WorldWideScience

Sample records for monolayer sam dechnps

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

    Directory of Open Access Journals (Sweden)

    Malgorzata Adamkiewicz

    2014-12-01

    Full Text Available 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.

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

    Science.gov (United States)

    Adamkiewicz, Malgorzata; O'Hagan, David; Hähner, Georg

    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.

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

    Science.gov (United States)

    Adamkiewicz, Malgorzata

    2014-01-01

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

  4. Drug delivery from therapeutic self-assembled monolayers (T-SAMs) on 316L stainless steel.

    Science.gov (United States)

    Mahapatro, Anil; Johnson, Dave M; Patel, Devang N; Feldman, Marc D; Ayon, Arturo A; Agrawal, C Mauli

    2008-01-01

    Delivery of therapeutic agents from self-assembled monolayers (SAMs) on 316L stainless steel (SS) has been demonstrated as a viable method to deliver drugs for localized coronary artery stent application. SAMs are highly-ordered, nano-sized molecular coatings, adding 1-10 nm thickness to a surface. Hydroxyl terminated alkanethiol SAMs of 11-mercapto-1-undecanol (-OH SAM) were formed on 316L SS with 48 hr immersion in ethanolic solutions. Attachment of ibuprofen (a model drug) to the functional SAMs was carried out in toluene for 5 hrs at 60 degrees C using Novozume-435 as a biocatalyst. SAM formation and subsequent attachment of ibuprofen was characterized collectively using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and contact angle (CA) measure-ments. The quantitative in vitro release of ibuprofen into a "physiological" buffer solution was characterized using reverse phase HPLC. Drug release kinetics showed that 14.1 microg of ibuprofen eluted over a period of 35 days with 2.7microg being eluted in the first day and the remaining being eluted over a period of 35 days. The drug release kinetics showed an increase in ibuprofen elution that occurred during first 14 days (2.7microg in 1 day to 9.5 microg in 14 days), following which there was a decrease in the rate of elution. Thus, functional SAMs on 316L SS could be used as tethers for drug attachment and could serve as a drug delivery mechanism from stainless steel implants such as coronary artery stents.

  5. Formation and Stability of Phenylphosphonic Acid Monolayers on ZnO: Comparison of In Situ and Ex Situ SAM Preparation.

    Science.gov (United States)

    Ostapenko, Alexandra; Klöffel, Tobias; Meyer, Bernd; Witte, Gregor

    2016-05-24

    Self-assembled monolayers (SAMs) enable an electronic interface tailoring of conductive metal oxides and offer an alternative to common transparent electrodes in optoelectronic devices. Here, the influence of surface orientation and pretreatment on the formation and stability of SAMs has been studied for the case of phenylphosphonic acid (PPA) on ZnO single crystals. Using thermal desorption spectroscopy (TDS), X-ray photoelectron spectroscopy (XPS), near-edge X-ray adsorption fine structure spectroscopy (NEXAFS) and density-functional theory (DFT) calculations, the thermal stability and orientational ordering of PPA-SAMs on the polar and mixed-terminated ZnO surfaces were analyzed. On all surfaces, PPA-SAMs remain stable up to 550 K, while at higher temperatures a C-P bond cleavage and dissociative desorption takes place yielding two distinct desorption peaks. Based on DFT calculations, these desorption channels are attributed to protonated and deprotonated chemisorbed PPA molecules, which can be related to tri- and bidentate species, hence allowing to determine their relative abundance from the intensity ratio. Beside immersion, an alternative monolayer preparation based on vacuum deposition in combination with controlled desorption of excess multilayers is demonstrated. This enables a SAM preparation on bare ZnO surfaces without any precoating due to exposure to ambient air, which is further compared with SAM formation on intentionally hydroxylated substrates. Corresponding TDS data indicate that initial hydroxylation favors the formation of tridentate and deprotonated bidentate, while the OMBD preparation on bare surfaces yields a larger fraction of protonated bidentate species. The orientation of PPA molecules adopted in the SAMs was determined from the dichroism of K-edge NEXAFS measurements and reveals an almost upright orientation for the deprotonated species, while a slight tilting is obtained for monolayer films with a large fraction of protonated

  6. Influence of chain ordering on frictional properties of self-assembled monolayers (SAMs) in nano-lubrication.

    Science.gov (United States)

    Cheng, Hefa; Hu, Yuanan

    2012-01-01

    Adhesion of organic films to substrates is important in applications that involve solid surfaces in sliding contact. Although the thickness of self-assembled monolayers (SAMs) is only a few nanometers, they can drastically modify the frictional properties of the underlying substrate, and thus have great potential for serving as boundary lubricants on micro- and nano-scales. This review focuses on the relationship between the structural and compositional properties of SAMs and their frictional response. Adhesion of SAMs to the substrate surface usually occurs through chemisorption of the head groups on the constituent molecules, with molecular interactions such as van der Waals interactions playing important roles in organizing the molecules into surface films, and in controlling their tribological behavior. The durability and wear resistance of SAMs depend on the nature and strength of the binding forces between the head groups and the substrate surfaces, while the adhesion and friction forces are strongly influenced by the interactions of the terminal groups with the counterfaces. Results from both experimental measurements and molecular dynamics simulations consistently indicate that structural ordering of alkyl chains in SAMs reduces their frictional response, and that SAMs formed by molecules with alkyl chains longer than 8 to 10 methylene units are well organized, exhibiting low levels of friction. Less densely packed or more disordered monolayers inherently possess greater numbers of conformational defects at room temperature and present lower barriers to defect creation under the action of a contacting surface, and thus exhibit higher friction. Cross-linking of the spacer chains can reduce the frictional response of disordered films by increasing the chain ordering, but has little impact on SAMs that are already well ordered. On the other hand, introduction of sterically demanding terminal groups and dissimilar molecules reduces molecular ordering in SAMs

  7. 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)

  8. 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.

  9. Fabrication and tribological properties of self-assembled monolayer of n-alkyltrimethoxysilane on silicon: Effect of SAM alkyl chain length

    Science.gov (United States)

    Huo, Lixia; Du, Pengcheng; Zhou, Hui; Zhang, Kaifeng; Liu, Peng

    2017-02-01

    It is well known that the self-assembled organic molecules on a solid surface exhibit the friction-reducing performance. However, the effect of the molecular size of the self-assembled organic molecules has not been established. In the present work, self-assembled monolayers (SAMs) of n-alkyltrimethoxysilanes with different alkyl chain lengths (C6, C12, or C18) were fabricated on silicon substrate. The water contact angles of the SAMs increased from 26.8° of the hydroxylated silicon substrate to near 60° after self-assembly. The atomic force microscopy (AFM) analysis results showed that the mean roughness (Ra) of the SAMs decreased with increasing the alkyl chain length. The tribological properties of the SAMs sliding against Al2O3 ball were evaluated on an UMT-2 tribometer, and the worn surfaces of the samples were analyzed by means of Nano Scratch Tester and surface profilometry. It was found that lowest friction coefficient and smallest width of wear were achieved with the SAMs of C12 alkyl chain (C12-SAM). The superior friction reduction and wear resistance of the SAMs in comparison with the bare silicon substrate are attributed to good adhesion of the self-assembled films to the substrate, especially the C12-SAM with desirable alkyl chain length.

  10. Colloidal silicon quantum dots: from preparation to the modification of self-assembled monolayers (SAMs) for bio-applications.

    Science.gov (United States)

    Cheng, Xiaoyu; Lowe, Stuart B; Reece, Peter J; Gooding, J Justin

    2014-04-21

    Concerns over possible toxicities of conventional metal-containing quantum dots have inspired growing research interests in colloidal silicon nanocrystals (SiNCs), or silicon quantum dots (SiQDs). This is related to their potential applications in a number of fields such as solar cells, optoelectronic devices and fluorescent bio-labelling agents. The past decade has seen significant progress in the understanding of fundamental physics and surface properties of silicon nanocrystals. Such understanding is based on the advances in the preparation and characterization of surface passivated colloidal silicon nanocrystals. In this critical review, we summarize recent advances in the methods of preparing high quality silicon nanocrystals and strategies for forming self-assembled monolayers (SAMs), with a focus on their bio-applications. We highlight some of the major challenges that remain, as well as lessons learnt when working with silicon nanocrystals (239 references).

  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. 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.

  13. 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

  14. Functionalization of Organic Semiconductors and Other Carbon-based Materials by Self-Assembled Monolayers (SAMs) and Charge Transport in Organic Field-effect Transistors (OFETs)

    Science.gov (United States)

    Lee, Bumsu

    In the first part of the thesis, studies of the charge carrier transport in organic semiconductors performed using organic field-effect transistors (OFETs) with polymeric gate dielectric (parylene) are presented. By combining OFET and ultraviolet photoelectron spectroscopy (UPS) studies, the effect of bias-stress instability at the semiconductor/insulator interface have been investigated and understood. The effect is understood in terms of the transfer of holes from an accumulation channel of the semiconductor to localized states of the insulator that depends on energetic overlap between HOMO band tails of the semiconductor and the insulator. Second, surface functionalization of various materials such as organic single crystals, conjugated semiconductor polymers, graphene and carbon nanotubes (CNTs) with Self-Assembled Monolayers (SAMs) is described. In most cases, an enhanced surface conductivity is observed as a result of SAM treatment. Especially, fluorinated alkyl-silane (FTS) SAM induces the highest density of p-type charge carriers (in excess of an order of 1013cm-2), which leads to a strong surface hole-doping of these materials. In this thesis, (1) the mechanism of SAM nucleation, growth process and doping effect at the surface of organic single crystals and graphene is revealed. SAM nucleation occurs predominantly at molecular step edges or defect sites present at the surface and a consecutive lateral growth proceeds by cross-linking between SAM molecules. The strong hole-doping is explained by an interfacial charge transfer that during SAM formation. In addition, conductive atomic force microscopy (C-AFM) confirms that conducting paths along the step edges are formed by FTS nucleation at the early stage of FTS growth on rubrene. (2) it is reported that conductivity of solution-deposited thin film of conjugated polymers increases by up to six orders of magnitude, reaching (1.1 ± 0.1) × 103 Scm-1 for poly (2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b

  15. Preparation of metal-SAM-dendrimer-SAM-metal junctions by supramolecular metal transfer printing

    NARCIS (Netherlands)

    Nijhuis, Christian A.; ter Maat, Jurjen; Bisri, Satria Z.; Weusthof, Marcel H. H.; Salm, Cora; Schmitz, Jurriaan; Ravoo, Bart Jan; Huskensa, Jurriaan; Reinhoudt, David N.

    2008-01-01

    Metal-self-assembled monolayer (SAM)-dendrimer-SAM-metal junctions were prepared by a new type of metal transfer printing (mTP) that uses multiple beta-cyclodextrin (beta CD) host-guest interactions between a metal-coated stamp decorated with a monolayer of host molecules and a substrate which is fu

  16. Preparation of metal-SAM-dendrimer-SAM-metal junctions by supramolecular metal transfer printing

    NARCIS (Netherlands)

    Nijhuis, Christian A.; Maat, ter Jurjen; Bisri, Satria Z.; Weusthof, Marcel H.H.; Salm, Cora; Schmitz, Jurriaan; Ravoo, Bart Jan; Huskens, Jurriaan; Reinhoudt, David N.

    2008-01-01

    Metal-self-assembled monolayer (SAM)-dendrimer-SAM-metal junctions were prepared by a new type of metal transfer printing (mTP) that uses multiple ß-cyclodextrin (ßCD) host-guest interactions between a metal-coated stamp decorated with a monolayer of host molecules and a substrate which is functiona

  17. A nano-patterned self assembled monolayer (SAM) rutile titania cancer chip for rapid, low cost, highly sensitive, direct cancer analysis in MALDI-MS.

    Science.gov (United States)

    Manikandan, M; Gopal, Judy; Hasan, Nazim; Wu, Hui-Fen

    2014-12-01

    We developed a cancer chip by nano-patterning a highly sensitive SAM titanium surface capable of capturing and sensing concentrations as low as 10 cancer cells/mL from the environment by Matrix Assisted Laser Desorption and Ionization Time of Flight Mass Spectrometry (MALDI-TOF MS). The current approach evades any form of pretreatment and sample preparation processes; it is time saving and does not require the (expensive) conventional MALDI target plate. The home made aluminium (Al) target holder cost, on which we loaded the cancer chips for MALDI-TOF MS analysis, is about 60 USD. While the conventional stainless steel MALDI target plate is more than 700 USD. The SAM surface was an effective platform leading to on-chip direct MALDI-MS detection of cancer cells. We compared the functionality of this chip with the unmodified titanium surfaces and thermally oxidized (TO) titanium surfaces. The lowest detectable concentration of the TO chip was 10(3) cells/mL, while the lowest detectable concentration of the control or unmodified titanium chips was 10(6) cells/mL. Compared to the control surface, the SAM cancer chip showed 100,000 times of enhanced sensitivity and compared with the TO chip, 1000 times of increased sensitivity. The high sensitivity of the SAM surfaces is attributed to the presence of the rutile SAM, surface roughness and surface wettability as confirmed by AFM, XRD, contact angle microscope and FE-SEM. This study opens a new avenue for the potent application of the SAM cancer chip for direct cancer diagnosis by MALDI-TOF MS in the near future.

  18. Sandwich Sam

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    SAM, a 28-year-old Canadian, has a nice family name: Goodman. Four years ago, he came to China and now he owns two cafes. Sam is not tall. To match his loose black sweater, he wears a pair of jeans which are so long that the trouser legs are wrinkled over his sneakers. Why did he think of running a cafe in Beijing? "After graduating from college, I went to Hong Kong to be a fitness coach for half a year. Then, I went to South Korea. While sightseeing, I taught English to make a living.

  19. Preparation of metal-SAM-dendrimer-SAM-metal junctions by supramolecular metal transfer printing

    NARCIS (Netherlands)

    Nijhuis, C.A.; Maat, ter J.; Bisri, S.Z.; Weusthof, M.H.H.; Salm, C.; Schmitz, J.; Ravoo, B.J.; Huskens, J.; Reinhoudt, D.N.

    2008-01-01

    Metal–self-assembled monolayer (SAM)–dendrimer–SAM–metal junctions were prepared by a new type of metal transfer printing (mTP) that uses multiple -cyclodextrin (CD) host–guest interactions between a metal-coated stamp decorated with a monolayer of host molecules and a substrate which is functionali

  20. 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.

    Directory of Open Access Journals (Sweden)

    Hanh T M Phan

    Full Text Available 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 concentration and pH value. Charged surfaces exhibited a greater quantity of bovine serum albumin adsorption, a larger bovine serum albumin layer thickness, and increased density of bovine serum albumin protein compared to neutral surfaces at neutral pH value. The quantity of adsorbed bovine serum albumin protein increased with increasing bovine serum albumin concentration. After equilibrium sorption was reached at pH 7.0, desorption of bovine serum albumin occurred when pH was lowered to 2.0, which is below the isoelectric point of bovine serum albumin. Our data provide further evidence that combinatorial quartz crystal microbalance with dissipation and spectroscopic ellipsometry is a sensitive analytical tool to evaluate attachment and detachment of adsorbed proteins in systems with environmental implications.

  1. Studies of Self-assembled Monolayers Formed by Imidazoline on Iron Surface by SEM and SECM

    Institute of Scientific and Technical Information of China (English)

    Xiu Yu LIU; Shen Hao CHEN; Shuai MIAO; Su Xiang WU; Li Xia SHEN; Yuan Xing CAI; Hong Yan ZHAI

    2006-01-01

    The self-assembled monolayers (SAMs) of imidazoline (IM) on the iron surface were characterized by scanning electron microscope (SEM) and scanning electrochemical microscopy(SECM). The results showed that SAMs were an effective inhibition film for iron.

  2. SAM in a Nutshell.

    Science.gov (United States)

    Givens, Larry R.

    2000-01-01

    Explains what the Association of Higher Education Facilities Officers' Strategic Assessment Model (SAM) is and how to use it to achieve organizational excellence through continuous improvement. Showing features of both the Malcolm Baldrige programs and the Balanced Scorecard, the SAM components are described along with an explanation of the four…

  3. SAM Photovoltaic Model Technical Reference

    Energy Technology Data Exchange (ETDEWEB)

    Gilman, P. [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

    2015-05-27

    This manual describes the photovoltaic performance model in the System Advisor Model (SAM). The U.S. Department of Energy’s National Renewable Energy Laboratory maintains and distributes SAM, which is available as a free download from https://sam.nrel.gov. These descriptions are based on SAM 2015.1.30 (SSC 41).

  4. Dynamics of SAMs in Boundary Lubrication

    Directory of Open Access Journals (Sweden)

    J. Manojlović

    2013-09-01

    Full Text Available Surfactant molecules have some properties responsible for a number ofremarkable phenomena, such as oriented adsorption of surfactants at surfaces and interfaces. The capability to self -assemble into well- defined structures is often seen as being more important than their surface activity. When a surfactant solution is in contact with a solid surface, the surfactant molecules adsorb onto the surface, ideally forming an adsorbed layer of a high order, termed as a self- assembled monolayer (SAM. Many surface properties are influenced bysuch a film, and therefore, SAMs offer the capability to form ordered organic surface coatings, suitable for various applications, such as wetting or corrosion protection. Due to the flexibility in choosing the molecular architecture, organic molecules have many interesting applications, such as biosensors, in Photoelectronics, in controlling water adsorption or boundary lubricant coating. This paper Focuses on cationic surfactants (quaternary ammonium surfactants with some unique properties that are not present in other surfactants.

  5. SAM Theory Manual

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Rui [Argonne National Lab. (ANL), Argonne, IL (United States)

    2017-03-01

    The System Analysis Module (SAM) is an advanced and modern system analysis tool being developed at Argonne National Laboratory under the U.S. DOE Office of Nuclear Energy’s Nuclear Energy Advanced Modeling and Simulation (NEAMS) program. SAM development aims for advances in physical modeling, numerical methods, and software engineering to enhance its user experience and usability for reactor transient analyses. To facilitate the code development, SAM utilizes an object-oriented application framework (MOOSE), and its underlying meshing and finite-element library (libMesh) and linear and non-linear solvers (PETSc), to leverage modern advanced software environments and numerical methods. SAM focuses on modeling advanced reactor concepts such as SFRs (sodium fast reactors), LFRs (lead-cooled fast reactors), and FHRs (fluoride-salt-cooled high temperature reactors) or MSRs (molten salt reactors). These advanced concepts are distinguished from light-water reactors in their use of single-phase, low-pressure, high-temperature, and low Prandtl number (sodium and lead) coolants. As a new code development, the initial effort has been focused on modeling and simulation capabilities of heat transfer and single-phase fluid dynamics responses in Sodium-cooled Fast Reactor (SFR) systems. The system-level simulation capabilities of fluid flow and heat transfer in general engineering systems and typical SFRs have been verified and validated. This document provides the theoretical and technical basis of the code to help users understand the underlying physical models (such as governing equations, closure models, and component models), system modeling approaches, numerical discretization and solution methods, and the overall capabilities in SAM. As the code is still under ongoing development, this SAM Theory Manual will be updated periodically to keep it consistent with the state of the development.

  6. Noncovalent Self-Assembled Monolayers on Graphene as a Highly Stable Platform for Molecular Tunnel Junctions.

    Science.gov (United States)

    Song, Peng; Sangeeth, C S Suchand; Thompson, Damien; Du, Wei; Loh, Kian Ping; Nijhuis, Christian A

    2016-01-27

    Monolayer graphene is used as the bottom electrode to fabricate stable and high-quality self-assembled monolayer (SAM)-based tunnel junctions. The SAMs are formed on graphene via noncovalent bonds without altering the structure of the graphene. This work paves the way to new types of molecular electronic junctions based on 2D materials.

  7. Nanoscale patterning of self-assembled monolayers using DNA nanostructure templates.

    Science.gov (United States)

    Surwade, S P; Zhou, F; Li, Z; Powell, A; O'Donnell, C; Liu, H

    2016-01-28

    We describe a method to pattern arbitrary-shaped silane self-assembled monolayers (SAMs) with nm scale resolution using DNA nanostructures as templates. The DNA nanostructures assembled on a silicon substrate act as a soft-mask to negatively pattern SAMs. Mixed SAMs can be prepared by back filling the negative tone patterns with a different silane.

  8. 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.

  9. Tuning of metal work functions with self-assembled monolayers

    NARCIS (Netherlands)

    de Boer, B; Hadipour, A; Foekema, R; van Woudenbergh, T; Mandoc, MM; Mihailetchi, VD; Blom, PWM; Heremans, PL; Muccini, M; Hofstraat, H

    2004-01-01

    Tuning the work functions of metals was demonstrated by chemically modifying the metal surface through the formation of chemisorbed self-assembled monolayers (SAMs) derived from 1H,1H,2H,2H-perfluorinated alkanethiols and hexadecanethiol. The ordering inherent in the SAMs creates an effective, molec

  10. Self-assembled monolayers on metal oxides : applications in nanotechnology

    NARCIS (Netherlands)

    Yildirim, O.

    2010-01-01

    The thesis describes the use of phosph(on)ate-based self-assembled monolayers (SAMs) to modify and pattern metal oxides. Metal oxides have interesting electronic and magnetic properties such as insulating, semiconducting, metallic, ferromagnetic etc. and SAMs can tailor the surface properties. FePt

  11. Chemical analyses of hydroxyapatite formation on SAM surfaces modified with COOH, NH(2), CH(3), and OH functions.

    Science.gov (United States)

    Hirata, Isao; Akamatsu, Mai; Fujii, Eri; Poolthong, Suchit; Okazaki, Masayuki

    2010-08-01

    Hydroxyapatite formation was examined at the surface of self-assembled monolayers (SAMs) modified with four functional groups, -COOH, -NH(2), -CH(3), and -OH. For COOH-SAM and NH(2)-SAM, scanning electron spectroscopic observation showed that flake-like sheet crystals covered the whole wafer and small broccoli-like crystals were observed occasionally on the flake-like crystal base layer. For CH(3)-SAM and OH-SAM, no flake-like sheet crystals were observed; broccoli-like crystals were observed in a dispersed manner for CH(3)-SAM, but in localized spots for OH-SAM. X-ray diffraction patterns showed a strong apatite pattern oriented toward the c-axis direction for COOH-SAM. ESCA analysis revealed distinct Ca, P, O peaks for COOH-, NH(2)-, CH(3)-, and OH-SAM. Surface plasmon resonance (SPR) analysis indicated that during the supply of supersaturated calcium phosphate solution, the deposition of precipitates increased monotonically with time for COOH-SAM, increased slightly for NH(2)-SAM, but little increase in deposition was detected for CH(3)-SAM and OH-SAM.

  12. Self-assembled monolayers applications for the development of electrochemical sensors

    OpenAIRE

    Renato S. Freire; Pessoa, Christiana A.; Lauro T. Kubota

    2003-01-01

    Self-assembled monolayers (SAMs) modified electrodes exhibit unique behavior that can greatly benefit electrochemical sensing. This brief review highlights the applications of SAM modified electrodes in electroanalytical chemistry. After a general introduction, which includes the approaches for SAM development, different electrochemical systems for detecting inorganic and organic species are described and discussed. Special attention to the coupling of biological sensing element to the SAM is...

  13. Grafted silane monolayers: reconsideration of growth mechanisms

    Science.gov (United States)

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

    1998-03-01

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

  14. CareSam

    DEFF Research Database (Denmark)

    Liveng, Anne; Christensen, Jonas

    2016-01-01

    negative cultural perceptions of help-needing elderly and the people who support them in everyday life? In answering these questions and thereby reflecting on our own work process we apply a caring, a learning and a political perspective. Hereby the article wishes to formulate a methodological point......This article presents findings and discussions generated on the basis of the Danish-Swedish development project CareSam. The article will on the one hand focus on how work in groups consisting of representatives from different levels in the elderly care sector at one time served as learning spaces...... in the project-groups this paper will ask whether it is possible to represent care work for elderly people with all the ambiguities it holds: How can we as researchers represent both meaningfulness and straining dimensions of care work? Can we avoid either supporting Florence Nightingale-ideals or cementing...

  15. Poly(ethylene glycol) monolayer formation and stability on gold and silicon nitride substrates.

    Science.gov (United States)

    Cerruti, Marta; Fissolo, Stefano; Carraro, Carlo; Ricciardi, Carlo; Majumdar, Arun; Maboudian, Roya

    2008-10-07

    Poly(ethylene glycol) (PEG) self-assembled monolayers (SAMs) are extensively used to modify substrates to prevent nonspecific protein adsorption and to increase hydrophilicity. X-ray photoelectron spectroscopy analysis, complemented by water contact angle measurements, is employed to investigate the formation and stability upon aging and heating of PEG monolayers formed on gold and silicon nitride substrates. In particular, thiolated PEG monolayers on gold, with and without the addition of an undecylic spacer chain, and PEG monolayers formed with oxysilane precursors on silicon nitride have been probed. It is found that PEG-thiol SAMs are degraded after less than two weeks of exposure to air and when heated at temperatures as low as 120 degrees C. On the contrary, PEG-silane SAMs are stable for more than two weeks, and fewer molecules are desorbed even after two months of aging, compared to those desorbed in two weeks from the PEG-thiol SAMs. A strongly bound hydration layer is found on PEG-silane SAMs aged for two months. Heating PEG-silane SAMs to temperatures as high as 160 degrees C improves the quality of the monolayer, desorbing weakly bound contaminants. The differences in stability between PEG-thiol SAMs and PEG-silane SAMs are ascribed to the different types of bonding to the surface and to the fact that the thiol-Au bond can be easily oxidized, thus causing desorption of PEG molecules from the surface.

  16. A simulation study on the thermal and wetting behavior of alkane thiol SAM on gold (111) surface

    Institute of Scientific and Technical Information of China (English)

    J. Meena Devi

    2014-01-01

    Molecular dynamics simulations have been performed to investigate the structural, thermal and wetting properties of self-assembled monolayer (SAM) of alkane thiol on gold surface. The specific heat capacity of the gold SAM surface was found to linearly increase with the temperature in the range 100-300 K. It was found to drop down at 400 K and this decrease might be attributed to the disorder of the SAM chains. Hydration of gold SAM surface for two different terminal groups, namely methyl (hydrophobic), and hydroxy (hydrophilic) was studied at room temperature. The difference in their wetting behavior and the structure of their interfacial water were examined from the estimation of the z density profile, radial distribution function, hydrogen bonds and orientation of water dipoles in the interfacial region. The present simulation results suggest that the wetting behavior of the gold SAM surface can be modified by altering the terminal functional group of the SAM chains.

  17. Self-Assembled Monolayers Generated from Unsymmetrical Partially Fluorinated Spiroalkanedithiols.

    Science.gov (United States)

    Chinwangso, Pawilai; Lee, Han Ju; Lee, T Randall

    2015-12-15

    Self-assembled monolayers (SAMs) were prepared on gold substrates from an unsymmetrical partially fluorinated spiroalkanedithiol adsorbate with the specific structure of [CH3(CH2)7][CF3(CF2)7(CH2)8]C[CH2SH]2 (SADT) and compared to SAMs formed from the semifluorinated monothiol F8H10SH [CF3(CF2)7(CH2)10SH] of analogous chain length and n-octadecanethiol. The adsorbate with two alkyl chains, one terminally fluorinated and the other nonfluorinated, was designed to form monolayers in which the bulky helical fluorocarbon segments assemble on top of an underlying layer of well-packed trans-extended alkyl chains. Different combinations of deposition solvents and temperatures were used to produce the bidentate SAMs. Characterization of the resulting monolayers revealed that SAMs formed in DMF at room temperature allow complete binding of the sulfur headgroups to the surface and exhibit higher conformational order than those produced using alternative solvent/temperature combinations. The reduced film thicknesses and enhanced wettability of the SADT SAMs, as compared to the SAMs generated from F8H10SH, suggest loose packing and an increase in the tilt of the terminal fluorocarbon chain segments. Nevertheless, the density of the underlying hydrocarbon chains of the SADT SAMs was higher than that of the F8H10SH SAMs, owing to the double-chained structure of the new adsorbate. The conformational orders of the SAM systems were observed to decrease as follows: C18SH > F8H10SH > SADT. However, the SAMs formed from this new double-chained bidentate adsorbate in DMF expose a fluorinated interface with a relatively low surface roughness, as determined by contact-angle hysteresis.

  18. Regioselective patterning of multiple SAMs and applications in surface-guided smart microfluidics.

    Science.gov (United States)

    Chen, Chuanzhao; Xu, Pengcheng; Li, Xinxin

    2014-12-24

    A top-down nanofabrication technology is developed to integrate multiple SAMs (self-assembled monolayers) into regioselective patterns. With ultraviolet light exposure through regioselectively hollowed hard mask, an existing SAM at designated microregions can be removed and a dissimilar kind of SAM can be regrown there. By repeating the photolithography-like process cycle, diverse kinds of SAM building blocks can be laid out as a desired pattern in one microfluidic channel. In order to ensure high quality of the surface modifications, the SAMs are vapor-phase deposited before the channel is closed by a bonding process. For the first time the technique makes it possible to integrate three or more kinds of SAMs in one microchannel. The technique is very useful for multiplex surface functionalization of microfluidic chips where different segments of a microfluidic channel need to be individually modified with different SAMs or into arrayed pattern for surface-guided fluidic properties like hydrophobicity/philicity and/or oleophobicity/philicity, etc. The technique has been well validated by experimental demonstration of various surface-directed flow-guiding functions. By modifying a microchannel surface into an arrayed pattern of multi-SAM "two-tone" stripe array, surface-guiding-induced 3D swirling flow is generated in a microfluidic channel that experimentally exhibits quick oil/water mixing and high-efficiency oil-to-water chemical extraction.

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

    DEFF Research Database (Denmark)

    Browne, W.R.; Kudernac, T.; Katsonis, N.

    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...

  20. 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.

  1. Preparation of organothiol self-assembled monolayers for use in templated crystallization.

    Science.gov (United States)

    Nielsen, Michael H; Lee, Jonathan R I

    2013-01-01

    Organothiol self-assembled monolayers (SAMs) have garnered much interest as templates for oriented crystallization of biominerals. While, on the surface, SAM preparation appears to be straightforward, there are many subtleties that may yield films that lack the desired effect on the mineral component in subsequent use for templated mineralization. Herein, we discuss literature that uses organothiol SAMs to understand various principles in biomineralization, to motivate the following discussion of preparation procedures and pitfalls that may arise while working with SAMs. We provide a range of parameters for each element of a SAM-forming process, which have been shown in the literature to produce monolayers suitable for mineralization experiments, and close with a step-by-step procedure, based on findings in the cited literature, that yields functional SAMs with very high fidelity.

  2. Molecular junctions based on SAMs of cruciform oligo(phenylene ethynylene)s

    DEFF Research Database (Denmark)

    Wei, Zhongming; Li, Tao; Jennum, Karsten Stein

    2012-01-01

    Cruciform oligo(phenylene ethynylene)s (OPEs) with an extended tetrathiafulvalene (TTF) donor moiety (OPE5-TTF and OPE3-TTF) and their simple analogues (OPE5-S and OPE3) without conjugated substituents were used to form high quality self-assembled monolayers (SAMs) on ultra-flat gold substrates...

  3. Self-Assembled Monolayer of Mixed Gold and Nickel Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    Yanni Jie; Huiqing Fan; Wei You

    2012-01-01

    Forming a monolayer of mixed nickel and gold nanoparticles through self-assembly via simple solu-tion processing constitutes an important step toward inexpensive nanoparticle-based carbon nanofiber growth. In this work, mixed gold and nickel nanoparticles were anchored on the silicon wafer using self-assembled monolayers (SAMs) as a template. SAMs of 3-mercaptopropyl trimethoxysilane (MPTS-SAMs) were formed on silicon wafer, with the exposed thiol functionality providing ligand exchange sites to form the mixed mono-layer of nickel and gold nanoparticles via a two-step sequential soaking approach. The densities of the nickel and gold nanoparticles on the surface can be varied by adjusting the soaking sequence.

  4. A Solid Ag Film Deposited from Solution on Self-assembled Mercaptopropyltrimethoxysilane (MPTS) Monolayer

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Mercaptopropyltrimethoxysilane (MPTS) bearing mercapto groups was used to form self-assembly monolayers (SAMs) on glass substrates by solution extraction. SEM, XRD and rubbing test analysis illustrated that the Ag film on the SAMs-modified glass was more durable than that on the commonly-modified glass and that the crystallinity of Ag film on the SAMs-modified glass was identical with those of the Ag film on the commonly-modified glass and pure Ag.

  5. Multicolor, large-area fluorescence sensing through oligothiophene-self-assembled monolayers.

    Science.gov (United States)

    Melucci, Manuela; Zambianchi, Massimo; Favaretto, Laura; Palermo, Vincenzo; Treossi, Emanuele; Montalti, Marco; Bonacchi, Sara; Cavallini, Massimiliano

    2011-02-14

    We present a new strategy to realize self-assembled monolayers (SAMs) on quartz and silicon with a multicolour fluorescence pattern starting from a single, proton sensitive oligothiophene dye exposed at a defined pH. Fine tuning of the SAMs emission color over the entire visible range, including white, is demonstrated. Finally, integration of SAMs in patterned thin layer cells (TLCs) is exploited to demonstrate cation sensing potential in real devices.

  6. Unveiling self-assembled monolayers' potential for molecular spintronics: spin transport at high voltage.

    Science.gov (United States)

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

    2012-12-18

    Molecular magnetic tunnel junctions using self-assembled monolayers (SAMs) as tunnel barriers show stable and efficient spin transport properties. Large tunnel magnetoresistance with a flat bias voltage dependence of the magnetoresistance is observed in La(2/3) Sr(1/3) MnO(3) /dodecylphosphonic acid SAM/Co nanocontacts. This opens the door to spintronic tailoring though SAM engineering and could also lead to new venues for spin injection in organic devices.

  7. Controlling the stereochemistry and regularity of butanethiol self-assembled monolayers on Au(111)

    DEFF Research Database (Denmark)

    Yan, Jiawei; Ouyang, Runhai; Jensen, Palle Skovhus;

    2014-01-01

    The rich stereochemistry of the self-assembled monolayers (SAMs) of four butanethiols on Au(111) is described, the SAMs containing up to 12 individual C, S, or Au chiral centers per surface unit cell. This is facilitated by synthesis of enantiomerically pure 2-butanethiol (the smallest unsubstitu...

  8. Deposition of metal Islands, metal clusters and metal containing single molecules on self-assembled monolayers

    NARCIS (Netherlands)

    Speets, Emiel Adrianus

    2005-01-01

    The central topic of this thesis is the deposition of metals on Self-Assembled Monolayers (SAMs). Metals are deposited in the form of submicron scale islands, nanometer scale clusters, and as supramolecular, organometallic coordination cages. Several SAMs on various substrates were prepared and anal

  9. Role of SAM Chain Length in Enhancing the Sensitivity of Nanopillar Modified Electrodes for Glucose Detection

    Directory of Open Access Journals (Sweden)

    2009-02-01

    Full Text Available In this report, alkanethiol self assembled monolayers (SAM with two different chain lengths were used to immobilize the functionalizing enzyme (glucose oxidase onto gold nanopillar modified electrodes and the electrochemical processes of these functionalized electrodes in glucose detection were investigated. First, the formation of these SAMs on the nanopillar modified electrodes was characterized by the cyclic voltammetry and electrochemical impedance spectroscopy techniques, and then the detection sensitivity of these functionalized electrodes to glucose was evaluated by the amperometry technique. Results showed that the SAM of alkanethiols with a longer chain length resulted in a higher degree of surface coverage with less defect and a higher electron transfer resistance, whereas the SAM of alkanethiols with a shorter chain length gave rise to a higher detection sensitivity to glucose. This study sheds some new insight into how to enhance the sensing performance of nanopillar modified electrodes.

  10. Emprego de monocamadas auto-organizadas no desenvolvimento de sensores eletroquímicos Self-assembled monolayers applications for the development of electrochemical sensors

    Directory of Open Access Journals (Sweden)

    Renato S. Freire

    2003-05-01

    Full Text Available Self-assembled monolayers (SAMs modified electrodes exhibit unique behavior that can greatly benefit electrochemical sensing. This brief review highlights the applications of SAM modified electrodes in electroanalytical chemistry. After a general introduction, which includes the approaches for SAM development, different electrochemical systems for detecting inorganic and organic species are described and discussed. Special attention to the coupling of biological sensing element to the SAM is given, which can selectively recognize the analyte. Future prospects are also evaluated.

  11. Friction Properties of OTS SAMs and Silicon Surface under Water Lubrication

    Institute of Scientific and Technical Information of China (English)

    WANG Xin; ZHANG Xiangjun; AHMED Imad; LIU Ying; WEN Shizhu

    2009-01-01

    The friction and wear properties of silicon surface covered with octadecyltrichloro-silane (OTS) self-assembled monolayers (SAMs) were investigated by a UMT-2 microtribometer with and without water as lubricant, and then compared with that of bare silicon surface. Dry friction measurement results show that OTS SAMs have a very low friction coefficient compared to bare silicon surface under lower sliding velocity and normal contact load. However, heavy wear occurs on OTS SAMs under higher contact stress and sliding velocity. Under water lubrication, OTS SAMs can prevent wear obviously and meanwhile present low coefficient of friction even under high velocities.The improved frictional and anti-wear property on OTS SAMs surface is attributed to the hydrophobic property of OTS and hydrodynamic effect of water. Furthermore, a wear critical phase diagram for OTS SAMs with and without water was proposed, which indicates that OTS SAMs working under water lubrication owns a wider range of available load and velocity to reduce friction and prevent wear.

  12. Improving the dielectric properties of ethylene-glycol alkanethiol self-assembled monolayers.

    Science.gov (United States)

    Zaccari, Irene; Catchpole, Benjamin G; Laurenson, Sophie X; Davies, A Giles; Wälti, Christoph

    2014-02-11

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

  13. 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.

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

    Science.gov (United States)

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

    2014-04-15

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

  15. 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.

  16. A modular approach for the construction and modification of glyco-SAMs utilizing 1,3-dipolar cycloaddition.

    Science.gov (United States)

    Kleinert, Mike; Winkler, Tobias; Terfort, Andreas; Lindhorst, Thisbe K

    2008-06-21

    We report the synthesis of a broad variety of functionalized molecules for assembly on gold, allowing the formation of biologically relevant SAMs by a modular approach: either utilizing 1,3-dipolar cycloaddition of alkynes and azides in solution or by 'click on SAM'. Extensive studies into the various parameters of SAM formation and stability have been carried out, leading us to deduce reliable conditions under which glyco-decorated self-assembled monolayers can be formed and studied such as in SPR-supported binding assays.

  17. System for Award Management (SAM) API

    Data.gov (United States)

    General Services Administration — The SAM API is a RESTful method of retrieving public information about the businesses, organizations, or individuals (referred to as entities) within the SAM entity...

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

    DEFF Research Database (Denmark)

    Marx, E.; Ginger, D.S.; Walzer, Karsten

    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 tran...

  19. 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.

  20. Donor/Acceptor Mixed Self-Assembled Monolayers for Realising a Multi-Redox-State Surface.

    Science.gov (United States)

    Casado-Montenegro, Javier; Marchante, Elena; Crivillers, Núria; Rovira, Concepció; Mas-Torrent, Marta

    2016-06-17

    Mixed molecular self-assembled monolayers (SAMs) on gold, based on two types of electroactive molecules, that is, electron-donor (ferrocene) and electron-acceptor (anthraquinone) molecules, are prepared as an approach to realise surfaces exhibiting multiple accessible redox states. The SAMs are investigated in different electrolyte media. The nature of these media has a strong impact on the types of redox processes that take place and on the redox potentials. Under optimised conditions, surfaces with three redox states are achieved. Such states are accessible in a relatively narrow potential window in which the SAMs on gold are stable. This communication elucidates the key challenges in fabricating bicomponent SAMs as electrochemical switches.

  1. Oxygen Attachment on Alkanethiolate SAMs Induced by Low-Energy Electron Irradiation

    OpenAIRE

    Massey, Sylvain; Bass, Andrew D.; Steffenhagen, Marie; Sanche, Léon

    2013-01-01

    Reactions of 18O2 with self-assembled monolayer (SAM) films of 1-dodecanethiol, 1-octadecanethiol, 1-butanethiol, and benzyl mercaptan chemisorbed on gold, were studied by the electron stimulated desorption (ESD) of anionic fragments over the incident electron energy range 2–20 eV. Dosing the SAMs with 18O2 at 50 K, results in the ESD of 18O− and 18OH−. Electron irradiation of samples prior to 18O2 deposition demonstrates that intensity of subsequent 18O− and 18OH− desorption signals increase...

  2. Rhodium deposition onto a 4-mercaptopyridine SAM on Au(1 1 1)

    Energy Technology Data Exchange (ETDEWEB)

    Manolova, M. [Institute of Electrochemistry, University of Ulm, 89069 Ulm (Germany); Kayser, M. [Institute of Electrochemistry, University of Ulm, 89069 Ulm (Germany); Kolb, D.M. [Institute of Electrochemistry, University of Ulm, 89069 Ulm (Germany)]. E-mail: dieter.kolb@uni-ulm.de; Boyen, H.-G. [Institute of Solid State Physics, University of Ulm, 89069 Ulm (Germany); Ziemann, P. [Institute of Solid State Physics, University of Ulm, 89069 Ulm (Germany); Mayer, D. [BASF Electronic Materials GmbH, 67056 Ludwigshafen (Germany); Wirth, A. [BASF Electronic Materials GmbH, 67056 Ludwigshafen (Germany)

    2007-02-10

    The application of a recently developed method for the deposition of Pd and Pt on top of a SAM, has been successfully extended to Rh, thus proving the versatility of the new concept. Experimental evidence from cyclic voltammetry, in situ STM and ex situ X-ray photoemission spectroscopy is presented for the deposition of monoatomic high rhodium islands onto a 4-mercaptopyridine self-assembled monolayer on a Au(1 1 1) electrode. By repetitive complexation of the Rh ions to the ring-nitrogen and reduction in a Rh-ion free solution, an almost completely covered SAM is obtained. The consequences of making contacts for molecular electronics are briefly discussed.

  3. Fluorescent self-assembled monolayers as new sensing materials

    NARCIS (Netherlands)

    Basabe Desmonts, Lourdes

    2006-01-01

    Fluorescent self-assembled monolayers (SAMs) on glass surfaces have been studied as a new material for chemical sensing. The new sensing system presented in this thesis is a label-free sensing approach suitable for metal ion and inorganic anions sensing in both organic solvents and aqueous solution.

  4. Reactive monolayers for surface gradients and biomolecular patterned interfaces

    NARCIS (Netherlands)

    Nicosia, C.

    2013-01-01

    Self-assembled monolayers (SAMs) are an excellent platform to implement and develop interfacial reactions for the preparation of versatile materials of pivotal importance for the fabrication of, among others, biochips, sensors, catalysts, smart surfaces and electronic devices. The development of met

  5. Mixed carboranethiol self-assembled monolayers on gold surfaces

    Science.gov (United States)

    Yavuz, Adem; Sohrabnia, Nima; Yilmaz, Ayşen; Danışman, M. Fatih

    2017-08-01

    Carboranethiol self-assembled monolayers on metal surfaces have been shown to be very convenient systems for surface engineering. Here we have studied pure and mixed self-assembled monolayers (SAMs) of three different carboranethiol (CT) isomers on gold surfaces. The isomers were chosen with dipole moments pointing parallel to (m-1-carboranethiol, M1), out of (m-9-carboranethiol, M9) and into (o-1-carboranethiol, O1) the surface plane, in order to investigate the effect of dipole moment orientation on the film properties. In addition, influence of the substrate surface morphology on the film properties was also studied by using flame annealed (FA) and template stripped (TS) gold surfaces. Contact angle measurements indicate that in M1/M9 and M1/O1 mixed SAMs, M1 is the dominant species on the surface even for low M1 ratio in the growth solution. Whereas for O1/M9 mixed SAMs no clear evidence could be observed indicating dominance of one of the species over the other one. Though contact angle values were lower and hysteresis values were higher for SAMs grown on TS gold surfaces, the trends in the behavior of the contact angles with changing mixing ratio were identical for SAMs grown on both substrates. Atomic force microscopy images of the SAMs on TS gold surfaces indicate that the films have similar morphological properties regardless of mixing ratio.

  6. Self assembled monolayers on silicon for molecular electronics.

    Science.gov (United States)

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

    2006-05-24

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Rajkumar, Ganesan; Sethuraman, Mathur Gopalakrishnan, E-mail: mgsethu@rediffmail.com

    2014-07-01

    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.

  8. Comparative Study of Protein Immobilization Properties on Calixarene Monolayers

    Directory of Open Access Journals (Sweden)

    Kwangnak Koh

    2007-06-01

    Full Text Available Three calix[4]arene (Cal-4 derivatives of which contain ethylester (1,carboxylic acid (2, and crownether (3 at the lower rim with a common reactive thiol at theupper rim were synthesized and constructed to self-assembled monolayers (SAMs on Aufilms. After spectroscopic characterization of monolayers, the interaction between Cal-4and surface confined bovine serum albumin (BSA in the SAMs was analyzed by surfaceplasmon resonance (SPR. The estimated surface concentration of BSA on the Cal-4 SAMwith crownether group was the highest among the three Cal-4 derivatives. Anti-hIgG andhIgG pair was employed for the investigation of protein-protein interaction. Molecularinteraction between anti-hIgG and hIgG can be detected in a concentration range of 10pg/mL to 200 pg/mL on the Cal-4 derivative 3 SAM modified SPR chip.

  9. A 3:1 site-differentiated [4Fe-4S] cluster immobilized on a self-assembled monolayer

    NARCIS (Netherlands)

    Geer, Erwin P.L. van der; Brom, Coenraad R. van den; Arfaoui, Imad; Houssiau, Laurent; Rudolf, Petra; Koten, Gerard van; Klein Gebbink, Robertus J.M.; Hessen, Bart

    2008-01-01

    A 3:1 site-differentiated [4Fe-4S] cluster is immobilized on a thiol-functionalized self-assembled monolayer (SAM) on Au(111) by thiol-thiolate exchange chemistry. Fe 2p signals observed by X-ray photoelectron spectroscopy support the presence of [4Fe-4S] clusters at the SAM surface; further evidenc

  10. 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...

  11. Fabrication and Surface Properties of Composite Films of SAM/Pt/ZnO/SiO 2

    KAUST Repository

    Yao, Ke Xin

    2008-12-16

    Through synthetic architecture and functionalization with self-assembled monolayers (SAMs), complex nanocomposite films of SAM/Pt/ZnO/SiO2 have been facilely prepared in this work. The nanostructured films are highly uniform and porous, showing a wide range of tunable wettabilities from superhydrophilicity to superhydrophobicity (water contact angles: 0° to 170°). Our approach offers synthetic flexibility in controlling film architecture, surface topography, coating texture, crystallite size, and chemical composition of modifiers (e.g., SAMs derived from alkanethiols). For example, wettability properties of the nanocomposite films can be finely tuned with both inorganic phase (i.e., ZnO/SiO2 and Pt/ZnO/SiO2) and organic phase (i.e., SAMs on Pt/ZnO/SiO2). Due to the presence of catalytic components Pt/ZnO within the nanocomposites, surface reactions of the organic modifiers can further take place at room temperature and elevated temperatures, which provides a means for SAM formation and elimination. Because the Pt/ZnO forms an excellent pair of metal-semiconductors for photocatalysis, the anchored SAMs can also be modified or depleted by UV irradiation (i.e., the films possess self-cleaning ability). Potential applications of these nanocomposite films have been addressed. Our durability tests also confirm that the films are thermally stable and structurally robust in modification- regeneration cycles. © 2008 American Chemical Society.

  12. Increasing the Fill Factor of Inverted P3HT:PCBM Solar Cells Through Surface Modification of Al-Doped ZnO via Phosphonic Acid-Anchored C60 SAMs

    DEFF Research Database (Denmark)

    Stubhan, Tobias; Salinas, Michael; Ebel, Alexander

    2012-01-01

    The influence of aluminum-doped zinc oxide (AZO) electron extraction layers modified with self-assembled monolayers (SAMs) on inverted polymer solar cells is investigated. It is found that AZO modification with phosphonic acid-anchored Fullerene–SAMs leads to a reduction of the series resistance...

  13. Interactions of doxorubicin with self-assembled monolayer-modified electrodes: electrochemical, surface plasmon resonance (SPR), and gravimetric studies.

    Science.gov (United States)

    Nieciecka, Dorota; Krysinski, Pawel

    2011-02-01

    We present the results on the partitioning of doxorubicin (DOX), a potent anticancer drug, through the model membrane system, self-assembled monolayers (SAMs) on gold electrodes. The monolayers were formed from alkanethiols of comparable length with different ω-terminal groups facing the aqueous electrolyte: the hydrophobic -CH(3) groups for the case of dodecanethiol SAMs or hydrophilic -OH groups of mercaptoundecanol SAMs. The electrochemical experiments combined with the surface plasmon resonance (SPR) and gravimetric studies show that doxorubicin is likely adsorbed onto the surface of hydrophilic monolayer, while for the case of the hydrophobic one the drug mostly penetrates the monolayer moiety. The adsorption of the drug hinders further penetration of doxorubicin into the monolayer moiety.

  14. Characterization of self-assembled monolayers of thiols on Au(111)

    Institute of Scientific and Technical Information of China (English)

    邓文礼; 杨大本; 方晔; 白春礼

    1996-01-01

    Self-assembled monolayers (SAMs) of n-butanethiol, n-dodecanethiol and their equimolar mixture on Au(111) were prepared and characterized by ellipsometry, contact angle measurement, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Results revealed that these SAMs are oriented ultrathin films with the thickness of nanometer scale, and the SAMs were influenced by the molecular chain length, the lattice orientation and cleanliness of the substrates. The surface of the longer chain SAM is hydrophobic. The thicknesses of three SAMs of n-butanethiol, n-dodecanethiol and their mixture revealed by ellipsometry and XPS are about 0.59 - 0.67nm, 1.60- 1.69 nm and 1.23 - 1.32nm, respectively. AFM images further demonstrated that the SAM formed by the mixture has some microdomains with two different thicknesses.

  15. Preparation and characterization of BiFeO3 thin films by the LPD on OH-functionalized organic SAMs

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    BiFeO3 (BFO) thin films were grown on OH-functionalized organic self-assembled monolayers (SAMs) via liquid-phase deposition (LPD) method at a temperature below 100°C. The BiFeO3 thin films were induced to synthesize on the OH-functionalized organic OTS monolayers prepared on hydroxylated glass substrate by self-assembling technique. The hydrophilic characteristic of the as-prepared OTS-SAMs was measured by contact angle tester. The crystal phase composition, microstructure and topography of the as-synthesized BFO thin films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy disperse spectroscopy (EDS) and atomic force microscope (AFM), respectively. Results show that compact and homogeneous BFO thin films can be formed on the OH-functionalized SAMs at low temperature.

  16. Triptycene-terminated thiolate and selenolate monolayers on Au(111

    Directory of Open Access Journals (Sweden)

    Jinxuan Liu

    2017-04-01

    Full Text Available To study the implications of highly space-demanding organic moieties on the properties of self-assembled monolayers (SAMs, triptycyl thiolates and selenolates with and without methylene spacers on Au(111 surfaces were comprehensively studied using ultra-high vacuum infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy and thermal desorption spectroscopy. Due to packing effects, the molecules in all monolayers are substantially tilted. In the presence of a methylene spacer the tilt is slightly less pronounced. The selenolate monolayers exhibit smaller defect densities and therefore are more densely packed than their thiolate analogues. The Se–Au binding energy in the investigated SAMs was found to be higher than the S–Au binding energy.

  17. Triptycene-terminated thiolate and selenolate monolayers on Au(111).

    Science.gov (United States)

    Liu, Jinxuan; Kind, Martin; Schüpbach, Björn; Käfer, Daniel; Winkler, Stefanie; Zhang, Wenhua; Terfort, Andreas; Wöll, Christof

    2017-01-01

    To study the implications of highly space-demanding organic moieties on the properties of self-assembled monolayers (SAMs), triptycyl thiolates and selenolates with and without methylene spacers on Au(111) surfaces were comprehensively studied using ultra-high vacuum infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy and thermal desorption spectroscopy. Due to packing effects, the molecules in all monolayers are substantially tilted. In the presence of a methylene spacer the tilt is slightly less pronounced. The selenolate monolayers exhibit smaller defect densities and therefore are more densely packed than their thiolate analogues. The Se-Au binding energy in the investigated SAMs was found to be higher than the S-Au binding energy.

  18. AFM-assisted fabrication of thiol SAM pattern with alternating quantified surface potential

    Directory of Open Access Journals (Sweden)

    Simons Janet

    2011-01-01

    Full Text Available Abstract Thiol self-assembled monolayers (SAMs are widely used in many nano- and bio-technology applications. We report a new approach to create and characterize a thiol SAMs micropattern with alternating charges on a flat gold-coated substrate using atomic force microscopy (AFM and Kelvin probe force microscopy (KPFM. We produced SAMs-patterns made of alternating positively charged, negatively charged, and hydrophobic-terminated thiols by an automated AFM-assisted manipulation, or nanografting. We show that these thiol patterns possess only small topographical differences as revealed by AFM, and distinguished differences in surface potential (20-50 mV, revealed by KPFM. The pattern can be helpful in the development of biosensor technologies, specifically for selective binding of biomolecules based on charge and hydrophobicity, and serve as a model for creating surfaces with quantified alternating surface potential distribution.

  19. Inhibition of copper corrosion in sodium chloride solution by the self-assembled monolayer of sodium diethyldithiocarbamate

    Energy Technology Data Exchange (ETDEWEB)

    Liao, Q.Q., E-mail: liaoqq1971@yahoo.com.c [Key Lab of Shanghai Colleges and Universities for Electric Power Corrosion Control and Applied Electrochemistry, Shanghai Engineering Research Center of Energy - Saving in Heat Exchange Systems, Shanghai University of Electric Power, Shanghai 200090 (China); Yue, Z.W.; Yang, D. [Key Lab of Shanghai Colleges and Universities for Electric Power Corrosion Control and Applied Electrochemistry, Shanghai Engineering Research Center of Energy - Saving in Heat Exchange Systems, Shanghai University of Electric Power, Shanghai 200090 (China); Wang, Z.H. [Department of Chemistry, Tongji University, Shanghai 200092 (China); Li, Z.H. [Department of Chemistry, Fudan University, Shanghai 200433 (China); Ge, H.H. [Key Lab of Shanghai Colleges and Universities for Electric Power Corrosion Control and Applied Electrochemistry, Shanghai Engineering Research Center of Energy - Saving in Heat Exchange Systems, Shanghai University of Electric Power, Shanghai 200090 (China); Li, Y.J. [Department of Chemistry, Tongji University, Shanghai 200092 (China)

    2011-05-15

    Research highlights: DDTC is of low toxicity. DDTC SAM had good corrosion inhibition effects on copper in 3% NaCl solution. DDTC SAM was chemisorbed on copper surface by its S atoms. - Abstract: Sodium diethyldithiocarbamate (DDTC) self-assembled monolayer (SAM) on copper surface has been investigated by SERS and EDS and the results show that DDTC SAM is chemisorbed on copper surface by its S atoms with tilted orientation. Corrosion inhibition ability of DDTC SAM was measured in 3% NaCl solution using electrochemical methods. The impedance results indicate that the maximum inhibition efficiency of DDTC SAM can reach 99%. Quantum chemical calculations show that DDTC has relatively small {Delta}E between HOMO and LUMO and large negative charge in its two sulfur atoms, which facilitates the formation of a DDTC SAM on copper surface.

