela; Mazzei, Franco [Department of Chemistry and Drug Technologies, Sapienza University of Rome, Piazzale Aldo Moro, 500185 Rome (Italy); D' Annibale, Andrea, E-mail: franco.mazzei@uniroma1.it [Department of Chemistry, Sapienza University of Rome, Piazzale Aldo Moro, 500185 Rome (Italy)

    2009-12-16

    In this paper we report the use of ferrocenyl-tethered dendrimer (Fc-D) as an electrode modifier supported by a self-assembled monolayer coated gold surface. The pretreatment of electrodes with Fc-D allows the covalent immobilization of glucose oxidase. The resulting integrated hybrid system provides electrical contact between the redox center of the enzyme and the electrode, and improves the overall bioelectrocatalyzed oxidation of glucose. Cyclic voltammetry combined with surface plasmon resonance (SPR) is used to investigate the redox-induced orientation changes of ferrocene-tethered dendrimers and the optimal electrical wiring of the enzyme, depending on the length of the alkyl chain of the ferrocene-tethered groups. The amount of substrate controls the steady-state concentration ratio of Fc/Fc{sup +} in the film composition. Therefore, the SPR spectrum of the film is controlled by the reversible change in the refractive index of the enzyme-integrated redox film. The proposed method demonstrates a new procedure for developing a stable amperometric redox enzyme-based sensor by designing a new nanostructured material that control the biosensing performance.

  4. Nanostructured materials based on the integration of ferrocenyl-tethered dendrimer and redox proteins on self-assembled monolayers: an efficient biosensor interface

    Science.gov (United States)

    Frasconi, Marco; Deriu, Daniela; D'Annibale, Andrea; Mazzei, Franco

    2009-12-01

    In this paper we report the use of ferrocenyl-tethered dendrimer (Fc-D) as an electrode modifier supported by a self-assembled monolayer coated gold surface. The pretreatment of electrodes with Fc-D allows the covalent immobilization of glucose oxidase. The resulting integrated hybrid system provides electrical contact between the redox center of the enzyme and the electrode, and improves the overall bioelectrocatalyzed oxidation of glucose. Cyclic voltammetry combined with surface plasmon resonance (SPR) is used to investigate the redox-induced orientation changes of ferrocene-tethered dendrimers and the optimal electrical wiring of the enzyme, depending on the length of the alkyl chain of the ferrocene-tethered groups. The amount of substrate controls the steady-state concentration ratio of Fc/Fc+ in the film composition. Therefore, the SPR spectrum of the film is controlled by the reversible change in the refractive index of the enzyme-integrated redox film. The proposed method demonstrates a new procedure for developing a stable amperometric redox enzyme-based sensor by designing a new nanostructured material that control the biosensing performance.

  5. Experimental Investigation of Microbially Induced Corrosion of Test Samples and Effect of Self-Assembled Hydrophobic Monolayers. Exposure of Test Samples to Continuous Microbial Cultures, Chemical Analysis, and Biochemical Studies

    Energy Technology Data Exchange (ETDEWEB)

    Laurinavichius, K.S.

    1998-09-30

    The study of biocorrosion of aluminum and beryllium samples were performed under conditions of continuous fermentation of thermophilic anaerobic microorganisms of different groups. This allowed us to examine the effect of various types of metabolic reactions of reduction-oxidation proceeding at different pH and temperatures under highly reduced conditions on aluminum and beryllium corrosion and effect of self-assembled hydrophobic monolayers.

  6. Controlling the reproducibility of Coulomb blockade phenomena for gold nanoparticles on an organic monolayer/silicon system.

    Science.gov (United States)

    Caillard, L; Sattayaporn, S; Lamic-Humblot, A-F; Casale, S; Campbell, P; Chabal, Y J; Pluchery, O

    2015-02-13

    Two types of highly ordered organic layers were prepared on silicon modified with an amine termination for binding gold nanoparticles (AuNPs). These two grafted organic monolayers (GOMs), consisting of alkyl chains with seven or 11 carbon atoms, were grafted on oxide-free Si(111) surfaces as tunnel barriers between the silicon electrode and the AuNPs. Three kinds of colloidal AuNPs were prepared by reducing HAuCl4 with three different reactants: citrate (Turkevich synthesis, diameter ∼16 nm), ascorbic acid (diameter ∼9 nm), or NaBH4 (Natan synthesis, diameter ∼7 nm). Scanning tunnel spectroscopy (STS) was performed in a UHV STM at 40 K, and Coulomb blockade behaviour was observed. The reproducibility of the Coulomb behavior was analysed as a function of several chemical and physical parameters: size, crystallinity of the AuNPs, influence of surrounding surfactant molecules, and quality of the GOM/Si interface (degree of oxidation after the full processing). Samples were characterized with scanning tunneling microscope, STS, atomic force microscope, Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy (XPS), and high resolution transmission electronic microscope. We show that the reproducibility in observing Coulomb behavior can be as high as ∼80% with the Natan synthesis of AuNPs and GOMs with short alkyl chains. PMID:25611611

  7. Interactions of gaseous HNO3 and water with individual and mixed alkyl self-assembled monolayers at room temperature

    Czech Academy of Sciences Publication Activity Database

    Nishino, N.; Hollingsworth, S. A.; Stern, A. C.; Roeselová, Martina; Tobias, D. J.; Finlayson-Pitts, B. J.

    2014-01-01

    Roč. 16, č. 6 (2014), s. 2358-2367. ISSN 1463-9076 R&D Projects: GA MŠk ME09064 Institutional support: RVO:61388963 Keywords : organic surface * molecular dynamics * nitric acid deprotonation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.493, year: 2014

  8. Cholesterol strongly affects the organization of lipid monolayers studied as models of the milk fat globule membrane: Condensing effect and change in the lipid domain morphology.

    Science.gov (United States)

    Murthy, Appala Venkata Ramana; Guyomarc'h, Fanny; Paboeuf, Gilles; Vié, Véronique; Lopez, Christelle

    2015-10-01

    The biological membrane that surrounds the milk fat globules exhibits phase separation of polar lipids that is poorly known. The objective of this study was to investigate the role played by cholesterol in the organization of monolayers prepared as models of the milk fat globule membrane (MFGM). Differential scanning calorimetry and X-ray diffraction experiments allowed characterization of the gel to liquid crystalline phase transition temperature of lipids, Tm ~35°C, in vesicles prepared with a MFGM lipid extract. For temperature below Tm, atomic force microscopy revealed phase separation of lipids at 30 mN·m(-1) in Langmuir-Blodgett monolayers of the MFGM lipid extract. The high Tm lipids form liquid condensed (LC) domains that protrude by about 1.5 nm from the continuous liquid expanded (LE) phase. Cholesterol was added to the MFGM extract up to 30% of polar lipids (cholesterol/milk sphingomyelin (MSM) molar ratio of 50/50). Compression isotherms evidenced the condensing effect of the cholesterol onto the MFGM lipid monolayers. Topography of the monolayers showed a decrease in the area of the LC domains and in the height difference H between the LC domains and the continuous LE phase, as the cholesterol content increased in the MFGM lipid monolayers. These results were interpreted in terms of nucleation effects of cholesterol and decrease of the line tension between LC domains and LE phase in the MFGM lipid monolayers. This study revealed the major structural role of cholesterol in the MFGM that could be involved in biological functions of this interface (e.g. mechanisms of milk fat globule digestion). PMID:26087463

  9. Simple direct formation of self-assembled N-heterocyclic carbene monolayers on gold and their application in biosensing.

    Science.gov (United States)

    Crudden, Cathleen M; Horton, J Hugh; Narouz, Mina R; Li, Zhijun; Smith, Christene A; Munro, Kim; Baddeley, Christopher J; Larrea, Christian R; Drevniok, Benedict; Thanabalasingam, Bheeshmon; McLean, Alastair B; Zenkina, Olena V; Ebralidze, Iraklii I; She, Zhe; Kraatz, Heinz-Bernhard; Mosey, Nicholas J; Saunders, Lisa N; Yagi, Akiko

    2016-01-01

    The formation of organic films on gold employing N-heterocyclic carbenes (NHCs) has been previously shown to be a useful strategy for generating stable organic films. However, NHCs or NHC precursors typically require inert atmosphere and harsh conditions for their generation and use. Herein we describe the use of benzimidazolium hydrogen carbonates as bench stable solid precursors for the preparation of NHC films in solution or by vapour-phase deposition from the solid state. The ability to prepare these films by vapour-phase deposition permitted the analysis of the films by a variety of surface science techniques, resulting in the first measurement of NHC desorption energy (158±10 kJ mol(-1)) and confirmation that the NHC sits upright on the surface. The use of these films in surface plasmon resonance-type biosensing is described, where they provide specific advantages versus traditional thiol-based films. PMID:27585494

  10. White organic light-emitting devices based on blue fluorescent dye combined with dual sub-monolayer

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Huishan, E-mail: yanghuishan1697@163.com

    2013-10-15

    White organic light-emitting devices have been realized by using highly blue fluorescent dye 4,4′-Bis(2,2-diphenyl-ethen-1-yl)-4,4′-di-(tert-butyl)phenyl(p-TDPVBi) and [2-methyl-6-[2-(2, 3,6,7-tetrahydro-1H, red fluorescent dye 5H-benzo[ij] quinolizin-9-yl) ethenyl]-4H-pyran-4-ylidene] propane-dinitrile(DCM2), together with well known green fluorescent dye quinacridone (QAD). The fabrication of multilayer WOLEDs did not involve the hard-to-control doping process. The structure of the device is ITO/m-MTDATA (45 nm)/NPB(8 nm)/p-TDPVBi(15 nm)/DCM2(x nm)/Alq{sub 3} (5 nm)/QAD(y nm)/Alq{sub 3}(55 nm)/LiF(1 nm)/Al, where 4,4′,4′′-tris{N,-(3-methylphenyl)-N-phenylamine}triphenylamine (m-MTDATA) acts as a hole injection layer, N,N′-bis-(1-naphthyl)-N, N′-diphenyl-1, 1′-biph-enyl-4, 4′-diamine (NPB) acts as a hole transport layer, p-TDPVBi acts as a blue emitting layer, DCM2 acts as a red emitting layer, QAD acts as a green emitting layer, tris-(8-hydroxyquinoline) aluminum (Alq{sub 3}) acts as an electron transport layer, and WOLEDs of devices A, B, C and D are different in layer thickness of DCM2 and QAD, respectively. To change the thickness of dual sub-monolayer DCM2 and QAD, the WOLEDs were obtained. When x, y=0.05, 0.1, the Commission Internationale de 1’Eclairage (CIE) coordinates of the device change from (0.4458, 0.4589) at 3 V to (0.3137, 0.3455) at 12 V that are well in the white region, and the color temperature and color rendering index were 5348 K and 85 at 8 V, respectively. Its maximum luminance was 35260 cd/m{sup 2} at 12 V, and maximum current efficiency and maximum power efficiency were 13.54 cd/A at 12 V and 6.68 lm/W at 5 V, respectively. Moreover, the current efficiency is largely insensitive to the applied voltage. The electroluminescence intensity of white EL devices varied only little at deferent dual sub-monolayer. Device D exhibited relatively high color rendering index (CRI) in the range of 88–90, which was essentially

  11. White organic light-emitting devices based on blue fluorescent dye combined with dual sub-monolayer

    International Nuclear Information System (INIS)

