Science.gov

Sample records for alkanethiolate self-assembled monolayers

  1. Frictional dynamics of fluorine-terminated alkanethiol self-assembled monolayers.

    PubMed

    Park, Byeongwon; Lorenz, Christian D; Chandross, Michael; Stevens, Mark J; Grest, Gary S; Borodin, Oleg A

    2004-11-01

    The frictional dynamics of fluorine-terminated alkanethiol (S(CH2)8CF3) self-assembled monolayers (SAMs) on gold are studied using molecular dynamics simulations. The simulations treat the interactions between two SAMs on flat surfaces. The structure and frictional behavior are investigated as a function of applied pressure (200 MPa to 1 GPa) for a shear velocity of 2 m/s and compared to methyl-terminated alkanethiol SAMs. The maximum adhesive pressure between the SAMs is 220 MPa for both end groups. In agreement with experiments on the molecular scale, the shear stress and the coefficient of friction for CF3-terminated alkanethiols are larger than for CH3-terminated alkanethiols. The main source for the difference is primarily the tighter packing of the fluorinated terminal group resulting in a higher degree of order. The molecular scale coefficient of friction is correlated with the degree of order among all the systems. PMID:15518487

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

    PubMed Central

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

    O'Dwyer, C.; Gay, G.; Viaris de Lesegno, B.; Weiner, J.; Mützel, M.; Haubrich, D.; Meschede, D.; Ludolph, K.; Georgiev, G.; Oesterschulze, E.

    2005-01-01

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

  4. Removal of self-assembled monolayers of alkanethiolates on gold by plasma cleaning

    NASA Astrophysics Data System (ADS)

    Raiber, Kevin; Terfort, Andreas; Benndorf, Carsten; Krings, Norman; Strehblow, Hans-Henning

    2005-12-01

    Plasmas of hydrogen or oxygen were used to remove self-assembled monolayers (SAMs) of alkanethiolates from gold surfaces. X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), ellipsometry, and contact angle measurements were used to compare the efficiency of the different plasmas and to explore their respective influence on the surface topology. Both plasmas were able to remove the SAM from the gold surface within less than 60 s. While the hydrogen plasma produces a de facto sulfur-free surface, oxygen plasma cleaning leads to an Au 2O 3 surface contaminated with oxidized sulfur species (probably sulfonates and sulfate). Nevertheless, the plasmas alter the roughness of the gold surfaces only marginally, as demonstrated by STM.

  5. Charge-transfer dynamics in azobenzene alkanethiolate self-assembled monolayers on gold

    NASA Astrophysics Data System (ADS)

    Gahl, Cornelius; Schmidt, Roland; Brete, Daniel; Paarmann, Stephanie; Weinelt, Martin

    2016-01-01

    We have studied the charge-transfer dynamics in azobenzene-functionalized alkanethiolate self-assembled monolayers. We compare the core-hole-clock technique, i.e., resonant vs. non-resonant contributions in the azobenzene autoionization of the Cls-π* core exciton, with the lifetime of a molecular resonance determined by two-photon photoemission spectroscopy using femtosecond laser pulses. Both techniques yield comparable charge-transfer times of 80 ± 20 fs for a linker consisting of three CH2 groups and one oxygen unit. Thus the quenching of the excitation is about one order of magnitude faster than the time required for the trans to cis isomerization of the azobenzene photoswitch in solution.

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

    PubMed Central

    2016-01-01

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

  7. Rapid Degradation of Alkanethiol-Based Self-Assembled Monolayers on Gold in Ambient Laboratory Conditions

    SciTech Connect

    Willey, T M; Vance, A L; van Buuren, T; Bostedt, C; Terminello, L J; Fadley, C S

    2004-07-21

    Self-assembled monolayers (SAMs) consisting of alkanethiols and similar sulfur-containing molecules on noble metal substrates are extensively used and explored for various chemical and biological surface-functionalization in the scientific community. SAMs consisting of thiol- or disulfide-containing molecules adsorbed on gold are commonly used due to their ease of preparation and stability. However, the gold-thiolate bond is easily and rapidly oxidized under ambient conditions, adversely affecting SAM quality and structure. Here, the oxidation of dodecanethiol on gold is explored for various 12-hour exposures to ambient laboratory air and light. SAM samples are freshly prepared, air-exposed, and stored in small, capped vials. X-ray photoelectron spectroscopy (XPS) reveals nearly complete oxidation of the thiolate in air-exposed samples, and a decrease in carbon signal on the surface. Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) at the Carbon K-edge shows a loss of upright orientational order upon air-exposure. Alternatively, the oxidation of the thiolate is minor when SAMs are stored in limited-air-containing small 15 ml vials. Thus, care must be taken to avoid SAM degradation by ensuring alkanethiolates on gold have sufficient durability for each intended environment and application.

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

    PubMed

    Engelkes, Vincent B; Frisbie, C Daniel

    2006-05-25

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

  9. Self-Assembled Monolayers of n-Alkanethiols Suppress Hydrogen Evolution and Increase the Efficiency of Rechargeable Iron Battery Electrodes

    SciTech Connect

    Malkhandi, S; Yang, B; Manohar, AK; Prakash, GKS; Narayanan, SR

    2013-01-09

    Iron-based rechargeable batteries, because of their low cost, eco-friendliness, and durability, are extremely attractive for large-scale energy storage. A principal challenge in the deployment of these batteries is their relatively low electrical efficiency. The low efficiency is due to parasitic hydrogen evolution that occurs on the iron electrode during charging and idle stand. In this study, we demonstrate for the first time that linear alkanethiols are very effective in suppressing hydrogen evolution on alkaline iron battery electrodes. The alkanethiols form self-assembled monolayers on the iron electrodes. The degree of suppression of hydrogen evolution by the alkanethiols was found to be greater than 90%, and the effectiveness of the alkanethiol increased with the chain length. Through steady-state potentiostatic polarization studies and impedance measurements on high-purity iron disk electrodes, we show that the self-assembly of alkanethiols suppressed the parasitic reaction by reducing the interfacial area available for the electrochemical reaction. We have modeled the effect of chain length of the alkanethiol on the surface coverage, charge-transfer resistance, and double-layer capacitance of the interface using a simple model that also yields a value for the interchain interaction energy. We have verified the improvement in charging efficiency resulting from the use of the alkanethiols in practical rechargeable iron battery electrodes. The results of battery tests indicate that alkanethiols yield among the highest faradaic efficiencies reported for the rechargeable iron electrodes, enabling the prospect of a large-scale energy storage solution based on low-cost iron-based rechargeable batteries.

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

    NASA Astrophysics Data System (ADS)

    Ramin, Leyla; Jabbarzadeh, Ahmad

    2012-11-01

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

  11. Bacterial adhesion to hydroxyl- and methyl-terminated alkanethiol self-assembled monolayers.

    PubMed Central

    Wiencek, K M; Fletcher, M

    1995-01-01

    The attachment of bacteria to solid surfaces is influenced by substratum chemistry, but to determine the mechanistic basis of this relationship, homogeneous, well-defined substrata are required. Self-assembled monolayers (SAMs) were constructed from alkanethiols to produce a range of substrata with different exposed functional groups, i.e., methyl and hydroxyl groups and a series of mixtures of the two. Percentages of hydroxyl groups in the SAMs and substratum wettability were measured by X-ray photoelectron spectroscopy and contact angles of water and hexadecane, respectively. SAMs exhibited various substratum compositions and wettabilities, ranging from hydrophilic, hydroxyl-terminated monolayers to hydrophobic, methyl-terminated monolayers. The kinetics of attachment of an estuarine bacterium to these surfaces in a laminar flow chamber were measured over periods of 120 min. The initial rate of net adhesion, the number of cells attached after 120 min, the percentage of attached cells that adsorbed or desorbed between successive measurements, and the residence times of attached cells were quantified by phase-contrast microscopy and digital image processing. The greatest numbers of attached cells occurred on hydrophobic surfaces, because (i) the initial rates of adhesion and the mean numbers of cells that attached after 120 min increased with the methyl content of the SAM and the contact angle of water and (ii) the percentage of cells that desorbed between successive measurements (ca. 2 min) decreased with increasing substratum hydrophobicity. With all surfaces, 60 to 80% of the cells that desorbed during the 120-min exposure period had residence times of less than 10 min, suggesting that establishment of firm adhesion occurred quickly on all of the test surfaces. PMID:7721687

  12. Structure and Phase Behavior of Mixed Self-Assembled Alkanethiolate Monolayers on Gold Nanoparticles: A Monte Carlo Study.

    PubMed

    Fetisov, Evgenii O; Siepmann, J Ilja

    2016-03-01

    Configurational-bias Monte Carlo (CBMC) simulations are carried out to investigate the structure and phase behavior of self-assembled monolayers consisting of equimolar alkanethiolate mixtures chemisorbed on the surface of gold nanoparticles. The simulations probe the effects of variations in the chain length, nanoparticle curvature, and exchange of alkanethiolates between nanoparticles. The TraPPE-UA force field is used for the alkanethiolates, whereas the nanoparticle is represented by gold atoms placed on the surface of a sphere. CBMC identity exchange moves are used to enhance sampling of the spatial distribution of the different ligands and to ensure that thermodynamic equilibrium is reached. At a temperature of 298 K, mixtures differing in length by four methylene units exhibit some degree of local segregation. In contrast, the hexanethiolate/tetradecanethiolate mixture yields Janus-like arrangement when the ligands are confined to a single nanoparticle but global demixing when the ligands are allowed to distribute between two nanoparticles. PMID:26702673

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

    NASA Astrophysics Data System (ADS)

    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.

  14. In vivo impedance evaluation of Au/PI microelectrode with surface modulated by alkanethiolate self-assembled monolayers.

    PubMed

    Lin, Hwa-Li; Lin, Chou-Ching K; Ju, Ming-Shaung; Liao, Jiunn-Der

    2011-02-01

    The goal of this study was to verify that a fully implanted microelectrode with modulated surface may have a reduced rising rate of total impedance and a longer life time. In the previous work, alkanethiolate self-assembled monolayers (SAMs) surface as protein-resistant spacer or cell-repulsive dense-packed spacer has been verified from in vitro experiments. In this study, microelectrodes with the same surface modulation were implanted into the subcutaneous layers of Wistar rats. Nine rats were implanted with the microelectrodes and the total impedance data were measured every 24 h for 2 weeks after implantation. An equivalent electrical circuit model of the electrode-tissue interface was established and parameters were estimated by using an optimization algorithm. Four out of nine rats had manifested acute inflammation reaction and the rests revealed only slight tissue response. Histological examination for the inflammatory group showed fibroblasts, macrophages, and polymorphonuclear leukocytes in adjacent to the electrode contact surface. In the inflammatory group, no significantly difference in total impedance was found in both types of electrodes. However, the trend of total impedance of SAMs-treated electrodes could maintain a steady state value after 1 week. For the non-inflammatory group, both types of electrodes could reduce the impedance value within implanted days. The tissue resistance might be related to the thickness of cells adhered upon the electrode contacts. PMID:20972888

  15. Effect of alkanethiol self-assembled monolayers on the plastic and elastic deformation of gold(111) films

    NASA Astrophysics Data System (ADS)

    Aponte, Milca I.

    Surface chemistry is known to affect the elastic deformation of nanocontacts, but its role in plastic deformation is less clear. Alkanethiol self-assembled monolayers (SAMs) were used to modify the surface energy and surface stress of Au(111) films. The chemical effect of this nanometer scale film on elastic and plastic deformation was investigated using nanoindentation combined with atomic force microscopy (AFM) imaging of indents. A range of maximum indentation displacements and SAM chain lengths were used. Comparisons were made between the mechanical response of the gold substrate alone and the gold modified with the different SAMs. The nanoindentation load-displacement curves and the mechanical properties were found to be dependent on the presence of the SAM. A decrease in the reduced elastic modulus was observed when indenting the SAM systems. The work of indentation and the hardness showed a similar effect with the SAM layer lowering hardness in both cases. Remarkably, the SAM was found to affect hardness, and hence plasticity, at indentation depths over 100 times the SAM thickness. Comparisons were made between the projected contact areas approximated using the Oliver and Pharr method with the actual areas directly measured by AFM analysis. This accounts for underestimation of the contact area due to pile-up of gold around the indent. AFM characterization of the residual nanoindentation impressions showed substantial differences between the indent shape and pile-up when comparing the gold to the gold plus SAM surfaces. The differences are more pronounced for the longer chain length SAM and as the indents become deeper. The SAM reduces the adhesion force between the indenter tip and surface which may affect the observed mechanical properties for shallow indents. For the deeper indentations the exothermic reaction of the alkanethiol molecules chemisorbed on the gold surface reduces the surface free energy of the gold substrate which favors the creation of new

  16. Theoretical study of the stereodynamics of CO collisions with CH3- and CF3-terminated alkanethiolate self-assembled monolayers.

    PubMed

    Alexander, William A; Morris, John R; Troya, Diego

    2009-04-23

    We present a classical-trajectory study of CO collisions with regular (CH3-terminated) and omega-fluorinated (CF3-terminated) alkanethiol self-assembled monolayers (SAMs) with a focus on analyzing the stereodynamics properties of the collision. The CO molecule is scattered with incident angles of either 30 degrees or 60 degrees with respect to the surface normal and with 60 kJ x mol(-1) collision energy, and we analyze final translational and rotational energy, mechanism of the collisions, and orientation and alignment of the rotational angular momentum. Analysis of the alignment of the final rotational angular momentum in collisions involving initially rotationally cold CO indicates a slight preference for "cartwheel" and "corkscrew" rotational motions. In contrast, collisions of initially excited CO slightly favor "helicopter" motion of the recoiling molecule. Moreover, studies of final orientation reveal that, while cartwheel "topspin" motion is favored for collisions in which initially cold CO becomes rotationally excited, no preferred handedness is observed when CO leaves the surfaces with "helicopter" motion. Analysis of trajectories involving initially rotationally excited CO in which the initial rotational angular momentum is aligned and/or oriented shows a non-negligible effect of the initial rotational motion on the dynamics of energy transfer. For instance, CO approaching the SAMs with helicopter motion retains a larger fraction of its initial rotation than molecules colliding with cartwheel-type motions. Conservation of the alignment and orientation of the initial rotational angular momentum vector is also enhanced with helicopter motion relative to cartwheel or random motions. The calculated trends in the stereodynamic properties for the two SAMs indicate that the CH3-SAM is effectively more corrugated than the CF3-SAM. PMID:19206227

  17. Empirical Evidence for Roughness-Dependent Limit in Observation of Odd-Even Effect in Wetting Properties of Polar Liquids on n-Alkanethiolate Self-Assembled Monolayers.

    PubMed

    Wang, Zhengjia; Chen, Jiahao; Oyola-Reynoso, Stephanie; Thuo, Martin

    2016-08-16

    Substrate roughness influences the wetting properties of self-assembled monolayers (SAMs), but details on this dependency at the sub-nanometer level are still lacking. This study investigates the effect of surface roughness on interfacial properties of n-alkanethiolate SAMs, specifically wetting, and confirms the predicted limit to the observation of the odd-even effect in hydrophobicity. This article studies static contact angles of polar and nonpolar probe liquids on a series of n-alkanethiolate SAMs on surfaces with tunable roughness. We prepared Ag surfaces with root-mean-square roughness (Rrms) of ∼0.6-2.2 nm and compared the wetting properties of n-alkanethiolate SAMs fabricated on these surfaces. We measured the static contact angles, θs, formed between SAM and probe liquids [water, glycerol, and hexadecane]. Hexadecane showed an odd-even effect on all surfaces irrespective of the degree of roughness. Polar liquids (water and glycerol), however, showed a dependency on the roughness of the substrate with an odd-even effect observable only on smooth, but not rougher (Rrms ≥ 1.15 nm), surfaces. These results confirm that the previously predicted limit to observation of the odd-even effect in hydrophobicity (here extended to polar liquids) is real. From the results with glycerol, we infer that this limit is not limited just to hydrophobicity but may extend to other polar liquids. Results from hexadecane, however, suggest that this limit may not be a universal property of the SAM. PMID:27448027

  18. Investigation of carboxylic-functionalized and n-alkanethiol self-assembled monolayers on gold and their application as pH-sensitive probes using scanning electrochemical microscopy

    NASA Astrophysics Data System (ADS)

    Boldt, Frank-Mario; Baltes, Norman; Borgwarth, Kai; Heinze, Jürgen

    2005-12-01

    We investigated the insulating properties of n-alkanethiol self-assembled monolayers (SAMs) of varying chain lengths [CH 3(CH 2) nSH; n = 7, 9, 11, 15] on polycrystalline gold electrodes using scanning electrochemical microscopy (SECM) and cyclic voltammetry. On the basis of SECM approach curves we examined the local ET through monolayers with increasing chain length in different redox mediators. We were able to distinguish the monolayers because of their different insulating properties and in addition, the status of SAM formation after immersion times of 2 h and 24 h, respectively, could be observed. Cyclic voltammetric measurements confirmed the SECM results and were in good agreement with other experimental data in the literature. High-resolution SECM images of hexadecanethiol SAM micropatterns down to 4 μm in diameter formed by microcontact printing (μCP) were obtained in the feedback mode. Furthermore, we studied the ET and the pH-dependent behavior of mercaptoundecanoic acid monolayers on gold at varying pH and in different redox mediator solutions to test their application as pH-sensors. An additional influence on the ET could be established based on Coulomb/ionic interactions between the charged monolayer and the redox mediator at changing pH. Therefore, we present a new approach for designing pH-sensitive SECM probes using 11-mercaptoundecanoic acid-coated 10 μm-diameter gold ultramicroelectrodes (HOOC-C 11SH/Au UMEs) in aqueous solutions containing hexacyanoferrate. Voltammetric measurements at HOOC-C 11SH/Au UMEs at different pH values enabled us to estimate the degree of dissociation of the carboxylic-terminated monolayers.

  19. Binary self-assembled monolayers of alkanethiols on gold: deposition from solution versus microcontact printing and the study of surface nanobubbles.

    PubMed

    Bayat, Haider; Tranchida, Davide; Song, Bo; Walczyk, Wiktoria; Sperotto, Elena; Schönherr, Holger

    2011-02-15

    The coadsorption of alkanethiols on noble metals has been recognized for a long time as a suitable means of affording surfaces with systematically varied wettability and other properties. In this article, we report on a comparative study of the composition of the mixed self-assembled monolayers (SAMs) obtained (i) by the coadsorption of octadecanethiol (ODT) and 16-mercaptohexadecanoic acid (MHDA) from ethanol and chloroform onto gold substrates and (ii) by microcontact printing using poly(dimethyl siloxane) (PDMS) stamps. SAMs prepared by coadsorption from solution showed a preferential adsorption of ODT for both solvents, but this trend was reversed in microcontact-printed SAMs when using chloroform as a solvent, as evidenced by contact angle and Fourier transform infrared (FTIR) spectroscopy measurements. An approximately linear relationship between the static contact angle and the degree of swelling with different solvents was observed, which suggests that the surface composition can be controlled by the interaction of the solvent and the PDMS elastomer. The altered preference is attributed to the different partitioning of the two thiols into solvent-swelled PDMS, as shown by (1)H NMR spectroscopy. Finally, molecularly mixed binary SAMs on ODT and MHDA on template-stripped gold were applied to study the effect of surface nanobubbles on wettability by atomic force microscopy (AFM). With a decreasing macroscopic contact angle measured through water, the nanoscopic contact angle was found to decrease as well. PMID:21117682

  20. Self-assembled monolayers of alkanethiols on gold prepared in a hexagonal lyotropic liquid crystalline phase of Triton X-100/water system.

    PubMed

    Ganesh, V; Lakshminarayanan, V

    2006-02-14

    In this paper, we have reported a new method of preparing self-assembled monolayers (SAMs) of decanethiol and hexadecanethiol on gold surface by using a lyotropic liquid crystalline phase as an adsorbing medium. The stability and blocking ability of these SAMs were characterized using grazing angle Fourier transform infrared (FTIR) spectroscopy and electrochemical techniques such as cyclic voltammetry and electrochemical impedance spectroscopy. The lyotropic liquid crystalline medium possesses a hexagonal structure consisting of a nonionic surfactant Triton X-100, water, and the corresponding thiol, which provides a highly hydrophobic environment to solubilize the alkanethiols and later to facilitate their delivery to the gold surface. We find that the SAMs formed from the hexagonal liquid crystalline phase are highly compact and have excellent electrochemical blocking ability towards the redox probes compared to conventional SAMs prepared from commonly used organic solvents such as ethanol. From the impedance studies, we have determined the capacitance of the monolayer-coated electrodes and the surface coverage of the SAM, which has been found to be >99.98% on gold surface. We have also estimated the extent of ionic permeability through the film and measured the rate constants for the redox reactions on the SAM-modified electrodes. Our results show that the rate constants of [Fe(CN)6](3-/4-) and [Ru(NH3)6](2+/3+) redox couples are very much lower in the case of monolayers prepared in liquid crystalline phase compared to the SAM formed in 1 mM thiol in ethanol solution, suggesting a better blocking ability of the SAMs in the former case. From the grazing angle FTIR spectroscopic studies and capacitance measurements, we have ruled out any coadsorption of surfactant molecules on the Au surface. These results suggest that SAMs of very low defect density and extremely low ionic permeability can be obtained when a hexagonal lyotropic liquid crystalline phase is used as

  1. Gold-Adatom-Mediated Bonding in Self-Assembled Short-Chain Alkanethiolate Species on the Au(111) Surface

    SciTech Connect

    Maksymovych, P.; Sorescu, D.C.; Yates, J.T., Jr.

    2006-10-06

    Microscopic evidence for Au-adatom-induced self-assembly of alkanethiolate species on the Au(111) surface is presented. Based on STM measurements and density-functional theory calculations, a new model for the low-coverage self-assembled monolayer of alkanethiolate on the Au(111) surface is developed, which involves the adsorbate complexes incorporating Au adatoms. It is also concluded that the Au(111) herringbone reconstruction is lifted by the alkanethiolate self-assembly because the reconstructed surface layer provides reactive Au adatoms that drive self-assembly.

  2. Interfacial structure in thin water layers formed by forced dewetting on self-assembled monolayers of omega-terminated alkanethiols on Ag.

    PubMed

    Tiani, Domenic J; Yoo, Heemin; Mudalige, Anoma; Pemberton, Jeanne E

    2008-12-01

    A method for the spectroscopic characterization of interfacial fluid molecular structure near solid substrates is reported. The thickness and interfacial molecular structure of residual ultrathin D20 films remaining after forced dewetting on alkanethiolate self-assembled monolayers (SAMs) of 11 1-mercaptoundecanoic acid (11-MUA), 11-mercaptoundecanol (11-MUD), and undecanethiol (UDT) on Ag are investigated using ellipsometry and surface Raman spectroscopy. The residual film thickness left after withdrawal is greater on hydrophilic SAMs than on hydrophobic SAMs. This behavior is rationalized on the basis of differing degrees of fluid slip within the interfacial region due to different interfacial molecular structure. The v(O-D) regions of surface Raman spectra clearly indicate unique interfacial molecular properties within these films that differ from bulk D20. Although the residual films are created by shear forces and Marangoni flow at the three-phase line during the forced dewetting process, the nature of the films sampled optically must also be considered from the standpoint of thin film stability after dewetting. Thus, the resulting D20 films exist in vastly different morphologies depending on the nature of the water-SAM interactions. Residual D20 is proposed to exist as small nanodroplets on UDT surfaces due tospontaneous rupture of the film after dewetting. In contrast, on 11-MUD and 11-MUA surfaces, these films exist in a metastable state that retains their conformal nature on the underlying modified surface. Analysis of the peak intensity ratios of the so-called "ice-like" to "liquid-like" v(O-D) modes suggests more ice-like D20 character near 11-MUD surfaces, but more liquid-like character near 11-MUA and UDT surfaces. The creation of residual ultrathin films by forced dewetting is thus demonstrated to be a powerful method for characterizing interfacial molecular structure of fluids near a solid substrate under ambient conditions of temperature and

  3. Scanning tunneling microscopy studies of growth medium & temperature dependent structural phases of alkanethiol self-assembled monolayers, reactive self-assembled monolayers, & flat gold nanoparticle/indium tin oxide substrates and a scanning surface photovoltage microscopy study for local mechanical stress characterization in complementary metal oxide semiconductor devices

    NASA Astrophysics Data System (ADS)

    Dahanayaka, Dahanayaka Liyanage Daminda Hemal

    Self-assembled monolayers (SAMs) of alkanethiolates on Au(111) represent promising platforms to study the molecular surfaces and interfaces for applications ranging from molecular electronics, nanophotonics to biology. Understanding the effect of growth conditions on SAMs particularly on their structural features is important from both fundamental and applied points of view. Knowledge of SAM structural features and structural phase transitions provides important insights into molecular packing for the control of the molecular self-assembly. We compared SAMs grown from different media, from 1 mM C10 solution in decalin, hexadecane and triethylene glycol and from C10 vapor. We present a molecularly-resolved scanning tunneling microscopy study showing the dependence of the SAM structure on the growth conditions. We have established conditions for making samples almost vacancy islands (VI) free with very large SAM domains of (2✓3 x 3)rect. superstructure and (✓3 x 4✓3)R30° striped-phase and investigated the orientation of low-index step edges of Au(111) for normal and striped-phase SAMs. We showed that the striped phase is stable to converting to (2✓3 x 3)rect. below 40°C. We demonstrate that flat gold nanoparticles (FGNPs) supported on indium tin oxide glass (ITO) are excellent substrates for molecularly-resolved STM imaging of alkanethiol SAMs. Nanoparticles were characterized using STM, TEM, and SEM techniques. Surface treatment techniques, Ar/O2 and H 2 plasma treatments, dry thermal annealing and exposures to UV/O 3, were used to prepare the surfaces of FGNPs supported on ITO and Au/mica substrates for high-resolution STM imaging of alkanethiol SAMs. We developed a convergent approach to functionalize SAM surfaces. Ordered mixed monolayers comprised of alkanethiols and azidoalkanethiols islands are formed and subsequent IMesCuIBr catalyzed [3+2] "click" cycloaddition reaction with substituted alkyne introduced dilute substituent onto the ordered surface

  4. Multifunctional self-assembled monolayers

    SciTech Connect

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

    1996-06-01

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

  5. Structure-Dependent Viscoelastic Properties of C(9)-Alkanethiol Monolayers

    SciTech Connect

    Mayer, Thomas M.; Michalske, Terry A.; Shinn, Neal D.

    1999-08-10

    Quartz crystal microbalance techniques and in situ spectroscopic ellipsometry are used to probe the structure-dependent intrinsic viscoelastic properties of self-assembled CH{sub 3}(CH{sub 2}){sub 8}SH alkanethiol monolayer adsorbed from the gas phase onto Au(111)-textured substrates. Physisorbed molecules, mixed chemisorbed-fluid/solid phases and solid-phase domain boundaries make sequentially dominant contributions to the measured energy dissipation in the growing monolayer. Deviations from Langmuir adsorption kinetics reveal a precursor-mediated adsorption channel. These studies reveal the impact of structural heterogeneity in tribological studies of monolayer lubricants.

  6. Water in nanoconfinement between hydrophilic self-assembled monolayers.

    PubMed

    Lane, J Matthew D; Chandross, Michael; Stevens, Mark J; Grest, Gary S

    2008-05-20

    Molecular dynamics (MD) simulations of water confined to subnanometer thicknesses between carboxyl-terminated alkanethiol self-assembled monolayers (SAMs) on gold were performed to address conflicts in the literature on the structure and response of water in confinement. The amount of water was varied to yield submonolayer to bilayer structures. The orientation of the water is affected by the confinement, especially in the submonolayer case. We find that the diffusion coefficient decreases as the film becomes thinner and at higher pressures. However, in all cases studied, liquid diffusion is always found. At maximal suppression, the diffusion constant is 2 orders of magnitude smaller than the bulk value. PMID:18412381

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

    NASA Astrophysics Data System (ADS)

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

    1996-12-01

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

  8. Single photon ionisation of self assembled monolayers

    NASA Astrophysics Data System (ADS)

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

    2002-05-01

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

  9. Directing reaction pathways by catalyst active-site selection using self-assembled monolayers.

    PubMed

    Pang, Simon H; Schoenbaum, Carolyn A; Schwartz, Daniel K; Medlin, J Will

    2013-01-01

    One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism. PMID:24025780

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

    PubMed

    Smith, Jeremy G; Jain, Prashant K

    2016-08-24

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

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

    PubMed

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

    2009-01-01

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

  12. Fast self-assembly kinetics of alkanethiols on gold nanoparticles: simulation and characterization by localized surface plasmon resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Asiaei, Sasan; Denomme, Ryan C.; Marr, Chelsea; Nieva, Patricia M.; Vijayan, Mathilakath M.

    2012-03-01

    This study demonstrates improved kinetics for the formation of self-assembled monolayers (SAMs) of alkanethiols on gold nanoparticle substrates. A computational model was developed to predict SAM growth kinetics. Based on the predictions from the model, SAMs of 11-mercaptoundecanoic acid (11-MUA) and 1-octanethiol (1-OT) were formed by incubation of gold nanoparticle chips in an ethanolic 10 mM solution within 20 min. The performance of this novel rapid SAM formation protocol was compared with a conventional 24 hour incubation protocol. Binding capacity of the alkanethiol SAM was investigated for a 20 min incubation protocol using biotin-streptavidin. For this purpose, the SAM loaded gold nanoparticle chips were modified with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) to allow attachment of EZ-Link amine PEG3 biotin to the 11-MUA molecules. Binding reactions were monitored in real time using localized surface plasmon resonance (LSPR) spectroscopy. The resulting LSPR absorbance peak shift was comparable to the experimental results for biotin-streptavidin reported in literature. Results of this study suggest that formation of a high quality alkanethiol SAM within 20 min on gold nanoparticles surfaces is possible and could greatly reduce the time and cost compared to conventional 24 h incubation protocols.