  20. Effect of Alkyl Chain Length on Carboxylic Acid SAMs on Ti-6Al-4V

    Directory of Open Access Journals (Sweden)

    Gavin A. Buckholtz

    2012-07-01

    Full Text Available The formation of methyl-terminated carboxylic acid self-assembled monolayers (SAMs with even numbers of carbons, from eighteen to thirty, was investigated on the oxide surface of Ti-6Al-4V and component metal oxides. Modified surfaces were characterized using diffuse reflectance infrared Fourier transform spectroscopy (DRIFT, matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS and contact angle analysis. Infrared spectroscopy indicated that using aerosol spray deposition techniques, stable, all-trans SAMs of octacosanoic (28 carbons and triacontanoic (30 carbons acids were formed on the alloy. Films were similarly formed on titanium and aluminum oxide. The surface of vanadium oxide exhibited limited reactivity. MALDI-TOF MS confirmed that formed films were monolayers, without multilayers or aggregates present. Water contact angles are indicative of the presence of hydrophobic methyl groups at the interface. This stable carboxylic acid SAM formation could be a useful alternative to phosphonic acid SAMs for corrosion and other applications.

  1. Cross-Reactive Sensor Array for Metal Ion Sensing Based on Fluorescent SAMs

    Directory of Open Access Journals (Sweden)

    Mercedes Crego-Calama

    2007-09-01

    Full Text Available Fluorescent self assembled monolayers (SAMs on glass were previouslydeveloped in our group as new sensing materials for metal ions. These fluorescent SAMs arecomprised by fluorophores and small molecules sequentially deposited on a monolayer onglass. The preorganization provided by the surface avoids the need for complex receptordesign, allowing for a combinatorial approach to sensing systems based on small molecules.Now we show the fabrication of an effective microarray for the screening of metal ions andthe properties of the sensing SAMs. A collection of fluorescent sensing SAMs wasgenerated by combinatorial methods and immobilized on the glass surfaces of a custom-made 140 well microtiter-plate. The resulting libraries are easily measured and show variedresponses to a series cations such as Cu2+ , Co2+ , Pb2+ , Ca2+ and Zn2+ . These surfaces are notdesigned to complex selectively a unique analyte but rather they are intended to producefingerprint type responses to a range of analytes by less specific interactions. The unselectiveresponses of the library to the presence of different cations generate a characteristic patternfor each analyte, a “finger print” response.

  2. Cross-Reactive Sensor Array for Metal Ion Sensing Based on Fluorescent SAMs

    Science.gov (United States)

    Basabe-Desmonts, Lourdes; van der Baan, Frederieke; Zimmerman, Rebecca S.; Reinhoudt, David N.; Crego-Calama, Mercedes

    2007-01-01

    Fluorescent self assembled monolayers (SAMs) on glass were previously developed in our group as new sensing materials for metal ions. These fluorescent SAMs are comprised by fluorophores and small molecules sequentially deposited on a monolayer on glass. The preorganization provided by the surface avoids the need for complex receptor design, allowing for a combinatorial approach to sensing systems based on small molecules. Now we show the fabrication of an effective microarray for the screening of metal ions and the properties of the sensing SAMs. A collection of fluorescent sensing SAMs was generated by combinatorial methods and immobilized on the glass surfaces of a custom-made 140 well microtiter-plate. The resulting libraries are easily measured and show varied responses to a series cations such as Cu2+, Co2+, Pb2+, Ca2+ and Zn2+. These surfaces are not designed to complex selectively a unique analyte but rather they are intended to produce fingerprint type responses to a range of analytes by less specific interactions. The unselective responses of the library to the presence of different cations generate a characteristic pattern for each analyte, a “finger print” response.

  3. Sam37 is crucial for formation of the mitochondrial TOM-SAM supercomplex, thereby promoting β-barrel biogenesis.

    Science.gov (United States)

    Wenz, Lena-Sophie; Ellenrieder, Lars; Qiu, Jian; Bohnert, Maria; Zufall, Nicole; van der Laan, Martin; Pfanner, Nikolaus; Wiedemann, Nils; Becker, Thomas

    2015-09-28

    Biogenesis of mitochondrial β-barrel proteins requires two preprotein translocases, the general translocase of the outer membrane (TOM) and the sorting and assembly machinery (SAM). TOM and SAM form a supercomplex that promotes transfer of β-barrel precursors. The SAM core complex contains the channel protein Sam50, which cooperates with Sam35 in precursor recognition, and the peripheral membrane protein Sam37. The molecular function of Sam37 has been unknown. We report that Sam37 is crucial for formation of the TOM-SAM supercomplex. Sam37 interacts with the receptor domain of Tom22 on the cytosolic side of the mitochondrial outer membrane and links TOM and SAM complexes. Sam37 thus promotes efficient transfer of β-barrel precursors to the SAM complex. We conclude that Sam37 functions as a coupling factor of the translocase supercomplex of the mitochondrial outer membrane. © 2015 Wenz et al.

  4. SAM and the Particle Physics Data Grid

    Institute of Scientific and Technical Information of China (English)

    LauriLoebel-Carpenter; LeeLueking; 等

    2001-01-01

    The D0 experiment's data and job management system software,SAM,is an operational prototype of many of the concepts being developed for Grid computing .We explain how the components of SAM map into the Data Grid architecture,We discuss the future use of Grid components to either replace existing components of SAM or to extend its functionality and utility.owrk being carried out as part of the Particle Physics Data Grid(PPDG) project.

  5. Self-assembled alkanethiol monolayers on gold surfaces: resolving the complex structure at the interface by STM.

    Science.gov (United States)

    Guo, Quanmin; Li, Fangsen

    2014-09-28

    The surface properties of metals and metal oxides can be modified by adding a single layer of organic molecules. A most popular route for depositing such a molecular layer is via the formation of self-assembled monolayers (SAMs). The molecules that form SAMs have a functionality which binds to the surface and the adsorption is self-regulated to terminate at exactly one single molecular layer. The very first example, which has become the most widely studied system, of SAMs on metal surfaces consists of chemisorbed alkylthiolate on gold. Despite the simplicity in the preparation of alkanethiol SAMs and the seemingly straightforward structure of such SAMs, the detailed bonding between the sulfur head group and gold is still subject to debate. Experimental and theoretical effort in the last six years has led to a much improved understanding of this classical system of SAMs. In this review, we will highlight the most recent progress in the study of the interfacial structure of alkanethiol SAMs on gold. We focus on the important phenomenon of phase transition that occurs from n-propanethiol to n-butanethiol, and propose a unified structural model to explain how the (3 × 4) phase for short chain alkanethiol monolayers (methyl-, ethyl- and propylthiolate monolayers) changes into the (3 × 2√3)-rect./c(4 × 2) phase for long chain molecular monolayers.

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

    Science.gov (United States)

    Cernetic, Nathan

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

  7. Atomic-level elucidation of the initial stages of self-assembled monolayer metallization and nanoparticle formation.

    Science.gov (United States)

    Keith, John A; Jacob, Timo

    2010-11-02

    The development of high-performance molecular electronics and nanotech applications requires deep understanding of atomic level structural, electronic, and magnetic properties of electrode/molecular interfaces. Recent electrochemical experiments on self-assembled monolayers (SAMs) have identified highly practical means to generate nanoparticles and metal monolayers suspended above substrate surfaces through SAM metallizations. A rational basis why this process is even possible is not yet well-understood. To clarify the initial stages of interface formation during SAM metallization, we used first-principles spin-polarized density functional theory (DFT) calculations to study Pd diffusion on top of 4-mercaptopyridine (4MP) SAMs on Au(111). After distinguishing potential-energy surfaces (PESs) for different spin configurations for transition metal atoms on the SAM, we find adatom diffusion is not possible over the clean 4MP-SAM surface. Pre-adsorption of transition-metal atoms, however, facilitates atomic diffusion that appears to explain multiple reports on experimentally observed island and monolayer formation on top of SAMs. Furthermore, these diffusions most likely occur by moving across low-lying and intersecting PESs of different spin states, opening the possibility of magnetic control over these systems. Vertical diffusion processes were also investigated, and the electrolyte was found to play a key role in preventing metal permeation through the SAM to the substrate.

  8. 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.

  9. Oxygen Attachment on Alkanethiolate SAMs Induced by Low-Energy Electron Irradiation

    Science.gov (United States)

    Massey, Sylvain; Bass, Andrew D.; Steffenhagen, Marie; Sanche, Léon

    2013-01-01

    Reactions of 18O2 with self-assembled monolayer (SAM) films of 1-dodecanethiol, 1-octadecanethiol, 1-butanethiol, and benzyl mercaptan chemisorbed on gold, were studied by the electron stimulated desorption (ESD) of anionic fragments over the incident electron energy range 2–20 eV. Dosing the SAMs with 18O2 at 50 K, results in the ESD of 18O− and 18OH−. Electron irradiation of samples prior to 18O2 deposition demonstrates that intensity of subsequent 18O− and 18OH− desorption signals increase with electron fluence and that absent electron pre-irradiation, no 18O− and 18OH− ESD signals are observed, since oxygen is unable to bind to the SAMs. A minimum incident electron energy of 6–7 eV is required to initiate the binding of 18O2 to the SAMs. O2 binding is proposed to proceed by the formation of CHx−1• radicals via resonant dissociative electron attachment and non-resonant C–H dissociation processes. The weaker signals of 18O− and 18OH− from short-chain SAMs are related to the latter’s resistance to electron induced damage, due to the charge-image dipole quenching and electron delocalization. Comparison between the present results and those for DNA oligonucleotides self-assembled on Au [Mirsaleh-Kohan, N. et al. J. Chem. Phys. 2012, 136, 235104] indicates that the oxygen binding mechanism is common to both systems. PMID:23537075

  10. Formation of octadecyltrichlorosilane (OTS) self-assembled monolayers on amorphous alumina

    Science.gov (United States)

    Kelkar, Sanket S.; Chiavetta, David; Wolden, Colin A.

    2013-10-01

    The kinetics and thermodynamics of octadecyltrichlorosilane (OTS) self-assembled monolayers (SAMs) on vapor deposited alumina were quantified. Ozone cleaning serves to create well-defined hydrophilic surfaces for OTS attachment, and the use of heptane as a solvent enables the formation of high quality SAMs under ambient conditions. The kinetics was characterized as a function of OTS concentration using contact angle goniometry, ellipsometry and Fourier transform infrared (FTIR) spectroscopy. The kinetics of SAM formation and the saturation contact angle (∼100̊) on alumina are comparable to what has been observed for OTS on silicon. The free energy of adsorption with ΔGads values ranged from -7.5 to -5.4 kcal/mol, and the SAMs were stable up to 230 ̊C. The critical surface tension of the OTS monolayer was found to be 21.4 dyne/cm.

  11. Formation of octadecyltrichlorosilane (OTS) self-assembled monolayers on amorphous alumina

    Energy Technology Data Exchange (ETDEWEB)

    Kelkar, Sanket S.; Chiavetta, David; Wolden, Colin A., E-mail: cwolden@mines.edu

    2013-10-01

    The kinetics and thermodynamics of octadecyltrichlorosilane (OTS) self-assembled monolayers (SAMs) on vapor deposited alumina were quantified. Ozone cleaning serves to create well-defined hydrophilic surfaces for OTS attachment, and the use of heptane as a solvent enables the formation of high quality SAMs under ambient conditions. The kinetics was characterized as a function of OTS concentration using contact angle goniometry, ellipsometry and Fourier transform infrared (FTIR) spectroscopy. The kinetics of SAM formation and the saturation contact angle (∼100{sup o}) on alumina are comparable to what has been observed for OTS on silicon. The free energy of adsorption with ΔG{sub ads} values ranged from −7.5 to −5.4 kcal/mol, and the SAMs were stable up to 230 {sup o}C. The critical surface tension of the OTS monolayer was found to be 21.4 dyne/cm.

  12. 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...

  13. Samsø Energy Vision 2030

    DEFF Research Database (Denmark)

    Mathiesen, Brian Vad; Hansen, Kenneth; Ridjan, Iva

    The purpose of this report is to investigate potential scenarios for converting Samsø into 100% renewable energy supply in 2030 with focus on local electricity and biomass resources. Firstly, a 2013 reference scenario is established to investigate whether Samsø is 100% renewable today. Next, scen...

  14. 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.

  15. Controlling charge injection by self-assembled monolayers in bottom-gate and top-gate organic field-effect transistors

    NARCIS (Netherlands)

    Gholamrezaie, F.; Asadi, K.; Kicken, R.A.H.J.; Langeveld-Voss, B.M.W.; Leeuw, D.M. de; Blom, P.W.M.

    2011-01-01

    We investigate the modulation of the charge injection in organic field-effect transistors with self-assembled monolayers (SAMs) using both a bottom-gate and a top-gate geometry. The current modulation by using SAMs is more pronounced in the top-gate geometry due to the better defined upper surface o

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

    Science.gov (United States)

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

  17. Study of the resistance of SAMs on aluminium to acidic and basic solutions using dynamic contact angle measurement.

    Science.gov (United States)

    Liakos, Ioannis L; Newman, Roger C; McAlpine, Eoghan; Alexander, Morgan R

    2007-01-30

    We report the development of a method to determine the aqueous stability of self-assembled monolayers (SAMs) using the Wilhelmy plate dynamic contact angle (DCA) experiment. The DCA is measured in solutions over a range of pH values for alkyl carboxylic and alkyl phosphonic acid SAMs formed on magnetron-sputtered aluminum. The change in DCA on repeated immersion is used as a measure of the degradation of the SAMs by hydrolytic attack. The short and intermediate chain length alkyl acids are not stable in water of neutral pH, whereas molecules with the longest alkyl chains show considerably greater stability in neutral and both high and low pH solutions. The packing density inferred from the DCA and the contact angle hysteresis suggests the C18CO2H monolayer to be slightly less well packed than that of the C18P(=O)(OH)2; this is consistent with related friction force microscopy and infrared reflection absorption spectroscopy findings published elsewhere (Foster, T. T.; Alexander, M. R.; Leggett, G. J.; McAlpine, E. Langmuir 2006, 22, 9254-9259). The resistance of the SAMs to acid and alkaline environments is discussed in the context of aluminum oxide solubility, SAM packing density, and the resistance of the interfacial phosphate and carboxylate functionalities to different aqueous conditions.

  18. Optimizing the quality of monoreactive perfluoroalkylsilane-based self-assembled monolayers.

    Science.gov (United States)

    Gong, Yuanyuan; Wang, Michael C P; Zhang, Xin; Ng, Him Wai; Gates, Byron D

    2012-08-14

    Self-assembled monolayers (or SAMs) created from monoreactive perfluoroalkylsilanes by deposition from a toluene solution are investigated for the dependence of their quality on processing conditions. Surface-sensitive spectroscopic techniques are used to provide feedback on the processing conditions in which solution temperature, silane concentration, and reaction time are optimized to improve the quality of these SAMs. For these analyses, monolayers are formed at 20, 40, 60, or 80 °C from solutions containing between 0.5 and 5 mM perfluoroalkylsilane over a period of up to 5 h. Physically adsorbed molecules are removed from these surfaces by extraction to determine the quality of the covalently bound monolayer. Water contact angle measurements, spectroscopic ellipsometry, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM), respectively, are used in combination to assess the uniformity of the surface hydrophobicity, monolayer thickness, composition of the assembled perfluoroalkylsilane molecules, and topography of these monolayers. A comparison is also presented for two approaches to fill defects within these solvent extracted monolayers with more perfluoroalkylsilane molecules, aiming to improve the quality of these SAMs. A detailed XPS analysis is used to assess both the relative changes in density and average tilt of molecules within the monolayers as the process temperature is increased in increments from 20 to 80 °C. The observed differences in quality of the SAMs are attributed to temperature- and time-dependent organization and reactivity of the silane molecules. Although the assembly of these monoreactive perfluoroalkylsilanes is driven by thermodynamics, the quality of the monolayer is ultimately limited by the kinetics and mass transport during this assembly process. Lessons from these studies can be exploited for improving the quality of monolayers composed of other alkylsilane molecules that are covalently bound to the surfaces

  19. Self-Assembled Monolayers Get Their Final Finish via a Quasi-Langmuir-Blodgett Transfer.

    Science.gov (United States)

    Meltzer, Christian; Dietrich, Hanno; Zahn, Dirk; Peukert, Wolfgang; Braunschweig, Björn

    2015-04-28

    The growth of self-assembled monolayers (SAMs) of octadecylphosphonic acid (ODPA) molecules on α-Al2O3(0001) and subsequent dewetting of the SAMs were studied with a combination of in situ sum-frequency generation (SFG) and molecular dynamics (MD) simulations. Although SAM growth after deposition times >8 h reduces to nearly negligible values, the resultant ODPA SAMs in solution are still not in a well-ordered state with the alkyl chains in all-trans configurations. In fact, in situ SFG spectroscopy revealed a comparatively high concentration of gauche defects of the SAM in the ODPA 2-propanol solution even after a growth time of 16 h. Here, results of the MD simulations strongly suggest that defects can be caused by ODPA molecules which are not attached to the substrate but are incorporated into the SAM layer with the polar headgroup oriented into the 2-propanol solvent. This inverted adsorption geometry of additional ODPA molecules blocks adsorption sites and thus stabilizes the SAM without improving ordering to an extent that all molecules are in the all-trans configuration. While persistent in solution, the observed defects can be healed out when the SAMs are transferred from the solvent to a gas phase. During this process, a quasi-Langmuir-Blodgett transfer of molecules takes place which drives the SAM into a higher conformational state and significantly improves its quality.

  20. 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.

  1. The Effects of Contact Interface on the Friction Characteristics of Self-assembly Monolayers

    Institute of Scientific and Technical Information of China (English)

    ZHANGHui-chen; GAOYu-zhou; YANLi

    2004-01-01

    The effects of different contact interfaces on the friction characteristics of OTS self-assembled monolayers were investigated by a universal micro-tribometer in different sliding velocities. The results indicate that there exist lower friction coefficients between OTS SAMs and Ti, Ni and Cu films deposited on GCrl5 steel balls than those between OTS SAMs and GCr15 steel ball. The friction coefftcient between OTS SAMs and Ti film is the largest, and the friction coefficient between OTS SAMs and Cu film is the least in these three films, which depends the iatrinsic characteristics of the materials. The friction coefficients between OTS SAMs and GCrI5 steel balland three nanometer films increase with the sliding velachy increasing, which can be explained by the relaxationcharacteristics of OTS molecules.

  2. Inhibition of copper corrosion by the formation of Schiff base self-assembled monolayers

    Science.gov (United States)

    Zhang, Jing; Liu, Zheng; Han, Guo-Cheng; Chen, Shi-Liang; Chen, Zhencheng

    2016-12-01

    Self-assembled monolayers (SAMs) of 4-((2-thiophenecarboxylic acid hydrazide) methylene) benzoic acid (HD2) (denoted as HD2-SAMs) were formed on copper surface. The SAMs were characterized by scanning electron microscopy and X-ray photoelectron spectroscopy. Polarization curve and weight loss methods indicated that the highest inhibition efficiency was 93.9% for CO2-saturated simulative oilfield water at a self-assembled time of 3 h. Potential-time curve, electrochemical impedance tests showed that HD2-SAMs on copper surface exhibited excellent inhibition effect at 30 °C. The adsorption behavior of HD2-SAMs on the copper surface followed the Langmuir adsorption isotherm, which was indicative of typically chemical adsorption. Quantum chemistry calculation showed that O and N atoms can interact with Cu atoms by coordination bonds which were the mainly active area of the adsorption of HD2 molecules.

  3. Preparation and characterization of 3-mercaptopropyl trimethoxysilane self-assembled monolayers

    Institute of Scientific and Technical Information of China (English)

    Tao Bai; Xianhua Cheng

    2008-01-01

    Silane coupling regent (3-mercaptopropyl trimethoxysilane (MPTS)) was prepared on the single-crystal silicon substrate to form 2-dimensional self-assembled monolayers (SAMs). The growth behavior of SAMs formed from 3-MPTS was investigated using atomic force microscopy (AFM), contact angle measurements, ellipsometry, and X-ray photoelectron spectroscopy (XPS). The formation behavior of MPTS SAMs was investigated by a series of AFM images and the roughness of MPTS SAMs on silicon sub- strates with the assembling time from 1 min to 24 h. The water contact angle measurements indicated the growth behavior of MPTS that correlated with the AFM measurements at different immersion times, too. The chemical states of the typical elements in the MPTS SAMs were analyzed using X-ray photoelectron spectroscopy. The results show that MPTS is self-assembled on the substrate. C 2008 University of Science and Technology Beijing. All rights reserved.

  4. Tribology of monolayer films: comparison between n-alkanethiols on gold and n-alkyl trichlorosilanes on silicon.

    Science.gov (United States)

    Booth, Brandon D; Vilt, Steven G; McCabe, Clare; Jennings, G Kane

    2009-09-01

    This Article presents a quantitative comparison of the frictional performance for monolayers derived from n-alkanethiolates on gold and n-alkyl trichlorosilanes on silicon. Monolayers were characterized by pin-on-disk tribometry, contact angle analysis, ellipsometry, and electrochemical impedance spectroscopy (EIS). Pin-on-disk microtribometry provided frictional analysis at applied normal loads from 10 to 1000 mN at a speed of 0.1 mm/s. At low loads (10 mN), methyl-terminated n-alkanethiolate self-assembled monolayers (SAMs) exhibited a 3-fold improvement in coefficient of friction over SAMs with hydroxyl- or carboxylic-acid-terminated surfaces. For monolayers prepared from both n-alkanethiols on gold and n-alkyl trichlorosilanes on silicon, a critical chain length of at least eight carbons is required for beneficial tribological performance at an applied load of 9.8 mN. Evidence for disruption of chemisorbed alkanethiolate SAMs with chain lengths n tribology wear tracks. The direct comparison between the tribological stability of alkanethiolate and silane monolayers shows that monolayers prepared from n-octadecyl dimethylchlorosilane and n-octadecyl trichlorosilane withstood normal loads at least 30 times larger than those that damaged octadecanethiolate SAMs. Collectively, our results show that the tribological properties of monolayer films are dependent on their internal stabilities, which are influenced by cohesive chain interactions (van der Waals) and the adsorbate-substrate bond.

  5. Determination of the shear modulus in self-assembled monolayers using quartz resonators

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, T.W.; Martin, S.J.; Frye, G.C.

    1994-06-01

    This work examined self-assembled monolayers (SAMs) of n-alkane thiols using quartz resonators to determine the shear storage and loss moduli. Network analyzer measurements of electrical admittance at fundamental and corresponding harmonic values are fit to an equivalent circuit model. Shear modulus depends on frequency; the modulus values are three orders of magnitude lower than expected for a liquid or elastomeric polymer, more like those of a dense gas or supercritical fluid. A density of around 0.45 g/cm{sup 3} is calculated for a dodecane thiol SAM; this is roughly half of the bulk density. In conclusion, quartz resonators can be used to inertially deform SAMs.

  6. Method for selective immobilization of macromolecules on self assembled monolayer surfaces

    Science.gov (United States)

    Laskin, Julia [Richland, WA; Wang, Peng [Billerica, MA

    2011-11-29

    Disclosed is a method for selective chemical binding and immobilization of macromolecules on solid supports in conjunction with self-assembled monolayer (SAM) surfaces. Immobilization involves selective binding of peptides and other macromolecules to SAM surfaces using reactive landing (RL) of mass-selected, gas phase ions. SAM surfaces provide a simple and convenient platform for tailoring chemical properties of a variety of substrates. The invention finds applications in biochemistry ranging from characterization of molecular recognition events at the amino acid level and identification of biologically active motifs in proteins, to development of novel biosensors and substrates for stimulated protein and cell adhesion.

  7. Characterization of self-assembled monolayers of porphyrins bearing multiple-thiol and photoelectric response

    Institute of Scientific and Technical Information of China (English)

    Jian Dong Yang; Xiao Quan Lu

    2012-01-01

    Self-assembled monolayers (SAMs) of thiol-derivatized porphyrin molecules on Au substrate have attracted extensively interest for use in sensing,optoelectronic devices and molecular electronics.In this paper,tetra-[p-(3-mercaptopropyloxy)-phenyl]-porphyrin was synthesized and self-assembled with thiol on Au substrate for porphyrin SAMs (PPS4).The electrochemical results demonstrated that PPS4 could form excellent SAMs on gold surface.Self-assembled nanojunctions of PPS4 were fabricated by using gold nanogap electrodes (gap width:ca.100 nm).With the light on/off,the nanojunctions showed current high/low as nanometer scaled photo switch.

  8. Fabrication of dynamic self-assembled monolayers for cell migration and adhesion studies.

    Science.gov (United States)

    Westcott, Nathan P; Yousaf, Muhammad N

    2011-01-01

    How cells interact with the extracellular matrix (ECM) is important for a number of fundamental -processes in cell biology. However, the ECM is highly complex and in order to simplify the matrix for cell biological studies, it has been modeled with self-assembled monolayers (SAMs) of alkanethiolates on gold substrates. In this chapter, we outline procedures to create dynamic surfaces by functionalizing SAMs. SAMs based on quinone, oxyamine, and alcohol-terminated thiols were used to immobilize cell adhesive peptides with spatial control. Cells were seeded to these surfaces to provide cell co-culture -patterns suitable for biological studies.

  9. Reactions Between Contaminants and Functionalized Organic Self-Assembled Monolayers in Aqueous Solutions

    Science.gov (United States)

    2006-05-16

    water disinfection , treatment can be costly, time consuming and require complex equipment. The use of self-assembled monolayers (SAMs) in this...ml of a solution containing 70 vol% of H2SO4 and 30 vol% of H2O2 (30 wt%) for 5 min. Subsequently, the powder was separated from the solution using...leaching of the SAM mainly due to oxidation of the CH2-units of the SAM by Oxone. Similar observations were made when H2O2 was used as the oxidation agent

  10. Photopatterning of self-assembled alkanethiolate monolayers on gold. A simple monolayer photoresist utilizing aqueous chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Huang, J.; Hemminger, J.C. (Univ. of California, Irvine, CA (United States)); Dahlgren, D.A. (Photometrics, Huntington Beach, CA (United States))

    1994-03-01

    In this paper we demonstrate that self-assembled monolayers (SAMs) of alkanethiols on gold can be used as effective photoresists. UV photolysis of an alkanethiol SAM generates the corresponding sulfonate in the monolayer film. The sulfonate is easily rinsed off of the surface with water, exposing a clean gold substrate, which can then be modified with subsequent chemistry. We describe here experiments in which an alkanethiol SAM on a gold film on silicon is irradiated through a mask, followed by immersion of the sample in an aqueous acid etching solution (HCI:HNO[sub 3]:H[sub 2]O = 3:1:4). The gold is etched away from the areas which have been exposed to UV radiation leaving a pattern which reproduces the original mask. The spatial resolution in the present experiments is limited by the mask which is a 6-[mu]m wire grid. Scanning electron microscopy images of patterned samples show sharp edges to the features suggesting that spatial patterning on the 1-[mu]m scale should be attainable with this simple chemistry. 11 refs., 4 figs.

  11. Molecular Dynamics Simulation of the Self-assembled Monolayers of 1-Adamantanethiolate and Its Derivatives on Au(111)Surfaces

    Institute of Scientific and Technical Information of China (English)

    ZHOU, Jun-Hong; ZHU, Rui-Xin; SHI, Liang-Wei; ZHANG, Tao; CHEN, Min-Bo

    2007-01-01

    The self-assembled monolayers (SAMs) of 1-adamantanethiolate and its derivatives on Au(111) surface were investigated. Density functional theory (DFT) calculation indicates that the most stable configuration for absorption is at the face centered cubic (fcc)-bridge site. Canonical ensemble molecular dynamics (MD) simulations were carried out to study the structures and energies of the SAMs. The ordered structures of the SAMs were analyzed by means of radial distribution function and the relative stability of the SAMs was compared. It was concluded by the comparison of various contributions to the SAM formation energy that the formation of the SAMs was determined by the intermolecular nonbonding interaction and the chemical bonding interaction of sulfur and gold.

  12. 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.

  13. Preparation of surface-tethered polymer layer on inorganic substrates by photoreactive self-assembled monolayer

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seong-Ho; Ohtsuka, Hanae [Tokyo University of Agriculture and Technology, Department of Organic and Polymer Materials Chemistry, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588 (Japan); Tria, Maria Celeste R. [University of Houston, Department of Chemistry, 136 Fleming Building, Houston, TX 77204-5008 (United States); Tanaka, Kuniaki [Tokyo University of Agriculture and Technology, Department of Organic and Polymer Materials Chemistry, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588 (Japan); Advincula, Rigoberto C. [Case Western Reserve University, Department of Macromolecular Science and Engineering, 2100 Adelbert Road, Cleveland, OH 44106 (United States); Usui, Hiroaki, E-mail: h_usui@cc.tuat.ac.jp [Tokyo University of Agriculture and Technology, Department of Organic and Polymer Materials Chemistry, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588 (Japan)

    2014-03-03

    A self-assembled monolayer (SAM) that has benzophenone (BP) terminal group was prepared on Si and indium–tin oxide (ITO) substrates, on which poly(9-vinyl carbazol) (PVK) was spin-coated and then irradiated with ultraviolet (UV) light. Upon UV irradiation, the BP unit reacted with the PVK backbone, yielding a crosslinked PVK layer that was covalently tethered to the substrate surface. Using this procedure, a patterned thin film of PVK was obtained by irradiating UV light through a photomask and then rinsing in chloroform. When polystylene (PSt) was spin-coated on the BP-SAM, only a thin interfacial layer was tethered by UV irradiation because PSt does not crosslink upon UV irradiation. The BP-SAM improved the adhesion strength between the PVK layer and ITO substrate without reducing the carrier injection from ITO to PVK. The photoreactive BP-SAM appeared to be an effective method to improve the interface between an inorganic electrode and a polymer layer deposited on its surface. - Highlights: • Polyvinylcarbazole (PVK) was tethered to substrate by self-assembled monolayer (SAM). • The photoreactive SAM was effective in improving adhesion strength of the films. • This process was applied for photopatterning of PVK layer. • The photoreactive SAM did not impede carrier injection from electrode to PVK.

  14. Sum-frequency generation analyses of the structure of water at amphoteric SAM-liquid water interfaces.

    Science.gov (United States)

    Nomura, Kouji; Nakaji-Hirabayashi, Tadashi; Gemmei-Ide, Makoto; Kitano, Hiromi; Noguchi, Hidenori; Uosaki, Kohei

    2014-09-01

    Surfaces of both a cover glass and the flat plane of a semi-cylindrical quartz prism were modified with a mixture of positively and negatively charged silane coupling reagents (3-aminopropyltriethoxysilane (APTES) and 3-(trihydroxysilyl)propylmethylphosphonate (THPMP), respectively). The glass surface modified with a self-assembled monolayer (SAM) prepared at a mixing ratio of APTES:THPMP=4:6 was electrically almost neutral and was resistant to non-specific adsorption of proteins, whereas fibroblasts gradually adhered to an amphoteric (mixed) SAM surface probably due to its stiffness, though the number of adhered cells was relatively small. Sum frequency generation (SFG) spectra indicated that total intensity of the OH stretching region (3000-3600cm(-1)) for the amphoteric SAM-modified quartz immersed in liquid water was smaller than those for the positively and negatively charged SAM-modified quartz prisms and a bare quartz prism in contact with liquid water. These results suggested that water molecules at the interface of water and an amphoteric SAM-modified quartz prism are not strongly oriented in comparison with those at the interface of a lopsidedly charged SAM-modified quartz prism and bare quartz. The importance of charge neutralization for the anti-biofouling properties of solid materials was strongly suggested.

  15. STM study of short chain hydrophobic thiol SAMs on HOPG and Au capped HOPG under ambient conditions

    Science.gov (United States)

    Bowers, Alexis; Maurer, Mackenzie; Senevirathne, Indrajith

    2015-03-01

    Self-assembled monolayer(SAM) surfaces provide common architecture in many device applications including sensor engineering. The conductivity characteristics and surface molecular structure and orientation of these SAM are important as physiochemical properties are dependent on the surface arrangement. SAMs used in this study are short chain -R terminated (hydrophobic) 1-Butanethiol on Highly Oriented Pyrolytic Graphite (HOPG) surface and on thermally annealed Au thin film capped on HOPG. Scanning Tunneling Microscopy (STM), contact angle measurements and reflective spectroscopy are used to assess the SAM layered surfaces. Solutions of 1-Butanethiol, dissolved in 200 proof Ethanol with 5mM concentration were prepared for the self-assembly process. These solutions were used in developing SAMs on purchased, freshly cleaved HOPG substrates. Au thin layers were sputter deposited on HOPG and subsequently annealed. Initial data shows low Au deposition yields rougher inconsistent surfaces. Ambient conditions under which data was obtained impose fresh surfaces for each investigation. Tentative surface structure, consistency and thiol molecular arrangement of the SAM layer on HOPG and Au capped HOPG will be discussed. National Science Foundation.

  16. Quality Control Guidelines for SAM Chemical Methods

    Science.gov (United States)

    Learn more about quality control guidelines and recommendations for the analysis of samples using the chemistry methods listed in EPA's Selected Analytical Methods for Environmental Remediation and Recovery (SAM).

  17. Quality Control Guidelines for SAM Biotoxin Methods

    Science.gov (United States)

    Learn more about quality control guidelines and recommendations for the analysis of samples using the pathogen methods listed in EPA's Selected Analytical Methods for Environmental Remediation and Recovery (SAM).

  18. Quality Control Guidelines for SAM Radiochemical Methods

    Science.gov (United States)

    Learn more about quality control guidelines and recommendations for the analysis of samples using the radiochemistry methods listed in EPA's Selected Analytical Methods for Environmental Remediation and Recovery (SAM).

  19. Quality Control Guidelines for SAM Pathogen Methods

    Science.gov (United States)

    Learn more about quality control guidelines and recommendations for the analysis of samples using the biotoxin methods listed in EPA's Selected Analytical Methods for Environmental Remediation and Recovery (SAM).

  20. Discovery of charmed particles : Sam Ting

    CERN Multimedia

    1974-01-01

    The great physics event of the year was the discovery of charmed particles in the USA. One of the co-discoverers, Sam Ting, was at CERN involved in an ISR experiment and described the discovery to a packed auditorium.

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

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Fan; Zhang, Dakuan; Wang, Jianyu; Sheng, Yun; Wang, Xinran; Chen, Kunji; Zhou, Minmin [Key Laboratory of Advanced Photonic and Electronic Materials and School of Electronic Science and Engineering, Nanjing University, Nanjing 210093 (China); Yan, Shancheng [Key Laboratory of Advanced Photonic and Electronic Materials and School of Electronic Science and Engineering, Nanjing University, Nanjing 210093 (China); School of Geography and Biological Information, Nanjing University of Posts and Telecommunications, Nanjing 210046 (China); Shen, Jiancang; Pan, Lijia; Shi, Yi, E-mail: yshi@nju.edu.cn [Key Laboratory of Advanced Photonic and Electronic Materials and School of Electronic Science and Engineering, Nanjing University, Nanjing 210093 (China); Collaborative Innovation Center of Advanced Micro-structures, Nanjing University, Nanjing 210093 (China)

    2015-01-26

    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.

  2. 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.

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

    Science.gov (United States)

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

    2011-10-04

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

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

    Science.gov (United States)

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

    2016-05-14

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

  5. Influencia del Estado de Oxidación del Ión Cobalto en la Estabilidad de Electrodos Modificados con Monocapas SAM-TOA-ANTA-Con+-HRP-NHis.

    Directory of Open Access Journals (Sweden)

    Pedro R. Matheus*

    Full Text Available Influence of state oxidation of cobalt ion in the stability electrodes modified with monolayers SAM-TOA-ANTA-Con+-HRP-NHis. Quartz Crystal Microbalance (QCM was used to investigate the adsorption of the HRP-NHis enzyme (horseradish peroxidase, which was modified by the addition of a tail of six histidine on its extreme N-terminal. The QCM operating at flow of 0.025 mL min-1 on a crystal whose gold electrode was modified with monolayers of SAM-TOA-ANTA-Co2+ and SAM-TOA-ANTA -Co3+. The oxidize form was obtained from the electrochemical oxidation of a monolayer of SAM-TOA-ANTA-Co2+. The results suggest that the HRP-NHis is attached to both monolayers in a similar way; on the contrary, the desortion of the attached protein is dramatically different. Thus, whereas the ligand-Co2+ bonds are reversible, which allows that the anchored protein is easily replaced by imidazol molecules. The 3+ oxidation state of the metal does not allow the interchange of protein by the imidazol molecules.

  6. Fluorescence detection and imaging of amino-functionalized organic monolayer

    Energy Technology Data Exchange (ETDEWEB)

    Shirahata, Naoto [National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan)], E-mail: SHIRAHATA.naoto@nims.go.jp; Furumi, Seiichi [National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Masuda, Yoshitake; Hozumi, Atsushi [National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimo-shidami, Moriyama, Nagoya 463-8560 (Japan); Sakka, Yoshio [National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan)

    2008-03-03

    Amino-terminated organic monolayer formed on silicon covered with native oxide (SiO{sub 2}/Si) was directly visualized under observation with fluorescent microscopy. This successful fluorescence visualization was achieved by a combination of fluorescamine method and photopatterning of the amino-terminated surface. As a typical example, an amino-terminated self-assembled monolayer (SAM) was formed on SiO{sub 2}/Si substrate in a vapor of 12.5 vol.% solution of N-(6-aminohexyl)-3-aminopropyltrimethoxysilane [H{sub 2}N(CH{sub 2}){sub 6}NH(CH{sub 2}){sub 3}Si(OCH{sub 3}){sub 3}, AHAPS] diluted with absolute toluene. A micropattern of AHAPS-SAM was photolithographycally prepared using 172 nm vacuum ultraviolet (VUV) light under a reduced pressure of 10 Pa for 30 min through a photomask. The resultant micropattern composed of AHAPS- and SiOH-covered regions was provided to fluorescamine method. Due to a nonluminescence of fluorescamine itself under UV/visible irradiation, a fluorescent emission could not be observed on SiOH regions of the micropattern. In contrast, fluorescamine reacted with the outermost amino group of the AHAPS-SAM to give a fluorescent emission. A comprehensible fluorescence method for verifying formation of an amino-terminated organic monolayer has been developed.

  7. Unraveling the dynamics and structure of functionalized self-assembled monolayers on gold using 2D IR spectroscopy and MD simulations.

    Science.gov (United States)

    Yan, Chang; Yuan, Rongfeng; Pfalzgraff, William C; Nishida, Jun; Wang, Lu; Markland, Thomas E; Fayer, Michael D

    2016-05-03

    Functionalized self-assembled monolayers (SAMs) are the focus of ongoing investigations because they can be chemically tuned to control their structure and dynamics for a wide variety of applications, including electrochemistry, catalysis, and as models of biological interfaces. Here we combine reflection 2D infrared vibrational echo spectroscopy (R-2D IR) and molecular dynamics simulations to determine the relationship between the structures of functionalized alkanethiol SAMs on gold surfaces and their underlying molecular motions on timescales of tens to hundreds of picoseconds. We find that at higher head group density, the monolayers have more disorder in the alkyl chain packing and faster dynamics. The dynamics of alkanethiol SAMs on gold are much slower than the dynamics of alkylsiloxane SAMs on silica. Using the simulations, we assess how the different molecular motions of the alkyl chain monolayers give rise to the dynamics observed in the experiments.

  8. Surface engineering and adhesion modification of SAM surfaces of 1-hexanethiol and 1-decanethiol: confining Staphylococcus aureus

    Science.gov (United States)

    Olsen, Morgan; Amroski, Alicia; Calabrese, Joseph; Senevirathne, Reshani; Senevirathne, Indrajith

    2012-02-01

    Engineering surfaces for adhesion and confinement of bacteria is interesting towards development of respective biosensors, and bio machine interfacing. Investigation was focused towards modification of surfaces towards confinement and entrapment of the nonpathogenic strain Staphylococcus aureus or similar pathogenic strains and to study surface engineering. Clean, flat Au(111) on mica surfaces were used for self assembly for Self Assembled Monolayers (SAM). 1-hexanethiol, and 1-decanethiol were used at total 5 mM solutions in varying ratios, in 200 proof Ethanol solution. Resulting SAM layers were investigated for surface corrugation, morphology and structure variation at different thiol ratios. Observations will be discussed, quantitatively and qualitatively. Eventual mixture ratios were so selected towards optimum conditions for confining Staphylococcus aureus as a model system. SAM surfaces were investigated using intermittent contact, noncontact, lateral force and contact modes of Atomic Force Microscopy (AFM).

  9. Long-term stability of self-assembled monolayers on 316L stainless steel.

    Science.gov (United States)

    Kaufmann, C R; Mani, G; Marton, D; Johnson, D M; Agrawal, C M

    2010-04-01

    316L stainless steel (316L SS) has been extensively used for making orthopedic, dental and cardiovascular implants. The use of phosphonic acid self-assembled monolayers (SAMs) on 316L SS has been previously explored for potential biomedical applications. In this study, we have investigated the long-term stability of methyl (-CH(3)) and carboxylic acid (-COOH)-terminated phosphonic acid SAMs on 316L under physiological conditions. The stability of SAMs on mechanically polished and electropolished 316L SS was also investigated as a part of this study. Well-ordered and uniform -CH(3)- and -COOH-terminated SAMs were coated on mechanically polished and electropolished 316L SS surfaces. The long-term stability of SAMs on 316L SS was investigated for up to 28 days in Tris-buffered saline (TBS) at 37 degrees C using x-ray photoelectron spectroscopy, atomic force microscopy and contact angle goniometry. A significant amount of phosphonic acid molecules was desorbed from the 316L SS surfaces within 1 to 7 days of TBS immersion followed by a slow desorption of molecules over the remaining days. The -COOH-terminated SAM was found to be more stable than the -CH(3)-terminated SAM on both mechanically and electropolished surfaces. No significant differences in the desorption behavior of SAMs were observed between mechanically and electropolished 316L SS surfaces.

  10. Molecular Understanding on the Underwater Oleophobicity of Self-Assembled Monolayers: Zwitterionic versus Nonionic.

    Science.gov (United States)

    Cheng, Gang; Liao, Mingrui; Zhao, Daohui; Zhou, Jian

    2017-02-21

    Molecular dynamics simulations are conducted to investigate the underwater oleophobicity of self-assembled monolayers (SAMs) with different head groups. Simulation results show that the order of underwater oleophobicity of SAMs is methyl oleophobicity have better antifouling performance. Further study on the effect of different alkyl ammonium ions on mixed-charged SAMs reveals that the underwater OCAs are >143.6° for all SAMs; mixed-charged SAMs containing primary alkyl ammonium ion are likely to possess the best underwater oleophobicity for its strong hydration capacity. It seems that alkyl sulfonate anion (SO3(-)) is more hydrophilic than alkyl trimethylammonium ion (NC3(+)) for the hydrophobic methyl groups on nitrogen atoms and that the hydration of SO3(-) in mixed-charged SAMs can be seriously blocked by NC3(+). The monomer of SO3(-) should be slightly longer than that of NC3(+) to obtain better underwater oleophobicity in NC3(+)-/SO3(-)-SAMs. In addition, the underwater oleophobicity of SAMs might become worse at low grafting densities. This work systematically proves that a zwitterionic surface is more underwater oleophobic than a nonionic surface. These results will help for the design and development of superoleophobic surfaces.

  11. Simultaneous Determination of Dopamine and Uric Acid at 2-Amino-5-mercapto-[1, 3, 4]triazole Self-assembled Monolayers Gold Electrode

    Institute of Scientific and Technical Information of China (English)

    Chuan Yin LIU; Li Zhu YANG; Feng SONG; Ling Yan JIANG; Guang Han LU

    2005-01-01

    A newly synthesized reagent 2-amino-5-mercapto-[ 1, 3, 4]triazole (MATZ) has been used to fabricate self-assembled monolayers (SAMs) on gold electrode for the first time. The SAMs electrode was characterized by electrochemical methods and scanning electronic microscopy (SEM),the SAMs electrode can be used to determinate dopamine (DA) and uric acid (UA) simultaneously with a detection limit of 8×10-7 mol/L for DA and 1×10-6 mol/L for UA respectively. The SAMs can also be used to detect the contents of DA and UA in synthetic urine sample with satisfactory results.

  12. 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

  13. Amino-terminated biphenylthiol self-assembled monolayers as highly reactive molecular templates

    Energy Technology Data Exchange (ETDEWEB)

    Meyerbroeker, N.; Waske, P.; Zharnikov, M., E-mail: Michael.Zharnikov@urz.uni-heidelberg.de

    2015-03-14

    Self-assembled monolayers (SAMs) with amino tail groups are of interest due to their ability of coupling further compounds. Such groups can be, in particular, created by electron irradiation of nitro- or nitrile-substituted aromatic SAMs, which provide a basis for chemical nanolithography and the fabrication of functionalized nanomembranes. An estimate of reactivity of the created amino groups requires a reference system of homogeneous, amino-terminated aromatic SAMs, which can also be used as a highly reactive molecular template. Here, we describe the synthesis of 4′-aminobiphenyl-4-thiol (ABPT) and SAMs prepared from this precursor on Au(111). The monolayers were characterized by X-ray photoelectron spectroscopy and near edge X-ray absorption fine structure spectroscopy, which revealed that they are well defined, chemically uniform, densely packed, and highly ordered. To examine the influence of electron irradiation on the reactivity of the terminal amino groups, ABPT SAMs were exposed to low energy (50 eV) electrons up to a dose of 40 mC/cm{sup 2} and, subsequently, immersed in either trifluoroacetic, pentafluoropropionic, or heptafluorobutyric anhydride. Analysing the amount of the attached anhydride species made it possible to determine the percentage of reactive amino groups as well as the effect of steric hindrance upon the coupling reaction. The above results are compared with those obtained for the well-established nitro-substituted biphenylthiol monolayers.

  14. Amino-terminated biphenylthiol self-assembled monolayers as highly reactive molecular templates.

    Science.gov (United States)

    Meyerbroeker, N; Waske, P; Zharnikov, M

    2015-03-14

    Self-assembled monolayers (SAMs) with amino tail groups are of interest due to their ability of coupling further compounds. Such groups can be, in particular, created by electron irradiation of nitro- or nitrile-substituted aromatic SAMs, which provide a basis for chemical nanolithography and the fabrication of functionalized nanomembranes. An estimate of reactivity of the created amino groups requires a reference system of homogeneous, amino-terminated aromatic SAMs, which can also be used as a highly reactive molecular template. Here, we describe the synthesis of 4'-aminobiphenyl-4-thiol (ABPT) and SAMs prepared from this precursor on Au(111). The monolayers were characterized by X-ray photoelectron spectroscopy and near edge X-ray absorption fine structure spectroscopy, which revealed that they are well defined, chemically uniform, densely packed, and highly ordered. To examine the influence of electron irradiation on the reactivity of the terminal amino groups, ABPT SAMs were exposed to low energy (50 eV) electrons up to a dose of 40 mC/cm(2) and, subsequently, immersed in either trifluoroacetic, pentafluoropropionic, or heptafluorobutyric anhydride. Analysing the amount of the attached anhydride species made it possible to determine the percentage of reactive amino groups as well as the effect of steric hindrance upon the coupling reaction. The above results are compared with those obtained for the well-established nitro-substituted biphenylthiol monolayers.

  15. Electrodeposition of gold templated by patterned thiol monolayers

    Science.gov (United States)

    She, Zhe; Di Falco, Andrea; Hähner, Georg; Buck, Manfred

    2016-06-01

    The electrochemical deposition of Au onto Au substrates modified by self-assembled monolayers (SAMs) was studied by linear sweep voltammetry (LSV), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Patterned SAMs exhibiting electrochemical contrast were prepared by two different methods. One used microcontact printing (μCP) to generate a binary SAM of ω-(4‧-methyl-biphenyl-4-yl)-propane thiol (CH3-C6H4-C6H4-(CH2)3-SH, MBP3) and octadecane thiol (CH3(CH2)17SH, ODT). Templated by the SAM, a gold microelectrode structure was electrodeposited featuring a line 15 μm wide and 3 mm long. After transfer to an epoxy substrate the structure proved to be electrically conductive across the full length. The other patterning method applied electron beam lithography (EBL) where electrochemical contrast was achieved by crosslinking molecules in a single component SAM of MBP3. An electron dose above 250 mC/cm2 results in a high deposition contrast. The choice of parameters for the deposition/lift-off process is found to be more critical for Au compared to Cu studied previously. The origin of the differences and implications for nanoscale patterning are discussed.

  16. UV/Vis and NIR Light-Responsive Spiropyran Self-Assembled Monolayers

    NARCIS (Netherlands)

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

    2013-01-01

    Self-assembled monolayers of a 6-nitro BIPS spiropyran (SP) modified with a disulfide-terminated aliphatic chain were prepared on polycrystalline gold surfaces and characterized by UV/vis absorption, surface-enhanced Raman scattering (SEAS), and X-ray photoelectron spectroscopies (XPS). The SAMs

  17. UV/Vis and NIR Light-Responsive Spiropyran Self-Assembled Monolayers

    NARCIS (Netherlands)

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

    2013-01-01

    Self-assembled monolayers of a 6-nitro BIPS spiropyran (SP) modified with a disulfide-terminated aliphatic chain were prepared on polycrystalline gold surfaces and characterized by UV/vis absorption, surface-enhanced Raman scattering (SEAS), and X-ray photoelectron spectroscopies (XPS). The SAMs obt

  18. Self-assembled monolayers on gold of ferrocene-terminated thiols and hydroxyalkanethiols

    NARCIS (Netherlands)

    Auletta, T.; van Veggel, F.C.J.M.; Reinhoudt, David

    2002-01-01

    this paper, a study on the adsorption of mixed self-assembled monolayers (SAMs) for two different combinations of thiols (Fc(CH2)6SH/HO(CH2)2SH and Fc(CH2)16SH/HO(CH2)11SH (Fc = ferrocene)) is presented, to obtain surfaces with single isolated ferrocenylalkanethiols embedded in shorter

  19. Dipole Formation at Interfaces of Alkanethiolate Self-assembled Monolayers and Ag(111)

    NARCIS (Netherlands)

    Rusu, Paul C.; Giovannetti, Gianluca; Brocks, Geert

    2007-01-01

    The formation of interface dipoles in self-assembled monolayers (SAMs) of −CH3 and −CF3 terminated short-chain alkanethiolates on Ag(111) is studied by means of density functional theory calculations. The interface dipoles are characterized by monitoring the change in the surface work function upon

  20. Redox mediation at 11-mercaptoundecanoic acid self-assembled monolayers on gold

    NARCIS (Netherlands)

    Cecchet, F; Marcaccio, M; Margotti, M; Paolucci, F; Rapino, S; Rudolf, P

    2006-01-01

    Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and digital simulation techniques were used to investigate quantitatively the mechanism of electron transfer (ET) through densely packed and well-ordered self-assembled monolayers (SAMs) of 11-mercaptoundecanoic acid on gold, eit

  1. Micro—patterning of Copper Based on Photolithographed Self—assembly Monolayers

    Institute of Scientific and Technical Information of China (English)

    LanHUANG; HaoYingSHEN; 等

    2002-01-01

    A new method has been develoed 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.

  2. 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.

  3. Immobilization of rhodium complexes at thiolate monolayers on gold surfaces : Catalytic and structural studies

    NARCIS (Netherlands)

    Belser, T; Stöhr, Meike; Pfaltz, A

    2005-01-01

    Chiral rhodium-diphosphine complexes have been incorporated into self-assembled thiolate monolayers (SAMS) on gold colloids. Catalysts of this type are of interest because they combine properties of homogeneous and heterogeneous systems. In addition, it should be possible to influence the catalytic

  4. Patterning functional materials using channel diffused plasma-etched self-assembled monolayer templates

    NARCIS (Netherlands)

    George, A.; Maijenburg, A.W.; Maas, M.G.; Blank, David H.A.; ten Elshof, Johan E.

    2011-01-01

    A simple and cost-effective methodology for large-area micrometer-scale patterning of a wide range of metallic and oxidic functional materials is presented. Self-assembled monolayers (SAM) of alkyl thiols on Au were micropatterned by channel-diffused oxygen plasma etching, a method in which selected

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

    NARCIS (Netherlands)

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

    2010-01-01

    FePt nanoparticles (NPs) were assembled on aluminum oxide substrates, and their ferromagnetic properties were studied before and after thermal annealing. For the first time, phosph(on)ates were used as an adsorbate to form self-assembled monolayers (SAMs) on alumina to direct the assembly of NPs ont

  6. Conventional Nanoindentation in Self-Assembled Monolayers Deposited on Gold and Silver Substrates

    Directory of Open Access Journals (Sweden)

    Leila Costelle

    2012-01-01

    Full Text Available Self-assembled monolayers (SAMs are promising materials for micromechanical applications. However, characterization of mechanical properties of monolayers is challenging for standard nanoindentation, and new efficient analysis techniques are needed. Hereby, a conventional nanoindentation method has been combined in a unique way with efficient data analysis based on consumed energy calculation and load-displacement data. The procedure has been applied on SAMs of 4,4′-biphenyldithiol (BPDT on Au, 1-tetradecanethiol (TDT, and 1-hexadecanethiol (HDT on Au and Ag substrates being the first study where SAMs of the same thiols on different substrates are analyzed by nanoindentation providing a new insight into the substrate effects. Unlike TDT and HDT SAMs, which are found to strongly enhance the homogeneity and stiffness of the underlying substrate, the BPDT covered Au substrate appears softer in mechanical response. In the case of TDT and HDT SAMs on Ag the structures are softer showing also faster relaxation than the corresponding structures on Au substrate. The proposed procedure enables a fast and efficient way of assessing the complex behaviour of SAM modified substrates. As a consequence, the results are relevant to practical issues dependent on layer activity and toughness.

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

    Science.gov (United States)

    Kim, Gi-Hwan; García de Arquer, F Pelayo; Yoon, Yung Jin; Lan, Xinzheng; Liu, Mengxia; Voznyy, Oleksandr; Jagadamma, Lethy Krishnan; Abbas, Abdullah Saud; Yang, Zhenyu; Fan, Fengjia; Ip, Alexander H; Kanjanaboos, Pongsakorn; Hoogland, Sjoerd; Kim, Jin Young; Sargent, Edward H

    2015-11-11

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

  8. Conformational morphology of polyaniline grown on self-assembled monolayer modified silicon

    Energy Technology Data Exchange (ETDEWEB)

    Sutar, D.S., E-mail: dssutar23@gmail.com [Central Surface Analytical Facility, Indian Institute of Technology Bombay, Mumbai 400076 (India); Department of Physics, Indian Institute of Technology Bombay, Mumbai 400076 (India); Major, S.S. [Department of Physics, Indian Institute of Technology Bombay, Mumbai 400076 (India); Srinivasa, R.S. [Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai 400076 (India); Yakhmi, J.V. [Technical Physics Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India)

    2011-10-31

    Polyaniline (PANI) films with pyramidal shaped crystallites were prepared by self-organization on self-assembled monolayer (SAM) modified Si substrates. High-resolution atomic force microscopy (HR-AFM) shows that SAM has tridymite structural order and the PANI film has biphasic conformational morphology corresponding to face-on orientation and edge-on orientation. Order parameters obtained from power spectral density analysis of HR-AFM images of SAM and PANI films show that the pyramidal crystallites are in emeraldine salt (ES-I) form and the region between the crystallites is in emeraldine base (EB-II) form. The ordered lattice of PANI crystallites as observed by cross-sectional HR-TEM confirms its single crystalline nature as well as epitaxial growth. The heteroepitaxial growth of PANI is attributed to the structural order of interfacial SAM on Si. - Highlights: > The structural order of self-assembled monolayer (SAM) on Si assists in hetero-epitaxial growth of polyaniline (PANI) films. > The power spectral density (PSD) analysis of the high-resolution AFM images provides the order parameters, which help to elucidate the ordering in SAM and PANI films. > PSD function could be used to analyze the high-resolution AFM images, which hitherto has been used mainly for low-resolution image analysis. > The ordered lattice image and SAED pattern obtained by HR-TEM confirms the single crystalline nature of pyramidal crystallites and their epitaxial growth at the interface.