    White organic light-emitting devices have been realized by using highly blue fluorescent dye 4,4′-Bis(2,2-diphenyl-ethen-1-yl)-4,4′-di-(tert-butyl)phenyl(p-TDPVBi) and [2-methyl-6-[2-(2, 3,6,7-tetrahydro-1H, red fluorescent dye 5H-benzo[ij] quinolizin-9-yl) ethenyl]-4H-pyran-4-ylidene] propane-dinitrile(DCM2), together with well known green fluorescent dye quinacridone (QAD). The fabrication of multilayer WOLEDs did not involve the hard-to-control doping process. The structure of the device is ITO/m-MTDATA (45 nm)/NPB(8 nm)/p-TDPVBi(15 nm)/DCM2(x nm)/Alq3 (5 nm)/QAD(y nm)/Alq3(55 nm)/LiF(1 nm)/Al, where 4,4′,4′′-tris{N,-(3-methylphenyl)-N-phenylamine}triphenylamine (m-MTDATA) acts as a hole injection layer, N,N′-bis-(1-naphthyl)-N, N′-diphenyl-1, 1′-biph-enyl-4, 4′-diamine (NPB) acts as a hole transport layer, p-TDPVBi acts as a blue emitting layer, DCM2 acts as a red emitting layer, QAD acts as a green emitting layer, tris-(8-hydroxyquinoline) aluminum (Alq3) acts as an electron transport layer, and WOLEDs of devices A, B, C and D are different in layer thickness of DCM2 and QAD, respectively. To change the thickness of dual sub-monolayer DCM2 and QAD, the WOLEDs were obtained. When x, y=0.05, 0.1, the Commission Internationale de 1’Eclairage (CIE) coordinates of the device change from (0.4458, 0.4589) at 3 V to (0.3137, 0.3455) at 12 V that are well in the white region, and the color temperature and color rendering index were 5348 K and 85 at 8 V, respectively. Its maximum luminance was 35260 cd/m2 at 12 V, and maximum current efficiency and maximum power efficiency were 13.54 cd/A at 12 V and 6.68 lm/W at 5 V, respectively. Moreover, the current efficiency is largely insensitive to the applied voltage. The electroluminescence intensity of white EL devices varied only little at deferent dual sub-monolayer. Device D exhibited relatively high color rendering index (CRI) in the range of 88–90, which was essentially voltage

  12. Electrically tunable organic-inorganic hybrid polaritons with monolayer WS2

    OpenAIRE

    Flatten, Lucas C.; Coles, David M.; He, Zhengyu; Lidzey, David G.; Taylor, Robert A.; Warner, Jamie H.; Smith, Jason M.

    2016-01-01

    Exciton-polaritons are quasiparticles consisting of a linear superposition of photonic and excitonic states, offering potential for a range of nonlinear optical devices. The excitonic component of the polariton gives rise to nonlinear behaviour, such that the different types of exciton found in organic materials (Frenkel) and inorganic materials (Wannier-Mott) are expected to produce polaritons with different properties. A hybrid polariton state provides a potential technological route toward...

  13. Assembly and magneto-electrical characterization of hybrid organic-inorganic systems

    OpenAIRE

    Gang, Tian

    2011-01-01

    Organic building blocks are increasingly applied in current nanoelectronics research and development. In this thesis, the assembly and magneto-electrical characterization of several hybrid organic-inorganic magnetically active systems were described. Several molecular approaches were developed to assemble magnetic nanoparticles on various substrates with controllable density. This is considered as a step forward towards nanoparticle based hybrid spintronics devices. An electron interferometer...

  14. Detection of Tetrodotoxins in Puffer Fish by a Self-Assembled Monolayer-Based Immunoassay and Comparison with Surface Plasmon Resonance, LC-MS/MS, and Mouse Bioassay.

    Science.gov (United States)

    Reverté, Laia; de la Iglesia, Pablo; del Río, Vanessa; Campbell, Katrina; Elliott, Christopher T; Kawatsu, Kentaro; Katikou, Panagiota; Diogène, Jorge; Campàs, Mònica

    2015-11-01

    The increasing occurrence of puffer fish containing tetrodotoxin (TTX) in the Mediterranean could represent a major food safety risk for European consumers and threaten the fishing industry. The work presented herein describes the development of a new enzyme linked immunosorbent assay (mELISA) based on the immobilization of TTX through dithiol monolayers self-assembled on maleimide plates, which provides an ordered and oriented antigen immobilization and favors the antigen-antibody affinity interaction. The mELISA was found to have a limit of detection (LOD) of TTX of 0.23 mg/kg of puffer fish matrix. The mELISA and a surface plasmon resonance (SPR) immunosensor previously developed were employed to establish the cross-reactivity factors (CRFs) of 5,6,11-trideoxy-TTX, 5,11-deoxy-TTX, 11-nor-TTX-6-ol, and 5,6,11-trideoxy-4-anhydro-TTX, as well as to determine TTX equivalent contents in puffer fish samples. Results obtained by both immunochemical tools were correlated (R(2) = 0.977). The puffer fish samples were also analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS), and the corresponding CRFs were applied to the individual TTX contents. Results provided by the immunochemical tools, when compared with those obtained by LC-MS/MS, showed a good degree of correlation (R(2) = 0.991 and 0.979 for mELISA and SPR, respectively). The mouse bioassay (MBA) slightly overestimated the CRF adjusted TTX content of samples when compared with the data obtained from the other techniques. The mELISA has been demonstrated to be fit for the purpose for screening samples in monitoring programs and in research activities. PMID:26424329

  15. Comparing the performances of electrochemical sensors using p-aminophenol redox cycling by different reductants on gold electrodes modified with self-assembled monolayers

    International Nuclear Information System (INIS)

    Highlights: • Performances of p-AP redox cycling using different reductants on gold surface are compared. • Background current decreases in order of hydrazine, Na2SO3, NaBH4, NADH, cysteamine, and TCEP. • Chemical reaction rate with QI increases in order of NADH, TCEP, and cysteamine. • NADH, TCEP and cysteamine are suitable for p-AP redox cycling on gold electrode. -- Abstract: p-Aminophenol (p-AP) redox cycling using chemical reductants is one strategy for developing sensitive electrochemical sensors. However, most of the reported reductants are only used on indium-tin oxide (ITO) electrodes but not gold electrodes due to the high background current caused by the oxidation reaction of the reductants on the highly electrocatalytic gold electrodes. Therefore, new strategies and/or reductants are in demand for expanding the application of p-AP redox cycling on gold electrodes. In this work, we compared the performances of several reductants in p-AP redox cycling on self-assembled monolayers (SAMs)-modified gold electrodes. Among the tested reagents, nicotinamide adenine dinucleotide (NADH), tris(2-carboxyethyl)phosphine (TCEP) and cysteamine were demonstrated to be suitable for p-AP redox cycling on the alkanethiol-modified gold electrodes because of their low background current. The rate of chemical reaction between reductants and p-quinone imine (QI, the electrochemically oxidized product of p-AP) increases in the order of NADH −1 was achieved. We believe that our work will be valuable for the development of electrochemical sensors using p-AP redox cycling on gold electrodes

  16. The use of mixed self-assembled monolayers as a strategy to improve the efficiency of carbamate detection in environmental monitoring

    International Nuclear Information System (INIS)

    We report a simple strategy to obtain an efficient enzymatic bioelectrochemical device, in which the enzyme acetylcholinesterase (AChE) was immobilized on gold electrodes functionalized with mixed self-assembled monolayer (SAMmix) of 11-mercaptoundecanoic acid (11-MUA) and 2-mercaptoethanol (C2OH). Development of the modified electrodes included the chemical adsorption of SAMmix on gold surface followed by immersion in AChE solution, resulting in the final Au/SAMmix/AChE configuration. For comparison, the electrochemical performance of Au/11-MUA/AChE and Au/C2OH/AChE electrodes were also investigated. The performance of the modified electrodes toward acetylthiocholine hydrolysis was investigated via cyclic voltammetry and chronoamperometric measurements, revealing a fast increase in anodic current with a well-defined peak upon addition of acetylthiocholine iodide to the electrolytic solution. The anodic currents for Au/SAMmix/AChE electrodes were significantly higher than those for Au/11-MUA/AChE and Au/C2OH/AChE electrodes. The Au/SAMmix/AChE architecture provided by the SAMmix surface promoted a high oxidation current of thiocholine at 0.31 V without the need of electron mediators. The chronoamperometric biosensor developed here provided a linear response to carbaryl in the concentration range of 0 to 1.75 μM. The detection limit and quantification values for carbaryl were found to be 3.45 × 10−10 M and 1.15 × 10−9 M, respectively. Michaelis–Menten kinetics, KMapp, of 0.46 mM was obtained, indicating that the electrode architecture employed is advantageous for fabrication of enzymatic devices via physical adsorption process with improvement of the biocatalytic properties.

  17. Improving Light Extraction of Organic Light-Emitting Devices by Attaching Nanostructures with Self-Assembled Photonic Crystal Patterns

    Directory of Open Access Journals (Sweden)

    Kai-Yu Peng

    2014-01-01

    Full Text Available A single-monolayered hexagonal self-assembled photonic crystal (PC pattern fabricated onto polyethylene terephthalate (PET films by using simple nanosphere lithography (NSL method has been demonstrated in this research work. The patterned nanostructures acted as a scattering medium to extract the trapped photons from substrate mode of optical-electronic device for improving the overall external quantum efficiency of the organic light-emitting diodes (OLEDs. With an optimum latex concentration, the distribution of self-assembled polystyrene (PS nanosphere patterns on PET films can be easily controlled by adjusting the rotation speed of spin-coater. After attaching the PS nanosphere array brightness enhancement film (BEF sheet as a photonic crystal pattern onto the device, the luminous intensity of OLEDs in the normal viewing direction is 161% higher than the one without any BEF attachment. The electroluminescent (EL spectrum of OLEDs with PS patterned BEF attachment also showed minor color offset and superior color stabilization characteristics, and thus it possessed the potential applications in all kinds of display technology and solid-state optical-electronic devices.

  18. Probing the Orientation and Conformation of alpha-Helix and beta-Strand Model Peptides on Self-Assembled Monolayers Using Sum Frequency Generation and NEXAFS Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Weidner, T.; Apte, J; Gamble, L; Castner, D

    2010-01-01

    The structure and orientation of amphiphilic {alpha}-helix and {beta}-strand model peptide films on self-assembled monolayers (SAMs) have been studied with sum frequency generation (SFG) vibrational spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The {alpha}-helix peptide is a 14-mer, and the {beta}-strand is a 15-mer of hydrophilic lysine and hydrophobic leucine residues with hydrophobic periodicities of 3.5 and 2, respectively. These periodicities result in the leucine side chains located on one side of the peptides and the lysine side chains on the other side. The SAMs were prepared from the assembly of either carboxylic acid- or methyl-terminated alkyl thiols onto gold surfaces. For SFG studies, the deuterated analog of the methyl SAM was used. SFG vibrational spectra in the C-H region of air-dried peptides films on both SAMs exhibit strong peaks near 2965, 2940, and 2875 cm{sup -1} related to ordered leucine side chains. The orientation of the leucine side chains was determined from the phase of these features relative to the nonresonant gold background. The relative phase for both the {alpha}-helix and {beta}-strand peptides showed that the leucine side chains were oriented away from the carboxylic acid SAM surface and oriented toward the methyl SAM surface. Amide I peaks observed near 1656 cm{sup -1} for the {alpha}-helix peptide confirm that the secondary structure is preserved on both SAMs. Strong linear dichroism related to the amide {pi}* orbital at 400.8 eV was observed in the nitrogen K-edge NEXAFS spectra for the adsorbed {beta}-strand peptides, suggesting that the peptide backbones are oriented parallel to the SAM surface with the side chains pointing toward or away from the interface. For the {alpha}-helix the dichroism of the amide {pi}* is significantly weaker, probably because of the broad distribution of amide bond orientations in the {alpha}-helix secondary structure.

  19. Controlling nucleation of monolayer WSe2 during metal-organic chemical vapor deposition growth

    Science.gov (United States)

    Eichfeld, Sarah M.; Oliveros Colon, Víctor; Nie, Yifan; Cho, Kyeongjae; Robinson, Joshua A.