  13. Ionically self-assembled monolayers (ISAMs)

    NASA Astrophysics Data System (ADS)

    Janik, John

    2001-04-01

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

  14. Photocatalytic nanolithography of self-assembled monolayers and proteins.

    PubMed

    Ul-Haq, Ehtsham; Patole, Samson; Moxey, Mark; Amstad, Esther; Vasilev, Cvetelin; Hunter, C Neil; Leggett, Graham J; Spencer, Nicholas D; Williams, Nicholas H

    2013-09-24

    Self-assembled monolayers of alkylthiolates on gold and alkylsilanes on silicon dioxide have been patterned photocatalytically on sub-100 nm length-scales using both apertured near-field and apertureless methods. Apertured lithography was carried out by means of an argon ion laser (364 nm) coupled to cantilever-type near-field probes with a thin film of titania deposited over the aperture. Apertureless lithography was carried out with a helium-cadmium laser (325 nm) to excite titanium-coated, contact-mode atomic force microscope (AFM) probes. This latter approach is readily implementable on any commercial AFM system. Photodegradation occurred in both cases through the localized photocatalytic degradation of the monolayer. For alkanethiols, degradation of one thiol exposed the bare substrate, enabling refunctionalization of the bare gold by a second, contrasting thiol. For alkylsilanes, degradation of the adsorbate molecule provided a facile means for protein patterning. Lines were written in a protein-resistant film formed by the adsorption of oligo(ethylene glycol)-functionalized trichlorosilanes on glass, leading to the formation of sub-100 nm adhesive, aldehyde-functionalized regions. These were derivatized with aminobutylnitrilotriacetic acid, and complexed with Ni(2+), enabling the binding of histidine-labeled green fluorescent protein, which yielded bright fluorescence from 70-nm-wide lines that could be imaged clearly in a confocal microscope. PMID:23971891

  15. Photocatalytic Nanolithography of Self-Assembled Monolayers and Proteins

    PubMed Central

    2013-01-01

    Self-assembled monolayers of alkylthiolates on gold and alkylsilanes on silicon dioxide have been patterned photocatalytically on sub-100 nm length-scales using both apertured near-field and apertureless methods. Apertured lithography was carried out by means of an argon ion laser (364 nm) coupled to cantilever-type near-field probes with a thin film of titania deposited over the aperture. Apertureless lithography was carried out with a helium–cadmium laser (325 nm) to excite titanium-coated, contact-mode atomic force microscope (AFM) probes. This latter approach is readily implementable on any commercial AFM system. Photodegradation occurred in both cases through the localized photocatalytic degradation of the monolayer. For alkanethiols, degradation of one thiol exposed the bare substrate, enabling refunctionalization of the bare gold by a second, contrasting thiol. For alkylsilanes, degradation of the adsorbate molecule provided a facile means for protein patterning. Lines were written in a protein-resistant film formed by the adsorption of oligo(ethylene glycol)-functionalized trichlorosilanes on glass, leading to the formation of sub-100 nm adhesive, aldehyde-functionalized regions. These were derivatized with aminobutylnitrilotriacetic acid, and complexed with Ni2+, enabling the binding of histidine-labeled green fluorescent protein, which yielded bright fluorescence from 70-nm-wide lines that could be imaged clearly in a confocal microscope. PMID:23971891

  16. Etchant-free graphene transfer using facile intercalation of alkanethiol self-assembled molecules at graphene/metal interfaces

    NASA Astrophysics Data System (ADS)

    Ohtomo, Manabu; Sekine, Yoshiaki; Wang, Shengnan; Hibino, Hiroki; Yamamoto, Hideki

    2016-06-01

    We report a novel etchant-free transfer method of graphene using the intercalation of alkanethiol self-assembled monolayers (SAMs) at the graphene/Cu interfaces. The early stage of intercalation proceeds through graphene grain boundaries or defects within a few seconds at room temperature until stable SAMs are formed after a few hours. The formation of SAMs releases the compressive strain of graphene induced by Cu substrates and make graphene slightly n-doped due to the formation of interface dipoles of the SAMs on metal surfaces. After SAM formation, the graphene is easily delaminated off from the metal substrates and transferred onto insulating substrates. The etchant-free process enables us to decrease the density of charged impurities and the magnitude of potential fluctuation in the transferred graphene, which suppress scattering of carriers. We also demonstrate the removal of alkanethiol SAMs and reuse the substrate. This method will dramatically reduce the cost of graphene transfer, which will benefit industrial applications such as of graphene transparent electrodes.We report a novel etchant-free transfer method of graphene using the intercalation of alkanethiol self-assembled monolayers (SAMs) at the graphene/Cu interfaces. The early stage of intercalation proceeds through graphene grain boundaries or defects within a few seconds at room temperature until stable SAMs are formed after a few hours. The formation of SAMs releases the compressive strain of graphene induced by Cu substrates and make graphene slightly n-doped due to the formation of interface dipoles of the SAMs on metal surfaces. After SAM formation, the graphene is easily delaminated off from the metal substrates and transferred onto insulating substrates. The etchant-free process enables us to decrease the density of charged impurities and the magnitude of potential fluctuation in the transferred graphene, which suppress scattering of carriers. We also demonstrate the removal of alkanethiol

  17. Etchant-free graphene transfer using facile intercalation of alkanethiol self-assembled molecules at graphene/metal interfaces.

    PubMed

    Ohtomo, Manabu; Sekine, Yoshiaki; Wang, Shengnan; Hibino, Hiroki; Yamamoto, Hideki

    2016-06-01

    We report a novel etchant-free transfer method of graphene using the intercalation of alkanethiol self-assembled monolayers (SAMs) at the graphene/Cu interfaces. The early stage of intercalation proceeds through graphene grain boundaries or defects within a few seconds at room temperature until stable SAMs are formed after a few hours. The formation of SAMs releases the compressive strain of graphene induced by Cu substrates and make graphene slightly n-doped due to the formation of interface dipoles of the SAMs on metal surfaces. After SAM formation, the graphene is easily delaminated off from the metal substrates and transferred onto insulating substrates. The etchant-free process enables us to decrease the density of charged impurities and the magnitude of potential fluctuation in the transferred graphene, which suppress scattering of carriers. We also demonstrate the removal of alkanethiol SAMs and reuse the substrate. This method will dramatically reduce the cost of graphene transfer, which will benefit industrial applications such as of graphene transparent electrodes. PMID:27198918

  18. Self-assembled monolayers of NH2-terminated thiolates: order, pKa, and specific adsorption.

    PubMed

    Marmisollé, Waldemar A; Capdevila, Daiana A; de la Llave, Ezequiel; Williams, Federico J; Murgida, Daniel H

    2013-04-30

    Self-assembled monolayers (SAMs) of amino-terminated alkanethiols on Au were characterized by a combination of electrochemical (LSV, CV, and EIS) and spectroscopic (XPS and SER) techniques. Clear correlations were obtained between the apparent surface pKa values determined by impedimetric titrations and order parameters such as the content of trans conformers in the SAMs. These results contrast with previous studies that exhibit dispersions of up to 6 pH units in the reported pKa values. In addition, we determined that inorganic and organic phosphate species bind specifically to these SAMs mediating adsorption and heterogeneous electron transfer of positively charged macromolecules such as cytochrome c. PMID:23560885

  19. Self-Assembled Monolayers as Templates for Heme Crystallization

    SciTech Connect

    Wang, Xuefeng; Ingall, Ellery; Lai, Barry; Stack, Andrew G; Allard Jr, Lawrence Frederick

    2010-01-01

    Homogeneous self-assembled monolayers (SAMs) of alkanethiols (HS(CH{sub 2}){sub n}X) on Au(111) were used as substrates for crystallization of ferriprotoporphyrin IX (heme) in acidic aqueous solution. Different terminal functional groups (X = OH, COOH, NH{sub 2}, CH{sub 3}) were used on the SAMs as models of sites where heme crystallization takes place in blood-feeding organisms. Atomic force microscopy, X-ray diffraction (XRD), and X-ray absorption near edge spectroscopy (XANES) were employed to characterize particle morphology, density, crystallographic orientation, and the coordination environment. It was found that the morphology and extent of growth of particulates were strongly affected by the environment in which they crystallize. As has been previously observed, acicular crystals form in DMSO-methanol solution, whereas irregular aggregates of crystals form in acidic aqueous solution. Here tabular crystals were found to form on -NH{sub 2} and -OH terminated SAMs, whereas inclined crystals formed on -COOH and -CH{sub 3} terminated substrates. Particulate coverage on these SAMs decreased in the order of -NH{sub 2}, -COOH, -CH{sub 3}, and -OH. Chloroquine, a widely used antimalaria drug, slowed particle nucleation rate on the SAMs with varying efficacy but was most efficient on the -COOH SAM. XANES measurements showed that the coordination environment surrounding iron in the particles was found to be the same, regardless of the preparation method and matches existing spectra of hemozoin produced in vivo and synthetic {beta}-hematin. Different crystallographic planes were found to be expressed depending on the identity of the SAM using XRD. The interaction between the terminal functional group of the SAM and the density and orientation of crystals is discussed.

  20. Self-Assembled Monolayers as Templates for Heme Crystallization.

    SciTech Connect

    Wang, Xuefeng; Ingall, Ellery; Lai, Barry; Stack, Andrew G

    2010-01-01

    Homogeneous self-assembled monolayers (SAMs) of alkanethiols (HS(CH{sub 2}){sub n}X) on Au(111) were used as substrates for crystallization of ferriprotoporphyrin IX (heme) in acidic aqueous solution. Different terminal functional groups (X = OH, COOH, NH{sub 2}, CH{sub 3}) were used on the SAMs as models of sites where heme crystallization takes place in blood-feeding organisms. Atomic force microscopy, X-ray diffraction (XRD), and X-ray absorption near edge spectroscopy (XANES) were employed to characterize particle morphology, density, crystallographic orientation, and the coordination environment. It was found that the morphology and extent of growth of particulates were strongly affected by the environment in which they crystallize. As has been previously observed, acicular crystals form in DMSO-methanol solution, whereas irregular aggregates of crystals form in acidic aqueous solution. Here tabular crystals were found to form on -NH{sub 2} and -OH terminated SAMs, whereas inclined crystals formed on -COOH and -CH{sub 3} terminated substrates. Particulate coverage on these SAMs decreased in the order of -NH{sub 2}, -COOH, -CH{sub 3}, and -OH. Chloroquine, a widely used antimalaria drug, slowed particle nucleation rate on the SAMs with varying efficacy but was most efficient on the -COOH SAM. XANES measurements showed that the coordination environment surrounding iron in the particles was found to be the same, regardless of the preparation method and matches existing spectra of hemozoin produced in vivo and synthetic {beta}-hematin. Different crystallographic planes were found to be expressed depending on the identity of the SAM using XRD. The interaction between the terminal functional group of the SAM and the density and orientation of crystals is discussed.

  1. Backfilled, self-assembled monolayers and methods of making same

    DOEpatents

    Fryxell, Glen E.; Zemanian, Thomas S.; Addleman, R. Shane; Aardahl, Christopher L.; Zheng, Feng; Busche, Brad; Egorov, Oleg B.

    2009-06-30

    Backfilled, self-assembled monolayers and methods of making the same are disclosed. The self-assembled monolayer comprises at least one functional organosilane species and a substantially random dispersion of at least one backfilling organosilane species among the functional organosilane species, wherein the functional and backfilling organosilane species have been sequentially deposited on a substrate. The method comprises depositing sequentially a first organosilane species followed by a backfilling organosilane species, and employing a relaxation agent before or during deposition of the backfilling organosilane species, wherein the first and backfilling organosilane species are substantially randomly dispersed on a substrate.

  2. A SERS study of the molecular structure of alkanethiol monolayers on Ag nanocubes in the presence of aqueous glucose

    NASA Astrophysics Data System (ADS)

    Rycenga, Matthew; McLellan, Joseph M.; Xia, Younan

    2008-09-01

    We report progress towards the surface-enhanced Raman scattering (SERS) characterization of self-assembled monolayers (SAMs) on uniform Ag nanocubes. This study quantifies changes in the SAMs induced by the presence of aqueous glucose. The SAMs were prepared from dodecanethiol and they were representative of highly ordered monolayers as indicated by SERS analysis. We examined the SAMs' response to glucose and observed conformational changes in the alkanethiolate SAMs. Analysis of the trans and gauche bands as well as the C-H stretching modes of the SAMs suggests that the analyte-SAM interactions were superficial and there was no penetration for the glucose molecules into the monolayers.

  3. A SERS study of the molecular structure of alkanethiol monolayers on Ag nanocubes in the presence of aqueous glucose

    PubMed Central

    Rycenga, Matthew; McLellan, Joseph M.; Xia, Younan

    2008-01-01

    We report progress towards the surface-enhanced Raman scattering (SERS) characterization of self-assembled monolayers (SAMs) on uniform Ag nanocubes. This study quantifies changes in the SAMs induced by the presence of aqueous glucose. The SAMs were prepared from dodecanethiol and they were representative of highly ordered monolayers as indicated by SERS analysis. We examined the SAMs response to glucose and observed conformational changes in the alkanethiolate SAMs. Analysis of the trans and gauche bands as well as the C-H stretching modes of the SAMs suggest that the analyte-SAM interactions were superficial and there was no penetration for the glucose molecules into the monolayers. PMID:20160847

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

    PubMed

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

    2005-03-01

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

  5. Actinide Sequestration Using Self-Assembled Monolayers on Mesoporous Supports

    SciTech Connect

    Fryxell, Glen E.; Lin, Yuehe; Fiskum, Sandra K.; Birnbaum, Jerome C.; Wu, Hong; Kemner, K. M.; Kelly, Shelley

    2005-03-01

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

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

    PubMed

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

    2012-11-27

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

  7. Conformation-dependent Molecular Orientation Deduced from First-principles Modeling of Oligo(ethylene glycol)-terminated and Amide Group Containing Alkanethiolates Self-assembled on Gold

    NASA Astrophysics Data System (ADS)

    Malysheva, L.; Onipko, A.; Valiokas, R.; Liedberg, B.

    2005-09-01

    We report orientation angles for the alkyl chain, amide group, and oligo(ethylene glycol) (OEG) portion within self-assembled monolayers (SAMs) of OEG-terminated and amide containing alkanethiolates which, depending on the OEG length and substrate temperature, display unique conformations — all-trans or helical. Optimized geometries of the molecular constituents, characteristic vibration frequencies and transition dipole moments are obtained by using DFT methods with gradient corrections. These ab initio data are subsequently used to simulate infrared reflection-absorption (RA) spectra associated with different conformations and orientations. The obtained results have generated a deeper knowledge of the internal SAM structure, which is crucial for understanding phase and folding characteristics, interaction with water and ultimately the protein repellent properties of OEG-containing SAMs.

  8. A Simple Bioconjugate Attachment Protocol for Use in Single Molecule Force Spectroscopy Experiments Based on Mixed Self-Assembled Monolayers

    PubMed Central

    Attwood, Simon J.; Simpson, Anna M. C.; Stone, Rachael; Hamaia, SamirW.; Roy, Debdulal; Farndale, RichardW.; Ouberai, Myriam; Welland, Mark E.

    2012-01-01

    Single molecule force spectroscopy is a technique that can be used to probe the interaction force between individual biomolecular species. We focus our attention on the tip and sample coupling chemistry, which is crucial to these experiments. We utilised a novel approach of mixed self-assembled monolayers of alkanethiols in conjunction with a heterobifunctional crosslinker. The effectiveness of the protocol is demonstrated by probing the biotin-avidin interaction. We measured unbinding forces comparable to previously reported values measured at similar loading rates. Specificity tests also demonstrated a significant decrease in recognition after blocking with free avidin. PMID:23202965

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

    PubMed

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

    2009-03-01

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

  10. Electrochemical Properties of Organosilane Self Assembled Monolayers on Aluminum 2024

    NASA Technical Reports Server (NTRS)

    Hintze, Paul E.; Calle, Luz Marina

    2004-01-01

    Self assembled monolayers are commonly used to modify surfaces. Within the last 15 years, self assembled monolayers have been investigated as a way to protect from corrosion[1,2] or biofouling.[3] In this study, self assembled monolayers of decitriethoxysilane (C10H21Si(OC2H5)3) and octadecyltriethoxysilane (C18H37Si(OC2H5)3) were formed on aluminum 2024-T3. The modified surfaces and bare Al 2024 were characterized by dynamic water contact angle measurements, x-ray photoelectron spectroscopy (XIPS) and infrared spectroscopy. Electrochemical impedance spectroscopy (EIS) in 0.5 M NaCl was used to characterize the monolayers and evaluate their corrosion protection properties. The advancing water contact angle and infrared measurements show that the mono layers form a surface where the hydrocarbon chains are packed and oriented away from the surface, consistent with what is found in similar systems. The contact angle hysteresis measured in these systems is relatively large, perhaps indicating that the hydrocarbon chains are not as well packed as monolayers formed on other substrates. The results of the EIS measurements were modeled using a Randle's circuit modified by changing the capacitor to a constant phase element. The constant phase element values were found to characterize the monolayer. The capacitance of the monolayer modified surface starts lower than the bare Al 2024, but approaches values similar to the bare Al 2024 within 24 hours as the monolayer is degraded. The n values found for bare Al 2024 quickly approach the value of a true capacitor and are greater than 0.9 within hours after the start of exposure. For the monolayer modified structure, n can stay lower than 0.9 for a longer period of time. In fact, n for the monolayer modified surfaces is different from the bare surface even after the capacitance values have converged. This indicates that the deviation from ideal capacitance is the most sensitive indicator of the presence of the monolayer.

  11. Molecular gated transistors: Role of self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Shaya, O.; Halpern, E.; Khamaisi, B.; Shaked, M.; Usherenko, Y.; Shalev, G.; Doron, A.; Levy, I.; Rosenwaks, Y.

    2010-07-01

    In order to understand the biosensing mechanism of field-effect based biosensors and optimize their performance, the effect of each of its molecular building block must be understood. In this work the gating effect of self-assembled linker molecules on field-effect transistor was studied in detail. We have combined Kelvin probe force microscopy, current-voltage measurements, capacitance-voltage measurements, equivalent circuit modeling and device simulations in order to trace the mechanism of silicon-on-insulator biological field-effect transistors. The measurements were conducted on the widely used linker molecules (3-aminopropyl)-trimethoxysilane (APTMS) and 11-aminoundecyl-triethoxysilane (AUTES), which were self-assembled on ozone activated silicon oxide surface covering the transistor channel. In a dry environment, the work function of the modified silicon oxide decreased by more than 1.5 eV, and the transistor threshold voltage increased by about 30 V following the self-assembly. A detailed analysis indicates that these changes are due to negative induced charges on the top dielectric layer, and an effective dipole due to the polar monolayer. However, the self-assembly did not change the silicon flat-band voltage when in contact with an electrolyte. This is attributed to electrostatic screening by the electrolyte.

  12. Self assembled monolayers of octadecyltrichlorosilane for dielectric materials

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  13. Self assembly of highly-ordered nanoparticle monolayers.

    SciTech Connect

    Bigioni, T. P.; Lin, X.-M.; Nguyen, T. T.; Corwin, E. I.; Witten, T. A.; Jaeger, H. M.; Univ. of Chicago

    2006-01-01

    When a drop of a colloidal solution of nanoparticles dries on a surface, it leaves behind coffee-stain-like rings of material with lace-like patterns or clumps of particles in the interior. These non-uniform mass distributions are manifestations of far-from-equilibrium effects, such as fluid flows and solvent fluctuations during late-stage drying. However, recently a strikingly different drying regime promising highly uniform, long-range-ordered nanocrystal monolayers has been found. Here we make direct, real-time and real-space observations of nanocrystal self-assembly to reveal the mechanism. We show how the morphology of drop-deposited nanoparticle films is controlled by evaporation kinetics and particle interactions with the liquid-air interface. In the presence of an attractive particle-interface interaction, rapid early-stage evaporation dynamically produces a two-dimensional solution of nanoparticles at the liquid-air interface, from which nanoparticle islands nucleate and grow. This self-assembly mechanism produces monolayers with exceptional long-range ordering that are compact over macroscopic areas, despite the far-from-equilibrium evaporation process. This new drop-drying regime is simple, robust and scalable, is insensitive to the substrate material and topography, and has a strong preference for forming monolayer films. As such, it stands out as an excellent candidate for the fabrication of technologically important ultra thin film materials for sensors, optical devices and magnetic storage media.

  14. Self-assembly of Epitaxial Monolayers for Vacuum Wafer Bonding.

    NASA Astrophysics Data System (ADS)

    Altfeder, Igor; Huang, Biqin; Appelbaum, Ian; Walker, Barry

    2007-03-01

    Self-assembled epitaxial metal monolayers can be used for hetero-integration of mismatched semiconductors, leading to simultaneously low interfacial resistance and high optical transparency. Lattice-mismatched wafers of Si(100) and Si(111) were bonded at room temperature in situ after vacuum deposition of a single atomic layer of Ag on them. The interfacial resistance was measured to be 3.9x 10-4 ohm. cm^ 2 and the optical transmission of the interface at 2500 nm is approximately 98%. We discuss the important role of electron confinement in ultrathin Ag layers as a possible contributor to the bonding energy.

  15. Self-assembly of epitaxial monolayers for vacuum wafer bonding

    NASA Astrophysics Data System (ADS)

    Altfeder, Igor; Huang, Biqin; Appelbaum, Ian; Walker, B. C.

    2006-11-01

    Self-assembled epitaxial metal monolayers can be used for heterointegration of mismatched semiconductors, leading to simultaneously low interfacial resistance and high optical transparency. Lattice-mismatched wafers of Si(100) and Si(111) were bonded at room temperature in situ after vacuum deposition of a single atomic layer of Ag. The interfacial resistance was measured to be 3.9×10-4Ωcm2 and the optical transmission of the interface at 2500nm is approximately 98%. Electron confinement in ultrathin Ag layers as a possible contributor to the bonding energy.

  16. Propagating Waves of Self-assembly in Organosilane Monolayers

    SciTech Connect

    Douglas,J.; Efimenko, K.; Fischer, D.; Phelan, F.; Genzer, J.

    2007-01-01

    Wavefronts associated with reaction-diffusion and self-assembly processes are ubiquitous in the natural world. For example, propagating fronts arise in crystallization and diverse other thermodynamic ordering processes, in polymerization fronts involved in cell movement and division, as well as in the competitive social interactions and population dynamics of animals at much larger scales. Although it is often claimed that self-sustaining or autocatalytic front propagation is well described by mean-field 'reaction-diffusion' or 'phase field' ordering models, it has recently become appreciated from simulations and theoretical arguments that fluctuation effects in lower spatial dimensions can lead to appreciable deviations from the classical mean-field theory (MFT) of this type of front propagation. The present work explores these fluctuation effects in a real physical system. In particular, we consider a high-resolution near-edge x-ray absorption fine structure spectroscopy (NEXAFS) study of the spontaneous frontal self-assembly of organosilane (OS) molecules into self-assembled monolayer (SAM) surface-energy gradients on oxidized silicon wafers. We find that these layers organize from the wafer edge as propagating wavefronts having well defined velocities. In accordance with two-dimensional simulations of this type of front propagation that take fluctuation effects into account, we find that the interfacial widths w(t) of these SAM self-assembly fronts exhibit a power-law broadening in time, w(t) {approx} t{sup {beta}}, rather than the constant width predicted by MFT. Moreover, the observed exponent values accord rather well with previous simulation and theoretical estimates. These observations have significant implications for diverse types of ordering fronts that occur under confinement conditions in biological or materials-processing contexts.

  17. Polymerization and electrochemical blocking of self-assembled alkylthiol monolayers

    SciTech Connect

    Peanasky, J.S.; Willicut, R.J.; Caston, S.L.

    1996-10-01

    Numerous advantages exist for the use of electroactive alkylthiol self-assembled monolayer modified gold electrodes over other monolayer/substrate systems for use as sensors or biosensors. Among these advantages are a wide electrical potential window, large variety of functionality, extensive order within the monolayer, and a vast amount of literature presently describing this system. One weakness is the facile gold-thiolate bond that results in desorption or displacement of the immobilized species from the surface. This is especially true when the {open_quotes}devices{close_quotes} are exposed to organic solutions. This study discusses the usefulness of photopolymerizing unsaturated functionalities located at internal or external positions on the alkyl chain to enhance immobilization of the electroactive species. Discussion focuses on electrochemical blocking by the monolayer before and after polymerization as determined using cyclic voltammetry. Structural changes within the monolayer, as determined by Fourier transform infrared spectroscopy, are related to changes seen electrochemically. Other parameters such as the type of unsaturated functionality, the alkyl chain length, and the exposure of the devices to oxygen are discussed.

  18. Control of crystal nucleation by patterned self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Aizenberg, Joanna; Black, Andrew J.; Whitesides, George M.

    1999-04-01

    An important requirement in the fabrication of advanced inorganic materials, such as ceramics and semiconductors, is control over crystallization. In principle, the synthetic growth of crystals can be guided by molecular recognition at interfaces. But it remains a practical challenge to control simultaneously the density and pattern of nucleation events, and the sizes and orientations of the growing crystals. Here we report a route to crystal formation, using micropatterned self-assembled monolayers,, which affords control over all these parameters. We begin with a metal substrate patterned with a self-assembled monolayer having areas of different nucleating activity-in this case, an array of acid-terminated regions separated by methyl-terminated regions. By immersing the patterned substrates in a calcium chloride solution and exposing them to carbon dioxide, we achieve ordered crystallization of calcite in the polar regions, where the rate of nucleation is fastest; crystallization can be completely suppressed elsewhere by a suitable choice of array spacing, which ensures that the solution is undersaturated in the methyl-terminated regions. The nucleation density (the number of crystals formed per active site) may be controlled by varying the area and distribution of the polar regions, and we can manipulate the crystallographic orientation by using different functional groups and substrates.

  19. Self assembled monolayers on silicon for molecular electronics.

    PubMed

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

    2006-05-24

    We present an overview of various aspects of the self-assembly of organic monolayers on silicon substrates for molecular electronics applications. Different chemical strategies employed for grafting the self-assembled monolayers (SAMs) of alkanes having different chain lengths on native oxide of Si or on bare Si have been reviewed. The utility of different characterization techniques in determination of the thickness, molecular ordering and orientation, surface coverage, growth kinetics and chemical composition of the SAMs has been discussed by choosing appropriate examples. The metal counterelectrodes are an integral part of SAMs for measuring their electrical properties as well as using them for molecular electronic devices. A brief discussion on the variety of options available for the deposition of metal counterelectrodes, that is, soft metal contacts, vapor deposition and soft lithography, has been presented. Various theoretical models, namely, tunneling (direct and Fowler-Nordheim), thermionic emission, Poole-Frenkel emission and hopping conduction, used for explaining the electronic transport in dielectric SAMs have been outlined and, some experimental data on alkane SAMs have been analyzed using these models. It has been found that short alkyl chains show excellent agreement with tunneling models; while more experimental data on long alkyl chains are required to understand their transport mechanism(s). Finally, the concepts and realization of various molecular electronic components, that is, diodes, resonant tunnel diodes, memories and transistors, based on appropriate architecture of SAMs comprising of alkyl chains (sigma- molecule) and conjugated molecules (pi-molecule) have been presented. PMID:17761249

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

    NASA Astrophysics Data System (ADS)

    Raigoza, Annette Fernandez

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

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

    PubMed

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

    2016-05-01

    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. PMID:27044113

  2. High-Yield Excited Triplet States in Pentacene Self-Assembled Monolayers on Gold Nanoparticles through Singlet Exciton Fission.

    PubMed

    Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V; Hasobe, Taku

    2016-04-18

    One of the major drawbacks of organic-dye-modified self-assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13-bis(triisopropylsilylethynyl)pentacene-alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time-resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface. PMID:26997657

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

    PubMed

    Noel, John; Teizer, Winfried; Hwang, Wonmuk

    2009-01-01

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

  4. Crossbar nanoarchitectonics of the crosslinked self-assembled monolayer

    PubMed Central

    2014-01-01

    A bottom-up approach was devised to build a crossbar device using the crosslinked SAM of the 5,5′-bis (mercaptomethyl)-2,2′-bipyridine-Ni2+ (BPD- Ni2+) on a gold surface. To avoid metal diffusion through the organic film, the author used (i) nanoscale bottom electrodes to reduce the probability of defects on the bottom electrodes and (ii) molecular crosslinked technology to avoid metal diffusion through the SAMs. The properties of the crosslinked self-assembled monolayer were determined by XPS. I-V characteristics of the device show thermally activated hopping transport. The implementation of this type of architecture will open up new vistas for a new class of devices for transport, storage, and computing. PMID:24994952

  5. A self assembled monolayer based microfluidic sensor for urea detection

    NASA Astrophysics Data System (ADS)

    Srivastava, Saurabh; Solanki, Pratima R.; Kaushik, Ajeet; Ali, Md. Azahar; Srivastava, Anchal; Malhotra, B. D.

    2011-07-01

    Urease (Urs) and glutamate dehydrogenase (GLDH) have been covalently co-immobilized onto a self-assembled monolayer (SAM) comprising of 10-carboxy-1-decanthiol (CDT) via EDC-NHS chemistry deposited onto one of the two patterned gold (Au) electrodes for estimation of urea using poly(dimethylsiloxane) based microfluidic channels (2 cm × 200 μm × 200 μm). The CDT/Au and Urs-GLDH/CDT/Au electrodes have been characterized using Fourier transform infrared (FTIR) spectroscopy, contact angle (CA), atomic force microscopy (AFM) and electrochemical cyclic voltammetry (CV) techniques. The electrochemical response measurement of a Urs-GLDH/CDT/Au bioelectrode obtained as a function of urea concentration using CV yield linearity as 10 to 100 mg dl-1, detection limit as 9 mg dl-1 and high sensitivity as 7.5 μA mM-1 cm-2.