  9. 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.

  10. Ripple-Free Graphene Sheets on Alkanethiol Self-Assembled Monolayers Provided from Unzipped Multi-Walled Carbon Nanotubes.

    Science.gov (United States)

    Koo, Hyunmo; Lee, Nam-Suk; Shin, Hoon-Kyu; Noh, Jaegeun; Majima, Yutaka; Cho, Gyoujin

    2015-02-01

    Octanethiol (C8S, CH3(CH2)7SH) self-assembled monolayers/Au(111) were utilized as an inert surface to provide ripple-free graphene oxide layers provided from chemically unzipped multi-walled carbon nanotubes (MWCNTs). The resulting graphene oxide monolayers were characterized with atomic resolution by UHV-STM. The honeycomb structure for the graphene monolayer and "three-for-six" triangular pattern for the multi-layer graphene sheets on C8S SAMs were clearly observed without ripples by the high-resolution UHV-STM. These results provide new insight into the preparation of ripple-free graphene monolayers.

  11. Increasing the fill factor of inverted P3HT:PCBM solar cells through surface modification of Al-doped ZnO via phosphonic acid-anchored C60 SAMs

    Energy Technology Data Exchange (ETDEWEB)

    Stubhan, Tobias [Institute of Materials for Electronics and Energy Technology (I-MEET), Friedrich-Alexander-University, Erlangen-Nuremberg, Erlangen (Germany); Salinas, Michael; Halik, Marcus [Organic Materials and Devices (OMD)-Institute of Polymer Materials, University Erlangen-Nuremberg, Erlangen (Germany); Ebel, Alexander; Hirsch, Andreas [Institute for Organic Chemistry II, Friedrich-Alexander-University, Erlangen-Nuremberg, Erlangen (Germany); Krebs, Frederick C. [Risoe National Laboratory for Sustainable Energy, Technical University of Denmark, Roskilde (Denmark); Brabec, Christoph J. [Institute of Materials for Electronics and Energy Technology (I-MEET), Friedrich-Alexander-University, Erlangen-Nuremberg, Erlangen (Germany); Bavarian Center for Applied Energy Research (ZAE Bayern), Erlangen (Germany)

    2012-05-15

    The influence of aluminum-doped zinc oxide (AZO) electron extraction layers modified with self-assembled monolayers (SAMs) on inverted polymer solar cells is investigated. It is found that AZO modification with phosphonic acid-anchored Fullerene-SAMs leads to a reduction of the series resistance, while increasing the parallel resistance. This results in an increased efficiency from 2.9 to 3.3%. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Vibrational Stark Effect of the Electric-Field Reporter 4-Mercaptobenzonitrile as a Tool for Investigating Electrostatics at Electrode/SAM/Solution Interfaces

    Directory of Open Access Journals (Sweden)

    Peter Hildebrandt

    2012-06-01

    Full Text Available 4-mercaptobenzonitrile (MBN in self-assembled monolayers (SAMs on Au and Ag electrodes was studied by surface enhanced infrared absorption and Raman spectroscopy, to correlate the nitrile stretching frequency with the local electric field exploiting the vibrational Stark effect (VSE. Using MBN SAMs in different metal/SAM interfaces, we sorted out the main factors controlling the nitrile stretching frequency, which comprise, in addition to external electric fields, the metal-MBN bond, the surface potential, and hydrogen bond interactions. On the basis of the linear relationships between the nitrile stretching and the electrode potential, an electrostatic description of the interfacial potential distribution is presented that allows for determining the electric field strengths on the SAM surface, as well as the effective potential of zero-charge of the SAM-coated metal. Comparing this latter quantity with calculated values derived from literature data, we note a very good agreement for Au/MBN but distinct deviations for Ag/MBN which may reflect either the approximations and simplifications of the model or the uncertainty in reported structural parameters for Ag/MBN. The present electrostatic model consistently explains the electric field strengths for MBN SAMs on Ag and Au as well as for thiophenol and mercaptohexanoic acid SAMs with MBN incorporated as a VSE reporter.

  13. The use of alkanethiol self-assembled monolayers on 316L stainless steel for coronary artery stent nanomedicine applications: an oxidative and in vitro stability study.

    Science.gov (United States)

    Mahapatro, Anil; Johnson, Dave M; Patel, Devang N; Feldman, Marc D; Ayon, Arturo A; Agrawal, C Mauli

    2006-09-01

    The use of self-assembled monolayers (SAMs) on medical devices offers a methodology for the incorporation of nanotechnology into medicine. SAMs are highly ordered nanosized molecular coatings, adding 1 to 10 nm thickness to a surface. This work is part of an overall goal to deliver therapeutic drugs from the surface of metal coronary stents using SAMs. In this study the oxidative and in vitro stability of functional alkylthiol SAMs on 316L stainless steel (SS) has been demonstrated. SAMs of 11-mercaptoundecanoic acid (-COOH SAM) and 11-mercapto-1-undecanol (-OH SAM) were formed on 316L SS. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and contact angle (CA) measurements collectively confirmed the formation of functional alkylthiol SAMs on 316L SS. Well-formed SAMs (CA: 82 deg +/- 9 deg) were achieved within 48 hours of immersion in ethanolic solutions, after which no significant improvement in CA was observed. The ratio of the thiolate peak (163.5 eV) to the oxidized sulfur (sulfonates) peak (166.5 eV) gives us an indication of the percentage SAMs that would bind to the metal and serve as a drug reservoir in vivo; which in turn represents the stability and viability of these SAMs, keeping in mind the cardiovascular application under consideration. Oxidative and in vitro stability studies showed that alkanethiol SAMs oxidized completely within 14 days. The SAMs tend to desorb and leave the metal surface after longer time periods (21 days) in phosphate-buffered saline (PBS) immersion, whereas for oxidative exposure the SAMs continue to remain on the metal surface in the form of sulfonates. Although the chemistry of bonding of alkylthiol with the 316L SS is not well understood, the nanosized alkylthiol SAMs demonstrate sufficient stability to justify further study on these systems for potential in vivo drug delivery in the chosen coronary artery stent applications.

  14. Effect of surface chemical composition on the work function of silicon substrates modified by binary self-assembled monolayers.

    Science.gov (United States)

    Kuo, Che-Hung; Liu, Chi-Ping; Lee, Szu-Hsian; Chang, Hsun-Yun; Lin, Wei-Chun; You, Yun-Wen; Liao, Hua-Yang; Shyue, Jing-Jong

    2011-09-07

    It has been shown that the application of self-assembled monolayers (SAMs) to semiconductors or metals may enhance the efficiency of optoelectronic devices by changing the surface properties and tuning the work functions at their interfaces. In this work, binary SAMs with various ratios of 3-aminopropyltrimethoxysilane (APTMS) and 3-mercaptopropyltrimethoxysilane (MPTMS) were used to modify the surface of Si to fine-tune the work function of Si to an arbitrary energy level. As an electron-donor, amine SAM (from APTMS) produced outward dipole moments, which led to a lower work function. Conversely, electron-accepting thiol SAM (from MPTMS) increased the work function. It was found that the work function of Si changed linearly with the chemical composition and increased with the concentration of thiol SAMs. Because dipoles of opposite directions cancelled each other out, homogeneously mixing them leads to a net dipole moment (hence the additional surface potential) between the extremes defined by each dipole and changes linearly with the chemical composition. As a result, the work function changed linearly with the chemical composition. Furthermore, the amine SAM possessed a stronger dipole than the thiol SAM. Therefore, the SAMs modified with APTMS showed a greater work function shift than did the SAMs modified with MPTMS.

  15. 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

  16. Comparative protective abilities of organothiols SAM coatings applied to copper dissolution in aqueous environments

    Energy Technology Data Exchange (ETDEWEB)

    Sinapi, F. [Fonds pour la Formation a la Recherche dans l' Industrie et dans l' Agriculture, Rue d' Egmont 5, B-1000 Bruxelles (Belgium); Lejeune, I. [Laboratoire de Chimie et d' Electrochimie des Surfaces, Facultes Universitaires Notre-Dame de la Paix, Rue de Bruxelles 61, B-5000 Namur (Belgium); Delhalle, J. [Laboratoire de Chimie et d' Electrochimie des Surfaces, Facultes Universitaires Notre-Dame de la Paix, Rue de Bruxelles 61, B-5000 Namur (Belgium); Mekhalif, Z. [Laboratoire de Chimie et d' Electrochimie des Surfaces, Facultes Universitaires Notre-Dame de la Paix, Rue de Bruxelles 61, B-5000 Namur (Belgium)]. E-mail: zineb.mekhalif@fundp.ac.be

    2007-04-30

    Self-assembled monolayers (SAMs) obtained by adsorption of n-organothiols molecules have been formed onto polycrystalline copper surfaces in order to build up barrier films protecting copper from oxidation. In this context, formation of n-dodecanethiol (DT), (3-mercaptopropyl)trimethoxysilane (MPTS) and 11-perfluorobutylundecanethiol (F{sub 4}H{sub 11}) monolayers has been elaborated on copper and evaluated by X-ray photoelectron spectroscopy while polarization and cyclic voltammetry curves were used to compare the inhibition efficiency of the three organic coatings. Furthermore, atomic absorption spectrometry measurements were carried out in domestic water and in NaCl 0.5 M solutions in order to evaluate and quantify the dissolution of copper electrodes before and after protection. Results showed evidences that, among the three organic compounds assessed, F{sub 4}H{sub 11} is the most suitable candidate to slow down the copper oxidation process.

  17. Electron transport across the alkanethiol self-assembled monolayer/Au(111) interface: role of the chemical anchor.

    Science.gov (United States)

    Lindstrom, C D; Muntwiler, M; Zhu, X-Y

    2005-11-24

    Alkanethiol self-assembled monolayers (SAMs) on Au(111) are model systems for molecular electronics. We probe the role of the chemisorption bond on electron dynamics at the SAM/Au interface using time-resolved two-photon photoemission. Formation of the Au-S bond is evidenced by a localized sigma resonance, which broadens and shifts upward in energy when the lying-down chemisorbed molecules stand up. The localized chemisorption bond does not affect the electronic coupling between delocalized image resonances and the metal substrate. Instead, lifetimes of image resonances are decreased due to scattering with S atoms within the thiol or thiolate monolayer.

  18. Noble metal nanoparticles deposited on self-assembled monolayers by pulsed laser deposition show coulomb blockade at room temperature.

    Science.gov (United States)

    Speets, Emiel A; Dordi, Barbara; Ravoo, Bart Jan; Oncel, Nuri; Hallbäck, Ann-Sofie; Zandvliet, Harold J W; Poelsema, Bene; Rijnders, Guus; Blank, Dave H A; Reinhoudt, David N

    2005-04-01

    Nanometer-sized noble-metal clusters are fabricated on top of alkylthiolate self-assembled monolayers (SAMs) on annealed gold by pulsed laser deposition at elevated pressures. The size distribution of the clusters depends on the metal and on the pressure during the deposition. Scanning tunneling microscopy (STM) and conductive probe atomic force microscopy (CP-AFM) showed that the metal clusters are insulated from the substrate on top of the SAM. Coulomb blockades could be measured at room temperature by STM for palladium clusters on decanethiol SAMs.

  19. Self-Spreading of Lipid Bilayer on a Hydrophobic Surface Made by Self-Assembled Monolayer with Short Alkyl Chain.

    Science.gov (United States)

    Omori, Yuya; Sakaue, Hiroyuki; Takahagi, Takayuki; Suzuki, Hitoshi

    2016-04-01

    Behaviors of self-spreading of lipid bilayer membrane on a glass surface modified with self-assembled monolayer (SAM) with short alkyl chain were observed with fluorescence microscopy. Hydrophobic surface made by SAM was found to hamper the self-spreading phenomenon but the lipid bilayer spread on a hydrophilic one where SAM was decomposed by oxidation. On a binary surface having a hydrophobic region and a hydrophilic one, the lipid bilayer spread on the hydrophilic region but it stopped at the boundary of the hydrophobic region.

  20. Electrodeposition of gold templated by patterned thiol monolayers

    Energy Technology Data Exchange (ETDEWEB)

    She, Zhe [EaStCHEM School of Chemistry, University of St. Andrews, KY16 9ST (United Kingdom); Di Falco, Andrea [SUPA, School of Physics and Astronomy, University of St. Andrews, KY16 9SS (United Kingdom); Hähner, Georg [EaStCHEM School of Chemistry, University of St. Andrews, KY16 9ST (United Kingdom); Buck, Manfred, E-mail: mb45@st-andrews.ac.uk [EaStCHEM School of Chemistry, University of St. Andrews, KY16 9ST (United Kingdom)

    2016-06-15

    Graphical abstract: - Highlights: • First demonstration of electrodeposition/lift-off of gold using thiol monolayers. • Microelectrode structures with large length to width ratio were generated. • Performance of two different patterning techniques was investigated. • Conditions for achieving good contrast in the electrodeposition were established. - Abstract: The electrochemical deposition of Au onto Au substrates modified by self-assembled monolayers (SAMs) was studied by linear sweep voltammetry (LSV), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Patterned SAMs exhibiting electrochemical contrast were prepared by two different methods. One used microcontact printing (μCP) to generate a binary SAM of ω-(4′-methyl-biphenyl-4-yl)-propane thiol (CH{sub 3}-C{sub 6}H{sub 4}-C{sub 6}H{sub 4}-(CH{sub 2}){sub 3}-SH, MBP3) and octadecane thiol (CH{sub 3}(CH{sub 2}){sub 17}SH, ODT). Templated by the SAM, a gold microelectrode structure was electrodeposited featuring a line 15 μm wide and 3 mm long. After transfer to an epoxy substrate the structure proved to be electrically conductive across the full length. The other patterning method applied electron beam lithography (EBL) where electrochemical contrast was achieved by crosslinking molecules in a single component SAM of MBP3. An electron dose above 250 mC/cm{sup 2} results in a high deposition contrast. The choice of parameters for the deposition/lift-off process is found to be more critical for Au compared to Cu studied previously. The origin of the differences and implications for nanoscale patterning are discussed.

  1. 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.

  2. Analysis of the Hysteresis Behavior of Perovskite Solar Cells with Interfacial Fullerene Self-Assembled Monolayers.

    Science.gov (United States)

    Valles-Pelarda, Marta; Hames, Bruno Clasen; García-Benito, Inés; Almora, Osbel; Molina-Ontoria, Agustin; Sánchez, Rafael S; Garcia-Belmonte, Germà; Martín, Nazario; Mora-Sero, Ivan

    2016-11-17

    The use of self-assembled monolayers (SAMs) of fullerene derivatives reduces the hysteresis of perovskite solar cells (PSCs). We have investigated three different fullerene derivatives observing a decrease on hysteresis for all the cases. Several processes can contribute to the hysteresis behavior on PSCs. We have determined that the reduced hysteresis observed for devices with SAMs is produced by a decrease of the capacitive hysteresis. In addition, with an appropriated functionalization, SAMs can increase photocurrent even when no electron selective contact (ESC) is present and a SAM is deposited just on top of the transparent conductive oxide. Appropriated functionalization of the fullerene derivative, as introducing -CN groups, can enhance cell performance and reduce hysteresis. This work paves the way for a future enhancement of PSCs by a tailored design of the fullerene molecules that could actuate as an ESC by themselves.

  3. Self-Assembled Monolayers Exposed by Metastable Helium for Nano-Patterning: Octanethiol and Dodecanethiol

    Institute of Scientific and Technical Information of China (English)

    巨新; 仓桥光纪; 铃木拓; 山内泰

    2003-01-01

    A large-area gold pattern with nanoscale edge on muscovite mica was fabricated by using a metastable helium beam and octanethiol(OT)and dodecanethiol(DDT)self-assembled monolayers(SAM),in which the width of edge was typically ~70nm for the OT SAM and ~90nm for the DDT SAM,respectively.The mask was reproduced with high fidelity.Combined the analysis of roughness with grain size,more flat surface and sharper edge of patterns were obtained by using the shorter chain molecules such as the OT.All the information indicated that the OT SAMs on atomically flat surfaces can be used as a resist for exposure to metastable atom beams.

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

    Science.gov (United States)

    Hakamada, Masataka; Kato, Naoki; Mabuchi, Mamoru

    2016-11-01

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

  5. Characterization of Self-assembled Monolayers on Gold Electrode Using Electrochemical Quartz Crystal Microbalance

    Institute of Scientific and Technical Information of China (English)

    Yonggui Dong

    2006-01-01

    The electrochemical quartz crystal microbatance (EQCM) is used to investigate the characteristics of the thiolated self-assembled monolayer(SAM) on gold surface. A 5MHz QCM element serves as both the mass-sensitive sensor and the working electrode of the electrochemical system. The 6-mecapto-1-hexanol and and the 16-mer oligonucleotide with a mercaptohexyl group at the 5'-phosphate end are utilized to form the SAM on the gold electrode. The frequency response of the QCM during cyclic voltammetry (CV) scanning and chronoamperometry are recorded together with the electrochemical current. The experimental results indicates that the frequency response is more sensitive to the surface coverage. Therefore, the response of the EQCM reveals more details of the SAM on gold electrode. It is especially useful for analysing the immobilization quality, such as probe orientation and coverage, of the SAM.

  6. Sensitivity Analysis for Multidisciplinary Systems (SAMS)

    Science.gov (United States)

    2016-12-01

    AFRL-RQ-WP-TM-2017-0017 SENSITIVITY ANALYSIS FOR MULTIDISCIPLINARY SYSTEMS (SAMS) Richard D. Snyder Design & Analysis Branch Aerospace Vehicles...for public release. Distribution is unlimited. 1 AFRL-NASA Collaboration Provide economical, accurate sensitivities for multidisciplinary design and... Concept Refinement Technology Development System Development & Demonstration Production & Deployment Operation & Support • Knowledge is most limited

  7. Essay: Physical Review Letters; Sam Goudsmit's Vision.

    Science.gov (United States)

    Adair, Robert K

    2008-01-18

    Sam Goudsmit implemented his vision of converting the Letters section of Physical Review into a distinct journal fifty years ago. Physical Review Letters was designed to publish "only papers that really deserve rapid communication." The new journal became so successful with physicists throughout the world that Physical Review Letters now publishes 3500 Letters per year.

  8. Sam's Journey to "Reach for the Stars"

    Science.gov (United States)

    Mayer, Sue

    2007-01-01

    In this article, the author shares her experiences as a parent of a child with Down syndrome. Although her son Sam's first years were filled with numerous hospitalizations and visits to pediatricians, which she feared would further delay his development, she soon discovered an organization known as the National Association of Child Development…

  9. 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.

  10. Molecular simulations of mixed self-assembled monolayer coated gold nanoparticles in water.

    Science.gov (United States)

    J, Meena Devi

    2015-06-01

    Molecular dynamics simulations have been employed to study the hydration of a series of nanoparticles, each of which was coated with a mixed self-assembled monolayer (SAM) comprising methyl- and hydroxy-terminated alkane thiol chains. The mixing ratio of those chains are different for each nanoparticle. The simulations focused on the wetting behavior of the SAM-coated gold nanoparticles and the distribution and structure of their interfacial water molecules. The interactions of the mixed SAM-coated gold nanoparticles with water were analyzed by evaluating the radial distribution function, hydrogen bonds, the dipole orientations of the water molecules, and the water residence time in the interfacial region. The wettability of the mixed SAM-coated gold nanoparticles improved as the concentration of terminal hydroxy moieties was increased. The distribution and dynamics of the interfacial water molecules were found to be influenced by the mixing ratio of the terminal moieties of the SAM chains. The results of our simulations suggest that the surface interactions of the mixed SAM-coated gold nanoparticles with the aqueous medium can be modulated by systematically altering the mixing ratio of the terminal methyl and hydroxy moieties. This work may lead to new biological and technological applications and inspire the development of novel biomimetic materials. Graphical Abstract Mixed SAM-coated gold nanoparticles.

  11. 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

  12. Structural Basis for Methyl Transfer by a Radical SAM Enzyme

    Energy Technology Data Exchange (ETDEWEB)

    Boal, Amie K.; Grove, Tyler L.; McLaughlin, Monica I.; Yennawar, Neela H.; Booker, Squire J.; Rosenzweig, Amy C. (NWU); (Penn)

    2014-10-02

    The radical S-adenosyl-l-methionine (SAM) enzymes RlmN and Cfr methylate 23S ribosomal RNA, modifying the C2 or C8 position of adenosine 2503. The methyl groups are installed by a two-step sequence involving initial methylation of a conserved Cys residue (RlmN Cys{sup 355}) by SAM. Methyl transfer to the substrate requires reductive cleavage of a second equivalent of SAM. Crystal structures of RlmN and RlmN with SAM show that a single molecule of SAM coordinates the [4Fe-4S] cluster. Residue Cys{sup 355} is S-methylated and located proximal to the SAM methyl group, suggesting the SAM that is involved in the initial methyl transfer binds at the same site. Thus, RlmN accomplishes its complex reaction with structural economy, harnessing the two most important reactivities of SAM within a single site.

  13. Determination of Surface pKa of Pure Mercaptoacetic Acid and 2- Mercaptobenzothiazole Mixed Monolayers by Impedance Titration

    Institute of Scientific and Technical Information of China (English)

    Guang Han LU; Chuan Yin LIU; Hong Yan ZHAO; Wei LIU; Li Ping JIANG; Ling Yan JIANG

    2004-01-01

    Interfacial proton transfer reactions of pure mercaptoacetic acid (MA) and 2-mercaptobenzothiazole (Mbz) mixed self-assembled monolayers (SAMs) have been studied using a.c. impedance titration method. The charge-transfer resistance (Rct) is measured with the monolayer composition and the ionic strength of pH solution. The surface pKa can be obtained by the plots of Rct and pH, the reasons of shifts of surface pKa are also explained.

  14. Selective in situ potential-assisted SAM formation on multi electrode arrays

    Science.gov (United States)

    Haag, Ann-Lauriene; Toader, Violeta; Lennox, R. Bruce; Grutter, Peter

    2016-11-01

    The selective modification of individual components in a biosensor array is challenging. To address this challenge, we present a generalizable approach to selectively modify and characterize individual gold surfaces in an array, in an in situ manner. This is achieved by taking advantage of the potential dependent adsorption/desorption of surface-modified organic molecules. Control of the applied potential of the individual sensors in an array where each acts as a working electrode provides differential derivatization of the sensor surfaces. To demonstrate this concept, two different self-assembled monolayer (SAM)-forming electrochemically addressable ω-ferrocenyl alkanethiols (C11) are chemisorbed onto independent but spatially adjacent gold electrodes. The ferrocene alkanethiol does not chemisorb onto the surface when the applied potential is cathodic relative to the adsorption potential and the electrode remains underivatized. However, applying potentials that are modestly positive relative to the adsorption potential leads to extensive coverage within 10 min. The resulting SAM remains in a stable state while held at potentials <200 mV above the adsorption potential. In this state, the chemisorbed SAM does not significantly desorb nor do new ferrocenylalkythiols adsorb. Using three set applied potentials provides for controlled submonolayer alkylthiol marker coverage of each independent gold electrode. These three applied potentials are dependent upon the specifics of the respective adsorbate. Characterization of the ferrocene-modified electrodes via cyclic voltammetry demonstrates that each specific ferrocene marker is exclusively adsorbed to the desired target electrode.

  15. Microtribological and electrochemical corrosion behaviors of polydopamine coating on APTS-SAM modified Si substrate

    Energy Technology Data Exchange (ETDEWEB)

    Ou Junfei [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Graduate University of Chinese Academy of Sciences, Beijing 100080 (China); Wang Jinqing, E-mail: jqwang@lzb.ac.cn [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Liu Sheng [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Graduate University of Chinese Academy of Sciences, Beijing 100080 (China); Zhou Jinfang [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Ren Sili, E-mail: slren@lzb.ac.cn [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Yang Shengrong [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)

    2009-11-15

    A polydopamine coating (coded as PDAc) was prepared successfully on a Si substrate through a two-step process. Briefly, to improve the adhesion of PDAc on the Si substrate, a self-assembled monolayer of 3-aminopropyl triethoxysilane (coded as APTS-SAM) was firstly generated on the bare Si wafer. Thereafter, the PDAc with different thickness was fabricated through the chemical adsorption and autopolymerization of the dopamine hydrochloride on the APTS-SAM coated Si substrate. The formation of PDAc on the APTS-SAM modified Si substrate was proved by the characterizations of contact angle measurement, attenuated total reflectance Fourier transform infrared (ATR-FTIR) analysis, and X-ray photoelectron spectroscope (XPS), etc. The ellipsometric thickness measurement and atomic force microscopy (AFM) image analysis showed that the PDAc became thicker and rougher with the deposition time prolongation. Microtribological study showed that the thickness and roughness of the PDAc played a significant role in the tribological properties. In comparison with the bare Si substrate, the PDAc with thinner thickness possessed lower friction and was anticipated to be used as protecting coating in the field of boundary lubrication. The electrochemical corrosion behaviors of the prepared PDAc were investigated using the electrochemical station and a low corrosion current density was revealed, implying that the PDAc had good anti-corrosion capability and might find potential applications in the field of corrosion resistance.

  16. Microtribological and electrochemical corrosion behaviors of polydopamine coating on APTS-SAM modified Si substrate

    Science.gov (United States)

    Ou, Junfei; Wang, Jinqing; Liu, Sheng; Zhou, Jinfang; Ren, Sili; Yang, Shengrong

    2009-11-01

    A polydopamine coating (coded as PDAc) was prepared successfully on a Si substrate through a two-step process. Briefly, to improve the adhesion of PDAc on the Si substrate, a self-assembled monolayer of 3-aminopropyl triethoxysilane (coded as APTS-SAM) was firstly generated on the bare Si wafer. Thereafter, the PDAc with different thickness was fabricated through the chemical adsorption and autopolymerization of the dopamine hydrochloride on the APTS-SAM coated Si substrate. The formation of PDAc on the APTS-SAM modified Si substrate was proved by the characterizations of contact angle measurement, attenuated total reflectance Fourier transform infrared (ATR-FTIR) analysis, and X-ray photoelectron spectroscope (XPS), etc. The ellipsometric thickness measurement and atomic force microscopy (AFM) image analysis showed that the PDAc became thicker and rougher with the deposition time prolongation. Microtribological study showed that the thickness and roughness of the PDAc played a significant role in the tribological properties. In comparison with the bare Si substrate, the PDAc with thinner thickness possessed lower friction and was anticipated to be used as protecting coating in the field of boundary lubrication. The electrochemical corrosion behaviors of the prepared PDAc were investigated using the electrochemical station and a low corrosion current density was revealed, implying that the PDAc had good anti-corrosion capability and might find potential applications in the field of corrosion resistance.

  17. N-Hydroxysuccinimide-terminated self-assembled monolayers on gold for biomolecules immobilisation

    Energy Technology Data Exchange (ETDEWEB)

    Cabrita, J.F. [Laboratorio de SPM, Faculdade de Ciencias da Universidade de Lisboa, Ed. ICAT, Campo Grande, 1749-016 Lisbon (Portugal); CQB, Departamento de Quimica e Bioquimica da Faculdade de Ciencias da Universidade de Lisboa, Campo Grande, 1749-016 Lisbon (Portugal); Abrantes, L.M. [Laboratorio de SPM, Faculdade de Ciencias da Universidade de Lisboa, Ed. ICAT, Campo Grande, 1749-016 Lisbon (Portugal); CQB, Departamento de Quimica e Bioquimica da Faculdade de Ciencias da Universidade de Lisboa, Campo Grande, 1749-016 Lisbon (Portugal); Viana, A.S. [Laboratorio de SPM, Faculdade de Ciencias da Universidade de Lisboa, Ed. ICAT, Campo Grande, 1749-016 Lisbon (Portugal)]. E-mail: anaviana@icat.fc.ul.pt

    2005-03-15

    Pure and mixed N-hydroxysuccinimide-terminated and butanethiol monolayers were prepared on flat gold (1 1 1) surfaces with the intent of developing suitable platforms for the direct biomolecules immobilisation. The self-assembled monolayers (SAMs) were characterised by electrochemical reductive desorption of the thiolate from the gold surface. The data have shown that certain solution proportions of the two compounds yield modified electrodes exhibiting intermediate electrochemical behaviour of the corresponding pure SAMs. The reactivity of the terminal N-hydroxysuccinimide (NHS) towards amine functionalities has been tested for the covalent attachment of Dopamine. The cyclic voltammetric responses of the investigated monolayers, after contacting with a Dopamine solution, have confirmed the chemical coupling of the amine as well as the formation of mixed SAMs. The Dopamine surface coverage increased with the amount of surface NHS. Laccase was also successfully immobilised onto this modified electrodes. The electrochemical behaviour of the modified SAMs with Laccase indicates direct electron transfer between the immobilised enzyme and the gold surface. Evidence for Laccase immobilisation was also provided by atomic force microscopic measurements.

  18. 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.

  19. Regulated growth of diatom cells on self-assembled monolayers

    Directory of Open Access Journals (Sweden)

    Kobayashi Koichi

    2007-03-01

    Full Text Available Abstract We succeeded in regulating the growth of diatom cells on chemically modified glass surfaces. Glass surfaces were functionalized with -CF3, -CH3, -COOH, and -NH2 groups using the technique of self-assembled monolayers (SAM, and diatom cells were subsequently cultured on these surfaces. When the samples were rinsed after the adhesion of the diatom cells on the modified surfaces, the diatoms formed two dimensional arrays; this was not possible without the rinsing treatment. Furthermore, we examined the number of cells that grew and their motility by time-lapse imaging in order to clarify the interaction between the cells and SAMs. We hope that our results will be a basis for developing biodevices using living photosynthetic diatom cells.

  20. Channel-forming activity of syringopeptin 25A in mercury-supported phospholipid monolayers and negatively charged bilayers.

    Science.gov (United States)

    Becucci, Lucia; Toppi, Arianna; Fiore, Alberto; Scaloni, Andrea; Guidelli, Rolando

    2016-10-01

    Interactions of the cationic lipodepsipeptide syringopeptin 25A (SP25A) with mercury-supported dioleoylphosphatidylcholine (DOPC), dioleoylphosphatidylserine (DOPS) and dioeleoylphosphatidic acid (DOPA) self-assembled monolayers (SAMs) were investigated by AC voltammetry in 0.1M KCl at pH3, 5.4 and 6.8. SP25A targets and penetrates the DOPS SAM much more effectively than the other SAMs not only at pH6.8, where the DOPS SAM is negatively charged, but also at pH3, where it is positively charged just as SP25A. Similar investigations at tethered bilayer lipid membranes (tBLMs) consisting of a thiolipid called DPTL anchored to mercury, with a DOPS, DOPA or DOPC distal monolayer on top of it, showed that, at physiological transmembrane potentials, SP25A forms ion channels spanning the tBLM only if DOPS is the distal monolayer. The distinguishing chemical feature of the DOPS SAM is the ionic interaction between the protonated amino group of a DOPS molecule and the carboxylate group of an adjacent phospholipid molecule. Under the reasonable assumption that SP25A preferentially interacts with this ion pair, the selective lipodepsipeptide antimicrobial activity against Gram-positive bacteria may be tentatively explained by its affinity for similar protonated amino-carboxylate pairs, which are expected to be present in the peptide moieties of peptidoglycan strands.

  1. 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

  2. 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

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

    OpenAIRE

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

    2010-01-01

    FePt nanoparticles (NPs) were assembled on aluminum oxide substrates, and their ferromagnetic properties were studied before and after thermal annealing. For the first time, phosph(on)ates were used as an adsorbate to form self-assembled monolayers (SAMs) on alumina to direct the assembly of NPs onto the surface. The Al2O3 substrates were functionalized with aminobutylphosphonic acid (ABP) or phosphonoundecanoic acid (PNDA) SAMs or with poly(ethyleneimine) (PEI) as a reference. FePt NPs assem...

  4. Noble metal nanoparticles deposited on self-assembled monolayers using Pulsed Laser Deposition show coulomb blockade at room temperature

    NARCIS (Netherlands)

    Speets, Emiel A.; Dordi, Barbara; Ravoo, Bart Jan; Oncel, Nuri; Hallbäck, Ann-Sofie; Zandvliet, Harold J.W.; Poelsema, Bene; Rijnders, Guus; Blank, Dave H.A.; Reinhoudt, David N.

    2005-01-01

    Nanometer-sized noble-metal clusters are fabricated on top of alkylthiolate self-assembled monolayers (SAMs) on annealed gold by pulsed laser deposition at elevated pressures. The size distribution of the clusters depends on the metal and on the pressure during the deposition. Scanning tunneling mic

  5. Charge Transport Across Insulating Self-Assembled Monolayers: Non-equilibrium Approaches and Modeling To Relate Current and Molecular Structure

    NARCIS (Netherlands)

    Mirjani, F.; Thijssen, J.M.; Whitesides, G.M.; Ratner, M.A.

    2014-01-01

    This paper examines charge transport by tunneling across a series of electrically insulating molecules with the structure HS(CH2)4CONH(CH2)2R) in the form of self-assembled monolayers (SAMs), supported on silver. The molecules examined were studied experimentally by Yoon et al. (Angew. Chem. Int. Ed

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

    Science.gov (United States)

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

    2008-01-01

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

  7. The Electrochemical Characteristics of Multilayer Assembly of Hemoglobin and Polystyrene Sulfonate at Self-assembled Monolayer Surface

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    A multilayer film of hemoglobin (Hb) molecules and polyelectrolyte sulfonate were fabricated on a thiol self-assembled monolayers (SAMs) by electrostatic force.The Hb maintains electroactive property in the multilayer film, methylene blue (MB) incorporated into the multilayer can enhance the electron transfer rate between the Hb and the electrode surface.

  8. Scanning Tunneling Microscopic Observation of Adatom-Mediated Motifs on Gold-Thiol Self-assembled Monolayers at High Coverage

    DEFF Research Database (Denmark)

    Wang, Yun; Chi, Qijin; Hush, Noel S.;

    2009-01-01

    Self-assembled monolayers (SAMs) formed by chemisorption of a branched-chain alkanethiol, 2-methyl-1-propanethiol, on Au(111) surfaces were studied by in situ scanning tunneling microscopy (STM) under electrochemical potential control and analyzed using extensive density functional theory (DFT) c...

  9. Interfacial Reactions in Confinement: Kinetics and Temperature Dependence of Reactions in Self-Assembled Monolayers Compared to Ultrathin Polymer Films

    NARCIS (Netherlands)

    Schönherr, Holger; Feng, C.L.; Shovsky, A.

    2003-01-01

    We report on a comparative study of the temperature dependence of the alkaline hydrolysis of N-hydroxy-succinimide (NHS) ester groups confined in self-assembled monolayers (SAMs) of 11,11'-dithiobis(N-hydroxysuccinimidylundecanoate) (NHS-C10) on gold and ultrathin films of poly(N-hydroxysuccinimidyl

  10. Formation of Metal Nano- and Micropatterns on Self-Assembled Monolayers by Pulsed Laser Deposition Through Nanostencils and Electroless Deposition

    NARCIS (Netherlands)

    Speets, Emiel A.; Riele, te Paul; Boogaart, van den Marc A.F.; Doeswijk, Lianne M.; Ravoo, Bart Jan; Rijnders, Guus; Brugger, Jürgen; Reinhoudt, David N.; Blank, Dave H.A.

    2006-01-01

    Patterns of noble-metal structures on top of self-assembled monolayers (SAMs) on Au and SiO2 substrates have been prepared following two approaches. The first approach consists of pulsed laser deposition (PLD) of Pt, Pd, Au, or Cu through nano- and microstencils. In the second approach, noble-metal

  11. Self-assembled monolayers of terminal acetylenes as replacements for thiols in bottom-up tunneling junctions

    NARCIS (Netherlands)

    Fracasso, Davide; Kumar, Sumit; Rudolf, Petra; Chiechi, Ryan C.

    2014-01-01

    Why use thiols in Molecular Electronics? They stink, oxidize readily, poison catalysts, and often require nontrivial protection/deprotection chemistry. In this communication we demonstrate the fabrication of tunneling junctions formed by contact of self-assembled monolayers (SAMs) of terminal alkyne

  12. Structural, electrochemical, and photophysical properties of a molecular shuttle attached to an acid-terminated self-assembled monolayer

    NARCIS (Netherlands)

    Cecchet, F; Rudolf, P; Rapino, S; Margotti, M; Paolucci, F; Baggerman, J; Kay, ER; Wong, JKY; Leigh, DA; Kay, Euan R.; Wong, Jenny K.Y.; Brouwer, A.M.

    2004-01-01

    A benzylic amide macrocycle containing a pyridine moiety (macrocycle 2) and a related benzylic amide macrocycle-based molecular shuttle (naphthalimide rotaxane) with two pyridine moieties on the macrocyclic unit were grafted onto a self-assembled monolayer (SAM) of 11-mercaptoundecanoic acid (11-MUA

  13. The Molecular Boat: A Hands-On Experiment to Demonstrate the Forces Applied to Self-Assembled Monolayers at Interfaces

    Science.gov (United States)

    Chan, Charlene J.; Salaita, Khalid

    2012-01-01

    Demonstrating how surface chemistry and self-assembled monolayers (SAMs) control the macroscopic properties of materials is challenging as it often necessitates the use of specialized instrumentation. In this hands-on experiment, students directly measure a macroscopic property, the floatation of glass coverslips on water as a function of…

  14. Synthesis of Crown Ether-tethered β-Cyclodextrin and Fabrication of Its Self-assembled Monolayer on Gold Surface

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A novel β-cyclodextrin derivative 6 bearing a crown ether moiety has been synthesized by a convenient method in 9.4% yield. Its self-assembled monolayer (SAM) was fabricated on the gold surface, which was characterized by using surface-enhanced Raman spectra.

  15. Dip-Pen Nanolithography on (Bio)Reactive Monolayer and Block-Copolymer Platforms: Deposition of Lines of Single Macromolecules

    NARCIS (Netherlands)

    Salazar, Ramon B.; Shovsky, A.; Schönherr, Holger; Vancso, Gyula J.

    2006-01-01

    The application of atomic force microscopy (AFM) tip-mediated molecular transfer (dip-pen nanolithography or DPN) to fabricate nanopatterned (bio)reactive platforms based on dendrimers on reactive self-assembled monolayer (SAM) and polymer thin films is discussed. The transfer of high-molar-mass

  16. Structural investigations of self-assembled monolayers for organic electronics: results from X-ray reflectivity.

    Science.gov (United States)

    Khassanov, Artoem; Steinrück, Hans-Georg; Schmaltz, Thomas; Magerl, Andreas; Halik, Marcus

    2015-07-21

    Self-assembled monolayers (SAMs) have been established as crucial interlayers and electronically active layers in organic electronic devices, such as organic light emitting diodes (OLEDs), organic photovoltaics (OPVs), organic thin film transistors (OTFTs), and nonvolatile memories (NVMs). The use of self-assembling functionalized organic molecules is beneficial due to mainly three advantages compared with common thin film deposition approaches. (1) Molecular self-assembly occurs with surface selectivity, determined by the interaction between the functional anchor group of the organic molecules and the target surface. (2) The film thickness of the resulting layers is perfectly controllable on the angstrom scale, due to the self-terminating film formation to only a single molecular layer. And finally, (3) the wide variability in the chemical structure of such molecules enables different SAM functionalities for devices, ranging from electrical insulation to charge storage to charge transport. The SAM approach can be further expanded by employing several functionalized molecules to create mixed SAMs with consequently mixed properties. The function of SAMs in devices depends not only on the chemical structure of the molecules but also on their final arrangement and orientation on the surface. A reliable and nondestructive in-depth characterization of SAMs on nonconductive oxide surfaces is still challenging because of the very small thickness and the impracticality of methods such as scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). In this Account, we illustrate how X-ray reflectivity (XRR) provides analytical access to major questions of SAM composition, morphology, and even formation by means of investigations of pure and mixed SAMs based on phosphonic acids (PAs) of various chain structures on flat alumina (AlOx) surfaces. XRR is an analytical method that provides access to spatially averaged structural depth profiles over a relatively

  17. A Thermodynamics Model for the Emergence of a Stripe-like Binary SAM on a Nanoparticle Surface.

    Science.gov (United States)

    Ge, Xinwei; Ke, Pu Chun; Davis, Thomas P; Ding, Feng

    2015-10-01

    It has been under debate if a self-assembled monolayer (SAM) with two immiscible ligands of different chain lengths and/or bulkiness can form a stripe-like pattern on a nanoparticle (NP) surface. The entropic gain upon such pattern formation due to difference in chain lengths and/or bulkiness has been proposed as the driving force in literature. Using atomistic discrete molecular dynamics simulations it is shown that stripe-like pattern could indeed emerge, but only for a subset of binary SAM systems. In addition to entropic contributions, the formation of a striped pattern also strongly depends upon interligand interactions governed by the physicochemical properties of the ligand constituents. Due to the interplay between entropy and enthalpy, a binary SAM system can be categorized into three different types depending on whether and under what condition a striped pattern can emerge. The results help clarify the ongoing debate and our proposed principle can aid in the engineering of novel binary SAMs on a NP surface.

  18. 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.

  19. 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

    2016-08-04

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

  20. Efecto de la polietilenimina en la actividad catalítica de la peroxidasa de rábano (horseradish peroxidase inmovilizada en electrodos de oro modificados con monocapas autoensambladas de tioles (SAMs.

    Directory of Open Access Journals (Sweden)

    Pedro R. Matheus

    2009-05-01

    Full Text Available Effect of the Polyethyleneimine in the Activity Catalytic of the horseradish peroxidase Immobilized on Gold Electrodes Modified with a Self-assembled Monolayer of Thiols (SAMs. Studies were conducted bycyclic voltammetry (CV to investigate the effect of the polymer polyethyleneimine (PEI in the electrochemical reversibility of the mediator thionine and thus the catalytic activity of the enzyme horseradish peroxidase of recombinant HRP-NHis (horseradish peroxidase to the has been added to a chain of six histidine in the extreme N-terminal protein. This self produced monolayers of thiols (SAMS on gold electrodes, with chemical modifications obtained through successive stages in the solid phase of the electrode. The gold electrodes were modified with monolayer SAM-TOA-[ANTA/DADOO] -Co2+ [SAM: self-assembled monolayers of thiols, TOA: dithioctic acid, ANTA: nitrilotriacetic acid, DADOO: 1,8-diamino-3,6-dioxa octane]. The results showed that the presence of the polymer improves the electrochemical reversibility of the mediator to endure catalyticcurrents as high as those that are obtained with molar ratios ANTA:DADOO 10:1 in the absence of PEI, and improve the response voltammetric obtained.

  1. 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.

  2. System Advisor Model, SAM 2014.1.14: General Description

    Energy Technology Data Exchange (ETDEWEB)

    Blair, N.; Dobos, A. P.; Freeman, J.; Neises, T.; Wagner, M.; Ferguson, T.; Gilman, P.; Janzou, S.

    2014-02-01

    This document describes the capabilities of the U.S. Department of Energy and National Renewable Energy Laboratory's System Advisor Model (SAM), Version 2013.9.20, released on September 9, 2013. SAM is a computer model that calculates performance and financial metrics of renewable energy systems. Project developers, policy makers, equipment manufacturers, and researchers use graphs and tables of SAM results in the process of evaluating financial, technology, and incentive options for renewable energy projects. SAM simulates the performance of photovoltaic, concentrating solar power, solar water heating, wind, geothermal, biomass, and conventional power systems. The financial model can represent financial structures for projects that either buy and sell electricity at retail rates (residential and commercial) or sell electricity at a price determined in a power purchase agreement (utility). SAM's advanced simulation options facilitate parametric and sensitivity analyses, and statistical analysis capabilities are available for Monte Carlo simulation and weather variability (P50/P90) studies. SAM can also read input variables from Microsoft Excel worksheets. For software developers, the SAM software development kit (SDK) makes it possible to use SAM simulation modules in their applications written in C/C++, C#, Java, Python, and MATLAB. NREL provides both SAM and the SDK as free downloads at http://sam.nrel.gov. Technical support and more information about the software are available on the website.

  3. Microfluidic lithography of SAMs on gold to create dynamic surfaces for directed cell migration and contiguous cell cocultures.

    Science.gov (United States)

    Lamb, Brian M; Barrett, Devin G; Westcott, Nathan P; Yousaf, Muhammad N

    2008-08-19

    A straightforward, flexible, and inexpensive method to create patterned self-assembled monolayers (SAMs) on gold using microfluidics-microfluidic lithography-has been developed. Using a microfluidic cassette, alkanethiols were rapidly patterned on gold surfaces to generate monolayers and mixed monolayers. The patterning methodology is flexible and, by controlling the solvent conditions and thiol concentration, permeation of alkanethiols into the surrounding PDMS microfluidic cassette can be advantageously used to create different patterned feature sizes and to generate well-defined SAM surface gradients with a single microfluidic chip. To demonstrate the utility of microfluidic lithography, multiple cell experiments were conducted. By patterning cell adhesive regions in an inert background, a combination of selective masking of the surface and centrifugation achieved spatial and temporal control of patterned cells, enabling the design of both dynamic surfaces for directed cell migration and contiguous cocultures. Cellular division and motility resulted in directed, dynamic migration, while the centrifugation-aided seeding of a second cell line produced contiguous cocultures with multiple sites for heterogeneous cell-cell interactions.

  4. Applications of Self-Assembled Monolayers in Surface-Enhanced Raman Scattering

    Directory of Open Access Journals (Sweden)

    Charles K. Klutse

    2012-01-01

    Full Text Available The increasing applications of surface-enhanced Raman scattering (SERS has led to the development of various SERS-active platforms (SERS substrates for SERS measurement. This work reviews the current optimization techniques available for improving the performance of some of these SERS substrates. The work particularly identifies self-assembled-monolayer- (SAM- based substrate modification for optimum SERS activity and wider applications. An overview of SERS, SAM, and studies involving SAM-modified substrates is highlighted. The focus of the paper then shifts to the use of SAMs to improve analytical applications of SERS substrates by addressing issues including long-term stability, selectivity, reproducibility, and functionalization, and so forth. The paper elaborates on the use of SAMs to achieve optimum SERS enhancement. Specific examples are based on novel multilayered SERS substrates developed in the author’s laboratory where SAMs have been demonstrated as excellent dielectric spacers for improving SERS enhancement more than 20-fold relative to conventional single layer SERS substrates. Such substrate optimization can significantly improve the sensitivity of the SERS method for analyte detection.

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

    Science.gov (United States)

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

    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 (-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.

  6. Self-assembled monolayers and titanium dioxide: From surface patterning to potential applications

    Directory of Open Access Journals (Sweden)

    Yaron Paz

    2011-12-01

    Full Text Available The ability to control the properties of self-assembled monolayers (SAMs attached to solid surfaces and the rare photocatalytic properties of titanium dioxide provide a rationale for the study of systems comprising both. Such systems can be realized in the form of SAMs grown on TiO2 or, in a complementary manner, as TiO2 grown on SAMs. Accordingly, the current status of knowledge regarding SAMs on TiO2 is described. Photocatalytic phenomena that are of specific relevance to SAMs, such as remote degradation, and cases where SAMs were used to study photocatalytic phenomena, are discussed as well. Mastering of micro-patterning is a key issue en route to a successful assimilation of a variety of titanium dioxide based devices. Accordingly, particular attention is given to the description of a variety of methods and techniques aimed at utilizing the photocatalytic properties of titanium dioxide for patterning. Reports on a variety of applications are discussed. These examples, representing the areas of photovoltaics, microelectronics, microelectromechanics, photocatalysis, corrosion prevention and even biomedicine should be regarded as appetizers paving the way for further studies to be performed.

  7. Assembly of citrate gold nanoparticles on hydrophilic monolayers

    OpenAIRE

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

    2016-01-01

    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 mi...

  8. Enhanced bias stability of solution-processed zinc-tin-oxide thin film transistors using self-assembled monolayer as a selective channel passivation.

    Science.gov (United States)

    Heo, Jae-Sang; Park, Sung-Kyu

    2013-10-01

    The enhanced positive bias stability of amorphous zinc-tin-oxide thin-film transistors (a-ZTO TFTs) were obtained by applying self-assembled monolayer (SAM) as a selective passivation layer on the metal-oxide back channel area. The a-ZTO TFTs with passivation layers such as poly(methyl methacylate) (PMMA), SAM, and SAM/PMMA were fabricated by simple solution methods. After deposition of the passivation layers, the electrical characteristics of a-ZTO TFTs have not been changed and the threshold voltage shift (deltaV(th)) under gate-bias stress for around 10(4) seconds was improved. The deltaV(th) of the devices with PMMA, SAM, and SAM/PMMA dual layer were 3.79 V, 3.2 V, and 2.17 V, respectively.

  9. Lubrication of polysilicon micromechanisms with self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Srinivasan, U.; Foster, J.D.; Habib, U.; Howe, R.T.; Maboudian, R. [Berkeley Sensor and Actuator Center, CA (United States); Senft, D.C.; Dugger, M.T. [Sandia National Labs., Albuquerque, NM (United States)

    1998-06-01

    Here, the authors report on the lubricating effects of self-assembled monolayers (SAMs) on MEMS by measuring static and dynamic friction with two polysilicon surface- micromachined devices. The first test structure is used to study friction between laterally sliding surfaces and with the second, friction between vertical sidewalls can be investigated. Both devices are SAM-coated following the sacrificial oxide etch and the microstructures emerge released and dry from the final water rinse. The coefficient of static friction, {mu}{sub s} was found to decrease from 2.1 {+-} 0.8 for the SiO{sub 2} coating to 0.11 {+-} 0.01 and 0.10 {+-} 0.01 for films derived from octadecyltrichloro-silane (OTS) and 1H,1H,2H,2H-perfluorodecyl-trichlorosilane (FDTS). Both OTS and FDTS SAM-coated structures exhibit dynamic coefficients of friction, {mu}{sub d} of 0.08 {+-} 0.01. These values were found to be independent of the apparent contact area, and remain unchanged after 1 million impacts at 5.6 {micro}N (17 kPa), indicating that these SAMs continue to act as boundary lubricants despite repeated impacts. Measurements during sliding friction from the sidewall friction testing structure give comparable initial {mu}{sub d} values of 0.02 at a contact pressure of 84 MPa. After 15 million wear cycles, {mu}{sub d} was found to rise to 0.27. Wear of the contacting surfaces was examined by SEM. Standard deviations in the {mu} data for SAM treatments indicate uniform coating coverage.

  10. Self-assembled monolayers of cyclohexyl-terminated phosphonic acids as a general dielectric surface for high-performance organic thin-film transistors.

    Science.gov (United States)

    Liu, Danqing; He, Zikai; Su, Yaorong; Diao, Ying; Mannsfeld, Stefan C B; Bao, Zhenan; Xu, Jianbin; Miao, Qian

    2014-11-12

    A novel self-assembled monolayer (SAM) on AlOy /TiOx is terminated with cyclohexyl groups, an unprecedented terminal group for all kinds of SAMs. The SAM-modified AlOy /TiOx functions as a general dielectric, enabling organic thin-film transistors with a field-effect mobility higher than 5 cm(2) V(-1) s(-1) for both holes and electrons, good air stability with low operating voltage, and general applicability to solution-processed and vacuum-deposited n-type and p-type organic semiconductors.

  11. Self-assembled monolayer of designed and synthesized triazinedithiolsilane molecule as interfacial adhesion enhancer for integrated circuit

    Directory of Open Access Journals (Sweden)

    Wang Fang

    2011-01-01

    Full Text Available Abstract Self-assembled monolayer (SAM with tunable surface chemistry and smooth surface provides an approach to adhesion improvement and suppressing deleterious chemical interactions. Here, we demonstrate the SAM comprising of designed and synthesized 6-(3-triethoxysilylpropylamino-1,3,5-triazine-2,4-dithiol molecule, which can enhance interfacial adhesion to inhibit copper diffusion used in device metallization. The formation of the triazinedithiolsilane SAM is confirmed by X-ray photoelectron spectroscopy. The adhesion strength between SAM-coated substrate and electroless deposition copper film was up to 13.8 MPa. The design strategy of triazinedithiolsilane molecule is expected to open up the possibilities for replacing traditional organosilane to be applied in microelectronic industry.

  12. pH-regulated release of dopamine from well-ordered self-assembled monolayers: electrochemical studies.

    Science.gov (United States)

    Kazemi, Sayed Habib; Alizadeh, Abdolhamid; Mohamadi, Rahim; Khodaei, Mohammad Mahdi; Kordestani, Davood

    2013-12-01

    In the present work, gold electrode modified with novel aldehyde-terminated self-assembled monolayers (SAMs) was used for controllable load and release of dopamine molecules by pH triggering. Electrochemical techniques including cyclic voltammetry (CV) and electrochemcial impedance spectroscopy (EIS) were employed to investigate the SAMs characteristic on the gold electrode surface. The electrochemical experiments indicated Faradaic behavior for the electrode surface after its modification with dopamine. Notably, it was observed that decreasing the conditioning pH, results in a decrease of peak currents, presumably due to the hydrolysis of the terminal imine bonds and releasing the dopamine moiety into the solution. Moreover, the preliminary kinetics studies were done for dopamine release from the SAMs surface as a model to design future drug delivery systems. Finally, the rate constant of dopamine release from the SAMs modified surface estimated to be 0.167 day(-1) at pH=3.

  13. Self-assembled monolayer of designed and synthesized triazinedithiolsilane molecule as interfacial adhesion enhancer for integrated circuit.

    Science.gov (United States)

    Wang, Fang; Li, Yanni; Wang, Yabin; Cao, Zhuo

    2011-08-03

    Self-assembled monolayer (SAM) with tunable surface chemistry and smooth surface provides an approach to adhesion improvement and suppressing deleterious chemical interactions. Here, we demonstrate the SAM comprising of designed and synthesized 6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-dithiol molecule, which can enhance interfacial adhesion to inhibit copper diffusion used in device metallization. The formation of the triazinedithiolsilane SAM is confirmed by X-ray photoelectron spectroscopy. The adhesion strength between SAM-coated substrate and electroless deposition copper film was up to 13.8 MPa. The design strategy of triazinedithiolsilane molecule is expected to open up the possibilities for replacing traditional organosilane to be applied in microelectronic industry.