    2016-06-01

    Tungsten diselenide (WSe2) is a semiconducting, two-dimensional (2D) material that has gained interest in the device community recently due to its electronic properties. The synthesis of atomically thin WSe2, however, is still in its infancy. In this work we elucidate the requirements for large selenium/tungsten precursor ratios and explain the effect of nucleation temperature on the synthesis of WSe2 via metal-organic chemical vapor deposition (MOCVD). The introduction of a nucleation-step prior to growth demonstrates that increasing nucleation temperature leads to a transition from a Volmer–Weber to Frank–van der Merwe growth mode. Additionally, the nucleation step prior to growth leads to an improvement of WSe2 layer coverage on the substrate. Finally, we note that the development of this two-step technique may allow for improved control and quality of 2D layers grown via CVD and MOCVD processes.

  20. From self-organization to self-assembly: a new materialism?

    Science.gov (United States)

    Vincent, Bernadette Bensaude

    2016-09-01

    While self-organization has been an integral part of academic discussions about the distinctive features of living organisms, at least since Immanuel Kant's Critique of Judgement, the term 'self-assembly' has only been used for a few decades as it became a hot research topic with the emergence of nanotechnology. Could it be considered as an attempt at reducing vital organization to a sort of assembly line of molecules? Considering the context of research on self-assembly I argue that the shift of attention from self-organization to self-assembly does not really challenge the boundary between chemistry and biology. Self-assembly was first and foremost investigated in an engineering context as a strategy for manufacturing without human intervention and did not raise new perspectives on the emergence of vital organization itself. However self-assembly implies metaphysical assumptions that this paper tries to disentangle. It first describes the emergence of self-assembly as a research field in the context of materials science and nanotechnology. The second section outlines the metaphysical implications and will emphasize a sharp contrast between the ontology underlying two practices of self-assembly developed under the umbrella of synthetic biology. And unexpectedly, we shall see that chemists are less on the reductionist side than most synthetic biologists. Finally, the third section ventures some reflections on the kind of design involved in self-assembly practices. PMID:27325057

  1. Self-assembled honeycomb lattice in the monolayer of cyclic thiazyl diradical BDTDA (= 4,4‧-bis(1,2,3,5-dithiadiazolyl)) on Cu(111) with a zero-bias tunneling spectra anomaly

    Science.gov (United States)

    Yamamoto, Masayuki; Suizu, Rie; Dutta, Sudipta; Mishra, Puneet; Nakayama, Tomonobu; Sakamoto, Kazuyuki; Wakabayashi, Katsunori; Uchihashi, Takashi; Awaga, Kunio

    2015-12-01

    Scanning tunneling microscopy (STM) observation reveals that a cyclic thiazyl diradical, BDTDA (= 4,4‧-bis(1,2,3,5-dithiadiazolyl)), forms a well-ordered monolayer honeycomb lattice consisting of paramagnetic corners with unpaired electrons on a clean Cu(111) surface. This BDTDA lattice is commensurate with the triangular lattice of Cu(111), with the former being 3 × 3 larger than the latter. The formation of the BDTDA monolayer structure, which is significantly different from its bulk form, is attributed to an interaction with the metal surface as well as the intermolecular assembling forces. STM spectroscopy measurements on the BDTDA molecules indicate the presence of a characteristic zero-bias anomaly centered at the Fermi energy. The origin of this zero-bias anomaly is discussed in terms of the Dirac cones inherent to the honeycomb structure.

  2. Atomic force measurements of 16-mercaptohexadecanoic acid and its salt with CH{sub 3}, OH, and CONHCH{sub 3} functionalized self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Morales-Cruz, Angel L. [Chemistry Department, University of Puerto Rico, Rio Piedras Campus, San Juan 00931-3346 (Puerto Rico); Tremont, Rolando [Chemistry Department, University of Puerto Rico, Rio Piedras Campus, San Juan 00931-3346 (Puerto Rico); Martinez, Ramon [Chemistry Department, University of Puerto Rico, Rio Piedras Campus, San Juan 00931-3346 (Puerto Rico); Roman-tilde ach, Rodolfo [Chemistry Department, University of Puerto Rico, Mayagueez Campus, Mayagueez 00681-5000 (Puerto Rico); Cabrera, Carlos R. [Chemistry Department, University of Puerto Rico, Rio Piedras Campus, San Juan 00931-3346 (Puerto Rico)]. E-mail: ccabrera@goliath.cnnet.clu.edu

    2005-03-15

    Chemical and mechanical properties of different compounds can be elucidated by measuring fundamental forces such as adhesion, attraction and repulsion, between modified surfaces by means of atomic force microscopy (AFM) in force mode calibration. This work presents a combination of AFM, self-assembled monolayers (SAMs), and crystallization techniques to study the forces of interaction between excipients and active ingredients used in pharmaceutical formulations. SAMs of 16-mercaptohexadecanoate, which represent magnesium stereate, were used to modify the probe tip, whereas CH{sub 3}-, OH- and CONHCH{sub 3}-functional SAMs were formed on a gold-coated mica substrate, and used as examples of the surfaces of lactose and theophylline. The crystals of lactose and theophylline were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The modification of gold surfaces with 16-mercaptohexadecanoate, 10-mercapto-1-decanol (OH-functional SAM), 1-decanethiol (CH{sub 3}-functional) and N-methyl-11-mercaptoundecanamide (CONHCH{sub 3}-functional SAM) was studied by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and Fourier transform-infrared spectroscopy (FT-IR) in specular reflectance mode. XPS and AES results of the modified surfaces showed the presence of sulfur binding, and kinetic energies that correspond to the presence of 10-mercapto-1-decanol, 1-decanethiol, N-methyl-11-mercaptoundecanamide and the salt of 16-mercaptohexadecanoic acid. The absorption bands in the IR spectra further confirm the modification of the gold-coated substrates with these compounds. Force versus distance measurements were performed between the modified tip and the modified gold-coated mica substrates. The mean adhesion forces between the COO{sup -}Ca{sup 2+} functionalized tip and the CH{sub 3}-, OH-, and CONHCH{sub 3}-modified substrates were determined to be 4.5, 8.9 and 6.3 nN, respectively. The magnitude of the adhesion force (ion

  3. Atomic force measurements of 16-mercaptohexadecanoic acid and its salt with CH3, OH, and CONHCH3 functionalized self-assembled monolayers

    International Nuclear Information System (INIS)

    Chemical and mechanical properties of different compounds can be elucidated by measuring fundamental forces such as adhesion, attraction and repulsion, between modified surfaces by means of atomic force microscopy (AFM) in force mode calibration. This work presents a combination of AFM, self-assembled monolayers (SAMs), and crystallization techniques to study the forces of interaction between excipients and active ingredients used in pharmaceutical formulations. SAMs of 16-mercaptohexadecanoate, which represent magnesium stereate, were used to modify the probe tip, whereas CH3-, OH- and CONHCH3-functional SAMs were formed on a gold-coated mica substrate, and used as examples of the surfaces of lactose and theophylline. The crystals of lactose and theophylline were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The modification of gold surfaces with 16-mercaptohexadecanoate, 10-mercapto-1-decanol (OH-functional SAM), 1-decanethiol (CH3-functional) and N-methyl-11-mercaptoundecanamide (CONHCH3-functional SAM) was studied by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and Fourier transform-infrared spectroscopy (FT-IR) in specular reflectance mode. XPS and AES results of the modified surfaces showed the presence of sulfur binding, and kinetic energies that correspond to the presence of 10-mercapto-1-decanol, 1-decanethiol, N-methyl-11-mercaptoundecanamide and the salt of 16-mercaptohexadecanoic acid. The absorption bands in the IR spectra further confirm the modification of the gold-coated substrates with these compounds. Force versus distance measurements were performed between the modified tip and the modified gold-coated mica substrates. The mean adhesion forces between the COO-Ca2+ functionalized tip and the CH3-, OH-, and CONHCH3-modified substrates were determined to be 4.5, 8.9 and 6.3 nN, respectively. The magnitude of the adhesion force (ion-dipole) interaction between the modified tip and

  4. Preparation of a well-defined amino-terminated self-assembled monolayer and copper microlines on a polyimide substrate covered with an oxide nanoskin.

    Science.gov (United States)

    Hozumi, Atsushi; Asakura, Shuichi; Fuwa, Akio; Shirahata, Naoto; Kameyama, Tetsuya

    2005-08-30

    A well-ordered, uniform amino (NH(2))-terminated organosilane self-assembled monolayer (SAM) was prepared on a polyimide (PI) substrate, the surface of which had silica-like reactivity. First, through chemical vapor deposition of 1,3,5,7-tetramethylcyclotetrasiloxane and subsequent photooxidation using 172 nm vacuum ultraviolet light, an extremely thin silicon dioxide (SiO(2)) layer about 1 nm thick, which we call an "oxide nanoskin" (ONS), was prepared on a PI substrate. Due to the presence of this ONS layer, the PI surface's properties became almost identical with those of Si covered with native oxide (SiO(2)/Si) without any marked change in surface morphology, as evidenced by zeta-potential measurements, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Next, this ONS-covered PI (ONS/PI) surface was exposed to vapor of a 12.5 vol % solution of N-(6-aminohexyl)(3-aminopropyl)trimethoxysilane (AHAPS) molecules diluted with absolute toluene. On the basis of contact angle analysis, the surface energy of this AHAPS/ONS/PI sample was mostly consistent with that of a SiO(2)/Si substrate covered with an AHAPS-SAM (AHAPS/SiO(2)/Si). On the other hand, the surface energy of an AHAPS-treated PI (AHAPS/PI) substrate was much smaller than that of the AHAPS/ONS/PI substrate due to insufficient surface coverage by the AHAPS molecules. This was also confirmed by lateral force microscopy using photolithographically micropatterned samples. Fabricated micropatterns composed of AHAPS- and SiO(2)-covered regions were clearly imaged on the AHAPS/ONS/PI substrate through their difference in friction, while the friction contrast of the micropatterned AHAPS/PI substrate was unclear. This marked difference in packing density of the AHAPS molecules had a direct influence on the adsorption behavior of palladium colloids and subsequent electroless plating of copper (Cu). As confirmed by AFM and XPS, metallization proceeded only on the AHAPS-covered regions, while

  5. From metal-organic squares to porous zeolite-like supramolecular assemblies

    KAUST Repository

    Wang, Shuang

    2010-12-29

    We report the synthesis, structure, and characterization of two novel porous zeolite-like supramolecular assemblies, ZSA-1 and ZSA-2, having zeolite gis and rho topologies, respectively. The two compounds were assembled from functional metal-organic squares (MOSs) via directional hydrogen-bonding interactions and exhibited permanent microporosity and thermal stability up to 300 °C. © 2010 American Chemical Society.

  6. Strongly Dichroic Organic Films via Controlled Assembly of Modular Aromatic Charge-Transfer Liquid Crystals.

    Science.gov (United States)

    Bé, Ariana Gray; Tran, Cheryl; Sechrist, Riley; Reczek, Joseph J

    2015-10-01

    The formation of highly anisotropic organic thin films based on the designed self-assembly of mixed-stack liquid crystals is reported. A series of alkoxyanthracene donors is combined in a modular fashion with a naphthalenediimide acceptor to generate new charge-transfer columnar liquid crystals. Materials characterization and molecular modeling provides insight into structure-function relationships in these organic materials that lead to the striking bulk dichroic properties of certain molecular assemblies. PMID:26375256

  7. Organic self-assembled layer-by-layer thin films for second-order nonlinear optics

    Science.gov (United States)

    Guzy, Matthew T.