  6. Nanoscale Nitrogen Doping in Silicon by Self-Assembled Monolayers

    PubMed Central

    Guan, Bin; Siampour, Hamidreza; Fan, Zhao; Wang, Shun; Kong, Xiang Yang; Mesli, Abdelmadjid; Zhang, Jian; Dan, Yaping

    2015-01-01

    This Report presents a nitrogen-doping method by chemically forming self-assembled monolayers on silicon. Van der Pauw technique, secondary-ion mass spectroscopy and low temperature Hall effect measurements are employed to characterize the nitrogen dopants. The experimental data show that the diffusion coefficient of nitrogen dopants is 3.66 × 10−15 cm2 s−1, 2 orders magnitude lower than that of phosphorus dopants in silicon. It is found that less than 1% of nitrogen dopants exhibit electrical activity. The analysis of Hall effect data at low temperatures indicates that the donor energy level for nitrogen dopants is located at 189 meV below the conduction band, consistent with the literature value. PMID:26227342

  7. Nanoscale Nitrogen Doping in Silicon by Self-Assembled Monolayers.

    PubMed

    Guan, Bin; Siampour, Hamidreza; Fan, Zhao; Wang, Shun; Kong, Xiang Yang; Mesli, Abdelmadjid; Zhang, Jian; Dan, Yaping

    2015-01-01

    This Report presents a nitrogen-doping method by chemically forming self-assembled monolayers on silicon. Van der Pauw technique, secondary-ion mass spectroscopy and low temperature Hall effect measurements are employed to characterize the nitrogen dopants. The experimental data show that the diffusion coefficient of nitrogen dopants is 3.66 × 10(-15) cm(2) s(-1), 2 orders magnitude lower than that of phosphorus dopants in silicon. It is found that less than 1% of nitrogen dopants exhibit electrical activity. The analysis of Hall effect data at low temperatures indicates that the donor energy level for nitrogen dopants is located at 189 meV below the conduction band, consistent with the literature value. PMID:26227342

  8. Nanoscale Nitrogen Doping in Silicon by Self-Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    Guan, Bin; Siampour, Hamidreza; Fan, Zhao; Wang, Shun; Kong, Xiang Yang; Mesli, Abdelmadjid; Zhang, Jian; Dan, Yaping

    2015-07-01

    This Report presents a nitrogen-doping method by chemically forming self-assembled monolayers on silicon. Van der Pauw technique, secondary-ion mass spectroscopy and low temperature Hall effect measurements are employed to characterize the nitrogen dopants. The experimental data show that the diffusion coefficient of nitrogen dopants is 3.66 × 10-15 cm2 s-1, 2 orders magnitude lower than that of phosphorus dopants in silicon. It is found that less than 1% of nitrogen dopants exhibit electrical activity. The analysis of Hall effect data at low temperatures indicates that the donor energy level for nitrogen dopants is located at 189 meV below the conduction band, consistent with the literature value.

  9. Mass Spectrometry of Self-Assembled Monolayers: A New Tool for Molecular Surface Science

    PubMed Central

    Mrksich, Milan

    2008-01-01

    Most reactions can be performed in solution and on a surface. Yet the challenges faced in applying known reactions or in developing entirely new reactions for modifying surfaces remain formidable. The products of many reactions performed in solution can be characterized in minutes and even products having complex structures can be characterized in hours. When performed on surfaces, even the most basic reactions require a substantial effort—requiring several weeks—to characterize the yields and structures of the products. This contrast stems from the lack of convenient analytical tools that provide rapid information on the structures of molecules attached to a surface. This review describes recent work that has established mass spectrometry as a powerful method for developing and characterizing a broad range of chemical reactions of molecules attached to self-assembled monolayers of alkanethiolates on gold. The SAMDI-TOF mass spectrometry technique will enable a next generation of applications of molecularly defined surfaces to problems in chemistry and biology. PMID:19206542

  10. Molecular Ordering of Poly(3-hexylthiophene) on Self-Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    Yimer, Yeneneh; Tsige, Mesfin

    2014-03-01

    The molecular ordering of semiconducting polymers such as Poly(3-hexylthiophene) (P3HT) at surfaces and interfaces has significant influence on the performance of organic solar cell devices. The charge-carrier transport and the charge collection at the electrodes strongly depend on the molecular ordering of P3HT at interfaces. Molecular ordering of P3HT can be tuned by varying the substrate surface chemistry and film processing conditions. Using all-atom molecular dynamics simulations and validated force field parameters, we have investigated the molecular ordering of P3HT on self-assembled monolayers (SAMs) of n-alkanethiols with varying end-functional groups and spacer length. In this study we elucidate the dependence of the molecular ordering of P3HT (edge-on or face-on conformation) on the surface chemistry of SAMs. Moreover, we investigated the effect of solvent on the molecular ordering of P3HT on SAMs surfaces. Understanding the correlation between P3HT morphology and surface chemistry will help in designing P3HT-based solar devices with better efficiency. This work is supported by the NSF (DMR0847580).

  11. Biomaterial-Mediated Retroviral Gene Transfer Using Self-Assembled Monolayers

    PubMed Central

    Gersbach, Charles A.; Coyer, Sean R.; Le Doux, Joseph M.; García, Andrés J.

    2007-01-01

    Biomaterial-mediated gene delivery has recently emerged as a promising alternative to conventional gene transfer technologies that focus on direct delivery of viral vectors or DNA-polymer/matrix complexes. However, biomaterial-based strategies have primarily targeted transient gene expression vehicles, including plasmid DNA and adenovirus particles. This study expands on this work by characterizing biomaterial properties conducive to the surface immobilization of retroviral particles and subsequent transduction of mammalian cells at the cell-material interface. Self-assembled monolayers (SAMs) of functionally-terminated alkanethiols on gold were used to establish biomaterial surfaces of defined chemical composition. Gene transfer was observed to be greater than 90% on NH2-terminated surfaces, approximately 50% on COOH-functionalized surfaces, and undetectable on CH3-terminated SAMs, similar to controls of tissue culture-treated polystyrene. Gene delivery via the NH2-SAM was further characterized as a function of coating time, virus concentration, and cell seeding density. Finally, SAM-mediated gene delivery was comparable to fibronectin- and poly-L-lysine-based methods for gene transfer. This work is significant to establishing safe and effective gene therapy strategies, developing efficient methods for gene delivery, and supporting recent progress in the field of biomaterial-mediated gene transfer. PMID:17698189

  12. Effects of Embedded Dipoles on the Electrical Response of Self Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    Zhang, P. P.; Cabarcos, O. M.; Daniel, T. A.; Weiss, P. S.; Allara, D. L.

    2009-03-01

    There has been recent interest in the use of polar molecules assembled at electrodes for tuning work functions and engineering charge injection barriers in organic electronic devices. With this in mind we have been investigating the electrostatic properties of simple model systems prepared from self-assembled alkanethiolate monolayers on Au111 with the incorporation of an embedded ester moiety [-(CO2)- = E] in the adsorbate molecules. The intrinsic static dipole moment of the ester moiety of ˜1 Debye magnitude leads to the formation of a strong, highly organized, planar electric dipole layer in the SAM. From our previous X-ray photoelectron spectroscopy data we observe a consistent shift of the C 1s photoelectron kinetic energies between the top and bottom alkyl segments, defined as -(CH2)m-E-(CH2)nCH3, regardless of the relative lengths m and n. This shift correlates well with the value of the electrostatic potential across the E layer. Our recent surface potential AFM measurements, however, reveal an apparently anomalous strong dependence of surface potential on the sizes and ratios of m and n, in contrast to the constant electrostatic potential observed in XPS measurements. Mechanisms underlying these effects will be discussed, with possible implications for the electrostatic behavior of more complicated organic and biological systems.

  13. Tribological properties of alkylsilane self-assembled monolayers.

    PubMed

    Lorenz, Christian D; Chandross, Michael; Grest, Gary S; Stevens, Mark J; Webb, Edmund B

    2005-12-01

    In this study, we perform molecular dynamics simulations of adhesive contact and friction between alkylsilane Si(OH)(3)(CX(2))(10)CX(3) and alkoxylsilane Si(OH)(2)(CX(2))(10)CX(3) (where X = H or F) self-assembled monolayers (SAMs) on an amorphous silica substrate. The alkylsilane SAMs are primarily hydrogen-bonded or physisorbed to the surface. The alkoxylsilane SAMs are covalently bonded or chemisorbed to the surface. Previously, we studied the chemisorbed systems. In this work, we study the physisorbed systems and compare the tribological properties with the chemisorbed systems. Furthermore, we examine how water at the interface of the SAMs and substrate affects the tribological properties of the physisorbed systems. When less than a third of a monolayer is present, very little difference in the microscopic friction coefficient mu or shear stresses is observed. For increasing amounts of water, the values of mu and the shear stresses decrease; this effect is somewhat more pronounced for fluorocarbon alkylsilane SAMs than for the hydrocarbon SAMs. The observed decrease in friction is a consequence of a slip plane that occurs in the water as the amount of water is increased. We studied the frictional behavior using relative shear velocities ranging from v = 2 cm/s to 2 m/s. Similar to previously reported results for alkoxylsilane SAMs, the values of the measured stress and mu for the alkylsilane SAM systems decrease monotonically with v. PMID:16316109

  14. Self-assembled monolayers on a ferromagnetic permalloy surface.

    PubMed

    Mattera, Michele; Torres-Cavanillas, Ramón; Prieto-Ruiz, Juan P; Prima-García, Helena; Tatay, Sergio; Forment-Aliaga, Alicia; Coronado, Eugenio

    2015-05-19

    Self-assembled monolayers (SAMs) are nowadays broadly used as surface protectors or modifiers and play a key role in many technological applications. This has motivated the study of their formation in all kind of materials; however, and despite the current interest in molecular spintronics, the study of SAMs on ferromagnetic surfaces remains almost unexplored. In this paper, we report for the first time a methodology for the formation of SAMs of n-alkylphosphonic acids on permalloy in ambient conditions. The formed monolayers have been fully characterized by means of contact angle measurements, atomic force microscopy, X-ray photoelectron spectroscopy, matrix assisted laser desorption ionization time-of-flight mass spectrometry, infrared reflection absorption spectroscopy, and X-ray reflectometry. Additionally, the magnetic stability of the modified permalloy after the solution process required for the SAM formation has been confirmed by magneto-optical Kerr effect magnetometry. Moreover, by means of microcontact printing lithography, very accurate SAM patterns have been transferred onto permalloy surfaces and used as resist mask in a chemical etching process giving rise to submicrometric permalloy surface patterns with potential interest in nanomagnetism, spintronics, and storage technologies. PMID:25919007

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  16. Sequence, structure, and function of peptide self-assembled monolayers.

    PubMed

    Nowinski, Ann K; Sun, Fang; White, Andrew D; Keefe, Andrew J; Jiang, Shaoyi

    2012-04-01

    Cysteine is commonly used to attach peptides onto gold surfaces. Here we show that the inclusion of an additional linker with a length of four residues (-PPPPC) and a rigid, hydrophobic nature is a better choice for forming peptide self-assembled monolayers (SAMs) with a well-ordered structure and high surface density. We compared the structure and function of the nonfouling peptide EKEKEKE-PPPPC-Am with EKEKEKE-C-Am. Circular dichroism, attenuated total internal reflection Fourier transform IR spectroscopy, and molecular dynamics results showed that EKEKEKE-PPPPC-Am forms a secondary structure while EKEKEKE-C-Am has a random structure. Surface plasmon resonance sensor results showed that protein adsorption on EKEKEKE-PPPPC-Am/gold is very low with small variation while protein adsorption on EKEKEKE-C-Am/gold is high with large variation. X-ray photoelectron spectroscopy results showed that both peptides have strong gold-thiol binding with the gold surface, indicating that their difference in protein adsorption is due to their assembled structures. Further experimental and simulation studies were performed to show that -PPPPC is a better linker than -PC, -PPC, and -PPPC. Finally, we extended EKEKEKE-PPPPC-Am with the cell-binding sequence RGD and demonstrated control over specific versus nonspecific cell adhesion without using poly(ethylene glycol). Adding a functional peptide to the nonfouling EK sequence avoids complex chemistries that are used for its connection to synthetic materials. PMID:22401132

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

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

    2005-05-26

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

  19. Self-assembled monolayer and method of making

    DOEpatents

    Fryxell, Glen E [Kennewick, WA; Zemanian, Thomas S [Richland, WA; Liu, Jun [West Richland, WA; Shin, Yongsoon [Richland, WA

    2003-03-11

    According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

  20. Self-assembled monolayer and method of making

    DOEpatents

    Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

    2004-05-11

    According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

  1. Self-Assembled Monolayer And Method Of Making

    DOEpatents

    Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

    2005-01-25

    According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

  2. Self-Assembled Monolayer And Method Of Making

    DOEpatents

    Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

    2004-06-22

    According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

  3. Asphaltene Adsorption onto Self-Assembled Monolayers of Mixed Aromatic

    SciTech Connect

    Turgman-Cohen, S.; Smith, M; Fischer, D; Kilpatrick, P; Genzer, J

    2009-01-01

    The adsorption of asphaltenes onto flat solid surfaces modified with mixed self-assembled monolayers (SAMs) of aliphatic and aromatic trichlorosilanes with varying wettabilities, aromaticities, and thicknesses is tested. The mixed SAMs are characterized by means of contact angle to assess hydrophobicity and molecular and chemical uniformity, spectroscopic ellipsometry to measure the thickness of the films, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy to assess chemical and molecular composition. The molecular characteristics of the adsorbed asphaltene layer and the extent of asphaltene adsorption are determined using NEXAFS and spectroscopic ellipsometry, respectively. The SAMs are formed by depositing phenyl-, phenethyl-, butyl-, and octadecyl- trichlorosilanes from toluene solutions onto silica-coated substrates; the chemical composition and the wettability of the SAM surface is tuned systematically by varying the trichlorosilane composition in the deposition solutions. The adsorption of asphaltenes on the substrates does not correlate strongly with the SAM chemical composition. Instead, the extent of asphaltene adsorption decreases with increasing SAM thickness. This observation suggests that the leading interaction governing the adsorption of asphaltenes is their interaction with the polar silica substrate and that the chemical composition of the SAM is of secondary importance.

  4. Free energy calculations in electroactive self-assembled monolayers (SAMs): impact of the chain length on the redox reaction.

    PubMed

    Filippini, Gaelle; Israeli, Yael; Goujon, Florent; Limoges, Benoit; Bonal, Christine; Malfreyt, Patrice

    2011-10-13

    The free energy approach is used to study the effect of the relative chain length of the two constituents of electroactive self-assembled monolayers (SAMs) on gold. In this study, the ferrocene groups are exposed to the electrolyte solution. This situation is achieved by using shorter diluent alkanethiol chains. To this end, the mixed monolayers formed by the self-assembly of 11-ferrocenylundecanethiol and butanethiol FcC(11)S/C(4)S and of 6-ferrocenylhexanethiol and butanethiol FcC(6)S/C(4)S onto a gold surface are studied. Calculation of enthalpy and entropy differences are also performed using molecular simulations. Additionally, the electrochemical signatures of these systems are determined to allow a direct comparison with our calculations. The thermodynamic properties are discussed in terms of enthalpy and entropy changes. Two effects account for the thermodynamic behavior. The first one involves the ion pairing between the ferrocenium group and the perchlorate anion. The second one concerns the desolvation of the first hydration shell of the anions. Finally, this work is also completed with a microscopic description associated with an energy characterization of these SAMs as a function of the surface coverage under conditions close to experiments. PMID:21866943

  5. Mixed alkanethiol monolayers on submicrometric gold patterns: a controlled platform for studying cell-ligand interactions.

    PubMed

    Fishler, Rami; Artzy-Schnirman, Arbel; Peer, Elad; Wolchinsky, Ron; Brener, Reuven; Waks, Tova; Eshhar, Zelig; Reiter, Yoram; Sivan, Uri

    2012-09-12

    Nanoscale organization of surface ligands often has a critical effect on cell-surface interactions. We have developed an experimental system that allows a high degree of control over the 2-D spatial distribution of ligands. As a proof of concept, we used the developed system to study how T-cell activation is independently affected by antigen density and antigen amount per cell. Arrays of submicrometer gold islands at varying surface coverage were defined on silicon by electron beam lithography (EBL). The gold islands were functionalized with alkanethiol self-assembled monolayers (SAMs) containing a small antigen, 2,4,6-trinotrophenyl (TNP), at various densities. Genetically engineered T-cell hybridomas expressing TNP-specific chimeric T-cell antigen receptor (CAR) were cultured on the SAMs, and their activation was assessed by IL-2 secretion and CD69 expression. It was found that, at constant antigen density, activation increased monotonically with the amount of antigen, while at constant antigen amount activation was maximal at an intermediate antigen density, whose value was independent of the amount of antigen. PMID:22900991

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

    ERIC Educational Resources Information Center

    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.

  7. Soft-Landing of CoIII(salen)+ and MnIII(salen)+ on Self-Assembled Monolayer Surfaces

    SciTech Connect

    Laskin, Julia; Wang, Peng; Hadjar, Omar

    2010-03-25

    Soft-landing of mass-selected CoIII(salen)+ and MnIII(salen)+ complexes was performed using self-assembled monolayer surfaces of alkanethiol (HSAM) and fluorinated alkanethiol (FSAM) on gold as targets. Physical processes associated with ion deposition were studied using time-resolved in situ secondary ion mass spectrometry (SIMS) in a specially designed Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). We demonstrate charge retention by a significant fraction of precursor ions on the FSAM and complete neutralization on the HSAM surface. Our results indicate efficient electron transfer from gold to the deposited species for the HSAM surface and inefficient, if any, electron transfer on the FSAM surface. Formation of abundant cluster ions observed in SIMS spectra is attributed to gas-phase reactions in the SIMS plume. Detailed analysis allowed us to extract the kinetics of both ionic and neutral complexes trapped on the FSAM surface. The results indicate that neutralization on this surface most likely takes place on the defect sites.

  8. Ordered self-assembled monolayers terminated with different chemical functional groups direct neural stem cell linage behaviours.

    PubMed

    Yao, Shenglian; Liu, Xi; He, Jin; Wang, Xiumei; Wang, Ying; Cui, Fu-Zhai

    2016-02-01

    Neural stem cells (NSCs) have been a promising candidate for stem cell-based nerve tissue regeneration. Therefore, the design of idea biomaterials that deliver precise regulatory signals to control stem cell fate is currently a crucial issue that depends on a profound understanding of the interactions between NSCs with the surrounding micro-environment. In this work, self-assembled monolayers of alkanethiols on gold with different chemical groups, including hydroxyl (-OH), amino (-NH2), carboxyl (-COOH) and methyl (-CH3), were used as a simple model to study the effects of surface chemistry on NSC fate decisions. Contact angle measurement and x-ray photoelectron spectroscopy (XPS) examination implied that all types of alkanethiols self-assembled on gold into a close-packed phase structure with similar molecular densities. In this study, we evaluated NSC adhesion, migration and differentiation in response to different chemical functional groups cultured under serum-free conditions. Our studies showed that NSCs exhibited certain phenotypes with extreme sensitivity to surface chemical groups. Compared with other functional groups, the SAMs with hydroxyl end-groups provided the best micro-environment in promoting NSC migration and maintaining an undifferentiated or neuronal differentiation state.  -NH2 surfaces directed neural stem cells into astrocytic lineages, while NSCs on  -COOH and  -CH3 surfaces had a similar potency to differentiate into three nerve lineages. To further investigate the possible signaling pathway, the gene expression of integrin β1 and β4 were examined. The results indicated that a high expression of β1 integrin would probably have a tight correlation with the expression of nestin, which implied the stemness of NSCs, while β4 integrin seemed to correspond to the differentiated NSCs. The results presented here give useful information for the future design of biomaterials to regulate the preservation, proliferation and

  9. Vortical superlattices in a gold nanorods' self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Xie, Yong; Liang, Yujia; Chen, Dongxue; Wu, Xiaochun; Dai, Luru; Liu, Qian

    2014-02-01

    This paper describes the novel vortical self-assembly of CTAB-capped gold nanorods. Representative left-hand, radial, and right-hand vortices are shown. Micelles formed by CTAB molecules enhance the organized self-assembly process. The drag force of solvent flow and dynamic vortex flow in the thin solvent layer are thought to be responsible for the final vortical superlattices. FDTD simulation suggests these structures have potential applications in nanofocusing and polarized light response.

  10. Patterned Growth of Organic Semiconductors: Selective Nucleation of Perylene on Self-Assembled Monolayers.

    PubMed

    Pick, André; Witte, Gregor

    2016-08-16

    Organic semiconductors (OSC) have received a large amount of attention because they afford the fabrication of flexible electronic devices. However, the limited resistance to radiation and etching of such materials does not permit their patterning by photolithography, which has been a driving force for the development of integrated circuits and therefore requires alternative structuring techniques. One approach is based on precoating the substrate with self-assembled monolayers (SAMs) to control the nucleation of subsequently deposited OSC layers, but the underlying mechanism is barely understood. Here, we used alkanethiols with different chemical terminations to prepare SAMs on gold substrates serving as model systems to identify the mechanism of selective nucleation for the case of the OSC perylene. Using atomic force microscopy and fluorescence microscopy, we demonstrate that the chemical functionalization of the SAMs determines the adhesion forces for the OSC that are smallest for CF3-terminated and largest for OH-terminated SAMs, hence yielding distinctly different sticking probabilities upon perylene deposition at room temperature. Microcontact printing and immersion were employed to prepare SAM patterns that enable the selective growth of polycrystalline perylene films. A quite different situation is found upon printing long-chain thiols with low vapor pressure, which leads to the transfer of multilayers and favors the growth of perylene single crystallites. In a more abstract scenario, patterns of silicone oil droplets were printed on a gold substrate, which was previously covered with a repelling fluorinated SAM. Such droplets provide nucleation centers for liquid-mediated growth, often yielding platelet-shaped perylene single crystallites without unwanted perylene nucleation on the remaining surface. PMID:27441921

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

    PubMed

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

    2014-08-01

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

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

    PubMed

    Hu, Qichi; Laskin, Julia

    2016-06-01

    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 nativelike 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 alkanethiols 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 a lower relative abundance of β-sheet conformations are 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. PMID:27192353

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

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

    Cernetic, Nathan

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

  15. Self assembled molecular monolayers on high surface area materials as molecular getters

    DOEpatents

    King, D.E.; Herdt, G.C.; Czanderna, A.W.

    1997-01-07

    The present invention relates to a gettering material that may be used as a filtration medium to remove pollutants from the environment. The gettering material comprises a high surface area material having a metal surface that chemically bonds n-alkanethiols in an organized manner thereby forming a molecular monolayer over the metal surface. The n-alkanethiols have a free functional group that interacts with the environment thereby binding specific pollutants that may be present. The gettering material may be exposed to streams of air in heating, ventilation, and air conditioning systems or streams of water to remove specific pollutants from either medium. 9 figs.

  16. Self assembled molecular monolayers on high surface area materials as molecular getters

    DOEpatents

    King, David E.; Herdt, Gregory C.; Czanderna, Alvin W.

    1997-01-01

    The present invention relates to a gettering material that may be used as a filtration medium to remove pollutants from the environment. The gettering material comprises a high surface area material having a metal surface that chemically bonds n-alkanethiols in an organized manner thereby forming a molecular monolayer over the metal surface. The n-alkanethiols have a free functional group that interacts with the environment thereby binding specific pollutants that may be present. The gettering material may be exposed to streams of air in heating, ventilation, and air conditioning systems or streams of water to remove specific pollutants from either medium.

  17. Orientation and Mg Incorporation of Calcite Grown on Functionalized Self-Assembled Monolayers: A Synchrotron X-ray Study

    SciTech Connect

    Kwak,S.; DiMasi, E.; Han, Y.; Aizenberg, J.; Kuzmenko, I.

    2005-01-01

    Calcite crystals were nucleated from MgCl2/CaCl2 solutions onto functionalized self-assembled monolayers adsorbed onto E-beam evaporated Au films. Synchrotron X-ray scattering studies of the crystals reveal new information about preferred orientation and Mg incorporation. The Au [111] axis is distributed within 2.6 degrees of the film surface normal, but the oriented crystals may be tilted up to 6 degrees away from this axis. For low Mg{sup 2+} content, SO{sub 3}--functionalized films nucleated primarily near the (106) calcite face, odd-chain-length carboxylic acid terminated alkanethiol films nucleated near the (012) face, and even-chain-length carboxylic acid terminated alkanethiol films nucleated near the (113) face. [Mg{sup 2+}]/[Ca{sup 2+}] concentration ratios (n) of 2 and greater defeated this preferred orientation and created a powder texture. Diffraction patterns within the layer plane from the coarse calcite powders indicated a shift to higher 2 accompanied by peak broadening with increasing n. For 0.5 < n < 3.5, a double set of calcite peaks is observed, showing that two distinct Mg calcite phases form: one of comparatively lower Mg content, derived from the templated crystals, and a Mg-rich phase derived from amorphous precursor particles. According to the refinement of lattice parameters, Mg incorporation of up to 18 mol % occurs for n = 4, independent of film functionality. We discuss the differences between the differently functionalized monolayers and also introduce the hypothesis that two separate routes to Mg calcite formation occur in this system.

  18. The dynamics of gas-surface energy exchange in collisions of Ar atoms with ω-functionalized self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Day, B. Scott; Shuler, Shelby F.; Ducre, Adonis; Morris, John R.

    2003-10-01

    Atomic-beam scattering experiments using n-alkanethiol and ω-functionalized alkanethiol self-assembled monolayers (SAMs) on gold are employed to explore the dynamics of gas-surface energy exchange in collisions with model organic surfaces. The studies are performed by directing a nearly monoenergetic beam of 80 kJ/mol Ar atoms onto a particular SAM at an incident angle of 30° with respect to the surface normal and recording the time-of-flight distributions for the atoms as they scatter from the surface at a final angle of 30°. Among the monolayers studied, long-chain CH3-terminated SAMs are found to be the most effective at dissipating the translational energy of impinging atoms. For alkanethiols with greater than seven total carbon atoms (HS(CH2)n>6CH3), we find that, for specular scattering conditions, over 80% of the incident energy is transferred to the surface and that over 60% of the impinging atoms approach thermal equilibrium with the surface before scattering back into the gas phase. In contrast to CH3-terminated monolayers, SAMs constructed from hydrogen-bonding alkanethiols: HS(CH2)11OH, HS(CH2)10COOH, and HS(CH2)11NH2, exhibit characteristics of more rigid collision partners. The Ar atoms transfer about 77% of their energy to these surfaces with only 43% of the atoms reaching thermal or near thermal equilibrium before recoiling. Further comparisons of mixed OH- and CH3-terminated SAMs and alkene-terminated SAMs suggest that intramonolayer hydrogen bonding of terminal functional groups may play an important role in determining the extent of energy transfer and thermalization.

  19. Low-voltage p- and n-type organic self-assembled monolayer field effect transistors.

    PubMed

    Novak, Michael; Ebel, Alexander; Meyer-Friedrichsen, Timo; Jedaa, Abdesselam; Vieweg, Benito F; Yang, Guang; Voitchovsky, Kislon; Stellacci, Francesco; Spiecker, Erdmann; Hirsch, Andreas; Halik, Marcus

    2011-01-12

    We report on p- and n-type organic self-assembled monolayer field effect transistors. On the base of quaterthiophene and fullerene units, multifunctional molecules were synthesized, which have the ability to self-assemble and provide multifunctional monolayers. The self-assembly approach, based on phosphonic acids, is very robust and allows the fabrication of functional devices even on larger areas. The p- and n-type transistor devices with only one molecular active layer were demonstrated for transistor channel lengths up to 10 μm. The monolayer composition is proven by electrical experiments and by high-resolution transmission electron microscopy, electron energy loss spectroscopy, XPS, and AFM experiments. Because of the molecular design and the contribution of isolating alkyl chains to the hybrid dielectric, our devices operate at low supply voltages (-4 V to +4 V), which is a key requirement for practical use and simplifies the integration in standard applications. The monolayer devices operate in ambient air and show hole and electron mobilities of 10(-5) cm(2)/(V s) and 10(-4) cm(2)/(V s) respectively. In particular the n-type operation of self-assembled monolayer transistors has not been reported before. Hereby, structure-property relations of the SAMs have been studied. Furthermore an approach to protect the sensitive C(60) from immediate degradation within the molecular design is provided. PMID:21133354

  20. Manipulation of graphene work function using a self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Seo, Jung-Tak; Bong, Jihye; Cha, Janghwan; Lim, Taekyung; Son, Junyoung; Park, Sung Ha; Hwang, Jungseek; Hong, Suklyun; Ju, Sanghyun

    2014-08-01

    We report an effective and reliable method to increase the work function of graphene to as high as 5.50 eV by applying a self-assembled monolayer on its surface. The work function of pristine graphene (4.56 eV) was increased by approximately +0.94 eV following trichlorosilane (HDF-S) self-assembly. This increase in the work function was confirmed by ab initio calculations. HDF-S self-assembled graphene exhibited no significant changes in structural, optical, or electrical characteristics compared with pristine graphene. In addition, we verified that the modified work function of HDF-S self-assembled graphene was not affected by the underlying substrates.

  1. The nucleation and growth of calcium phosphate onto self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Tarasevich, Barbara J.

    The nucleation and growth of calcium phosphate is of great importance to the formation of mammalian hard tissue structures such as bone and teeth and for unwanted, ectopic calcium phosphate deposition on arteries and implants. In spite of its importance, the mechanisms of nucleation and growth of calcium phosphate are not well known, but are believed to involve an organic template. The nucleation and growth of calcium phosphate was studied onto model nucleation templates composed of alkanethiol self-assembled monolayers on gold that were developed and tailored to have various surface functionalities, various surface site densities composed of mixtures of two thiols, and various degrees of conformational disorder composed of mixtures of SAMs of various chain lengths. The quartz crystal microbalance was developed as an in-situ technique to study the nucleation and growth kinetics and ex-situ techniques such as X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy were used to assess adsorbate molecular chemistry in the initial stages of deposition. Significant nucleation and growth of calcium phosphate onto SAMs involved the adsorption of solution-formed critical nuclei. This mechanism is in contrast to heterogeneous nucleation and may have important implications for bone formation. An initial slow growth region occurred which involved the adsorption and assembly of solution-formed nanometer-sized particles. A second fast growth period occurred which involved the adsorption and growth of solution-formed critical nuclei or the assembly of supercritical particles. There was evidence for the heterogeneous nucleation of a very low density of crystals at low solution supersaturation. Heterogeneous nucleation may be limited due to the use of planar surfaces and to limits on phosphate adsorption due to electrostatic double layer anisotropy at the charged interfaces. Surface selective deposition was found in the initial slow growth region with

  2. Self-Assembled Monolayers of Dithiophosphinic Acids on Gold

    NASA Astrophysics Data System (ADS)

    San Juan, Ronan Roca

    This dissertation reports the synthesis of derivatives of dithiophosphinic acids (R1R2DTPAs), and the formation and characterization of DTPA SAMs on gold to build a knowledge base on their nature of binding, organization of the alkyl chains and electrochemical barrier properties. The binding of DTPA molecules on gold depends on the morphology of the gold film: They bind in a mixed monodentate and bidentate modes on standard as-deposited (As-Dep) gold, while they fully chelate on smoother template-stripped (TS) gold. Chapter 2 focuses on van der Waals interactions of various alkyl chain lengths of symmetrical R2DTPA SAMs, which increase with increasing chain lengths similar to those of the analogous n-alkanethiol SAMs, but with alkyl chains that are generally less dense than those of n-alkanethiol SAMs. Chapter 3 addresses why the DTPA compounds do not chelate on the standard As-Dep gold by comparing (C16)2DTPA SAM to (C16 )2DDP SAM. Here, side chain crystallinity stabilizes DTPA SAM structure at the expense of chelation of the DTPA molecules, which leads to a mixture of bidentate and monodentate DTPA molecules, whereas the increased flexibility of the chains in DDP due to the oxygen atoms retains chelation of the DDP molecules. Chapter 4 focuses on the SAMs formed from RlongRshort DTPAs, which shows that the length of the short chain spacer affects SAM packing density and thickness. The SAMs of these molecules also show homogeneous mixing of Rlong and Rshort chains. Chapter 5 investigates PhRDTPA SAMs in preparation for molecular junction studies. The chelation of PhRDTPA molecules on TS gold allows the PhRDTPAs to act as molecular alligator clips. The length of the alkyl chains controls the density of the phenyl group and they fill in the voids between adsorbates to prevent electrical shorting. Finally, Chapter 6 incorporates OH tail group(s) to control the wettability of DTPA SAMs. The presence of OH groups in DTPAs forms hydrophilic SAMs. The symmetrical OH

  3. Charge Transport of MoS2 Supported by Thiol-Decorated Self-Assembled Monolayer

    NASA Astrophysics Data System (ADS)

    Naveh, Doron; Artel, Vlada; Kirshner, Moshe

    2015-03-01

    Intrinsic charge transport in MoS2 supported by thiols was recently reported and was attributed to passivation of sulfur vacancies and suppression of charged impurities from the dielectric substrate. In this talk we will present the transport characteristics of single layer and few-layer MoS2 on thiol-decorated self-assembled alkyl-siloxane monolayer.