  14. Self-assembled monolayer of designed and synthesized triazinedithiolsilane molecule as interfacial adhesion enhancer for integrated circuit

    Science.gov (United States)

    2011-01-01

    Self-assembled monolayer (SAM) with tunable surface chemistry and smooth surface provides an approach to adhesion improvement and suppressing deleterious chemical interactions. Here, we demonstrate the SAM comprising of designed and synthesized 6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2,4-dithiol molecule, which can enhance interfacial adhesion to inhibit copper diffusion used in device metallization. The formation of the triazinedithiolsilane SAM is confirmed by X-ray photoelectron spectroscopy. The adhesion strength between SAM-coated substrate and electroless deposition copper film was up to 13.8 MPa. The design strategy of triazinedithiolsilane molecule is expected to open up the possibilities for replacing traditional organosilane to be applied in microelectronic industry. PMID:21812994

  15. Membrane protein resistance of oligo(ethylene oxide) self-assembled monolayers.

    Science.gov (United States)

    Vaish, Amit; Vanderah, David J; Vierling, Ryan; Crawshaw, Fay; Gallagher, D Travis; Walker, Marlon L

    2014-10-01

    As part of an effort to develop biointerfaces for structure-function studies of integral membrane proteins (IMPs) a series of oligo(ethylene oxide) self-assembled monolayers (OEO-SAMs) were evaluated for their resistance to protein adsorption (RPA) of IMPs on Au and Pt. Spectroscopic ellipsometry (SE) was used to determine SAM thicknesses and compare the RPA of HS(CH2)3O(CH2CH2O)6CH3 (1), HS(CH2)3O(CH2CH2O)6H (2), [HS(CH2)3]2CHO(CH2CH2O)6CH3 (3) and [HS(CH2)3]2CHO(CH2CH2O)6H (4), assembled from water. For both substrates, SAM thicknesses for 1 to 4 were found to be comparable indicating SAMs with similar surface coverages and OEO chain order and packing densities. Fibrinogen (Fb), a soluble plasma protein, and rhodopsin (Rd), an integral membrane G-protein coupled receptor, adsorbed to the SAMs of 1, as expected from previous reports, but not to the hydroxy-terminated SAMs of 2 and 4. The methoxy-terminated SAMs of 3 were resistant to Fb but, surprisingly, not to Rd. The stark difference between the adsorption of Rd to the SAMs of 3 and 4 clearly indicate that a hydroxy-terminus of the OEO chain is essential for high RPA of IMPs. The similar thicknesses and high RPA of the SAMs of 2 and 4 show the conditions of protein resistance (screening the underlying substrate, packing densities, SAM order, and conformational mobility of the OEO chains) defined from previous studies on Au are applicable to Pt. In addition, the SAMs of 4, exhibiting the highest resistance to Fb and Rd, were placed in contact with undiluted fetal bovine serum for 2h. Low protein adsorption (≈12.4ng/cm(2)), obtained under these more challenging conditions, denote a high potential of the SAMs of 4 for various applications requiring the suppression of non-specific protein adsorption.

  16. Photosystem I in Langmuir-Blodgett and Langmuir-Schaefer monolayers.

    Science.gov (United States)

    Yan, Xun; Faulkner, Christopher J; Jennings, G Kane; Cliffel, David E

    2012-10-23

    Photosystem I (PSI) is a membrane protein complex that generates photoinduced electrons and transfers them across the thylakoid membrane during photosynthesis. The PSI complex, separated from spinach leaves, was spread onto the air-water interface as a monolayer and transferred onto a gold electrode surface that was precoated with a self-assembled monolayer (SAM). The electrochemical properties of the transferred PSI monolayer, including cyclic voltammetry and photoinduced chronoamperometry, were measured. The results showed that PSI retained its bioactivity after the manipulation. Its capability of converting photoenergy into electrical potential was demonstrated by its reducing an electron acceptor, dichloroindophenol (DCIP), and by oxidizing an electron donor, sodium ascorbate (ASC). We have shown that the protein has two possible orientations at the water interface. The orientation distribution was determined by comparing the controlled reductive and oxidative photocurrents generated from Langmuir-Blodgett and Langmuir-Schaefer monolayers.

  17. Influence of the molecular-scale structures of 1-dodecanethiol and 4-methylbenzenethiol self-assembled monolayers on gold nanoparticles adsorption pattern.

    Science.gov (United States)

    Mamun, Abdulla Hel Al; Yoon, Sangwoon; Hahn, Jae Ryang

    2014-07-01

    In an effort to understand the effects of the molecular structures of self-assembled monolayers on the patterns formed by immobilized Au nanoparticles (AuNPs), we characterized and compared the morphologies and properties of AuNPs adsorbed onto self-assembled monolayers formed by 1-dodecanethiol (DDT-SAM) or 4-methylbenzenethiol (MBT-SAM) assembled on Au(111) surfaces. The AuNP adsorption pattern on the MBT-SAM surface was well-dispersed and characterized by a low degree of corrugation. By contrast, an aggregated and highly corrugated AuNP pattern was observed on the surface of the DDT-SAM. This difference was attributed to the retention or removal of citrate anions present on the AuNPs during adsorption onto the SAM surface. Direct interactions between the AuNPs and the highly corrugated hydrophobic surfaces of the DDT-SAMs could strip the citrate layers from the AuNP surfaces, leading to aggregated adsorption. The water molecules appeared to mediate the adsorption of the AuNPs by reducing the hydrophobicity of the MBT-SAM surface and promoting a more dispersed adsorption configuration.

  18. Preparation and Characterization of Covalently Binding of Rat Anti-human IgG Monolayer on Thiol-Modified Gold Surface

    Directory of Open Access Journals (Sweden)

    Lv Zhengjian

    2009-01-01

    Full Text Available Abstract The 16-mercaptohexadecanoic acid (MHA film and rat anti-human IgG protein monolayer were fabricated on gold substrates using self-assembled monolayer (SAM method. The surface properties of the bare gold substrate, the MHA film and the protein monolayer were characterized by contact angle measurements, atomic force microscopy (AFM, grazing incidence X-ray diffraction (GIXRD method and X-ray photoelectron spectroscopy, respectively. The contact angles of the MHA film and the protein monolayer were 18° and 12°, respectively, all being hydrophilic. AFM images show dissimilar topographic nanostructures between different surfaces, and the thickness of the MHA film and the protein monolayer was estimated to be 1.51 and 5.53 nm, respectively. The GIXRD 2θ degrees of the MHA film and the protein monolayer ranged from 0° to 15°, significantly smaller than that of the bare gold surface, but the MHA film and the protein monolayer displayed very different profiles and distributions of their diffraction peaks. Moreover, the spectra of binding energy measured from these different surfaces could be well fitted with either Au4f, S2p or N1s, respectively. Taken together, these results indicate that MHA film and protein monolayer were successfully formed with homogeneous surfaces, and thus demonstrate that the SAM method is a reliable technique for fabricating protein monolayer.

  19. Enantiopure chiral poly(glycerol methacrylate) self-assembled monolayers knock down protein adsorption and cell adhesion.

    Science.gov (United States)

    Li, Zheng; Köwitsch, Alexander; Zhou, Guoying; Groth, Thomas; Fuhrmann, Bodo; Niepel, Marcus; Amado, Elkin; Kressler, Jörg

    2013-10-01

    Chirality plays a fundamental role not only in biological systems, but also in synthetic materials intended for bio-applications. Self-assembled monolayers (SAMs) are prepared on gold surfaces through a "grafting to" method from racemic or enantiopure chiral poly(glycerol methacrylate)s (PGMA(rac), PGMA(R), and PGMA(S)), having a thiol endgroup. Such SAMs constitute a chemically and structurally well-defined model substrate for studying protein adsorption and cell adhesion as a function of the polymer chirality. Surface plasmon resonance measurements reveal that PGMA SAMs greatly reduce the adsorption of bovine serum albumin (BSA) compared to bare gold surfaces. Interestingly, enantiopure SAMs based on PGMA(R) or PGMA(S) show a significantly larger reduction in BSA adsorption than PGMA(rac)-covered surfaces. Studies with the monocytic cell line THP-1 show a similar relationship between enantiopurity of PGMA SAMs and the extent of cell adhesion. Ellipsometry and Raman spectroscopy measurements indicate that SAMs formed by PGMA(rac) have a higher grafting density compared to SAMs of PGMA(R) and PGMA(S). This seems to be due to the ability of PGMA(rac) to form more intermolecular hydrogen bonds among polymer chains compared to the enantiopure PGMAs. Circular dichroism spectroscopy provide evidence that enantiopure polymers adopt a chiral ordered conformation, most likely helical, in aqueous solutions. It is concluded that a higher water content of SAMs formed by enantiopure PGMA(S) and PGMA(R) SAMs arises from the macromolecular chiral conformation adopted by their enantiopure PGMA chains, and it is the decisive reason for the reduced BSA adsorption and cell adhesion as compared to PGMA(rac) SAMs.

  20. Preparation and characterization of alkylphosphonic acid self-assembled monolayers on titanium alloy by chemisorption and electrochemical deposition.

    Science.gov (United States)

    Metoki, Noah; Liu, Liang; Beilis, Edith; Eliaz, Noam; Mandler, Daniel

    2014-06-17

    Ti-6Al-4V alloy is the most commonly used alloy for dental and orthopedic implants. In order to improve osseointegration, different surface modification methods are usually employed, including self-assembled monolayers (SAMs). This study presents an investigation of both active (electroassisted) and passive (adsorption) approaches for the modification of Ti-6Al-4V using alkylphosphonic acid. The monolayers were characterized by cyclic voltammetry, double-layer capacitance, contact angle measurements, X-ray photoelectron spectroscopy, polarization modulation infrared reflection adsorption spectroscopy, electrochemical impedance spectroscopy, and corrosion potentiodynamic polarization measurements. It is shown that the electrochemically assisted monolayers, which are assembled faster, exhibit better control over surface properties, a superior degree of order, and a somewhat higher packing density. The electrosorbed SAMs also exhibit better blockage of electron transfer across the interface and thus have better corrosion resistance.

  1. 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.

  2. 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.

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

    Science.gov (United States)

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

    2012-11-15

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

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

    Science.gov (United States)

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

    2011-08-22

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

  5. General Quality Control (QC) Guidelines for SAM Methods

    Science.gov (United States)

    Learn more about quality control guidelines and recommendations for the analysis of samples using the methods listed in EPA's Selected Analytical Methods for Environmental Remediation and Recovery (SAM).

  6. SOAR Adaptive Module (SAM): Seeing Improvement with a UV Laser

    Science.gov (United States)

    Tokovinin, Andrei; Cantarutti, Rolando; Tighe, Roberto; Schurter, Patricio; Martinez, Manuel; Thomas, Sandrine; van der Bliek, Nicole

    2016-12-01

    The adaptive module of the 4.1 m SOAR telescope, SOAR Adaptive Module (SAM), corrects ground-layer turbulence using an ultraviolet laser guide star. It has been commissioned in 2013 and it is in regular science operation since 2014. SAM works with the CCD imager covering a 3‧ field or with the speckle camera. It operates routinely and stably, delivering resolution in the I band equal to the free-atmosphere seeing. This paper describes the SAM system as a whole, providing essential reference for its users and technical information of interest to instrumentalists. Operation of the instrument, its performance, and science projects done with SAM so far are reviewed.

  7. SOAR Adaptive Module (SAM): seeing improvement with a UV laser

    CERN Document Server

    Tokovinin, Andrei; Tighe, Roberto; Schurter, Patricio; Martinez, Manuel; Thomas, Sandrine; van der Bliek, Nicole

    2016-01-01

    The adaptive module of the 4.1-m SOAR telescope, SAM, corrects ground-layer turbulence using a UV laser guide star. It has been commissioned in 2013 and it is in regular science operation since 2014. SAM works with the CCD imager covering a 3' field or with the speckle camera. It operates routinely and stably, delivering resolution in the I band equal to the free-atmosphere seeing. This paper describes the SAM system as a whole, providing essential reference for its users and technical information of interest to instrumentalists. Operation of the instrument, its performance, and science projects done with SAM so far are reviewed.

  8. Probing molecular interactions with methylene blue derivatized self-assembled monolayers

    Directory of Open Access Journals (Sweden)

    Eleni Koutsoumpeli

    2015-12-01

    Full Text Available The emergence of stratified and personalised medicine and the associated need for highly multiplexed detection strategies are driving the development of innovative sensor technology. Electronic immunosensor arrays capable of label-free and highly parallel monitoring of ligand binding have emerged as a particularly promising technology capable of meeting these new diagnostic challenges. In this study, we present an approach for interrogating molecular interactions electronically using redox active molecular monolayers. Specifically, we have synthesised self-assembled molecular monolayers assembled from long-chain alkanethiols (LCAT incorporating oligoethyleneglycol (OEG linkers that can be derivatized with a range of functional groups, including the redox active molecule methylene blue. Critically, we show that the electron transport properties of this redox-active monolayer are highly sensitive to the electrochemical environment, including the local concentration of protons and the electrostatic potential at the plane of electron transfer. Using a combination of cyclic voltammetry and QCM-D to study in detail the behaviour of the monolayer during functionalisation and analyte binding, we demonstrate that these redox properties can be exploited for the electrochemical sensing of molecular interactions (biotin–avidin in our case on SAMs. Given the versatility of LCAT-OEG monolayers, in terms of linker lengths, choice of functional group, and ability to create mixed component layers and the straight-forward assembly of mixed SAMs of high quality, our electrochemical sensing approach forms an excellent and generic label-free platform for probing a wide range of molecular interactions.

  9. Investigation of the mechanism of electroless deposition of copper on functionalized alkanethiolate self-assembled monolayers adsorbed on gold.

    Science.gov (United States)

    Lu, Peng; Walker, Amy V

    2007-12-04

    We have investigated the reaction pathways involved in the unseeded electroless deposition of copper on self-assembled monolayers (SAMs) adsorbed on Au, using time-of-flight secondary ion mass spectrometry, optical microscopy, and scanning electron microscopy. At 22 degrees C copper deposits on both -CH3 and -COOH terminated SAMs. No copper deposition is observed on -OH terminated SAMs because the hydroxyl terminal groups react with formaldehyde in the plating solution, forming an acetal which prevents Cu deposition. At higher deposition temperatures (45 degrees C), no Cu is observed to deposit on -CH3 terminated SAMs because Cu2+ ions are not stabilized on the SAM surface. Copper complexes are still able to form with the -COOH terminal group at 45 degrees C, and so copper continues to be deposited on -COOH terminated SAMs. Copper also penetrates through -CH3 and -COOH terminated SAMs to the Au/S interface, suggesting that soft deposition techniques do not prevent the penetration of low-to-moderate reactivity metals through organic films.

  10. Patterned deposition of multi-walled carbon nanotubes on self-assembled monolayers

    Institute of Scientific and Technical Information of China (English)

    PENG Yitian; HU Yuanzhong; WANG Hui

    2006-01-01

    Patterned chemical template consisting of both amine- and methyl-terminated self-assembled monolayers has been fabricated. The deposition of carbon nanotubes is carried out by immerging the patterned substrate into dimethylformamide (DMF) solution with suspended carbon nanotubes (CNTs). SEM images show a successful patterned deposition that carbon nanotubes selectively deposit in the area with amino-terminated SAMs due to the strong attract force between the monolayer and the suspended CNTs. This experiment provides an opportunity for manipulating individual CNTs, and represents a significant step in development of CNTs-based nanodevices.

  11. Chemically sensitive surface plasmon devices employing a self-assembled monolayer composite film

    Science.gov (United States)

    DePriest, J. C.; Meriaudeau, Fabrice; Oden, Patrick I.; Downey, Todd R.; Passian, A.; Wig, A. G.; Ferrell, Trinidad L.

    1998-12-01

    In this paper the results of detecting volatile organic compounds (VOC) employing surface plasmon-based sensors are presented. The initial step in preparing the sensing elements herein requires depositing Au degree(s) on a quartz slide. The sensing elements are based on either (1) freshly deposited Au degree(s) or (2) growth of a self assembled monolayer composite film (SAM) on to a freshly deposited Au degree(s) surface. The desired SAM is either (1) acid terminated using (omega) -mercaptoundecanoic acid (MUA-COOH) or (2) Cu2+ metal ion terminated yielding (omega) - mercaptoundecanoic acid-Cu2+ (MUA-Cu2+). The experimental apparatus shown here measures the reflectivity of the Au degree(s) surface as a function of time at a given angle. The response of this surface plasmon device to various VOC's is correlated to the composition of the SAM film.

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

    Science.gov (United States)

    Liu, Ting; Li, Meixian; Li, Qianyuan

    2004-07-01

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

  13. Packing density of HS(CH2)(n)COOH self-assembled monolayers.

    Science.gov (United States)

    Snow, A W; Jernigan, G G; Ancona, M G

    2011-12-01

    Self-assembled monolayers (SAMs) of HS(CH(2))(n)COOH, n = 5, 10, 15 deposited from ethanol solution onto gold are prepared by five approaches, and their packing densities are evaluated by X-ray photoelectron spectroscopy (XPS) measurements. The five approaches are: (1) direct deposition; (2) acetic-acid-assisted deposition; (3) butyl-amine-assisted deposition; (4) displacement of a preformed HS(CH(2))(n)CH(3) (n = 5, 10, 15) SAMs; and (5) co-deposition with HS(CH(2))(n)CH(3) (n = 5, 10, 15). Packing density metrics are calculated from measurements of SAM and substrate photoemission intensities and their attenuations by two methods. In one case the attenuated photoemissions are expressed as a ratio relative to comparable measurements on an experimental HS(CH(2))(n)CH(3) model system. In the other case a new method is introduced where a calculated attenuation based on theoretical random coil and extended chain models is used as the reference to determine a packing density fraction. Packing densities are also correlated with the S2p(Au-bonded):Au4f peak area ratios and with shifts in the C1s binding energies. SAMs prepared by the direct deposition are a partial multilayer where a second molecular layer is physisorbed onto the SAM and not removable by solvent washing. The addition of acetic acid to the deposition solution disrupts dimer associations of HS(CH(2))(n)COOH in solution and at the surface of the monolayer and yields the most ordered monolayer with the highest density of -COOH groups. The addition of butyl amine results in a labile ammonium carbonate ion pair formation but results in a lower packing density in the SAM. The displacement of the preformed HS(CH(2))(n)CH(3) SAM and the co-deposition of HS(CH(2))(n)CH(3) with HS(CH(2))(n)COOH result in SAMs with little incorporation of the -COOH component.

  14. Neutral Radical Molecules Ordered in Self-Assembled Monolayer Systems for Quantum Information Processing

    CERN Document Server

    Tamulis, A; Tretiak, S; Berman, G P; Allara, D L

    2003-01-01

    Implementation of quantum information processing based on spatially localized electronic spins in stable molecular radicals is discussed. The necessary operating conditions for such molecules are formulated in self-assembled monolayer (SAM) systems. As a model system we start with 1, 3 -diketone types of neutral radicals. Using first principles quantum chemical calculations we prove that these molecules have the stable localized electron spin, which may represent a qubit in quantum information processing.

  15. Micro-patterning of self-assembled organic monolayers by using tunable ultrafast laser pulses

    Science.gov (United States)

    Maragkaki, Stella; Aumann, Andreas; Schulz, Florian; Schröter, Anja; Schöps, Benjamin; Franzka, Steffen; Hartmann, Nils; Ostendorf, Andreas

    2014-03-01

    We study the application of tunable ultrafast laser pulses in micropatterning self- assembled organic monolayer (SAMs) employing non collinear optical parametric amplification (NOPA). SAMs are ultrathin organic monolayers, which can be used in a variety of ways to assemble functionalized surface structures. In our study, we investigate the characteristics of SAMs as monomolecular resists during etching of gold. NOPA is a versatile method which provides the generation of ultrafast laser pulses, with a tunable wavelength in the visible and near infrared range. Due to the noncollinear geometry, a broadened spectral range can be amplified. The NOPA delivers wavelengths in the range of 480 nm to 950 nm at laser pulse lengths in the sub- 30 femtosecond range using a prism compressor after the nonlinear conversion. The ultrashort laser technology together with the advantages of the NOPA system guarantee high precision and allows us to determine the optimum conditions of sub-wavelength patterning by studying the effects of the fluence and the wavelength. At the same time, single-pulse processing allows us to selectively remove the ultrathin organic coating, while it ensures short processing time. In our study we used thiol-based SAMs as ultrathin layers on gold-coated glass substrates with a film thickness of 1-2 nm and 40 nm respectively.

  16. Modulation of electrochemical hydrogen evolution rate by araliphatic thiol monolayers on gold

    Science.gov (United States)

    Muglali, Mutlu I.; Erbe, Andreas; Chen, Ying; Barth, Christoph; Koelsch, Patrick; Rohwerder, Michael

    2013-01-01

    Electroreductive desorption of a highly ordered self-assembled monolayer (SAM) formed by the araliphatic thiol (4-(4-(4-pyridyl)phenyl)phenyl)methanethiol leads to a concurrent rapid hydrogen evolution reaction (HER). The desorption process and resulting interfacial structure were investigated by voltammetric techniques, in situ spectroscopic ellipsometry, and in situ vibrational sum–frequency–generation (SFG) spectroscopy. Voltammetric experiments on SAM-modified electrodes exhibit extraordinarily high peak currents, which di er between Au(111) and polycrystalline Au substrates. Association of reductive desorption with HER is shown to be the origin of the observed excess cathodic charges. The studied SAM preserves its two–dimensional order near Au surface throughout a fast voltammetric scan even when the vertex potential is set several hundred millivolt beyond the desorption potential. A model is developed for the explanation of the observed rapid HER involving ordering and pre–orientation of water present in the nanometer–sized reaction volume between desorbed SAM and the Au electrode, by the structurally extremely stable monolayer, leading to the observed catalysis of the HER. PMID:24235778

  17. Modulation of electrochemical hydrogen evolution rate by araliphatic thiol monolayers on gold.

    Science.gov (United States)

    Muglali, Mutlu I; Erbe, Andreas; Chen, Ying; Barth, Christoph; Koelsch, Patrick; Rohwerder, Michael

    2013-02-15

    Electroreductive desorption of a highly ordered self-assembled monolayer (SAM) formed by the araliphatic thiol (4-(4-(4-pyridyl)phenyl)phenyl)methanethiol leads to a concurrent rapid hydrogen evolution reaction (HER). The desorption process and resulting interfacial structure were investigated by voltammetric techniques, in situ spectroscopic ellipsometry, and in situ vibrational sum-frequency-generation (SFG) spectroscopy. Voltammetric experiments on SAM-modified electrodes exhibit extraordinarily high peak currents, which di er between Au(111) and polycrystalline Au substrates. Association of reductive desorption with HER is shown to be the origin of the observed excess cathodic charges. The studied SAM preserves its two-dimensional order near Au surface throughout a fast voltammetric scan even when the vertex potential is set several hundred millivolt beyond the desorption potential. A model is developed for the explanation of the observed rapid HER involving ordering and pre-orientation of water present in the nanometer-sized reaction volume between desorbed SAM and the Au electrode, by the structurally extremely stable monolayer, leading to the observed catalysis of the HER.

  18. Self-assembled monolayer-functionalized half-metallic manganite for molecular spintronics.

    Science.gov (United States)

    Tatay, Sergio; Barraud, Clément; Galbiati, Marta; Seneor, Pierre; Mattana, Richard; Bouzehouane, Karim; Deranlot, Cyrile; Jacquet, Eric; Forment-Aliaga, Alicia; Jegou, Pascale; Fert, Albert; Petroff, Frédéric

    2012-10-23

    (La,Sr)MnO(3) manganite (LSMO) has emerged as the standard ferromagnetic electrode in organic spintronic devices due to its highly spin-polarized character and air stability. Whereas organic semiconductors and polymers have been mainly envisaged to propagate spin information, self-assembled monolayers (SAMs) have been overlooked and should be considered as promising materials for molecular engineering of spintronic devices. Surprisingly, up to now the first key step of SAM grafting protocols over LSMO surface thin films is still missing. We report the grafting of dodecyl (C12P) and octadecyl (C18P) phosphonic acids over the LSMO half-metallic oxide. Alkylphosphonic acids form ordered self-assembled monolayers, with the phosphonic group coordinated to the surface and alkyl chains tilted from the surface vertical by 43° (C12P) and 27° (C18P). We have electrically characterized these SAMs in nanodevices and found that they act as tunnel barriers, opening the door toward the integration of alkylphosphonic acid//LSMO SAMs into future molecular/organic spintronic devices such as spin OLEDs.

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

    Directory of Open Access Journals (Sweden)

    Hongxia Chen

    2014-03-01

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

  20. Optimisation and Characterisation of Anti-Fouling Ternary SAM Layers for Impedance-Based Aptasensors

    Directory of Open Access Journals (Sweden)

    Anna Miodek

    2015-09-01

    Full Text Available An aptasensor with enhanced anti-fouling properties has been developed. As a case study, the aptasensor was designed with specificity for human thrombin. The sensing platform was developed on screen printed electrodes and is composed of a self-assembled monolayer made from a ternary mixture of 15-base thiolated DNA aptamers specific for human thrombin co-immobilised with 1,6-hexanedithiol (HDT and further passivated with 1-mercapto-6-hexanol (MCH. HDT binds to the surface by two of its thiol groups forming alkyl chain bridges and this architecture protects from non-specific attachment of molecules to the electrode surface. Using Electrochemical Impedance Spectroscopy (EIS, the aptasensor is able to detect human thrombin as variations in charge transfer resistance (Rct upon protein binding. After exposure to a high concentration of non-specific Bovine Serum Albumin (BSA solution, no changes in the Rct value were observed, highlighting the bio-fouling resistance of the surface generated. In this paper, we present the optimisation and characterisation of the aptasensor based on the ternary self-assembled monolayer (SAM layer. We show that anti-fouling properties depend on the type of gold surface used for biosensor construction, which was also confirmed by contact angle measurements. We further studied the ratio between aptamers and HDT, which can determine the specificity and selectivity of the sensing layer. We also report the influence of buffer pH and temperature used for incubation of electrodes with proteins on detection and anti-fouling properties. Finally, the stability of the aptasensor was studied by storage of modified electrodes for up to 28 days in different buffers and atmospheric conditions. Aptasensors based on ternary SAM layers are highly promising for clinical applications for detection of a range of proteins in real biological samples.

  1. Optimisation and Characterisation of Anti-Fouling Ternary SAM Layers for Impedance-Based Aptasensors.

    Science.gov (United States)

    Miodek, Anna; Regan, Edward M; Bhalla, Nikhil; Hopkins, Neal A E; Goodchild, Sarah A; Estrela, Pedro

    2015-09-29

    An aptasensor with enhanced anti-fouling properties has been developed. As a case study, the aptasensor was designed with specificity for human thrombin. The sensing platform was developed on screen printed electrodes and is composed of a self-assembled monolayer made from a ternary mixture of 15-base thiolated DNA aptamers specific for human thrombin co-immobilised with 1,6-hexanedithiol (HDT) and further passivated with 1-mercapto-6-hexanol (MCH). HDT binds to the surface by two of its thiol groups forming alkyl chain bridges and this architecture protects from non-specific attachment of molecules to the electrode surface. Using Electrochemical Impedance Spectroscopy (EIS), the aptasensor is able to detect human thrombin as variations in charge transfer resistance (Rct) upon protein binding. After exposure to a high concentration of non-specific Bovine Serum Albumin (BSA) solution, no changes in the Rct value were observed, highlighting the bio-fouling resistance of the surface generated. In this paper, we present the optimisation and characterisation of the aptasensor based on the ternary self-assembled monolayer (SAM) layer. We show that anti-fouling properties depend on the type of gold surface used for biosensor construction, which was also confirmed by contact angle measurements. We further studied the ratio between aptamers and HDT, which can determine the specificity and selectivity of the sensing layer. We also report the influence of buffer pH and temperature used for incubation of electrodes with proteins on detection and anti-fouling properties. Finally, the stability of the aptasensor was studied by storage of modified electrodes for up to 28 days in different buffers and atmospheric conditions. Aptasensors based on ternary SAM layers are highly promising for clinical applications for detection of a range of proteins in real biological samples.

  2. Voltammetric Determination of Prochlorperazine and Ethopropazine Using a Gold Electrode Modified with Decanethiol SAM

    Directory of Open Access Journals (Sweden)

    Baizhao Zeng

    2003-12-01

    Full Text Available The voltammetric behavior of prochlorperazine and ethopropazine at a decanethiol (DEC self-assembled monolayer (SAM modified gold electrode (DEC/Au has been studied. It was observed that prochlorperazine exhibited an anodic peak at about 0.60 V (vs SCE, while ethopropazine exhibited two anodic peaks at about 0.49 V and 0.58 V on DEC/Au in pH 10 sodium carbonate buffer. This was due to their different electrochemical oxidation mechanisms. In this case, the oxidation of prochlorperazine and ethopropazine included one 2e step and two 1e steps, respectively. In the presence of some reductants such as ascorbic acid, the oxidation products of them can catalyze the oxidation of the reductants and thus make the peaks grow. In addition, it was found that the SAM structure became not so compact when prochlorperazine and ethopropazine were present, resulting from their permeating in the SAM. Various conditions were optimized for their determination. Under the selected conditions (i.e. 0.080 M pH 10 sodium carbonate buffer; scan rate: 100 mV/s; accumulation potential: –0.4 V or 0 V; accumulation time: 60 s, the peak currents were linear to prochlorperazine concentration in the ranges of 0.1~2.0 μM and 5.0~50 μM, and linear with ethopropazine in the ranges of 10 nM~0.1 μM and 0.5~20 μM. The RSD was 4.28% for 8 successive measurements of 1.0 μM prochlorperazine. The influence of some coexistents was examined.

  3. Directed immobilization of reduced antibody fragments onto a novel SAM on gold for myoglobin impedance immunosensing.

    Science.gov (United States)

    Billah, Md Morsaline; Hodges, Christopher S; Hays, Henry C W; Millner, P A

    2010-11-01

    The successful construction of an immunosensor depends on having an effective procedure for immobilising the bio-recognition element to the transducer surface. In the present study, an amino-terminated 4-aminothiophenol (ATP) self-assembled monolayer (SAM) was modified with heterobifunctional crosslinker sulfosuccinimidyl 4-[N-maleimidomethyl] cyclohexane-1-carboxylate to couple reduced anti-myoglobin half-antibody fragments. The disulphide groups present in the hinge region of IgG molecules were selectively cleaved by 2-mercaptoethylamine to produce reduced half-antibody fragments with free sulphydryl groups. The maleimide terminated 4-ATP SAM modified surface was coupled to these reduced antibody fragments to produce highly oriented immobilization of the half-antibody via its Fc domain and to allow free access to the Fv bindings sites. This represents an improvement by comparison with biotin/avidin mediated IgG attachment which is essentially randomly oriented. Functional immunosensors were able to detect myoglobin in both phosphate buffered saline and whole serum over the range of concentrations from 10(-13)M to 10(-6)M, and order of magnitude better than avidin/biotin linked immunosensors. In addition, atomic force microscopy (AFM) was carried out to elucidate the nanotopology of the immunosensor surface at different stages of fabrication; the images demonstrate that half antibodies bind as described and show structural changes on subsequent antigen binding.

  4. Superhydrophobic SAM Modified Electrodes for Enhanced Current Limiting Properties in Intrinsic Conducting Polymer Surge Protection Devices.

    Science.gov (United States)

    Jabarullah, Noor H; Verrelli, Emanuele; Mauldin, Clayton; Navarro, Luis A; Golden, Josh H; Madianos, Leonidas M; Kemp, Neil T

    2015-06-09

    Surface interface engineering using superhydrophobic gold electrodes made with 1-dodecanethiol self-assembled monolayer (SAM) has been used to enhance the current limiting properties of novel surge protection devices based on the intrinsic conducting polymer, polyaniline doped with methanesulfonic acid. The resulting devices show significantly enhanced current limiting characteristics, including current saturation, foldback, and negative differential effects. We show how SAM modification changes the morphology of the polymer film directly adjacent to the electrodes, leading to the formation of an interfacial compact thin film that lowers the contact resistance at the Au-polymer interface. We attribute the enhanced current limiting properties of the devices to a combination of lower contact resistance and increased Joule heating within this interface region which during a current surge produces a current blocking resistive barrier due to a thermally induced dedoping effect caused by the rapid diffusion of moisture away from this region. The effect is exacerbated at higher applied voltages as the higher temperature leads to stronger depletion of charge carriers in this region, resulting in a negative differential resistance effect.

  5. Absence of molecular slip on ultraclean and SAM-coated surfaces

    Science.gov (United States)

    Pye, Justin; Wood, Clay; Burton, Justin

    2016-11-01

    The liquid/solid boundary condition is a complex problem that is becoming increasingly important for the development of nanoscale fluidic devices. Many groups have now measured slip near an interface at nanoscale dimensions using a variety of experimental techniques. In simple systems, large slip lengths are generally measured for non-wetting liquid/solid combinations, but many conflicting measurements and interpretations remain. We have developed a novel pseudo-differential technique using a quartz crystal microbalance (QCM) to measure slip lengths on various surfaces. A drop of one liquid is grown on the QCM in the presence of a second, ambient liquid. We have isolated any anomalous boundary effects such as interfacial slip by choosing two liquids which have identical bulk effects on the QCM frequency and dissipation in the presence of no-slip. Slip lengths are -less than 2 nm- for water (relative to undecane) on all surfaces measured, including plasma cleaned gold, SiO2, and two different self assembled monolayers (SAMs), regardless of contact angle. We also find that surface cleanliness is crucial to accurately measure slip lengths. Additionally, clean glass substrates appear to have a significant adsorbed water layer and SAM surfaces show excess dissipation, possibly associated with contact line motion. In addition to investigating other liquid pairs, future work will include extending this technique to surfaces with independently controllable chemistry and roughness, both of which are known to strongly affect interfacial hydrodynamics.

  6. 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.

  7. Providing output of DIRAC-SAM jobs to the IT-based SAM-Nagios framework

    CERN Document Server

    Volkl, Valentin

    2013-01-01

    Information available on LHCb grid sites in the SAM-Nagios monitor- ing framework - gathered mainly through functional tests - has been sup- plemented with results from LHCbDIRAC SAMJobs published by means of message client newly integrated in LHCbDIRAC. These are displayed as a new metric org.lhcb.DiracTest-lhcb giving additional debug in- formation to system administrators and influencing reports on grid site performances in the future

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

    Science.gov (United States)

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

    2016-12-01

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

  9. 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.

  10. Optical imaging beyond the diffraction limit by SNEM: Effects of AFM tip modifications with thiol monolayers on imaging quality

    Energy Technology Data Exchange (ETDEWEB)

    Cumurcu, Aysegul [Materials Science and Technology of Polymers, MESA+ Institute for Nanotechnology, University of Twente, Enschede NL-7500 (Netherlands); Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX, Eindhoven (Netherlands); Diaz, Jordi [Scientific and Technological Centers of the University of Barcelona, C/ Lluís Solé i Sabaris, 1-3, 08028 Barcelona (Spain); Lindsay, Ian D. [Nanophysics and Soft Matter Group, H.H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Beer, Sissi de; Duvigneau, Joost [Materials Science and Technology of Polymers, MESA+ Institute for Nanotechnology, University of Twente, Enschede NL-7500 (Netherlands); Schön, Peter [Materials Science and Technology of Polymers, MESA+ Institute for Nanotechnology, University of Twente, Enschede NL-7500 (Netherlands); NanoBioInterface, Research Center Design and Technology, Saxion University of Applied Sciences, 7500 KB Enschede (Netherlands); Julius Vancso, G., E-mail: g.j.vancso@utwente.nl [Materials Science and Technology of Polymers, MESA+ Institute for Nanotechnology, University of Twente, Enschede NL-7500 (Netherlands)

    2015-03-15

    Tip-enhanced nanoscale optical imaging techniques such as apertureless scanning near-field optical microscopy (a-SNOM) and scanning near-field ellipsometric microscopy (SNEM) applications can suffer from a steady degradation in performance due to adhesion of atmospheric contaminants to the metal coated tip. Here, we demonstrate that a self-assembled monolayer (SAM) of ethanethiol (EtSH) is an effective means of protecting gold-coated atomic force microscopy (AFM) probe tips from accumulation of surface contaminants during prolonged exposure to ambient air. The period over which they yield consistent and reproducible results for scanning near-field ellipsometric microscopy (SNEM) imaging is thus extended. SNEM optical images of a microphase separated polystyrene-block-poly (methylmethacrylate) (PS-b-PMMA) diblock copolymer film, which were captured with bare and SAM-protected gold-coated AFM probes, both immediately after coating and following five days of storage in ambient air, were compared. During this period the intensity of the optical signals from the untreated gold tip fell by 66%, while those from the SAM protected tip fell by 14%. Additionally, gold coated AFM probe tips were modified with various lengths of alkanethiols to measure the change in intensity variation in the optical images with SAM layer thickness. The experimental results were compared to point dipole model calculations. While a SAM of 1-dodecanethiol (DoSH) was found to strongly suppress field enhancement we find that it can be locally removed from the tip apex by deforming the molecules under load, restoring SNEM image contrast. - Highlights: • SAM of ethanethiol is used to prevent contamination of gold coated tips. • Functionalizing gold coated tips with a SAM lead to reproducible SNEM imaging. • Point dipole model agreed with the experimental results of the SNEM images. • SAM of 1-dodecanethiol was found to strongly suppress field enhancement in SNEM. • SAM of 1-dodecanethiol

  11. Simulation and Modeling of Self-Assembled Monolayers of Carboxylic Acid Thiols on Flat and Nanoparticle Gold Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Techane, Sirnegeda D.; Baer, Donald R.; Castner, David G.

    2011-09-01

    Quantitative analysis of the 16-mercaptohexadecanoic acid self-assembled monolayer (C16 COOH-SAM) layer thickness on gold nanoparticles (AuNPs) was performed using simulation of electron spectra for surface analysis (SESSA) and x-ray photoelectron spectroscopy (XPS). XPS measurements of C16 COOH SAMs on flat gold surfaces were made at 9 different photoelectron take-off angles (5o to 85o in 5o increments), corrected using geometric weighting factors and then summed together to approximate spherical AuNPs. The SAM thickness and relative surface roughness (RSA) in SESSA were optimized to determine the best agreement between simulated and experimental surface composition. Based on the glancing angle results, it was found that inclusion of a hydrocarbon contamination layer on top the C16 COOH-SAM was necessary to improve the agreement between the SESSA and XPS results. For the 16 COOH-SAMs on flat Au surfaces, using a SAM thickness of 1.1Å/CH2 group, an RSA of 1.05 and a 1.5Å CH2-contamination overlayer (total film thickness = 21.5Å) for the SESSA calculations provided the best agreement with the experimental XPS data. After applying the appropriate geometric corrections and summing the SESSA flat surface compositions, the best fit results for the 16 COOH-SAM thickness and surface roughness on the AuNPs were determined to be 0.9Å/CH2 group and 1.06 RSA with a 1.5Å CH2-contamination overlayer (total film thickness = 18.5Å). The three angstrom difference in SAM thickness between the flat Au and AuNP surfaces suggests the alkyl chains of the SAM are slightly more tilted or disordered on the AuNP surfaces.

  12. 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.

  13. Electron transfer behavior at polyoxometalate-adsorbed alkanethiol self-assembled monolayers

    Science.gov (United States)

    Chu, Yeonyi; Kim, Jandee; Choi, Suhee; Rhee, Choong Kyun; Kim, Jongwon

    2011-09-01

    The interaction between polyoxometalate (POM) anions, SiMo 12O 404-, and a self-assembled monolayer (SAM) of dodecanethiol (DT) on Au surfaces was investigated using electrochemical methods, X-ray photoelectron spectroscopy, and scanning probe microscopy. The SiMo 12O 404- ions adsorb on the SAM of DT on Au to form a composite organic-inorganic hybrid layer. The adsorbed SiMo 12O 404- ion on the SAM layer shows its characteristic redox waves with an electron transfer rate slower than that on a bare Au electrode. The electron transfer behavior at DT-SAM could be regulated by the adsorption of SiMo 12O 404- depending on the charge of the investigated electroactive species: a significant increase toward a positively charged Ru(NH 3) 63+ ion, a moderate increase toward a neutral 1,1'-ferrocenedimethanol molecule and a slight decrease toward a negatively charged Fe(CN) 63- ion. The effect of the chain length of alkanethiols on the adsorption of SiMo 12O 404- ion was also investigated: as the chain length decreases, the amount of the adsorbed POM increases and the electron transfer rate through the composite layers increases. The nature of SiMo 12O 404- ions adsorbed on the SAMs of alkanethiols on Au is discussed in detail.

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

    Science.gov (United States)

    Shen, Cai; Buck, Manfred

    2014-01-01

    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-yl)ethanethiol (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.

  15. Controlling the stereochemistry and regularity of butanethiol self-assembled monolayers on au(111).

    Science.gov (United States)

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

    2014-12-10

    The rich stereochemistry of the self-assembled monolayers (SAMs) of four butanethiols on Au(111) is described, the SAMs containing up to 12 individual C, S, or Au chiral centers per surface unit cell. This is facilitated by synthesis of enantiomerically pure 2-butanethiol (the smallest unsubstituted chiral alkanethiol), followed by in situ scanning tunneling microscopy (STM) imaging combined with density functional theory molecular dynamics STM image simulations. Even though butanethiol SAMs manifest strong headgroup interactions, steric interactions are shown to dominate SAM structure and chirality. Indeed, steric interactions are shown to dictate the nature of the headgroup itself, whether it takes on the adatom-bound motif RS(•)Au(0)S(•)R or involves direct binding of RS(•) to face-centered-cubic or hexagonal-close-packed sites. Binding as RS(•) produces large, organizationally chiral domains even when R is achiral, while adatom binding leads to rectangular plane groups that suppress long-range expression of chirality. Binding as RS(•) also inhibits the pitting intrinsically associated with adatom binding, desirably producing more regularly structured SAMs.

  16. 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.

  17. Sam68 is a novel marker for aggressive neuroblastoma

    Directory of Open Access Journals (Sweden)

    Zhao X

    2013-12-01

    Full Text Available Xiaohong Zhao,1,* Zuoqing Li,2,* Benfu He,3 Juncheng Liu,2 Suisheng Li,2 Li Zhou,2 Cuiling Pan,2 Zhe Yu,4 Zhe Xu21State Key Laboratory of Oncology in Southern China, Department of Experimental Research, Cancer Center, Sun Yat-sen University, 2Department of Pediatric Surgery, First Affiliated Hospital of Sun Yat-sen University, 3Oncology Department, PLA421 Hospital, 4Laura Biotech Co, Ltd, Guangzhou, People’s Republic of China*These authors contributed equally to this workBackground: Neuroblastoma (NB is the most common solid extracranial tumor in children. However, the molecular mechanism and progression of NB is largely unknown, and unfortunately, the prognosis is poor. Src-associated in mitosis with a molecular weight of 68 kDa (Sam68 is associated with carcinogenesis and neurogenesis. The present study aimed to investigate the clinical and prognostic significance of Sam68 in NB.Methods: The expression of Sam68 in immortalized normal epithelial cells, NB cell lines, and in four cases of paired NB tissue and adjacent normal tissue from the same patient was examined using Western blotting, reverse transcription-polymerase chain reaction (PCR and real-time reverse transcription-PCR. The proliferation of NB cells was determined by 3-(4,5-dimethylthiazol-2-yl-2,5-diphenyltetrazolium bromide (MTT assay. Furthermore, Sam68 protein expression was analyzed in 90 NB cases characterized as clinicopathological using immunohistochemistry. Statistical analyses were applied to evaluate the diagnostic value and associations of Sam68 with clinical parameters.Results: Western blotting and reverse transcription-PCR showed that the expression level of Sam68 was markedly higher in NB cell lines than in the immortalized normal epithelial cells at both messenger RNA and protein levels. The MTT assay revealed that Sam68 expression supported proliferation of NB cells. Sam68 expression levels were significantly up-regulated in tumor tissues in comparison to the

  18. 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.

  19. Controlled modulation of electronic properties of graphene by self-assembled monolayers on SiO2 substrates.

    Science.gov (United States)

    Yan, Zheng; Sun, Zhengzong; Lu, Wei; Yao, Jun; Zhu, Yu; Tour, James M

    2011-02-22

    In this study, with self-assembled monolayers (SAMs) of aminopropyl-, ammoniumpropyl-, butyl-, and 1H,1H,2H,2H-perfluorooctyltriethoxysilanes deposited in-between graphene and the SiO(2) substrate, a controlled doping of graphene was realized with a threshold voltage ranging from -18 to 30 V. In addition, the SAMs are covalently bonded to the SiO(2) surface rather than the graphene surface, thereby producing minimal effects on the mobility of the graphene. Finally, it is more stable than conventional noncovalent dopants.

  20. Charge retention of soft-landed phosphotungstate Keggin anions on self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-01

    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.

  1. Gold Mining by Alkanethiol Radicals: Vacancies and Pits in the Self-Assembled Monolayers of 1-Propanethiol and 1-Butanethiol on Au(111)

    DEFF Research Database (Denmark)

    Wang, Yun; Chi, Qijin; Hush, Noel S.;

    2011-01-01

    Scanning-tunneling microscopy (STM) under electrochemical control (in situ STM) in aqueous solution, combined with a priori density functional theory (DFT) image simulations at room temperature, reveals the atomic nature of the interface between Au(111) and self-assembled monolayers (SAMs) of 1-p...

  2. 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;

    2015-01-01

    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 tw...

  3. Formation of carboxy- and amide-terminated alkyl monolayers on silicon(111) investigated by ATR-FTIR, XPS, and X-ray scattering: Construction of photoswitchable surfaces

    DEFF Research Database (Denmark)

    Rück-Braun, Karola; Petersen, Michael Åxman; Michalik, Fabian

    2013-01-01

    We have prepared high-quality, densely packed, self-assembled monolayers (SAMs) of carboxy-terminated alkyl chains on Si(111). The samples were made by thermal grafting of methyl undec-10-enoate under an inert atmosphere and subsequent cleavage of the ester functionality to disclose the carboxyli...

  4. Multivalent host-guest interactions between ss-cyclodextrin self-assembled monolayers and poly (isobutene-alt-maleic acid)s modified with hydrophobic guest moeties

    NARCIS (Netherlands)

    Crespo biel, O.; Péter, M.; Bruinink, C.M.; Ravoo, B.J.; Reinhoudt, David; Huskens, Jurriaan

    2005-01-01

    Poly(isobutene-alt-maleic acid)s modified with p-tert-butylphenyl or adamantyl groups interact with ß-cyclodextrin self-assembled monolayers (ß-CD SAMs) by inclusion of the hydrophobic substituents in the B-cyclodextrin cavities. The adsorption was shown to be strong, specific, and irreversible.

  5. Thiol-yne adsorbates for stable, low-density, self-assembled monolayers on gold.

    Science.gov (United States)

    Stevens, Christopher A; Safazadeh, Leila; Berron, Brad J

    2014-03-04

    We present a novel approach toward carboxylate-terminated, low-density monolayers on gold, which provides exceptional adsorbate stability and conformational freedom of interfacial functional groups. Adsorbates are synthesized through the thiol-yne addition of two thiol-containing head groups to an alkyne-containing tail group. The resulting monolayers have two distinct phases: a highly crystalline head phase adjacent to the gold substrate, and a reduced density tail phase, which is in contact with the environment. The ellipsometric thickness of 27 Å is consistent with the proposed structure, where a densely packed decanedithiol monolayer is capped with an 11 carbon long, second layer at 50% lateral chain density. The Fourier transform infrared peak at 1710 cm(-1) supports the presence of the carbonyl group. Further, the peaks associated with asymmetric and symmetric methylene stretching are shifted toward higher wavenumbers compared to those of well-packed self-assembled monolayers (SAMs), which shows a lower average crystallinity of the thiol-yne monolayers compared to a typical monolayer. Contact angle measurements indicate an intermediate surface energy for the thiol-yne monolayer surface, owing to the contribution of exposed methylene functionality at the surface in addition to the carbonyl terminal group. The conformational freedom at the surface was demonstrated through remodeling the thiol-yne surface under an applied potential. Changes in the receding contact angle in response to an external potential support the capacity for reorientation of the surface presenting groups. Despite the low packing at the solution interface, thiol-yne monolayers are resistant to water and ion transport (R(f) ~ 10(5)), supporting the presence of a densely structured layer at the gold surface. Further, the electrochemical stability of the thiol-yne adsorbates exceeded that of well-packed SAMs, requiring a more reductive potential to desorb the thiol-yne monolayers from the

  6. System Advisor Model, SAM 2011.12.2: General Description

    Energy Technology Data Exchange (ETDEWEB)

    Gilman, P.; Dobos, A.

    2012-02-01

    This document describes the capabilities of the U.S. Department of Energy and National Renewable Energy Laboratory's System Advisor Model (SAM), Version 2011.12.2, released on December 2, 2011. SAM is software that models the cost and performance of renewable energy systems. Project developers, policy makers, equipment manufacturers, and researchers use graphs and tables of SAM results in the process of evaluating financial, technology, and incentive options for renewable energy projects. SAM simulates the performance of solar, wind, geothermal, biomass, and conventional power systems. The financial model can represent financing structures for projects that either buy and sell electricity at retail rates (residential and commercial) or sell electricity at a price determined in a power purchase agreement (utility). Advanced analysis options facilitate parametric, sensitivity, and statistical analyses, and allow for interfacing SAM with Microsoft Excel or with other computer programs. SAM is available as a free download at http://sam.nrel.gov. Technical support and more information about the software are available on the website.

  7. SAM Gcms Chromatography Performed at Mars : Elements of Interpretation

    Science.gov (United States)

    Szopa, C.; Coll, P. J.; Buch, A.; François, P.; Cabane, M.; Coscia, D.; Teinturier, S.; Navarro-Gonzalez, R.; Glavin, D. P.; Freissinet, C.; Mahaffy, P. R.

    2013-12-01

    The characterisation of the chemical and mineralogical composition of regolith samples collected with the Curiosity rover is a primary objective of the SAM experiment. These data should provide essential clues on the past habitability of Gale crater. Interpretation of the data collected after SAM pyrolysis evolved gas analysis (EGA) and gas chromatography mass spectrometry (GC-MS) experiments on the first soil samples collected by MSL at the Rocknest Aeolian Deposit in Gale Crater has been challenging due to the concomitant presence in the ovens of an oxychlorine phase present in the samples, and a derivatization agent coming from the SAM wet chemistry experiment (Glavin et al., 2013). Moreover, accurate identification and quantification, in the SAM EGA mode, of volatiles released from the heated sample, or generated by reactions occurring in the SAM pyrolysis oven, is also difficult for a few compounds due to evolution over similar temperature ranges and overlap of their MS signatures. Hence, the GC analyses, coupled with MS, enabled the separation and identification and quantification of most of the volatile compounds detected. These results can have been obtained through tests and calibration done with GC individual spare components and with the SAM testbed. This paper will present a view of the interpretation of the chromatograms obtained when analyzing the Rocknest and John Klein solid samples delivered to SAM, on sols 96 and 199 respectively, supported by laboratory calibrations.

  8. Structural and functional characterization of S-adenosylmethionine (SAM) synthetase from Pichia ciferrii.

    Science.gov (United States)

    Yoon, Sangyoung; Lee, Wonkyu; Kim, Minsoo; Kim, T Doohun; Ryu, Yeonwoo

    2012-01-01

    S-adenosylmethionine synthetase (SAM-s) catalyzes the synthesis of S-adenosylmethionine (SAM), which is essential for methylation, transcription, proliferation, and production of secondary metabolites. Here SAM-s from Pichia ciferrii were selectively cloned using RNA CapFishing and rapid amplification of cDNA ends (RACE). The putative full-length cDNA of SAM-s encoded a 383 amino acid protein (42.6 kDa), which has highly conserved metal binding sites, a phosphate-binding site, and functionally important motifs. The corresponding enzyme was over-expressed in a heterologous host of Pichia pastoris, and then purified to a homogenous form. Enzyme kinetics, immunoblotting, circular dichroism (CD), high performance liquid chromatography (HPLC), and molecular modeling were conducted to characterize the SAM-s from P. ciferrii. Structural and functional studies of SAM-s will provide important insights for industrial applications.

  9. 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.

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

    Science.gov (United States)

    Bandyopadhyay, Sabyasachi; Chattopadhyay, Samir; Dey, Abhishek

    2015-10-14

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

  11. Morphology of self assembled monolayers using liquid phase reaction on silica and their effect on the morphology of adsorbed insulin

    Science.gov (United States)

    Sharma, Indu; Pattanayek, Sudip K.; Aggarwal, Varsha; Ghosh, Subhasis

    2017-05-01

    The effect of roughness of two different categories of self-assembled monolayers (SAMs) with propyl amine and propyl groups respectively on the morphology of adsorbed insulin is observed. SAMs are obtained by liquid phase reaction of silica with organo silane coupling agents (SCA). The influence of the morphology and physical characteristics of the SAMs on the reaction time and concentration of the modifiers are explored. We have tested three SCA containing propyl amine with varying groups linked to Si present on it. In addition, we have used a silane coupling agent to prepare SAM of methyl head group. The approach of these molecules towards the surface depends on the head group and the groups linked to Si of the SCA. The morphology of the surfaces is analysed using power spectral density distribution (PSD), skewness, ellipsometry thickness and surface energy. Both chemical nature and physical morphology of the adsorbent influence the morphology of the adsorbed insulin. In general, a low number of aggregates of big size are formed on the surfaces obtained from low concentration of SAMs, while a higher number but of smaller size of aggregates are formed over surfaces obtained from 1% concentration of SAMs modifiers. The peak to valley ratio of the aggregates of insulin is strongly influenced by the size of grains of SCA over the adsorbent.

  12. 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.

  13. 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.

  14. Crystal structures of the SAM-III/S[subscript MK] riboswitch reveal the SAM-dependent translation inhibition mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Lu, C.; Smith, A.M.; Fuchs, R.T.; Ding, F.; Rajashankar, K.; Henkin, T.M.; Ke, A. (Cornell); (OSU)

    2010-01-07

    Three distinct classes of S-adenosyl-L-methionine (SAM)-responsive riboswitches have been identified that regulate bacterial gene expression at the levels of transcription attenuation or translation inhibition. The SMK box (SAM-III) translational riboswitch has been identified in the SAM synthetase gene in members of the Lactobacillales. Here we report the 2.2-{angstrom} crystal structure of the Enterococcus faecalis SMK box riboswitch. The Y-shaped riboswitch organizes its conserved nucleotides around a three-way junction for SAM recognition. The Shine-Dalgarno sequence, which is sequestered by base-pairing with the anti-Shine-Dalgarno sequence in response to SAM binding, also directly participates in SAM recognition. The riboswitch makes extensive interactions with the adenosine and sulfonium moieties of SAM but does not appear to recognize the tail of the methionine moiety. We captured a structural snapshot of the SMK box riboswitch sampling the near-cognate ligand S-adenosyl-L-homocysteine (SAH) in which SAH was found to adopt an alternative conformation and fails to make several key interactions.