    Layer-by-layer deposition techniques were used to fabricate films with second order nonlinear optical (NLO) properties. These materials are key to the development of electro-optic modulators used in fiber optic communication systems. Performance benefits and lower manufacturing costs are driving the development of organic NLO materials as replacements for inorganic crystalline materials such as lithium niobate. The layer-by-layer deposition technique in which polyelectrolytes are deposited on a surface by electrostatic effects is called the Ionically Self-Assembled Monolayer or ISAM method. The role of the optically inactive polycation's structure on deposition and chromophore orientation was studied by fabricating films with several different polycations. While the specific interactions responsible for chromophore orientation in ISAM films remains unclear, hydrogen bonding and electrostatic effects are ruled out as the sole sources of orientation. The highest values of chi(2) were observed under pH conditions that resulted in flat and thin layers. The relationship between pH and the optical homogeneity of the film was also explored. Deposition of polymers under pH conditions in which the polymer chains were aggregated in solution results in films that are not suitable for use in devices. In this work, a new layer-by-layer deposition technique was developed. Coined hybrid deposition, it relies on covalent bonds and electrostatic interactions for film fabrication. Optically inactive polyamines were used as sources of positive charges and as binding sites with optically active low molecular weight chromophores functionalized with a reactive triazine ring and negative charged sulfonate groups. Polar ordering of the chromophores was obtained when the deposition was done under conditions in which covalent bonding was the preferred attachment mechanism for the chromophore molecules. pH conditions in which electrostatic attachment dominated resulted in poorer orientation

  8. A generalized network evolution model and self-organization theory on community assembly

    Directory of Open Access Journals (Sweden)

    WenJun Zhang

    2015-09-01

    Full Text Available Community assembly is the process that species grow and interact to establish a community. In present study, a generalized, rule-based network evolution model, CommAssembly, for community assembly was proposed. The model is based on difference equations with different number of species in different stages of evolution. It consists of pioneer rule, invasion and growth rule, extinction rule, connection (flow rule and termination rule, etc. Species invades, grows in, or quits the community following specific rules. In addition, I proposed the self-organization theory on community assembly. In this theory, I think that community assembly is a self-organization process. In terms of the model proposed, the practical community can spontaneously adjust its A(t, and guarantee itself to evolve in a natural way. Temporal dynamics and species composition of community depend on species composition of species pool, between-species interactions, intrinsic growth of species, environmental capacity (resource availability, and the probability, strength and history of invasions, etc. The invasion, establishment, growth, and extinction of species follow a series of rules. Community assembly can be best described and modeled with self-organization approaches. The model provides the basis to build self-organization models of community assembly.

  9. Symmetric organization of self-assembled carbon nitride

    International Nuclear Information System (INIS)

    A scheme for creating 'flower-like' nanostructures of carbon nitride is described that involves the self-assembly of nanocrystals following laser ablation of a solid graphite target immersed in aqueous ammonia solution. The primary nanocrystals possess rod-like symmetry, and then self-assemble upon drying to form nanoleaf or nanopetal shaped structures. Samples were characterized using x-ray diffraction (XRD), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM), x-ray photoelectron microscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The analyses confirmed their composition to be consistent with that of crystalline β-phase carbon nitride. The morphologies of the carbon nitride nanostructures depended strongly on the synthesis conditions and upon the conditions under which the aqueous suspension of ablated particles were dried

  10. 铜表面硬脂酸自组装膜的制备及耐腐蚀性能%Preparation and corrosion resistance of self-assembled stearic acid monolayer on copper surface

    Institute of Scientific and Technical Information of China (English)

    余相仁; 李淑英; 范洪强; 钱备; 张琳

    2011-01-01

    A stearic acid (STA) self-assembled monolayer (SAM) was prepared on the surface of Cu(OH)2 nanowire/ hierarchical CuO structure by self-assembly technology. The optimal STA concentration and self-assembly time for SAM formation were studied via electrochemical impedance spectroscopy. The corrosion inhibition performance of stearic acid self-assembled monolayer on copper electrode in a 0.1 mol/L NaCl solution was examined by polarization curve measurement and cyclic voltammetry. The results showed that the stearic acid self-assembled monolayer prepared on CuO/Cu(OH)2 electrode by immersing it in a 8 mmol/L stearic acid solution for 24 h can remarkably improve the corrosion resistance of the copper electrode. Compared with the bare copper electrode, the SAM-CuO/Cu(OH)2 electrode has a corrosion current density decreased by two orders of magnitude, and its inhibition efficiency is up to 98.81%.%应用自组装技术在Cu(OH)2纳米柱/CuO微花阶层结构表面制备硬脂酸自组装膜(SAM),运用电化学阻抗谱探讨了形成自组装膜的较佳浓度和自组装时间,通过极化曲线和循环伏安法考察了硬脂酸自组装膜在0.1 mol/L NaCl溶液中对铜电极的缓蚀性能.结果表明,当CuO/Cu(OH)2电极在8 mmol/L硬脂酸溶液中自组装24 h时,得到的硬脂酸自组装膜能显著提高铜电极的耐蚀性;与裸铜电极相比,SAM-CuO/Cu(OH)2电极的腐蚀电流降低了2个数量级,缓蚀效率达到98.81%.

  11. Highly mesoporous metal–organic framework assembled in a switchable solvent

    OpenAIRE

    PENG Li; Zhang, Jianling; Xue, Zhimin; Han, Buxing; Sang, Xinxin; Liu, Chengcheng; Yang, Guanying

    2014-01-01

    The mesoporous metal–organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal–organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal–organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal–organic fra...

  12. Bonus Organisms in High-Throughput Eukaryotic Whole-Genome Shorgun Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Pangilinan, Jasmyn; Shapiro, Harris; Tu, Hank; Platt, Darren

    2006-02-06

    The DOE Joint Genome Institute has sequenced over 50 eukaryotic genomes, ranging in size from 15 MB to 1.6 GB, over a wide range of organism types. In the course of doing so, it has become clear that a substantial fraction of these data sets contains bonus organisms, usually prokaryotes, in addition to the desired genome. While some of these additional organisms are extraneous contamination, they are sometimes symbionts, and so can be of biological interest. Therefore, it is desirable to assemble the bonus organisms along with the main genome. This transforms the problem into one of metagenomic assembly, which is considerably more challenging than traditional whole-genome shotgun (WGS) assembly. The different organisms will usually be present at different sequence depths, which is difficult to handle in most WGS assemblers. In addition, with multiple distinct genomes present, chimerism can produce cross-organism combinations. Finally, there is no guarantee that only a single bonus organism will be present. For example, one JGI project contained at least two different prokaryotic contaminants, plus a 145 KB plasmid of unknown origin. We have developed techniques to routinely identify and handle such bonus organisms in a high-throughput sequencing environment. Approaches include screening and partitioning the unassembled data, and iterative subassemblies. These methods are applicable not only to bonus organisms, but also to desired components such as organelles. These procedures have the additional benefit of identifying, and allowing for the removal of, cloning artifacts such as E.coli and spurious vector inclusions.

  13. Assembly and Folding of Twisted Baskets in Organic Solvents.

    Science.gov (United States)

    Pratumyot, Yaowalak; Chen, Shigui; Hu, Lei; Polen, Shane M; Hadad, Christopher M; Badjić, Jovica D

    2016-09-01

    A synthetic method for obtaining enantiopure and twisted baskets of type (P)-3 is described. These chiral cavitands were found to fold quinoline gates, at the rim of their twisted platform, in acetonitrile and give molecular capsules that assemble into large unilamellar vesicles. In a less polar dichloromethane, however, cup-shaped (P)-3 packed into vesicles but with the quinoline gates in an unfolded orientation. The ability of twisted baskets to form functional nanostructured materials could be of interest for building stereoselective sensors and catalysts. PMID:27513214

  14. Functional metal-organic framework based materials and assemblies

    OpenAIRE

    AMELOOT, Rob

    2011-01-01

    Porous solids, such as zeolites and activated carbons, are strategic materials because of the applications they imply. Recently, metal-organic frameworks (MOFs) were introduced as a novel class of porous and crystalline materials. The crystal lattice of these compounds is constructed by coordination bonds between nodes of metal ions and multidentate organic ligands. Because of the wide range of metal ions and ligands that can be combined as MOF building blocks, a vast variety of crystal struc...

  15. Organic Solvents Mediate Self-assembly of GAV-9 Peptide on Mica Surface

    Institute of Scientific and Technical Information of China (English)

    Hai LI; Feng ZHANG; Yi ZHANG; Jianhua HE; Jun HU

    2007-01-01

    Self-assembly of peptides into fibrils and other morphologies has attracted much attention in many fields, especially in nanofabrication, pathology and biochemistry. In this paper, self-assembly of GAV-9 peptide in organic solvents, ethanol and acetone, was investigated using atomic force microscopy (AFM)and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). The results indicated that GAV-9 self- assembled into various nanostructures in both solvents after deposited and evaporated on mica. Fibrils with β-sheet conformation were observed in both solvents when the peptide concentration was higher than 280 μM. However, ordered fibrils with β-sheet conformation were formed in ethanol, but not in acetone, with a peptide concentration ranging from 7 μM to 28 μM. We attribute the formation of various nanostructures to the different physicochemical properties of the polar organic solvents on the self-assembly of GAV-9 peptide.

  16. Influences of hydrophilic and hydrophobic substituents on the organization of supramolecular assemblies of porphyrin derivatives formed at the air/water interface

    International Nuclear Information System (INIS)

    Monolayers and Langmuir-Blodgett (LB) films of several kinds of porphyrin derivatives that have different substituted alkyl chain length, chain numbers and central metals were studied by π-A isotherms, UV-Vis, polarized UV-Vis and fluorescence spectroscopy and low angle X-ray diffractometry (LAXD). The orientation angles of porphyrin rings and alkyl chains were derived from the polarized UV-Vis spectra and LAXD patterns of the monolayers or LB films, respectively. The rings of the freebase porphyrins with different alkyl chain length or number have similar orientation angles in the films due to the same hydrophilic groups on the rings, and those of metal porphyrins have different orientation angles from each other. The orientation of the alkyl chains is related to the special positions of the chains on the rings and the orientation of the rings. The influences of the hydrophilicity of the hydrophilic groups and the alkyl chain number and length on the organization of the supramolecular assemblies of the porphyrin derivatives were discussed

  17. Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface.

    Science.gov (United States)

    Tinel, Liselotte; Rossignol, Stéphanie; Ciuraru, Raluca; George, Christian

    2015-04-01

    Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface. Liselotte Tinel, Stéphanie Rossignol, Raluca Ciuraru and Christian George Université de Lyon, Université Lyon 1, CNRS, UMR5256, IRCELYON, Institut de recherches sur la catalyse et l'environnement de Lyon, Villeurbanne, F-69626, France Recently the surface microlayer (SML) has received growing attention for its role in the deposition and emission of trace gases. This SML is presumably a highly efficient environment for photochemical reactions thanks to its physical and chemical properties, showing enrichment in chromophores [1]. Still, little is known about the possible photochemical processes that could influence the emission and deposition of volatile organic compounds (VOCs) in the SML. A recent study underlines the particularity of the presence of an organic microlayer, showing enhanced formation of peptide bonds at the air-water interface, although this reaction is thermodynamically disfavoured in bulk water [2]. Also, emissions of small gas phase carbonyl compounds formed photochemically by dissolved organic matter have been measured above natural water and glyoxal, for example, measured above the open ocean is thought to be photochemically produced [3, 4]. This study presents the results of a set of laboratory studies set up in order to better understand the role of the SML in the photochemical production of VOCs. Recently, our group has shown the formation of VOCs by light driven reactions in a small quartz reactor (14mL) containing aqueous solutions of humic acids (HA) in the presence of an organic (artificial or natural) microlayer [5]. The main VOCs produced were oxidized species, such as aldehydes, ketones and alcohols, as classically can be expected by the oxidation of the organics present at the interface initiated by triplet excited chromophores present in the HA. But also alkenes, dienes, including isoprene and