  4. Controlling the adhesion of conducting polymer films with patterned self-assembled monolayers

    SciTech Connect

    Rozsnyai, L.F.; Wrighton, M.S.

    1996-02-01

    A photosensitive self-assembled monolayer (SAM) is selectively irradiated to fabricate a pattern on an Au electrode, and a thin film of aniline or 3-methylthiophene is deposited on it by electopolymerization. Adhesion of the polymer films can be controlled by the monolayer terminal group. Applying tape to the sample and peeling it away selectively removes the conducting polymer film to the tape in a near-micron resolution pattern. 14 refs., 1 fig.

  5. Self-assembled monolayers for studying enzyme immobilization and ion recognition

    NASA Astrophysics Data System (ADS)

    Kang, Jie

    This thesis explores the use of self-assembled monolayers on gold for studying enzyme immobilization and ion recognition. Chapter 1 serves as a general introduction to biosensing, self-assembled monolayers, protein immobilization, and surface characterization techniques. Chapter 2 through Chapter 5 describe the immobilization of a redox enzyme, glucose oxidase, to a variety of functional self-assembled monolayers by either noncovalent adsorption or covalent attachment. The characteristics of different immobilization methods are investigated, and the activity of the immobilized enzyme is assessed electrochemically. Chapter 2 presents detailed procedures for measuring glucose oxidase activity by an electrochemical technique---cyclic voltammetry. Chapter 3 describes the adsorption of glucose oxidase to hydrophobic and hydrophilic self-assembled monolayers (SAMs). Significant glucose oxidase adsorption to hydrophobic, methyl-terminated SAMs was observed, while long chain, hydrophilic SAMs terminated by hydroxyl and carboxyl groups resist enzyme adsorption. Chapter 4 examines the covalent attachment of glucose oxidase to N-hydroxysuccinimide ester (NHS ester)-terminated self-assembled monolayers. The reactivity of the surface NHS ester group is found to increase as its coverage is lowered. This observation is explained by the steric effect. Chapter 5 reports the electrostatic adsorption of glucose oxidase to self-assembled monolayers of cystamine. The adsorbed enzyme shows superior activity to enzyme immobilized by other means. The rate constants of surface enzyme catalysis are determined and compared with those of the enzyme in solution. Chapter 6 is concerned with iron (III) recognition by a self-assembled monolayer terminated with a siderophore group, desferrioxamine (H3DFO). We first demonstrate that the iron coverage of the ferrioxamine (FeDFO)-terminated SAM can be successfully assayed by cyclic voltammetry. We then present results for iron (III) binding to the H3

  6. Spectral and electrochemical properties of phenylazonaphthalene based on a self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Zhang, Aidong; Qin, Jingui; Gu, Jianhua; Lu, Zu-Hong

    1998-08-01

    A thiol-terminated phenylazonaphthalene derivative, namely 1-mercapto-6-[1-(4-phenylazonaphthoxy)]hexane 1, was synthesized by diazo coupling of aniline with 1-naphthol, etherification with 1,6-dibromohexane and thiol derivatization, subsequently. By self-assembly technology, the compound was spontaneously absorbed in thin, optically transparent gold film and formed stable self-assembled monolayer (SAM). The self-assembly course was monitored by UV-visible absorption spectra which gave direct evidence for the self-assembly mechanism of self-assembled monolayer, i.e., chemically adsorbed firstly, then came through a long- time orientation. Meanwhile, cyclic voltammogram was employed to study the electrochemical reduction and oxidation of the immobilized phenylazonaphthalene. The single molecular area obtained using the two methods was almost the same: ca. 0.9 nm2. The irreversibility of the electrode process, sluggish reaction and reduction peak splitting all were originated from the well molecular orientation, not the dense packing in the SAM. This implied the process of oxidation and reduction accompanied the molecular conformation change which needed more free space for the movement of the molecular chain during the electrode processes.

  7. Characterization of self-assembled monolayers for biosensor applications

    SciTech Connect

    Nyquist, R.M.; Eberhardt, A.S.; Silks, L.A. III; Li, Z.; Yang, X.; Swanson, B.I.

    2000-02-22

    Mixed monolayers of thiol-terminated poly(ethylene glycol) (PEG) and thioacetyl GM1 glycolipid on Au(111) were examined utilizing atomic force microscopy, infrared spectroscopy, and grazing incidence X-ray diffraction to determine the composition, structure, and morphology and to characterize the specific and nonspecific interactions with protein. These monolayer architectures are robust and are readily controlled to provide a network of receptor GM1 in the PEG-terminated matrix. However, the authors also find significant levels of nonspecific and nonnative protein binding that render this simplistic model system unsuitable for highly sensitive biosensor device applications.

  8. Interfacial tension analysis of oligo(ethylene glycol)-terminated self-assembled monolayers and their resistance to bacterial attachment.

    PubMed

    Ista, Linnea K; López, Gabriel P

    2012-09-01

    The fouling resistance of oligo(ethylene glycol) (OEG)-terminated self-assembled monolayers (SAMs) of alkanethiolates on gold has been well established. Although hydration of the OEG chains seems key to OEG-SAM resistance to macromolecular adsorption and cellular attachment, the details of how hydration prevents biofouling have been inferred largely through computational methods. Because OEG-SAMs of different lengths exhibit differing degrees of fouling resistance, the interactions between water and OEG-SAMs leading to fouling resistance can be deduced by comparing the properties of fouling and nonfouling OEG-SAMs. While all OEG-SAMs had similar water contact angles, contact angles taken with glycerol were able to individuate between different OEG-SAMs and between fouling and nonfouling OEG-SAMs. Subsequent estimation of surface and interfacial tension using a colloidal model showed that nonfouling surfaces are associated with an increased negative interfacial tension between those OEG-SAMs that resisted attachment and water. Further analysis of this interfacial tension experimentally confirmed current mathematical models that cite OEG-water hydrogen-bond formation as a driving force behind short-term fouling resistance. Finally, we found a correlation between solid-water interfacial tension and packing density and molecular density of ethylene glycol. PMID:22891854

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

    PubMed

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

    2009-11-26

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

  10. Morphological control of PbS grown on functionalized self-assembled monolayers by chemical bath deposition.

    PubMed

    Yang, Jing; Walker, Amy V

    2014-06-17

    We have investigated the chemical bath deposition (CBD) of PbS on functionalized alkanethiolate self-assembled monolayers (SAMs) using time-of-flight secondary ion mass spectrometry (SIMS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. The deposition mechanism involves both cluster-by-cluster and ion-by-ion growth. The dominant reaction pathway and the chemical composition and morphology of the deposited layer are dependent on both the SAM terminal group and the experimental conditions. On -COOH-terminated SAMs, three types of crystallites are observed: nanocrystals formed by heterogeneous ion-by-ion growth, larger needle-like particles, and ~2 μm particles deposited by homogeneous cluster-by-cluster deposition. The nanocrystals nucleate at Pb(2+)-carboxylate surface complexes, and so strongly adhere to the substrate. On -OH- and -CH3-terminated SAMs, only the micrometer-sized particles are formed by a cluster-by-cluster deposition mechanism. These particles do not adhere strongly to the SAM surface and can be easily removed. SIMS and XPS analyses indicate that the larger needle-like crystals and micrometer-sized particles are composed of oxidized lead sulfide and lead oxides, while the nanocrystals are composed of ≥85% PbS. Using sonication-assisted CBD, we demonstrate that PbS is deposited by ion-by-ion growth alone on -COOH-terminated SAMs. The deposited film is more compact with a smaller grain size and is >90% PbS. PMID:24854067

  11. Photochemical Reactions in Self-Assembled Organic Monolayers Characterized by using Scanning Tunneling Microscopy.

    PubMed

    Guo, Chao; Li, Min; Kang, ShiZhao

    2016-03-16

    Research on the supramolecular self-assembly behavior at interfaces is of great importance to improving the performance of nanodevices that are based on optical functional materials. In this Minireview, several photoinduced isomerization and polymerization reactions in self-assembled organic monolayers on surfaces are discussed. Typical organic molecules contain azobenzene, alkynyl, or olefins groups. The feature surface base is a highly oriented pyrolytic graphite (HOPG) surface or a gold surface. Scanning tunneling microscopy (STM) is used as a strong tool to characterize new species' structures before and after illumination. PMID:26797865

  12. Small molecule and self-assembled monolayer templating strategies

    NASA Astrophysics Data System (ADS)

    Salami, Tolulope O.

    This dissertation explores the templating and self-assembly techniques in the synthesis of extended Sn-based compounds, multipurpose nanodevice coatings and molecular electronics. An anionic templating technique was used in a pyridine-water system to synthesize extended tin compounds, leading to the isolation of seven new tin extended compounds. In addition, several known compounds were synthesized in a purer form than earlier reported in literature. The compounds are denoted BING-n, where BING stands for Binghamton university. Of the seven structures, one is a chain compound BING-4 [Sn(C2O4)(C5H 5N) which exhibit an oxalate chain capped by pyridine]. A 3D framework BING-1 [Na4Sn4(C2O4)3F 6] material, the other five compounds are layered BING-2 [KSn(C 2O4)F] is a potassium fluoride ring sandwiched by tin oxalate layers, BING-7 ([Sn(C2O4)F-][NH 4+],19 a fluorinated tin oxalate layered compound, BING-8 ([Sn(PO4H)F-][NH4 +],19 an anionic fluorinated tin phosphate compounds with interlamellar charge-balancing ammonium cations, BING-12 [NaSnF 3], a tin fluoride layered compound with fluoride galleries in between the layers and a layered tin mixed-cobalt compound [(SnCo2O (OH) 2(HPO4)2] with tin locked in the inter layer space. The known compound is a condensed phase tin fluoro phosphate [Sn3F 3PO4]. The compounds were characterized by a variety of techniques, including VT-variable Temperature Powder X-ray Diffraction (PXRD), Powder X-ray Diffraction (PXRD), Thermogravimetric Analyzer (TGA), Fourier Transfer Infrared spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). The solvent system and its influence on the formation of these materials are discussed. The general formation technique as it relates to the oxidation state and prevalent geometries of tin compounds is also discussed. The templating technique used is a new anionic templating technique, but the templates in most cases formed part of the framework. The multi-purpose bilayer ceramic coating was

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

    PubMed Central

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

    1996-01-01

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

  14. Molecular self-assembly at bare semiconductor surfaces: preparation and characterization of highly organized octadecanethiolate monolayers on GaAs(001).

    PubMed

    McGuiness, Christine L; Shaporenko, Andrey; Mars, Carole K; Uppili, Sundararajan; Zharnikov, Michael; Allara, David L

    2006-04-19

    Through rigorous control of preparation conditions, organized monolayers with a highly reproducible structure can be formed by solution self-assembly of octadecanethiol on GaAs (001) at ambient temperature. A combination of characterization probes reveal a structure with conformationally ordered alkyl chains tilted on average at 14 +/- 1 degrees from the surface normal with a 43 +/- 5 degrees twist, a highly oleophobic and hydrophobic ambient surface, and direct S-GaAs attachment. Analysis of the tilt angle and film thickness data shows a significant mismatch of the average adsorbate molecule spacings with the spacings of an intrinsic GaAs(001) surface lattice. The monolayers are stable up to approximately 100 degrees C and exhibit an overall thermal stability which is lower than that of the same monolayers on Au[111] surfaces. A two-step solution assembly process is observed: rapid adsorption of molecules over the first several hours to form disordered structures with molecules lying close to the substrate surface, followed by a slow densification and asymptotic approach to final ordering. This process, while similar to the assembly of alkanethiols on Au[111], is nearly 2 orders of magnitude slower. Finally, despite differences in assembly rates and the thermal stability, exchange experiments with isotopically tagged molecules show that the octadecanethiol on GaAs(001) monolayers undergo exchange with solute thiol molecules at roughly the same rate as the corresponding exchanges of the same monolayers on Au[111]. PMID:16608359

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

    SciTech Connect

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

    2007-02-19

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

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

    PubMed

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

    2016-01-01

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates. PMID:27302863

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    DOEpatents

    Alivisatos, A. Paul; Colvin, Vicki L.

    1998-01-01

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

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

    DOEpatents

    Alivisatos, A.P.; Colvin, V.L.

    1998-05-12

    Methods are described for attaching semiconductor nanocrystals to solid inorganic surfaces, using self-assembled bifunctional organic monolayers as bridge compounds. Two different techniques are presented. One relies on the formation of self-assembled monolayers on these surfaces. When exposed to solutions of nanocrystals, these bridge compounds bind the crystals and anchor them to the surface. The second technique attaches nanocrystals already coated with bridge compounds to the surfaces. Analyses indicate the presence of quantum confined clusters on the surfaces at the nanolayer level. These materials allow electron spectroscopies to be completed on condensed phase clusters, and represent a first step towards synthesis of an organized assembly of clusters. These new products are also disclosed. 10 figs.

  20. Infrared spectroscopy of organic semiconductors modified by self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Khatib, O.; Lee, B.; Podzorov, V.; Yuen, J.; Heeger, A. J.; Li, Z. Q.; di Ventra, M.; Basov, D. N.

    2009-03-01

    Recently, self-assembled monolayers (SAMs) were used to modify electronic surface properties of organic single crystals, leading to several orders of magnitude increase in the electrical conductivity^1. Motivated by this discovery, the same technique was applied to polymers. Here we present a thorough spectroscopic investigation of organic semiconductors based on poly(3-hexlthiophene) (P3HT) that have been treated with a fluorinated trichlorosilane SAM. Infrared spectroscopy offers access to details of charge injection, electrostatic doping, and the electronic structure that are not always available from transport measurements, which can be dominated by defects and contact effects. In polymer films, the SAM molecules penetrate into the bulk, leading to a rich spectrum of electronic excitations in the mid-infrared energy range. ^1 M. F. Calhoun, J. Sanchez, D. Olaya, M. E. Gershenson, V. Podzorov, Electronic functionalization of the surface of organic semiconductors with self-assembled monolayers, Nature Mater. 7, 84--89 (2008)

  1. Memory characteristics of a self-assembled monolayer of Pt nanoparticles as a charge trapping layer

    NASA Astrophysics Data System (ADS)

    Choi, Hyejung; Choi, Byung-Sang; Kim, Tae-Wook; Jung, Seung-Jae; Chang, Man; Lee, Takhee; Hwang, Hyunsang

    2008-07-01

    A self-assembled monolayer of Pt nanoparticles (NPs) was studied as a charge trapping layer for non-volatile memory (NVM) applications. Pt NPs with a narrow size distribution (diameter ~4 nm) were synthesized via an alcohol reduction method. The monolayer of these Pt NPs was immobilized on a SiO2 substrate using poly(4-vinylpyridine) (P4VP) as a surface modifier. A metal-oxide-semiconductor (MOS) type memory device with Pt NPs exhibits a relatively large memory window of 5.8 V under ± 7 V for program/erase voltage. These results indicate that the self-assembled Pt NPs can be utilized for NVM devices.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    PubMed Central

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

    2016-01-01

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates. PMID:27302863

  4. Polarized neutron reflectivity from monolayers of self-assembled magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Mishra, D.; Petracic, O.; Devishvili, A.; Theis-Bröhl, K.; Toperverg, B. P.; Zabel, H.

    2015-04-01

    We prepared monolayers of iron oxide nanoparticles via self-assembly on a bare silicon wafer and on a vanadium film sputter deposited onto a plane sapphire substrate. The magnetic configuration of nanoparticles in such a dense assembly was investigated by polarized neutron reflectivity. A theoretical model fit shows that the magnetic moments of nanoparticles form quasi domain-like configurations at remanence. This is attributed to the dipolar coupling amongst the nanoparticles.

  5. Polarity switching of charge transport and thermoelectricity in self-assembled monolayer devices.

    PubMed

    Egger, David A; Rissner, Ferdinand; Zojer, Egbert; Heimel, Georg

    2012-08-22

    Self-assembled monolayer devices can exhibit drastically different charge-transport characteristics and thermoelectric properties despite being composed of isomeric molecules with essentially identical frontier-orbital energies. This is rationalized by the cooperative electrostatic action of local intramolecular dipoles in otherwise nonpolar species, thus revealing new challenges but also new opportunities for the targeted design of functional building blocks in future nanoelectronics. PMID:22807087

  6. NHC-based Self-assembled Monolayers on Solid Gold Substrates

    SciTech Connect

    T Weidner; J Baio; A Mundstock; C Grosse; C Bruhn; U Siemeling

    2011-12-31

    Thin films of 1,3-diethylbenzimidazol-2-ylidene (BIEt) were fabricated from THF solution on solid gold substrates and characterised by high-resolution X-ray photoelectron and near-edge X-ray absorption fine structure spectroscopy. The surface-analytical data are in accord with the formation of self-assembled monolayers of BIEt molecules exhibiting an approximately vertical orientation on the substrate. The crystal structure of (BIEt){sub 2} was also determined.

  7. Dynamic nanoproteins: self-assembled peptide surfaces on monolayer protected gold nanoparticles.

    PubMed

    Garcia Martin, Sergio; Prins, Leonard J

    2016-07-19

    Here, we demonstrate the formation of dynamic peptide surfaces through the self-assembly of small peptides on the surface of monolayer protected gold nanoparticles. The complexity of the peptide surface can be simply tuned by changing the chemical nature of the added peptides and the ratio in which these are added. The dynamic nature of the surface permits adaptation to changes in the environment. PMID:27374419

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

    SciTech Connect

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

    2011-12-31

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

  9. Attachment of Algal Cells to Zwitterionic Self-Assembled Monolayers Comprised of Different Anionic Compounds.

    PubMed

    Bauer, S; Finlay, J A; Thomé, I; Nolte, K; Franco, S C; Ralston, E; Swain, G E; Clare, A S; Rosenhahn, A

    2016-06-01

    The influence of zwitterionic self-assembled monolayers on settlement and removal of algae was studied. The monolayers were constructed either from zwitterionic thiols or from solutions of positively and negatively charged thiols. The cationic component was composed of quaternary ammonium terminated thiols and the anionic component contained sulfate or carboxylate termination. During assembly, all surfaces showed a strong tendency for equilibration of the surface charge. Settlement and adhesion assays with zoospores of Ulva linza and the diatom Navicula incerta, and field tests of the initial surface colonization revealed the relevance of charge equilibration for the biological inertness of the prepared surfaces. PMID:27182766

  10. Lanthanide Selective Sorbents: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)

    SciTech Connect

    Fryxell, Glen E.; Wu, Hong; Lin, Yuehe; Shaw, Wendy J.; Birnbaum, Jerome C.; Linehan, John C.; Nie, Zimin; Kemner, Kenneth M.; Kelly, Shelley

    2004-11-01

    Through the marriage of mesoporous ceramics with self-assembled monolayer chemistry, the genesis of a powerful new class of environmental sorbent materials has been realized. By coating the mesoporous ceramic backbone with a monolayer terminated with a lanthanide-specific ligand, it is possible to couple high lanthanide binding affinity with the high loading capacity (resulting from the extremely high surface area of the support). This lanthanide-specific ligand field is created by pairing a “hard” anionic Lewis base with a suitable synergistic ligand, in a favorable chelating geometry. Details of the synthesis, characterization, lanthanide binding studies, binding kinetics, competition experiments and sorbent regeneration studies are summarized.

  11. Lanthanide Selective Sorbents: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)

    SciTech Connect

    Fryxell, Glen E.; Wu, Hong; Lin, Yuehe; Shaw, Wendy J.; Birnbaum, Jerome C.; Linehan, John C.; Nie, Zimin; Kemner, K. M.; Kelly, Shelley

    2004-11-01

    Through the marriage of mesoporous ceramics with self-assembled monolayer chemistry, the genesis of a powerful new class of environmental sorbent materials has been realized. By coating the mesoporous ceramic backbone with a monolayer terminated with a lanthanide-specific ligand, it is possible to couple high lanthanide binding affinity with the high loading capacity (resulting from the extremely high surface area of the support). This lanthanide-specific ligand field is created by pairing a ''hard'' anionic Lewis base with a suitable synergistic ligand, in a favorable chelating geometry. Details of the synthesis, characterization, lanthanide binding studies, binding kinetics, competition experiments and sorbent regeneration studies are summarized

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  13. Pseudorotational epitaxy of self-assembled octadecyltrichlorosilane monolayers on sapphire (0001)

    DOE PAGESBeta

    Steinrück, H. -G.; Magerl, A.; Deutsch, M.; Ocko, B. M.

    2014-10-06

    The structure of octadecyltrichlorosilane self-assembled monolayers (SAMs) on sapphire (0001) was studied by Å-resolution surface-specific x-ray scattering methods. The monolayer was found to consist of three sublayers where the outermost layer corresponds to vertically oriented, closely packed alkyl tails. Laterally, the monolayer is hexagonally packed and exhibits pseudorotational epitaxy to the sapphire, manifested by a broad scattering peak at zero relative azimuthal rotation, with long powderlike tails. The lattice mismatch of ~1% – 3% to the sapphire’s and the different length scale introduced by the lateral Si-O-Si bonding prohibit positional epitaxy. However, the substrate induces an intriguing increase in themore » crystalline coherence length of the SAM’s powderlike crystallites when rotationally aligned with the sapphire’s lattice. As a result, the increase correlates well with the rotational dependence of the separation of corresponding substrate-monolayer lattice sites.« less

  14. An epitaxial organic film. The self-assembled monolayer of docosanoic acid on silver(111)

    SciTech Connect

    Samant, M.G.; Brown, C.A.; Gordon, J.G. II )

    1993-04-01

    Docosanoic acid in solution spontaneously forms an ordered self-assembled (SA) monolayer on the silver(111) surface, exposing methyl groups to the atmosphere. The contact wetting angles for water and hexadecane are 116[degrees] and 55[degrees], respectively. Surface X-ray diffraction shows that the in-plane structure of the SA monolayer is p(2 [times] 2). The SA monolayer is present in domains of about 215 A with a mosaic spread of 0.85[degrees]C. The chains within the monolayer are titled at 27 [+-] 1[degrees] from the surface normal toward the near neighbors. We conclude that the carboxylate group is bound nearly normal to specific sites on the Ag surface and that this determines the interchain spacing. The tilt angle is a consequence of this interchain spacing. 17 refs., 6 figs., 1 tab.

  15. Pseudorotational epitaxy of self-assembled octadecyltrichlorosilane monolayers on sapphire (0001)

    SciTech Connect

    Steinrück, H. -G.; Magerl, A.; Deutsch, M.; Ocko, B. M.

    2014-10-06

    The structure of octadecyltrichlorosilane self-assembled monolayers (SAMs) on sapphire (0001) was studied by Å-resolution surface-specific x-ray scattering methods. The monolayer was found to consist of three sublayers where the outermost layer corresponds to vertically oriented, closely packed alkyl tails. Laterally, the monolayer is hexagonally packed and exhibits pseudorotational epitaxy to the sapphire, manifested by a broad scattering peak at zero relative azimuthal rotation, with long powderlike tails. The lattice mismatch of ~1% – 3% to the sapphire’s and the different length scale introduced by the lateral Si-O-Si bonding prohibit positional epitaxy. However, the substrate induces an intriguing increase in the crystalline coherence length of the SAM’s powderlike crystallites when rotationally aligned with the sapphire’s lattice. As a result, the increase correlates well with the rotational dependence of the separation of corresponding substrate-monolayer lattice sites.

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

    NASA Astrophysics Data System (ADS)

    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).

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

    SciTech Connect

    Stanley, Jacob; Boucheron, Leandra; Shpyrko, Oleg E-mail: oshpyrko@physics.ucsd.edu; Lin, Binhua E-mail: oshpyrko@physics.ucsd.edu; Meron, Mati

    2015-04-20

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

  18. In-situ second harmonic generation measurements of the formation of ionically self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Brands, Charles; Neyman, Patrick J.; Guzy, M.; Shah, S. M.; Davis, Rick M.; Van Cott, Kevin; Wang, Hong; Gibson, Harry W.; Heflin, James R.

    2001-12-01

    Recently, ionically self-assembled monolayers (ISAMs) of polymers with nonlinear optical chromophores have been shown to spontaneously exhibit a preferential ordering during the deposition process. This gives rise to a substantial second order nonlinear optical (NLO) response. Here, we use this second harmonic generation (SHG) to our advantage in the in situ study of the deposition of ISAMs. Upon immersion in the NLO-active polyelectrolyte solution, the SHG rises sharply over the first minute, demonstrating a rapid adsorption process. Immersion in the NLO-inactive partner polyelectrolyte leads to an instantaneous reduction in the SHG signal. We also show that the adsorption and ordering of a noncentrosymmetric nonlinear optical polymer increases with increasing PCBS concentration. These studies provide deeper understanding of the processes by which noncentrosymmetric order is formed in ISAM films and allows design of improved self-assembled nonlinear optical materials.

  19. Durability of self-assembled monolayers on aluminum oxide surface for determining surface wettability

    NASA Astrophysics Data System (ADS)

    Lee, Jaejun; Bong, Jihye; Ha, Young-Geun; Park, Sangyoon; Ju, Sanghyun

    2015-03-01

    The durable non-wettability of functionalized aluminum oxide (Al2O3) thin films coated with two different self-assembled monolayers (SAMs), phosphonic acid (HDF-PA) and trichlorosilane (HDF-S), was investigated by a water flow test method. After exposing the surface to 5 L of water droplets, the contact angle of HDF-S coated Al2O3 thin films remained at the initial value of ∼102.7°, while the contact angle of HDF-PA coated Al2O3 thin films decreased from an initial value of ∼99.9° to a value of ∼69.3°. Thermal annealing effect at various temperature post formation of the self-assembled HDF-PA on the Al2O3 were investigated and shown to enhance the durability of SAMs with a constant contact angle (∼100°) annealed at 100-150 °C.

  20. Structural organization of DMPC lipid layers on chemically micropatterned self-assembled monolayers as biomimetic systems.

    PubMed

    Brechling, A; Pohl, M; Kleineberg, U; Heinzmann, U

    2004-08-26

    The growth structure of DMPC lipid layers on hydrophobic and hydrophilic alkylsilane-based self-assembled monolayers adsorbed on silicon has been investigated by means of X-ray reflectometry and atomic force microscopy. Hydrophilic modification of hydrophobically terminated ODS-SAMs has been achieved by dose-controlled irradiation with DUV light. While island formation of small DMPC bilayer islands is observed on hydrophobic SAM surfaces, closed layers of DMPC monolayers are formed on hydrophilic SAM surfaces. Furthermore, DMPC adsorption on chemically micropatterned substrates with alternating hydrophobic/hydrophilic surface properties has been studied by imaging ellipsometry and photoemission microscopy. Indication for at least partial bridging of hydrophobic areas by an adsorbed DMPC monolayer has been found. PMID:15288947

  1. Organic memory device with self-assembly monolayered aptamer conjugated nanoparticles

    NASA Astrophysics Data System (ADS)

    Oh, Sewook; Kim, Minkeun; Kim, Yejin; Jung, Hunsang; Yoon, Tae-Sik; Choi, Young-Jin; Jung Kang, Chi; Moon, Myeong-Ju; Jeong, Yong-Yeon; Park, In-Kyu; Ho Lee, Hyun

    2013-08-01

    An organic memory structure using monolayered aptamer conjugated gold nanoparticles (Au NPs) as charge storage nodes was demonstrated. Metal-pentacene-insulator-semiconductor device was adopted for the non-volatile memory effect through self assembly monolayer of A10-aptamer conjugated Au NPs, which was formed on functionalized insulator surface with prostate-specific membrane antigen protein. The capacitance versus voltage (C-V) curves obtained for the monolayered Au NPs capacitor exhibited substantial flat-band voltage shift (ΔVFB) or memory window of 3.76 V under (+/-)7 V voltage sweep. The memory device format can be potentially expanded to a highly specific capacitive sensor for the aptamer-specific biomolecule detection.