  15. Self-assembled selenium monolayers: from nanotechnology to materials science and adaptive catalysis.

    Science.gov (United States)

    Romashov, Leonid V; Ananikov, Valentine P

    2013-12-23

    Self-assembled monolayers (SAMs) of selenium have emerged into a rapidly developing field of nanotechnology with several promising opportunities in materials chemistry and catalysis. Comparison between sulfur-based self-assembled monolayers and newly developed selenium-based monolayers reveal outstanding complimentary features on surface chemistry and highlighted the key role of the headgroup element. Diverse structural properties and reactivity of organosulfur and organoselenium groups on the surface provide flexible frameworks to create new generations of materials and adaptive catalysts with unprecedented selectivity. Important practical utility of adaptive catalytic systems deals with development of sustainable technologies and industrial processes based on natural resources. Independent development of nanotechnology, materials science and catalysis has led to the discovery of common fundamental principles of the surface chemistry of chalcogen compounds.

  16. 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.

  17. Work-Function Engineering of Graphene Electrodes by Self-Assembled Monolayers for High-Performance Organic Field-Effect Transistors.

    Science.gov (United States)

    Park, Jaesung; Lee, Wi Hyoung; Huh, Sung; Sim, Sung Hyun; Kim, Seung Bin; Cho, Kilwon; Hong, Byung Hee; Kim, Kwang S

    2011-04-21

    We have devised a method to optimize the performance of organic field-effect transistors (OFETs) by controlling the work functions of graphene electrodes by functionalizing the surface of SiO2 substrates with self-assembled monolayers (SAMs). The electron-donating NH2-terminated SAMs induce strong n-doping in graphene, whereas the CH3-terminated SAMs neutralize the p-doping induced by SiO2 substrates, resulting in considerable changes in the work functions of graphene electrodes. This approach was successfully utilized to optimize electrical properties of graphene field-effect transistors and organic electronic devices using graphene electrodes. Considering the patternability and robustness of SAMs, this method would find numerous applications in graphene-based organic electronics and optoelectronic devices such as organic light-emitting diodes and organic photovoltaic devices.

  18. BSA adsorption on aliphatic and aromatic acid SAMs: investigating the effect of residual surface charge and sublayer nature.

    Science.gov (United States)

    Vallée, Anne; Humblot, Vincent; Al Housseiny, Rana; Boujday, Souhir; Pradier, Claire-Marie

    2013-09-01

    In this work, the influence of surface charge and layer rigidity on Bovin Serum Albumin (BSA) adsorption has been investigated. To this aim, Self Assembled Monolayers (SAMs) bearing terminal COOH or COO(-) groups were built on gold surfaces. The rigidity of the acid terminated SAMs was modified using either an aliphatic, mercaptoundecanoic acid (MUA), or an aromatic, mercaptobenzoic acid (MBA) thiol. X-Ray Photoelectron Spectroscopy (XPS), Polarization Modulation Reflection Absorption Infrared Spectroscopy (PM-RAIRS) and contact angle measurements, were used to deeply characterize the so-built layers. The surface charge was successfully modified by varying the pH of the rinsing solution. Indeed, COOH were the dominating species upon rinsing at pH 2 and COO(-) species dominated upon rinsing at pH 11. Rinsing at an intermediate pH, 5.5, led to the coexistence of both carboxylic and carboxylate moieties. The hydrophilic character of the surface was also found to depend on the rinsing pH, with a minimum after rinsing at intermediate pH. Using aromatic or aliphatic thiols did not affect the speciation but led to considerable differences in the hydrophilic character of these surfaces. Eventually, the adsorption of BSA on the acidic layers was investigated using PM-RAIRS. The results showed interesting differences between the charged layers. Thus, for both MUA and MBA -based SAMs, the amount of adsorbed proteins decreased when the amount of COO(-) on the surface increased. Interestingly, these effects were totally annihilated when the adsorption was carried out in PBS buffer. Moreover, for similar surface charges, the aromatic layers were able to bind higher amounts of proteins than the aliphatic ones. This work points out the key role of both surface charge and rigidity on protein adsorption. The influence of additional parameters, such as hydrophilicity and SAMs' rigidity is also established.

  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. 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.

  1. Sam D. Hamilton Noxubee National Wildlife Refuge: Comprehensive Conservation Plan

    Data.gov (United States)

    US Fish and Wildlife Service, Department of the Interior — This Comprehensive Conservation Plan (CCP) was written to guide management on Sam D. Hamilton Noxubee NWR for the next 15 years. This plan outlines the Refuge vision...

  2. Sam Wagstaffi unustatud kired / Ahto Külvet

    Index Scriptorium Estoniae

    Külvet, Ahto

    2008-01-01

    Dokumentaalfilm "Black, White & Gray: Sam Wagstaff and Robert Mapplethorpe" : autor ja režissöör James Crump : Ameerika Ühendriigid 2007. Filmi näidati filminädala "Art in America" raames Tallinnas

  3. Kuula. Kuu artist Sam Sparro. Kuu plaat / Mart Juur

    Index Scriptorium Estoniae

    Juur, Mart, 1964-

    2008-01-01

    Artistist Sam Sparrost. Heliplaatidest: "Sex And The City" Original Motion Picture Soundtrack, "Maestro: Blue Note Trip", Melvin/Soo/Remmel/Julm "Geografix", Alanis Morrisette "Flavors Of Entanglement", Guillemots "Red"

  4. SAM: A Simple Averaging Model of Impression Formation

    Science.gov (United States)

    Lewis, Robert A.

    1976-01-01

    Describes the Simple Averaging Model (SAM) which was developed to demonstrate impression-formation computer modeling with less complex and less expensive procedures than are required by most established programs. (RC)

  5. Sam Wagstaffi unustatud kired / Ahto Külvet

    Index Scriptorium Estoniae

    Külvet, Ahto

    2008-01-01

    Dokumentaalfilm "Black, White & Gray: Sam Wagstaff and Robert Mapplethorpe" : autor ja režissöör James Crump : Ameerika Ühendriigid 2007. Filmi näidati filminädala "Art in America" raames Tallinnas

  6. NACO/SAM observations of sources at the Galactic Center

    CERN Document Server

    Sanchez-Bermudez, J; Alberdi, A; Pott, J U

    2012-01-01

    Sparse aperture masking (SAM) interferometry combined with Adaptive Optics (AO) is a technique that is uniquely suited to investigate structures near the diffraction limit of large telescopes. The strengths of the technique are a robust calibration of the Point Spread Function (PSF) while maintaining a relatively high dynamic range. We used SAM+AO observations to investigate the circumstellar environment of several bright sources with infrared excess in the central parsec of the Galaxy. For our observations, unstable atmospheric conditions as well as significant residuals after the background subtraction presented serious problems for the standard approach of calibrating SAM data via interspersed observations of reference stars. We circumvented these difficulties by constructing a synthesized calibrator directly from sources within the field-of-view. When observing crowded fields, this novel method can boost the efficiency of SAM observations because it renders interspersed calibrator observations unnecessary...

  7. Technical Manual for the SAM Physical Trough Model

    Energy Technology Data Exchange (ETDEWEB)

    Wagner, M. J.; Gilman, P.

    2011-06-01

    NREL, in conjunction with Sandia National Lab and the U.S Department of Energy, developed the System Advisor Model (SAM) analysis tool for renewable energy system performance and economic analysis. This paper documents the technical background and engineering formulation for one of SAM's two parabolic trough system models in SAM. The Physical Trough model calculates performance relationships based on physical first principles where possible, allowing the modeler to predict electricity production for a wider range of component geometries than is possible in the Empirical Trough model. This document describes the major parabolic trough plant subsystems in detail including the solar field, power block, thermal storage, piping, auxiliary heating, and control systems. This model makes use of both existing subsystem performance modeling approaches, and new approaches developed specifically for SAM.

  8. Kuula. Kuu artist Sam Sparro. Kuu plaat / Mart Juur

    Index Scriptorium Estoniae

    Juur, Mart, 1964-

    2008-01-01

    Artistist Sam Sparrost. Heliplaatidest: "Sex And The City" Original Motion Picture Soundtrack, "Maestro: Blue Note Trip", Melvin/Soo/Remmel/Julm "Geografix", Alanis Morrisette "Flavors Of Entanglement", Guillemots "Red"

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

    Energy Technology Data Exchange (ETDEWEB)

    Gnanappa, Arun Kumar, E-mail: arun@imel.demokritos.gr [Tyndall National Institute, Lee Maltings, Prospect Row, Cork (Ireland); Institute of Microelectronics, NCSR Demokritos, Athens (Greece); O' Murchu, Cian; Slattery, Orla; Peters, Frank [Tyndall National Institute, Lee Maltings, Prospect Row, Cork (Ireland); O' Hara, Tony [Memsstar Technology (registered) , Starlaw Park, Starlaw Road, Livingston (United Kingdom); Aszalos-Kiss, Balazs; Tofail, Syed A.M. [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland)

    2011-02-15

    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 N{sub 2}-annealed film due to agglomeration. A relative abundance of CF{sub 3} and CF{sub 2} 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Noyhouzer, Tomer [Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem 91904 (Israel); Mandler, Daniel, E-mail: mandler@vms.huji.ac.il [Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem 91904 (Israel)

    2011-01-17

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

  11. Cloning and Analysis of Genes SAMS From Glycine soja

    Institute of Scientific and Technical Information of China (English)

    FAN Jinping; BAI Xi; LI Yong; JI Wei; WANG Xi; ZHU Yanming

    2008-01-01

    S-adenosylmethionine (SAM) plays important role in trans-methyl reactions. Under the condition of drought (30%PEG),salinity (200 mmol·L-1 NaCI) and low temperature (4℃),total RNA was extracted from the leaf and the first strand of eDNA was synthesized with reverse transcription.S-adenosylmethionine synthetase gene (SAMS gene) was amplified by PeR with the first strand eDNA as template and a pair of primers which was based on constructed ESTs sequence.Full-length SAMS gene sequence was obtained by BLAST comparison. According to the analysis, completed sequence of SAMS gene was integrality.The sequence of the SAMS gene was 1185 bp in length with an opening reading frame (ORF) encoding 394 amino acids.The cDNA sequence showed a significant homology to the SAM genes from Phaseolus lunatus (89%),Medicago sativa (85%).A prokaryotie expression vectors based on pET-32b had been constructed and prokaryotie expression was analyzed in order to lay a strong foundation for resist adversity function analysis through situation of genie expression analysis.

  12. Influence of surface structure on single or mixed component self-assembled monolayers via in situ spectroelectrochemical fluorescence imaging of the complete stereographic triangle on a single crystal Au bead electrode.

    Science.gov (United States)

    Yu, Zhinan Landis; Casanova-Moreno, Jannu; Guryanov, Ivan; Maran, Flavio; Bizzotto, Dan

    2015-01-14

    The use of a single crystal gold bead electrode is demonstrated for characterization of self-assembled monolayers (SAM)s formed on the bead surface expressing a complete set of face centered cubic (fcc) surface structures represented by a stereographic projection. Simultaneous analysis of many crystallographic orientations was accomplished through the use of an in situ fluorescence microscopic imaging technique coupled with electrochemical measurements. SAMs were prepared from different classes of molecules, which were modified with a fluorescent tag enabling characterization of the influence of electrical potential and a direct comparison of the influence of surface structure on SAMs adsorbed onto low index, vicinal and chiral surfaces. The assembly of alkylthiol, Aib peptide and DNA SAMs are studied as a function of the electrical potential of the interface revealing how the organization of these SAMs depend on the surface crystallographic orientation, all in one measurement. This approach allows for a simultaneous determination of SAMs assembled onto an electrode surface onto which the whole fcc stereographic triangle can be mapped, revealing the influence of intermolecular interactions as well as the atomic arrangement of the substrate. Moreover, this method enables study of the influence of the Au surface atom arrangement on SAMs that were created and analyzed, both under identical conditions, something that can be challenging for the typical studies of this kind using individual gold single crystal electrodes. Also demonstrated is the analysis of a SAM containing two components prepared using thiol exchange. The two component SAM shows remarkable differences in the surface coverage, which strongly depends on the surface crystallography enabling estimates of the thiol exchange energetics. In addition, these electrode surfaces enable studies of molecular adsorption onto the symmetry related chiral surfaces since more than one stereographic triangle can be

  13. Anodic passivation of tin by alkanethiol self-assembled monolayers examined by cyclic voltammetry and coulometry.

    Science.gov (United States)

    Worley, Barrett C; Ricks, William A; Prendergast, Michael P; Gregory, Brian W; Collins, Ross; Cassimus, John J; Thompson, Raymond G

    2013-10-22

    The self-assembly of medium chain length alkanethiol monolayers on polycrystalline Sn electrodes has been investigated by cyclic voltammetry and coulometry. These studies have been performed in order to ascertain the conditions under which their oxidative deposition can be achieved directly on the oxide-free Sn surface, and the extent to which these electrochemically prepared self-assembled monolayers (SAMs) act as barriers to surface oxide growth. This work has shown that the potentials for their oxidative deposition are more cathodic (by 100-200 mV) than those for Sn surface oxidation and that the passivating abilities of these SAMs improve with increasing film thickness (or chain length). Oxidative desorption potentials for these films have been observed to shift more positively, and in a highly linear fashion, with increasing film thickness (~75 mV/CH2). Although reductive desorption potentials for the SAMs are in close proximity to those for reduction of the surface oxide (SnOx), little or no SnOx formation occurs unless the potential is made sufficiently anodic that the monolayers start to be removed oxidatively. Our coulometric data indicate that the charge involved with alkanethiol reductive desorption or oxidative deposition is consistent with the formation of a close-packed monolayer, given uncertainties attributable to surface roughness and heterogeneity phenomena. These experiments also reveal that the quantity of charge passed during oxidative desorption is significantly larger than what would be predicted for simple alkylsulfinate or alkylsulfonate formation, suggesting that oxidative removal involves a more complex oxidation mechanism. Analogous chronocoulometric experiments for short-chain alkanethiols on polycrystalline Au electrodes have evidenced similar oxidative charge densities. This implies that the mechanism for oxidative desorption on both surfaces may be very similar, despite the significant differences in the inherent dissolution

  14. Chemical conversion of self-assembled hexadecyl monolayers with active oxygen species generated by vacuum ultraviolet irradiation in an atmospheric environment.

    Science.gov (United States)

    Soliman, Ahmed I A; Ichii, Takashi; Utsunomiya, Toru; Sugimura, Hiroyuki

    2015-07-28

    Vacuum ultraviolet (VUV, λ = 172 nm) irradiation of alkyl self-assembled monolayers (SAMs) in the presence of dry air alters their surface properties. In this work, UV photochemically prepared hexadecyl (HD)-SAMs on hydrogen-terminated silicon substrates were irradiated by VUV light in dry air, which generated active oxygen species upon excitation of the atmospheric oxygen molecules. These active oxygen species converted the terminal methyl groups of the SAMs to polar functional groups, which were examined quantitatively by X-ray photoelectron spectroscopy (XPS) and chemical labeling. At the first stage of VUV irradiation, the surface of SAMs was functionalized, and the ratios of the generated polar functional groups markedly increased. With the elongation of the irradiation period, the SAMs gradually degraded, and the total polar group percentages gradually decreased. The difference between the oxygenated carbon components derived by the deconvolution of the XPS carbon (C1s) spectrum and the chemical labeling of polar groups revealed enormous quantities of ethereal and ester groups that cannot react with the labeling reagents but are included in the C1s spectral envelope. These modifications were reflected on morphological structures of SAMs, which were gradually distorted until a complete amorphous structure was obtained after the complete elimination of HD-SAMs.

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

    Science.gov (United States)

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

    2015-04-07

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

  16. 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.

  17. A Rationally Designed Thymidine-Based Self-Assembled Monolayer on a Gold Electrode for Electroanalytical Applications.

    Science.gov (United States)

    Datta, Dhrubajyoti; Bera, Raj Kumar; Jana, Saibal; Manna, Bhaskar; Roy, Debayan; Anoop, Anakuthil; Raj, C Retna; Pathak, Tanmaya

    2015-07-01

    A self-assembled monolayer (SAM) of 1-(3,5-epidithio-2,3,5-trideoxy-β-D-threo-pentofuranosyl)thymine (EFT) on a gold electrode was prepared and characterized by Raman spectral and electrochemical measurements. Voltammetric and electrochemical impedance measurements show that the SAM of EFT on a Au electrode impedes the electron-transfer reaction. The SAM of EFT was successfully used for the voltammetric sensing of urate in neutral solution. The coexisting ascorbate anion does not interfere and therefore the EFT-based electrode was able to quantify urate at the micromolar level in the presence of a large excess amount of ascorbate. To demonstrate the practical applications, the amount of urate in two different human serum samples was quantified by using the EFT-based electrode; the results are in good agreement with those determined by the clinical method. DFT calculations show that both ascorbate and urate have noncovalent interactions including hydrogen-bonding interactions with EFT.

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

    Science.gov (United States)

    Platzman, Ilia; Haick, Hossam; Tannenbaum, Rina

    2010-09-01

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

  19. 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.

  20. Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

    Energy Technology Data Exchange (ETDEWEB)

    Willey, T M; Fabbri, J; Lee, J I; Schreiner, P; Fokin, A A; Tkachenko, B A; Fokina, N A; Dahl, J; Carlson, B; Vance, A L; Yang, W; Terminello, L J; van Buuren, T; Melosh, N

    2007-11-27

    Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface-modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 {+-} 0.05 eV and 0.16 {+-} 0.04 eV respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different amounts of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond clusters.

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

    Science.gov (United States)

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

    2013-01-28

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

  2. Effects of interface roughness on cohesive strength of self-assembled monolayers

    Science.gov (United States)

    Zhang, Chen; Awasthi, Amnaya P.; Geubelle, Philippe H.; Grady, Martha E.; Sottos, Nancy R.

    2017-03-01

    Self-assembled monolayers (SAMs) are aggregates of small molecular chains that have the property to form highly ordered assemblies. The choice of terminal groups on the chains makes them excellent contenders of molecular-level tailoring. Molecular dynamics (MD) simulations and experimental observations of spallation of two SAM-enhanced gold-film/silicon-substrate interfaces have shown that the cohesive strength of SAM-enriched transfer-printed interfaces is strongly dependent on the choice of terminal groups. Though the MD results of perfectly ordered atomistic surfaces show the same qualitative trend as the experiments, they over-predict the interfacial cohesive strengths by a factor of about 50. Results from AFM studies have revealed that the roughness of these interfaces is of the same order (∼1 nm) as the range of atomistic interactions. Hence, surface roughness is a key contributor in significantly reducing interfacial cohesive strength in these systems. In this manuscript, a continuum-level study is performed to investigate the influence of surface roughness on the cohesive strength of the interface between a Si/SAM substrate and a transfer-printed gold film. We approximate the film as a deformable continuum interacting with a rough substrate of SAMs represented by a harmonic function. Using a cohesive law derived from MD, spallation is simulated to evaluate the effective traction-separation characteristics for the rough SAM-gold interface. Our analysis shows that incorporating roughness may reduce the interfacial cohesive strength by an order of magnitude depending on the film properties and the surface roughness. Additionally, we observe that the gold film adopts unique separation attributes based on roughness parameters and material properties.

  3. Secondary Structures of Ubiquitin Ions Soft-Landed onto Self-Assembled Monolayer Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Qichi; Laskin, Julia

    2016-06-09

    The secondary structures of multiply charged ubiquitin ions soft-landed onto self-assembled monolayer (SAM) surfaces were studied using in situ infrared reflection-absorption spectroscopy (IRRAS). Two charge states of ubiquitin, 5+ and 13+, were mass selected separately from a mixture of different charge states produced by electrospray ionization (ESI). The low 5+ charge state represents a native-like folded state of ubiquitin, while the high 13+ charge state assumes an extended, almost linear conformation. Each of the two charge states was soft-landed onto a CH3- and COOH-terminated SAM of alkylthiols on gold (HSAM and COOH-SAM). HSAM is a hydrophobic surface known to stabilize helical conformations of soft-landed protonated peptides, whereas COOH-SAM is a hydrophilic surface that preferentially stabilizes β-sheet conformations. IRRAS spectra of the soft-landed ubiquitin ions were acquired as a function of time during and after ion soft-landing. Similar to smaller peptide ions, helical conformations of ubiquitin are found to be more abundant on HSAM, while the relative abundance of β-sheet conformations increases on COOH-SAM. The initial charge state of ubiquitin also has a pronounced effect on its conformation on the surface. Specifically, on both surfaces, a higher relative abundance of helical conformations and lower relative abundance of β-sheet conformations is observed for the 13+ charge state compared to the 5+ charge state. Time-resolved experiments indicate that the α-helical band in the spectrum of the 13+ charge state slowly increases with time on the HSAM surface and decreases in the spectrum of the 13+ charge state on COOH-SAM. These results further support the preference of the hydrophobic HSAM surface toward helical conformations and demonstrate that soft-landed protein ions may undergo slow conformational changes during and after deposition.

  4. Assembly of citrate gold nanoparticles on hydrophilic monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Vikholm-Lundin, Inger, E-mail: inger.vikholm-lundin@uta.fi [University of Tampere, BioMediTech, Tampere (Finland); Fimlab Laboratories Ltd., Tampere (Finland); Rosqvist, Emil; Ihalainen, Petri [Abo Akademi University, Center for Functional Materials, Laboratory of Physical Chemistry (Finland); Munter, Tony [VTT Technical Research Centre of Finland, Process Chemistry end Environmental Engineering, Tampere (Finland); Honkimaa, Anni [University of Tampere, Department of Virology, School of Medicine, Tampere (Finland); Marjomäki, Varpu [University of Jyväskylä, Department of Biological and Environmental Science, Nanoscience Center, Jyväskylä (Finland); Albers, Willem M. [BioNavis Oy Ltd., Ylöjärvi, Tampere (Finland); Peltonen, Jouko [Abo Akademi University, Center for Functional Materials, Laboratory of Physical Chemistry (Finland)

    2016-08-15

    Highlights: • The self-assembled layers were all hydrophilic with Lipa-pTHMMAA exhibiting close to full wetting. • The polyacrylamide layers smoothen the gold surface to a higher extent than the polyethylene glycol and lipoic acid terminated with an amino group. • SPR resonance curves shift to higher angles and become increasingly damped when large nanoparticles assembled on the surface. • 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. - Abstract: 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

  5. Monolayers and multilayers of conjugated polymers as nanosized electronic components.

    Science.gov (United States)

    Zotti, Gianni; Vercelli, Barbara; Berlin, Anna

    2008-09-01

    Conjugated polymers (CPs) are interesting materials for preparing devices based on nanoscopic molecular architectures because they exhibit electrical, electronic, magnetic, and optical properties similar to those of metals or semiconductors while maintaining the flexibility and ease of processing of polymers. The production of well-defined mono- and multilayers of CPs on electrodes with nanometer-scale, one-dimensional resolution remains, however, an important challenge. In this Account, we describe the preparation and conductive properties of nanometer-sized CP molecular structures formed on electrode surfaces--namely, self-assembled monolayer (SAM), brush-type, and self-assembled multilayer CPs--and in combination with gold nanoparticles (AuNPs). We have electrochemically polymerized SAMs of carboxyalkyl-functionalized terthiophenes aligned either perpendicular or parallel to the electrode surface. Anodic coupling of various pyrrole- and thiophene-based monomers in solution with the oligothiophene-based SAMs produced brush-like films. Microcontact printing of these SAMs produced patterns that, after heterocoupling, exhibited large height enhancements, as measured using atomic force microscopy (AFM). We have employed layer-by-layer self-assembly of water-soluble polythiophene-based polyelectrolytes to form self-assembled multilayers. The combination of isostructural polycationic and polyanionic polythiophenes produced layers of chains aligned parallel to the substrate plane. These stable, robust, and dense layers formed with high regularity on the preformed monolayers, with minimal interchain penetration. Infrared reflection/adsorption spectroscopy and X-ray diffraction analyses revealed unprecedented degrees of order. Deposition of soluble polypyrroles produced molecular layers that, when analyzed using a gold-coated AFM tip, formed gold-polymer-gold junctions that were either ohmic or rectifying, depending of the layer sequence. We also describe the electronic

  6. Mechanical characterization of carbon nanomembranes from self-assembled monolayers

    Directory of Open Access Journals (Sweden)

    Xianghui Zhang

    2011-12-01

    Full Text Available This paper reports on the mechanical characterization of carbon nanomembranes (CNMs with a thickness of 1 nm that are fabricated by electron-induced crosslinking of aromatic self-assembled monolayers (SAMs. A novel type of in situ bulge test employing an atomic force microscope (AFM is utilized to investigate their mechanical properties. A series of biphenyl-based molecules with different types of terminal and/or anchor groups were used to prepare the CNMs, such as 4'-[(3-trimethoxysilylpropoxy]-[1,1'-biphenyl]-4-carbonitrile (CBPS, 1,1'-biphenyl-4-thiol (BPT and 4-nitro-1,1'-biphenyl-4-thiol (NBPT. The elastic properties, viscoelastic behaviors and ultimate tensile strength of these biphenyl-based CNMs are investigated and discussed.

  7. Formation of Self-Assembled Monolayer on Cerium Conversion Coated AZ31 Mg Alloy

    Science.gov (United States)

    Salman, S. A.; Akira, N.; Kuroda, K.; Okido, M.

    Magnesium alloys are recognized as alternatives to Al alloys and steel to reduce the weight of structural materials. However, a major obstacle to the widespread use of magnesium alloys is its poor corrosion resistance. Therefore, further surface treatment of magnesium and its alloy is important in meeting several industrial specifications. In a previous research, we investigated the surface treatment of AZ31 magnesium alloy using cerium conversion coating. The anticorrosion properties could be improved with the cerium treatment. In this present research, self-assembled monolayer (SAM) was adsorbed on the surface of cerium conversion coated AZ31 magnesium alloy. The SAM thin film was deposited using (Tridecafluoro-1, 1, 2, 2-tetrahydrooctyl) trimethoxysilane (FAS13) and Tetrakis(trimethylsiloxy)titanium (TTMS) as a catalyst. The corrosion resistance of cerium conversion coated AZ31 Mg alloy was improved with SAM post treatment. Furthermore, the contact angle increases from 13 deg. to 169 deg. indicating to production of super hydrophobic surface with SAM post treatment.

  8. Origin of the contact angle hysteresis of water on chemisorbed and physisorbed self-assembled monolayers.

    Science.gov (United States)

    Belman, Nataly; Jin, Kejia; Golan, Yuval; Israelachvili, Jacob N; Pesika, Noshir S

    2012-10-16

    Self-assembled monolayers (SAMs) are known to form on a variety of substrates either via chemisorption (i.e., through chemical interactions such as a covalent bond) or physisorption (i.e., through physical interactions such as van der Waals forces or "ionic" bonds). We have studied the behavior and effects of water on the structures and surface energies of both chemisorbed octadecanethiol and physisorbed octadecylamine SAMs on GaAs using a number of complementary techniques including "dynamic" contact angle measurements (with important time and rate-dependent effects), AFM, and electron microscopy. We conclude that both molecular overturning and submolecular structural changes occur over different time scales when such SAMs are exposed to water. These results provide new insights into the time-dependent interactions between surfaces and colloids functionalized with SAMs when synthesized in or exposed to high humidity or bulk water or wetted by water. The study has implications for a wide array of phenomena and applications such as adhesion, friction/lubrication and wear (tribology), surfactant-solid surface interactions, the organization of surfactant-coated nanoparticles, etc.

  9. Temperature-responsive self-assembled monolayers of oligo(ethylene glycol): control of biomolecular recognition.

    Science.gov (United States)

    Zareie, Hadi M; Boyer, Cyrille; Bulmus, Volga; Nateghi, Ebrahim; Davis, Thomas P

    2008-04-01

    Self-assembled monolayers (SAMs) of oligo(ethylene glycol) (OEG)-tethered molecules on gold are important for various biorelevant applications ranging from biomaterials to bioanalytical devices, where surface resistance to nonspecific protein adsorption is needed. Incorporation of a stimuli-responsive character to the OEG SAMs enables the creation of nonfouling surfaces with switchable functionality. Here we present an OEG-derived structure that is highly responsive to temperature changes in the vicinity of the physiological temperature, 37 degrees C. The temperature-responsive solution behavior of this new compound was demonstrated by UV-vis and nuclear magnetic resonance spectroscopy. Its chemisorption onto gold(111), and the retention of responsive behavior after chemisorption have been demonstrated by surface plasmon resonance (SPR), X-ray photoelectron spectroscopy (XPS), and atomic force and scanning tunneling microscopy. The OEG-derived SAMs have been shown to reversibly switch the wettability of the surface, as determined by contact angle measurements. More importantly, SPR and AFM studies showed that the OEG SAMs can be utilized to control the affinity binding of streptavidin to the biotin-tethered surface in a temperature-dependent manner while still offering the nonspecific protein-resistance to the surface.

  10. Self-Assembled Monolayers of Perfluoroanthracenylaminoalkane Thiolates on Gold as Potential Electron Injection Layers.

    Science.gov (United States)

    Zhang, Zibin; Wächter, Tobias; Kind, Martin; Schuster, Swen; Bats, Jan W; Nefedov, Alexei; Zharnikov, Michael; Terfort, Andreas

    2016-03-23

    As a material with relatively small band gap and low lying valence orbitals, perfluoroanthracene (PFA) is of interest for the modification of electrode surfaces, for example, as charge injection layers for n-type organic semiconductors. To covalently attach PFA in the form of self-assembled monolayers (SAMs), we developed a synthesis of derivatives with a sulfur termination, linked to the 2-position of the PFA moieties by an -NH- group and a short alkane chain with two and three methylene groups, respectively. Spectroscopic characterization of the SAMs reveals that the molecules adopt an almost upright orientation on the gold surface, with the packing density mostly determined by the steric demands of the PFA units. The number of the methylene groups in the -NH-alkyl linker has only a minor impact on the SAM structure because of the nonsymmetric attachment of the PFA units, which permits the compensation of the orientational constraints imposed by the bending potential. The investigated SAMs alter the work function of gold by +(0.59-0.64) eV, suggesting comparably strong depolarization effects, affecting the extent of the work function modification.

  11. Scanning tunneling microscopy study of organic molecules and self-assembled monolayers

    Science.gov (United States)

    Park, Hayn

    In this dissertation I present my findings on alkanethiol self-assembled monolayers (SAM) on Au(111), as well as investigations of the self-assembly and electron transport properties of a custom-synthesized organic molecule (bis-phenyloxazole: BPO) chosen for its interesting physical and electronic structure. Utilizing scanning tunneling microscopy (STM) techniques, we observed unique molecular structures at the boundaries of single-species alkanethiol SAM domains, and propose packing arrangements for the observed structures. We also found evidence for island formation in alkanethiol SAMs; these islands were dynamic and exhibited ordered packing of the adsorbed molecules. For codeposited two-species (dodecanethiol, octanethiol) SAMs, we observed preferential insertion of the longer molecules at domain boundaries, edges, and defect sites, and found that they tended to segregate into separate domains. Scanning tunneling spectroscopy (STS) of the inserted dodecanethiol molecules revealed evidence of conduction resonances within the HOMO-LUMO gap. We explored the charge transport and self-assembly properties of the BPO molecules on a Au(111) surface. The molecules self-assembled into a novel columnar structure after annealing in vacuum. We compare tunneling spectroscopy results to ab initio computations of the molecular orbitals.

  12. Binary self-assembled monolayers modified Au nanoparticles as carriers in biological applications.

    Science.gov (United States)

    Chang, Hsun-Yun; You, Yun-Wen; Liao, Hua-Yang; Shyue, Jing-Jong

    2014-12-01

    Gold nanoparticles (AuNPs) are good nonviral carriers because of their ease of synthesis and conjugation in biochemistry, and self-assembled monolayers (SAMs) provide a tunable system to change their interfacial properties. Using homogeneously mixed carboxylic acid and amine functional groups, a series of surface potentials and isoelectric points (IEPs) could be obtained and allow systematic study of the effect of surface potential. In this work, the result of the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay revealed that binary-SAM modified AuNPs have high biocompatibility with HEK293T cells. The amount of AuNPs ingested by the cells was found to increase with increasing surface potential and the difference was also confirmed with a scanning transmission electron microscope. The ability of binary-SAM modified AuNPs as carriers was examined, and the plasmid deoxyribose nucleic acid (DNA)-containing eGFP reporter gene was used as the model cargo. Fluorescence imaging revealed that the transfection efficiency generally increased with increasing surface potential. More importantly, when the IEP of the AuNPs was higher than that of the environment of the endosome but lower than that of the cytoplasm, the plasmid DNA can be protected better and released more easily during the endocytosis process hence higher efficiency is obtained with 60% NH2 and 40% COOH in the binary-SAM.

  13. 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.

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

    Science.gov (United States)

    Shen, Cai

    2014-01-01

    Summary 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-yl)ethanethiol (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. PMID:24778947

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

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H. [Faculty of Engineering, Shinshu Universuty, 4-17-1 Wakasato, Nagano 380 8553 (Japan); Saito, N., E-mail: hiro@eco-t.esi.nagoya-u.ac.jp [Department of Materials, Physics and Energy Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464 8603 (Japan); Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464 8603 (Japan); Takai, O. [EcoTopia Science Institute, Nagoya University, Furo-cho, Chikusa, Nagoya 464 8603 (Japan)

    2009-06-30

    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.

  16. 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.

  17. Sub-micron scale patterning using femtosecond laser and self-assembled monolayers interaction

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Wonseok [Nanoprocess Group, Korea Institute of Machinery and Materials, 171 Jang-dong, Yusong-gu, Daejeon 305-343 (Korea, Republic of)]. E-mail: paul@kimm.re.kr; Choi, Moojin [Nanoprocess Group, Korea Institute of Machinery and Materials, 171 Jang-dong, Yusong-gu, Daejeon 305-343 (Korea, Republic of); Kim, Jaegu [Nanoprocess Group, Korea Institute of Machinery and Materials, 171 Jang-dong, Yusong-gu, Daejeon 305-343 (Korea, Republic of); Cho, Sunghak [Nanoprocess Group, Korea Institute of Machinery and Materials, 171 Jang-dong, Yusong-gu, Daejeon 305-343 (Korea, Republic of); Whang, Kyunghyun [Nanoprocess Group, Korea Institute of Machinery and Materials, 171 Jang-dong, Yusong-gu, Daejeon 305-343 (Korea, Republic of)

    2005-02-15

    Standard positive photoresist techniques were adapted to generate sub-micron scale patterns of gold substrate using self-assembled monolayers (SAMs) and femtosecond laser. Self-assembled monolayers formed by the adsorption of alkanethiols onto gold substrate are employed as very thin photoresists. The process underlying photopatterning of SAMs on gold is well-known at the phenomenological level. Alkanethiolates formed by the adsorption of alkanethiols are oxidized on exposure to UV light in the presence of air to alkylsulfonates. Specifically, it is known that deep UV light of wavelength less than 200 nm is necessary for oxidation to occur. In this study, solid state femtosecond laser of wavelength 800 nm is applied for photolithography. The results show that ultrafast laser of near infrared (NIR) range wavelength can replace deep UV laser source for photopatterning using thin organic films. The essential basis of our approach is the photochemical excitation of specific reactions in a particular functional group (in this case a thiolate sulfur atom) distributed with monolayer coverage on a solid surface. Femtosecond laser photolithography could be applied to fabricate the patterning of surface chemical structure and the creation of three-dimensional nanostructures by combination with suitable etching methods.

  18. Ion-induced erosion of organic self-assembled monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Cyganik, P. E-mail: cyganik@castor.if.uj.edu.pl; Postawa, Z.; Meserole, C.A.; Vandeweert, E.; Winograd, N

    1999-01-02

    Laser post-ionization mass spectrometry combined with Scanning Tunneling Microscopy (STM) has been used to investigate processes of ion-stimulated erosion of self-assembled monolayers (SAM) of phenethyl mercaptan C{sub 6}H{sub 5}CH{sub 2}CH{sub 2}S (PEM) deposited on gold. Results indicate that only PEM fragments are emitted from the surface. Most of the PEM fragments (predominantly C{sub 6}H{sub 5}CH{sub 2}CH{sub 3} with m/z=106) are emitted with thermal kinetic energies. STM images collected on 8 keV H{sup +}{sub 2}-irradiated surfaces with a system tuned to probe electronic states of sulfur atoms show no additional damage induced by irradiation. This indicates that sulfur atoms are not removed from the surface during hydrogen bombardment. It is proposed that the emission of SAM molecules is initiated by chemical reactions which gently break C-S bonds.

  19. Obituary: Sam Roweis (1972-2010)

    Science.gov (United States)

    Hogg, David

    2011-12-01

    Computer scientist and statistical astronomer Sam Roweis took his own life in New York City on 2010 January 12. He was a brilliant and accomplished researcher in the field of machine learning, and a strong advocate for the use of computational statistics for automating discovery and scientific data analysis. He made several important contributions to astronomy and was working on adaptive astronomical data analysis at the time of his death. Roweis obtained his PhD in 1999 from the California Institute of Technology, where he worked on a remarkable range of subjects, including DNA computing, modeling of dynamical systems, signal processing, and speech recognition. During this time he unified and clarified some of the most important data analysis techniques, including Principal Component Analysis, Hidden Markov Models, and Expectation Maximization. His work was aimed at making data analysis and modeling faster, but also better justified scientifically. The last years of his PhD were spent in Princeton NJ, where he came in contact with a young generation of cosmologists thinking about microwave background and large-scale structure data. In a postdoc at University College London, Roweis co-created the Locally Linear Embedding (LLE) algorithm; a simple but flexible technique for mapping a large data set onto a low-dimensional manifold. The LLE paper obtained more than 2700 citations in 9 years, launched a new sub-field of machine learning known as "manifold learning," and inspired work in data visualization, search, and applied mathematics. In 2001, Roweis took a faculty job at the University of Toronto Computer Science Department. He continued working on data analysis methods that have probabilistic interpretation and therefore scientific applicability, but at the same time have good performance on large data sets. He was awarded a Sloan Fellowship, a Canada Research Chair, and a fellowship of the Canadian Institute for Advanced Research, among other honors and awards

  20. Characterization of benzenethiolate self-assembled monolayer on Cu(1 0 0) by XPS and NEXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Beccari, Marco [Dipartimento di Chimica, Universita di Roma ' La Sapienza' , Piazzale Aldo Moro 2, I-00185 Roma (Italy)], E-mail: Marco.Beccari@uniroma1.it; Kanjilal, Aloke [INFM-CNR Center on nanoStructures and bioSystems at Surfaces (S3), Via G. Campi 231/A, I-41100 Modena (Italy); Betti, Maria Grazia; Mariani, Carlo [Dipartimento di Fisica, CNISM, CNIS, Universita di Roma ' La Sapienza' , Piazzale Aldo Moro 2, I-00185 Roma (Italy); Floreano, Luca; Cossaro, Albano [Laboratorio TASC-INFM, Basovizza SS14 Km 163.5, I-34012 Trieste (Italy); Di Castro, Valeria [Dipartimento di Chimica, Universita di Roma ' La Sapienza' , Piazzale Aldo Moro 2, I-00185 Roma (Italy)

    2009-05-15

    The composition, electronic structure and molecular orientation of a self-assembled monolayer (SAM) of benzenethiolate on the Cu(1 0 0) surface have been investigated by means of X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS). An ordered benzenethiolate SAM with c(2 x 6) superstructure has been obtained by the reaction of diphenyldisulfide with the Cu(1 0 0) surface at room temperature. S 2p and C 1s XP spectra show S-Cu bond formation without significant thiolate decomposition. The strong dichroic signal of C K-edge NEXAFS upon varying polarization angle indicates upstanding of the adsorbed molecules with the benzene ring tilted by 20 deg. from the surface normal.

  1. An Electrically Driven and Readable Molecular Monolayer Switch Based on a Solid Electrolyte.

    Science.gov (United States)

    Marchante, Elena; Crivillers, Núria; Buhl, Moritz; Veciana, Jaume; Mas-Torrent, Marta

    2016-01-01

    The potential application of molecular switches as active elements in information storage has been demonstrated through numerous works. Importantly, such switching capabilities have also been reported for self-assembled monolayers (SAMs). SAMs of electroactive molecules have recently been exploited as electrochemical switches. Typically, the state of these switches could be read out through their optical and/or magnetic response. These output reading processes are difficult to integrate into devices, and furthermore, there is a need to use liquid environments for switching the redox-active molecular systems. In this work, both of these challenges were overcome by using an ionic gel as the electrolyte medium, which led to an unprecedented solid-state device based on a single molecular layer. Moreover, electrochemical impedance has been successfully exploited as the output of the system.

  2. 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.

  3. Inkjet printed electrode arrays for potential modulation of DNA self-assembled monolayers on gold.

    Science.gov (United States)

    Li, Yunchao; Li, Paul C H; Parameswaran, M Ash; Yu, Hua-Zhong

    2008-11-15

    In this paper, we report a novel and cost-effective fabrication technique to produce electrode arrays that can be used for monitoring and electrical manipulation of the molecular orientation of DNA self-assembled monolayers (SAMs) on gold. The electrode arrays were prepared from gold coated glass sides or compact discs (CD-Rs) by using standard office inkjet printers without any hardware or software modifications. In this method, electrode arrays of varied shape and size (from submillimeter to centimeter) can be rapidly fabricated and are suitable for standard electrochemical measurements. We were able to use a dual-channel potentiostat to control the electrodes individually and a fluorescence (FL) scanner to image the electrode array simultaneously. With such an integrated modulation setup, the structural switching behavior (from "lying" to "standing" position) and the enhanced hybridization reactivity of thiolate DNA SAMs on gold under potential control have been successfully demonstrated.

  4. Atomic stick-slip friction between commensurate self-assembled monolayers

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The classical molecular dynamics simulations have been used to examine the compression and friction between commensurate self-assembled monolayers (SAMs) on Au (111). The friction force changes in a period corresponding to the geometric structure of sliding surfaces. The simulations reveal an ordered atomic stick-slip motion and discontinuous movements of diverse monomers, mainly head and tail groups. All of the head groups of the static film have 2~3 metastable positions (MPs). They oscillate around one of the MPs in stick phases and jump simultaneously to a new MP in slip phases. The tail groups of the sliding film are pulled forward together with opposite ones while sticking and jump forward half of the lattice constant relative to opposite ones while slipping. A complete vision of the motion of SAM chains is thereby built up and compared with the molecule behavior predicted by the Tomlinson model.

  5. Characterization of monolayer formation on aluminum-doped zinc oxide thin films.

    Science.gov (United States)

    Rhodes, Crissy L; Lappi, Simon; Fischer, Daniel; Sambasivan, Sharadha; Genzer, Jan; Franzen, Stefan

    2008-01-15

    The optical and electronic properties of aluminum-doped zinc oxide (AZO) thin films on a glass substrate are investigated experimentally and theoretically. Optical studies with coupling in the Kretschmann configuration reveal an angle-dependent plasma frequency in the mid-IR for p-polarized radiation, suggestive of the detection of a Drude plasma frequency. These studies are complemented by oxygen depletion density functional theory studies for the calculation of the charge carrier concentration and plasma frequency for bulk AZO. In addition, we report on the optical and physical properties of thin film adlayers of n-hexadecanethiol (HDT) and n-octadecanethiol (ODT) self-assembled monolayers (SAMs) on AZO surfaces using reflectance FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), contact angle, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Our characterization of the SAM deposition onto the AZO thin film reveals a range of possible applications for this conducting metal oxide.

  6. Critical role of wettability in assembly of zirconia nanoparticles on a self-assembled monolayer-patterned substrate

    Science.gov (United States)

    Yang, Mi-Sun; Lee, Seung-Hoon; Moon, Byung Kee; Yoo, Seung Ryul; Hwang, Seongpil; Jang, Jae-Won

    2016-08-01

    This study investigated which factors decisively influence colloidal nanoparticle (NP) assembly on a self-assembled monolayer (SAM)-patterned substrate. Zirconia (ZrO2) NP assembly on a poly(dimethylsiloxane) (PDMS)-stamped SAM-patterned Au substrate was carried out while the size and surface charge state of the NPs and the substrate wettability were altered. ZrO2 particles with diameters of 350 nm, 560 nm, and 1100 nm were employed to examine the effect of NP size on the assembly. Bare ZrO2 NPs with a negatively charged surface and ZrO2 NPs with a positively charged surface through 3-aminopropyltriethoxysilane encapsulation were prepared for the NP assembly. Moreover, the substrate wettability effect on the NP assembly was evaluated by comparing the assembly on substrates with the PDMS-patterned SAMs of thiols with polar and non-polar functional groups. From the characterization of the number of NPs in a pattern and the effective area of assembled NPs (Aeff), positively charged ZrO2 NP assembly on negatively charged patterns showed the highest number density of particles in a pattern compared with the other combinations in both 350-nm and 560-nm ZrO2 NPs. This observation can be attributed to negatively charged 16-mercaptohexadecanoic acid SAMs having greater polarity (more polar groups) than positively charged 11-amino-1-undecanethiol SAMs within the condition of the colloidal ZrO2 NP assembly.

  7. Ferroelectric Switching of Vinylidene and Trifluoroethylene Copolymer Thin Films on Au Electrodes Modified with Self-Assembled Monolayers

    Directory of Open Access Journals (Sweden)

    Naoto Tsutsumi

    2014-09-01

    Full Text Available The ferroelectric switching characteristics of a vinylidene fluoride and trifluoroethylene copolymer were significantly changed via the chemical modification of a gold electrode with an alkanethiol self-assembled monolayer (SAM. The alkanethiol SAM-Au electrode successfully suppressed the leakage current (dark current from the electrode to the bulk ferroelectric. Smaller leakage currents led to the formation of an effective electric field in the bulk ferroelectric. At switching cycles ranging from 10 to 100 kHz, significant changes in the ferroelectric properties were observed. At 100 kHz, a remanent polarization (Pr of 68 mC·m−2 was measured, whereas a very small Pr value of 2.4 mC·m−2 was measured for the sample without a SAM. The switching speed of the SAM-Au electrode is as twice as fast as that of the unmodified electrode. A large potential barrier was formed via the insertion of a SAM between the Au electrode and the ferroelectric, effectively changing the ferroelectric switching characteristics.

  8. 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.

  9. Energy-Level Engineering at ZnO/Oligophenylene Interfaces with Phosphonate-Based Self-Assembled Monolayers.

    Science.gov (United States)

    Timpel, Melanie; Nardi, Marco V; Ligorio, Giovanni; Wegner, Berthold; Pätzel, Michael; Kobin, Björn; Hecht, Stefan; Koch, Norbert

    2015-06-10

    We used aromatic phosphonates with substituted phenyl rings with different molecular dipole moments to form self-assembled monolayers (SAMs) on the Zn-terminated ZnO(0001) surface in order to engineer the energy-level alignment at hybrid inorganic/organic semiconductor interfaces, with an oligophenylene as organic component. The work function of ZnO was tuned over a wide range of more than 1.7 eV by different SAMs. The difference in the morphology and polarity of the SAM-modified ZnO surfaces led to different oligophenylene orientation, which resulted in an orientation-dependent ionization energy that varied by 0.7 eV. The interplay of SAM-induced work function modification and oligophenylene orientation changes allowed tuning of the offsets between the molecular frontier energy levels and the semiconductor band edges over a wide range. Our results demonstrate the versatile use of appropriate SAMs to tune the energy levels of ZnO-based hybrid semiconductor heterojunctions, which is important to optimize its function, e.g., targeting either interfacial energy- or charge-transfer.

  10. Surface properties of self-assembled monolayer films of tetra-substituted cobalt, iron and manganese alkylthio phthalocyanine complexes

    Energy Technology Data Exchange (ETDEWEB)

    Akinbulu, Isaac Adebayo; Khene, Samson [Department of Chemistry, Rhodes University, Grahamstown 6140 (South Africa); Nyokong, Tebello, E-mail: t.nyokong@ru.ac.z [Department of Chemistry, Rhodes University, Grahamstown 6140 (South Africa)

    2010-09-30

    Self-assembled monolayer (SAM) films of iron (SAM-1), cobalt (SAM-2) and manganese (SAM-3) phthalocyanine complexes, tetra-substituted with diethylaminoethanethio at the non-peripheral positions, were formed on gold electrode in dimethylformamide (DMF). Electrochemical, impedimentary and surface properties of the SAM films were investigated. Cyclic voltammetry was used to investigate the electrochemical properties of the films. Ability of the films to inhibit common faradaic processes on bare gold surface (gold oxidation, solution redox chemistry of [Fe(H{sub 2}O){sub 6}]{sup 3+}/[Fe(H{sub 2}O){sub 6}]{sup 2+} and underpotential deposition (UDP) of copper) was investigated. Electrochemical impedance spectroscopy (EIS), using [Fe(CN){sub 6}]{sup 3-/4-} redox process as a probe, offered insights into the electrical properties of the films/electrode interfaces. Surface properties of the films were probed using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The films were employed for the electrocatalytic oxidation of the pesticide, carbofuran. Electrocatalysis was evidenced from enhanced current signal and less positive oxidation potential of the pesticide on each film, relative to that observed on the bare gold electrode. Mechanism of electrocatalytic oxidation of the pesticide was studied using rotating disc electrode voltammetry.

  11. Native interface of the SAM domain polymer of TEL

    Directory of Open Access Journals (Sweden)

    Bowie James U

    2002-08-01

    Full Text Available Abstract Background TEL is a transcriptional repressor containing a SAM domain that forms a helical polymer. In a number of hematologic malignancies, chromosomal translocations lead to aberrant fusions of TEL-SAM to a variety of other proteins, including many tyrosine kinases. TEL-SAM polymerization results in constitutive activation of the tyrosine kinase domains to which it becomes fused, leading to cell transformation. Thus, inhibitors of TEL-SAM self-association could abrogate transformation in these cells. In previous work, we determined the structure of a mutant TEL-SAM polymer bearing a Val to Glu substitution in center of the subunit interface. It remained unclear how much the mutation affected the architecture of the polymer, however. Results Here we determine the structure of the native polymer interface. To accomplish this goal, we introduced mutations that block polymer extension, producing a heterodimer with a wild-type interface. We find that the structure of the wild-type polymer interface is quite similar to the mutant structure determined previously. With the structure of the native interface, it is possible to evaluate the potential for developing therapeutic inhibitors of the interaction. We find that the interacting surfaces of the protein are relatively flat, containing no obvious pockets for the design of small molecule inhibitors. Conclusion Our results confirm the architecture of the TEL-SAM polymer proposed previously based on a mutant structure. The fact that the interface contains no obvious potential binding pockets suggests that it may be difficult to find small molecule inhibitors to treat malignancies in this way.

  12. Long term testing for dropwise condensation using self-assembled monolayer coatings of n-octadecyl mercaptan

    Energy Technology Data Exchange (ETDEWEB)

    Vemuri, S.; Kim, K.J. [Department of Mechanical Engineering, University of Nevada, Reno, NV 89557 (United States); Wood, B.D. [Mechanical and Aerospace Engineering Department, Utah State University, Logan, UT 84322 (United States); Govindaraju, S.; Bell, T.W. [Department of Chemistry, University of Nevada, Reno, NV 89557 (United States)

    2006-03-01

    Two different types of hydrophobic coatings have been analyzed experimentally for their ability to promote dropwise condensation (DWC). For any technique used for promoting dropwise condensation, the longevity of the coating is critical if it is to be used in any further applications. Previous studies using self-assembled monolayers of n-octadecyl mercaptan have not reported any information on the ability for promoting DWC beyond 500h of experimentation. In the current research experiments were carried out using self-assembled monolayers for more than 2600h of experimentation and it showed good dropwise phenomena. Stearic acid solution (SAM-1) and n-octadecyl mercaptan solution (SAM-2) were used to form an ultra-thin organic hydrophobic film on the surface. An oxide layer was initially formed on the substrate surface before coating the surface with monolayers. The oxide layer formed on the substrate surface tends to improve the bonding between the substrate and the monolayers which eventually improves the longevity of the coating. In general, a SAM system with a long-chain, hydrophobic group is nano-resistant, meaning that such a system forms a protective hydrophobic layer with negligible heat transfer resistance but a much stronger bond. When compared to complete filmwise condensation, the SAM-2 (n-octadecyl mercaptan) coating increased the condensation heat transfer coefficient by a factor of approximately 3 after 100h of experimentation and by a factor of approximately 1.8 after 2600h of experimentation for copper alloy surfaces, under vacuum condition (33.86kPa). Lifetime of maintaining dropwise condensation is greatly dependent on the bonding of SAM coating to the condensing surface, form the experimental investigation it was evident that n-octadecyl mercaptan showed good DWC due to its covalent bonding with the substrate surface when compared to that of stearic acid which is bonded to the substrate surface by hydrogen bonding. Contact angles were measured for

  13. Technoeconomic Modeling of Battery Energy Storage in SAM

    Energy Technology Data Exchange (ETDEWEB)

    DiOrio, Nicholas [National Renewable Energy Lab. (NREL), Golden, CO (United States); Dobos, Aron [National Renewable Energy Lab. (NREL), Golden, CO (United States); Janzou, Steven [National Renewable Energy Lab. (NREL), Golden, CO (United States); Nelson, Austin [National Renewable Energy Lab. (NREL), Golden, CO (United States); Lundstrom, Blake [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2015-09-01

    Detailed comprehensive lead-acid and lithium-ion battery models have been integrated with photovoltaic models in an effort to allow System Advisor Model (SAM) to offer the ability to predict the performance and economic benefit of behind the meter storage. In a system with storage, excess PV energy can be saved until later in the day when PV production has fallen, or until times of peak demand when it is more valuable. Complex dispatch strategies can be developed to leverage storage to reduce energy consumption or power demand based on the utility rate structure. This document describes the details of the battery performance and economic models in SAM.

  14. Monolayer patterning using ketone dipoles.

    Science.gov (United States)

    Kim, Min Kyoung; Xue, Yi; Pašková, Tereza; Zimmt, Matthew B

    2013-08-14

    The self-assembly of multi-component monolayers with designed patterns requires molecular recognition among components. Dipolar interactions have been found to influence morphologies of self-assembled monolayers and can affect molecular recognition functions. Ketone groups have large dipole moments (2.6 D) and are easily incorporated into molecules. The potential of ketone groups for dipolar patterning has been evaluated through synthesis of two 1,5-disubstituted anthracenes bearing mono-ketone side chains, STM characterization of monolayers self-assembled from their single and two component solutions and molecular mechanics simulations to determine their self-assembly energetics. The results reveal that (i) anthracenes bearing self-repulsive mono-ketone side chains assemble in an atypical monolayer morphology that establishes dipolar attraction, instead of repulsion, between ketones in adjacent side chains; (ii) pairs of anthracene molecules whose self-repulsive ketone side chains are dipolar complementary spontaneously assemble compositionally patterned monolayers, in which the two components segregate into neighboring, single component columns, driven by side chain dipolar interactions; (iii) compositionally patterned monolayers also assemble from dipolar complementary anthracene pairs that employ different dipolar groups (ketones or CF2 groups) in their side chains; (iv) the ketone group, with its larger dipole moment and size, provides comparable driving force for patterned monolayer formation to that of the smaller dipole, and smaller size, CF2 group.