  18. Supramolecular Assembly of Calcium Metal - Organic Frameworks with Structural Transformation

    Czech Academy of Sciences Publication Activity Database

    Liang, P.-Ch.; Liu, H.-K.; Yeh, Ch.-T.; Lin, Ch.-H.; Zima, Vítězslav

    2011-01-01

    Roč. 11, č. 3 (2011), 699-708. ISSN 1528-7483 R&D Projects: GA ČR GA203/08/0208 Institutional research plan: CEZ:AV0Z40500505 Keywords : metal - organic frameworks * calcium * structure Subject RIV: CA - Inorganic Chemistry Impact factor: 4.720, year: 2011

  19. An introduction to ultrathin organic films from Langmuir-Blodgett to self-assembly

    CERN Document Server

    Ulman, Abraham

    1991-01-01

    The development of oriented organic monomolecular layers by the Langmuir-Blodgett (LB) and self-assembly (SA) techniques has led researchers toward their goal of assembling individual molecules into highly ordered architectures. Thus the continually growing contribution of LB and SA systems to the chemistry and physics of thin organic films is widely recognized. Equally well-known is the difficulty in keeping up to date with the burgeoning multidisciplinary research in this area. Dr. Ulman provides a massive survey of the available literature. The book begins with a section on analytical tools

  20. Assembly, molecular organization, and membrane-binding properties of development-specific septins.

    Science.gov (United States)

    Garcia, Galo; Finnigan, Gregory C; Heasley, Lydia R; Sterling, Sarah M; Aggarwal, Adeeti; Pearson, Chad G; Nogales, Eva; McMurray, Michael A; Thorner, Jeremy

    2016-02-29

    Septin complexes display remarkable plasticity in subunit composition, yet how a new subunit assembled into higher-order structures confers different functions is not fully understood. Here, this question is addressed in budding yeast, where during meiosis Spr3 and Spr28 replace the mitotic septin subunits Cdc12 and Cdc11 (and Shs1), respectively. In vitro, the sole stable complex that contains both meiosis-specific septins is a linear Spr28-Spr3-Cdc3-Cdc10-Cdc10-Cdc3-Spr3-Spr28 hetero-octamer. Only coexpressed Spr3 and Spr28 colocalize with Cdc3 and Cdc10 in mitotic cells, indicating that incorporation requires a Spr28-Spr3 protomer. Unlike their mitotic counterparts, Spr28-Spr3-capped rods are unable to form higher-order structures in solution but assemble to form long paired filaments on lipid monolayers containing phosphatidylinositol-4,5-bisphosphate, mimicking presence of this phosphoinositide in the prospore membrane. Spr28 and Spr3 fail to rescue the lethality of a cdc11Δ cdc12Δ mutant, and Cdc11 and Cdc12 fail to restore sporulation proficiency to spr3Δ/spr3Δ spr28Δ/spr28Δ diploids. Thus, specific meiotic and mitotic subunits endow septin complexes with functionally distinct properties. PMID:26929450

  1. Fundamentals and application of ordered molecular assemblies to affinity biosensing.

    Science.gov (United States)

    Matharu, Zimple; Bandodkar, Amay Jairaj; Gupta, Vinay; Malhotra, Bansi Dhar

    2012-02-01

    Organization of biomolecules in two/three dimensional assemblies has recently aroused much interest in nanobiotechnology. In this context, the development of techniques for controlling spatial arrangement and orientation of the desired molecules to generate highly-ordered nanostructures in the form of a mono/multi layer is considered highly significant. The studies of monolayer films to date have focused on three distinct methods of preparation: (i) the Langmuir-Blodgett (LB) technique, involving the transfer of a monolayer assembled at the gas-liquid interface; (ii) self-assembly at the liquid-solid interface, based on spontaneous adsorption of desired molecules from a solution directly onto a solid surface; and (iii) Layer-by-layer (LBL) self-assembly at a liquid-solid interface, based on inter-layer electrostatic attractions for fabrication of multilayers. A variety of monolayers have been utilized to fabricate biomolecular electronic devices including biosensors. The composition of a monolayer based matrix has been found to influence the activity(ies) of biomolecule(s). We present comprehensive and critical analysis of ordered molecular assemblies formed by LB and self-assembly with potential applications to affinity biosensing. This critical review on fundamentals and application of ordered molecular assemblies to affinity biosensing is likely to benefit researchers working in this as well as related fields of research (401 references). PMID:22105315

  2. Electrophoretic assembly of organic molecules and composites for electrochemical supercapacitors.

    Science.gov (United States)

    Su, Y; Zhitomirsky, I

    2013-02-15

    Electrophoretic deposition (EPD) method has been developed for the fabrication of 1-pyrenebutyric acid (PBH) films from aqueous solutions. The films can be deposited at constant voltage or potentiodynamic conditions. The method allowed the formation of 0.1-2 μm thick films, containing needle-shape PBH particles. The deposition mechanism involved the electrophoresis, pH decrease at the anode surface, charge neutralization and formation of insoluble PBH films. The film morphology and shape of the PBH particles are controlled by the π-π stacking mechanism of the polyaromatic PBH molecules. The important finding was the possibility of controlled EPD of multiwalled carbon nanotubes (MWCNTs) using PBH as a charging, dispersing and film forming agent. It was found that at low voltages or low PBH concentrations the deposits contained mainly MWCNT. The increase in the deposition voltage or/and PBH concentration resulted in co-deposition of MWCNT and needle-shape PBH particles. The new approach to the deposition of MWCNT was used for the fabrication of composite MnO(2)-MWCNT films for electrodes of electrochemical supercapacitors, which showed a specific capacitance of 250 F g(-1). The EPD method developed in this investigation paves the way for the deposition of other small organic molecules and composites and their applications in new materials and devices, utilizing functional properties of the organic molecules, CNT, and other advanced materials. PMID:23141761

  3. Assembly of Human Organs from Stem Cells to Study Liver Disease

    Science.gov (United States)

    Handa, Kan; Matsubara, Kentaro; Fukumitsu, Ken; Guzman-Lepe, Jorge; Watson, Alicia; Soto-Gutierrez, Alejandro

    2015-01-01

    Recently, significant developments in the field of liver tissue engineering have raised new possibilities for the study of complex physiological and pathophysiological processes in vitro, as well as the potential to assemble entire organs for transplantation. Human-induced pluripotent stem cells have been differentiated into relatively functional populations of hepatic cells, and novel techniques to generate whole organ acellular three-dimensional scaffolds have been developed. In this review, we highlight the most recent advances in organ assembly regarding the development of liver tissue in vitro. We emphasize applications that involve multiple types of cells with a biomimetic spatial organization for which three-dimensional configurations could be used for drug development or to explain mechanisms of disease. We also discuss applications of liver organotypic surrogates and the challenges of translating the highly promising new field of tissue engineering into a proven platform for predicting drug metabolism and toxicity. PMID:24333262

  4. Supramolecular Langmuir monolayers and multilayered vesicles of self-assembling DNA–lipid surface structures and their further implications in polyelectrolyte-based cell transfections

    Energy Technology Data Exchange (ETDEWEB)

    Demirsoy, Fatma Funda Kaya [Ankara University, The Central Laboratory of The Institute of Biotechnology (Turkey); Eruygur, Nuraniye [Gazi University, Department of Pharmacognosy, Faculty of Pharmacy (Turkey); Süleymanoğlu, Erhan, E-mail: erhans@mail.ru [Gazi University, Department of Pharmaceutical Chemistry, Faculty of Pharmacy (Turkey)

    2015-01-15

    The basic interfacial characteristics of DNA–lipid recognitions have been studied. The complex structures of individual unbound DNA molecules and their binary and ternary complexes with zwitterionic lipids and divalent cations were followed by employing lipid monolayers at the air–liquid interfaces, as well as by performing various microscopic, spectroscopic, and thermodynamic measurements with multilayered vesicles. The pressure-area isotherms depicted that Mg{sup 2+}-ions increase the surface pressure of lipid films and thus give rise to electrostatic and hydrophobic lipid–DNA interactions in terms of DNA adsorption, adhesion, and compaction. These features were further approached by using multilamellar vesicles with a mean diameter of 850 nm, where a metal ion-directed nucleic acid compaction and condensation effects were shown. The data obtained show the effectiveness of Langmuir monolayers and lipid multilayers in studying nucleic acid–lipid recognitions. The data provide with further details and support previous reports on mainly structural features of these recognitions. Biomolecular surface recognition events were presented in direct link with spectral and thermodynamic features of lipid vesicle–polynucleotide complex formations. The results serve to build a theoretical model considering the use of neutral lipids in lipoplex designs as a polyelectrolyte alternatives to the currently employed cytotoxic cationic liposomes. The supramolecular structures formed and their possible roles in interfacial electrostatic and hydrophobic mechanisms of endosomal escape in relevant cell transfection assays are particularly emphasized.

  5. Self-Assembly, Guest Capture, and NMR Spectroscopy of a Metal-Organic Cage in Water

    Science.gov (United States)

    Go, Eun Bin; Srisuknimit, Veerasak; Cheng, Stephanie L.; Vosburg, David A.

    2016-01-01

    A green organic-inorganic laboratory experiment has been developed in which students prepare a self-assembling iron cage in D[subscript 2]O at room temperature. The tetrahedral cage captures a small, neutral molecule such as cyclohexane or tetrahydrofuran. [Superscript 1]H NMR analysis distinguishes captured and free guests through diagnostic…

  6. Assembly of Human Organs from Stem Cells to Study Liver Disease

    OpenAIRE

    Handa, Kan; Matsubara, Kentaro; Fukumitsu, Ken; Guzman-Lepe, Jorge; Watson, Alicia; Soto-Gutierrez, Alejandro

    2014-01-01

    Recently, significant developments in the field of liver tissue engineering have raised new possibilities for the study of complex physiological and pathophysiological processes in vitro, as well as the potential to assemble entire organs for transplantation. Human-induced pluripotent stem cells have been differentiated into relatively functional populations of hepatic cells, and novel techniques to generate whole organ acellular three-dimensional scaffolds have been developed. In this review...

  7. Fabrication and study of organic solar cells composed of P3HT/PCBM blend with monolayers of P(VDF-TrFE)

    Science.gov (United States)

    Carrasco, Hector; Vedrine, Josee; Luis Rosa Collaboration

    2014-03-01

    Organic polymeric materials that are conducting provide an added facility in device fabrication, particularly in solar cell applications. In this work, we study the electrical and morphological properties of bulk hetero-junction solar cells fabricated with poly (3-hexylthiophene-2,5-diyl) (P3HT) and phenyl-C61-butyric-acid-methyl ester (PCBM) blends, when a monolayer of the ferroelectric polymer poly[(vinylidenefluoride-co-trifluoroethylene] [P(VDF-TrFE)] is deposited between ITO conductor and bulk heterojunction. The bulk heterojunction and ferroelectric films are annealed at 140 °C under vacuum atmosphere to improve their crystallinity, which may assist in enhanced charge transfer. We measure device photovoltaic properties with changing blend thickness, while keeping the ferroelectric layer constant.. The current-voltage characteristics are measured and compared for the different film thicknesses. AFM techniques are used to analyze their morphological and conductive properties.

  8. Formation of n-Alkyl Monolayers by Organomercury Deposition on Gold

    Czech Academy of Sciences Publication Activity Database

    Scholz, F.; Kaletová, Eva; Stensrud, Elizabeth; Ford, W. E.; Kohutová, Anna; Mucha, Malgorzata; Stibor, Ivan; Michl, Josef; Wrochem von, F.

    2013-01-01

    Roč. 4, č. 16 (2013), s. 2624-2629. ISSN 1948-7185 R&D Projects: GA ČR GA203/07/1619; GA ČR GA203/09/0705 EU Projects: European Commission(XE) 213382 - FUNMOL; European Commission(XE) 227756 - DIPOLAR ROTOR ARRAY Institutional support: RVO:61388963 Keywords : self-assembled monolayer s * ray photoelectron-spectroscopy * altitudinal molecular rotors Subject RIV: CC - Organic Chemistry Impact factor: 6.687, year: 2013

  9. Expanded Porphyrin-Anion Supramolecular Assemblies: Environmentally Responsive Sensors for Organic Solvents and Anions.