  2. Self-assembled monolayers of alkanethiolates on surface chemistry groups in osteosarcoma cells

    PubMed Central

    DENG, YING-HU; LI, LI-HUA; HE, JIN; LI, MEI; ZHANG, YU; WANG, XIU-MEI; CUI, FU-ZHAI; XIA, HONG

    2015-01-01

    Cell biomedical behavior is influenced by a number of factors, and the extracellular matrix (ECM) of the cellular microenvironment affects certain cancer cells. In the current study, U-2OS cells were cultured on gold surfaces modified with different terminal chemical groups [methyl (-CH3), amino (-NH2), hydroxyl (-OH) and carboxyl (-COOH)]. The results revealed that different chemical surfaces convey different behaviors. The density of the different functional surfaces was confirmed by atomic force microscopy. Cell morphology, proliferation rate and cell cycle were investigated using scanning electron microscopy, cell counting and flow cytometry. In conclusion, the type of chemical group on a biomaterial is an important property for the growth of osteosarcoma cells; -NH2 and -COOH surfaces sustained visible cell adhesion and promoted cell growth. PMID:25373556

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

    PubMed

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

    2012-11-15

    A stable suspension of α-Fe(2)O(3) (hematite) was synthesized according to the method of Matijevic and Scheiner by an acidic hydrolysis of ferric chloride. The average size of the particles was determined by dynamic light scattering (DLS) and atomic force microscopy (AFM) and was 22 nm. The electrophoretic mobility and zeta potential of particles were determined as a function of ionic strength and pH. The zeta potential of the hematite particles was positive for pH<8.9 (isoelectric point) and negative otherwise. Using the suspension, systematic studies of particle deposition kinetics on mica were carried out. The coverage of self-assembled particle monolayers was determined by AFM and SEM imaging. Particle deposition was diffusion controlled, with the initial rate proportional to the bulk concentration of particles. On the other hand, for long times, the saturation coverage was attained, increasing systematically with ionic strength. The deposition kinetic runs were adequately reflected by the random sequential adsorption (RSA) model. Additionally, particle desorption kinetics, from previously formed monolayers, were studied using the AFM and SEM methods. It was confirmed that hematite particle desorption was practically negligible within the time period of 60 h. Our experimental data proved, therefore, that it is feasible to produce uniform and stable hematite particle monolayers of desired coverage in self-assembly processes controlled by the bulk suspension concentration and the ionic strength. PMID:22909964

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  5. Second-harmonic generation in resonant waveguide gratings incorporating ionic self-assembled monolayer polymer films.

    PubMed

    Purvinis, Georgeanne; Priambodo, Purnomo S; Pomerantz, Martin; Zhou, Ming; Maldonado, Theresa A; Magnusson, Robert

    2004-05-15

    Experimental results on resonantly excited second-harmonic generation (SHG) in a periodic ionically self-assembled monolayer (ISAM) film are reported. A double-layer guided-mode resonance filter (GMRF) structure is coated with 40 bilayers of pyrlium-based chi(2) ISAM thin film and excited with the fundamental of a Nd:YAG laser. Enhanced second-harmonic conversion in the ISAM film is achieved because of the local field enhancement associated with the fundamental resonating leaky mode. This method of SHG is particularly promising, as the ISAM films under investigation exhibit anomalous dispersion that may be applied for phase matching to improve nonlinear conversion efficiency. PMID:15182001

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  7. Second-harmonic generation in resonant waveguide gratings incorporating ionic self-assembled monolayer polymer films

    NASA Astrophysics Data System (ADS)

    Purvinis, Georgeanne; Priambodo, Purnomo S.; Pomerantz, Martin; Zhou, Ming; Maldonado, Theresa A.; Magnusson, Robert

    2004-05-01

    Experimental results on resonantly excited second-harmonic generation (SHG) in a periodic ionically self-assembled monolayer (ISAM) film are reported. A double-layer guided-mode resonance filter (GMRF) structure is coated with 40 bilayers of pyrlium-based chi^(2) ISAM thin film and excited with the fundamental of a Nd:YAG laser. Enhanced second-harmonic conversion in the ISAM film is achieved because of the local field enhancement associated with the fundamental resonating leaky mode. This method of SHG is particularly promising, as the ISAM films under investigation exhibit anomalous dispersion that may be applied for phase matching to improve nonlinear conversion efficiency.

  8. Examining the effects of self-assembled monolayers on nanoporous gold based amperometric glucose biosensors.

    PubMed

    Xiao, Xinxin; Li, Hui; Wang, Meng'en; Zhang, Kai; Si, Pengchao

    2014-01-21

    Nanoporous gold (NPG) based biosensors have been constructed by covalently immobilizing glucose oxidase (GOx) onto self-assembled monolayers (SAMs). With p-benzoquinone (BQ) as a mediator, diffusion behavior and amperometric biosensor performance are evaluated by electrochemical characterization. The enzyme modified electrodes are demonstrated to show a thickness-sensitive behavior. Compared with planar polycrystalline gold, the unique porous structure of NPG has also been characterized via an electrochemical surface reconstruction process. Single-crystal gold-like electrochemical behavior on NPG and a comprehensive understanding of its impacts on sensor performance have been proposed. PMID:24256634

  9. The nucleation and growth of calcium oxalate monohydrate on self- assembled monolayers (SAMs)

    SciTech Connect

    Campbell, A.A.; Tarasevich, B.J.; Graff, G.L.; Fryxell, G.E.; Rieke, P.C.

    1992-05-01

    A physical chemical approach was used to study calcium oxalate monohydrate (COM) nucleation and growth on various organic interfaces. Self-assembling monolayers (SAMs), containing derivatized organic functional groups, were designed to mimic various amino acid residues present in both urine and stone matrix macromolecules. Derivatized surfaces include SAMs with terminal methyl, bromo, imidazole, and thiazolidine-carboxylic acid functional groups. Pronounced differences in COM deposition were observed for the various interfaces with the imidazole and thiazolidine surfaces having the greatest effect and the methyl and bromo groups having little or no nucleating potential.

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

    DOEpatents

    Laskin, Julia; Wang, Peng

    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.

  11. Hermetically sealed microwell with a lipid bilayer created using a self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Forbes, Ruaridh; Kashimura, Yoshiaki; Sumitomo, Koji

    2015-11-01

    To provide a platform for biodevices designed to characterize membrane proteins, we fabricated a new type of microwell sealed with a lipid membrane on a SiO2 substrate. The microwell is surrounded by a Au ring with a self-assembled monolayer, on which a lipid membrane is formed to create a seal. Fluorescence and electrophysiological studies reveal that the structure prevents unfavorable ion leakage from/into microwells. By separating the microwells and outer regions, ion diffusion through the water layer between the membrane and the substrate is reduced. This study offers a promising approach for the functional analysis of membrane proteins.

  12. Reversible lability by in situ reaction of self-assembled monolayers.

    PubMed

    Saavedra, Héctor M; Thompson, Christopher M; Hohman, J Nathan; Crespi, Vincent H; Weiss, Paul S

    2009-02-18

    We describe a new methodology for the fabrication of controllably displaceable monolayers using a carboxyl-functionalized self-assembled monolayer and in situ Fischer esterification, a simple and reversible chemical reaction. Using an 11-mercaptoundecanoic acid monolayer as a model system, we show that in situ esterification results in the creation of subtle chemical and structural defects. These defects promote molecular exchange reactions with n-dodecanethiol molecules, leading to the complete and rapid displacement of the exposed areas. Displacement results in well-ordered crystalline n-dodecanethiolate monolayer films. We also show that the complementary hydrolysis reaction can be employed to quench the reacted monolayer, significantly hindering further displacement. The generality of reversible lability was tested by applying the in situ esterification reaction to the structurally distinct carboxyl-functionalized molecule 3-mercapto-1-adamantanecarboxylic acid. Beyond its applicability to create mixed-composition monolayers, this methodology could be combined with chemical patterning techniques, such as microdisplacement printing, to fabricate complex functional surfaces. PMID:19170497

  13. Self-assembled monolayer of graphene/Pt as counter electrode for efficient dye-sensitized solar cell.

    PubMed

    Gong, Feng; Wang, Hong; Wang, Zhong-Sheng

    2011-10-21

    Monolayer of PDDA/graphene/PDDA/H(2)PtCl(6) is fabricated on conductive glass using electrostatic layer-by-layer self-assembly technique, which is then converted to graphene/Pt monolayer for use as counter electrode in dye-sensitized solar cell (DSSC). As compared to the sputtered Pt counter electrode, the self-assembled monolayer reduces the Pt amount by about 1000-fold but exhibits comparable photovoltaic performance. This finding provides a new route to fabrication of cheap and efficient counter electrodes for flow-line production of DSSCs. PMID:21909512

  14. Nonlinear Optical Studies of Self-Assembled Monolayers (SAM) Silica-SAM-Water Interface Probed With Second Harmonic Generation

    NASA Astrophysics Data System (ADS)

    James, Kenneth

    2010-03-01

    Second harmonic generation (SHG) is a successful and widely used technique for the study of surfaces and surface phenomena. We present a novel technique using second harmonic generation from oriented water molecules in the Gouy-Chapman diffuse layer at the alkylsiloxane and biomolecular self assembled monolayer (SAM) interface with water to measure distance between the solid surface and the average location of the oriented water in the diffuse layer. Distances of one nanometer can be distinguished. This in situ probe is applicable for organic adsorbates which in general will push the diffuse layer away from the solid surface. The organic layer thickness can be used to obtain the adsorption fraction. From this and an understanding of the likely chemistry, the orientation of the molecules can be inferred. We have demonstrated this technique on three molecular systems: hydrophobic self assembled monolayers of methoxysilane molecules of varying hydrocarbon chain length, self assembled monolayers of streptavidin glycoproteins and the combined streptavidin-biotinylated antibody monolayer.

  15. A van der Waals density functional investigation of carboranethiol self-assembled monolayers on Au(111).

    PubMed

    Mete, Ersen; Yılmaz, Ayşen; Danışman, Mehmet Fatih

    2016-05-14

    Isolated and full monolayer adsorption of various carboranethiol (C2B10H12S) isomers on the gold(111) surface has been investigated using both the standard and van der Waals density functional theory calculations. The effect of different molecular dipole moment orientations on the low energy adlayer geometries, the binding characteristics and the electronic properties of the self-assembled monolayers of these isomers has been studied. Specifically, the binding energy and work function changes associated with different molecules show a correlation with their dipole moments. The adsorption is favored for the isomers with dipole moments parallel to the surface. Of the two possible unit cell structures, (5 × 5) was found to be more stable than . PMID:27108565

  16. Multichannel surface imaging and analysis of self-assembled monolayers and proteins

    NASA Astrophysics Data System (ADS)

    Pyo, Hyeon-Bong; Shin, Yong-Beom; Kim, Min-Gon; Yoon, Hyun C.

    2004-03-01

    Multichannel images of 11-Mercaptoundecanoic acid and 11-Mercapto-1-undecanol self-assembled monolayers (SAMs) together with a biospecific interferon-gamma (IFN-gamma)/anti-IFN-gamma antibody immunoreaction were observed by two-dimensional surface plasmon resonance (2D-SPR) imaging system. Patterning process for SAM was simplified by exploiting direct photooxidation of thiol bonding (photolysis) instead of conventional photolithography. Sharper images were resolved by using a white light source in combination with a narrow bandpass filter, minimizing the diffraction patterns on the images. The line profile calibration of the image contrast caused by different resonance conditions at each points on the sensor surface enabled us to discriminate the monolayer thickness in a sub-nanometer scale. For protein patterning, a precipitation scheme induced by biocatalytic reaction was implied for the signal amplification. Specific binding of IFN-gamma antigen with surface-immobilized antibody was found detectable down to the concentration of 1 ng/mL.

  17. Morphology control of perovskite light-emitting diodes by using amino acid self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Wang, Nana; Cheng, Lu; Si, Junjie; Liang, Xiaoyong; Jin, Yizheng; Wang, Jianpu; Huang, Wei

    2016-04-01

    Amino acid self-assembled monolayers are used in the fabrication of light-emitting diodes based on organic-inorganic halide perovskites. The monolayers of amino acids provide modified interfaces by anchoring to the surfaces of ZnO charge-transporting layers using carboxyl groups, leaving the amino groups to facilitate the nucleation of MAPbBr3 perovskite films. This surface-modification strategy, together with chlorobenzene-assisted fast crystallization method, results in good surface coverage and reduced defect density of the perovskite films. These efforts lead to green perovskite light emitting diodes with a low turn-on voltage of 2 V and an external quantum efficiency of 0.43% at a brightness of ˜5000 cd m-2.

  18. Controlling surface functionality through generation of thiol groups in a self-assembled monolayer.

    SciTech Connect

    Lud, S. Q.; Neppl, S.; Richter, G.; Bruno, P.; Gruen, D. M.; Jordan, R.; Feulner, P.; Stutzmann, M.; Garrido, J. A.; Materials Science Division; Technische Univ. Munchen

    2010-01-01

    A lithographic method to generate reactive thiol groups on functionalized synthetic diamond for biosensor and molecular electronic applications is developed. We demonstrate that ultrananocrystalline diamond (UNCD) thin films covalently functionalized with surface-generated thiol groups allow controlled thiol-disulfide exchange surface hybridization processes. The generation of the thiol functional head groups was obtained by irradiating phenylsulfonic acid (PSA) monolayers on UNCD surfaces. The conversion of the functional headgroup of the self-assembled monolayer was verified by using X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and fluorescence microscopy. Our findings indicate the selective generation of reactive thiol surface groups. Furthermore, we demonstrate the grafting of yeast cytochrome c to the thiol-modified diamond surface and the electron transfer between protein and electrode.

  19. Formation of a polymer particle monolayer by continuous self-assembly from a colloidal solution.

    PubMed

    Kim, Soohyun; Choi, Hee-Dok; Kim, Il-Doo; Lee, Jong-Chan; Rhee, Bum Ku; Lim, Jung Ah; Hong, Jae-Min

    2012-02-15

    The preparation of two-dimensional monolayers of polymer particles over a large area was demonstrated via a facile solution process. Polymer microspheres were continuously self-assembled into a close-packed monolayer from a colloidal solution confined between two plates such that the top plate was carefully dragged at a constant velocity in the direction opposite that of the monolayer growth. In situ direct observation of the particle movement during the coating process confirmed that particle transport was directed toward the contact line of the solution meniscus by evaporation-induced convective flow. Sliding of the top plate apparently effectively counterbalanced the convective flow to provide the particles with a contact line for growth of a monolayer particle array. The influence of particle concentration, sliding speed of the top plate, and surface wettability of the bottom substrate were investigated and optimized. Monolayer particle arrays were successfully demonstrated as a template for the preparation of ZnO films with ordered hollow hemispherical structures. This approach is applicable to the fabrication of ordered structures of monodispersed particles composed of various materials over large areas. PMID:22169181

  20. Functionalized self-assembled monolayers on mesoporous silica nanoparticles with high surface coverage

    PubMed Central

    2012-01-01

    Mesoporous silica nanoparticles (MSNs) containing vinyl-, propyl-, isobutyl- and phenyl functionalized monolayers were reported. These functionalized MSNs were prepared via molecular self-assembly of organosilanes on the mesoporous supports. The relative surface coverage of the organic monolayers can reach up to 100% (about 5.06 silanes/nm2). These monolayer functionalize MSNs were analyzed by a number of techniques including transmission electron microscope, fourier transform infrared spectroscopy, X-ray diffraction pattern, cross-polarized Si29 MAS NMR spectroscopy, and nitrogen sorption measurement. The main elements (i.e., the number of absorbed water, the reactivity of organosilanes, and the stereochemistry of organosilane) that greatly affected the surface coverage and the quality of the organic functionalized monolayers on MSNs were fully discussed. The results show that the proper amount of physically absorbed water, the use of high active trichlorosilanes, and the functional groups with less steric hindrance are essential to generate MSNs with high surface coverage of monolayers. PMID:22720819

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

    PubMed

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1999-08-01

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

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

    DOE PAGESBeta

    Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; Kim, Yi-Yeoun; Schenk, Anna S.; Kulak, Alexander N.; Comyn, Timothy P.; Chammas, Oliver; Harder, Ross J.; Duffy, Dorothy M.; et al

    2016-06-15

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

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

    PubMed

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

    2015-11-11

    The optoelectronic tunability offered by colloidal quantum dots (CQDs) is attractive for photovoltaic applications but demands proper band alignment at electrodes for efficient charge extraction at minimal cost to voltage. With this goal in mind, self-assembled monolayers (SAMs) can be used to modify interface energy levels locally. However, to be effective SAMs must be made robust to treatment using the various solvents and ligands required for to fabricate high quality CQD solids. We report robust self-assembled monolayers (R-SAMs) that enable us to increase the efficiency of CQD photovoltaics. Only by developing a process for secure anchoring of aromatic SAMs, aided by deposition of the SAMs in a water-free deposition environment, were we able to provide an interface modification that was robust against the ensuing chemical treatments needed in the fabrication of CQD solids. The energy alignment at the rectifying interface was tailored by tuning the R-SAM for optimal alignment relative to the CQD quantum-confined electron energy levels. This resulted in a CQD PV record power conversion efficiency (PCE) of 10.7% with enhanced reproducibility relative to controls. PMID:26509283

  5. Atomic force microscopy reveals two phases in single stranded DNA self-assembled monolayers.

    PubMed

    Kosaka, Priscila M; González, Sheila; Domínguez, Carmen M; Cebollada, Alfonso; San Paulo, Alvaro; Calleja, Montserrat; Tamayo, Javier

    2013-08-21

    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. PMID:23832284

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

    NASA Astrophysics Data System (ADS)

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

    2007-11-01

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

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

    PubMed Central

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

    2013-01-01

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

  8. Microcavity substrates casted from self-assembled microsphere monolayers for spheroid cell culture

    PubMed Central

    Shen, Keyue; Lee, Jungwoo; Yarmush, Martin L.

    2015-01-01

    Multicellular spheroids are an important 3-dimensional cell culture model that reflects many key aspects of in vivo microenvironments. This paper presents a scalable, self-assembly based approach for fabricating microcavity substrates for multicellular spheroid cell culture. Hydrophobic glass microbeads were self-assembled into a tightly packed monolayer through the combined actions of surface tension, gravity, and lateral capillary forces at the water-air interface of a polymer solution. The packed bead monolayer was subsequently embedded in the dried polymer layer. The surface was used as a template for replicating microcavity substrates with perfect spherical shapes. We demonstrated the use of the substrate in monitoring the formation process of tumor spheroids, a proof-of-concept scale-up fabrication procedure into standard microplate formats, and its application in testing cancer drug responses in the context of bone marrow stromal cells. The presented technique offers a simple and effective way of forming high-density uniformlysized spheroids without microfabrication equipment for biological and drug screening applications. PMID:24781882

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

    NASA Technical Reports Server (NTRS)

    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

  10. Studies of metal ion binding by apo-metallothioneins attached onto preformed self-assembled monolayers using a highly sensitive surface plasmon resonance spectrometer

    PubMed Central

    Zhang, Yintang; Xu, Maotian; Wang, Yanju; Toledo, Freddy; Zhou, Feimeng

    2007-01-01

    The use of a flow-injection surface plasmon resonance (FI-SPR) spectrometer equipped with a bicell detector or a position-sensitive device for determining coordination of heavy metal ions (Cd2+ and Hg2+) by surface-confined apo-metallothionein (apo-MT) molecules is described. To facilitate the formation of a compact MT adsorbate layer with a uniform surface orientation, MT molecules were attached onto a preformed alkanethiol self-assembled monolayer. The method resorts to the generation of apo-MT at the surface by treating the MT-covered sensor chip with glycine–HCl and the measurement of the apo-MT conformation changes upon metal ion incorporation. Domain-specific metal ion binding processes by the apo-MT molecules were observed. Competitive replacement of one metal ion by another can be monitored in real time by FI-SPR. The tandem use of an immobilization scheme for forming a sub-monolayer of MT molecules at the sensor surface and the highly sensitive FI-SPR instrument affords a low concentration detection level. The detection level for Cd2+ (0.1 μM or 15 ppb) compares favorably with similar studies and the methodology complements to other well-established sensitive analytical techniques. The extent of metal incorporation by apo-MT molecules was also determined. PMID:18493298

  11. X-ray spectroscopy characterization of self-assembled monolayers of nitrile-substituted oligo(phenylene ethynylene)s with variable chain length

    PubMed Central

    Hamoudi, Hicham; Kao, Ping; Nefedov, Alexei; Allara, David L

    2012-01-01

    Summary Self-assembled monolayers (SAMs) of nitrile-substituted oligo(phenylene ethynylene) thiols (NC-OPEn) with a variable chain length n (n ranging from one to three structural units) on Au(111) were studied by synchrotron-based high-resolution X-ray photoelectron spectroscopy and near-edge absorption fine-structure spectroscopy. The experimental data suggest that the NC-OPEn molecules form well-defined SAMs on Au(111), with all the molecules bound to the substrate through the gold–thiolate anchor and the nitrile tail groups located at the SAM–ambient interface. The packing density in these SAMs was found to be close to that of alkanethiolate monolayers on Au(111), independent of the chain length. Similar behavior was found for the molecular inclination, with an average tilt angle of ~33–36° for all the target systems. In contrast, the average twist of the OPEn backbone (planar conformation) was found to depend on the molecular length, being close to 45° for the films comprising the short OPE chains and ~53.5° for the long chains. Analysis of the data suggests that the attachment of the nitrile moiety, which served as a spectroscopic marker group, to the OPEn backbone did not significantly affect the molecular orientation in the SAMs. PMID:22428092

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

    NASA Astrophysics Data System (ADS)

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

    2009-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  14. Conversion of self-assembled monolayers into nanocrystalline graphene: structure and electric transport.

    PubMed

    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. PMID:21491948

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

    SciTech Connect

    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{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.

  16. The impact of solution agglomeration on the deposition of self-assembled monolayers

    SciTech Connect

    BUNKER,BRUCE C.; CARPICK,ROBERT W.; ASSINK,ROGER A.; THOMAS,MICHAEL L.; HANKINS,MATTHEW G.; VOIGT,JAMES A.; SIPOLA,DIANA L.; DE BOER,MAARTEN P.; GULLEY,GERALD L.

    2000-04-17

    Self-assembled monolayers (SAMS) are commonly produced by immersing substrates in organic solutions containing trichlorosilane coupling agents. Unfortunately, such deposition solutions can also form alternate structures including inverse micelles and lamellar phases. The formation of alternate phases is one reason for the sensitivity of SAM depositions to factors such as the water content of the deposition solvent. If such phases are present, the performance of thin films used for applications such as minimization of friction and stiction in micromachines can be seriously compromised. Inverse micelle formation has been studied in detail for depositions involve 1H-, 1H-, 2H-, 2H-perfluorodecyltrichlorosilane (FDTS) in isooctane. Nuclear magnetic resonance experiments have been used to monitor the kinetics of hydrolysis and condensation reactions between water and FDTS. Light scattering experiments show that when hydrolyzed FDTS concentrations reach a critical concentration, there is a burst of nucleation to form high concentrations of spherical agglomerates. Atomic force microscopy results show that the agglomerates then deposit on substrate surfaces. Deposition conditions leading to monolayer formation involve using deposition times that are short relative to the induction time for agglomeration. After deposition, inverse micelles can be converted into lamellar or monolayer structures with appropriate heat treatments if surface concentrations are relatively low.

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

    NASA Astrophysics Data System (ADS)

    Kind, Martin; Wöll, Christof

    2009-07-01

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

  18. Formation of Ordered 4-Fluorobenzenethiol Self-Assembled Monolayers on Au(111) from Vapor Phase Deposition.

    PubMed

    Kang, Hungu; Ito, Eisuke; Hara, Masahiko; Noh, Jaegeun

    2016-03-01

    Self-assembled monolayers (SAMs) were formed by the spontaneous adsorption of 4-fluorobenzenethiol (4-FBT) on Au(111) using both solution and ambient-pressure vapor deposition methods at room temperature. The surface structure and thermal desorption properties of 4-FBT SAMs were examined by scanning tunneling microscopy (STM) and thermal desorption spectroscopy (TDS). STM imaging showed that 4-FBT SAMs formed in solution at room temperature mainly contained disordered phase with gold adatom islands, while those formed by ambient-pressure vapor deposition had well-ordered phase, which can be described as a (2 x 2√13)R45 degrees structure. In addition, thermal desorption spectroscopy (TDS) measurements showed that strong desorption peak for parent mass fragment (m/z = 128, FC6H5SH+) for 4-FBT SAMs on Au(111) was observed at 460 K, as a result of hydrogen abstract reaction of chemisorbed thiolates during desorption. PMID:27455712

  19. Soft-Landing of Peptide IOns Onto Self-Assembled Monolayer Surfaces: an Overview

    SciTech Connect

    Laskin, Julia; Wang, Peng; Hadjar, Omar

    2008-02-28

    This review is focused on what has been learned in recent research studies concerned with fundamental aspects of soft-landing and reactive landing of peptide ions on self-assembled monolayer surfaces (SAMs). Peptide ions are particularly attractive model systems that provide important insights on the behavior of soft landed proteins, while SAMs provide a convenient and flexible platform for tailoring the interfacial properties of metals and semiconductor surfaces. Deposition of mass-selected ions on surfaces is accompanied by a number of processes including charge reduction, neutralization, covalent and non-covalent binding, and thermal desorption of ions and molecules from the substrate. Factors that affect the competition between these processes are discussed.

  20. Nanomechanical actuation of a silicon cantilever using an azo dye, self-assembled monolayer.

    PubMed

    Rastegar, A Joseph; Vosgueritchian, Michael; Doll, Joseph C; Mallon, Joseph R; Pruitt, Beth L

    2013-06-11

    The emerging fields of nanomotors and optomechanics are based on the harnessing of light to generate force. However, our ability to detect small surface stresses is limited by temperature drift, environmental noise, and low-frequency flicker electronic noise. To address these limitations, we functionalized microfabricated silicon cantilevers with an azo dye, silane-based self-assembled monolayer and modulated the surface stress by exciting the optical switch with a 405-nm laser. Atomic force microscopy, contact angle analysis, ellipsometry, and X-ray photoelectron spectroscopy verified successful assembly of molecules on the cantilever. Ultraviolet and visible spectra demonstrate optical switching of the synthesized molecule in solution. By turning the laser on and off at a specific rate (e.g., 1 Hz), the cantilever deflection can be measured via Fourier techniques, thus separating the signal of interest from the noise. This technique empowers the design of highly sensitive surface stress measurements. PMID:23663108

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

    SciTech Connect

    Mi, Hongyi; Mikael, Solomon; Seo, Jung-Hun; Gui, Gui; Ma, Alice L.; Ma, Zhenqiang E-mail: mazq@engr.wisc.edu; Liu, Chi-Chun; Nealey, Paul F. E-mail: mazq@engr.wisc.edu

    2015-10-05

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

  2. Neutron Reflection Study of Bovine β-Casein Adsorbed on OTS Self- Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    Fragneto, Giovanna; Thomas, Robert K.; Rennie, Adrian R.; Penfold, Jeffrey

    1995-02-01

    Specular neutron reflection has been used to determine the structure and composition of bovine β-casein adsorbed on a solid surface from an aqueous phosphate-buffered solution at pH 7. The protein was adsorbed on a hydrophobic monolayer self-assembled from deuterated octadecyltrichlorosilane solution on a silicon (111) surface. A two-layer structure formed consisting of one dense layer of thickness 23 ± 1 angstroms and a surface coverage of 1.9 milligrams per square meter adjacent to the surface and an external layer protruding into the solution of thickness 35 ± 1 angstroms and 12 percent protein volume fraction. The structure of the (β-casein) layer is explained in terms of the charge distribution in the protein.

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

    NASA Astrophysics Data System (ADS)

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

    2005-03-01

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

  4. Protein interactions with self-assembled monolayers presenting multimodal ligands: a surface plasmon resonance study.

    PubMed

    Vutukuru, Srinavya; Bethi, Sridhar R; Kane, Ravi S

    2006-11-21

    This paper describes the use of surface plasmon resonance (SPR) spectroscopy and self-assembled monolayers (SAMs) to understand the characteristics of surfaces that promote the adsorption of proteins at high ionic strengths (high-salt conditions). We synthesized SAMs presenting different multimodal ligands and determined the influence of surface composition, solution composition, and the nature of the protein on the extent of protein adsorption onto the SAMs. Our results confirm that hydrophobic interactions can contribute significantly to protein adsorption under high-salt conditions. In particular, the extent of protein adsorption under high-salt conditions increased with increasing surface hydrophobicity. The extent of protein adsorption was also influenced by the solution composition and decreased with an increase in the chaotropicity of the anion. The combination of SPR and SAMs is well-suited for studying the interaction of proteins with complex surfaces of relevance to chromatography. PMID:17107014

  5. Zinc oxide growth morphology on self-assembled monolayer modified silver surfaces.

    PubMed

    Hsu, Julia W P; Clift, W Miles; Brewer, Luke N

    2008-05-20

    Using organic molecules to direct inorganic crystal growth has opened up new avenues for controlled synthesis on surfaces. Combined with soft lithography to form patterned templates, self-assembled monolayers (SAMs) have been shown to be a powerful approach for the assembly of inorganic nanostructures. In this work, we show that the surface free energy of SAM-modified silver, which depends on end groups and deposition method of SAMs, has a dramatic effect on the nucleation and growth of crystalline ZnO, a technologically important material, from supersaturated solutions. For SAMs with inert methyl end groups, ZnO nucleation is inhibited. For SAMs with chemically active (carboxylic or thiol) end groups, the ZnO morphology is found to be three-dimensional nanorods on low-surface-energy surfaces and two-dimensional thin films on high-energy surfaces. PMID:18399664

  6. Nanoimprinting of Photonic-Bandgap Devices in Ionically Self-Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    Li, J.; Evoy, S.; Duncan, R.; Vercinello, M.; Stevenson, P.; Heflin, J. R.

    2003-03-01

    Photonic Crystals (PCs) are a new class of materials providing new opportunities for the enhancement control of the propagation of light in waveguides and laser action in 2D distributed feedback structures. However, in order to possess nonzero even-order nonlinear optical susceptibilities, a material must lack a center of inversion at the macroscopic level. As a result several novel methods for creating noncentrosymmetric materials incorporating organic molecules with large molecular susceptibilities have been developed over the past decade. Using commercial ionic polymer dyes, ionically self-assembled monolayers (ISAMs) provide a new platform to produce such noncentrosymmetric arrangement of nonlinear optical chromophores Originally developed by Chou, nanoimprinting techniques provide a powerful alternative to e-beam lithography for definition of photonic structures in ISAM films. Here we report the nanoimprinting of photonic structures in such films.