  15. Self-assembled monolayers of cholesterol and cholesteryl esters on graphite.

    Science.gov (United States)

    Hibino, Masahiro; Tsuchiya, Hiroshi

    2014-06-17

    The molecular arrangements of self-assembled monolayers (SAMs) of cholesterol, cholesteryl laurate, and cholesteryl stearate adsorbed on a graphite surface were studied using scanning tunneling microscopy (STM) at the liquid-solid interface. The STM images of the SAMs showed two-dimensional periodic arrays of bright regions that corresponded to the sterol rings. However, individual sterol rings could not be observed in the bright regions in the STM images of the cholesterol monolayers. Nevertheless, by comparing the STM images and the crystallographic data, it is concluded that the cholesterol molecules are arranged in pairs oriented head-to-head owing to the hydrogen bonds between the hydroxyl groups. These dimers, in turn, are oriented parallel to each other, owing to the interactions between the sterol rings. The STM images of cholesteryl ester monolayers had molecular resolution and showed pairs of cholesteryl ester molecules oriented in an antiparallel manner, with their fatty acid chains located in the central regions. Furthermore, the fatty acid chains of cholesteryl stearate were observed to be oriented in the (1120) zigzag direction of the graphite lattice, whereas those of cholesteryl laurate were oriented in the (1010) armchair direction. These observations reveal that the interactions between the fatty acid chains affect the structure of the SAMs. The molecular arrangements also depend on the lengths of the fatty acid chains of the cholesterol esters and hence on the interactions between the alkyl chains and the graphite surface. The self-assembly at the liquid-solid interface is therefore controlled by the interactions between sterol rings, between alkyl chains, and between alkyl chains and the substrate.

  16. 5-(4-pyridinyl)-1,3,4-oxadiazole-2-thiol on gold: SAM formation and electroactivity

    Energy Technology Data Exchange (ETDEWEB)

    Paulo, Tercio de F.; Silva, Maria A.S. da; Pinheiro, Solange de O.; Meyer, Emerson; Moreira, Icaro de S.; Diogenes, Izaura C.N. [Universidade Federal do Ceara (UFC), Fortaleza, CE (Brazil). Dept. de Quimica Organica e Inorganica]. E-mail: izaura@dqoi.ufc.br; Pinheiro, Lucidalva S.; Freire, Jose A. [Universidade Federal do Ceara (UFC), Fortaleza, CE (Brazil). Dept. de Fisica; Tanaka, Auro A. [Universidade Federal do Maranhao (UFMA), Sao Luis, MA (Brazil). Dept. de Quimica; Lima Neto, Pedro de [Universidade Federal do Ceara (UFC), Fortaleza, CE (Brazil). Dept. de Quimica Analitica e Fisico Quimica

    2008-07-01

    5-(4-pyridinyl)-1,3,4-oxadiazole-2-thiol (Hpyt) spontaneously adsorbs on gold forming SAMs (self-assembled monolayers) that, based on STM (Scanning Tunneling Microscopy) and electrochemical data, contain pinholes through which [Fe(CN){sub 6}]{sup 4-} and [Ru(NH{sub 3}){sub 6}]{sup 3+} probe molecules access the underlying gold electrode. For the former molecule, the dependence of the faradaic current on the electrolyte solution pH value allowed the evaluation of the surface pKa as 4.2. The thermodynamic parameters {delta}H{sub ads} and {delta}G{sub ads} for the Hpyt adsorption process could be described by the Langmuir model and were calculated as -20.01 and -39.39 kJ mol{sup -1}, respectively. Electrodic redox reaction of cytochrome c metalloprotein was accessed by using the Hpyt SAM with a heterogeneous electron transfer rate constant of 2.29 x 10{sup -3} cm s{sup -1}. (author)

  17. Comparative electrochemical scanning tunneling microscopy study of nonionic fluorosurfactant zonyl FSN self-assembled monolayers on Au(111) and Au(100): a potential-induced structural transition.

    Science.gov (United States)

    Tang, Yongan; Yan, Jiawei; Zhu, Feng; Sun, Chunfeng; Mao, Bingwei

    2011-02-01

    We investigate the structure of nonionic fluorosurfactant zonyl FSN self-assembled monolayers on Au(111) and Au(100) in 0.05 M H(2)SO(4) as a function of the electrode potential by electrochemical scanning tunneling microscopy (ECSTM). On Au(111), a (3(1/2) × 3(1/2))R30° arrangement of the FSN SAMs is observed, which remains unchanged in the potential range where the redox reaction of FSN molecules does not occur. On Au(100), some parallel corrugations of the FSN SAMs are observed, which originate from the smaller distance and the repulsive interaction between FSN molecules to make the FSN molecules deviate from the bridging sites, and ECSTM reveals a potential-induced structural transition of the FSN SAMs. The experimental observations are rationalized by the effect of the intermolecular interaction. The smaller distance between molecules on Au(100) results in the repulsive force, which increases the probability of structural change induced by external factors (i.e., the electrode potential). The appropriate distance and interactions of FSN molecules account for the stable structure of FSN SAMs on Au(111). Surface crystallography may influence the intermolecular interaction through changing the molecular arrangements of the SAMs. The results benefit the molecular-scale understanding of the behavior of the FSN SAMs under electrochemical potential control.

  18. Surface Modification of TiO2 Photoanodes with Fluorinated Self-Assembled Monolayers for Highly Efficient Dye-Sensitized Solar Cells.

    Science.gov (United States)

    Wooh, Sanghyuk; Kim, Tea-Yon; Song, Donghoon; Lee, Yong-Gun; Lee, Tae Kyung; Bergmann, Victor W; Weber, Stefan A L; Bisquert, Juan; Kang, Yong Soo; Char, Kookheon

    2015-11-25

    Dye aggregation and electron recombination in TiO2 photoanodes are the two major phenomena lowering the energy conversion efficiency of dye-sensitized solar cells (DSCs). Herein, we introduce a novel surface modification strategy of TiO2 photoanodes by the fluorinated self-assembled monolayer (F-SAM) formation with 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFTS), blocking the vacant sites of the TiO2 surface after dye adsorption. The F-SAM helps to efficiently lower the surface tension, resulting in efficient repelling ions, e.g., I3(-), in the electrolyte to decrease the electron recombination rate, and the role of F-SAM is characterized in detail by impedance spectroscopy using a diffusion-recombination model. In addition, the dye aggregates on the TiO2 surface are relaxed by the F-SAM with large conformational perturbation (i.e., helix structure) seemingly because of steric hindrance developed during the SAM formation. Such multifunctional effects suppress the electron recombination as well as the intermolecular interactions of dye aggregates without the loss of adsorbed dyes, enhancing both the photocurrent density (11.9 → 13.5 mA cm(-2)) and open-circuit voltage (0.67 → 0.72 V). Moreover, the combined surface modification with the F-SAM and the classical coadsorbent further improves the photovoltaic performance in DSCs.

  19. Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

    DEFF Research Database (Denmark)

    Zhang, Jingdong; Welinder, Anna Christina; Chi, Qijin

    2011-01-01

    Self-assembled organization of functional molecules on solid surfaces has developed into a powerful and sophisticated tool for surface chemistry and nanotechnology. A number of reviews on the topic have been available since the mid 1990s. This perspective article aims to focus on recent development...... in the investigations of electronic structures and assembling dynamics of electrochemically controlled self-assembled monolayers (SAMs) of thiol containing molecules on gold surfaces. A brief introduction is first given and particularly illustrated by a Table summarizing the molecules studied, the surface lattice...

  20. 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

  1. Scattering properties of gas molecules on self-assembled monolayers using molecular dynamics simulation

    Science.gov (United States)

    Takeuchi, Hideki

    2016-11-01

    The scattering properties of argon gas molecules on the SAM (self-assembled monolayer) surface which consists of 1-propanethiol molecules chemically adsorbed on a gold surface have been investigated by using the molecular dynamics method. The trapping probability, the angular distribution and the angular scattering distribution for the gas molecule have been obtained for various incident energies and angles. It is shown that the trapping probability decreases with increasing the incident energy. The angular distribution for small incident angle is almost close to the cosine distribution. In addition, the partial accommodation coefficients of tangential momentum and energy for gas molecules are discussed.

  2. 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

  3. 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

  4. Tip-enhanced Raman spectroscopic imaging of patterned thiol monolayers

    Directory of Open Access Journals (Sweden)

    Johannes Stadler

    2011-08-01

    Full Text Available Full spectroscopic imaging by means of tip-enhanced Raman spectroscopy (TERS was used to measure the distribution of two isomeric thiols (2-mercaptopyridine (2-PySH and 4-mercaptopyridine (4-PySH in a self-assembled monolayer (SAM on a gold surface. From a patterned sample created by microcontact printing, an image with full spectral information in every pixel was acquired. The spectroscopic data is in good agreement with the expected molecular distribution on the sample surface due to the microcontact printing process. Using specific marker bands at 1000 cm−1 for 2-PySH and 1100 cm−1 for 4-PySH, both isomers could be localized on the surface and semi-quantitative information was deduced from the band intensities. Even though nanometer size resolution information was not required, the large signal enhancement of TERS was employed here to detect a monolayer coverage of weakly scattering analytes that were not detectable with normal Raman spectroscopy, emphasizing the usefulness of TERS.

  5. Simulated SAM A-scans on multilayer MEMS components

    DEFF Research Database (Denmark)

    Janting, Jakob; Petersen, Dirch Hjorth; Greisen, Christoffer

    2002-01-01

    A spreadsheet program for simulation of Scanning Acoustic Microscopy (SAM) A-scans on multilayer structures has been developed. Using this program, structure variations in samples can be analysed better. Further samples can be prepared to get optimal signal for enhanced failure and materials anal...

  6. Ensuring GRID resource availability with the SAM framework in LHCb

    CERN Document Server

    Closier, J; Santinelli, R

    2008-01-01

    The LHCb experiment has chosen to use the SAM framework (Service Availability Monitoring Environment from EGEE-II) [1] make extensive tests of the LHCb environment at all the accessible grid resources. The availability and the proper definition of the local Computing and Storage Elements, user interfaces as well as the WLCG software environment are checked. The SAM framework is also used to pre-install the LHCb applications in the shared software area provided by each site. The deployment of the LHCb applications is based on a python tool developed inside the experiment. It is used for software management including incremental installation of interdependent packages and clean package removal. After the application software is installed a validation test of the whole MC chain is run. According to the results of the experiment specific SAM tests, the sites are (re)integrated into the LHCb production system managed by DIRAC [2]. The possibility of automated dynamic site certification using the SAM test suite is ...

  7. ISO19770-1:2012 SAM process guidance

    CERN Document Server

    Canavan, Rory

    2012-01-01

    The pocket guide offers a concise summary of the principles of software asset management as conveyed by ISO 19770-1: 2012, and provides advice and guidance on how to kick-start your own SAM programme - something the Standard alone doesn't offer.

  8. Automation of one-loop calculations with GoSam

    Energy Technology Data Exchange (ETDEWEB)

    Soden-Fraunhofen, Johann Felix von [Max-Planck-Institut fuer Physik, Muenchen (Germany)

    2012-07-01

    The program package GoSam can be used to calculate multi-leg one-loop amplitudes within and beyond the Standard Model. An extension is additionally presented which allows to calculate integrals where the rank is larger than the number of propagators. One possible application of this feature is the calculation of QCD corrections within models involving extra dimensions.

  9. Social Activity Method (SAM): A Fractal Language for Mathematics

    Science.gov (United States)

    Dowling, Paul

    2013-01-01

    In this paper I shall present and develop my organisational language, "social activity method" (SAM), and illustrate some of its applications. I shall introduce a new scheme for "modes of recontextualisation" that enables the analysis of the ways in which one activity--which might be school mathematics or social research or any…

  10. 77 FR 67813 - Sam Rayburn Dam Project Power Rate

    Science.gov (United States)

    2012-11-14

    ..., Assistant Administrator, Southwestern Power Administration, Department of Energy, Williams Center Tower I... Southwestern Power Administration Sam Rayburn Dam Project Power Rate AGENCY: Southwestern Power Administration, DOE. ACTION: Notice of Rate Order Approving an Extension of Power Rate on an Interim Basis....

  11. Sample Analysis at Mars Organic Contaminants Library (SAM-OCL)

    Science.gov (United States)

    Garcia-Sanchez, Raul; Misra, Prabhakar; Canham, John; Mahaffy, Paul

    2013-04-01

    The Sample Analysis at Mars Organic Contaminants Library (SAM-OCL) was developed as one of several components for the Mars rover mission's Contamination Control Protocol. The purpose of SAM-OCL is to determine the Gas Chromatography-Mass Spectroscopy (GCMS) signals of different materials composing the Mars Science Laboratory rover. In turn, this allows us to determine which GCMS signals originate from terrestrial contamination or rover material outgassing. The GCMS spectral library has several supplemental components, of which its descriptor spreadsheets are the most important, aimed to make SAM-OCL easily and readily accessible to users in and out of the Mars rover mission. One spreadsheet describes the contaminants that can be found in each file, while the other describes the information regarding each file. The library, along with its supplemental materials, is useful from an organizational and practical sense. Through them we are able to organize large volumes of GCMS data while breaking down the components that each material sample is made off. This allows us easy and fast access to information that will be critical when doing analysis in the data that the SAM instrumentation will obtain.

  12. Role of Sam68 in Post-Transcriptional Gene Regulation

    Directory of Open Access Journals (Sweden)

    Flora Sánchez-Jiménez

    2013-11-01

    Full Text Available The STAR family of proteins links signaling pathways to various aspects of post-transcriptional regulation and processing of RNAs. Sam68 belongs to this class of heteronuclear ribonucleoprotein particle K (hnRNP K homology (KH single domain-containing family of RNA-binding proteins that also contains some domains predicted to bind critical components in signal transduction pathways. In response to phosphorylation and other post-transcriptional modifications, Sam68 has been shown to have the ability to link signal transduction pathways to downstream effects regulating RNA metabolism, including transcription, alternative splicing or RNA transport. In addition to its function as a docking protein in some signaling pathways, this prototypic STAR protein has been identified to have a nuclear localization and to take part in the formation of both nuclear and cytosolic multi-molecular complexes such as Sam68 nuclear bodies and stress granules. Coupling with other proteins and RNA targets, Sam68 may play a role in the regulation of differential expression and mRNA processing and translation according to internal and external signals, thus mediating important physiological functions, such as cell death, proliferation or cell differentiation.

  13. Phenomenological Modeling for Langmuir Monolayers

    Science.gov (United States)

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

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

  14. The Effect of Ring Substitution Position on the Structural Conformation of Mercaptobenzoic Acid Self-Assembled Monolayers on Au(111)

    Energy Technology Data Exchange (ETDEWEB)

    Lee, J; Willey, T; Nilsson, J; Terminello, L; De Yoreo, J; van Buuren, T

    2006-04-12

    Near edge X-ray absorption fine structure (NEX-AFS) spectroscopy, photoemission spectroscopy (PES) and contact angle measurements have been used to examine the structure and bonding of self-assembled monolayers (SAMs) prepared on Au(111) from the positional isomers of mercaptobenzoic acid (MBA). The isomer of MBA and solvent chosen in SAM preparation has considerable bearing upon film morphology. Carbon K-edge NEXAFS measurements indicate that the monomers of 2-, 3- and 4-MBA have well-defined orientations within their respective SAMs. Monomers of 3- and 4-MBA assume an upright orientation on the Au substrates in monolayers prepared using an acetic acid in ethanol solvent. The aryl ring and carboxyl group of these molecules are tilted from the surface normal by a colatitudal angle of {approx} 30{sup o}. Preparation of 4-MBA SAMs using pure ethanol solvent, a more traditional means of synthesis, had no appreciable effect upon the monomer orientation. Nonetheless, S(2p) PES measurements illustrate that it results in extensive bilayer formation via carboxyl group hydrogen-bonding between 4-MBA monomers. In 2-MBA monolayers prepared using acetic acid/ethanol solvent, the monomers adopt a more prostrate orientation on the Au substrates, in which the aryl ring and carboxyl group of the molecules are tilted {approx} 50{sup o} from the surface normal. This configuration is consistent with an interaction between both the mercaptan sulfur and carboxyl group of 2-MBA with the underlying substrate. S(2p) and C(1s) PES experiments provide supporting evidence for a bidentate interaction between 2-MBA and Au(111).

  15. Spatio-angularly multiplexed (SAM) holographic storage in photorefractive crystals

    Science.gov (United States)

    Tao, Shiquan

    In this thesis a novel multiplexing scheme for dense holographic storage in photorefractive crystals, Spatio-Angular Multiplexing (or SAM), is described in detail. In SAM Fourier transform holograms are formed in spatially overlapping regions of a crystal and are distinguished from one another by using variously angled reference beams. SAM takes advantage of both the high storage density possible using angularly multiplexed volume holograms and also the low crosstalk possible using spatially multiplexed Fourier transform holograms. Compared to pure spatial multiplexing, SAM increases the storage capacity by fully utilising the volume of the storage medium. On the other hand, SAM reduces the number of holograms overlapping any one hologram in a given volume, and so increases the diffraction efficiency achievable as compared to pure angular multiplexing. SAM offers the possibility of incorporating the recorded crystal into a content addressable memory (CAM) system for parallel access of all stored patterns. In order to obtain the maximum diffraction efficiency and signal to noise ratio, the hologram must be replayed by a readout beam incident at the correct angle of readout beam. The optimum angle may be shifted away from the angle used in recording by a ''Bragg-shift", caused (under certain conditions) by phase coupling between the two writing beams during recording. Although this Bragg shift is small, a large diffraction efficiency enhancement is obtained when the grating is read out at the optimum angle. We have calculated the Bragg shift, using a numerical calculation based on an earlier theory, and have obtained good agreement with experiment. Using the novel SAM scheme, we have succeeded in storing 756 high resolution binary patterns in an Fe:LiNbO3 crystal of volume 1cm3, with an average diffraction efficiency of 0.5%. This large database is designed for practical use in a novel associative memory system, called a high order feedback neural network (HOFNET

  16. 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.

  17. Carbodiimide/NHS derivatization of COOH-terminated SAMs: activation or byproduct formation?

    Science.gov (United States)

    Palazon, Francisco; Benavides, Cindy Montenegro; Léonard, Didier; Souteyrand, Éliane; Chevolot, Yann; Cloarec, Jean-Pierre

    2014-04-29

    COOH-terminated self-assembled monolayers (SAMs) are widely used in biosensor technology to bind different amine-containing biomolecules. A covalent amide bond, however, can be achieved only if the carboxylic acids are activated. This activation process usually consists of forming an N-hydroxysuccinimidyl ester (NHS-ester) by consecutively reacting carboxylic acids with a carbodiimide and NHS. Though many papers report using this method,1-8 the experimental conditions vary greatly between them and chemical characterization at this stage is often omitted. Evidence of an efficient activation is therefore rarely shown. Furthermore, recent publications9-11 have highlighted the complexity of this process, with the possible formation of different byproducts. In this paper, we have conducted a study on NHS activation under different conditions with chemical characterization by polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). Our results indicate that the nature of the solvent and carbodiimide and the reactant concentrations play crucial roles in activation kinetics and efficiency.

  18. Reactive Landing of Gramicidin S and Ubiquitin Ions onto Activated Self-Assembled Monolayer Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Laskin, Julia; Hu, Qichi

    2017-03-13

    Using mass-selected ion deposition combined with in situ infrared reflection absorption spectroscopy (IRRAS), we examined the reactive landing of gramicidin S and ubiquitin ions onto activated self-assembled monolayer (SAM) surfaces terminated with N-hydroxysuccinimidyl ester (NHS-SAM) and acyl fluoride (COF-SAM) groups. Doubly protonated gramicidin S, [GS+2H]2+, and two charge states of ubiquitin, [U+5H]5+ and [U+13H]13+, were used as model systems, allowing us to explore the effect of the number of free amino groups and the secondary structure on the efficiency of covalent bond formation between the projectile ion and the surface. For all projectile ions, ion deposition resulted in the depletion of IRRAS bands corresponding to the terminal groups on the SAM and the appearance of several new bands not associated with the deposited species. These new bands were assigned to the C=O stretching vibrations of COOH and COO- groups formed on the surface as a result of ion deposition. The presence of these bands was attributed to an alternative reactive landing pathway that competes with covalent bond formation. This pathway with similar yields for both gramicidin S and ubiquitin ions is analogous to the hydrolysis of the NHS ester bond in solution. The covalent bond formation efficiency increased linearly with the number of free amino groups and was found to be lower for the more compact conformation of ubiquitin compared with the fully unfolded conformation. This observation was attributed to the limited availability of amino groups on the surface of the folded conformation. Our results have provided new insights on the efficiency and mechanism of reactive landing of peptides and proteins onto activated SAMs

  19. Reactive Landing of Gramicidin S and Ubiquitin Ions onto Activated Self-Assembled Monolayer Surfaces

    Science.gov (United States)

    Laskin, Julia; Hu, Qichi

    2017-03-01

    Using mass-selected ion deposition combined with in situ infrared reflection absorption spectroscopy (IRRAS), we examined the reactive landing of gramicidin S and ubiquitin ions onto activated self-assembled monolayer (SAM) surfaces terminated with N-hydroxysuccinimidyl ester (NHS-SAM) and acyl fluoride (COF-SAM) groups. Doubly protonated gramicidin S, [GS + 2H]2+, and two charge states of ubiquitin, [U + 5H]5+ and [U + 13H]13+, were used as model systems, allowing us to explore the effect of the number of free amino groups and the secondary structure on the efficiency of covalent bond formation between the projectile ion and the surface. For all projectile ions, ion deposition resulted in the depletion of IRRAS bands corresponding to the terminal groups on the SAM and the appearance of several new bands not associated with the deposited species. These new bands were assigned to the C=O stretching vibrations of COOH and COO- groups formed on the surface as a result of ion deposition. The presence of these bands was attributed to an alternative reactive landing pathway that competes with covalent bond formation. This pathway with similar yields for both gramicidin S and ubiquitin ions is analogous to the hydrolysis of the NHS ester bond in solution. The covalent bond formation efficiency increased linearly with the number of free amino groups and was found to be lower for the more compact conformation of ubiquitin compared with the fully unfolded conformation. This observation was attributed to the limited availability of amino groups on the surface of the folded conformation. Our results have provided new insights on the efficiency and mechanism of reactive landing of peptides and proteins onto activated SAMs.

  20. Reactive Landing of Gramicidin S and Ubiquitin Ions onto Activated Self-Assembled Monolayer Surfaces

    Science.gov (United States)

    Laskin, Julia; Hu, Qichi

    2017-07-01

    Using mass-selected ion deposition combined with in situ infrared reflection absorption spectroscopy (IRRAS), we examined the reactive landing of gramicidin S and ubiquitin ions onto activated self-assembled monolayer (SAM) surfaces terminated with N-hydroxysuccinimidyl ester (NHS-SAM) and acyl fluoride (COF-SAM) groups. Doubly protonated gramicidin S, [GS + 2H]2+, and two charge states of ubiquitin, [U + 5H]5+ and [U + 13H]13+, were used as model systems, allowing us to explore the effect of the number of free amino groups and the secondary structure on the efficiency of covalent bond formation between the projectile ion and the surface. For all projectile ions, ion deposition resulted in the depletion of IRRAS bands corresponding to the terminal groups on the SAM and the appearance of several new bands not associated with the deposited species. These new bands were assigned to the C=O stretching vibrations of COOH and COO- groups formed on the surface as a result of ion deposition. The presence of these bands was attributed to an alternative reactive landing pathway that competes with covalent bond formation. This pathway with similar yields for both gramicidin S and ubiquitin ions is analogous to the hydrolysis of the NHS ester bond in solution. The covalent bond formation efficiency increased linearly with the number of free amino groups and was found to be lower for the more compact conformation of ubiquitin compared with the fully unfolded conformation. This observation was attributed to the limited availability of amino groups on the surface of the folded conformation. Our results have provided new insights on the efficiency and mechanism of reactive landing of peptides and proteins onto activated SAMs.

  1. Study on the formation of self-assembled monolayers on sol-gel processed hafnium oxide as dielectric layers.

    Science.gov (United States)

    Ting, Guy G; Acton, Orb; Ma, Hong; Ka, Jae Won; Jen, Alex K-Y

    2009-02-17

    High dielectric constant (k) metal oxides such as hafnium oxide (HfO2) have gained significant interest due to their applications in microelectronics. In order to study and control the surface properties of hafnium oxide, self-assembled monolayers (SAMs) of four different long aliphatic molecules with binding groups of phosphonic acid, carboxylic acid, and catechol were formed and characterized. Surface modification was performed to improve the interface between metal oxide and top deposited materials as well as to create suitable dielectric properties, that is, leakage current and capacitance densities, which are important in organic thin film transistors. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, contact angle goniometry, atomic force microscopy (AFM), and simple metal-HfO2-SAM-metal devices were used to characterize the surfaces before and after SAM modification on sol-gel processed hafnium oxide. The alkylphosphonic acid provided the best monolayer formation on sol-gel processed hafnium oxide to generate a well-packed, ultrathin dielectric exhibiting a low leakage current density of 2x10(-8) A/cm2 at an applied voltage of -2.0 V and high capacitance density of 0.55 microF/cm2 at 10 kHz. Dialkylcatechol showed similar characteristics and the potential for using the catechol SAMs to modify HfO2 surfaces. In addition, the integration of this alkylphosphonic acid SAM/hafnium oxide hybrid dielectric into pentacene-based thin film transistors yields low-voltage operation within 1.5 V and improved performance over bare hafnium oxide.

  2. The Performance of CSAM SAM when Cycle Length is extended

    Energy Technology Data Exchange (ETDEWEB)

    Roh, Kyung-ho; Moon, Sang-rae [KHNP, Daejeon (Korea, Republic of)

    2016-10-15

    In order to verify validation of that, CPC Axial Power Distribution is compared with Axial Power Distribution based on ICI every week. The difference between CPC Axial Power Distribution and Axial Power Distribution based on ICI increases according as fuels are burned. It is called CPC Axial Power Distribution Root Mean Square Error (CPC RMS Error). SAM and calibration of ex-core detector are important factors influencing the magnitude of the difference. According to vendor, the difference is limited by 8%. Otherwise, CPC penalty increases as many as difference increase. Therefore, KHNP developed Constrained Simulated Annealing Method (CSAM), which has better performance than that of Least Square Method (LSM), to calculate SAM constant. The CSA SAM contributed largely to maintain CPC operating margin. Somewhat, KHNP is developing the technology to be able to operate nuclear power plants for 24 month to optimize their efficiency. This paper shows trends of CPC RMS Error in a case of 24 months operation. Trends are based on data of a few OPR1000s under operation. It is data of OPR1000s that CSA SAM is applied. KHNP is developing the technology to extend operation cycle length in order to optimize the operation efficiency of OPR1000. To verify effect of extended operation cycle length on CPC, CPC Axial Power Distribution RMS Error in a case of 24 months operation was expected using operation data of six cycles in OPR1000. In cases that CPC Axial Power Distribution RMS Error exceeds threshold, operation margin is decreased due to CPC penalty. To prevent CPC operation margin from being decreased, improved method to calculate SAM or to calibrate ex-core detector is required. KHNP will consider the way to maintain CPC operation margin along with 24 month operation technology development, hereafter.

  3. Influence of the wet chemistry on the SAM GCMS analysis

    Science.gov (United States)

    Buch, A.; Freissinet, C.; Szopa, C.; Glavin, D. P.; Miller, K.; Eigendbrode, J.; Navarro-Gonzalez, R.; Stern, J. C.; Pinnick, V. T.; Coll, P. J.; François, P.; Cabane, M.; Teinturier, S.; Coscia, D.; Dworkin, J. P.; Summons, R. E.; Mahaffy, P. R.

    2013-12-01

    The SAM GC-MS instrument on the Curiosity rover allows to analyze volatile compounds from the atmosphere or volatile compounds from the Martian regolith and refractory compounds in the regolith after sample treatment using wet chemistry. One portion of the wet chemistry experiment is composed of MTBSTFA (N-methyl-N-tert-butyldimethylsilyltrifluoroacetamide) / DMF (dimethylformamide). Indeed, chemical derivatization of polar molecular compounds is achieved by the MTBSTFA silylation reaction in order to transform refractory polar compounds into a more volatile form that can be analyzed and detected by GC-MS. Results obtained on Rocknest (Leshin et al. 2013; Glavin et al. 2013) and John Klein showed the presence of MTBSTFA reaction products in the system. This means that MTBSTFA is part of the background signal under its gaseous phase and is derived from at least one of the seven MTBSTFA/DMF filled derivatization cups in SAM. Since MTBSTFA is able to react in the gaseous phase, its detection implies the possibility to have some MTBSTFA reactions with all the labile compounds possibly present in the Martian soil, in the sampling system and/or inside the SAM instrument. As such, in order to better understand the portion of products detected coming from internal reactions, we have performed several lab experiments to mimic the SAM pyrolysis and gas processing system. Specifically, we have investigated possible MTBSTFA reactions with organics at high temperatures (100°C up to 600°C) from the SAM trap (Tenax) and with oxychlorine compounds present on Mars (Glavin et al. 2013). References: Leshin et al. Science, in press; Glavin et al. JGR-Planets, accepted.

  4. Determination of self-exchange rate of alkanethiolates in self-assembled monolayers on gold using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    Science.gov (United States)

    Kang, Hyunook; Kim, Yongbin; Choi, Inseong; Chang, Rakwoo; Yeo, Woon-Seok

    2014-09-16

    In this paper, we describe a new method for determining the exchange rates of alkanethiolates in self-assembled monolayers (SAMs) on gold using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to analyze the compositions of the alkanethiolate in SAMs rapidly and directly. In particular, to investigate the self-exchange of alkanethiols, we prepared a deuterated alkanethiol that has the same molecular properties as the non-deuterated alkanethiol but a different molecular weight. SAMs consisting of deuterated alkanethiolates were immersed in a solution of the non-deuterated alkanethiol, and the influences of the immersion time, temperature, concentration, and solvent on the self-exchange rates were investigated. Furthermore, we assessed the exchange rates among alkanethiols with different carbon chain lengths and different size of ethylene glycol units. In addition, we performed molecular dynamics simulations using a model SAM system in order to understand the molecular mechanism of the exchange process.

  5. Skin-like self-assembled monolayers on InAs/GaSb superlattice photodetectors

    Science.gov (United States)

    Salihoglu, Omer; Muti, Abdullah; Kutluer, Kutlu; Tansel, Tunay; Turan, Rasit; Aydinli, Atilla

    2012-09-01

    We report on the effects of monolayer (ML) thick skin-like octadecanethiol (ODT, CH3[CH2]17SH) on type-II InAs/GaSb MWIR photodetectors. Circumventing the ageing effects of conventional sulfur compounds, we use ODT, a self-assembling, long molecular chain headed with a sulfur atom. Photodiodes coated with and without the self-assembled monolayer (SAM) ODT were compared for their electrical and optical performances. For ODT-coated diodes, the dark current density was improved by two orders of magnitude at 77 K under -100 mV bias. The zero bias responsivity and detectivity were 1.04 A W-1 and 2.15 × 1013 Jones, respectively, at 4 µm and 77 K. The quantum efficiency was determined to be 37% for a cutoff wavelength of 5.1 µm.

  6. Surface effects of monolayer-protected gold nanoparticles on the redox reactions between ferricyanide and thiosulfate

    Institute of Scientific and Technical Information of China (English)

    LI Di; SUN Chunyan; HUANG Yunjie; LI Jinghong; CHEN Shaowei

    2005-01-01

    Electron transfer through the self-assembled monolayers (SAMs) on gold nanoparticles is investigated by using the monolayer protected gold nanoclusters (MPCs) as electron-transfer mediators. 3-Mercaptopropionic acid (MPA) and 11-meraptoundecanoic acid (MUA) MPCs were employed to catalyze the redox reaction between potassium ferricyanide and sodium thiosulfate. The catalytic mechanism was proposed that the MPCs act as diffusing electron-mediators and electron transfers to and from the MPCs surface. Therefore the electron transfer rate through the capping layers would be proportional to the MPCs catalyzed reaction rate, which was monitored by the UV absorbance of ferricyanide. The calculated apparent rate constant was orders of magnitude smaller than that of the maximum of tunneling current, which was attributed to the splited energy level of the nanoscale particles.

  7. Pit Formation during the Self-Assembly of Dithiol Monolayers on Au(111)

    Science.gov (United States)

    Macdairmid, A. R.; Cappello, M. L.; Keeler, W. J.; Banks, J. T.; Gallagher, M. C.

    2000-03-01

    The formation of pits one gold atom deep during the growth of alkanethiol monolayers on Au(111), has been observed previously by others. Explanations for pit formation include etching of the substrate, or mass transport of gold atom + thiol molecule on the surface, due to changes in surface energy^1. We have investigated the structure of dithiothreitol (DTT) SAMs on Au(111). Ex situ STM measurements indicate similar pitting occurs during formation of the dithiol monolayer. The degree of pitting depends on exposure time, sample temperature during formation, and subsequent annealing of the sample. Pitting is enhanced considerasbly when DTT is coordinated with Ti, in fact DTT/Ti films exhibit considerable pit motion during STM imaging. ^1 F. Teran et al. Electrochimica Acta 44, 1053 (1998).

  8. DNA adenine methylation of sams1 gene in symbiont-bearing Amoeba proteus.

    Science.gov (United States)

    Jeon, Taeck J

    2008-10-01

    The expression of amoeba sams genes is switched from sams1 to sams2 when amoebae are infected with Legionella jeonii. To elucidate the mechanism for the inactivation of host sams1 gene by endosymbiotic bacteria, methylation states of the sams1 gene of D and xD amoebae was compared in this study. The sams1 gene of amoebae was methylated at an internal adenine residue of GATC site in symbiont-bearing xD amoebae but not in symbiont-free D amoebae, suggesting that the modification might have caused the inactivation of sams1 in xD amoebae. The sams1 gene of xD amoebae was inactivated at the transcriptional level. Analysis of DNA showed that adenine residues in L. jeonii sams were also methylated, implying that L. jeonii bacteria belong to a Dam methylase-positive strain. In addition, both SAM and Met appeared to act as negative regulators for the expression of sams1 whereas the expression of sams2 was not affected in amoebae.

  9. Adsorption of biopolymers human serum albumin and human gamma globulin to well-defined surfaces of self-assembled monolayers

    Science.gov (United States)

    Cregger, Tricia Ann

    The tenacity with which the blood proteins Human Serum Albumin (HSA) and Human Gamma Globulin (HGG) adsorb to a surface modified with a monomolecular coating varies with the packing of the alkyl chains in the coating. The adsorption of proteins onto well-defined surfaces of self-assembled monolayers (SAMs) was studied with X-ray reflectometry (XR), neutron reflectometry (NR), optical reflectometry, and total internal reflection fluorescence (TIRF). NR and XR was used to study adsorption in the absence of flow, while optical reflectometry and TIRF were used to probe the adsorption under flow conditions. In particular, competitive adsorption measurements of binary solutions of HSA, HGG and Fibrinogen (FIB) were performed with TIRE The properties of the surface were varied by altering the alkyl chains' packing density and the chain end functionality of the SAMs. The depth profiles of protein concentration near the adsorbing surface measured by NR were dependent upon the chain packing density in the case of HSA. The concentration depth profile of HGG was unaltered by varying chain packing density. Measurements performed under flow using optical reflectometry showed a different behavior: the surface excess of adsorbed HSA was relatively independent of the surface packing, while the surface excess of HGG depended on the packing density of the SAM. The tenacity with which the proteins adsorbed to different functionalized surfaces was determined by attempting to remove the protein using a strong surfactant, sodium dodecyl sulfate (SDS). Ex situ XR measurements suggested that both HSA and HGG adsorb more tenaciously to a less densely-packed monolayer, almost independent of surface functionality. Two exceptions were a less densely-packed vinyl-terminated monolayer and a less densely-packed bromine-terminated monolayer, from which HSA could not be removed at all.

  10. Submicro photopatterning of alkanethiolate self-assembled monolayer using a negative mask and its application in the fabrication of biomolecular photodiode

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Se Young; Choi, Hyung Seok; Jie, Hang Sok; Park, Je Kyun

    2004-01-05

    Alkanethiolate self-assembled monolayer (SAM) formed by the adsorption of 11-mercaptoundecanoic acid (11-MUDA) molecules on a gold substrate. The alkanethiolate was oxidized by the irradiation of deep UV light with a 700-nm negative mask and then developed with a deionized water. A uniform submicro-pattern of 11-MUDA SAM was obtained. In order to array cytochrome c molecules along the patterned substrate, the well-characterized cytochrome c was immobilized. Electrochemical properties and morphology of the cytochrome c monolayer were investigated through the measurements of cyclic voltammetry and AFM. In addition, current-voltage characteristics of biomolecular multilayers consisting of cytochrome c and green fluorescent protein (GFP) were studied with a scanning tunneling microscope (STM)

  11. 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.

  12. 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.

  13. 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.

  14. Interface control between an indium–tin-oxide electrode and a hole-transport polymer via reactive self-assembled monolayers

    Science.gov (United States)

    Ono, Sotaro; Usui, Satoshi; Tanaka, Kuniaki; Usui, Hiroaki

    2017-04-01

    The indium–tin-oxide (ITO) surface was modified with self-assembled monolayers (SAMs) having different terminal groups including methyl, vinyl, benzophenone, and azo units. A hole-transport layer of fluorene-phenoxazine copolymer was spin-coated on the surface and then irradiated with UV light to induce photochemical reaction at the interface between the SAMs and the polymer. It was observed that the SAMs having the benzophenone and azo terminal groups can tether the spin-coated polymer after UV irradiation. The photochemical tethering was effective in improving charge injection from the ITO anode to the hole-transport polymer as well as in improving the adhesion strength of the polymer to the substrate. It is considered that the covalent tethering can be an important factor for improving the interfacial characteristics of organic/inorganic junctions.

  15. 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

    2015-10-01

    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.

  16. Ionic Strength, Surface Charge, and Packing Density Effects on the Properties of Peptide Self-Assembled Monolayers.

    Science.gov (United States)

    Leo, Norman; Liu, Juan; Archbold, Ian; Tang, Yongan; Zeng, Xiangqun

    2017-02-28

    The various environmental parameters of packing density, ionic strength, and solution charge were examined for their effects on the properties of the immobilized peptide mimotope CH19 (CGSGSGSQLGPYELWELSH) that binds with the therapeutic antibody Trastuzumab (Herceptin) on a gold substrate. The immobilization of CH19 onto gold was examined with a quartz crystal microbalance (QCM). The QCM data showed the presence of intermolecular interactions resulting in the increase of viscoelastic properties of the peptide self-assembled monolayer (SAM). The CH19 SAM was diluted with CS7 (CGSGSGS) to decrease the packing density as CH19/CS7. The packing density and ionic strength parameters were evaluated by atomic force microscopy (AFM), ellipsometry, and QCM. AFM and ellipsometry showed a distinct conformational difference between CH19 and CH19/CS7, indicating a relationship between packing density and conformational state of the immobilized peptide. The CH19 SAM thickness was 40 Å with a rough topology, while the CH19/CS7 SAM thickness was 20 Å with a smooth topology. The affinity studies showed that the affinity of CH19 and CH19/CS7 to Trastuzumab were both on the order of 10(7) M(-1) in undiluted PBS buffer, while the dilution of the buffer by 1000× increased both SAMs affinities to Trastuzumab to the order of 10(15) M(-2) and changed the binding behavior from noncooperative to cooperative binding. This indicated that ionic strength had a more pronounced effect on binding properties of the CH19 SAM than packing density. Electrochemical impedance spectroscopy (EIS) was conducted on the CH19/CS7 SAM, which showed an increase in impedance after each EIS measurement cycle. Cyclic voltammetry on the CH19/CS7 SAM decreased impedance to near initial values. The impact of the packing density, buffer ionic strength, and local charge perturbation of the peptide SAM properties was interpreted based on the titratable sites in CH19 that could participate in the proton transfer and

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

    Energy Technology Data Exchange (ETDEWEB)

    Alizadeh, Vali [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Mousavi, Mir Fazlollah, E-mail: mousavim@modares.ac.ir [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Mehrgardi, Masoud Ayatollahi [Department of Chemistry, University of Isfahan, Isfahan (Iran, Islamic Republic of); Kazemi, Sayed Habib [Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan (Iran, Islamic Republic of); Sharghi, Hashem [Department of Chemistry, Shiraz University, Shiraz (Iran, Islamic Republic of)

    2011-07-01

    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{sup -1} and (2.0 {+-} 0.5) x 10{sup 7} cm{sup 3} mol{sup -1} s{sup -1}, respectively.

  18. Interface electronic structures of reversible double-docking self-assembled monolayers on an Au(111) surface.

    Science.gov (United States)

    Zhang, Tian; Ma, Zhongyun; Wang, Linjun; Xi, Jinyang; Shuai, Zhigang

    2014-04-13

    Double-docking self-assembled monolayers (DDSAMs), namely self-assembled monolayers (SAMs) formed by molecules possessing two docking groups, provide great flexibility to tune the work function of metal electrodes and the tunnelling barrier between metal electrodes and the SAMs, and thus offer promising applications in both organic and molecular electronics. Based on the dispersion-corrected density functional theory (DFT) in comparison with conventional DFT, we carry out a systematic investigation on the dual configurations of a series of DDSAMs on an Au(111) surface. Through analysing the interface electronic structures, we obtain the relationship between single molecular properties and the SAM-induced work-function modification as well as the level alignment between the metal Fermi level and molecular frontier states. The two possible conformations of one type of DDSAM on a metal surface reveal a strong difference in the work-function modification and the electron/hole tunnelling barriers. Fermi-level pinning is found to be a key factor to understand the interface electronic properties.

  19. Effects of solvent on the formation of the MUA monolayer on Si and its diffusion barrier properties for Cu metallization

    Science.gov (United States)

    Rahman, Mohammad Arifur; Han, Jung Suk; Jeong, Kyunghoon; Nam, Ho-seok; Lee, Jaegab

    2014-05-01

    We investigated the effects of solvents, such as ethanol and isooctane, on self-assembly of the mercaptoundecanoic acid (MUA) monolayer on Si and its diffusion barrier properties for Cu metallization. The use of isooctane as a solvent produced MUA self-assembled monolayers (SAMs) (˜1.3 nm thick) on Si. These acted as an effective diffusion barrier against Cu diffusion up to 200°C. In contrast, the MUA SAMs produced by ethanol allowed the diffusion of Cu to a MUA-Si interface at 200°C, stimulating the out-diffusion of Si into Cu and thus resulting in the degraded diffusion barrier properties. This was possibly due to the partial formation of interplane hydrogen bonding between the terminal groups of the bound acid and free thiol groups. This provided less dense thiol surface groups, thus leading to poor adhesion of Cu to MUA SAMs. The fabricated Cu/isooctane-assisted MUA source/drain electrode a-Si:H thin film transistors with a channel length of 10 µm exhibited an excellent electron mobility of 0.74 cm2/V-s, threshold voltage of -0.51 V, I on / I off ratio of 3.25 × 106, specific contact resistance of 4.24 Ω-cm2 after annealing at 200°C.

  20. 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

    2016-02-07

    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.

  1. Enhanced vertical carrier mobility in poly(3-alkylthiophene) thin films sandwiched between self-assembled monolayers and surface-segregated layers.

    Science.gov (United States)

    Ma, Jusha; Hashimoto, Kazuhito; Koganezawa, Tomoyuki; Tajima, Keisuke

    2014-04-07

    End-functionalized poly(3-butylthiophene) with a thiol group (P3BT-S) was synthesized and used to form a self-assembled monolayer (SAM). It can induce the end-on orientation in the thin film which has the potential to further enhance hole mobility up to 1.1 × 10(-2) cm(2) V(-1) s(-1) in the vertical direction.

  2. Self-assembled monolayer of ammonium pyrrolidine dithiocarbamate on copper detected using electrochemical methods, surface enhanced Raman scattering and quantum chemistry calculations

    Energy Technology Data Exchange (ETDEWEB)

    Liao, Q.-Q., E-mail: liaoqq1971@yahoo.com.cn [Key Lab of Shanghai Colleges and Universities for Electric Power Corrosion Control and Applied Electrochemistry, Shanghai Engineering Research Center of Energy-Saving in Heat Exchange Systems, Shanghai University of Electric Power, Shanghai 200090 (China); Yue, Z.-W.; Yang, D. [Key Lab of Shanghai Colleges and Universities for Electric Power Corrosion Control and Applied Electrochemistry, Shanghai Engineering Research Center of Energy-Saving in Heat Exchange Systems, Shanghai University of Electric Power, Shanghai 200090 (China); Wang, Z.-H. [Department of Chemistry, Tongji University, Shanghai 200092 (China); Li, Z.-H. [Department of Chemistry, Fudan University, Shanghai 200433 (China); Ge, H.-H. [Key Lab of Shanghai Colleges and Universities for Electric Power Corrosion Control and Applied Electrochemistry, Shanghai Engineering Research Center of Energy-Saving in Heat Exchange Systems, Shanghai University of Electric Power, Shanghai 200090 (China); Li, Y.-J. [Department of Chemistry, Tongji University, Shanghai 200092 (China)

    2011-07-29

    Ammonium pyrrolidine dithiocarbamate (APDTC) monolayer was self-assembled on fresh copper surface obtained after oxidation-reduction cycle treatment in 0.1 mol L{sup -1} potassium chloride solution at ambient temperature. The APDTC self-assembled monolayer (SAM) on copper surface was investigated by surface enhanced Raman scattering spectroscopy and the results show that APDTC SAM is chemisorbed on copper surface by its sulfur atoms with perpendicular orientation. The optimum immersing period for SAM formation is 4 h at 0.01 mol L{sup -1} concentration of APDTC. The impedance results indicate that APDTC SAM has good corrosion inhibition effects for copper in 0.5 mol L{sup -1} hydrochloric acid solution and its maximum inhibition efficiency could reach 95%. Quantum chemical calculations show that APDTC has relatively small {Delta}E between the highest occupied molecular orbital and the lowest unoccupied molecular orbital and large negative charge in its two sulfur atoms, which facilitate formation of an insulating Cu/APDTC film on copper surface.

  3. 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.

  4. Genome sequencing and annotation of Stenotrophomonas sp. SAM8

    Directory of Open Access Journals (Sweden)

    Samy Selim

    2015-12-01

    Full Text Available We report draft genome sequence of Stenotrophomonas sp. strain SAM8, isolated from environmental water. The draft genome size is 3,665,538 bp with a G + C content of 67.2% and contains 6 rRNA sequence (single copies of 5S, 16S & 23S rRNA. The genome sequence can be accessed at DDBJ/EMBL/GenBank under the accession no. LDAV00000000.

  5. Jo Ann Baumgartner and Sam Earnshaw: Organizers and Farmers

    OpenAIRE

    Rabkin, Sarah

    2010-01-01

    Jo Ann Baumgartner directs the Wild Farm Alliance, based in Watsonville, California. WFA’s mission, as described on the organization’s website, is “to promote agriculture that helps to protect and restore wild Nature.” Through research, publications, presentations, events, policy work, and consulting, the organization works to “connect food systems with ecosystems.” Sam Earnshaw is Central Coast regional coordinator of the Community Alliance with Family Farmers. Working with CAFF’s f...

  6. Technical Manual for the SAM Biomass Power Generation Model

    Energy Technology Data Exchange (ETDEWEB)

    Jorgenson, J.; Gilman, P.; Dobos, A.

    2011-09-01

    This technical manual provides context for the implementation of the biomass electric power generation performance model in the National Renewable Energy Laboratory's (NREL's) System Advisor Model (SAM). Additionally, the report details the engineering and scientific principles behind the underlying calculations in the model. The framework established in this manual is designed to give users a complete understanding of behind-the-scenes calculations and the results generated.

  7. Mechanistic Enzymology of the Radical SAM Enzyme DesII.

    Science.gov (United States)

    Ruszczycky, Mark W; Liu, Hung-Wen

    2015-04-01

    DesII is a member of the radical SAM family of enzymes that catalyzes radical-mediated transformations of TDP-4-amino-4,6-didexoy-D-glucose as well as other sugar nucleotide diphosphates. Like nearly all radical SAM enzymes, the reactions begin with the reductive homolysis of SAM to produce a 5'-deoxyadenosyl radical which is followed by regiospecific hydrogen atom abstraction from the substrate. What happens next, however, depends on the nature of the substrate radical so produced. In the case of the biosynthetically relevant substrate, a radical-mediated deamination ensues; however, when this amino group is replaced with a hydroxyl, one instead observes dehydrogenation. The factors that govern the fate of the initially generated substrate radical as well as the mechanistic details underlying these transformations have been a key focus of research into the chemistry of DesII. This review will discuss recent discoveries pertaining to the enzymology of DesII, how it may relate to understanding other radical-mediated lyases and dehydrogenases and the working hypotheses currently being investigated regarding the mechanism of DesII catalysis.

  8. CE-SAM: a conversational interface for ISR mission support

    Science.gov (United States)

    Pizzocaro, Diego; Parizas, Christos; Preece, Alun; Braines, Dave; Mott, David; Bakdash, Jonathan Z.

    2013-05-01

    There is considerable interest in natural language conversational interfaces. These allow for complex user interactions with systems, such as fulfilling information requirements in dynamic environments, without requiring extensive training or a technical background (e.g. in formal query languages or schemas). To leverage the advantages of conversational interactions we propose CE-SAM (Controlled English Sensor Assignment to Missions), a system that guides users through refining and satisfying their information needs in the context of Intelligence, Surveillance, and Reconnaissance (ISR) operations. The rapidly-increasing availability of sensing assets and other information sources poses substantial challenges to effective ISR resource management. In a coalition context, the problem is even more complex, because assets may be "owned" by different partners. We show how CE-SAM allows a user to refine and relate their ISR information needs to pre-existing concepts in an ISR knowledge base, via conversational interaction implemented on a tablet device. The knowledge base is represented using Controlled English (CE) - a form of controlled natural language that is both human-readable and machine processable (i.e. can be used to implement automated reasoning). Users interact with the CE-SAM conversational interface using natural language, which the system converts to CE for feeding-back to the user for confirmation (e.g. to reduce misunderstanding). We show that this process not only allows users to access the assets that can support their mission needs, but also assists them in extending the CE knowledge base with new concepts.

  9. 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.

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

    Science.gov (United States)

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

    2010-03-19

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

  11. 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.

  12. Atomic force microscopy reveals two phases in single stranded DNA self-assembled monolayers

    Science.gov (United States)

    Kosaka, Priscila M.; González, Sheila; Domínguez, Carmen M.; Cebollada, Alfonso; San Paulo, Alvaro; Calleja, Montserrat; Tamayo, Javier

    2013-07-01

    We have investigated the structure of single-stranded (ss) DNA self-assembled monolayers (SAMs) on gold by combining peak force tapping, Kelvin probe and phase contrast atomic force microscopy (AFM) techniques. The adhesion, surface potential and phase shift signals show heterogeneities in the DNA film structure at two levels: microscale and nanoscale; which cannot be clearly discerned in the topography. Firstly, there is multilayer aggregation covering less than 5% of the surface. The DNA multilayers seem to be ordered phases and their existence suggests that DNA end-to-end interaction can play a role in the self-assembly process. Secondly, we find the formation of two phases in the DNA monolayer, which differ both in surface energy and surface potential. We relate the two domains to differences in the packing density and in the ssDNA conformation. The discovered heterogeneities in ssDNA SAMs provide a new scenario in our vision of these relevant films that have direct consequences on their biological, chemical and physical properties.

  13. Nanoseeding via dual surface modification of alkyl monolayer for site-controlled electroless metallization.

    Science.gov (United States)

    Chen, Sung-Te; Chen, Giin-Shan

    2011-10-04

    In this work, an attempt to fabricate nanostructured metallization patterns on SiO(2) dielectric layers is made by using plasma-patterned self-assembled monolayers (SAMs), in conjunction with a novel aqueous seeding and electroless process. Taking octadecyltrichlorosilane (OTS) as a test material, the authors demonstrate that optimizing the N(2)-H(2) plasma conditions leads to the successive conversion of the topmost aliphatic chains of alkyl SAMs to carboxyl (COOH) and hydroxyl (C-OH) functional groups, which was previously found in alkyl SAMs only by exposure to "oxygen-based" plasma. Further modifying the plasma-exposed (either COOH or C-OH terminated) regions with an aqueous solution (SC-1) creates surface functionalities that are viable for site-controlled metallic seeding (e.g., Co or Ni) with an adsorption selectivity of greater than 1000:1. Neither the combination of costly PdCl(2) and complex additives nor the demerits of the associated aqueous chemistry (e.g., seed agglomeration and seed sparseness) are involved. Therefore, the seed particles are only 3 nm in size. Simultaneously, there are sufficient particle densities previously unattainable for electroless deposition to trigger highly resolved Cu metallization patterns with a film thickness of less than 10 nm. The formation of the seed-adsorbing sites is discussed, based on a plasma-dissociated, water-mediated chemical oxidation route.

  14. Self-assembled monolayers of semifluorinated alkaneselenolates on noble metal substrates.

    Science.gov (United States)

    Shaporenko, A; Cyganik, P; Buck, M; Ulman, A; Zharnikov, M

    2005-08-30

    Self-assembled monolayers (SAMs) formed from semifluorinated dialkyldiselenol (CF(3)(CF(2))(5)(CH(2))(2)Se-)(2) (F6H2SeSeH2F6) on polycrystalline Au(111) and Ag(111) were characterized by high-resolution X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, near edge X-ray absorption fine structure spectroscopy, scanning tunneling microscopy, and contact angle measurements. The Se-Se linkage of F6H2SeSeH2F6 was found to be cleaved upon the adsorption, followed by the formation of selenolate-metal bond. The resulting F6H2Se SAMs are well-ordered, densely packed, and contamination-free. The packing density of these films is governed by the bulky fluorocarbon part, which exhibits the expected helical conformation. A noncommensurate hexagonal arrangement of the F6H2Se molecules with an average nearest-neighbor spacing of about 5.8 +/- 0.2 A, close to the van der Waals diameter the fluorocarbon chain, was observed on Au(111). The orientation of the fluorocarbon chains in the F6H2Se SAMs does not depend on the substrate-the average tilt angle of these moieties was estimated to be about 21-22 degrees on both Au and Ag.

  15. Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized on L-glutathione self-assembled monolayers

    Institute of Scientific and Technical Information of China (English)

    Chuan Yin Liu; Ji Ming Hu

    2008-01-01

    A novel hydrogen peroxide biosensor has been fabricated based on covalently linked horseradish peroxidase (HRP) onto Lglutathione self-assembled monolayers (SAMs). The SAMs-based electrode was characterized by electrochemical methods, and direct electrochemistry of HRP can be achieved with formal potential of-0.242 V (vs. saturated Ag/AgCl) in pH7 phosphate buffer solution (PBS), the redox peak current is linear to scan rate and rate constant can be calculated to be 0.042 s-1. The HRP-SAMs-based biosensors show its better electrocatalysis to hydrogen peroxide in the concentration range of 1 × 10-6 mol/L to 1.2 × 10-3 mol/L with a detection limit of 4 × 10-7 mol/L. The apparent Michealis-Menten constant is 3.12 mmol/L. The biosensor can effectively eliminate the interferences of dopamine, ascorbic acid, uric acid, catechol and p-acetaminophen.

  16. Depth profiling of APTES self-assembled monolayers using surface-enhanced confocal Raman microspectroscopy

    Science.gov (United States)

    Sun, Yingying; Yanagisawa, Masahiro; Kunimoto, Masahiro; Nakamura, Masatoshi; Homma, Takayuki

    2017-09-01

    The internal structure of self-assembled monolayers (SAMs) such as 3-aminopropyltriethoxysilane (APTES) fabricated on a glass substrate is difficult to characterize and analyze at nanometer level. In this study, we employed surface-enhanced Raman spectroscopy (SERS) to study the internal molecular structure of APTES SAMs. The sample APTES SAMs were deposited with Ag nanoparticles to enhance the Raman signal and to obtain subtler structure information, which were supported by density functional theory calculations. In addition, in order to carry out high-resolution analysis, especially for vertical direction, a fine piezo electric positioner was used to control the depth scanning with a step of 0.1 nm. We measured and distinguished the vertical Raman intensity variations of specific groups in APTES, such as Ag/NH2, CH2, and Sisbnd O, with high resolution. The interfacial bond at the two interfaces of Ag-APTES and APTES-SiO2 was identified. Moreover, APTES molecule orientation was demonstrated to be inhomogeneous from frequency shift.