    Science.gov (United States)

    Zhang, Zhan; Kim, Dong Sub; Lin, Chung-Yon; Zhang, Huacheng; Lammer, Aaron D; Lynch, Vincent M; Popov, Ilya; Miljanić, Ognjen Š; Anslyn, Eric V; Sessler, Jonathan L

    2015-06-24

    Porphyrins have been used frequently to construct supramolecular assemblies. In contrast, noncovalent ensembles derived from expanded porphyrins, larger congeners of naturally occurring tetrapyrrole macrocycles, are all but unknown. Here we report a series of expanded porphyrin-anion supramolecular assemblies. These systems display unique environmentally responsive behavior. Addition of polar organic solvents or common anions to the ensembles leads to either a visible color change, a change in the fluorescence emission features, or differences in solubility. The actual response, which could be followed easily by the naked eye, was found to depend on the specifics of the assembly, as well as the choice of analyte. Using the ensembles of this study, it proved possible to differentiate between common solvents, such as diethyl ether, THF, ethyl acetate, acetone, alcohol, acetonitrile, DMF, and DMSO, identify complex solvent systems, as well as distinguish between the fluoride, chloride, bromide, nitrate, and sulfate anions. PMID:25965790

  10. Reactive self-assembled monolayers on flat and nanoparticle surfaces, and their application in soft and scanning probe lithographic nanofabrication technologies

    NARCIS (Netherlands)

    Li, Xue-Mei; Huskens, Jurriaan; Reinhoudt, David N.

    2004-01-01

    Self-assembly is an interesting process both for its biological relevance and because it provides a novel approach to complex structures having nanometer-scale dimensions. These structures are difficult or impossible to prepare by traditional methods. In this article, a general review on the use of

  11. Dissecting the function and assembly of acentriolar microtubule organizing centers in Drosophila cells in vivo.

    Directory of Open Access Journals (Sweden)

    Janina Baumbach

    2015-05-01

    Full Text Available Acentriolar microtubule organizing centers (aMTOCs are formed during meiosis and mitosis in several cell types, but their function and assembly mechanism is unclear. Importantly, aMTOCs can be overactive in cancer cells, enhancing multipolar spindle formation, merotelic kinetochore attachment and aneuploidy. Here we show that aMTOCs can form in acentriolar Drosophila somatic cells in vivo via an assembly pathway that depends on Asl, Cnn and, to a lesser extent, Spd-2--the same proteins that appear to drive mitotic centrosome assembly in flies. This finding enabled us to ablate aMTOC formation in acentriolar cells, and so perform a detailed genetic analysis of the contribution of aMTOCs to acentriolar mitotic spindle formation. Here we show that although aMTOCs can nucleate microtubules, they do not detectably increase the efficiency of acentriolar spindle assembly in somatic fly cells. We find that they are required, however, for robust microtubule array assembly in cells without centrioles that also lack microtubule nucleation from around the chromatin. Importantly, aMTOCs are also essential for dynein-dependent acentriolar spindle pole focusing and for robust cell proliferation in the absence of centrioles and HSET/Ncd (a kinesin essential for acentriolar spindle pole focusing in many systems. We propose an updated model for acentriolar spindle pole coalescence by the molecular motors Ncd/HSET and dynein in conjunction with aMTOCs.

  12. Dissecting the function and assembly of acentriolar microtubule organizing centers in Drosophila cells in vivo.

    Science.gov (United States)

    Baumbach, Janina; Novak, Zsofia Anna; Raff, Jordan W; Wainman, Alan

    2015-05-01

    Acentriolar microtubule organizing centers (aMTOCs) are formed during meiosis and mitosis in several cell types, but their function and assembly mechanism is unclear. Importantly, aMTOCs can be overactive in cancer cells, enhancing multipolar spindle formation, merotelic kinetochore attachment and aneuploidy. Here we show that aMTOCs can form in acentriolar Drosophila somatic cells in vivo via an assembly pathway that depends on Asl, Cnn and, to a lesser extent, Spd-2--the same proteins that appear to drive mitotic centrosome assembly in flies. This finding enabled us to ablate aMTOC formation in acentriolar cells, and so perform a detailed genetic analysis of the contribution of aMTOCs to acentriolar mitotic spindle formation. Here we show that although aMTOCs can nucleate microtubules, they do not detectably increase the efficiency of acentriolar spindle assembly in somatic fly cells. We find that they are required, however, for robust microtubule array assembly in cells without centrioles that also lack microtubule nucleation from around the chromatin. Importantly, aMTOCs are also essential for dynein-dependent acentriolar spindle pole focusing and for robust cell proliferation in the absence of centrioles and HSET/Ncd (a kinesin essential for acentriolar spindle pole focusing in many systems). We propose an updated model for acentriolar spindle pole coalescence by the molecular motors Ncd/HSET and dynein in conjunction with aMTOCs. PMID:26020779

  13. Development of Self-Assembled Supramolecular Catalysts and Their Applications to Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    Shiro IKEGAMI

    2005-01-01

    @@ 1Introduction In modern synthetic organic chemistry, the development of efficient reagent or catalyst recycling systems is regarded as one of the most important topics. We have previously reported a self-assembled process between poly(N-isopropylacrylamide) (PNIPAAm) based polymer ligands and an inorganic species[1]. This process afforded a networked supramolecular complex where the polymers are cross-linked together by the inorganic species. Thus obtained complex was insoluble in water and worked as an efficient triphase catalyst.

  14. Self-assembled hybrid metal oxide base catalysts prepared by simply mixing with organic modifiers

    OpenAIRE

    Tamura, Masazumi; Kishi, Ryota; Nakagawa, Yoshinao; Tomishige, Keiichi

    2015-01-01

    Multidentate materials formed by simply mixing heterogeneous and homogeneous components are promising for construction of versatile active sites on the surface of heterogeneous compounds, however, to the best of our knowledge, there are no reports on such materials. Self-assembly of hetero-hybrid catalytic materials occurs when heterogeneous catalysts having adjacent Lewis acid-Lewis base sites are mixed with an organic modifier that contains at least two Lewis base functional groups. Here we...

  15. Selective Surface Acoustic Wave-Based Organophosphorus Sensor Employing a Host-Guest Self-Assembly Monolayer of β-Cyclodextrin Derivative.

    Science.gov (United States)

    Pan, Yong; Mu, Ning; Shao, Shengyu; Yang, Liu; Wang, Wen; Xie, Xiao; He, Shitang

    2015-01-01

    Self-assembly and molecular imprinting technologies are very attractive technologies for the development of artificial recognition systems and provide chemical recognition based on need and not happenstance. In this paper, we employed a b-cyclodextrin derivative surface acoustic wave (SAW) chemical sensor for detecting the chemical warfare agents (CWAs) sarin (O-Isoprophyl methylphosphonofluoridate, GB). Using sarin acid (isoprophyl hydrogen methylphosphonate) as an imprinting template, mono[6-deoxy-6-[(mercaptodecamethylene)thio

  16. Selective Surface Acoustic Wave-Based Organophosphorus Sensor Employing a Host-Guest Self-Assembly Monolayer of β-Cyclodextrin Derivative

    Directory of Open Access Journals (Sweden)

    Yong Pan

    2015-07-01

    Full Text Available Self-assembly and molecular imprinting technologies are very attractive technologies for the development of artificial recognition systems and provide chemical recognition based on need and not happenstance. In this paper, we employed a b-cyclodextrin derivative surface acoustic wave (SAW chemical sensor for detecting the chemical warfare agents (CWAs sarin (O-Isoprophyl methylphosphonofluoridate, GB. Using sarin acid (isoprophyl hydrogen methylphosphonate as an imprinting template, mono[6-deoxy-6-[(mercaptodecamethylenethio

  17. The supramolecular organization of self-assembling chlorosomal bacteriochlorophyll c, d, or e mimics.

    Science.gov (United States)

    Jochum, Tobias; Reddy, Chilla Malla; Eichhöfer, Andreas; Buth, Gernot; Szmytkowski, Jedrzej; Kalt, Heinz; Moss, David; Balaban, Teodor Silviu

    2008-09-01

    Bacteriochlorophylls (BChls) c, d, and e are the main light-harvesting pigments of green photosynthetic bacteria that self-assemble into nanostructures within the chlorosomes forming the most efficient antennas of photosynthetic organisms. All previous models of the chlorosomal antennae, which are quite controversially discussed because no single crystals could be grown so far from these organelles, involve a strong hydrogen-bonding interaction between the 3(1) hydroxyl group and the 13(1) carbonyl group. We have synthesized different self-assemblies of BChl c mimics having the same functional groups as the natural counterparts, that is, a hydroxyethyl substituent, a carbonyl group and a divalent metal atom ligated by a tetrapyrrole. These artificial BChl mimics have been shown by single crystal x-ray diffraction to form extended stacks that are packed by hydrophobic interactions and in the absence of hydrogen bonding. Time-resolved photoluminescence proves the ordered nature of the self-assembled stacks. FT-IR spectra show that on self-assembly the carbonyl frequency is shifted by approximately 30 cm(-1) to lower wavenumbers. From the FT-IR data we can infer the proximal interactions between the BChls in the chlorosomes consistent with a single crystal x-ray structure that shows a weak electrostatic interaction between carbonyl groups and the central zinc atom. PMID:18755898

  18. The structure of percolating lipid monolayers.

    Science.gov (United States)

    Risović, D; Frka, S; Kozarac, Z

    2012-05-01

    The lattice structure and in plane molecular organization of Langmuir monolayer of amphiphilic material is usually determined from grazing incidence X-ray diffraction (GIXD) or neutron reflectivity. Here we present results of a different approach for determination of monolayer lattice structure based on application of fractal analysis and percolation theory in combination with Brewster angle microscopy. The considerations of compressibility modulus and fractal dimension dynamics provide information on percolation threshold and consequently by application of percolation theory on the lattice structure of a monolayer. We have applied this approach to determine the monolayer lattice structures of single chain and double chain lipids. The compressibility moduli were determined from measured π-A isotherms and fractal dimensions from corresponding BAM images. The monolayer lattice structures of stearic acid, 1-hexadecanol, DPPC and DPPA, obtained in this way conform to the corresponding lattice structures determined previously by other authors using GIXD. PMID:22209411

  19. Combined atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and quartz crystal microbalance (QCM) studies of glucose oxidase (GOx) immobilised onto self-assembled monolayer on the gold film

    International Nuclear Information System (INIS)

    In fabrication of biosensors, self-assembled monolayers (SAM) are an attractive method of immobilising enzymes at electrode surface since it allows precise control over the amount and spatial distribution of the immobilized enzyme. The covalent attachment of glucose oxidase (GOx) to a carboxylic terminated SAM chemisorbed onto gold films was achieved via carbodiimide activation of the carboxylic acids to a reactive intermediate susceptible to nucleophilic attack by amines on free lysine chains of the enzyme. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and quartz crystal microbalance (QCM) measurements were used for characterisation of GOx modified gold surfaces. Tapping mode AFM studies have revealed that GOx molecules form slightly disordered arrays of pentagonal or hexagonal clusters. Observed features of immobilised GOx are distributed as a submonolayer on the SAM surface which has allowed visualisation of native and unfolded enzyme structure. The presence of the SAM and enzyme on the gold surface was detected by XPS spectroscopy. Spectra show typical peaks for the C 1s, O 1s and N 1s regions. A kinetic study of the adsorption of GOx onto activated SAM using in-situ QCM allowed determination the amount of immobilised GOx on the layer and consequently the optimal immobilisation conditions. Performance parameters of the biosensor such as sensitivity to glucose concentration as a function of enzyme loading were evaluated amperometrically using the redox mediator p-benzoquinone