  7. Infrared spectroscopy of large scale single layer graphene on self assembled organic monolayer

    SciTech Connect

    Woo Kim, Nak; Youn Kim, Joo; Lee, Chul; Choi, E. J.; Jin Kim, Sang; Hee Hong, Byung

    2014-01-27

    We study the effect of self-assembled monolayer (SAM) organic molecule substrate on large scale single layer graphene using infrared transmission measurement on Graphene/SAM/SiO{sub 2}/Si composite samples. From the Drude weight of the chemically inert CH{sub 3}-SAM, the electron-donating NH{sub 2}-SAM, and the SAM-less graphene, we determine the carrier density doped into graphene by the three sources—the SiO{sub 2} substrate, the gas-adsorption, and the functional group of the SAM's—separately. The SAM-treatment leads to the low carrier density N ∼ 4 × 10{sup 11} cm{sup −2} by blocking the dominant SiO{sub 2}- driven doping. The carrier scattering increases by the SAM-treatment rather than decreases. However, the transport mobility is nevertheless improved due to the reduced carrier doping.

  8. Infrared spectroscopy of large scale single layer graphene on self assembled organic monolayer

    NASA Astrophysics Data System (ADS)

    Woo Kim, Nak; Youn Kim, Joo; Lee, Chul; Jin Kim, Sang; Hee Hong, Byung; Choi, E. J.

    2014-01-01

    We study the effect of self-assembled monolayer (SAM) organic molecule substrate on large scale single layer graphene using infrared transmission measurement on Graphene/SAM/SiO2/Si composite samples. From the Drude weight of the chemically inert CH3-SAM, the electron-donating NH2-SAM, and the SAM-less graphene, we determine the carrier density doped into graphene by the three sources—the SiO2 substrate, the gas-adsorption, and the functional group of the SAM's—separately. The SAM-treatment leads to the low carrier density N ˜ 4 × 1011 cm-2 by blocking the dominant SiO2- driven doping. The carrier scattering increases by the SAM-treatment rather than decreases. However, the transport mobility is nevertheless improved due to the reduced carrier doping.

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

    SciTech Connect

    Tyagi, Mukta; Agrawal, V. V.; Chandran, Achu; Joshi, Tilak; Prakash, Jai; Biradar, A. M.

    2014-04-14

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

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

    NASA Astrophysics Data System (ADS)

    Tyagi, Mukta; Chandran, Achu; Joshi, Tilak; Prakash, Jai; Agrawal, V. V.; Biradar, A. M.

    2014-04-01

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

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Self-assembled monolayers of shape-persistent macrocycles on graphite: interior design and conformational polymorphism

    PubMed Central

    Vollmeyer, Joscha; Eberhagen, Friederike; Höger, Sigurd

    2014-01-01

    Summary Three shape-persistent naphthylene–phenylene–acetylene macrocycles of identical backbone structures and extraannular substitution patterns but different (empty, apolar, polar) nanopore fillings are self-assembled at the solid/liquid interface of highly oriented pyrolytic graphite and 1,2,4-trichlorobenzene. Submolecularly resolved images of the resulting two-dimensional (2D) crystalline monolayer patterns are obtained by in situ scanning tunneling microscopy. A concentration-dependent conformational polymorphism is found, and open and more dense packing motifs are observed. For all three compounds alike lattice parameters are found, therefore the intermolecular macrocycle distances are mainly determined by their size and symmetry. This is an excellent example that the graphite acts as a template for the macrocycle organization independent from their specific interior. PMID:25550743

  13. Low-damage atomic layer modification of self-assembled monolayer using neutral beam process

    NASA Astrophysics Data System (ADS)

    Ishikawa, Yasushi; Samukawa, Seiji; Ishida, Takao

    2006-09-01

    Damage-free surface nitridation of terphenyl methanethiol self-assembled monolayers (TP1-SAMs) was investigated using a novel low-energy N2 neutral beam (NB) irradiation technique. When a conventional inductively coupled plasma process was used, x-ray photoelectron spectra confirmed that the TP1-SAM was quickly broken because ions or ultraviolet (UV) photons enhance the surface decomposition and molecular desorption. Conversely, with the N2 NB radiation process, which is free of ions and UV photons, there was little difference in the atomic ratios of x-ray photoelectron spectra before and after NB irradiation. These results suggest that low-damage surface modification is possible through the authors' NB technique.

  14. Low-crosstalk high-density polymeric integrated optics incorporating self-assembled scattering monolayer.

    PubMed

    Huang, Guang-Hao; Kim, Jun-Whee; Chu, Woo-Sung; Oh, Min-Cheol; Seo, Jun-Kyu; Noh, Young-Ouk; Lee, Hyung-Jong

    2014-06-16

    Highly integrated optical components are strongly demanded because they enable wavelength-division multiplexing optical communication systems to achieve smaller footprints, lower power consumption, and enhanced reliability. Variable optical attenuator (VOA) arrays are often used with optical switches in cascaded form for reconfigurable optical add-drop multiplexer systems. Although VOAs and optical switches based on polymer waveguide technology are commercially available, it is still not viable to integrate these two array devices on a single chip because of significant interchannel crosstalk. In this work, we resolved the issue of crosstalk and integrated the arrays of optical switch and VOA on a single chip by incorporating a self-assembled scattering monolayer (SASM). The SASM was effective for scattering the planar guided mode; consequently, the crosstalk into an adjacent channel was significantly reduced, to less than -35 dB. PMID:24977521

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

    PubMed

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

    2015-01-01

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

  16. Molecular-like hierarchical self-assembly of monolayers of mixtures of particles

    PubMed Central

    Singh, P.; Hossain, M.; Gurupatham, S. K.; Shah, K.; Amah, E.; Ju, D.; Janjua, M.; Nudurupati, S.; Fischer, I.

    2014-01-01

    We present a technique that uses an externally applied electric field to self-assemble monolayers of mixtures of particles into molecular-like hierarchical arrangements on fluid-liquid interfaces. The arrangements consist of composite particles (analogous to molecules) which are arranged in a pattern. The structure of a composite particle depends on factors such as the relative sizes of the particles and their polarizabilities, and the electric field intensity. If the particles sizes differ by a factor of two or more, the composite particle has a larger particle at its core and several smaller particles form a ring around it. The number of particles in the ring and the spacing between the composite particles depend on their polarizabilities and the electric field intensity. Approximately same sized particles form chains (analogous to polymeric molecules) in which positively and negatively polarized particles alternate. PMID:25510331

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

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

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

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

    PubMed

    Ghosh, Soumya; Hammes-Schiffer, Sharon

    2015-01-01

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

  19. Controlling liquid crystal alignment using photocleavable cyanobiphenyl self-assembled monolayers.

    PubMed

    Prompinit, Panida; Achalkumar, Ammathnadu S; Bramble, Jonathan P; Bushby, Richard J; Wälti, Christoph; Evans, Stephen D

    2010-12-01

    We report on the development of novel cyano-biphenyl-based thiolate self-assembled monolayers designed to promote homeotropic alignment of calamitic liquid crystals. The molecules developed contain an ortho-nitrobenzyl protected carboxylic acid group that on irradiation by soft UV (365 nm) is cleaved to yield carboxylic acid groups exposed at the surface that promote planar alignment. Using a combination of wetting, X-ray photoelectron spectroscopy, Fourier transform-infrared reflection absorption spectroscopy, and ellipsometry we show that high photolysis yields (>90%) can be achieved and that the patterned SAMs are suitable for the controlled alignment of calamitic liquid crystals. This study further shows that such photo-patterned SAMs can be used to control the formation of focal conic domains (FCDs) in the smectic-A phase in terms of positioning and size confinement on surfaces. PMID:21069978

  20. Atomic Structure of Self-Assembled Monolayer of Thiolates on a Tetragonal Au92 Nanocrystal.

    PubMed

    Zeng, Chenjie; Liu, Chong; Chen, Yuxiang; Rosi, Nathaniel L; Jin, Rongchao

    2016-07-20

    Unveiling the ligand binding mode on the crystalline surfaces is important for deciphering the long-standing structural enigma in self-assembled monolayers (SAMs). Here, the binding and patterning structures of thiolates (SR) on the Au(100) crystalline facet are revealed on the basis of the atomic structure of a highly regular, single crystalline Au92(SR)44 nanocrystal. The six exposed facets of this tetragonal nanocrystal give rise to six pieces of "nanoSAMs". We found that thiolates bind to the planar (100) facets of the nanocrystal via a simple bridge-like mode and are assembled into an overlayer with c(2 × 2) symmetry. The Au-S binding mode and translational symmetry in the kernel and on the surface of the Au92 nanocrystal can be generalized infinitely to construct the bulk two-dimensional SAMs and various tetragonal nanocrystals. PMID:27355843

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

    PubMed

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

    2009-12-01

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

  2. Overcoming metal-induced fluorescence quenching on plasmo-photonic metasurfaces coated by a self-assembled monolayer.

    PubMed

    Choi, Bongseok; Iwanaga, Masanobu; Miyazaki, Hideki T; Sugimoto, Yoshimasa; Ohtake, Akihiro; Sakoda, Kazuaki

    2015-07-21

    We have experimentally shown significant suppression of metal-induced fluorescence (FL) quenching on plasmo-photonic metasurfaces by incorporating a self-assembled monolayer (SAM) of sub-nm thickness. The FL signals of rhodamine dye molecules have been several-ten-fold enhanced by introducing the SAM, in comparison with the previous configuration contacting molecules and metal surfaces. PMID:26088784

  3. Molecular self-assembly guided by surface reconstruction: CH 3SH monolayer on the Au(1 1 1) surface

    NASA Astrophysics Data System (ADS)

    Maksymovych, Peter; Dougherty, Daniel B.

    2008-06-01

    Self-assembly of methanethiol (CH 3SH) on Au(1 1 1) was studied using scanning tunneling microscopy at T < 150 K when the S-H bond is intact. The CH 3SH monolayer assumes a commensurate structure with a

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

    ERIC Educational Resources Information Center

    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…

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

    PubMed

    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. PMID:25550756

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

    PubMed Central

    Adamkiewicz, Malgorzata

    2014-01-01

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

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

    ERIC Educational Resources Information Center

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

    2008-01-01

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

  8. Rapid Self-Assembly of Shaped Microtiles into Large, Close-Packed Crystalline Monolayers on Solid Surfaces.

    PubMed

    Wang, Peng-Yuan; Shields, C W; Zhao, Tianheng; Jami, Hesamodin; López, Gabriel P; Kingshott, Peter

    2016-03-01

    The rapid self-assembly of photolithographic microtiles into large crystalline monolayers is achieved. Crystalline monolayers get trapped at the liquid-liquid interface and re-emerge at the air-liquid interface by mixing a cosolvent, which then deposits on the solid surface in seconds. This method has the potential to assemble different shapes and sizes of microtiles into complex architectures. PMID:26756607

  9. First-Principles Surface Stress Calculations and Multiscale Deformation Analysis of a Self-Assembled Monolayer Adsorbed on a Micro-Cantilever

    PubMed Central

    Shih, Yu-Ching; Chen, Chuin-Shan; Wu, Kuang-Chong

    2014-01-01

    Micro-cantilever sensors are widely used to detect biomolecules, chemical gases, and ionic species. However, the theoretical descriptions and predictive modeling of these devices are not well developed, and lag behind advances in fabrication and applications. In this paper, we present a novel multiscale simulation framework for nanomechanical sensors. This framework, combining density functional theory (DFT) calculations and finite element method (FEM) analysis, is capable of analyzing molecular adsorption-induced deformation and stress fields in the sensors from the molecular scale to the device scale. Adsorption of alkanethiolate self-assembled monolayer (SAM) on the Au(111) surface of the micro-cantilever sensor is studied in detail to demonstrate the applicability of this framework. DFT calculations are employed to investigate the molecular adsorption-induced surface stress upon the gold surface. The 3D shell elements with initial stresses obtained from the DFT calculations serve as SAM domains in the adsorption layer, while FEM is employed to analyze the deformation and stress of the sensor devices. We find that the micro-cantilever tip deflection has a linear relationship with the coverage of the SAM domains. With full coverage, the tip deflection decreases as the molecular chain length increases. The multiscale simulation framework provides a quantitative analysis of the displacement and stress fields, and can be used to predict the response of nanomechanical sensors subjected to complex molecular adsorption. PMID:24763217

  10. Characterizing the molecular order of phosphonic acid self-assembled monolayers on indium tin oxide surfaces.

    PubMed

    Losego, Mark D; Guske, Joshua T; Efremenko, Alina; Maria, Jon-Paul; Franzen, Stefan

    2011-10-01

    Self-assembled monolayers (SAMs) of alkanephosphonic acids with chain lengths between 8 and 18 carbon units were formed on thin films of indium tin oxide (ITO) sputter-deposited on silicon substrates with 400 nm thermally grown SiO(2). The silicon substrates, while not intended for use in near-IR or visible optics applications, do provide smooth surfaces that permit systematic engineering of grain size and surface roughness as a function of the sputter pressure. Argon sputter pressures from 4 to 20 mTorr show systematic changes in surface morphology ranging from smooth, micrometer-sized grain structures to <50 nm grains with 3× higher surface roughness. Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy experiments are conducted for alkanephosphonic acids deposited on these wide range of ITO surfaces to evaluate the effects of these morphological features on monolayer ordering. Results indicate that long-chain SAMs are more highly ordered, and have a smaller tilt angle, than short-chain SAMs. Surprisingly, the 1-octadecyl phosphonic acids maintain their order as the lateral grain dimensions of the ITO surface shrink to ∼50 nm. It is only when the ITO surface roughness becomes greater than the SAM chain length (∼15 Å) that SAMs are observed to become relatively disordered. PMID:21863828

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

    NASA Astrophysics Data System (ADS)

    Ishikawa, Atsushi; Tanaka, Takuo

    2015-07-01

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

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

    PubMed

    Ishikawa, Atsushi; Tanaka, Takuo

    2015-01-01

    The emerging field of plasmonic metamaterials has introduced new degree of freedom to manipulate optical field from nano to macroscopic scale, offering an attractive platform for sensing applications. So far, metamaterial sensor concepts, however, have focused on hot-spot engineering to improve the near-field enhancement, rather than fully exploiting tailored material properties. Here, we present a novel spectroscopic technique based on the metamaterial infrared (IR) absorber allowing for a low-background detection scheme as well as significant plasmonic enhancement. Specifically, we experimentally demonstrate the resonant coupling of plasmonic modes of a metamaterial absorber and IR vibrational modes of a molecular self-assembled monolayer. The metamaterial consisting of an array of Au/MgF2/Au structures exhibits an anomalous absorption at ~ 3000 cm(-1), which spectrally overlaps with C-H stretching vibrational modes. Symmetric/asymmetric C-H stretching modes of a 16-Mercaptohexadecanoic acid monolayer are clearly observed as Fano-like anti-resonance peaks within a broad plasmonic absorption of the metamaterial. Spectral analysis using Fano line-shape fitting reveals the underlying resonant interference in plasmon-molecular coupled systems. Our metamaterial approach achieves the attomole sensitivity with a large signal-to-noise ratio in the far-field measurement, thus may open up new avenues for realizing ultrasensitive IR inspection technologies. PMID:26229011

  13. Disordered self assembled monolayer dielectric induced hysteresis in organic field effect transistors.

    PubMed

    Padma, N; Saxena, Vibha; Sudarsan, V; Rava, Harshil; Sen, Shaswati

    2014-06-01

    A memory device using an organic field effect transistor (OFET) with copper phthalocyanine (CuPc) as active material was fabricated and studied. For this purpose, SiO2 dielectric surface was modified with a disordered self assembled monolayer (SAM) of octadecyltrichlorosilane (OTS) molecule which was found to induce large disorder in CuPc film thereby generating more traps for charge carriers. Drain current-drain voltage characteristics at zero gate voltage exhibited large hysteresis which was not observed in OFET devices with ordered OTS monolayer modified and unmodified SiO2 dielectrics. The extent of hysteresis and drain current on/off ratio, reading voltage etc. were found to be dependent on the sweep rate/step voltage employed during scanning. Highest hysteresis with on/off ratio of about 240 was obtained for an optimum step voltage of 2 V while it decreased with further reduction in the same. This was attributed to the longer scanning time leading to release of trapped carriers during forward scan itself. The OFET device was found to exhibit excellent memory retention capability where OFF and ON current measured for about 2 hours after stressing the device at write and erase voltages showed good retention of on/off ratio. PMID:24738406

  14. Structure and Order of Phosphonic Acid-Based Self-Assembled Monolayers on Si(100)

    PubMed Central

    Dubey, Manish; Weidner, Tobias; Gamble, Lara J.; Castner, David G.

    2010-01-01

    Organophosphonic acid self-assembled monolayers (SAMs) on oxide surfaces have recently seen increased use in electrical and biological sensor applications. The reliability and reproducibility of these sensors require good molecular organization in these SAMs. In this regard, packing, order and alignment in the SAMs is important, as it influences the electron transport measurements. In this study, we examine the order of hydroxyl- and methyl- terminated phosphonate films deposited onto silicon oxide surfaces by the tethering by aggregation and growth method using complementary, state-of-art surface characterization tools. Near edge x-ray absorption fine structure (NEXAFS) spectroscopy and in situ sum frequency generation (SFG) spectroscopy are used to study the order of the phosphonate SAMs in vacuum and under aqueous conditions, respectively. X-ray photoelectron spectroscopy and time of flight secondary ion mass spectrometry results show that these samples form chemically intact monolayer phosphonate films. NEXAFS and SFG spectroscopy showed that molecular order exists in the octadecylphosphonic acid and 11-hydroxyundecylphosphonic acid SAMs. The chain tilt angles in these SAMs were approximately 37° and 45°, respectively. PMID:20735054

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

    PubMed Central

    Ishikawa, Atsushi; Tanaka, Takuo

    2015-01-01

    The emerging field of plasmonic metamaterials has introduced new degree of freedom to manipulate optical field from nano to macroscopic scale, offering an attractive platform for sensing applications. So far, metamaterial sensor concepts, however, have focused on hot-spot engineering to improve the near-field enhancement, rather than fully exploiting tailored material properties. Here, we present a novel spectroscopic technique based on the metamaterial infrared (IR) absorber allowing for a low-background detection scheme as well as significant plasmonic enhancement. Specifically, we experimentally demonstrate the resonant coupling of plasmonic modes of a metamaterial absorber and IR vibrational modes of a molecular self-assembled monolayer. The metamaterial consisting of an array of Au/MgF2/Au structures exhibits an anomalous absorption at ~3000 cm−1, which spectrally overlaps with C-H stretching vibrational modes. Symmetric/asymmetric C-H stretching modes of a 16-Mercaptohexadecanoic acid monolayer are clearly observed as Fano-like anti-resonance peaks within a broad plasmonic absorption of the metamaterial. Spectral analysis using Fano line-shape fitting reveals the underlying resonant interference in plasmon-molecular coupled systems. Our metamaterial approach achieves the attomole sensitivity with a large signal-to-noise ratio in the far-field measurement, thus may open up new avenues for realizing ultrasensitive IR inspection technologies. PMID:26229011

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

    PubMed

    Wang, Qing Hua; Hersam, Mark C

    2009-06-01

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

  17. High density silver nanoparticle monolayers produced by colloid self-assembly on polyelectrolyte supporting layers.

    PubMed

    Oćwieja, Magdalena; Adamczyk, Zbigniew; Morga, Maria; Michna, Aneta

    2011-12-01

    A stable silver nanoparticle suspension was synthesized via the reduction of silver nitrate using sodium borohydride and sodium citrate. The particle's shape and size distribution were measured by various methods. The electrophoretic mobility measurements revealed that the zeta potential of particles was highly negative, increasing slightly with the ionic strength, from -52 mV for I=10(-5) M to -35 mV for I=3×10(-2) M (for pH=5.5). The zeta potential of mica modified by the adsorption of cationic polyelectrolytes: PEI and PAH was also determined using the streaming potential measurements. The modified mica sheets were used as substrates for particle monolayers formed via colloid self assembly. The kinetics of this process, proceeding under diffusion-controlled transport conditions, was quantitatively evaluated by a direct enumeration of particles using the AFM and SEM techniques. Both the kinetics of particle deposition and the maximum surface concentration were determined. From the slope of the initial deposition rates, the equivalent diameter of particles was determined to be 16 nm, in agreement with previous measurements. Based on this finding, an efficient method of determining particle size in suspension was proposed. It was also demonstrated that for higher ionic strengths, the maximum coverage of particle monolayers on PAH modified mica exceeded 0.39. The kinetic data were quantitatively interpreted in terms of the random sequential adsorption (RSA) model using the effective hard particle concept. PMID:21889157

  18. Preparation and characterization of self-assembled monolayers and mesoscale protein patterning

    NASA Astrophysics Data System (ADS)

    Noomuna, Panae

    Bottom-up approach was used to develop self-assembled monolayers of octadecyltrichlorosilane (OTS) and undecenyltrichlorosilane(UTS) on Si(100) wafer. Undecenyltrichlorosilane monolayer was oxidized at the vinyl terminal to generate a carboxylic acid group. Lysozyme protein was immobilized on the polar carboxylic acid group. The developed protein patterns were investigated using fluorescence microscopy. Lysozyme has an isoelectronic point of 11.35. At a pH below this value the protein is positively charged making it a good candidate for electrostatic adsorption on the negatively charge -COO- group. Fluorescence images confirm formation of lysozyme across the silicon wafer. The patterned Si(100) wafer can be used as a biosensor against lysozyme antibodies. Another approach to develop varied surface properties was used to grow OTS on oxidized UTSox via chemical phase deposition (CVD). In this case we used polystyrene and silicon nanospheres as masking agents on the already developed and oxidized UTS. Fluorescence images revealed that OTS layers were formed on the interstitial spaces of the nanosphere masks. Varied protein can be immobilized on this surface due to different terminal groups on the surface.

  19. Ultrafast vibrational dynamics and spectroscopy of a siloxane self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Nihonyanagi, Satoshi; Eftekhari-Bafrooei, Ali; Borguet, Eric

    2011-02-01

    Time and frequency domain sum-frequency generation (SFG) were combined to study the dynamics and structure of self-assembled monolayers (SAMs) on a fused silica surface. SFG-free induction decay (SFG-FID) of octadecylsilane SAM in the CH stretching region shows a relatively long time scale oscillation that reveals that six vibrational modes are involved in the response of the system. Five of the modes have commonly been used for the fitting of SFG spectra in the CH stretching region, namely the symmetric stretch and Fermi resonance of the methyl group, the antisymmetric stretch of the methyl, as well as the symmetric and antisymmetric stretches of the methylene group. The assignment of the sixth mode to the terminal CH2 group was confirmed by performing a density function theory calculation. The SFG-FID measures the vibrational dephasing time (T2) of each of the modes, including a specific CH2 group within the SAM, the terminal CH2, which had never been measured before. The relatively long (˜1.3 ps) dephasing of the terminal CH2 suggests that alkyl monolayer structure is close to that of the liquid condensed phase of Langmuir Blodgett films.

  20. 1-Dodecanethiol based highly stable self-assembled monolayers for germanium passivation

    NASA Astrophysics Data System (ADS)

    Cai, Qi; Xu, Baojian; Ye, Lin; Di, Zengfeng; Huang, Shanluo; Du, Xiaowei; Zhang, Jishen; Jin, Qinghui; Zhao, Jianlong

    2015-10-01

    As a typical semiconductor material, germanium has the potential to replace silicon for future-generation microelectronics, due to its better electrical properties. However, the lack of stable surface state has limited its extensive use for several decades. In this work, we demonstrated highly stable self-assembled monolayers (SAMs) on Ge surface to prevent oxidization for further applications. After the pretreatment in hydrochloric acid, the oxide-free and Cl-terminated Ge could be further coated with 1-dodecanethiol (NDM) SAMs. The influence factors including reaction time, solvent component and reaction temperature were optimized to obtain stable passivated monolayer for oxidation resistance. Contact angle analysis, atomic force microscopy, ellipsometer and X-ray photoelectron spectroscopy were performed to characterize the functionalized Ge surface respectively. Meanwhile, the reaction mechanism and stability of thiols SAMs on Ge (1 1 1) surface were investigated. Finally, highly stable passivated NDM SAMs on Ge surface could be formed through immersing oxide-free Ge in mixture solvent (water/ethanol, v/v = 1:1) at appropriately elevated temperature (∼80 °C) for 24 h. And the corresponding optimized passivated Ge surface was stable for more than 10 days even in water condition, which was much longer than the data reported and paved the way for the future practical applications of Ge.

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

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

    2011-09-01

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

  3. Supramolecular Chemistry And Self-assembly Special Feature: Selective immobilization of proteins to self-assembled monolayers presenting active site-directed capture ligands

    NASA Astrophysics Data System (ADS)

    Hodneland, Christian D.; Lee, Young-Sam; Min, Dal-Hee; Mrksich, Milan

    2002-04-01

    This paper describes a method for the selective and covalent immobilization of proteins to surfaces with control over the density and orientation of the protein. The strategy is based on binding of the serine esterase cutinase to a self-assembled monolayer presenting a phosphonate ligand and the subsequent displacement reaction that covalently binds the ligand to the enzyme active site. Surface plasmon resonance (SPR) spectroscopy showed that cutinase binds irreversibly to a monolayer presenting the capture ligand at a density of 1% mixed among tri(ethylene glycol) groups. The covalent immobilization is specific for cutinase, and the glycol-terminated monolayer effectively prevents unwanted nonspecific adsorption of proteins. To demonstrate that the method could be used to immobilize proteins of interest, a cutinase-calmodulin fusion protein was constructed and immobilized to the monolayer. SPR showed that calcineurin selectively associated with the immobilized calmodulin. This capture ligand immobilization method combines the advantages that the immobilization reaction is highly selective for the intended protein, the tether is covalent and, hence, stable, and the method avoids the need for synthetic modification and rigorous purification of proteins before immobilization. These characteristics make the method well suited to a range of applications and, in particular, for constructing protein microarrays.

  4. Carboranedithiols: building blocks for self-assembled monolayers on copper surfaces.

    PubMed

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

    2012-08-28

    Two different positional isomers of 1,2-dicarba-closo-dodecaboranedithiols, 1,2-(HS)(2)-1,2-C(2)B(10)H(10) (1) and 9,12-(HS)(2)-1,2-C(2)B(10)H(10) (2), have been investigated as cluster building blocks for self-assembled monolayers (SAMs) on copper surfaces. These two isomers represent a convenient system in which the attachment of SH groups at different positions on the skeleton affects their acidic character and thus also determines their reactivity with a copper surface. Isomer 1 exhibited etching of polycrystalline Cu films, and a detailed investigation of the experimental conditions showed that both the acidic character of SH groups and the presence of oxygen at the copper surface play crucial roles in how the surface reaction proceeds: whether toward a self-assembled monolayer or toward copper film etching. We found that each positional isomer requires completely different conditions for the preparation of a SAM on copper surfaces. Optimized conditions for the former isomer required the exposure of a freshly prepared Cu surface to vapor of 1 in vacuum, which avoided the presence of oxygen and moisture. Adsorption from a dichloromethane solution afforded a sparsely covered Cu(0) surface; isomer 1 effectively removes the surface copper(I) oxide, forming a soluble product, but apparently binds only weakly to the clean Cu(0) surface. In contrast, adsorption of the latter, less volatile isomer proceeded better from a dichloromethane solution than from the vapor phase. Isomer 2 was even able to densely cover the copper surface cleaned up by the dichloromethane solution of 1. Both isomers exhibited high capacity to remove oxygen atoms from the surface copper(I) oxide that forms immediately after the exposure of freshly prepared copper films to ambient atmosphere. Isomer 2 showed suppression of Cu film oxidation. A number of methods including X-ray photoelectron spectroscopy (XPS), X-ray Rutherford back scattering (RBS), proton-induced X-ray emission (PIXE) analysis

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

    NASA Astrophysics Data System (ADS)

    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

  6. Substrate Changes Associated with the Chemistry of Self-Assembled Monolayers on Silicon.

    SciTech Connect

    Mcintire, Theresa M.; Smalley, Rachelle; Newberg, J. T.; Lea, Alan S.; Hemminger, J. C.; Finlayson-Pitts, Barbara J.

    2006-05-18

    Alkylsiloxane self-assembled monolayers (SAMs) are used in the semi-conductor industry, and more recently as proxies for organics adsorbed on airborne mineral dust and on buildings and construction materials. A number of methods have been used for removing the SAM from the substrate after reaction or use, particularly plasmas or piranha (H2SO4:H2O2) solution. However, the impact of these cleaning methods on the chemistry of subsequently formed SAMs on the surface is not known. We report here AFM, XPS, Auger and FTIR studies of changes in the silicon substrate on repetitive deposition and removal of SAMs by these two methods. It is shown that a layer of silicon oxide is formed, and the surface becomes very irregular and roughened, particularly for the piranha treatment. This layer of silica impacts the structure of SAMs attached to it and can serve as a reservoir for trace gases that adsorb on it, potentially contributing to the subsequent reactions of the SAM. The implications for the use of such surfaces as a proxy for reactions of organics on airborne dust particles and on structures in the boundary layer are discussed.

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

    SciTech Connect

    Huang, Jie; Lee, Mingun; Kim, Jiyoung

    2012-01-15

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

  8. Regulating charge injection in ambipolar organic field-effect transistors by mixed self-assembled monolayers.

    PubMed

    Xu, Yong; Baeg, Kang-Jun; Park, Won-Tae; Cho, Ara; Choi, Eun-Young; Noh, Yong-Young

    2014-08-27

    We report on a technique using mixed self-assembled monolayers (SAMs) to finely regulate ambipolar charge injection in polymer organic field-effect transistors. Differing from the other works that employ single SAM specifically for efficient charge injection in p-type and n-type transistors, we blend two different SAMs of alkyl- and perfluoroalkyl thiols at different ratios and apply them to ambipolar OFETs and inverter. Thanks to the utilization of ambipolar semiconductor and one SAM mixture, the device and circuit fabrications are facile with only one step for semiconductor deposition and another for SAM treatment. This is much simpler with respect to the conventional scheme for the unipolar-device-based complementary circuitry that demands separate deposition and processing for individual p-channel and n-channel transistors. Our results show that the mixed-SAM treatments not only improve ambipolar charge injection manifesting as higher hole- and electron-mobility and smaller threshold voltage but also gradually tune the device characteristics to reach a desired condition for circuit application. Therefore, this simple but useful approach is promising for ambipolar electronics. PMID:25093699

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Reactive Landing of Dendrimer Ions onto Activated Self-assembled Monolayer Surfaces

    SciTech Connect

    Hu, Qichi; Laskin, Julia

    2014-02-06

    The reactivity of gaseous, amine-terminated polyamidoamine (PAMAM) dendrimer ions with activated self-assembled monolayer (SAM) surfaces terminated with N-hydroxysuccinimidyl ester groups (NHS-SAM) is examined using mass-selected ion deposition combined with in situ infrared reflection absorption spectroscopy (IRRAS). The reaction extent is determined from depletion of the infrared band at 1753 cm-1, corresponding to the stretching vibration of the NHS carbonyl groups following ion deposition. For reaction yields below 10%, NHS band depletion follows a linear dependence on the ion dose. By comparing the kinetics plots obtained for 1,12-dodecanediamine and different generations of dendrimer ions (G0–G3) containing 4, 8, 16, and 32 terminal amino group, we demonstrate that the relative reaction efficiency increases linearly with the number of NH2 groups in the molecule. This finding is rationalized assuming the formation of multiple amide bonds upon collision of higher-generation dendrimers with NHS-SAM. Furthermore, by comparing the NHS band depletion following deposition of [M+4H]4+ ions of the G2 dendrimer at 30, 80, and 120 eV, we demonstrate that the ion’s kinetic energy has no measurable effect on reaction efficiency. Similarly, the ion’s charge state only has a minor effect on the reactive landing efficiency of dendrimer ions. Our results indicate that reactive landing is an efficient approach for highly selective covalent immobilization of complex multifunctional molecules onto organic surfaces terminated with labile functional groups.