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

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Woo Kyung [Department of Chemistry and School of Molecular Science (BK21), Center for Molecular Design and Synthesis, KAIST, Daejeon 305-701 (Korea, Republic of); Park, Sangjin [Research Center for Biomolecular Nanotechnology, Department of Life Science, Gwangju Institute of Science and Technology, Gwangju 500-712 (Korea, Republic of); Jon, Sangyong [Research Center for Biomolecular Nanotechnology, Department of Life Science, Gwangju Institute of Science and Technology, Gwangju 500-712 (Korea, Republic of); Choi, Insung S [Department of Chemistry and School of Molecular Science (BK21), Center for Molecular Design and Synthesis, KAIST, Daejeon 305-701 (Korea, Republic of)

    2007-10-03

    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 {approx}163 deg., which is indicative of superhydrophobic surfaces.

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

    Science.gov (United States)

    Cho, Woo Kyung; Park, Sangjin; Jon, Sangyong; Choi, Insung S.

    2007-10-01

    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® 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°, which is indicative of superhydrophobic surfaces.

  19. Molecular dynamics analysis of reflected gas molecules on self-assembled monolayers

    Science.gov (United States)

    Takeuchi, Hideki

    2015-11-01

    In order to investigate the gas flow of high Knudsen number, it is necessary to specify the boundary condition for the reflected gas molecules at a solid surface. In most cases of the analysis, the diffuse reflection is generally assumed, but there are many cases for which this reflection cannot be applied. The characteristics of the reflected gas molecules depend on the state of the solid surface as well as the gas-surface interaction. The present author analyzed the scattering properties of monoatomic and diatomic gases on various solid surfaces based on the molecular dynamics (MD) method and proposed the boundary condition of reflected gas molecule (Phys. Fluids 18, 046103, 2006). Recently, self-assembled monolayers (SAMs) for the functionalization of the solid surface have been used in the development of micro/nano devices such as microarray and nanosensor. Therefore, it is interesting to study the scattering behavior of the reflected gas molecules on the SAM surface and make the scattering model of gases for the boundary condition. In this study, the angular distribution and the trapping probability for gas molecule on the SAM surface are observed by using MD simulation. The scattering probability at different incident energies is also discussed. JSPS KAKENHI Grant Number 26870813.

  20. High-performance and high-sensitivity applications of graphene transistors with self-assembled monolayers.

    Science.gov (United States)

    Yeh, Chao-Hui; Kumar, Vinod; Moyano, David Ricardo; Wen, Shao-Hsuan; Parashar, Vyom; Hsiao, She-Hsin; Srivastava, Anchal; Saxena, Preeti S; Huang, Kun-Ping; Chang, Chien-Chung; Chiu, Po-Wen

    2016-03-15

    Charge impurities and polar molecules on the surface of dielectric substrates has long been a critical obstacle to using graphene for its niche applications that involve graphene's high mobility and high sensitivity nature. Self-assembled monolayers (SAMs) have been found to effectively reduce the impact of long-range scatterings induced by the external charges. Yet, demonstrations of scalable device applications using the SAMs technique remains missing due to the difficulties in the device fabrication arising from the strong surface tension of the modified dielectric environment. Here, we use patterned SAM arrays to build graphene electronic devices with transport channels confined on the modified areas. For high-mobility applications, both rigid and flexible radio-frequency graphene field-effect transistors (G-FETs) were demonstrated, with extrinsic cutoff frequency and maximum oscillation frequency enhanced by a factor of ~2 on SiO2/Si substrates. For high sensitivity applications, G-FETs were functionalized by monoclonal antibodies specific to cancer biomarker chondroitin sulfate proteoglycan 4, enabling its detection at a concentration of 0.01 fM, five orders of magnitude lower than that detectable by a conventional colorimetric assay. These devices can be very useful in the early diagnosis and monitoring of a malignant disease.

  1. One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

    Science.gov (United States)

    Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J.

    2017-02-01

    The Huisgen cycloaddition reaction (;click; chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

  2. Positional order in Langmuir monolayers

    DEFF Research Database (Denmark)

    Kaganer, V.M.; Brezesinski, G.; Möhwald, H.;

    1998-01-01

    We find that a structural solid-solid phase transition in a two-dimensional Langmuir film is accompanied by strong positional disorder. Specifically, we find by a grazing-incidence x-ray diffraction experiment that in monolayers of octadecanol both the hexagonal phase LS and the centered rectangu......We find that a structural solid-solid phase transition in a two-dimensional Langmuir film is accompanied by strong positional disorder. Specifically, we find by a grazing-incidence x-ray diffraction experiment that in monolayers of octadecanol both the hexagonal phase LS and the centered...

  3. Electromelting of Confined Monolayer Ice

    CERN Document Server

    Qiu, Hu

    2013-01-01

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

  4. Immobilisation of a thrombopoietin peptidic mimic by self-assembled monolayers for culture of CD34+ cells.

    Science.gov (United States)

    Lee, Eun-Ju; Be, Cheang Ly; Vinson, Andrew R; Riches, Andrew G; Fehr, Friederike; Gardiner, James; Gengenbach, Thomas R; Winkler, David A; Haylock, David

    2015-01-01

    Compared to soluble cytokines, surface-tethered ligands can deliver biological signalling with precise control of spatial positioning and concentration. A strategy that immobilises ligand molecules on a surface in a uniform orientation using non-cleavable linkages under physiological conditions would enhance the specific and systemic delivery of signalling in the local environment. We used mixed self-assembled monolayers (SAMs) of oxyamine- and oligo(ethylene glycol)-terminated thiols on gold to covalently install aldehyde- or ketone-functionalised ligands via oxime conjugation. Characterisation by electrochemistry and X-ray photoelectron spectroscopy showed quantitative immobilisation of the ligands on SAM surfaces. The thrombopoietin mimetic peptide, RILL, was immobilised on SAMs and the bioactivity of the substrate was demonstrated by culturing factor-dependent cells. We also optimised the immobilisation and wash conditions so that the peptide was not released into the culture medium and the immobilised RILL could be re-used for consecutive cell cultures. The surface also supported the growth of haematopoietic CD34+ cells comparable to the standard thrombopoietin-supplemented culture. Furthermore, the RILL-immobilised SAM surface was as effective in expanding uncommitted CD34+ cells as standard culture. The stimulatory effect of surface-tethered ligands in haematopoietic stem cell expansion supports the use of ligand immobilisation strategies to replicate the haematopoietic stem cell niche.

  5. Site-selective assembly of quantum dots on patterned self-assembled monolayers fabricated by laser direct-writing

    Science.gov (United States)

    Wu, Chong; Wang, Yongsheng; Han, Xuemingyue; Hu, Xinming; Cheng, Qianyi; Han, Baohang; Liu, Qian; Ren, Tianling; He, Yonghong; Sun, Shuqing; Ma, Hui

    2012-06-01

    A simple and efficient route for quantum dot (QDs) patterning using self-assembled monolayers (SAMs) as templates is described. By means of a laser direct-writing (LDW) technique, SAMs of octadecylphosphonic acid formed by adsorption on native oxide layer of titanium film were patterned through laser-induced ablation of the SAM molecules. This technique allows the creation of chemical-specific patterns accompanied by slight change in the topography. Using atomic force microscopy and friction force microscopy, the dependence of feature size and characteristics on the irradiation dose was demonstrated. Upon immersion of a substrate with patterned SAMs bearing thiol as the terminal group into a dispersion of QDs resulted in the assembly of QDs on the specific thiol-terminated areas. Patterns of QDs with different photoluminescent wavelength were generated. The LDW technique, which is convenient and flexible due to its path-directed and maskless fabrication process, provided a new powerful approach for patterning materials on surfaces for various applications.

  6. A priori calculations of the free energy of formation from solution of polymorphic self-assembled monolayers.

    Science.gov (United States)

    Reimers, Jeffrey R; Panduwinata, Dwi; Visser, Johan; Chin, Yiing; Tang, Chunguang; Goerigk, Lars; Ford, Michael J; Sintic, Maxine; Sum, Tze-Jing; Coenen, Michiel J J; Hendriksen, Bas L M; Elemans, Johannes A A W; Hush, Noel S; Crossley, Maxwell J

    2015-11-10

    Modern quantum chemical electronic structure methods typically applied to localized chemical bonding are developed to predict atomic structures and free energies for meso-tetraalkylporphyrin self-assembled monolayer (SAM) polymorph formation from organic solution on highly ordered pyrolytic graphite surfaces. Large polymorph-dependent dispersion-induced substrate-molecule interactions (e.g., -100 kcal mol(-1) to -150 kcal mol(-1) for tetratrisdecylporphyrin) are found to drive SAM formation, opposed nearly completely by large polymorph-dependent dispersion-induced solvent interactions (70-110 kcal mol(-1)) and entropy effects (25-40 kcal mol(-1) at 298 K) favoring dissolution. Dielectric continuum models of the solvent are used, facilitating consideration of many possible SAM polymorphs, along with quantum mechanical/molecular mechanical and dispersion-corrected density functional theory calculations. These predict and interpret newly measured and existing high-resolution scanning tunnelling microscopy images of SAM structure, rationalizing polymorph formation conditions. A wide range of molecular condensed matter properties at room temperature now appear suitable for prediction and analysis using electronic structure calculations.

  7. Optimized modification of gold nanoparticles with a self-assembled monolayer for suppression of nonspecific binding in DNA assays

    Science.gov (United States)

    Esashika, Keiko; Saiki, Toshiharu

    2016-10-01

    Homogeneous DNA assays using gold nanoparticles (AuNPs) require the reduction of nonspecific binding between AuNPs to improve sensitivity in detecting the target molecule. In this study, we employed alkanethiol self-assembled monolayers (SAMs) for modifying the AuNP surface to attain both good dispersability and high hybridization efficiency. The alkanethiol SAMs enhance the repulsive interaction between AuNPs, reducing nonspecific binding and promoting the extension of surface-immobilized ssDNA into the solvent, thus enhancing the hybridization process. Introduction of oligoethylene glycol into the alkanethiol prevented nonspecific binding caused by the entanglement of alkane chains. Finally, the conditions were optimized by controlling the surface charge density through the introduction of a COOH group at the alkanethiol terminus, resulting in the complete blocking of nonspecific binding and the maintenance of high hybridization efficiency.

  8. Optical properties of azobenzene-functionalized self-assembled monolayers: Intermolecular coupling and many-body interactions

    Science.gov (United States)

    Cocchi, Caterina; Moldt, Thomas; Gahl, Cornelius; Weinelt, Martin; Draxl, Claudia

    2016-12-01

    In a joint theoretical and experimental work, the optical properties of azobenzene-functionalized self-assembled monolayers (SAMs) are studied at different molecular packing densities. Our results, based on density-functional and many-body perturbation theory, as well as on differential reflectance (DR) spectroscopy, shed light on the microscopic mechanisms ruling photo-absorption in these systems. While the optical excitations are intrinsically excitonic in nature, regardless of the molecular concentration, in densely packed SAMs intermolecular coupling and local-field effects are responsible for a sizable weakening of the exciton binding strength. Through a detailed analysis of the character of the electron-hole pairs, we show that distinct excitations involved in the photo-isomerization at low molecular concentrations are dramatically broadened by intermolecular interactions. Spectral shifts in the calculated DR spectra are in good agreement with the experimental results. Our findings represent an important step forward to rationalize the excited-state properties of these complex materials.

  9. 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.

  10. Biological Activation of Inert Ceramics: Recent Advances Using Tailored Self-Assembled Monolayers on Implant Ceramic Surfaces

    Directory of Open Access Journals (Sweden)

    Frederik Böke

    2014-06-01

    Full Text Available High-strength ceramics as materials for medical implants have a long, research-intensive history. Yet, especially on applications where the ceramic components are in direct contact with the surrounding tissue, an unresolved issue is its inherent property of biological inertness. To combat this, several strategies have been investigated over the last couple of years. One promising approach investigates the technique of Self-Assembled Monolayers (SAM and subsequent chemical functionalization to create a biologically active tissue-facing surface layer. Implementation of this would have a beneficial impact on several fields in modern implant medicine such as hip and knee arthroplasty, dental applications and related fields. This review aims to give a summarizing overview of the latest advances in this recently emerging field, along with thorough introductions of the underlying mechanism of SAMs and surface cell attachment mechanics on the cell side.

  11. In Situ Analysis of the Growth and Dielectric Properties of Organic Self-Assembled Monolayers: A Way To Tailor Organic Layers for Electronic Applications.

    Science.gov (United States)

    Markov, Aleksandr; Greben, Kyrylo; Mayer, Dirk; Offenhäusser, Andreas; Wördenweber, Roger

    2016-06-29

    Organic nanoscale science and technology relies on the control of phenomena occurring at the molecular level. This is of particular importance for the self-assembly of molecular monolayers (SAM) that can be used in various applications ranging from organic electronics to bioelectronic applications. However, the understanding of the elementary nanoscopic processes in molecular film growth is still in its infancy. Here, we developed a novel in situ and extremely sensitive detection method for the analysis of the electronic properties of molecular layer during molecular layer deposition. This low-frequency sensor (1 kHz) is employed to analyze the standard vapor deposition process of SAMs of molecules and, subsequently, it is used to optimize the growth process itself. By combining this method with an ex situ determination of the effective thickness of the resulting layers via ellipsometry, we observe a large difference of the permittivity (1 kHz) of the examined aminosilanes in the liquid state (εliquid = 5.5-8.8) and in SAMsSAM = 22-52, electric field in the plane of the layer). We ascribe this difference to either the different orientation and order of the molecules, the different density of molecules, or a combination of both effects. Our novel in situ analyses not only allows monitoring and optimizing the deposition of organic layers but also demonstrates the high potential of organic SAMs as organic high-k layers in electronic devices.

  12. Ablation of the Sam68 RNA binding protein protects mice from age-related bone loss.

    Directory of Open Access Journals (Sweden)

    Stéphane Richard

    2005-12-01

    Full Text Available The Src substrate associated in mitosis of 68 kDa (Sam68 is a KH-type RNA binding protein that has been shown to regulate several aspects of RNA metabolism; however, its physiologic role has remained elusive. Herein we report the generation of Sam68-null mice by homologous recombination. Aged Sam68-/- mice preserved their bone mass, in sharp contrast with 12-month-old wild-type littermates in which bone mass was decreased up to approximately 75%. In fact, the bone volume of the 12-month-old Sam68-/- mice was virtually indistinguishable from that of 4-month-old wild-type or Sam68-/- mice. Sam68-/- bone marrow stromal cells had a differentiation advantage for the osteogenic pathway. Moreover, the knockdown of Sam68 using short hairpin RNA in the embryonic mesenchymal multipotential progenitor C3H10T1/2 cells resulted in more pronounced expression of the mature osteoblast marker osteocalcin when differentiation was induced with bone morphogenetic protein-2. Cultures of mouse embryo fibroblasts generated from Sam68+/+ and Sam68-/- littermates were induced to differentiate into adipocytes with culture medium containing pioglitazone and the Sam68-/- mouse embryo fibroblasts shown to have impaired adipocyte differentiation. Furthermore, in vivo it was shown that sections of bone from 12-month-old Sam68-/- mice had few marrow adipocytes compared with their age-matched wild-type littermate controls, which exhibited fatty bone marrow. Our findings identify endogenous Sam68 as a positive regulator of adipocyte differentiation and a negative regulator of osteoblast differentiation, which is consistent with Sam68 being a modulator of bone marrow mesenchymal cell differentiation, and hence bone metabolism, in aged mice.

  13. Low adhesion, non-wetting phosphonate self-assembled monolayer films formed on copper oxide surfaces.

    Science.gov (United States)

    Hoque, E; DeRose, J A; Bhushan, B; Hipps, K W

    2009-07-01

    Self-assembled monolayer (SAM) films have been formed on oxidized copper (Cu) substrates by reaction with 1H,1H,2H,2H-perfluorodecylphosphonic acid (PFDP), octadecylphosphonic acid (ODP), decylphosphonic acid (DP), and octylphosphonic acid (OP) and then investigated by X-ray photoelectron spectroscopy (XPS), contact angle measurement (CAM), and atomic force microscopy (AFM). The presence of alkyl phosphonate molecules, PFDP, ODP, DP, and OP, on Cu were confirmed by CAM and XPS analysis. No alkyl phosphonate molecules were seen by XPS on unmodified Cu as a control. The PFDP/Cu and ODP/Cu SAMs were found to be very hydrophobic having water sessile drop static contact angles of more than 140 degrees , while DP/Cu and OP/Cu have contact angles of 119 degrees and 76 degrees , respectively. PFDP/Cu, ODP/Cu, DP/Cu, and OP/Cu SAMs were studied by friction force microscopy, a derivative of AFM, to better understand their micro/nanotribological properties. PFDP/Cu, ODP/Cu, and DP/Cu had comparable adhesive force, which is much lower than that for unmodified Cu. ODP/Cu had the lowest friction coefficient followed by PFDP/Cu, DP/Cu, and OP/Cu while unmodified Cu had the highest. XPS data gives some indication that a bidentate bond forms between the alkyl phosphonate molecules and the oxidized Cu surface. Hydrophobic phosphonate SAMs could be useful as corrosion inhibitors in micro/nanoelectronic devices and/or as promoters for anti-wetting, low adhesion surfaces.

  14. The Pattern Growth of Carbon Nanotubes by Self-assembled Monolayers Techniques

    Institute of Scientific and Technical Information of China (English)

    KUO Chengtzu; KUO Deshan; CHEN Polin

    2004-01-01

    The well controllable selective growth of carbon nanotubes (CNTs)on the desired area is an important issue for their future applications. In this study, a novel method for selective growth of CNTs was proposed by using the technology of self-assembly monolayers (SAMs) and the Fe-assisted CNTs growth. The Si wafers with the a: Si/Si3N4 layer patterns were first prepared by low pressure chemical vapor deposition (LPCVD)and lithography techniques to act as the substrates for selective deposition of SAMs. The selectivity of SAMs from APTMS solution (N-(2-aminoethyl)-3-aminopropyltrimethoxsilane) is based on its greater reactivity of head group on a-Si than Si3N4 films. The areas of pattern with SAMs will first chelate the Fe3+ ions by their diamine-terminated group. The Fe3+ ions were then consolidated to become Fe-hydroxides in sodium boron hydride solution to form the Fe-hydroxides pattern. Finally, the Fe-hydroxides pattern was pretreated in H plasma to become a well-distributed Fe nano-particles on the surface, and followed by CNTs deposition using Fe as catalyst in a microwave plasma-chemical vapor deposition (MP-CVD) system to become the CNTs pattern. The products in each processing step, including microstructures and lattice images of CNTs, were characterized by contact angle measurements, scanning electron microscopy(SEM), XPS, Auger spectroscopy, transmission electron microscopy (TEM) and high resolution TEM (HRTEM)deposition. The results show that the main process parameters include the surface activation process and its atmosphere, consolidation time and temperature, H plasma pretreatment. The function of each processing step will be discussed.

  15. The Pattern Growth of Carbon Nanotubes by Self-assembled Monolayers Techniques

    Institute of Scientific and Technical Information of China (English)

    KUO Chengtzu; KUO Deshan; CHEN Polin

    2004-01-01

    The well controllable selective growth of carbon nanotubes (CNTs)on the desired area is an important issue for their future applications. In this study, a novel method for selective growth of CNTs was proposed by using the technology of self-assembly monolayers (SAMs) and the Fe-assisted CNTs growth. The Si wafers with the a : Si/Si3N4 layer patterns were first prepared by low pressure chemical vapor deposition (LPCVD)and lithography techniques to act as the substrates for selective deposition of SAMs. The selectivity of SAMs from APTMS solution (N-(2-aminoethyl)-3-aminopropyltrimethoxsilane) is based on its greater reactivity of head group on a-Si than Si3N4 films. The areas of pattern with SAMs will first chelate the Fe3+ ions by their diamine-terminated group. The Fe3+ ions were then consolidated to become Fe-hydroxides in sodium boron hydride solution to form the Fe-hydroxides pattern. Finally, the Fe-hydroxides pattern was pretreated in H plasma to become a well-distributed Fe nano-particles on the surface, and followed by CNTs deposition using Fe as catalyst in a microwave plasma-chemical vapor deposition (MP-CVD) system to become the CNTs pattern. The products in each processing step, including microstructures and lattice images of CNTs, were characterized by contact angle measurements, scanning electron microscopy (SEM), XPS, Auger spectroscopy, transmission electron microscopy (TEM) and high resolution TEM (HRTEM)deposition. The results show that the main process parameters include the surface activation process and its atmosphere, consolidation time and temperature, H plasma pretreatment. The function of each processing step will be discussed.

  16. 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.

  17. SAM Overview and Operation at the D0 Experiment

    Institute of Scientific and Technical Information of China (English)

    LauriLoebel-Carpenter; LeeLueking; 等

    2001-01-01

    SAM is a network-distributed data management system developed at Fermilab for use with Run II data,It is being Employed by the D0 Experiment to store,manage,deliver,and track processing of all data.We describe the design and features of the system including resource management and data transfer mechanisms,We show the operational experience D0 has accumulated to date including data acquisition processing,and all levels of access and delivery.We present various configurations of the system and describe their use in the collaboration.

  18. Multiple endmember spectral-angle-mapper (SAM) analysis improves discrimination of Savanna tree species

    CSIR Research Space (South Africa)

    Cho, Moses A

    2009-08-01

    Full Text Available architecture. Several mapping methods are applied in remote sensing to quantify species or vegetation community distribution at the local to regional scale. The most commonly used methods include maximum likelihood, spectral mixture analysis (SMA)[1...] and spectral angle mapper (SAM)[2]. The application of some of these methods including SAM and SMA has become popular with the advent of hyperspectral remote sensing. SAM determines the degree of similarity between two spectra by treating the spectra...

  19. Cardiological aging in SAM model: effect of chronic treatment with growth hormone.

    Science.gov (United States)

    Forman, K; Vara, E; García, C; Ariznavarreta, C; Escames, G; Tresguerres, J A F

    2010-06-01

    The purpose of this study was to investigate the effect of aging on different parameters related to inflammation, oxidative stress and apoptosis in hearts from two types of male mice models: senescence-accelerated mice (SAM-P8) and senescence-accelerated-resistant (SAM-R1), and the influence of chronic administration of Growth Hormone (GH) on old SAM-P8 mice. Forty male mice were used. Animals were divided into five experimental groups: two 10 month old untreated groups (SAM-P8/SAM-R1), two 2 month old young groups (SAM-P8/SAM-R1) and one 10 month old group (SAM-P8) treated with GH for 30 days. The expression of tumor necrosis factor-alpha, interleukin 1, interleukin 10, heme oxygenases 1 and 2, endothelial and inducible nitric oxide synthases, NFkB, Bad, Bax and Bcl-2 were determined by real-time reverse transcription polymerase chain reaction (RT-PCR). Results were submitted to a two way ANOVA statistical evaluation using the Statgraphics program. Inflammation, as well as, oxidative stress and apoptosis markers were increased in the heart of old SAM-P8 males, as compared to young controls and this situation was not observed in the old SAM-R1 mice. Exogenous GH administration reverted the effect of aging in the described parameters of old SAM-P8 mice. Our results suggest that inflammation, apoptosis and oxidative stress could play an important role in the observed cardiovascular alterations related to aging of SAM-P8 mice and that GH may play a potential protective effect on the cardiovascular system of these animals.

  20. [Effects of Sam68 gene silence on proliferation of acute T lymphoblastic leukemia cell line Jurkat].

    Science.gov (United States)

    Wang, Chi-Juan; Xu, Hua; Zhang, Hai-Rui; Wang, Jian; Lin, Ya-Ni; Pang, Tian-Xiang; Li, Qing-Hua

    2014-08-01

    This study was purpose to investigate the effect of Sam68 gene silence on proliferation of human acute T lymphoblastic leukemia cell line Jurkat. The sequence of shRNA targeting the site 531-552 of Sam68 mRNA was designed and chemically synthesized, then a single-vector lentiviral, Tet-inducible shRNA-Sam68 system (pLKO-Tet-On) was constructed; next the Jurkat cells were infected with lentivirus to create stable cell clones with regulatable Sam68 gene expression. The inhibitory efficiency of Sam68 gene was assayed by Real-time PCR and Western blot; the cell activity of Jurkat cells was detected with MTT assay; the change of colony forming potential of Jurkat cells was analyzed by colony forming test; the cell cycle distribution was tested by flow cytometry. The results indicated that the expression of Sam68 in experimental cells was statistically decreased as compared with that of the control cells; the cells activity and colony forming capacity of the Jurkat cells with Sam68 gene silence were significantly inhibited; with Sam68 gene silencing, the percentage of S phase cells was significantly increased, while the percentage of G2 phase cells was significantly decreased. It is concluded that the silencing Sam68 gene using shRNA interference can effectively inhibit the proliferation of human acute T lymphoblastic leukemia cell line Jurkat.

  1. SAM-2 ground-truth plan: Correlative measurements for the Stratospheric Aerosol Measurement-2 (SAM 2) sensor on the Nimbus G satellite

    Science.gov (United States)

    Russell, P. B.; Mccormick, M. P.; Mcmaster, L. R.; Pepin, T. J.; Chu, W. P.; Swissler, T. J.

    1978-01-01

    The SAM-2 will fly aboard the Nimbus-G satellite for launch in the fall of 1978 and measure stratospheric vertical profiles of aerosol extinction in high latitude bands. The plan gives details of the location and times for the simultaneous satellite/correlative measurements for the nominal launch time, the rationale and choice of the correlative sensors, their characteristics and expected accuracies, and the conversion of their data to extinction profiles. The SAM-2 expected instrument performance and data inversion results are presented. Various atmospheric models representative of polar stratospheric aerosols are used in the SAM-2 and correlative sensor analyses.

  2. de regresión OLS y SAM

    Directory of Open Access Journals (Sweden)

    Carlos J. Vilalta y Perdomo

    2006-01-01

    Full Text Available El propósito de este trabajo es demostrar que debido a que algunos fenómenos sociales presentan variación espacial, la modelación de los mismos tiene implicaciones metodológicas importantes, y por lo tanto es recomendable utilizar una técnica de regresión que incorpore la espacialidad de los datos en su diseño. Se siguen dos procedimientos generales: primero se calcula el coeficiente de autocorrelación I de Moran para demostrar la espacialidad del comportamiento electoral en el México urbano entre 1994 y 2000; después se comparan dos técnicas de regresión, ols y sam. De la comparación se concluye que la técnica sam es más robusta que la ols con base en que la primera obtiene coeficientes de regresión más precisos y detecta efectos regionales estadísticamente significativos aun en la presencia de modelos con problemas de heterodasticidad.

  3. Optical imaging beyond the diffraction limit by SNEM: effects of AFM tip modifications with thiol monolayers on imaging quality.

    Science.gov (United States)

    Cumurcu, Aysegul; Diaz, Jordi; Lindsay, Ian D; de Beer, Sissi; Duvigneau, Joost; Schön, Peter; Vancso, G Julius

    2015-03-01

    Tip-enhanced nanoscale optical imaging techniques such as apertureless scanning near-field optical microscopy (a-SNOM) and scanning near-field ellipsometric microscopy (SNEM) applications can suffer from a steady degradation in performance due to adhesion of atmospheric contaminants to the metal coated tip. Here, we demonstrate that a self-assembled monolayer (SAM) of ethanethiol (EtSH) is an effective means of protecting gold-coated atomic force microscopy (AFM) probe tips from accumulation of surface contaminants during prolonged exposure to ambient air. The period over which they yield consistent and reproducible results for scanning near-field ellipsometric microscopy (SNEM) imaging is thus extended. SNEM optical images of a microphase separated polystyrene-block-poly (methylmethacrylate) (PS-b-PMMA) diblock copolymer film, which were captured with bare and SAM-protected gold-coated AFM probes, both immediately after coating and following five days of storage in ambient air, were compared. During this period the intensity of the optical signals from the untreated gold tip fell by 66%, while those from the SAM protected tip fell by 14%. Additionally, gold coated AFM probe tips were modified with various lengths of alkanethiols to measure the change in intensity variation in the optical images with SAM layer thickness. The experimental results were compared to point dipole model calculations. While a SAM of 1-dodecanethiol (DoSH) was found to strongly suppress field enhancement we find that it can be locally removed from the tip apex by deforming the molecules under load, restoring SNEM image contrast.

  4. Intrinsic Electronic Transport through Alkanedithiol Self-Assembled Monolayer

    Science.gov (United States)

    Lee, Takhee; Wang, Wenyong; Reed, Mark A.

    2005-01-01

    Electronic transport through an alkanedithiol self-assembled monolayer (SAM) is investigated using a nanometer scale device. Temperature-independent current-voltage characteristics are observed, indicating tunneling is the main conduction mechanism. The measured current-voltage characteristics are analyzed with a metal-insulator-metal tunneling model. The inelastic electron tunneling spectroscopy (IETS) study on the octanedithiol device clearly shows the vibrational signatures of molecules. The pronounced IETS peaks correspond to vibrational modes perpendicular to the junction interface, which include the stretching modes of Au-S (at 33 mV) and C-C (at 133 mV), and wagging mode of CH2 (at 158 mV). Intrinsic linewidths are determined as 1.69 (upper limit), 3.73± 0.98, and 13.5± 2.4 meV for Au-S, C-C streching modes, and CH2 wagging mode, respectively. The observed peak intensities and peak widths are in good agreement with theoretical predictions.

  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. Catalytic self-assembled monolayers on Au nanoparticles: the source of catalysis of a transphosphorylation reaction.

    Science.gov (United States)

    Zaupa, Giovanni; Mora, Claudia; Bonomi, Renato; Prins, Leonard J; Scrimin, Paolo

    2011-04-18

    The catalytic activity of a series of Au monolayer protected colloids (Au MPCs) containing different ratios of the catalytic unit triazacyclononane⋅Zn(II) (TACN⋅Zn(II) ) and an inert triethyleneglycol (TEG) unit was measured. The catalytic self-assembled monolayers (SAMs) are highly efficient in the transphosphorylation of 2-hydroxy propyl 4-nitrophenyl phosphate (HPNPP), an RNA model substrate, exhibiting maximum values for the Michaelis-Menten parameters k(cat) and K(M) of 6.7×10(-3) s(-1) and 3.1×10(-4) M, respectively, normalized per catalytic unit. Despite the structural simplicity of the catalytic units, this renders these nanoparticles among the most active catalysts known for this substrate. Both k(cat) and K(M) parameters were determined as a function of the mole fraction of catalytic unit (x(1)) in the SAM. Within this nanoparticle (NP) series, k(cat) increases up till x(1) ≈0.4, after which it remains constant and K(M) decreases exponentially over the range studied. A theoretical analysis demonstrated that these trends are an intrinsic property of catalytic SAMs, in which catalysis originates from the cooperative effect between two neighboring catalytic units. The multivalency of the system causes an increase of the number of potential dimeric catalytic sites composed of two catalytic units as a function of the x(1) , which causes an apparent increase in binding affinity (decrease in K(M)). Simultaneously, the k(cat) value is determined by the number of substrate molecules bound at saturation. For values of x(1) >0.4, isolated catalytic units are no longer present and all catalytic units are involved in catalysis at saturation. Importantly, the observed trends are indicative of a random distribution of the thiols in the SAM. As indicated by the theoretical analysis, and confirmed by a control experiment, in case of clustering both k(cat) and K(M) values remain constant over the entire range of x(1) .

  7. Packing of ganglioside-phospholipid monolayers

    DEFF Research Database (Denmark)

    Majewski, J.; Kuhl, T.L.; Kjær, K.

    2001-01-01

    DPPE monolayer and does not distort the hexagonal in-plane unit cell or out-of-plane two-dimensional (2-D) packing compared with a pure DPPE monolayer. The oligosaccharide headgroups were found to extend normally from the monolayer surface, and the incorporation of these glycolipids into DPPE...... monolayers did not affect hydrocarbon tail packing (fluidization or condensation of the hydrocarbon region). This is in contrast to previous investigations of lipopolymer-lipid mixtures, where the packing structure of phospholipid monolayers was greatly altered by the inclusion of lipids bearing hydrophilic...... polymer groups. Indeed, the lack of packing disruptions by the oligosaccharide groups indicates that protein-GM, interactions, including binding, insertion, chain fluidization, and domain formation (lipid rafts), can be studied in 2-D monolayers using scattering techniques....

  8. Modeling Stimuli-Responsive Nanoparticle Monolayer

    Science.gov (United States)

    Yong, Xin

    2015-03-01

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

  9. Winning Attitude & Dedication to Physical Therapy Keep Sam Schmidt on Track

    Science.gov (United States)

    Bosley, Nikki Prevenslik

    2006-01-01

    This article relates how Sam Schmidt returned to living a productive life after an accident left him with spinal cord injury. Schmidt was a former Indy Racing League driver who founded Sam Schmidt Motorsports after his accident in 2000. Schmidt's car hit the wall as he exited turn two during a practice session at Walt Disney World Speedway in…

  10. A Bifunctional Thioether Linked Coumarin Appended Calix[4]arene Acquires Selectivity Toward Cu(2+) Sensing on Going from Solution to SAM on Gold.

    Science.gov (United States)

    Samanta, Kushal; Rao, Chebrolu Pulla

    2016-02-10

    A bifunctional calix[4]arene molecule bearing coumarin moiety on the lower rim and thioether moiety on the upper rim (L1), has been synthesized and well characterized by (1)H, (13)C NMR and mass spectrometry. Suitably functionalized coumarin moieties are well suited for selective recognition of various cations and anions. Among the 10 different metal ions studied, only Cu(2+) and Fe(3+) exhibit appreciable changes in the absorption spectra owing to the availability of functional moieties present at both the lower as well as the upper rim of free L1 in acetonitrile solution. To bring better selectivity, we blocked one of these functional moieties by coating on to a surface so that only the other one is exposed to the environment for sensing. Such a study carried out in the present case using the self-assembled monolayer (SAM) of L1 on Au(111) resulted in selective sensing of Cu(2+) over several other metal ions as studied by surface plasmon resonance (SPR). The SAM of L1 on Au(111) was confirmed by different techniques, such as grazing incidence FT-IR, contact angle measurement, cyclic voltammetry and scanning tunneling microscopy. Thus, L1 is proven to be a suitable sensor for Cu(2+) when attached to gold surface.

  11. Sam Shepard's plays according to Slovenian theatre directors

    Directory of Open Access Journals (Sweden)

    Anina Oblak

    2003-12-01

    Full Text Available The article focuses on the productions of Sam Shepard's plays in Slovenia during 1985-2000 and the author of the paper primarily pays attention to the Slovenian directors' approach to Shepard's works and the problems that have arisen in the process. Five of Shepard's plays have been staged to date in Slovenia, two early works and three works of new realism. In interviews with the directors (Vinko Möderndorfer, Primož Bebler, Boris Kobal, Dušan Jovanovic and Boris Cavazza as well as three actresses and a choreographer (Alenka Vidrih, Barbara Babič, Vesna Jevnikar, Tanja Zgonc it has emerged that the transplantation of typically American issues to Slovenia and their treatment necessitated a different approach from the one normally taken by the Slovenian directors and actors. Shepard's plays being idiosyncratic, the theatre artists had to either accommodate his material or treat it with different methods that were adapted to suit the Slovenian environment.

  12. NaCo/SAM observations of sources at the Galactic Center

    Science.gov (United States)

    Sanchez-Bermudez, J.; Schödel, R.; Alberdi, A.; Pott, J. U.

    2012-07-01

    Sparse aperture masking (SAM) interferometry combined with Adaptive Optics (AO) is a technique that is uniquely suited to investigate structures near the diffraction limit of large telescopes. The strengths of the technique are a robust calibration of the Point Spread Function (PSF) while maintaining a relatively high dynamic range. We used SAM+AO observations to investigate the circumstellar environment of several bright sources with infrared excess in the central parsec of the Galaxy. For our observations, unstable atmospheric conditions as well as significant residuals after the background subtraction presented serious problems for the standard approach of calibrating SAM data via interspersed observations of reference stars. We circumvented these difficulties by constructing a synthesized calibrator directly from sources within the field-of-view. When observing crowded fields, this novel method can boost the efficiency of SAM observations because it renders interspersed calibrator observations unnecessary. Here, we presented the first NaCo/SAM images reconstructed using this method.

  13. Social activity method (SAM): A fractal language for mathematics

    Science.gov (United States)

    Dowling, Paul

    2013-09-01

    In this paper I shall present and develop my organisational language, social activity method (SAM), and illustrate some of its applications. I shall introduce a new scheme for modes of recontextualisation that enables the analysis of the ways in which one activity - which might be school mathematics or social research or any empirically observed regularity of practice - recontextualises the practice of another and I shall also present, deploy, and develop an existing scheme - domains of action - in an analysis of school mathematics examination papers and in the structuring of what I refer to as the esoteric domain. This domain is here conceived as a hybrid domain of, first, linguistic and extralinguistic resources that are unambiguously mathematical in terms of both expression and content and, second, pedagogic theory - often tacit - that enables the mathematical gaze onto other practices and so recontextualises them. A second and more general theme that runs through the paper is the claim that there is nothing that is beyond semiosis, that there is nothing to which we have direct access, unmediated by interpretation. This state of affairs has implications for mathematics education. Specifically, insofar as an individual's mathematical semiotic system is under continuous development - the curriculum never being graspable all at once - understanding - as a stable semiotic moment - of any aspect or object of mathematics is always localised to the individual and is at best transient, and the sequencing of such moments may well also be more individualised than consistent in some correspondence with the sequencing of the curriculum. This being the case, a concentration on understanding as a goal may well serve to inhibit the pragmatic acquisition and deployment of mathematical technologies, which should be the principal aim of mathematics teaching and learning. The paper is primarily concerned with mathematics education. SAM, however, is a language that is available for

  14. Economic Analysis Case Studies of Battery Energy Storage with SAM

    Energy Technology Data Exchange (ETDEWEB)

    DiOrio, Nicholas [National Renewable Energy Lab. (NREL), Golden, CO (United States); Dobos, Aron [National Renewable Energy Lab. (NREL), Golden, CO (United States); Janzou, Steven [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2015-11-01

    Interest in energy storage has continued to increase as states like California have introduced mandates and subsidies to spur adoption. This energy storage includes customer sited behind-the-meter storage coupled with photovoltaics (PV). This paper presents case study results from California and Tennessee, which were performed to assess the economic benefit of customer-installed systems. Different dispatch strategies, including manual scheduling and automated peak-shaving were explored to determine ideal ways to use the storage system to increase the system value and mitigate demand charges. Incentives, complex electric tariffs, and site specific load and PV data were used to perform detailed analysis. The analysis was performed using the free, publically available System Advisor Model (SAM) tool. We find that installation of photovoltaics with a lithium-ion battery system priced at $300/kWh in Los Angeles under a high demand charge utility rate structure and dispatched using perfect day-ahead forecasting yields a positive net-present value, while all other scenarios cost the customer more than the savings accrued. Different dispatch strategies, including manual scheduling and automated peak-shaving were explored to determine ideal ways to use the storage system to increase the system value and mitigate demand charges. Incentives, complex electric tariffs, and site specific load and PV data were used to perform detailed analysis. The analysis was performed using the free, publically available System Advisor Model (SAM) tool. We find that installation of photovoltaics with a lithium-ion battery system priced at $300/kWh in Los Angeles under a high demand charge utility rate structure and dispatched using perfect day-ahead forecasting yields a positive net-present value, while all other scenarios cost the customer more than the savings accrued.

  15. 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.

  16. Tuning the molecular order of C60-based self-assembled monolayers in field-effect transistors.

    Science.gov (United States)

    Schmaltz, Thomas; Khassanov, Artoem; Steinrück, Hans-Georg; Magerl, Andreas; Hirsch, Andreas; Halik, Marcus

    2014-11-07

    The control of order in organic semiconductor systems is crucial to achieve desired properties in electronic devices. We have studied the order in fullerene functionalized self-assembled monolayers by mixing the active molecules with supporting alkyl phosphonic acids of different chain length. By adjusting the length of the molecules, structural modifications of the alignment of the C60 head groups within the SAM can be tuned in a controlled way. These changes on the sub-nanometre scale were analysed by grazing incidence X-ray diffraction and X-ray reflectivity. To study the electron transport properties across these layers, self-assembled monolayer field-effect transistors (SAMFETs) were fabricated containing only the single fullerene monolayer as semiconductor. Electrical measurements revealed that a high 2D crystalline order is not the only important aspect. If the fullerene head groups are too confined by the supporting alkyl phosphonic acid molecules, defects in the crystalline C60 film, such as grain boundaries, start to strongly limit the charge transport properties. By close interpretation of the results of structural investigations and correlating them to the results of electrical characterization, an optimum chain length of the supporting alkyl phosphonic acids in the range of C10 was determined. With this study we show that minor changes in the order on the sub-nanometre scale, can strongly influence electronic properties of functional self-assembled monolayers.

  17. Surface sealing using self-assembled monolayers and its effect on metal diffusion in porous low-k dielectrics studied using monoenergetic positron beams

    Energy Technology Data Exchange (ETDEWEB)

    Uedono, Akira, E-mail: uedono.akira.gb@u.tsukuba.ac.jp [Division of Applied Physics, Faculty of Pure and Applied Science, University of Tsukuba, Tsukuba, Ibaraki 305-8573 (Japan); Armini, Silvia; Zhang, Yu [IMEC, Kapeldreef 75, B-3001 Heverlee, Leuven (Belgium); Kakizaki, Takeaki [Division of Applied Physics, Faculty of Pure and Applied Science, University of Tsukuba, Tsukuba, Ibaraki 305-8573 (Japan); Krause-Rehberg, Reinhard [Department of Physics, Martin Luther University Halle, 06099 Halle (Germany); Anwand, Wolfgang; Wagner, Andreas [Institute for Radiation Physics, Helmholtz-Zentrum Dresden-Rossendorf, 01314 Dresden (Germany)

    2016-04-15

    Graphical abstract: - Highlights: • Pores with cubic pore side lengths of 1.1 and 3.1 nm coexisted in the low-k film. • For the sample without the SAM sealing process, metal atoms diffused from the top Cu/MnN layer into the OSG film and were trapped by the pores. Almost all pore interiors were covered by those metals. • For the sample damaged by a plasma etch treatment before the SAM sealing process, self-assembled molecules diffused into the OSG film, and they were preferentially trapped by larger pores. - Abstract: 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, C{sub 4}F{sub 8} 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/C{sub 4}F{sub 8} 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.

  18. Molecular dynamics simulations of water confined between matched pairs of hydrophobic and hydrophilic self-assembled monolayers.

    Energy Technology Data Exchange (ETDEWEB)

    Chandross, Michael Evan; Grest, Gary Stephen; Lane, J. Matthew D.; Lorenz, Christian Douglas (King' s College London, London, UK); Stevens, Mark Jackson

    2008-12-01

    We have conducted a molecular dynamics (MD) simulation study of water confined between methyl-terminated and carboxyl-terminated alkylsilane self-assembled monolayers (SAMs) on amorphous silica substrates. In doing so, we have investigated the dynamic and structural behavior of the water molecules when compressed to loads ranging from 20 to 950 MPa for two different amounts of water (27 and 58 water molecules/nm{sup 2}). Within the studied range of loads, we observe that no water molecules penetrate the hydrophobic region of the carboxyl-terminated SAMs. However, we observe that at loads larger than 150 MPa water molecules penetrate the methyl-terminated SAMs and form hydrogen-bonded chains that connect to the bulk water. The diffusion coefficient of the water molecules decreases as the water film becomes thinner and pressure increases. When compared to bulk diffusion coefficients of water molecules at the various loads, we found that the diffusion coefficients for the systems with 27 water molecules/nm{sup 2} are reduced by a factor of 20 at low loads and by a factor of 40 at high loads, while the diffusion coefficients for the systems with 58 water molecules/nm{sup 2} are reduced by a factor of 25 at all loads.

  19. Site-selective electroless metallization on porous organosilica films by multisurface modification of alkyl monolayer and vacuum plasma.

    Science.gov (United States)

    Chen, Giin-Shan; Chen, Sung-Te; Chen, Yenying W; Hsu, Yen-Che

    2013-01-15

    Taking plasma-enhanced chemical vapor deposited porous SiOCH (p-SiOCH) and octadecyltrichlorosilane (OTS) as model cases, this study elucidates the chemical reaction pathways for alkyl-based self-assembled monolayers (SAMs) on porous carbon-doped organosilica films under N(2)-H(2) vacuum plasma illumination. In contrast to previous findings that carboxylic groups are found in alkyl-based SAMs only by exposure to oxygen-based plasma, this study discovers that, upon exposure to reductive nitrogen-based vacuum plasma, surface carboxylic functional groups can be instantly formed on OTS-coated p-SiOCH films. Particular attention is given to developing a multisurface modification process, starting with the modification of p-SiOCH films by N(2)-H(2) plasma and continuing with SAM deposition and plasma patterning; this ultimately leads to site-selective seeding for the spatially controlled fabrication of Cu-wire metallization by electroless deposition. Plasma diagnosis and X-ray near-edge absorption and Fourier transform infrared spectroscopies show that, by adequately controlling the plasma parameters, the bulk of the p-SiOCH films are free from plasma damage (in terms of degradation in bonding structures and electrical properties); the formation of the seed-trapping carboxylic functional groups on the surface, the key factor for the validity of this new seeding process, is due to a water-mediated chemical oxygenation route.

  20. 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.

  1. Dynamic pattern formation of liquid crystals using binary self-assembled monolayers on an ITO surface under DC voltage.

    Science.gov (United States)

    Ishida, Takao; Oyama, Makiko; Terada, Kei-ichi; Haga, Masa-aki

    2014-12-07

    There have been numerous studies of liquid crystal (LC) convection using sandwich-type LC cells under AC voltage. In contrast to previous LC convection studies under AC voltage, we propose the use of a binary self-assembled monolayer (SAM) with a redox-active Ru complex and insulating octadecyl phosphonic acid (C18) molecules on an indium tin oxide (ITO) surface as the electrode of sandwich-type LC cells under DC bias voltage. This is because the functionalized molecules immobilized on the ITO surface are expected to control the LC orientation and electrical conduction of LC cells, under an exact DC bias voltage. We successfully achieved LC pattern formation using ITO electrodes with binary SAMs in LC cells. Moreover, we confirmed that the LC pattern size was increased by increasing the coverage of the Ru complex in binary SAMs. We consider that a combination of three factors, electrical conduction change, controlling of LC orientation in the initial stage and redox-activity of the Ru-complex, is the reason for LC convection although we cannot fully explain the distribution of these three factors. We believe that our LC pattern formation is promising for new type devices e.g., artificial compound eyes using the LC device technology.

  2. 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.

  3. Electrochemistry of the Self-Assembled Monolayers of Dyads Consisting of Tripod-Shaped Trithiol and Bithiophene on Gold

    Directory of Open Access Journals (Sweden)

    Toshikazu Kitagawa

    2014-09-01

    Full Text Available Self-assembled monolayers (SAMs of tripod-shaped trithiols, consisting of an adamantane core with three CH2SH legs and a bithiophene group, were prepared on a Au(111 surface. Adsorption in a tripod-like fashion was supported by polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS of the SAMs, which indicated the absence of free SH groups. Cyclic voltammetry showed an irreversible cathodic wave due to reductive desorption. The SAM also showed an anodic wave due to the single-electron oxidation of the bithiophene moiety without concomitant desorption of the molecules. Although oxidation was irreversible in the absence of a protecting group, it became reversible with the introduction of a terminal phenyl group. The charge of the oxidation was one-third that of the reductive desorption, confirming a three-point adsorption. The surface coverage was ca. 50% of that expected for the anti bithiophene conformation, which suggested that an increase in the surface area per molecule had been caused by the presence of an energetically high-lying syn conformer. In accordance with this, the line shape of the oxidation wave suggested an electrostatic repulsive interaction between neighboring molecules.

  4. Evidence of click and coordination reactions on a self-assembled monolayer by synchrotron radiation based XPS and NEXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Darlatt, Erik [BAM - Bundesanstalt fuer Materialforschung und -pruefung, 12200 Berlin (Germany); Traulsen, Christoph H.-H.; Poppenberg, Johannes; Richter, Sebastian [Institut fuer Chemie und Biochemie, Freie Universitaet Berlin, Takustrasse 3, 14195 Berlin (Germany); Kuehn, Julius [BAM - Bundesanstalt fuer Materialforschung und -pruefung, 12200 Berlin (Germany); Schalley, Christoph A., E-mail: schalley@chemie.fu-berlin.de [Institut fuer Chemie und Biochemie, Freie Universitaet Berlin, Takustrasse 3, 14195 Berlin (Germany); Unger, Wolfgang E.S., E-mail: Wolfgang.Unger@BAM.de [BAM - Bundesanstalt fuer Materialforschung und -pruefung, 12200 Berlin (Germany)

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer Ethynyl terpyridines were clicked to azide-terminated SAMs on gold. Black-Right-Pointing-Pointer Azides and clicked terpyridines were characterized by N and C K-NEXAFS and N 1s XPS. Black-Right-Pointing-Pointer S 1s + S 2p XPS was used to characterize the buried gold-sulfur interface of the SAM. Black-Right-Pointing-Pointer Higher click reaction temperature leads to an increased amount of terpyridyl groups. Black-Right-Pointing-Pointer Introduced terpyridyl groups are accessible for Pd(II) ion coordination. - Abstract: An ethynylterpyridine was 'clicked' to an azide-terminated self-assembled monolayer on gold and characterized by synchrotron radiation based surface analysis as NEXAFS and XPS. The detection of azide and terpyridine signatures confirmed a partial click reaction at room temperature. The absence of the azides after reaction at 50 Degree-Sign C indicates an almost complete conversion. For the latter case successful Pd(II) coordination has been proven. The Au-S interface of the SAMs has been characterized by S 1s and S 2p XPS.

  5. Size-controlled electrochemical growth of PbS nanostructures into electrochemically patterned self-assembled monolayers.

    Science.gov (United States)

    Nişancı, Fatma Bayrakçeken; Demir, Ümit

    2012-06-05

    1-Hexadecanethiol self-assembled monolayers (HDT SAMs) on Au(111) were used as a molecular resist to fabricate nanosized patterns by electrochemical reductive partial desorption for subsequent electrodeposition of PbS from the same solution simultaneously. The influences of potential steps of variable pulse width and amplitude on the size and the number of patterns were investigated. The kinetics of pattern formation by reductive desorption appears to be instantaneous according to chronoamperometric and morphological investigations. PbS structures were deposited electrochemically into the patterns on HDT SAMs by a combined electrochemical technique, based on the codeposition from the same saturated PbS solution at the underpotential deposition of Pb and S. Scanning tunneling microscopy measurements showed that all of the PbS deposits were disk shaped and uniformly distributed on Au(111) surfaces. Preliminary results indicated that the diameter and the density of PbS deposits can be controlled by controlling the pulse width and amplitude of potential applied at the reductive removal stage of HDT SAMs and the deposition time during the electrochemical deposition step.

  6. Voltametric Behavior of Noradrenaline at 2-Mercaptoethanol Self-Assembled Monolayer Modified Gold Electrode and its Analytical Application

    Directory of Open Access Journals (Sweden)

    ShengFu Wang

    2003-02-01

    Full Text Available 2-Mercaptoethanol self-assembled monolayer (ME/Au SAMs was prepared on a gold electrode. The ME/Au SAMs was characterized by using ATR-FTIR and dynamic contact angle measurements. The electrochemical behaviors of noradrenaline (NE on the ME/Au SAMs were studied in BR buffer solution. The modified electrode accelerated electron transfer rate of the redox of NE and showed an excellent eletrocatalytic activity. The diffusion coefficient (D of NE was obtained to be 4.3×10-8 cm2 s-1. The catalytic current increased linearly with the concentration of NE in the range of 2.0×10-6 -1.0×10-3 M by square wave voltammetry response. The modified electrode could eliminate the interference of ascorbic acid (AA at 40-fold concentration of NE and could be satisfactorily used for the determination of NE in the drug injection.

  7. Highly active engineered-enzyme oriented monolayers: formation, characterization and sensing applications

    Directory of Open Access Journals (Sweden)

    Patolsky Fernando

    2011-06-01

    Full Text Available Abstract Background The interest in introducing ecologically-clean, and efficient enzymes into modern industry has been growing steadily. However, difficulties associated with controlling their orientation, and maintaining their selectivity and reactivity is still a significant obstacle. We have developed precise immobilization of biomolecules, while retaining their native functionality, and report a new, fast, easy, and reliable procedure of protein immobilization, with the use of Adenylate kinase as a model system. Methods Self-assembled monolayers of hexane-1,6-dithiol were formed on gold surfaces. The monolayers were characterized by contact-angle measurements, Elman-reagent reaction, QCM, and XPS. A specifically designed, mutated Adenylate kinase, where cysteine was inserted at the 75 residue, and the cysteine at residue 77 was replaced by serine, was used for attachment to the SAM surface via spontaneously formed disulfide (S-S bonds. QCM, and XPS were used for characterization of the immobilized protein layer. Curve fitting in XPS measurements used a Gaussian-Lorentzian function. Results and Discussion Water contact angle (65-70°, as well as all characterization techniques used, confirmed the formation of self-assembled monolayer with surface SH groups. X-ray photoelectron spectroscopy showed clearly the two types of sulfur atom, one attached to the gold (triolate and the other (SH/S-S at the ω-position for the hexane-1,6-dithiol SAMs. The formation of a protein monolayer was confirmed using XPS, and QCM, where the QCM-determined amount of protein on the surface was in agreement with a model that considered the surface area of a single protein molecule. Enzymatic activity tests of the immobilized protein confirmed that there is no change in enzymatic functionality, and reveal activity ~100 times that expected for the same amount of protein in solution. Conclusions To the best of our knowledge, immobilization of a protein by the method

  8. Electrochemical Study of Biotin-Modified Self-Assembled Monolayers: Recommendations for Robust Preparation

    Directory of Open Access Journals (Sweden)

    Richard J.C. Brown

    2006-01-01

    Full Text Available The development of the underpinning methodology for the production of robust, well-formed, and densely packed biotin-HPDP functionalised gold surfaces, the crucial first step in immobilising bimolecules on surfaces, is described. Self-assembled monolayers (SAMs with biotin end-groups were prepared on polycrystalline gold surfaces according to a published method. The layers formed were studied using cyclic voltammetry to determine the composition of the layer and its quality. Crystal impedance spectroscopy was also applied as a complimentary indicator of the composition of the layer.For the first time, the effect of assembly time on the properties of the layer was studied along with the composition of the layer and the ability of the precursor molecule to self-assemble by oxidative addition.