  20. Scaling up self-assembly: bottom-up approaches to macroscopic particle organization.

    Science.gov (United States)

    Lash, M H; Fedorchak, M V; McCarthy, J J; Little, S R

    2015-07-28

    This review presents an overview of recent work in the field of non-Brownian particle self-assembly. Compared to nanoparticles that naturally self-assemble due to Brownian motion, larger, non-Brownian particles (d > 6 μm) are less prone to autonomously organize into crystalline arrays. The tendency for particle systems to experience immobilization and kinetic arrest grows with particle radius. In order to overcome this kinetic limitation, some type of external driver must be applied to act as an artificial "thermalizing force" upon non-Brownian particles, inducing particle motion and subsequent crystallization. Many groups have explored the use of various agitation methods to overcome the natural barriers preventing self-assembly to which non-Brownian particles are susceptible. The ability to create materials from a bottom-up approach with these characteristics would allow for precise control over their pore structure (size and distribution) and surface properties (topography, functionalization and area), resulting in improved regulation of key characteristics such as mechanical strength, diffusive properties, and possibly even photonic properties. This review will highlight these approaches, as well as discuss the potential impact of bottom-up macroscale particle assembly. The applications of such technology range from customizable and autonomously self-assembled niche microenvironments for drug delivery and tissue engineering to new acoustic dampening, battery, and filtration materials, among others. Additionally, crystals made from non-Brownian particles resemble naturally derived materials such as opals, zeolites, and biological tissue (i.e. bone, cartilage and lung), due to their high surface area, pore distribution, and tunable (multilevel) hierarchy. PMID:25947543

  1. Sum-frequency vibrational spectroscopy of a monolayer self-assembled on gold: interference between resonant and nonresonant contributions of nonlinear polarization

    Science.gov (United States)

    Tanaka, Yoshihito; Lin, S.; Aono, M.; Suzuki, T.

    The spectral profiles of sum-frequency signal from CH vibrational modes of octadecanethiol (ODT) self-assembled on gold have been studied for several optical configurations of incident beams. The observed spectra, generally of the shape of dispersion type, have been interpreted by the interference between the resonant contribution from the CH stretching modes of adsorbed molecules and the nonresonant contribution from the gold substrate. We have shown for the first time that the contribution from the zzz component of the resonant nonlinear susceptibility χzzz(R) is dominant in the observed resonant signals, whereas all of the ijk components contribute to the nonresonant signal. The transition frequencies and the relative amplitude of resonant signals are also determined for the CH3 vibrational modes of ODT on gold.

  2. Assembly of europium organic framework–gold nanoparticle composite thin films on silicon substrate

    International Nuclear Information System (INIS)

    Metal organic frameworks are a sub-class of coordination polymers and rapidly generating huge research interests in several technological areas. One of the emerging areas of their potential applications is the photovoltaics. The present study proposes the assembly of europium organic framework–gold nanoparticle nanocomposite thin film on silicon substrate. Microscopic, X-ray diffraction, surface area measurement and thermal studies have indicated the formation of the desired thin film. Spectral studies have been used to highlight their solid state optical property. Current–voltage studies have established semiconducting property of the above thin films. - Highlights: • Thin film of europium organic framework/gold nanoparticles is prepared on silicon. • Fairly homogeneous films with a roughness factor of 5–10 nm are obtained. • Above thin films offer solid-state photoluminescence and semiconducting properties

  3. Organization of Mitochondrial Gene Expression in Two Distinct Ribosome-Containing Assemblies

    Directory of Open Access Journals (Sweden)

    Kirsten Kehrein

    2015-02-01

    Full Text Available Mitochondria contain their own genetic system that provides subunits of the complexes driving oxidative phosphorylation. A quarter of the mitochondrial proteome participates in gene expression, but how all these factors are orchestrated and spatially organized is currently unknown. Here, we established a method to purify and analyze native and intact complexes of mitochondrial ribosomes. Quantitative mass spectrometry revealed extensive interactions of ribosomes with factors involved in all the steps of posttranscriptional gene expression. These interactions result in large expressosome-like assemblies that we termed mitochondrial organization of gene expression (MIOREX complexes. Superresolution microscopy revealed that most MIOREX complexes are evenly distributed throughout the mitochondrial network, whereas a subset is present as nucleoid-MIOREX complexes that unite the whole spectrum of organellar gene expression. Our work therefore provides a conceptual framework for the spatial organization of mitochondrial protein synthesis that likely developed to facilitate gene expression in the organelle.

  4. Assembly of europium organic framework–gold nanoparticle composite thin films on silicon substrate

    Energy Technology Data Exchange (ETDEWEB)

    Deep, Akash, E-mail: dr.akashdeep@gmail.com [Central Scientific Instruments Organisation (CSIR-CSIO), Sector 30 C, Chandigarh 160030 (India); Academy of Scientific and Innovative Research, CSIR-CSIO, Sector 30 C, Chandigarh 160030 (India); Kaur, Rajnish [Central Scientific Instruments Organisation (CSIR-CSIO), Sector 30 C, Chandigarh 160030 (India); Academy of Scientific and Innovative Research, CSIR-CSIO, Sector 30 C, Chandigarh 160030 (India); Kumar, Parveen [Central Scientific Instruments Organisation (CSIR-CSIO), Sector 30 C, Chandigarh 160030 (India); Kumar, Pawan; Paul, A.K. [Central Scientific Instruments Organisation (CSIR-CSIO), Sector 30 C, Chandigarh 160030 (India); Academy of Scientific and Innovative Research, CSIR-CSIO, Sector 30 C, Chandigarh 160030 (India)

    2014-08-28

    Metal organic frameworks are a sub-class of coordination polymers and rapidly generating huge research interests in several technological areas. One of the emerging areas of their potential applications is the photovoltaics. The present study proposes the assembly of europium organic framework–gold nanoparticle nanocomposite thin film on silicon substrate. Microscopic, X-ray diffraction, surface area measurement and thermal studies have indicated the formation of the desired thin film. Spectral studies have been used to highlight their solid state optical property. Current–voltage studies have established semiconducting property of the above thin films. - Highlights: • Thin film of europium organic framework/gold nanoparticles is prepared on silicon. • Fairly homogeneous films with a roughness factor of 5–10 nm are obtained. • Above thin films offer solid-state photoluminescence and semiconducting properties.

  5. Highly mesoporous metal-organic framework assembled in a switchable solvent

    Science.gov (United States)

    Peng, Li; Zhang, Jianling; Xue, Zhimin; Han, Buxing; Sang, Xinxin; Liu, Chengcheng; Yang, Guanying

    2014-07-01

    The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

  6. Does oxidation make the organic aerosol coatings more hydrophilic? Insight from molecular dynamics study of oxidized surfactant monolayers

    Czech Academy of Sciences Publication Activity Database

    Roeselová, Martina; Khabiri, Morteza; Cwiklik, Lukasz

    Praha: Česká aerosolová společnost, 2012 - (Vodička, P.; Zíková, N.), s. 51-54 ISBN 978-80-86186-40-5. [Výroční konference České aerosolové společnosti /13./. Třeboň (CZ), 25.10.2012-26.10.2012] R&D Projects: GA MŠk ME09064 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40400503 Keywords : atmospheric aerosols * organic coatings * hydrophilic * hydrophobic * oxidation Subject RIV: CF - Physical ; Theoretical Chemistry

  7. Probing the chemical structure of monolayer covalent-organic frameworks grown via Schiff-base condensation reactions.

    Science.gov (United States)

    Hu, Ya; Goodeal, Niall; Chen, Ying; Ganose, Alex M; Palgrave, Robert G; Bronstein, Hugo; Blunt, Matthew O

    2016-08-01

    Two-dimensional covalent-organic frameworks (2D-COFs) on surfaces offer a facile route to new 2D materials. Schiff-base condensation reactions have proven to be an effective fabrication route for such materials. We present scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) studies of porphyrin 2D-COFs grown at a solid-vapour interface. XPS shows that covalent links between porphyrins consist of a mixture of imines and hemiaminals, a non-conjugated intermediate in the Schiff-base condensation reaction. These results demonstrate that environmental conditions during growth can have an important impact on the chemical composition of Schiff-base 2D-COFs. PMID:27436064

  8. Electrochemical Impedance Immunosensor Based on Self-Assembled Monolayers for Rapid Detection of Escherichia coli O157:H7 with Signal Amplification Using Lectin

    Directory of Open Access Journals (Sweden)

    Zhanming Li

    2015-08-01

    Full Text Available Escherichia coli O157:H7 is a predominant foodborne pathogen with severe pathogenicity, leading to increasing attention given to rapid and sensitive detection. Herein, we propose an impedance biosensor using new kinds of screen-printed interdigitated microelectrodes (SPIMs and wheat germ agglutinin (WGA for signal amplification to detect E. coli O157:H7 with high sensitivity and time-efficiency. The SPIMs integrate the high sensitivity and short response time of the interdigitated electrodes and the low cost of the screen-printed electrodes. Self-assembling of bi-functional 3-dithiobis-(sulfosuccinimidyl-propionate (DTSP on the SPIMs was investigated and was proved to be able to improve adsorption quantity and stability of biomaterials. WGA was further adopted to enhance the signal taking advantage of the abundant lectin-binding sites on the bacteria surface. The immunosensor exhibited a detection limit of 102 cfu·mL−1, with a linear detection range from 102 to 107 cfu·mL−1 (r2 = 0.98. The total detection time was less than 1 h, showing its comparable sensitivity and rapid response. Furthermore, the low cost of one SPIM significantly reduced the detection cost of the biosensor. The biosensor may have great promise in food safety analysis and lead to a portable biosensing system for routine monitoring of foodborne pathogens.

  9. Self-Assembling Organic Micro-/Nano-Pillars on Gold and Glass Surfaces

    Directory of Open Access Journals (Sweden)

    Hai-Feng Ji

    2014-09-01

    Full Text Available In this work, we report the formation of a family of organic micro-/nano-pillars prepared from surface-assisted self-assembly processes and factors controlling the growth of the pillars. These acids include cyanuric acid (CA, 1,3,5-benzenetricarboxylic acid (TMA, 1,2,4,5-benzenetetracarboxylic acid (TA and 3,4,9,10-perylenetetracarboxylic acid (PTA. Aqueous solutions mixed with acids and melamine (M can be fine-tuned to prepare ordered micro-/nano-pillars on substrates, which can be further optimized for their applications

  10. Are Regional Organizations the 'Parties' in the United Nations General Assembly? Comments on a Misconception

    DEFF Research Database (Denmark)

    Burmester, Nicolas; Jankowski, Michael

    In the field of international relations, regional organizations (ROs) are not only assumed to play an important role in the regional context, but also on the international level. A growing number of studies analyze ROs’ voting behavior in the United Nations General Assembly (UNGA) in a similar way...... to the analyses of parties in national parliaments. In this paper, we reflect on the question whether ROs can be treated as ‘political party’-like entities. First, based on literature on political parties and legislative voting, we develop two criteria to evaluate ROs in the UNGA. Second, we analyze...

  11. A study on organized assemblies in the sodium alkylcarboxylate/ fatty alcohol/water systems

    Institute of Scientific and Technical Information of China (English)

    MAO, Mina; FU, Hong-Lanb; ZHU, Bu-Yaoa; HE, Xua; SHI, Hong-Taoa; HUANG, Jian-Bin

    2000-01-01

    The phase behavior and evolution of self-organized assembling sttructures in the sodium allkylcarboxylate/fatty alcohol systems were investigated by TEM. With increasing concentration of fatty alcohd, the micelles transform into lamellar- La phase, sponge L3 phase, multilamellar vesicle, and transform back to lamellar La phase. At higher alcohol concentration, a stable two aqueous phase coexisting region has been observed in this kind of systems after aged two months. Unilamellar vesicles were found both in two separated phases but the vesicle densi ty ofthe upper phase is much higher than that of the bottom phase.