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

    PubMed

    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. PMID:25835342

  12. Vapor-phase-processed fluorinated self-assembled monolayer for organic thin-film transistors

    NASA Astrophysics Data System (ADS)

    Roh, Jeongkyun; Lee, Changhee; Kwak, Jeonghun; Jung, Byung Jun; Kim, Hyeok

    2015-09-01

    A vapor-phase-processed fluorinated silazane self-assembled monolayer (SAM), 1,3-bis(trifluoropropyl)-1,1,3,3-tetramethyldisilazane (FPDS), was introduced as a surface modifier for pentacene-based organic thin-film transistors (OTFTs). A remarkable improvement in the field effect mobility from 0.25 cm2/Vs (without SAM-treatment) to 0.42 cm2/Vs (with FPDS-treatment) was observed, which was attributed to the better pentacene growth on a hydrophobic surface. A significant reduction in the contact resistance was also observed by FPDS treatment due to the improved bulk conductivity and diminished charge trapping at the gate dielectric surface by the SAM treatment. In addition, FPDS treatment efficiently improved the bias stability of the OTFTs; the drain-to-source current degradation by the bias stress was greatly reduced from 80% to 50% by FPDS treatment, and the characteristic time for charge trapping of the FPDS treated OTFTs was approximately one order of magnitude larger than that of the OTFTs without SAM treatment.

  13. Effects of surface chemistry prepared by self-assembled monolayers on osteoblast behavior.

    PubMed

    Nakaoka, Ryusuke; Yamakoshi, Yoko; Isama, Kazuo; Tsuchiya, Toshie

    2010-08-01

    A surface of biomaterials is known to affect the behavior of cells after their adhesion on the surface, indicating that surface characteristics of biomaterials play an important role in cell adhesion, proliferation, and differentiation. To assess the effects of functional groups on biomaterial surface, normal human osteoblasts (NHOsts) were cultured on surfaces coated with self-assembled monolayers (SAMs) containing various functional groups, and the adhesion, proliferation, differentiation, and gap junctional intercellular communication (GJIC) of the NHOsts were investigated. In the case of SAM with terminal methyl groups (hydrophobic surface), NHOst adhesion and proliferation was less prevalent. In contrast, NHOsts were adhered well on SAMs with hydroxyl, carboxyl, amino, phosphate, and sulfate group, which are relatively hydrophilic, their proliferation and differentiation level were dependent on the type of functional groups. Especially, when they were cultured on either SAMs with phosphate or sulfate group, both their alkaline phosphate activity and the calcium deposition by them were enhanced more than those cultured on a collagen-coated dish. More interestingly, GJIC of NHOsts, which has been reported to play a role in cell differentiation as well as homeostasis of cells, were not significantly different among the SAM surfaces tested. These suggest that a specific functional group on a material surface can regulate NHOst adhesion, proliferation, and differentiation via cell-functional group interaction without influencing their homeostasis. PMID:20186768

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  15. AFM Observation of Self-Assembled Monolayer Films on GaAs (110)

    NASA Astrophysics Data System (ADS)

    Ohno, Hirotaka; Motomatsu, Makoto; Mizutani, Wataru; Tokumoto, Hiroshi

    1995-02-01

    We have confirmed that a self-assembled monolayer (SAM) film of octadecanethiol (ODT), CH3(CH2)17SH, can be formed on a cleaved GaAs (110) surface, by using an atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). Circular depressions were observed on the surface after film formation. The area of the circular depressions increased with immersion time, indicating that the solution oxidized the interface between ODT molecules and the GaAs surface, resulting in removal of ODT molecules. The oxidation was considerably faster in pure ethanol solution than that in ODT solution, demonstrating that the SAM film protects the GaAs surface from oxidation. High-resolution lateral force microscope (LFM) images revealed a periodic structure that had two types of lines: periodic lines 0.57 nm apart and lines rotated 55° with respect to them. A structural model of the SAM successfully explained both the features in high-resolution LFM images and the depression depth observed in AFM images.

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

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

  17. Redox Equilibria of Cytochrome C3 Immobilised on Self-Assembled Monolayers Coated Silver Electrodes

    NASA Astrophysics Data System (ADS)

    Di Paolo, R. E.; Rivas, L.; Murgida, D.; Hildebrandt, P.

    2005-01-01

    Cytochromes c3 are soluble electron transfer proteins in the periplasm of sulphate-reducing bacteria. They act as electron-proton couplers between hydrogenase and the electron transfer chain of sulphate respiration. In this work, cytochrome c3 (Cyt-c3) obtained from both Desulfovibrio vulgaris and Desulfovibrio gigas, is electrostatically adsorbed on Ag electrodes coated with self-assembled monolayers of 11-mercaptoundecanoic acid. The redox equilibria of the adsorbed tetraheme protein are studied by surface enhanced resonance Raman spectroscopy (SERRS). The quantitative analysis of the SERR spectra, which were measured as a function of the electrode potential, allows determining the redox potentials for the individual hemes of Cyt-c3. The values obtained of the redox potentials are compared with the data provided by NMR experiments and by molecular dynamics simulation studies of the electrostatically bound protein on a coated electrode. It is found that immobilisation causes substantial shifts of the redox potential, which would have an impact on the intramolecular electron flow.

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

    PubMed

    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. PMID:26926185

  19. Simulations of water at the interface with hydrophilic self-assembled monolayers.

    PubMed

    Stevens, Mark J; Grest, Gary S

    2008-09-01

    Simulations of water at hydrophilic self-assembled monolayer (SAM) surfaces are especially relevant for biological interfaces. Well-defined, atomically smooth surfaces that can be continuously varied are possible with SAMs. These characteristics enable more accurate measurements than many other surfaces with the added advantage of tailoring the surface to treat specific chemical groups. A fundamental question is how solid surfaces affect the structure and dynamics of water. Measurements of the structure and dynamics of water at solid surfaces have improved significantly, but there remain differences among the experiments. In this article, the authors review simulations of water at the interface with hydrophilic SAMs. These simulations find that while the interfacial water molecules are slower than the bulk water molecules, the interfacial dynamics remains that of a liquid. A major biological application of SAMs is for making coatings resistant to protein adsorption. SAMs terminated with ethylene glycol monomers have proven to be excellent at resisting protein adsorption. Understanding the mechanisms behind this resistance remains an unresolved issue. Recent simulations suggest a new perspective of the role of interfacial water and the inseparable interplay between the SAM and the water. PMID:20408690

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

    PubMed

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

    2007-04-11

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

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

    PubMed Central

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

    2014-01-01

    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. PMID:24739812

  2. Conformational flexibility of a model protein upon immobilization on self-assembled monolayers.

    PubMed

    Bigdeli, Saharnaz; Talasaz, AmirAli H; Ståhl, Patrik; Persson, Henrik H J; Ronaghi, Mostafa; Davis, Ronald W; Nemat-Gorgani, Mohsen

    2008-05-01

    The present study reports on the retention of conformational flexibility of a model allosteric protein upon immobilization on self-assembled monolayers (SAMs) on gold. Organothiolated SAMs of different compositions were utilized for adsorptive and covalent attachment of bovine liver glutamate dehydrogenase (GDH), a well-characterized allosteric enzyme. Sensitive fluorimetric assays were developed to determine immobilization capacity, specific activity, and allosteric properties of the immobilized preparations as well as the potential for repeated use and continuous catalytic transformations. The allosteric response of the free and immobilized forms towards ADP, L-leucine and high concentrations of NAD(+), some of the well-known activators for this enzyme, were determined and compared. The enzyme immobilized by adsorption or chemical binding responded similarly to the activators with a greater degree of activation, as compared to the free form. Also loss of activity involving the two immobilization procedures were similar, suggesting that residues essential for catalytic activity or allosteric properties of GDH remained unchanged in the course of chemical modification. A recently established method was used to predict GDH orientation upon immobilization, which was found to explain some of the experimental results presented. The general significance of these observations in connection with retention of native properties of protein structures upon immobilization on SAMs is discussed. PMID:18078298

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

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

    SciTech Connect

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

    2007-03-21

    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 degree sign for pure water and a 'surface energy' (which is proportional to the Zisman critical surface tension for a Cu surface with 0 rms roughness) of 14.5 mJ/m{sup 2}(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 degree sign C) solutions for at least 30 min. Furthermore, no SAM degradation was observed when PFMS/Cu was exposed to warm nitric acid solution for up to 70 min at 60 degree sign C or 50 min at 80 degree sign 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.

  5. Comparing Surfaces and Engineered Interfaces using Self-Assembled Monolayers (SAMs) and Injected SAMs Silanes

    SciTech Connect

    Morris, Mark J.; Simmons, Kevin L.

    2003-11-01

    The objective of this study was to show a comparison between property changes by formation of a self-assembled monolayer on the surface of PPG synthetic precipitated silica, which is a technique developed at PNNL, and by adding the SAMs silane chemical directly into the mixing bowl. These coatings have the potential to greatly increase the bond strength and enhance other properties between the particle and the rubber matrix of a rubber compound. Tensile testing measured peak stress and elongation at break. The increase in tensile strength shows how well the polymer-filler interfacial adhesion is doing. The study used five different SAM systems with a sulfur cured styrene butadiene rubber (SBR) tire rubber formulation. The three propylsilanes were propyl triethoxysilane, allyl triethoxysilane and 3-mercaptopropyl triethoxysilane. Five combinations of silanes were used in this study. The application of the silanes were 100% propyl triethoxy silane (100% Alkyl); a 10/90 mixture of allyl and propyl triethoxy silanes (10% vinyl/90% alkyl); a 50/50 mixture of the allyl and propyl (50% vinyl/50% alkyl); a 10/90mixture of 3-mercaptopropyl trimethoxysilane and propyl trimethoxysilane (10% mercaptan/90% alkyl) and lastly a 50/50 3-mercaptopropyl and propylsilanes (50% mercaptan/alkyl). The data not only shows improvement with SAMs, the peak stress data (ultimate strength) shows that the by changing the amount of silane content can change the physical properties

  6. Mediator free cholesterol biosensor based on self-assembled monolayer platform.

    PubMed

    Matharu, Zimple; Solanki, Pratima R; Gupta, Vinay; Malhotra, B D

    2012-02-01

    Self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) has been investigated for immobilization of bi-enzymes (ChOx and ChEt) towards development of enzyme biosensors for detection of free and total cholesterol. This enzyme immobilized SAM surface has been characterized by scanning electron microscopy and electrochemical measurements. The results of electrochemical response studies reveal fast enzymatic reaction in phosphate buffer saline solution without using any artificial mediator. This may be attributed to the molecular wire type behavior of short 4-ATP molecule that promotes electron transfer between enzyme and the electrode surface due to its conjugated structure. Interference free estimation of free and total cholesterol has been realized at low operating potential of 0.33 V with range of detection as 25 to 400 mg dl(-1), sensitivity of 542.3 nA mM(-1) (for ChOx/4-ATP/Au) and 886.6 nA mM(-1) (for ChEt-ChOx/4-ATP/Au) with a response time of 20 s at pH 7.4. PMID:22132413

  7. Enhancing the Thermal Conductance of Polymer and Sapphire Interface via Self-Assembled Monolayer.

    PubMed

    Zheng, Kun; Sun, Fangyuan; Zhu, Jie; Ma, Yongmei; Li, Xiaobo; Tang, Dawei; Wang, Fosong; Wang, Xiaojia

    2016-08-23

    Interfacial thermal conductance (ITC) receives enormous consideration because of its significance in determining thermal performance of hybrid materials, such as polymer based nanocomposites. In this study, the ITC between sapphire and polystyrene (PS) was systematically investigated by time domain thermoreflectance (TDTR) method. Silane based self-assembled monolayers (SAMs) with varying end groups, -NH2, -Cl, -SH and -H, were introduced into sapphire/PS interface, and their effects on ITC were investigated. The ITC was found to be enhanced up by a factor of 7 through functionalizing the sapphire surface with SAM, which ends with a chloride group (-Cl). The results show that the enhancement of the thermal transport across the SAM-functionalized interface comes from both strong covalent bonding between sapphire and silane-based SAM, and the high compatibility between the SAM and PS. Among the SAMs studied in this work, we found that the ITC almost linearly depends on solubility parameters, which could be the dominant factor influencing on the ITC compared with wettability and adhesion. The SAMs serve as an intermediate layer that bridges the sapphire and PS. Such a feature can be applied to ceramic-polymer immiscible interfaces by functionalizing the ceramic surface with molecules that are miscible with the polymer materials. This research provides guidance on the design of critical-heat transfer materials such as composites and nanofluids for thermal management. PMID:27501117

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

    PubMed

    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. PMID:23498233

  9. Click functionalization of phenyl-capped bithiophene on azide-terminated self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Zheng, Yijun; Cui, Jiaxi; Ikeda, Taichi

    2015-11-01

    We immobilized tetra(ethylene glycol)-substituted phenyl-capped bithiophene with alkyne terminals (Ph2TPh-alkyne) on azide-terminated self-assembled monolayers (N3-SAMs) by Cu-catalyzed azide-alkyne cycloaddition reaction. Ph2TPh-functionalized SAMs on a gold substrate showed reversible electrochemical response. The surface densities of the azide groups in N3-SAMs and Ph2TPh units in Ph2TPh-functionalized SAMs were estimated to be 7.3 ± 0.3 × 10-10 mol cm-2 and 4.6 ± 0.3 × 10-10 mol cm-2, respectively, by quartz crystal microbalance (QCM). Most of Ph2TPh-alkynes are considered to be anchored on N3-SAMs via both terminal groups. Ph2TPh-functionalized SAMs exhibited reversible redox peaks in cyclic voltammetry (CV). In redox reaction, reversible capture and release of the counter anion could be monitored by electrochemical QCM (E-QCM).

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  11. Self-assembled monolayer based impedimetric platform for food borne mycotoxin detection.

    PubMed

    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/Au electrode, 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 NH2 groups 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. PMID:20953508

  12. Asphaltene Adsorption onto Self-Assembled Monolayers of Alkyltrichlorosilanes of Varying Chain Length

    SciTech Connect

    Turgman-Cohen, S.; Fischer, D; Kilpatrick, P; Genzer, J

    2009-01-01

    The adsorption of asphaltenes onto flat silica surfaces modified with self-assembled monolayers (SAMs) of alkyltrichlorosilanes of varying thickness due to a variable number of carbon atoms (N{sub C}) has been studied by means of contact angle measurements, spectroscopic ellipsometry, and near-edge X-ray absorption fine structure spectroscopy. The extent of asphaltene adsorption was found to depend primarily on the ability of the SAM layer to shield the underlying silicon substrate from interacting with the asphaltenes present in solution. Specifically, asphaltene adsorption decreased with an increase in NC and/or an increase in SAM grafting density, {sigma}{sub SAM}, (i.e., number of SAM molecules per unit area). The effect of the solvent quality on the extent of asphaltene adsorption was gauged by adsorbing asphaltenes from toluene, 1-methylnaphthalene, tetralin, decalin, and toluene-heptanes mixtures. The extent of asphaltene adsorption was found to increase proportionally with a decrease in the Hildebrand solubility parameter of the solvent.

  13. Aqueous solution deposition kinetics of iron oxyhydroxide on sulfonic acid terminated self-assembled monolayers

    SciTech Connect

    Rieke, P.C.; Marsh, B.D.; Wood, L.L.; Tarasevich, B.J.; Liu, J.; Song, L.; Fryxell, G.E. )

    1995-01-01

    The deposition kinetics of iron oxyhydroxide on sulfonic acid terminated self-assembled monolayers were studied. The thin films of FeOOH were formed on the substrates by thermal hydrolysis of millimolar aqueous solutions of Fe(NO[sub 3])[sub 3] at a pH of approximately 2.0. The thickness of the films was measured ellipsometrically at various times. Both Fe(NO[sub 3])[sub 3] and HNO[sub 3] concentrations were independently varied to provide varying degrees of solution supersaturation. Depending on these concentrations, an induction time was observed before film growth commenced. The correlation between supersaturation and induction time was modeled using classical nucleation theory. Very good agreement was observed regardless of whether supersaturation was varied via the concentration of Fe(NO[sub 3])[sub 3] or HNO[sub 3]. From these results an interfacial free energy for nucleation of 148 mJ/m[sup 2] was calculated. The critical nucleus species was identified as a tetrameric iron species by considering the order of nucleation. 49 refs., 11 figs., 1 tab.

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

    SciTech Connect

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

    2000-03-23

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

  15. Self-assembled monolayer based impedimetric platform for food borne mycotoxin detection

    NASA Astrophysics Data System (ADS)

    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.

  16. Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold

    NASA Astrophysics Data System (ADS)

    Crudden, Cathleen M.; Horton, J. Hugh; Ebralidze, Iraklii I.; Zenkina, Olena V.; McLean, Alastair B.; Drevniok, Benedict; She, Zhe; Kraatz, Heinz-Bernhard; Mosey, Nicholas J.; Seki, Tomohiro; Keske, Eric C.; Leake, Joanna D.; Rousina-Webb, Alexander; Wu, Gang

    2014-05-01

    Since the first report of thiol-based self-assembled monolayers (SAMs) 30 years ago, these structures have been examined in a huge variety of applications. The oxidative and thermal instabilities of these systems are widely known, however, and are an impediment to their widespread commercial use. Here, we describe the generation of N-heterocyclic carbene (NHC)-based SAMs on gold that demonstrate considerably greater resistance to heat and chemical reagents than the thiol-based counterparts. This increased stability is related to the increased strength of the gold-carbon bond relative to that of a gold-sulfur bond, and to a different mode of bonding in the case of the carbene ligand. Once bound to gold, NHCs are not displaced by thiols or thioethers, and are stable to high temperatures, boiling water, organic solvents, pH extremes, electrochemical cycling above 0 V and 1% hydrogen peroxide. In particular, benzimidazole-derived carbenes provide films with the highest stabilities and evidence of short-range molecular ordering. Chemical derivatization can be employed to adjust the surface properties of NHC-based SAMs.

  17. Activation and deformation of immobilized lipase on self-assembled monolayers with tailored wettability.

    PubMed

    Chen, Peng-Cheng; Huang, Xiao-Jun; Xu, Zhi-Kang

    2015-05-28

    In this work, lipase from Candida rugosa (CRL) was immobilized on self-assembled monolayers (SAMs) with various wettabilities ranging from highly hydrophilic to highly hydrophobic by adsorption in order to clearly elucidate the interfacial activation character of lipases. The SAMs were made of 11-hydroxyundecane-1-thiol and 1-dodecanethiol. The adsorption behavior was monitored in situ by quartz crystal microbalance with dissipation (QCM-D), and the enzyme binding constants indicated a stronger affinity between CRL and more hydrophobic surfaces. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the morphologies of the adsorbed lipases. Amide I band attenuated total reflection/Fourier transformed infrared (ART/FTIR) spectroscopy showed an increasing fraction of intermolecular β-sheet content on surfaces with higher hydrophilicities. Moreover, liquid chromatography (LC) verified that the activity of CRL adsorbed on a hydrophobic surface was higher than that of CRL adsorbed on a hydrophilic surface. This work related the enzyme activity to the substrate properties, adsorption behavior, distribution, and morphology of lipases, helping to achieve the external control of both the immobilization process and enzyme utilization. PMID:25929434

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

    NASA Astrophysics Data System (ADS)

    Kawanago, Takamasa; Oda, Shunri

    2016-01-01

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

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

    PubMed Central

    2011-01-01

    Summary 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. PMID:22259769

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

    PubMed

    Dobberschütz, S; Rimmen, M; Hassenkam, T; Andersson, M P; Stipp, S L S

    2015-09-01

    The interaction of aromatic compounds with various ions in aqueous solutions plays a role in a number of fields, as diverse as protein folding and enhanced oil recovery, among others. Therefore, we have investigated the effect of the four electrolytes, KCl, NaCl, MgCl2 and CaCl2, on the hydrophobic interaction of benzene self-assembled monolayers. Using the jump to contact phenomenon of an atomic force microscope (AFM) tip as an indicator of attractive forces between the surfaces of a sample and the tip, we discovered lower frequencies in the snap in as well as narrower distributions for the snap in distance for the monovalent ions, especially for K(+), compared with the behaviour for the divalent ions. These observations are explained by the accumulation of charge at the surface by cation-π interactions and an influence of the ions on the formation of capillaries that bridge the tip to the surface. Bridging capillaries, i.e. nanometre scale gas bubbles, are some of the factors contributing to the long range hydrophobic interaction. The results demonstrate how ions influence the attraction of hydrophobic entities in aqueous solutions. PMID:26220291

  1. An investigation of the effects of self-assembled monolayers on protein crystallisation.

    PubMed

    Zhang, Chen-Yan; Shen, He-Fang; Wang, Qian-Jin; Guo, Yun-Zhu; He, Jin; Cao, Hui-Ling; Liu, Yong-Ming; Shang, Peng; Yin, Da-Chuan

    2013-01-01

    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. PMID:23749116

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

    SciTech Connect

    Ghosh, Soumya; Hammes-Schiffer, Sharon

    2015-01-02

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

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

    NASA Astrophysics Data System (ADS)

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

    2006-02-01

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

  4. Comparative study of decyl thiocyanate and decanethiol self-assembled monolayers on gold substrates

    NASA Astrophysics Data System (ADS)

    Dreesen, L.; Volcke, C.; Sartenaer, Y.; Peremans, A.; Thiry, P. A.; Humbert, C.; Grugier, J.; Marchand-Brynaert, J.

    2006-09-01

    In a recent paper Ciszek et al. [J.W. Ciszek, M.P. Stewart, J.M. Tour, J. Am. Chem. Soc. 126 (2004) 13172] showed that organic thiocyanates may be an interesting alternative to the use of thiols for thiolate assemblies. We use scanning tunnelling microscopy (STM), infrared reflection absorption and sum-frequency generation spectroscopies (IRRAS and SFG) in order to study the adsorption properties of decyl thiocyanates (DTCN) and compare them to the decanethiol (DT) ones. Firstly, IRRAS measurements show that DTCN molecules form self-assembled monolayers (SAMs) on gold via a thiolate link with the metallic substrate. Secondly, the DTCN SAM on gold is less ordered than the DT one as highlighted by SFG spectroscopy. Indeed, the intensities of the methyl vibration modes vanish while the methylene ones increase when DTCN molecules are adsorbed on the substrate instead of DT. We explain the differences in SAMs quality on the basis of STM measurements which reveal differences in molecular order and packing.

  5. Nanoscale dynamics and protein adhesivity of alkylamine self-assembled monolayers on graphene.

    PubMed

    O'Mahony, S; O'Dwyer, C; Nijhuis, C A; Greer, J C; Quinn, A J; Thompson, D

    2013-06-18

    Atomic-scale molecular dynamics computer simulations are used to probe the structure, dynamics, and energetics of alkylamine self-assembled monolayer (SAM) films on graphene and to model the formation of molecular bilayers and protein complexes on the films. Routes toward the development and exploitation of functionalized graphene structures are detailed here, and we show that the SAM architecture can be tailored for use in emerging applications (e.g., electrically stimulated nerve fiber growth via the targeted binding of specific cell surface peptide sequences on the functionalized graphene scaffold). The simulations quantify the changes in film physisorption on graphene and the alkyl chain packing efficiency as the film surface is made more polar by changing the terminal groups from methyl (-CH3) to amine (-NH2) to hydroxyl (-OH). The mode of molecule packing dictates the orientation and spacing between terminal groups on the surface of the SAM, which determines the way in which successive layers build up on the surface, whether via the formation of bilayers of the molecule or the immobilization of other (macro)molecules (e.g., proteins) on the SAM. The simulations show the formation of ordered, stable assemblies of monolayers and bilayers of decylamine-based molecules on graphene. These films can serve as protein adsorption platforms, with a hydrophobin protein showing strong and selective adsorption by binding via its hydrophobic patch to methyl-terminated films and binding to amine-terminated films using its more hydrophilic surface regions. Design rules obtained from modeling the atomic-scale structure of the films and interfaces may provide input into experiments for the rational design of assemblies in which the electronic, physicochemical, and mechanical properties of the substrate, film, and protein layer can be tuned to provide the desired functionality. PMID:23301836

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

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

    PubMed

    Jang, Ling-Sheng; Keng, Hao-Kai

    2008-04-01

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

  8. Water adsorption on hydrophilic and hydrophobic self-assembled monolayers as proxies for atmospheric surfaces. A grand canonical Monte Carlo simulation study.

    PubMed

    Szori, Milán; Jedlovszky, Pál; Roeselová, Martina

    2010-05-14

    Grand canonical Monte Carlo simulations are used to determine water adsorption on prototypical organic surfaces as a function of relative humidity at 300 K. Three model surfaces formed by well-ordered self-assembled monolayers (SAMs) of alkanethiolate chains on gold are investigated: (i) a smooth hydrophobic surface of methyl-terminated C(7)-CH(3) SAM; (ii) a rough hydrophobic surface of randomly mixed two-component SAM, composed of equal fractions of C(5)-CH(3) and C(7)-CH(3) chains (C(5)/C(7)-CH(3) SAM); and (iii) a smooth hydrophilic surface of carboxyl-terminated C(7)-COOH SAM. The all atom CHARMM22 force field is used for the SAM chains together with the SPC/E model for water. No noticeable water adsorption is observed on the smooth hydrophobic surface up to saturation. The mild surface roughness introduced by the uneven chain length of the two components constituting the C(5)/C(7)-CH(3) SAM has no significant effect on the surface hydrophobicity, and the rough hydrophobic surface also remains dry up to the point when water condensation occurs. In contrast, water readily adsorbs onto the hydrophilic surface by forming hydrogen bonds with the COOH groups of the substrate. In addition, hydrogen bonding with pre-adsorbed water molecules contributes to the mechanism of water uptake. Under low humidity conditions, water is present on the hydrophilic surface as individual molecules or small water clusters and, with increasing relative humidity, the surface coverage grows continuously beyond a monolayer formation. The adsorbed water film is observed to be rather inhomogeneous with patches of bare surface exposed. The amount of water constituting a stable adsorption layer prior to condensation is estimated to consist of about 2-5 molecular layers. Detailed analysis of the simulation results is used to obtain important insights into the structure and energetics of water adsorbed on highly oxidized organic surfaces exposed to ambient air of increasing relative humidity

  9. Electrical transport and mechanical properties of alkylsilane self-assembled monolayers on silicon surfaces probed by atomic force microscopy

    SciTech Connect

    Park, Jeong Young; Qi, Yabing; Ashby, Paul D.; Hendriksen, Bas L.M.; Salmeron, Miquel

    2009-02-06

    The correlation between molecular conductivity and mechanical properties (molecular deformation and frictional responses) of hexadecylsilane self-assembled monolayers was studied with conductive probe atomic force microscopy/friction force microscopy in ultrahigh vacuum. Current and friction were measured as a function of applied pressure, simultaneously, while imaging the topography of self-assembled monolayer molecule islands and silicon surfaces covered with a thin oxide layer. Friction images reveal lower friction over the molecules forming islands than over the bare silicon surface, indicating the lubricating functionality of alkylsilane molecules. By measuring the tunneling current change due to changing of the height of the molecular islands by tilting the molecules under pressure from the tip, we obtained an effective conductance decay constant ({beta}) of 0.52/{angstrom}.

  10. Understanding Chemical versus Electrostatic Shifts in X-ray Photoelectron Spectra of Organic Self-Assembled Monolayers

    PubMed Central

    2016-01-01

    The focus of the present article is on understanding the insight that X-ray photoelectron spectroscopy (XPS) measurements can provide when studying self-assembled monolayers. Comparing density functional theory calculations to experimental data on deliberately chosen model systems, we show that both the chemical environment and electrostatic effects arising from a superposition of molecular dipoles influence the measured core-level binding energies to a significant degree. The crucial role of the often overlooked electrostatic effects in polar self-assembled monolayers (SAMs) is unambiguously demonstrated by changing the dipole density through varying the SAM coverage. As a consequence of this effect, care has to be taken when extracting chemical information from the XP spectra of ordered organic adsorbate layers. Our results, furthermore, imply that XPS is a powerful tool for probing local variations in the electrostatic energy in nanoscopic systems, especially in SAMs. PMID:26937264

  11. Resistive switching of alkanethiolated nanoparticle monolayers patterned by electron-beam exposure.

    PubMed

    Reissner, Patrick A; Fedoryshyn, Yuriy; Tisserant, Jean-Nicolas; Stemmer, Andreas

    2016-08-17

    Carbon-based electronic devices are promising candidates for complementing silicon-based electronics in memory device applications. For example, sputtered thin films of amorphous carbon exhibit memristive behavior. The reported devices, however, have a minimal active area of about 50 nm diameter, leading to large set currents in the μA range. Although power efficiency would benefit from reduced drive currents, resistive switching of amorphous carbon confined to a few cubic nanometers has remained largely unexplored. Here, we investigate resistive switching in 30 nm long and 25 nm wide monolayer arrays of 10 nm gold nanoparticles patterned by direct electron-beam exposure followed by a purpose-designed emulsion-based development process. Electron-beam irradiation transforms the alkanethiol ligands of the gold nanoparticles into a solvent-resistant amorphous carbonaceous matrix allowing pattern development and imparting electronic function. We measure changes in conductivity of up to five orders of magnitude for set currents in the nA range. PMID:27492444

  12. Spin-Cast and Patterned Organophosphonate Self-Assembled Monolayer Dielectrics on Metal-Oxide-Activated Si

    SciTech Connect

    O Acton; D Hutchins; L Arnadottir; T Weidner; N Cernetic; G Ting; T Kim; D Castner; H Ma; A Jen

    2011-12-31

    An efficient process is developed for modifying Si with self-assembled monolayers (SAMs) through in situ metal oxide surface activation and microcontact printing or spin-coating of phosphonic-acid-based molecules. The utility of this process is demonstrated by fabricating self-organized and solution-processed low-voltage organic thin-film transistors enabled by patterned and spin-cast phosphonate SAM/metal oxide hybrid dielectrics.