  9. Electrochemical studies of cystine modified self-assembled monolayer for Escherichia coli detection

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Chandra Mouli; Sumana, Gajjala [Department of Science and Technology Centre on Biomolecular Electronics, Biomedical Instrumentation Section, Materials Physics and Engineering Division, National Physical Laboratory (Council of Scientific and Industrial Research), Dr. K. S. Krishnan Marg, New Delhi 110012 (India); Sood, K.N. [Electron Microscope Section, Division of Material Characterization, National Physical Laboratory, Dr. K. S. Krishnan Marg, New Delhi 110012 (India); Malhotra, B.D., E-mail: bansi.malhotra@gmail.co [Department of Science and Technology Centre on Biomolecular Electronics, Biomedical Instrumentation Section, Materials Physics and Engineering Division, National Physical Laboratory (Council of Scientific and Industrial Research), Dr. K. S. Krishnan Marg, New Delhi 110012 (India)

    2010-11-30

    An electrochemical DNA biosensor based on cystine modified self-assembled monolayer (cys-SAM) onto gold electrode (AuE) has been fabricated for Escherichia coli (E. coli) detection. This biosensing electrode has been characterized using scanning electron microscopy (SEM), FT-IR spectroscopy, cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). Under the optimum conditions, this DNA biosensor can be used to detect complementary target DNA concentration in the range of 1 x 10{sup -6} M to 1 x 10{sup -20} M within 60 s of hybridization time at 25 {sup o}C and has been found to be stable for about four months when stored at 4 {sup o}C.

  10. Lateral pressure profiles in lipid monolayers

    NARCIS (Netherlands)

    Baoukina, Svetlana; Marrink, Siewert J.; Tieleman, D. Peter

    2010-01-01

    We have used molecular dynamics simulations with coarse-grained and atomistic models to study the lateral pressure profiles in lipid monolayers. We first consider simple oil/air and oil/water interfaces, and then proceed to lipid monolayers at air/water and oil/water interfaces. The results are qual

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

    Science.gov (United States)

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

    2016-11-01

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

  12. Structural investigation of 1,1'-biphenyl-4-thiol self-assembled monolayers on Au(111) by scanning tunneling microscopy and low-energy electron diffraction.

    Science.gov (United States)

    Matei, D G; Muzik, H; Gölzhäuser, A; Turchanin, A

    2012-10-02

    Self-assembled monolayers (SAMs) of 1,1'-biphenyl-4-thiol (H-(C(6)H(4))(2)-SH) on Au(111) were prepared from solution or via vapor deposition in ultrahigh vacuum and characterized by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and X-ray photoelectron spectroscopy (XPS). In contrast to the typically observed for densely packed alkane-thiol SAMs on Au(111) (√3 × √3)R30° structure, the densely packed aromatic biphenylthiol SAMs prepared by both methods exhibit an unusual hexagonal (2 × 2) structure. Upon annealing at 100 °C, this structure evolves into the (2 × 7√3) structure resulting in the formation of highly ordered pinstripes oriented along the [1 -1 0] directions. Lower density SAMs, prepared by vapor deposition in vacuum, show mixed structures comprising the hexagonal (2 × 2) structure and two rectangular arrangements with the unit cells of (3√3 × 9) and (2√3 × 8). An extinction of the (3√3 × 9) structure in the favor of the (2√3 × 8) structure is observed upon annealing at temperatures of ~100 °C.

  13. Investigation of the deposition and thermal behavior of striped phases of unsymmetric disulfide self-assembled monolayers on Au(111): The case of 11-hydroxyundecyl decyl disulfide

    Energy Technology Data Exchange (ETDEWEB)

    Albayrak, Erol [Department of Materials and Metallurgical Engineering, Ahi Evran University, Kırşehir 40000 (Turkey); Karabuga, Semistan [Department of Chemistry, Kahramanmaraş Sütçü İmam University, Kahramanmaraş 46030 (Turkey); Bracco, Gianangelo [CNR-IMEM and Department of Physics, University of Genoa, via Dodecaneso 33, Genoa 16146 (Italy); Danışman, M. Fatih, E-mail: danisman@metu.edu.tr [Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey)

    2015-01-07

    Self-assembled monolayers (SAMs) of unsymmetric disulfides on Au(111) are used to form mixed SAMs that can be utilized in many applications. Here, we have studied 11-hydroxyundecyl decyl disulfide (CH{sub 3}–(CH{sub 2}){sub 9}–S–S–(CH{sub 2}){sub 11}–OH, HDD) SAMs produced by supersonic molecular beam deposition and characterized by He diffraction. The film growth was monitored at different temperatures up to a coverage which corresponds to a full lying down phase and the diffraction analysis shows that below 250 K the phase is different from the phase measured above 300 K. During the annealing of the film, two phase transitions were observed, at 250 K and 350 K. The overall data suggest that the former is related to an irreversible phase separation of HDD above 250 K to decanethiolate (–S–(CH{sub 2}){sub 9}–CH{sub 3}, DTT) and hydroxyundecylthiolate (–S–(CH{sub 2}){sub 11}–OH, MUDT), while the latter to a reversible melting of the film. Above 450 K, the specular intensity shows an increase related to film desorption and different chemisorbed states were observed with energies in the same range as observed for decanethiol (H–S–(CH{sub 2}){sub 9}–CH{sub 3}, DT) and mercaptoundecanol (H–S–(CH{sub 2}){sub 11}–OH, MUD) SAMs.

  14. Synchrotron radiation stimulated etching of SiO sub 2 thin films with a Co contact mask for the area-selective deposition of self-assembled monolayer

    CERN Document Server

    Wang, C

    2003-01-01

    The area-selective deposition of a self-assembled monolayer (SAM) was demonstrated on a pattern structure fabricated by synchrotron radiation (SR) stimulated etching of a SiO sub 2 thin film on the Si substrate. The etching was conducted by irradiating the SiO sub 2 thin film with SR through a Co contact mask and using a mixture of SF sub 6 + O sub 2 as the reaction gas. The SR etching stopped completely at the SiO sub 2 /Si interface. After the SR etching, the Si surface and the SiO sub 2 surface beneath the Co mask were evaluated by an atomic force microscope (AFM). A dodecene SAM was deposited on the Si surface, and trichlorosilane-derived SAMs (octadecyltrichlorosilane, and octenyltrichlorosilane) were deposited on the SiO sub 2 surface beneath the Co mask. The structure of the deposited SAMs showed a densely packed and well-ordered molecular architecture, which was characterized by infrared spectroscopy, ellipsometry, and water contact angle (WCA) measurements. (author)

  15. Analysis of a regional change in the sign of the SAM-temperature relationship in Antarctica

    Science.gov (United States)

    Marshall, Gareth J.; di Battista, Stefano; Naik, Sushant S.; Thamban, Meloth

    2011-01-01

    This study examines regional atmospheric circulation changes associated with a reversal in the sign of the relationship between the Southern Annular Mode (SAM) and near-surface temperatures at Halley station, East Antarctica, during the 1980s. We show that the key factor affecting the regional SAM-temperature relationship (STR) is the relative magnitude of two climatological low pressure centres to the west and east of the area, which determines the source region of air masses advected into the locality. The principal difference affecting the STR is shown to be a trend towards a significantly weaker climatological low (higher pressure) at ~20°E during a positive phase of the SAM. Specifically, it is variations in the phase and magnitude of the wave number three patterns of atmospheric circulation, the non-annular component of the SAM, which are the principal factors governing the regional STR. A similar reversal is observed in the sign of the correlation between the SAM and oxygen-isotope values from an ice core located some 1,200 km east of Halley. This relationship is examined throughout the 20th Century, by comparing the isotope data to SAM reconstructions, and demonstrates marked decadal variability. Thus, these data suggest that switches in the STR are more likely to reflect natural variability in the long-wave patterns over the Southern Ocean rather than the influence of an anthropogenic forcing. This finding is important when considering the potential utility of Antarctic isotope data as a proxy for the SAM.

  16. The integrated conjugative plasmid pSAM2 of Streptomyces ambofaciens is related to temperate bacteriophages.

    Science.gov (United States)

    Boccard, F; Smokvina, T; Pernodet, J L; Friedmann, A; Guérineau, M

    1989-03-01

    Streptomyces ambofaciens ATCC23877 and derivatives contain the 11-kb element pSAM2 present in an integrated state or as a free and integrated plasmid. This element, able to integrate site-specifically in the genome of different Streptomyces species, is conjugative and mobilizes chromosomal markers. Besides these plasmid functions, we have shown that the site-specific recombination system of pSAM2 presents strong similarities with that of several temperate phages. The integration event is promoted by a site-specific recombinase of the integrase family. The int gene encoding this integrase is closely linked to the plasmid attachment site (attP). A small open reading frame (ORF) overlaps the int gene and the predicted protein exhibits similarities with Xis proteins involved in phages excision. The integrated copy of pSAM2 in strain ATCC23877 is flanked by att sequences (attL and attR). Another att sequence (attX) is present in this strain and attX and attL are the boundaries of a 42-kb fragment (xSAM1) absent, as well as pSAM2, from S.ambofaciens DSM40697. Sequences partially similar to pSAM2 int gene are found near the chromosomal integration zone in both S.ambofaciens strains. The possible origin of pSAM2, an element carrying plasmid as well as phage features, is discussed.

  17. Sam68 exerts separable effects on cell cycle progression and apoptosis

    Directory of Open Access Journals (Sweden)

    Resnick Ross J

    2004-01-01

    Full Text Available Abstract Background The RNA-binding protein Sam68 has been implicated in a number of cellular processes, including transcription, RNA splicing and export, translation, signal transduction, cell cycle progression and replication of the human immunodeficiency virus and poliovirus. However, the precise impact it has on essential cellular functions remains largely obscure. Results In this report we show that conditional overexpression of Sam68 in fibroblasts results in both cell cycle arrest and apoptosis. Arrest in G1 phase of the cell cycle is associated with decreased levels of cyclins D1 and E RNA and protein, resulting in dramatically reduced Rb phosphorylation. Interestingly, cell cycle arrest does not require the specific RNA binding ability of Sam68. In marked contrast, induction of apoptosis by Sam68 absolutely requires a fully-functional RNA binding domain. Moreover, the anti-cancer agent trichostatin A potentiates Sam68-driven apoptosis. Conclusions For the first time we have shown that Sam68, an RNA binding protein with multiple apparent functions, exerts functionally separable effects on cell proliferation and survival, dependent on its ability to bind specifically to RNA. These findings shed new light on the ability of signal transducing RNA binding proteins to influence essential cell function. Moreover, the ability of a class of anti-cancer therapeutics to modulate its ability to promote apoptosis suggests that Sam68 status may impact some cancer treatments.

  18. Structural analysis of a putative SAM-dependent methyltransferase, YtqB, from Bacillus subtilis.

    Science.gov (United States)

    Park, Sun Cheol; Song, Wan Seok; Yoon, Sung-il

    2014-04-18

    S-adenosyl-L-methionine (SAM)-dependent methyltransferases (MTases) methylate diverse biological molecules using a SAM cofactor. The ytqB gene of Bacillus subtilis encodes a putative MTase and its biological function has never been characterized. To reveal the structural features and the cofactor binding mode of YtqB, we have determined the crystal structures of YtqB alone and in complex with its cofactor, SAM, at 1.9 Å and 2.2 Å resolutions, respectively. YtqB folds into a β-sheet sandwiched by two α-helical layers, and assembles into a dimeric form. Each YtqB monomer contains one SAM binding site, which shapes SAM into a slightly curved conformation and exposes the reactive methyl group of SAM potentially to a substrate. Our comparative structural analysis of YtqB and its homologues indicates that YtqB is a SAM-dependent class I MTase, and provides insights into the substrate binding site of YtqB.

  19. Polyamine uptake by DUR3 and SAM3 in Saccharomyces cerevisiae.

    Science.gov (United States)

    Uemura, Takeshi; Kashiwagi, Keiko; Igarashi, Kazuei

    2007-03-09

    It has been reported that GAP1 and AGP2 catalyze the uptake of polyamines together with amino acids in Saccharomyces cerevisiae. We have looked for polyamine-preferential uptake proteins in S. cerevisiae. DUR3 catalyzed the uptake of polyamines together with urea, and SAM3 was found to catalyze the uptake of polyamines together with S-adenosylmethionine, glutamic acid, and lysine. Polyamine uptake was greatly decreased in both DUR3- and SAM3-deficient cells. The K(m) values for putrescine and spermidine of DUR3 were 479 and 21.2 mum, respectively, and those of SAM3 were 433 and 20.7 mum, respectively. Polyamine stimulation of cell growth of a polyamine requiring mutant, which is deficient in ornithine decarboxylase, was not influenced by the disruption of GAP1 and AGP2, but it was diminished by the disruption of DUR3 and SAM3. Furthermore, the polyamine stimulation of cell growth of a polyamine-requiring mutant was completely inhibited by the disruption of both DUR3 and SAM3. The results indicate that DUR3 and SAM3 are major polyamine uptake proteins in yeast. We previously reported that polyamine transport protein kinase 2 regulates polyamine transport. It was found that DUR3 (but not SAM3) was activated by phosphorylation of Thr(250), Ser(251), and Thr(684) by polyamine transport protein kinase 2.

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

    Science.gov (United States)

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

    2007-04-10

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

  1. Conversion of self-assembled monolayers into nanocrystalline graphene: structure and electric transport.

    Science.gov (United States)

    Turchanin, Andrey; Weber, Dirk; Büenfeld, Matthias; Kisielowski, Christian; Fistul, Mikhail V; Efetov, Konstantin B; Weimann, Thomas; Stosch, Rainer; Mayer, Joachim; Gölzhäuser, Armin

    2011-05-24

    Graphene-based materials have been suggested for applications ranging from nanoelectronics to nanobiotechnology. However, the realization of graphene-based technologies will require large quantities of free-standing two-dimensional (2D) carbon materials with tunable physical and chemical properties. Bottom-up approaches via molecular self-assembly have great potential to fulfill this demand. Here, we report on the fabrication and characterization of graphene made by electron-radiation induced cross-linking of aromatic self-assembled monolayers (SAMs) and their subsequent annealing. In this process, the SAM is converted into a nanocrystalline graphene sheet with well-defined thickness and arbitrary dimensions. Electric transport data demonstrate that this transformation is accompanied by an insulator to metal transition that can be utilized to control electrical properties such as conductivity, electron mobility, and ambipolar electric field effect of the fabricated graphene sheets. The suggested route opens broad prospects toward the engineering of free-standing 2D carbon materials with tunable properties on various solid substrates and on holey substrates as suspended membranes.

  2. Optimized immobilization of lectins using self-assembled monolayers on polysilicon encoded materials for cell tagging.

    Science.gov (United States)

    Penon, Oriol; Siapkas, Dimitrios; Novo, Sergi; Durán, Sara; Oncins, Gerard; Errachid, Abdelhamid; Barrios, Lleonard; Nogués, Carme; Duch, Marta; Plaza, José Antonio; Pérez-García, Lluïsa

    2014-04-01

    Self-assembled monolayers (SAMs) have been used for the preparation of functional microtools consisting of encoded polysilicon barcodes biofunctionalized with proteins of the lectin family. These hybrid microtools exploit the lectins ability for recognizing specific carbohydrates of the cell membrane to give an efficient system for cell tagging. This work describes how the control of the methodology for SAM formation on polysilicon surfaces followed by lectin immobilization has a crucial influence on the microtool biofunction. Several parameters (silanization time, silane molar concentration, type of solvent or deposition methodology) have been studied to establish optimal function. Furthermore, silanes incorporating different terminal groups, such as aldehyde, activated ester or epoxide groups were tested in order to analyze their chemical coupling with the biomolecules, as well as their influence on the biofunctionality of the immobilized protein. Two different lectins - wheat germ agglutinin (WGA) and phytohemagglutinin (PHA-L) - were immobilized, because they have different and specific cell recognition behaviour and exhibit different cell toxicity. In this way we can assess the effect of intrinsic bulk toxicity with that of the cell compatibility once immobilized as well as the importance of cell affinity. A variety of nanometrical techniques were used to characterize the active surfaces, and lectin immobilization was quantified using ultraviolet-visible absorption spectroscopy (UV-vis) and optical waveguide light mode spectroscopy (OWLS). Once the best protocol was found, WGA and PHA were immobilized on polysilicon coded barcodes, and these microtools showed excellent cell tagging on living mouse embryos when WGA was used.

  3. Self-assembled monolayer based impedimetric platform for food borne mycotoxin detection

    Science.gov (United States)

    Solanki, Pratima Rathee; Kaushik, Ajeet; Manaka, T.; Pandey, Manoj Kumar; Iwamoto, M.; Agrawal, Ved Varun; Malhotra, Bansi Dhar

    2010-12-01

    A self-assembled monolayer (SAM) of 11-amino-1-undecanethiol (AUT) has been fabricated onto a gold (Au) substrate to co-immobilize anti-ochratoxin-A antibodies (AO-IgGs) and bovine serum albumin (BSA) to detect food borne mycotoxin [i.e., ochratoxin-A (OTA)]. AUT/Auelectrode, AO-IgGs/AUT/Au immunoelectrode and BSA/IgGs/AUT/Au immunoelectrode have been characterized using scanning electron microscopy (SEM) and electrochemical studies such as cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). Electrochemical studies reveal that the AUT-SAM with NH2groups provide favorable conditions to immobilize AO-IgGs with better orientation, resulting in enhanced electron transport to obtain improved sensing characteristics. The EIS response studies of the BSA/AO-IgGs/AUT/Au immunoelectrode obtained as a function of OTA concentration reveal that the value of the charge transfer resistance (RCT) increases with increased OTA concentration. The BSA/AO-IgGs/AUT/Au immunoelectrode exhibits linearity over 0.5-6.0 ng/dl, detection limit of 0.08 ng/dl using 3σb/m criteria, response time of 30 s and sensitivity of ~36.83 Ω/ng dl-1 cm-2 with a regression coefficient of 0.999. Attempts have been made to monitor the change in RCT of BSA/AO-IgGs/AUT/Au immunoelectrode on addition of coffee samples.

  4. Sam68 Mediates the Activation of Insulin and Leptin Signalling in Breast Cancer Cells.

    Directory of Open Access Journals (Sweden)

    Antonio Pérez-Pérez

    Full Text Available Obesity is a well-known risk factor for breast cancer development in postmenopausal women. High insulin and leptin levels seem to have a role modulating the growth of these tumours. Sam68 is an RNA-binding protein with signalling functions that has been found to be overexpressed in breast cancer. Moreover, Sam68 may be recruited to insulin and leptin signalling pathways, mediating its effects on survival, growth and proliferation in different cellular types. We aimed to study the expression of Sam68 and its phosphorylation level upon insulin and leptin stimulation, and the role of Sam68 in the proliferative effect and signalling pathways that are activated by insulin or leptin in human breast adenocarcinoma cells. In the human breast adenocarcinoma cell lines MCF7, MDA-MB-231 and BT-474, Sam68 protein quantity and gene expression were increased upon leptin or insulin stimulation, as it was checked by qPCR and immunoblot. Moreover, both insulin and leptin stimulation promoted an increase in Sam68 tyrosine phosphorylation and negatively regulated its RNA binding capacity. siRNA was used to downregulate Sam68 expression, which resulted in lower proliferative effects of both insulin and leptin, as well as a lower activation of MAPK and PI3K pathways promoted by both hormones. These effects may be partly explained by the decrease in IRS-1 expression by down-regulation of Sam68. These results suggest the participation of Sam68 in both leptin and insulin receptor signaling in human breast cancer cells, mediating the trophic effects of these hormones in proliferation and cellular growth.

  5. Formation of a 1,8-octanedithiol self-assembled monolayer on Au(111) prepared in a lyotropic liquid-crystalline medium.

    Science.gov (United States)

    García Raya, Daniel; Madueño, Rafael; Blázquez, Manuel; Pineda, Teresa

    2010-07-20

    A characterization of the 1,8-octanedithiol (ODT) self-assembled monolayer (SAM) formed from a Triton X-100 lyotropic medium has been conducted by electrochemical techniques. It is found that an ODT layer of standing-up molecules is obtained at short modification time without removing oxygen from the medium. The electrochemical study shows that the ODT layer formed after 15 min of modification time has similar electron-transfer blocking properties to the layers formed from organic solvents at much longer modification times. On the basis of XPS data, it is demonstrated that the inability to bind gold nanoparticles (AuNPs) is due to the presence of extra ODT molecules either interdigited or on top of the layer. Treatment consisting of an acid washing step following the formation of the ODT-Au(111) SAM produces a layer that is able to attach AuNPs as demonstrated by electrochemical techniques and atomic force microscopy (AFM) images.

  6. Coulomb excitations of monolayer germanene

    Science.gov (United States)

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

    2017-01-01

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

  7. Automation of One-Loop Calculations with GoSam: Present Status and Future Outlook

    CERN Document Server

    Cullen, Gavin; Heinrich, Gudrun; Luisoni, Gionata; Mastrolia, Pierpaolo; Ossola, Giovanni; Reiter, Thomas; Tramontano, Francesco

    2011-01-01

    In this presentation, we describe the GoSam (Golem/Samurai) framework for the automated computation of multi-particle scattering amplitudes at the one-loop level. The amplitudes are generated analytically in terms of Feynman diagrams, and can be evaluated using either D-dimensional integrand reduction or tensor decomposition. GoSam can be used to compute one-loop corrections to Standard Model (QCD and EW) processes, and it is ready to link generic model files for theories Beyond SM. We show the main features of GoSam through its application to several examples of different complexity.

  8. Enhanced Collective Magnetic Properties in 2D Monolayers of Iron Oxide Nanoparticles Favored by Local Order and Local 1D Shape Anisotropy.

    Science.gov (United States)

    Toulemon, Delphine; Liu, Yu; Cattoën, Xavier; Leuvrey, Cédric; Bégin-Colin, Sylvie; Pichon, Benoit P

    2016-02-16

    Magnetic nanoparticle arrays represent a very attractive research field because their collective properties can be efficiently modulated as a function of the structure of the assembly. Nevertheless, understanding the way dipolar interactions influence the intrinsic magnetic properties of nanoparticles still remains a great challenge. In this study, we report on the preparation of 2D assemblies of iron oxide nanoparticles as monolayers deposited onto substrates. Assemblies have been prepared by using the Langmuir-Blodgett technique and the SAM assisted assembling technique combined to CuAAC "click" reaction. These techniques afford to control the formation of well-defined monolayers of nanoparticles on large areas. The LB technique controls local ordering of nanoparticles, while adjusting the kinetics of CuAAC "click" reaction strongly affects the spatial arrangement of nanoparticles in monolayers. Fast kinetics favor disordered assemblies while slow kinetics favor the formation of chain-like structures. Such anisotropic assemblies are induced by dipolar interactions between nanoparticles as no magnetic field is applied and no solvent evaporation is performed. The collective magnetic properties of monolayers are studied as a function of average interparticle distance, local order and local shape anisotropy. We demonstrate that local control on spatial arrangement of nanoparticles in monolayers significantly strengthens dipolar interactions which enhances collective properties and results in possible super ferromagnetic order.

  9. Efficient Data Mining in SAMS through Association Rule

    Directory of Open Access Journals (Sweden)

    Mr. Rahul B. Diwate

    2014-05-01

    Full Text Available We propose a protocol for secure mining of association rules in distributed databases. Previous techniques all people deals with different database, now a day’s people also deals with the distributed database. Can we develop a kind of application in which the people can access the distributed data which is already store in remote location in encrypted format? This proposes system technique is used for efficient data mining in SAMS (Student Assessment Management System through association rules in distributed databases. The current leading techniques are that of Kantarcioglu and Clifton. This proposed system is ready to implements two methods, one that computes the union of private subsets that each of the interacting users hold, and another that tests the inclusion of an element held by one user in a subset held by another .We propose a protocol for secure mining through association rule consist a different level of execution process to secure storage of data and access of data. This paper will focus on such process for secure storage plus secure access of data

  10. Sam Goudsmit--His Physics and His Statesmanship

    Science.gov (United States)

    Bederson, Benjamin

    2010-03-01

    Sam Goudsmit was already a famous theoretical physicist in his thirties, mainly because of his co-discovery of electron spin with George Uhlenbeck while both were students of Paul Ehrenfest in Holland in 1925. He and Uhlenbeck continued their thriving careers at the University of Michigan. Goudsmit's style as a physicist was always to make as close a connection between theory and experiment as possible. Thus, for example, his development with his student Robert Bacher of the technique called ``fractional parentage'' used fruitfully in both atomic and nuclear physics to compute energy levels of unknown states in terms of know ones. He also delved deeply into problems related to determinations of nuclear spins and moments. Partly because of his service as scientific leader of the Alsos project at the end of WWII he became a leading statesman of science. I will describe some of his achievements both as a physicist and as a statesman, prior to his becoming Editor in Chief of the American Physical Society.

  11. Dynamics of Energy Transfer and Soft-Landing in Collisions of Protonated Dialanine with Perfluorinated Self-Assembled Monolayer Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Pratihar, Subha; Kohale, Swapnil C.; Bhakta, Dhruv G.; Laskin, Julia; Hase, William L.

    2014-11-21

    Chemical dynamics simulations are reported which provide atomistic details of collisions of protonated dialanine, ala2-H+, with a perfluorinateted octanethiolate self-assembled monolayer (F-SAM ) surface. The simulations are performed at collisions energy Ei of 5.0, 13.5, 22.5, 30.00, and 70 eV, and incident angles 0o 0 (normal) and grazing 45o. Excellent agreement with experiment (J. Am. Chem. Soc. 2000, 122, 9703-9714) is found for both the average fraction and distribution of the collision energy transferred to the ala2-H+ internal degrees of freedom. The dominant pathway for this energy transfer is to ala2-H+ vibration, but for Ei = 5.0 eV ~20% of the energy transfer is to ala2-H+ rotation. Energy transfer to ala2-H+ rotation decreases with increase in Ei and becomes negligible at high Ei. Three types of collisions are observed in the simulations: i.e. those for which ala2-H+ (1) directly scatters off the F-SAM surface; (2) sticks/physisorbs on//in the surface, but desorbs within the 10 ps numerical integration of the simulations; and (3) remains trapped (i.e. soft-landed) on/in the surface when the simulations are terminated. Penetration of the F-SAM by ala2-H+ is important for the latter two types of events. The trapped trajectories are expected to have relatively long residence times on the surface, since a previous molecular dynamics simulation (J. Phys. Chem. B 2014, 118, 5577-5588) shows that thermally accommodated ala2-H+ ions have an binding energy with the F-SAM surface of at least ~15 kcal/mol.

  12. Structural analysis of HS(CD(2))(12)(O-CH(2)-CH(2))(6)OCH(3) monolayers on gold by means of polarization modulation infrared reflection absorption spectroscopy. progress of the reaction with bromine.

    Science.gov (United States)

    Brand, Izabella; Nullmeier, Martina; Klüner, Thorsten; Jogireddy, Rajamalleswaramma; Christoffers, Jens; Wittstock, Gunther

    2010-01-05

    A self-assembled monolayer (SAM) on gold was formed with specifically perdeuterated hexaethylene glycol-terminated alkanethiol HS(CD(2))(12)(O-CH(2)-CH(2))(6)OCH(3) (D-OEG). The structure of the d-alkane and the oligoethylene glycol (OEG) parts of the molecule in a SAM was studied by means of polarization modulation infrared reflection absorption spectroscopy. The D-OEG monolayers are highly ordered and exist in a crystalline phase. The d-alkane chain adopts an all-trans conformation. Both, the d-alkane chain and long axis of the OEG part make an angle of 26.0 degrees +/- 1.5 degrees with respect to the surface normal, a value characteristic for the tilt of solid n-alkane thiols in the SAMs on Au. The positions of nu(as)(COC) and CH(2) wagging and rocking modes indicate a helical arrangement of the OEG chains. The D-OEG SAMs were exposed to 25 muM Br(2) in two ways: (i) by immersion into the Br(2) solution and (ii) in the galvanic cell Au|D-OEG SAM|25 muM Br(2) + 0.1 M Na(2)SO(4)|| 50 muM KBr + 0.1 M Na(2)SO(4)|Au. In the galvanic cell, the oxidant (Br(2)) is scavenged by a heterogeneous electron transfer reaction, slowing the reaction of D-OEG with Br(2). The slow progress of the reaction with Br(2) allowed us to draw conclusions about molecular rearrangements taking place during this reaction. The reaction with Br(2) starts on boundaries and/or defects present in the SAM. First, at the defect place, the alpha-C atom of the OEG chain reacts with Br(2) and the OEG part of the molecule is removed from the monolayer. In consequence an increase in disorder in the OEG part of the SAM is observed. The same mechanism of the reaction with Br(2) is applied for the d-dodecane alkanethiol part of the molecule. This reaction is slow, thus the order and the tilt of the hydrocarbon chain changes only a little during the reaction time.

  13. Drug induced `softening' in phospholipid monolayers

    Science.gov (United States)

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

    2015-06-01

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

  14. Electrochemical Deposition Of Thiolate Monolayers On Metals

    Science.gov (United States)

    Porter, Marc D.; Weissharr, Duane E.

    1995-01-01

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

  15. "Click" Patterning of Self-Assembled Monolayers on Hydrogen-Terminated Silicon Surfaces and Their Characterization Using Light-Addressable Potentiometric Sensors.

    Science.gov (United States)

    Wang, Jian; Wu, Fan; Watkinson, Michael; Zhu, Jingyuan; Krause, Steffi

    2015-09-08

    Two potential strategies for chemically patterning alkyne-terminated self-assembled monolayers (SAMs) on oxide-free silicon or silicon-on-sapphire (SOS) substrates were investigated and compared. The patterned surfaces were validated using a light-addressable potentiometric sensor (LAPS) for the first time. The first strategy involved an integration of photolithography with "click" chemistry. Detailed surface characterization (i.e. water contact angle, ellipsometry, AFM, and XPS) and LAPS measurements showed that photoresist processing not only decreases the coverage of organic monolayers but also introduces chemically bonded contaminants on the surfaces, thus significantly reducing the quality of the SAMs and the utility of "click" surface modification. The formation of chemical contaminants in photolithography was also observed on carboxylic acid- and alkyl-terminated monolayers using LAPS. In contrast, a second approach combined microcontact printing (μCP) with "click" chemistry; that is azide (azido-oligo(ethylene glycol) (OEG)-NH2) inks were printed on alkyne-terminated SAMs on silicon or SOS through PDMS stamps. The surface characterization results for the sample printed with a flat featureless PDMS stamp demonstrated a nondestructive and efficient method of μCP to perform "click" reactions on alkyne-terminated, oxide-free silicon surfaces for the first time. For the sample printed with a featured PDMS stamp, LAPS imaging showed a good agreement with the pattern of the PDMS stamp, indicating the successful chemical patterning on non-oxidized silicon and SOS substrates and the capability of LAPS to image the molecular patterns with high sensitivity.

  16. Must, valge + hall : Sam Wagstaffi ja Robert Mapplethorpe'i portree / Madis Palm

    Index Scriptorium Estoniae

    Palm, Madis

    2008-01-01

    Dokumentaalfilm "Black, White & Gray: Sam Wagstaff and Robert Mapplethorpe" : autor ja režissöör James Crump : Ameerika Ühendriigid 2007. Filmi näidati filminädala "Art in America" raames Tallinnas

  17. Smoking-Attributable Mortality, Morbidity, and Economic Costs (SAMMEC) - Smoking-Attributable Mortality (SAM)

    Data.gov (United States)

    U.S. Department of Health & Human Services — 2005-2009. SAMMEC - Smoking-Attributable Mortality, Morbidity, and Economic Costs. Smoking-attributable mortality (SAM) is the number of deaths caused by cigarette...

  18. Smoking-Attributable Mortality, Morbidity, and Economic Costs (SAMMEC) - Smoking-Attributable Mortality (SAM)

    Data.gov (United States)

    U.S. Department of Health & Human Services — 2005-2009. SAMMEC - Smoking-Attributable Mortality, Morbidity, and Economic Costs. Smoking-attributable mortality (SAM) is the number of deaths caused by cigarette...

  19. Tandem SAM Domain Structure of Human Caskin1: A Presynaptic, Self-Assembling Scaffold for CASK

    Energy Technology Data Exchange (ETDEWEB)

    Stafford, Ryan L.; Hinde, Elizabeth; Knight, Mary Jane; Pennella, Mario A.; Ear, Jason; Digman, Michelle A.; Gratton, Enrico; Bowie, James U. (UCI); (UCLA)

    2012-02-07

    The synaptic scaffolding proteins CASK and Caskin1 are part of the fibrous mesh of proteins that organize the active zones of neural synapses. CASK binds to a region of Caskin1 called the CASK interaction domain (CID). Adjacent to the CID, Caskin1 contains two tandem sterile a motif (SAM) domains. Many SAM domains form polymers so they are good candidates for forming the fibrous structures seen in the active zone. We show here that the SAM domains of Caskin1 form a new type of SAM helical polymer. The Caskin1 polymer interface exhibits a remarkable segregation of charged residues, resulting in a high sensitivity to ionic strength in vitro. The Caskin1 polymers can be decorated with CASK proteins, illustrating how these proteins may work together to organize the cytomatrix in active zones.

  20. Must, valge + hall : Sam Wagstaffi ja Robert Mapplethorpe'i portree / Madis Palm

    Index Scriptorium Estoniae

    Palm, Madis

    2008-01-01

    Dokumentaalfilm "Black, White & Gray: Sam Wagstaff and Robert Mapplethorpe" : autor ja režissöör James Crump : Ameerika Ühendriigid 2007. Filmi näidati filminädala "Art in America" raames Tallinnas

  1. Frequency response and design consideration of GaN SAM avalanche photodiodes

    Science.gov (United States)

    Xie, Feng; Yang, Guofeng; Zhou, Dong; Lu, Hai; Wang, Guosheng

    2016-11-01

    In this work, a method is developed for estimating the frequency response characteristics of GaN avalanche photodiodes (APDs) with separated absorption and multiplication regions (SAM). The method calculates the total diode current with varying frequency by solving transport equations analytically and uses a commercial device simulator as a supplement for determining the exact electrical field profile within the device. Due to the high carrier saturation velocity of GaN, a high-gain-bandwidth product over THz is found achievable for GaN SAM-APDs. The potential performances of GaN SAM-APDs with different structural designs are further compared through numerical studies. It is found that a close-to-reach-through design is attractive for simultaneously achieving both relatively low operation voltage and high working frequency. In addition, transit-time limit and RC-delay limit for the frequency response of GaN SAM-APDs are also discussed.

  2. Enhanced sensitivity of self-assembled-monolayer-based SPR immunosensor for detection of benzaldehyde using a single-step multi-sandwich immunoassay.

    Science.gov (United States)

    Gobi, K Vengatajalabathy; Matsumoto, Kiyoshi; Toko, Kiyoshi; Ikezaki, Hidekazu; Miura, Norio

    2007-04-01

    This paper describes the fabrication and sensing characteristics of a self-assembled monolayer (SAM)-based surface plasmon resonance (SPR) immunosensor for detection of benzaldehyde (BZ). The functional sensing surface was fabricated by the immobilization of a benzaldehyde-ovalbumin conjugate (BZ-OVA) on Au-thiolate SAMs containing carboxyl end groups. Covalent binding of BZ-OVA on SAM was found to be dependent on the composition of the base SAM, and it is improved very much with the use of a mixed monolayer strategy. Based on SPR angle measurements, the functional sensor surface is established as a compact monolayer of BZ-OVA bound on the mixed SAM. The BZ-OVA-bound sensor surface undergoes immunoaffinity binding with anti-benzaldehyde antibody (BZ-Ab) selectively. An indirect inhibition immunoassay principle has been applied, in which analyte benzaldehyde solution was incubated with an optimal concentration of BZ-Ab for 5 min and injected over the sensor chip. Analyte benzaldehyde undergoes immunoreaction with BZ-Ab and makes it inactive for binding to BZ-OVA on the sensor chip. As a result, the SPR angle response decreases with an increase in the concentration of benzaldehyde. The fabricated immunosensor demonstrates a low detection limit (LDL) of 50 ppt (pg mL(-1)) with a response time of 5 min. Antibodies bound to the sensor chip during an immunoassay could be detached by a brief exposure to acidic pepsin. With this surface regeneration, reusability of the same sensor chip for as many as 30 determination cycles has been established. Sensitivity has been enhanced further with the application of an additional single-step multi-sandwich immunoassay step, in which the BZ-Ab bound to the sensor chip was treated with a mixture of biotin-labeled secondary antibody, streptavidin and biotin-bovine serum albumin (Bio-BSA) conjugate. With this approach, the SPR sensor signal increased by ca. 12 times and the low detection limit improved to 5 ppt with a total response

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

    Science.gov (United States)

    Stoebner, Susan E.; Mani, Gopinath

    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

  4. Bringing a Chemical Laboratory Named Sam to Mars on the 2011 Curiosity Rover

    Science.gov (United States)

    Mahaffy, P. R.; Bleacher, L.; Jones, A.; Atreya, S. K.; Manning, H. L.; Cabane, M.; Webster, C. R.; Sam Team

    2010-12-01

    Introduction: An important goal of upcoming missions to Mars is to understand if life could have developed there. The task of the Sample Analysis at Mars (SAM) suite of instruments [1] and the other Curiosity investigations [2] is to move us steadily toward that goal with an assessment of the habitability of our neighboring planet through a series of chemical and geological measurements. SAM is designed to search for organic compounds and inorganic volatiles and measure isotope ratios. Other instruments on Curiosity will provide elemental analysis and identify minerals. SAM will analyze both atmospheric samples and gases evolved from powdered rocks that may have formed billions of years ago with Curiosity providing access to interesting sites scouted by orbiting cameras and spectrometers. SAM Instrument Suite: SAM’s instruments are a Quadrupole Mass Spectrometer (QMS), a 6-column Gas Chromatograph (GC), and a 2-channel Tunable Laser Spectrometer (TLS). SAM can identify organic compounds in Mars rocks to sub-ppb sensitivity and secure precise isotope ratios for C, H, and O in carbon dioxide and water and measure trace levels of methane and its carbon 13 isotope. The SAM gas processing system consists of valves, heaters, pressure sensors, gas scrubbers and getters, traps, and gas tanks used for calibration or combustion experiments [2]. A variety of calibrant compounds interior and exterior to SAM will allow the science and engineering teams to assess SAM’s performance. SAM has been calibrated and tested in a Mars-like environment. Keeping Educators and the Public Informed: The Education and Public Outreach (EPO) goals of the SAM team are to make this complex chemical laboratory and its data widely available to educators, students, and the public. Formal education activities include developing templates for professional development workshops for educators to teach them about SAM and Curiosity, incorporating data into Mars Student Data Teams, and writing articles

  5. Benchmark Simulation of Natural Circulation Cooling System with Salt Working Fluid Using SAM

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, K. K.; Scarlat, R. O.; Hu, R.

    2017-09-03

    Liquid salt-cooled reactors, such as the Fluoride Salt-Cooled High-Temperature Reactor (FHR), offer passive decay heat removal through natural circulation using Direct Reactor Auxiliary Cooling System (DRACS) loops. The behavior of such systems should be well-understood through performance analysis. The advanced system thermal-hydraulics tool System Analysis Module (SAM) from Argonne National Laboratory has been selected for this purpose. The work presented here is part of a larger study in which SAM modeling capabilities are being enhanced for the system analyses of FHR or Molten Salt Reactors (MSR). Liquid salt thermophysical properties have been implemented in SAM, as well as properties of Dowtherm A, which is used as a simulant fluid for scaled experiments, for future code validation studies. Additional physics modules to represent phenomena specific to salt-cooled reactors, such as freezing of coolant, are being implemented in SAM. This study presents a useful first benchmark for the applicability of SAM to liquid salt-cooled reactors: it provides steady-state and transient comparisons for a salt reactor system. A RELAP5-3D model of the Mark-1 Pebble-Bed FHR (Mk1 PB-FHR), and in particular its DRACS loop for emergency heat removal, provides steady state and transient results for flow rates and temperatures in the system that are used here for code-to-code comparison with SAM. The transient studied is a loss of forced circulation with SCRAM event. To the knowledge of the authors, this is the first application of SAM to FHR or any other molten salt reactors. While building these models in SAM, any gaps in the code’s capability to simulate such systems are identified and addressed immediately, or listed as future improvements to the code.

  6. Identification of trans-acting factors regulating SamDC expression in Oryza sativa

    Energy Technology Data Exchange (ETDEWEB)

    Basu, Supratim, E-mail: supratim_genetics@yahoo.co.in [Department of Crop Soil and Environmental Sciences, University of Arkansas, Fayetteville, AR 72701 (United States); Division of Plant Biology, Bose Institute, Kolkata (India); Roychoudhury, Aryadeep [Post Graduate Department of Biotechnology, St. Xavier' s College (Autonomous), 30, Mother Teresa Sarani, Kolkata - 700016, West Bengal (India); Sengupta, Dibyendu N. [Division of Plant Biology, Bose Institute, Kolkata (India)

    2014-03-07

    Highlights: • Identification of cis elements responsible for SamDC expression by in silico analysis. • qPCR analysis of SamDC expression to abiotic and biotic stress treatments. • Detection of SamDC regulators using identified cis-elements as probe by EMSA. • Southwestern Blot analysis to predict the size of the trans-acting factors. - Abstract: Abiotic stress affects the growth and productivity of crop plants; to cope with the adverse environmental conditions, plants have developed efficient defense machinery comprising of antioxidants like phenolics and flavonoids, and osmolytes like polyamines. SamDC is a key enzyme in the polyamine biosynthesis pathway in plants. In our present communication we have done in silico analysis of the promoter region of SamDC to look for the presence of different cis-regulatory elements contributing to its expression. Based on the presence of different cis-regulatory elements we completed comparative analysis of SamDC gene expression in rice lamina of IR-29 and Nonabokra by qPCR in response to the abiotic stress treatments of salinity, drought, cold and the biotic stress treatments of ABA and light. Additionally, to explore the role of the cis-regulatory elements in regulating the expression of SamDC gene in plants we comparatively analyzed the binding of rice nuclear proteins prepared from IR-29 and Nonabokra undergoing various stress treatments. The intensity of the complex formed was low and inducible in IR-29 in contrast to Nonabokra. Southwestern blot analysis helped in predicting the size of the trans-acting factors binding to these cis-elements. To our knowledge this is the first report on the comprehensive analysis of SamDC gene expression in rice and identification of the trans-acting factors regulating its expression.

  7. The Combustion Experiment on the Sample Analysis at Mars (SAM) Instrument Suite on the Curiosity Rover

    Science.gov (United States)

    Stern, J. C.; Malespin, C. A.; Eigenbrode, J. L.; Graham, H. V.; Archer, P. D., Jr.; Brunner, A. E.; Freissinet, C.; Franz, H. B.; Fuentes, J.; Glavin, D. P.; hide

    2014-01-01

    The combustion experiment on the Sample Analysis at Mars (SAM) suite on Curiosity will heat a sample of Mars regolith in the presence of oxygen and measure composition of the evolved gases using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS). QMS will enable detection of combustion products such as CO, CO2, NO, and other oxidized species, while TLS will enable precise measurements of the abundance and carbon isotopic composition (delta(sup 13)C) of the evolved CO2 and hydrogen isotopic composition (deltaD) of H2O. SAM will perform a two-step combustion to isolate combustible materials below approx.550 C and above approx.550 C. The combustion experiment on SAM, if properly designed and executed, has the potential to answer multiple questions regarding the origins of volatiles seen thus far in SAM evolved gas analysis (EGA) on Mars. Constraints imposed by SAM and MSL time and power resources, as well as SAM consumables (oxygen gas), will limit the number of SAM combustion experiments, so it is imperative to design an experiment targeting the most pressing science questions. Low temperature combustion experiments will primarily target the quantification of carbon (and nitrogen) contributed by SAM wet chemistry reagants MTBSTFA (N-Methyl-N-tert-butyldimethylsilyltrifluoroacetamide) and DMF (Dimethylformamide), which have been identified in the background of blank and sample runs and may adsorb to the sample while the cup is in the Sample Manipulation System (SMS). In addition, differences between the sample and "blank" may yield information regarding abundance and delta(sup 13)C of bulk (both organic and inorganic) martian carbon. High temperature combustion experiments primarily aim to detect refractory organic matter, if present in Cumberland fines, as well as address the question of quantification and deltaD value of water evolution associated with hydroxyl hydrogen in clay minerals.

  8. 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, Trevor M. [Univ. of California, Davis, CA (United States)

    2004-04-01

    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

  9. Mechanism and Correlated Factors of SAM Phenomenon after Aortic Valve Replacement

    Institute of Scientific and Technical Information of China (English)

    XU Jing; WEN Jianguo; SHU Liliang; LIU Chao; ZHANG Jingchao; ZHAO Wenzeng

    2007-01-01

    To investigate the mechanism and correlated factors of systolic anterior motion (SAM) phenomenon after aortic valve replacement, 48 patients with severe aortic valvular stenosis were studied. Tested by echo-Doppler one week after aortic valve replacement, the patients were divided into two groups: SAM group and non-SAM group. The data of the left ventricular end-diastolic diameters, the left ventricular end-systolic diameters, the left ventricular outflow diameters, the thickness of the interventricular septum, the posterior wall of left ventricle, the blood velocities of left ventricular outflow and intra-cavitary gradients were recorded and compared. The results showed that no patients died during or after the operation. The blood velocities of left ventricular outflow was increased significantly in 9 patients (>2.5 m/s), and 6 of them developed SAM phenomenon. There was significant difference in all indexes (P<0.05 or P<0.01) except the posterior wall of left ventricle (P>0.05) between two groups. These indicated that the present of SAM phenomenon after aortic valve replacement may be directly related to the increase of blood velocities of left ventricular outflow and intra-cavitary gradients. It is also suggested that smaller left ventricular diastolic diameters, left ventricular systolic diameters, left ventricular outflow diameters and hypertrophy of interventricular septum may be the anatomy basis of SAM phenomenon.

  10. ParaSAM: a parallelized version of the significance analysis of microarrays algorithm.

    Science.gov (United States)

    Sharma, Ashok; Zhao, Jieping; Podolsky, Robert; McIndoe, Richard A

    2010-06-01

    Significance analysis of microarrays (SAM) is a widely used permutation-based approach to identifying differentially expressed genes in microarray datasets. While SAM is freely available as an Excel plug-in and as an R-package, analyses are often limited for large datasets due to very high memory requirements. We have developed a parallelized version of the SAM algorithm called ParaSAM to overcome the memory limitations. This high performance multithreaded application provides the scientific community with an easy and manageable client-server Windows application with graphical user interface and does not require programming experience to run. The parallel nature of the application comes from the use of web services to perform the permutations. Our results indicate that ParaSAM is not only faster than the serial version, but also can analyze extremely large datasets that cannot be performed using existing implementations. A web version open to the public is available at http://bioanalysis.genomics.mcg.edu/parasam. For local installations, both the windows and web implementations of ParaSAM are available for free at http://www.amdcc.org/bioinformatics/software/parasam.aspx.

  11. Fast and slow responses of Southern Ocean sea surface temperature to SAM in coupled climate models

    Science.gov (United States)

    Kostov, Yavor; Marshall, John; Hausmann, Ute; Armour, Kyle C.; Ferreira, David; Holland, Marika M.

    2017-03-01

    We investigate how sea surface temperatures (SSTs) around Antarctica respond to the Southern Annular Mode (SAM) on multiple timescales. To that end we examine the relationship between SAM and SST within unperturbed preindustrial control simulations of coupled general circulation models (GCMs) included in the Climate Modeling Intercomparison Project phase 5 (CMIP5). We develop a technique to extract the response of the Southern Ocean SST (55°S-70°S) to a hypothetical step increase in the SAM index. We demonstrate that in many GCMs, the expected SST step response function is nonmonotonic in time. Following a shift to a positive SAM anomaly, an initial cooling regime can transition into surface warming around Antarctica. However, there are large differences across the CMIP5 ensemble. In some models the step response function never changes sign and cooling persists, while in other GCMs the SST anomaly crosses over from negative to positive values only 3 years after a step increase in the SAM. This intermodel diversity can be related to differences in the models' climatological thermal ocean stratification in the region of seasonal sea ice around Antarctica. Exploiting this relationship, we use observational data for the time-mean meridional and vertical temperature gradients to constrain the real Southern Ocean response to SAM on fast and slow timescales.

  12. Discrimination between Closely Related Cellular Metabolites by the SAM-I Riboswitch

    Energy Technology Data Exchange (ETDEWEB)

    Montange, R.; Mondragon, E; van Tyne, D; Garst, A; Ceres, P; Batey, R

    2010-01-01

    The SAM-I riboswitch is a cis-acting element of genetic control found in bacterial mRNAs that specifically binds S-adenosylmethionine (SAM). We previously determined the 2.9-{angstrom} X-ray crystal structure of the effector-binding domain of this RNA element, revealing details of RNA-ligand recognition. To improve this structure, variations were made to the RNA sequence to alter lattice contacts, resulting in a 0.5-{angstrom} improvement in crystallographic resolution and allowing for a more accurate refinement of the crystallographic model. The basis for SAM specificity was addressed by a structural analysis of the RNA complexed to S-adenosylhomocysteine (SAH) and sinefungin and by measuring the affinity of SAM and SAH for a series of mutants using isothermal titration calorimetry. These data illustrate the importance of two universally conserved base pairs in the RNA that form electrostatic interactions with the positively charged sulfonium group of SAM, thereby providing a basis for discrimination between SAM and SAH.

  13. The impact of a ligand binding on strand migration in the SAM-I riboswitch.

    Directory of Open Access Journals (Sweden)

    Wei Huang

    Full Text Available Riboswitches sense cellular concentrations of small molecules and use this information to adjust synthesis rates of related metabolites. Riboswitches include an aptamer domain to detect the ligand and an expression platform to control gene expression. Previous structural studies of riboswitches largely focused on aptamers, truncating the expression domain to suppress conformational switching. To link ligand/aptamer binding to conformational switching, we constructed models of an S-adenosyl methionine (SAM-I riboswitch RNA segment incorporating elements of the expression platform, allowing formation of an antiterminator (AT helix. Using Anton, a computer specially developed for long timescale Molecular Dynamics (MD, we simulated an extended (three microseconds MD trajectory with SAM bound to a modeled riboswitch RNA segment. Remarkably, we observed a strand migration, converting three base pairs from an antiterminator (AT helix, characteristic of the transcription ON state, to a P1 helix, characteristic of the OFF state. This conformational switching towards the OFF state is observed only in the presence of SAM. Among seven extended trajectories with three starting structures, the presence of SAM enhances the trend towards the OFF state for two out of three starting structures tested. Our simulation provides a visual demonstration of how a small molecule (<500 MW binding to a limited surface can trigger a large scale conformational rearrangement in a 40 kDa RNA by perturbing the Free Energy Landscape. Such a mechanism can explain minimal requirements for SAM binding and transcription termination for SAM-I riboswitches previously reported experimentally.

  14. Alternative function for the mitochondrial SAM complex in biogenesis of alpha-helical TOM proteins.

    Science.gov (United States)

    Stojanovski, Diana; Guiard, Bernard; Kozjak-Pavlovic, Vera; Pfanner, Nikolaus; Meisinger, Chris

    2007-12-03

    The mitochondrial outer membrane contains two preprotein translocases: the general translocase of outer membrane (TOM) and the beta-barrel-specific sorting and assembly machinery (SAM). TOM functions as the central entry gate for nuclear-encoded proteins. The channel-forming Tom40 is a beta-barrel protein, whereas all Tom receptors and small Tom proteins are membrane anchored by a transmembrane alpha-helical segment in their N- or C-terminal portion. Synthesis of Tom precursors takes place in the cytosol, and their import occurs via preexisting TOM complexes. The precursor of Tom40 is then transferred to SAM for membrane insertion and assembly. Unexpectedly, we find that the biogenesis of alpha-helical Tom proteins with a membrane anchor in the C-terminal portion is SAM dependent. Each SAM protein is necessary for efficient membrane integration of the receptor Tom22, whereas assembly of the small Tom proteins depends on Sam37. Thus, the substrate specificity of SAM is not restricted to beta-barrel proteins but also includes the majority of alpha-helical Tom proteins.

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

    Science.gov (United States)

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

    2013-01-01

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

  16. 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.

  17. Method to synthesize metal chalcogenide monolayer nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-12-13

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

  18. Decaborane thiols as building blocks for self-assembled monolayers on metal surfaces.

    Science.gov (United States)

    Bould, Jonathan; Macháček, Jan; Londesborough, Michael G S; Macías, Ramón; Kennedy, John D; Bastl, Zdeněk; Rupper, Patrick; Baše, Tomáš

    2012-02-01

    Three nido-decaborane thiol cluster compounds, [1-(HS)-nido-B(10)H(13)] 1, [2-(HS)-nido-B(10)H(13)] 2, and [1,2-(HS)(2)-nido-B(10)H(12)] 3 have been characterized using NMR spectroscopy, single-crystal X-ray diffraction analysis, and quantum-chemical calculations. In the solid state, 1, 2, and 3 feature weak intermolecular hydrogen bonding between the sulfur atom and the relatively positive bridging hydrogen atoms on the open face of an adjacent cluster. Density functional theory (DFT) calculations show that the value of the interaction energy is approximately proportional to the number of hydrogen atoms involved in the interaction and that these values are consistent with a related bridging-hydrogen atom interaction calculated for a B(18)H(22)·C(6)H(6) solvate. Self-assembled monolayers (SAMs) of 1, 2, and 3 on gold and silver surfaces have been prepared and characterized using X-ray photoelectron spectroscopy. The variations in the measured sulfur binding energies, as thiolates on the surface, correlate with the (CC2) calculated atomic charge for the relevant boron vertices and for the associated sulfur substituents for the parent B(10)H(13)(SH) compounds. The calculated charges also correlate with the measured and DFT-calculated thiol (1)H chemical shifts. Wetting-angle measurements indicate that the hydrophilic open face of the cluster is directed upward from the substrate surface, allowing the bridging hydrogen atoms to exhibit a similar reactivity to that of the bulk compound. Thus, [PtMe(2)(PMe(2)Ph)(2)] reacts with the exposed and acidic B-H-B bridging hydrogen atoms of a SAM of 1 on a gold substrate, affording the addition of the metal moiety to the cluster. The XPS-derived stoichiometry is very similar to that for a SAM produced directly from the adsorption of [1-(HS)-7,7-(PMe(2)Ph)(2)-nido-7-PtB(10)H(11)] 4. The use of reactive boron hydride SAMs as templates on which further chemistry may be carried out is unprecedented, and the principle may be

  19. Fracture Characteristics of Monolayer CVD-Graphene

    OpenAIRE

    Hwangbo, Yun; Lee, Choong-Kwang; Kim, Sang-Min; Kim, Jae-Hyun; Kim, Kwang-Seop; Jang, Bongkyun; Lee, Hak-Joo; Lee, Seoung-Ki; Kim, Seong-Su; Ahn, Jong-Hyun; Lee, Seung-Mo

    2014-01-01

    We have observed and analyzed the fracture characteristics of the monolayer CVD-graphene using pressure bulge testing setup. The monolayer CVD-graphene has appeared to undergo environmentally assisted subcritical crack growth in room condition, i.e. stress corrosion cracking arising from the adsorption of water vapor on the graphene and the subsequent chemical reactions. The crack propagation in graphene has appeared to be able to be reasonably tamed by adjusting applied humidity and stress. ...

  20. Mass spectrometric analysis of monolayer protected nanoparticles

    Science.gov (United States)

    Zhu, Zhengjiang

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