  12. 2-Mercaptobenzothiazole monolayers on zinc and silver surfaces for anticorrosion

    International Nuclear Information System (INIS)

    Anticorrosive behaviors of 2-mercaptobenzothiazole (MBT) self-assembled monolayers (SAMs) on silver and zinc electrodes were comparatively studied by means of electrochemical impedance spectroscopy (EIS). The promising inhibition effect of the MBT for silver and zinc from corrosion had been confirmed. The adsorption geometries of MBT monolayers on zinc and silver electrodes were observed by surface enhanced Raman scattering (SERS) technique. The SERS spectra implied that monolayers of MBT could be self-assembled on Ag surface through S10 and N3 atoms and the molecular plane should be tilted with respect to the surface. On Zn surface, MBT molecules formed monolayers via both S atoms and the other moieties of the molecule away from the surface. From the in situ electrochemical SERS results it can be found that MBT monolayers on both Ag and Zn surfaces experienced the changes of adsorption fashions as the potential shifting to more negative direction

  13. Second-order nonlinear optical characteristics of nanoscale self-assembled multilayer organic films

    Science.gov (United States)

    Neyman, Patrick J.

    Ionically self-assembled monolayer (ISAM) films are typically an assemblage of oppositely charged polymers built layer by layer through Coulombic attraction utilizing an environmentally friendly process to form ordered structures that are uniform, molecularly smooth and physically robust. ISAM films have been shown to be capable of the noncentrosymmetric order requisite for a second-order nonlinear optical response with excellent temporal and thermal stability. However, such films fabricated with a nonlinear optical (NLO) polyanion result in significant cancellation of the chromophore orientations. This cancellation occurs by two mechanisms: competitive orientation due to the ionic bonding of the polymer chromophore with the subsequent polycation layer, and random orientation of the chromophores within the bulk of each polyanion layer. A reduction in film thickness accompanied by an increase in net polar ordering is one possible avenue to obtain the second-order susceptibility chi (2) necessary for practical application in electro-optic devices. In this thesis, we discuss the structural characteristics of ISAM films and explore a novel approach to obtain the desired characteristics for nonlinear optical response. This approach involves a hybrid covalent/ionic self-assembly technique which affords improved net dipole alignment and concentration of monomer chromophores in the film. This technique yields a substantial increase in chi(2) due to the preferential chromophore orientation being locked in place by a covalent bond to the preceding polycation layer. The films fabricated in this manner yield a chi(2) (56 x 10-9 esu) that substantially exceeds that of any known polymer-polymer ISAM film (˜0.3 x 10-9 esu). This covalent-hybrid ionically self-assembled multilayer (CHISAM) technique is demonstrated to result in films suitable for electro-optic devices, with measured electro-optic coefficient (14 pm/V) comparable to that of the inorganic crystal lithium niobate

  14. Fracton pairing mechanism for unconventional superconductors: Self-assembling organic polymers and copper-oxide compounds

    DEFF Research Database (Denmark)

    Milovanov, A.V.; Juul Rasmussen, J.

    2002-01-01

    Self-assembling organic polymers and copper-oxide compounds are two classes of unconventional superconductors, whose challenging behavior does not comply with the traditional picture of Bardeen-Cooper-Schrieffer (BCS) superconductivity in regular crystals. In this paper, we propose a theoretical...... holes) exchange fracton excitations, quantum oscillations of fractal lattices that mimic the complex microscopic organization of the unconventional superconductors. For the copper oxides, the superconducting transition temperature T-c as predicted by the fracton mechanism is of the order of similar to......150 K. We suggest that the marginal ingredient of the high-temperature superconducting phase is provided by fracton coupled holes that condensate in the conducting copper-oxygen planes owing to the intrinsic field-effect-transistor configuration of the cuprate compounds. For the gate...

  15. Electrodeposition of gold nanoparticles onto an etched stainless steel wire followed by a self-assembled monolayer of octanedithiol as a fiber coating for selective solid-phase microextraction.

    Science.gov (United States)

    Yang, Yaoxia; Li, Yi; Liu, Haixia; Wang, Xuemei; Du, Xinzhen

    2014-11-01

    In the present study, a novel approach for rapid electrodeposition on an etched stainless steel (SS) wire followed by self-assembled monolayer (SAM) was proposed for the fabrication of solid-phase microextraction (SPME) fiber. The etched SS wire offers a rough surface structure for subsequent electrochemical deposition of gold nanoparticles (AuNPs). As a result, uniform AuNPs coating was tightly attached to the etched SS wire substrate. After SAM of 1,8-octanedithiol onto AuNPs coating via Au-S bonding, a unique floccular structure with extremely large surface area was obtained for the fabricated fiber. The mercaptooctyl groups modified AuNPs coated etched SS fiber (C8-S-AuNPs/SS) was then assessed for SPME of phthalate esters (PAEs), polychlorinated biphenyls (PCBs), chlorophenols (CPs), ultraviolet (UV) filters, polycyclic aromatic hydrocarbons (PAHs) and substituted anilines coupled to high-performance liquid chromatography with UV detection. This fiber exhibits higher extraction capability and better selectivity for some PCBs, CPs, UV filters and PAHs. Extraction conditions were investigated and optimized for SPME performance of UV filters. Under the optimized conditions, the developed method showed good linearity between 0.10 and 400μgL(-1) with corresponding coefficients in the range of 0.9989-0.9998. The limits of detection ranged from 0.025 to 0.056μgL(-1). The relative standard deviation for fiber-to-fiber reproducibility of five fabricated fibers was less than 9.4%. The developed method was successfully applied to the preconcentration and determination of trace UV filters from environmental water samples. Furthermore the fabrication of the C8-S-AuNPs/SS fiber can be performed in a highly reproducible manner. This fabricated fiber exhibits good stability and long lifetime, and could be a potential alternative for the conventional fused silica fiber. PMID:25465004

  16. Dynamics of Hyperthermal Energy Ion-Surface Collisions: Dissociative and non-dissociative Scattering of Ethanol cations from a Self-Assembled Monolayer Surface of Fluorinated Alkyl Thiol on Au (111)

    International Nuclear Information System (INIS)

    Dissociation and inelastic scattering of ethanol molecular ions from self-assembled monolayers (SAM) surface of fluorinated alkyl thiol on an Au (111) monocrystal have been studied at 28.9 and 52.9 eV collision energies. A single dynamics mechanism for quasi0inelastic scattering was found at both energies. Ions recoil nearly parallel to the surface with very small kinetic energy losses of the order of < 2 eV. Dissociation dynamics features for the main dissociation channel, loss of methyl radical, are dramatically different from that of inelastically scattered primary ions and are different at the two collision energies studies. At 28.9 eV two energetically and angularly resolved features are observed, one corresponding to the loss of very large amounts (nearly all) of ions translational energy and the other appearing to gain energy (superelastic scattering). This implies a lifetime of such excited ions of more than 5s. The same dynamics features are observed at 52.9 eV ion energy except that a second inelastic process begins to compete with the nearly fully inelastic process. Moreover, at this energy the delayed ion dissociation mechanism is the dominant mechanism. The hypothesis that collision of ethanol cations useful rationale for the observed dynamics. Support for this hypotheses is provided by Newton diagrams, which summarize momentum conservation relationships in terms of a common center-of-mass, cmeff, which provides a basis for describing different ion-surface interactions contributing to surface-induced dissociation of ethanol ions. Preliminary experiments with Ar+ scattered from the same surface exhibit very similar dynamics features to the observed for ethanol cations. Finally, we note that intensities of scattered primary or fragment ions never approach the specular angle at the energies investigated here

  17. Organic spintronics

    International Nuclear Information System (INIS)

    We review the emerging field of organic spintronics, where organic materials are applied as a medium to transport and control spin-polarized signals. The contacts for injecting and detecting spins are formed by ferromagnetic metals, oxides, or inorganic semiconductors. First, the basic concepts of spintronics and organic electronics are addressed, and phenomena which are in particular relevant for organic spintronics are highlighted. Experiments using different organic materials, including carbon nanotubes, organic thin films, self-assembled monolayers and single molecules are then reviewed. Observed magnetoresistance points toward successful spin injection and detection, but spurious magnetoresistance effects can easily be confused with spin accumulation. A few studies report long spin relaxation times and lengths, which forms a promising basis for further research. We conclude with discussing outstanding questions and problems. (topical review)

  18. Self-assembly of ferromagnetic organic-inorganic perovskite-like films.

    Science.gov (United States)

    Akhtar, Naureen; Polyakov, Alexey O; Aqeel, Aisha; Gordiichuk, Pavlo; Blake, Graeme R; Baas, Jacob; Amenitsch, Heinz; Herrmann, Andreas; Rudolf, Petra; Palstra, Thomas T M

    2014-12-10

    Perovskite-based organic-inorganic hybrids hold great potential as active layers in electronics or optoelectronics or as components of biosensors. However, many of these applications require thin films grown with good control over structure and thickness--a major challenge that needs to be addressed. The work presented here is an effort towards this goal and concerns the layer-by-layer deposition at ambient conditions of ferromagnetic organic-inorganic hybrids consisting of alternating CuCl4-octahedra and organic layers. The Langmuir-Blodgett technique used to assemble these structures provides intrinsic control over the molecular organization and film thickness down to the molecular level. Magnetic characterization reveals that the coercive field for these thin films is larger than that for solution-grown layered bulk crystals. The strategy presented here suggests a promising cost effective route to facilitate the excellently controlled growth of sophisticated materials on a wide variety of substrates that have properties relevant for the high density storage media and spintronic devices. PMID:25059565

  19. Self-Assembling Amphiphilic Molecules: A Possible Relationship Between Interstellar Chemistry and Meteoritic Organics

    Science.gov (United States)

    Sandford, Scott A.; Dworkin, Jason P.; Deamer, David W.; Allamandola, Louis J.; DeVincenzi, Donald (Technical Monitor)

    2001-01-01

    Interstellar gas and dust comprise the primary material from which the solar system formed. Evidence that some of this material was organic in nature and survived incorporation into the protosolar nebula is provided by the presence of deuterium-enriched organics in meteorites and interplanetary dust particles. Once the inner planets had sufficiently cooled, late accretionary infall of meteoroids and cosmic dust must have seeded them with some of these complex organic compounds. Delivery of such extraterrestrial compounds may have contributed to the organic inventory necessary for the origin of life. Interstellar ices, the building blocks of comets, tie up a large fraction of the biogenic elements available in molecular clouds. In our efforts to understand their synthesis, chemical composition, and physical properties, we report here that a complex mixture of molecules is produced by ultraviolet (UV) photolysis of realistic, interstellar ice analogs, and that some of the components have properties relevant to the origin of life, including the ability to self-assemble into vesicular structures.

  20. Assembly of metal ions and ligands with adaptable coordinative tendencies as a route to functional metal-organic solids

    International Nuclear Information System (INIS)

    The majority of efforts on metal-organic frameworks (MOFs) concern their rational design and, intuitively, researchers are drawn to assembly units with well-defined, reliable coordinating tendencies. Assembly units with less well-defined properties are generally less employed. This concept paper discusses the merits of using adaptable components for the assembly of functional MOFs. 'Adaptable' components, whether for the metal ion or for the ligating group, are defined as those having several coordination modes within a narrow energetic range. Use of these assembly units can lead to new solids with: (i) highly dynamic properties; (ii) new inorganic structural motifs; and possibly (iii) high thermal stabilities. The article, to facilitate comparison, considers a framework on the basis of metal ion, coordinating functionality, and organic spacer. Networks with one, two and three 'adaptable' units are then discussed. Ultimately, the illustration that less well-defined properties does not necessarily translate to less functional materials will be made