  13. Modeling charge transport in C{sub 60}-based self-assembled monolayers for applications in field-effect transistors

    SciTech Connect

    Leitherer, S. E-mail: Michael.Thoss@physik.uni-erlangen.de; Thoss, M. E-mail: Michael.Thoss@physik.uni-erlangen.de; Halik, M.

    2014-05-28

    We have investigated the conductance properties of C{sub 60}-containing self-assembled monolayers (SAMs), which are used in organic field-effect transistors, employing a combination of molecular-dynamics simulations, semiempirical electronic structure calculations, and Landauer transport theory. The results reveal the close relation between the transport characteristics and the structural and electronic properties of the SAM. Furthermore, both local pathways of charge transport in the SAMs and the influence of structural fluctuations are analyzed.

  14. Spatially Modulating Interfacial Properties of Transparent Conductive Oxides: Patterning Work Function with Phosphonic Acid Self-Assembled Monolayers

    SciTech Connect

    Knesting, Kristina M.; Hotchkiss, Peter J.; MacLeod, Bradley A.; Marder, Seth R.; Ginger, David S.

    2011-09-29

    The interface between an organic semiconductor and a transparent conducting oxide is crucial to the performance of organic optoelectronics. We use microcontact printing to pattern pentafluorobenzyl phosphonic acid self-assembled monolayers (SAMs) on indium tin oxide (ITO). We obtain high-fidelity patterns with sharply defined edges and with large work function contrast (comparable to that obtained from phosphonic acid SAMs deposited from solution).

  15. Enzyme-free Detection of Hydrogen Peroxide from Cerium Oxide Nanoparticles Immobilized on Poly(4-vinylpyridine) Self-Assembled Monolayers

    SciTech Connect

    Gaynor, James D.; Karakoti, Ajay S.; Inerbaev, Talgat; Sanghavi, Shail P.; Nachimuthu, Ponnusamy; Shutthanandan, V.; Seal, Sudipta; Thevuthasan, Suntharampillai

    2013-05-02

    A single layer of oxygen-deficient cerium oxide nanoparticles (CNPs) are immobilized on microscopic glass slide using poly(4-vinylpyridine) (PVP) self-assembled monolayers (SAMs). A specific colorimetric property of CNPs when reacted with hydrogen peroxide allows for the direct, single-step peroxide detection which can be used in medical diagnosis and explosives detection. Multiple PVP-CNP immobilized layers improve sensitivity of detection and the sensor can be regenerated for reuse.

  16. Surface-enhanced Raman spectroscopy of functionalized self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Ye, Qi

    1997-09-01

    The central theme of this research is to study Self-Assembled Monolayers (SAMs) with Surface-Enhanced Raman Spectroscopy (SERS). SERS is a relatively new surface characterization technique, but it is very promising because of its submonolayer sensitivity and in-situ applicability in aqueous systems. In this thesis, we have assessed the potential of this technique by presenting our studies in SERS enhancement mechanisms and in applications of SERS to SAM electrochemistry, stability, polymerization, and molecular interactions. Studying SERS-active substrate provides the bases for any quantitative study involving SERS. Based on examination of various substrates, we have developed a new type of SERS-active substrate that supports a reproducible, stable, and large enhancement factor. This best substrate is further characterized with a scanning probe microscope. Useful probe range of SERS has been established by studying the distance dependence of SERS from an azobenzene Raman label covalently attached to the end of a self-assembling molecule. The distance dependence curves have been analyzed using a previously reported electromagnetic enhancement theory. Electrochamical properties of azobenzene SAMs have been investigated by a combined methodology of cyclic voltammetry and Raman spectroscopy. Electron transfer through the alkyl spacer is a tunneling process that is chain length dependent. We propose that electron transfer to and from the azobenzene redox center is a two-electron, two proton redox process, based on our in-situ SERS spectroscopic data. Stability of SAMs under various chemical and electrochemical conditions has been studied by an experimental technique which we named "cyclic voltarammetry". By monitoring the in-situ Raman spectra during potential cycling, we can study the desorption of SAMs in various media. In order to improve SAM stability, topochemical polymerization of SAMs containing diacetylene groups has been designed and explored. Our results

  17. Effects of polarized organosilane self-assembled monolayers on organic single-crystal field-effect transistors

    NASA Astrophysics Data System (ADS)

    Takeya, J.; Nishikawa, T.; Takenobu, T.; Kobayashi, S.; Iwasa, Y.; Mitani, T.; Goldmann, C.; Krellner, C.; Batlogg, B.

    2004-11-01

    The surface conductivity is measured by a four-probe technique for pentacene and rubrene single crystals laminated on polarized and nearly unpolarized molecular monolayers with application of perpendicular electric fields. The polarization of the self-assembled monolayers (SAMs) shifts the threshold gate voltage, while maintaining a very low subthreshold swing of the single-crystal devices (0.11 V/decade). The results, excluding influences of parasitic contacts and grain boundaries, demonstrate SAM-induced nanoscale charge injection up to ˜1012cm-2 at the surface of the organic single crystals.

  18. Capacitance and conductance characterization of ferrocene-containing self-assembled monolayers on silicon surfaces for memory applications

    NASA Astrophysics Data System (ADS)

    Li, Qiliang; Mathur, Guru; Homsi, Mais; Surthi, Shyam; Misra, Veena; Malinovskii, Vladimir; Schweikart, Karl-Heinz; Yu, Lianhe; Lindsey, Jonathan S.; Liu, Zhiming

    2002-08-01

    Self-assembled monolayers of 4-ferrocenylbenzyl alcohol attached to silicon provided the basis for electrolyte-molecule-silicon capacitors. Characterization by conventional capacitance and conductance techniques showed very high capacitance and conductance peaks near approx0.6 V associated with charging and discharging of electrons into and from discrete levels in the monolayer owing to the presence of the redox-active ferrocenes. The reversible charge trapping of these molecules suggest their potential application in memory devices. Due to the molecular scalability and low-power operation, molecular-silicon hybrid devices may be strong candidates for next-generation electronic devices.

  19. Nonlinear optical studies of self-assembled monolayers (SAM) silica-SAM-water interface probed with second harmonic generation

    NASA Astrophysics Data System (ADS)

    James, Kenneth Edward

    Second harmonic generation (SHG) is a successful and widely used technique for the study of surfaces and surface phenomena. We present a novel technique using second harmonic generation from oriented water molecules in the Gouy-Chapman diffuse layer at the alkylsiloxane and biomolecular self assembled monolayer (SAM) interface with water to measure distance between the solid surface and the average location of the oriented water in the diffuse layer. This distance is manifest in the SHG angular dependence profile from the relative phases of the second harmonic light generated at the diffuse layer and at the solid surface. Distances of one nanometer can be distinguished. Values for the diffuse layer potential, diffuse layer decay length, magnitude and phase of the nonlinear susceptibility were obtained. This in situ probe is universally applicable for organic adsorbates which in general will push the diffuse layer away from the solid surface. The organic layer thickness can be used to obtain the adsorption fraction. From this and an understanding of the likely chemistry, the orientation of the molecules can be inferred. We have demonstrated this technique on three molecular systems: hydrophobic self assembled monolayers of methoxysilane molecules of varying hydrocarbon chain length, self assembled monolayers of streptavidin glycoproteins and the combined streptavidin-biotinylated antibody monolayer. In the methoxysilane monolayers a relationship between hydrophobicity and molecular orientation was observed. The thickness of the streptavidin monolayer was determined to be 5.6 nm. This is strikingly close to the length of the of the streptavidin molecule which implies a close packed monolayer of streptavidin molecules. The average height of the antibodies was determined to be 10.9 nm or about two thirds the height of an antibody molecule. This too confirms a monolayer and allows for good approximation of surface coverage. This method does nothing to disturb or alter

  20. Study of lnter-Molecular Dynamics within Alkylsiloxane Self-Assembled Monolayer and Elastomer Systems

    NASA Astrophysics Data System (ADS)

    Roman, Michael

    In this work, molecular motion, and in particular, glassy relaxations are studied in two novel experimental systems. Both experimental systems offer a significant degree of control over molecule-molecule, or group-group (where group refers to a portion of a molecule), interactions by controlling density and the type of inter-molecular interaction. Both systems have rigid elements that decrease the tendency of bulk materials to spontaneously change their density with temperature. Thus, density can be maintained and controlled and the effect of density and temperature can be (at least in part) de-convolved. The goal of this work is to experimentally observe the transition from simple, local relaxations to glassy dynamics as density is increased and to understand how this transition differs as the inter-molecular interactions are altered. In both approaches, the system is fabricated from individual parts where the nature, spacing, and particular arrangement of the parts can be controlled and the resultant changes in molecular motion can be observed. Building up a custom system from parts enables fundamental investigation into the glass transition (as discussed above) and also makes possible the development of materials that have engineered responses as a function of temperature. As a short-hand, we refer to the two systems as the monolayer or SAM (short for Self-Assembled Monolayer) and elastomer approaches. In Chapters 4-7 we discuss results from the monolayer approach. Chapter 8 summarizes results from the elastomer approach. In particular, Chapter 4 introduces you to dielectric spectroscopy and briefly summarizes the previous work by former students in the Clarke group which identified the local and glass relaxations in silane monolayers of substituted alkyl chains as analogous to the local and glassy relaxations in polymeric systems containing phase segregated alkyl chains, and similar to the local and glass modes in poly(ethylene). The remainder of Chapter 4

  1. Interactions of Na+, K+, Mg2+, and Ca2+ with benzene self-assembled monolayers.

    PubMed

    Rimmen, M; Matthiesen, J; Bovet, N; Hassenkam, T; Pedersen, C S; Stipp, S L S

    2014-08-01

    Interactions between cations and organic molecules are found throughout nature, from the functionality and structure of proteins in humans and animals to the exchange of ions in minerals in soil and oil reservoirs with the fluid phases. We have explored the behavior of the s-block elements that are most common in the natural world, namely, Na(+), K(+), Mg(2+), and Ca(2+). Specifically, we investigated how these ions affect the interactions between surfaces covered by self-assembled monolayers (SAMs) terminated with benzene molecules. We used a flat oxidized silicon substrate and an atomic force microscopy (AFM) tip that were both functionalized with 11-phenoxyundecane-1-thiol and measured the adhesion force between them in solutions of each of the four chloride salts. We observed that the adhesion increased in the order of the Hofmeister series: K(+) < Na(+) ≈ Mg(2+) < Ca(2+). Supplementary evidence from X-ray photoelectron spectroscopy (XPS) allowed us to conclude that K(+) binds in the benzene layers, creating a positive surface charge on the benzene-covered surfaces, thus leading to lower adhesion in KCl solutions than in pure water. Evidence suggested that Ca(2+) does not bind to the surfaces but forms bridges between the layers, leading to higher adhesion than in pure water. In Na(+) and Mg(2+) solutions, adhesion is quite similar to that in pure water, indicating a lack of interaction between these two ions and the surfaces, or at least that the interaction is too weak to be detected by our measurements. The results of our studies clearly show that even a nonpolar, hydrophobic molecule, such as benzene, has a role to play in the behavior of aqueous solutions and that it interacts differently depending on which ions are present. Even ions from the same column in the periodic table behave differently. PMID:25003588

  2. Chemically well-defined self-assembled monolayers for cell culture: toward mimicking the natural ECM

    PubMed Central

    Hudalla, Gregory A.

    2014-01-01

    The extracellular matrix (ECM) is a network of biological macromolecules that surrounds cells within tissues. In addition to serving as a physical support, the ECM actively influences cell behavior by providing sites for cell adhesion, establishing soluble factor gradients, and forming interfaces between different cell types within a tissue. Thus, elucidating the influence of ECM-derived biomolecules on cell behavior is an important aspect of cell biology. Self-assembled monolayers (SAMs) have emerged as promising tools to mimic the ECM as they provide chemically well-defined substrates that can be precisely tailored for specific cell culture applications, and their application in this regard is the focus of this review. In particular, this review will describe various approaches to prepare SAM-based culture substrates via non-specific adsorption, covalent immobilization, or non-covalent sequestering of ECM-derived biomolecules. Additionally, this review will highlight SAMs that present ECM-derived biomolecules to cells to probe the role of these molecules in cell-ECM interactions, including cell attachment, spreading and ‘outside-in’ signaling via focal adhesion complex formation. Finally, this review will introduce SAMs that can present or sequester soluble signaling molecules, such as growth factors, to study the influence of localized soluble factor activity on cell behavior. Together, these examples demonstrate that the chemical specificity and variability afforded by SAMs can provide robust, well-defined substrates for cell culture that can simplify experimental design and analysis by eliminating many of the confounding factors associated with traditional culture substrates. PMID:25214878

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

    PubMed

    Patterson, James E; Dlott, Dana D

    2005-03-24

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

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

    PubMed

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

    2016-04-01

    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, PW12O40(3-) (WPOM(3-)) and PW12O40(2-) (WPOM(2-)), 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 WPOM(3-) was soft-landed onto the fluorinated SAM (FSAM), while the charge state distribution was dominated by the 2- charge after both WPOM(3-) and WPOM(2-) 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 WPOM(3-), the relative abundance of WPOM(3-) on FSAM decreased while that of WPOM(2-) increased. We propose that the higher stability of immobilized WPOM(2-) in comparison with WPOM(3-) 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. PMID:26966731

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

    SciTech Connect

    Feng, Xiangdong; Liu, Jun; Fryxell, G.

    1997-10-01

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

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

    SciTech Connect

    Kim, Sungwook; Chang, In Soon; McDevitt, John T.

    2005-04-11

    Although extensive amounts of research have been carried out on superconductor-normal metal-superconductor (SNS) electronic devices, the fabrication of superconductor SNS devices still remains difficult. Surface modification of high-temperature superconductors could be a way to control the interface of SNS electronic device fabrication. Here, we developed a cleaning method for thin films of high-temperature superconductor surface based on self-assembled monolayers. High-quality c-axis orientated YBa{sub 2}Cu{sub 3}O{sub 7-{delta}} (i.e., YBCO) and Y{sub 0.6}Ca{sub 0.4}Ba{sub 1.6}La{sub 0.4}Cu{sub 3}O{sub 7-{delta}} (i.e., TX-YBCO) thin films were deposited by standard laser ablation methods. YBCO/Au/YBCO and TX-YBCO/Au/TX-YBCO planar type junctions were fabricated by photolithography, focused-ion-beam milling, and ex situ sputter depositions. A 40-50 nm nanotrench was ion milled on the thin film by FIB, and a thin gold layer was deposited by an ex situ method on the nanotrench to connect the two separated high-temperature superconductor electrodes. SEM, AFM, and R vs T resistivity measurements were used to compare the corrosion layer formed in the interface of the SNS junctions with the SAM cleaned SNS junction. Evidence here suggests that the SAM cleaning method can be used to remove the degradation layer on the surface of cuprate superconductors. The obtained contact resistivity value (10{sup -8} {omega} cm{sup 2}) for a SNS junction with SAM treatment is comparable with that of SNS junctions fabricated by the in situ methods.

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

    PubMed

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

    2016-04-01

    The self-assembly of molecules on surfaces into 2D structures is important for the bottom-up fabrication of functional nanomaterials, and the self-assembled structure depends on the interplay between molecule-molecule interactions and molecule-surface interactions. Halogenated benzene derivatives on platinum have been shown to have two distinct adsorption states: a physisorbed state and a chemisorbed state, and the interplay between the two can be expected to have a profound effect on the self-assembly and phase behaviour of these systems. We developed a lattice model that explicitly includes both adsorption states, with representative interactions parameterised using density functional theory calculations. This model was used in Monte Carlo simulations to investigate pattern formation of hexahalogenated benzene molecules on the platinum surface. Molecules that prefer the physisorbed state were found to self-assemble with ease, depending on the interactions between physisorbed molecules. In contrast, molecules that preferentially chemisorb tend to get arrested in disordered phases. However, changing the interactions between chemisorbed and physisorbed molecules affects the phase behaviour. We propose functionalising molecules in order to tune their adsorption states, as an innovative way to control monolayer structure, leading to a promising avenue for directed assembly of novel 2D structures. PMID:27059585

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  9. Optimizing the preparation procedure of self-assembled monolayer of stearic acid for protection of cupronickel alloy.

    PubMed

    Marušić, Katarina; Hajdari, Zana; Ćurković, Helena Otmačić

    2014-01-01

    The aim of this work is to examine the possibility of CuNi protection in chloride media by self-assembled monolayers (SAMs) of stearic acid (SA). In order to obtain a compact, well ordered monolayer, that will provide long term protection, different SAM preparation procedures are studied. The influence of CuNi pretreatment, SA solution temperature and temperature of the drying period followed after the SA treatment on the protective properties of stearic acid self-assembled layer are examined by electrochemical methods and surface analysis techniques. The obtained results show that for complete self-assembled film formation it is necessary to have a drying period after exposing the sample to the stearic acid solution. Heating of the SA solution and drying period at higher temperatures result in layers with better stability in chloride media. The most compact surface layer, that provides long lasting and efficient protection to the underlying alloy, is obtained when prior to SA solution exposure an oxide layer on CuNi surface was formed at elevated temperatures. PMID:25125116

  10. Steering the Self-Assembly of Octadecylamine Monolayers on Mica by Controlled Mechanical Energy Transfer from the AFM Tip

    SciTech Connect

    Benitez, J.J.; Heredia-Guerrero, J.A.; Salmeron, M.

    2010-06-24

    We have studied the effect of mechanical energy transfer from the tip of an Atomic Force Microscope on the dynamics of self-assembly of monolayer films of octadecylamine on mica. The formation of the self-assembled film proceeds in two successive stages, the first being a fast adsorption from solution that follows a Langmuir isotherm. The second is a slower process of island growth by aggregation of the molecules dispersed on the surface. We found that the dynamics of aggregation can be altered substantially by the addition of mechanical energy into the system through controlled tip-surface interactions. This leads to either the creation of pinholes in existing islands as a consequence of vacancy concentration, and to the assembly of residual molecules into more compact islands.

  11. Hybrid subtractive micro-patterning of a self-assembled SiO2 nano/microsphere monolayer

    NASA Astrophysics Data System (ADS)

    Han, Seungyong; Hong, Sukjoon; Kang, Hyun Wook; Wanit, Manorokul; Kang, Bongchul; Ko, Seung Hwan

    2015-10-01

    Colloidal self-assembly and direct micro-patterning of functional materials have drawn intense interest as an alternative to the conventional photolithography based microelectronics fabrication process. In this paper, we introduce a facile subtractive micro contact printing method to create a patterned colloidal nano/micro sphere monolayer on a wafer scale by combining an additive ‘bottom-up’ self-assembly and subtractive ‘top-down’ printing process. A vacuum-assisted contact printing method enabled precise and uniform pressure control to directly fabricate a large-area micro-patterned hexagonally close packed structure of nano/micro spheres on the target substrate very fast, at low cost, under ambient conditions. In addition, analysis on the hybrid printing pressure and the patterning time has been conducted.

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

    PubMed

    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. PMID:24823616

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

    NASA Astrophysics Data System (ADS)

    Xie, Yun; Liu, Meifeng; Zhou, Jian

    2012-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2001-04-01

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

  15. Chemical kinetics in dynamic reaction fronts and in etching of self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Yen, Andrew Tze-Chung

    1997-11-01

    related to some traditional applications, such as chromatography and electrophoresis, but also to surface adhesion and microelectronic structures in silicon waffers. The etching process of organosilane self-assembled-monolayers was studied. The unusual power law dependence observed experimentally compares well with simulations based on a reaction-diffusion model.

  16. Charge Retention by Organometallic Dications on Self-Assembled Monolayer Surfaces

    SciTech Connect

    Laskin, Julia; Wang, Peng

    2014-05-15

    Charge retention by mass-selected ruthenium trisbipyridine dications, or Ru(bpy)32+, soft-landed onto self-assembled monolayer (SAM) surfaces of 1H, 1H, 2H, 2H-perfluorodecane-1-thiol (FSAM), 11-mercaptoundecanoic acid (COOH-SAM), and 11-amino-1-undecanethiol (HSAM) on gold was examined using in situ time-resolved secondary ion mass spectrometry in a Fourier transform ion cyclotron resonance apparatus (FT-ICR SIMS). FT-ICR SIMS analysis was performed during ion soft-landing and for 8–15 hours after the ion beam was switched off. Our results demonstrate efficient retention of the doubly charged precursor ion on the FSAM and COOH-SAM surfaces manifested by the abundant Ru(bpy)32+ ions in the SIMS spectra. In contrast, only the singly charged Ru(bpy)3+ and Ru(bpy)2+ ions were observed on HSAM, indicating rapid loss of at least one charge by the deposited dications. The signal of Ru(bpy)32+ on COOH-SAM remained almost constant for more than 8 hours after the end of ion soft-landing, while a relatively fast decay followed by a plateau region was observed on the FSAM surface. However, we found that SIMS analysis of Ru(bpy)32+ ions soft-landed onto FSAM is complicated by facile ion-molecule reactivity occurring either on the surface or in the SIMS plume, making it difficult to accurately measure the charge reduction kinetics. Efficient retention of the doubly charged Ru(bpy)32+ ions on COOH-SAM is remarkably different from facile neutralization of protonated peptides deposited onto this surface reported in previous studies. Our results indicate different mechanisms of charge reduction of protonated molecules and permanent ions, such as Ru(bpy)32+, on SAM surfaces. Thus, we propose that proton loss is the major charge reduction channel for the protonated species, while electron transfer through the insulating SAM is responsible for the charge loss by permanent ions. Fundamental understanding of charge reduction phenomena is essential for controlled preparation of

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

    PubMed

    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. PMID:25124834

  18. Interfacial energetics of blood plasma and serum adsorption to a hydrophobic self-assembled monolayer surface.

    PubMed

    Krishnan, Anandi; Cha, Paul; Liu, Yi-Hsiu; Allara, David; Vogler, Erwin A

    2006-06-01

    Interfacial energetics of blood plasma and serum adsorption to a hydrophobic, methyl-terminated self-assembled monolayer (SAM) surface (solid-liquid SL interface) are shown to be essentially the same as to the buffer-air interface (liquid-vapor LV interface). Specifically, spreading pressure (Pia) isotherms scaled on a w/v concentration basis constructed from advancing contact angles (thetaa) of serially diluted plasma/serum derived from four different mammalian species (bovine, equine, human, and ovine) on the SAM surface are not resolvable at the 99% confidence level and furthermore are found to be strikingly similar to isotherms of purified human-blood proteins. Maximum advancing spreading pressures Piamax for protein mixtures fall within a relatively narrow 17

  19. Controlling the surface environment of heterogeneous catalysts using self-assembled monolayers.

    PubMed

    Schoenbaum, Carolyn A; Schwartz, Daniel K; Medlin, J Will

    2014-04-15

    Rationally designing and producing suitable catalysts to promote specific reaction pathways remains a major objective in heterogeneous catalysis. One approach involves using traditional catalytic materials modified with self-assembled monolayers (SAMs) to create a more favorable surface environment for specific product formation. A major advantage of SAM-based modifiers is their tendency to form consistent, highly ordered assembly structures on metal surfaces. In addition, both the attachment chemistry and tail structures can easily be tuned to facilitate specific interactions between reactants and the catalyst. In this Account, we summarize our recent modification approaches for tuning monolayer structure to improve catalytic performance for hydrogenation reactions on palladium and platinum catalysts. Each approach serves to direct selectivity by tuning a particular aspect of the system including the availability of specific active sites (active-site selection), intermolecular interactions between the reactants and modifiers (molecular recognition), and general steric or crowding effects. We have demonstrated that the tail moiety can be tuned to control the density of SAM modifiers on the surface. Infrared spectra of adsorbed CO probe molecules reveal that increasing the density of the thiols restricts the availability of contiguous active sites on catalyst terraces while maintaining accessibility to sites located at particle edges and steps. This technique was utilized to direct selectivity for the hydrogenation of furfural. Results obtained from SAM coatings with different surface densities indicated that, for this reaction, formation of the desirable products occurs primarily at particle edges and steps, whereas the undesired pathway occurs on particle terrace sites. As an alternative approach, the tail structure of the SAM precursor can be tuned to promote specific intermolecular interactions between the modifier and reactant in order to position reactant

  20. Kinetics of mediated electron transfer between viologen groups in a self-assembled monolayer and metal complexes in solution

    NASA Astrophysics Data System (ADS)

    Schneider, Thomas; Hiley, Shauna; Buttry, Daniel A.

    1993-05-01

    Self-assembled monolayers are used in an experimental configuration which allows the extraction of the cross reaction electron exchange rate constant for the electron transfer between a viologen group embedded within the SAM and a metal complex in solution. This cross reaction rate constant is compared with predictions from the Marcus theory using the cross reaction relation and the known self-exchange rate constants for the two reagents. The results reveal that the intrinsic barrier to the electron transfer is relatively unchanged in the SAM, while the rate constant is somewhat depressed due to the long distance over which the electron must transfer.

  1. Photoreactive self-assembled monolayer for the stabilization of tilt orientation of a director in vertically aligned nematic liquid crystals.

    PubMed

    Oh, Su Yeon; Kang, Shin-Woong

    2013-12-16

    Photo-reactive self-assembled monolayer (PR-SAM) is employed to mediate alignment of liquid crystals (LC) and stabilize the tilt orientation of a nematic director for a vertically aligned liquid crystal. Bifunctional PR-SAM formed by silane coupling reaction to oxide surfaces efficiently induces a homeotropic alignment and stabilizes LC director by the photo-polymerization under applied electric field. As a result, the substantial enhancement of electro-optic performance has been achieved after the PR-SAM assisted stabilization of tilt orientation of director. This approach for pretilt stabilization has multifarious advantages over the conventional PSVA. PMID:24514711

  2. Preparation of a hole transport layer tethered to ITO surface via a self-assembled monolayer with reactive terminal group

    NASA Astrophysics Data System (ADS)

    Hagihara, Yuya; Kim, Seong-Ho; Tanaka, Kuniaki; Advincula, Rigoberto C.; Usui, Hiroaki

    2014-01-01

    Characteristics of a junction between a polymer thin film and an indium-tin oxide (ITO) substrate was controlled by forming covalent chemical bonds at the interface through self-assembled monolayers (SAMs) with reactive terminal groups. For this purpose, SAMs with vinyl, epoxide, and benzophenone terminal groups were formed on ITO substrates, on which a vinyl derivative of a hole transport molecule was vapor-deposited, and then annealed in vacuum. This procedure produced a polymer layer strongly attached to the substrate surface. It was also found that the charge injection from the ITO electrode to the polymer layer can be improved by chemically tethering the interface via the SAMs.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  4. Limits to the Effect of Substrate Roughness or Smoothness on the Odd-Even Effect in Wetting Properties of n-Alkanethiolate Monolayers.

    PubMed

    Chen, Jiahao; Wang, Zhengjia; Oyola-Reynoso, Stephanie; Gathiaka, Symon M; Thuo, Martin

    2015-06-30

    This study investigates the effect of roughness on interfacial properties of an n-alkanethiolate self-assembled monolayer (SAM) and uses hydrophobicity to demonstrate the existence of upper and lower limits. This article also sheds light on the origin of the previously unexplained gradual increase in contact angles with increases in the size of the molecule making the SAM. We prepared Au surfaces with a root-mean-square (RMS) roughness of ∼0.2-0.5 nm and compared the wetting properties of n-alkanethiolate (C10-C16) SAMs fabricated on these surfaces. Static contact angles, θ(s), formed between the SAM and water, diethylene glycol, and hexadecane showed an odd-even effect irrespective of the solvent properties. The average differences in subsequent SAM(E) and SAM(O) are Δθ(s|n  – (n+1)|) ≈ 1.7° (n = even) and Δθ(s|n – (n+1)|) ≈ 3.1° (n = odd). A gradual increase in θ(s) with increasing length of the molecule was observed, with values ranging from water 104.7-110.7° (overall Δθ(s) = 6.0° while for the evens Δθ(s)(E) = 4.4° and odds Δθ(s)(O) = 3.5°) to diethylene glycol 72.9-80.4° (overall Δθ(s) = 7.5° while for the evens Δθ(s)(E) = 2.9° and odds Δθ(s)(O) = 2.4°) and hexadecane 40.4–49.4° (overall Δθ(s) = 9.0° while for the evens Δθ(s)(E) = 3.7° and odds Δθ(s)(O) = 2.1°). This article establishes that the gradual increase in θ(s) with increasing molecular size in SAMs is due to asymmetry in the zigzag oscillation in the odd-even effect. Comparison of the magnitude and proportion differences in this asymmetry allows us to establish the reduction in interfacial dispersive forces, due to increasing SAM crystallinity with increasing molecular size, as the origin of this asymmetry. By comparing the dependence of θ(s) on surface roughness we infer that (i) RMS roughness ≈ 1 nm is a theoretical limit beyond which the odd-even effect cannot be observed and (ii) on a hypothetically flat surface the maximum difference

  5. Review and outlook: from single nanoparticles to self-assembled monolayers and granular GMR sensors.

    PubMed

    Weddemann, Alexander; Ennen, Inga; Regtmeier, Anna; Albon, Camelia; Wolff, Annalena; Eckstädt, Katrin; Mill, Nadine; Peter, Michael K-H; Mattay, Jochen; Plattner, Carolin; Sewald, Norbert; Hütten, Andreas

    2010-01-01

    This paper highlights recent advances in synthesis, self-assembly and sensing applications of monodisperse magnetic Co and Co-alloyed nanoparticles. A brief introduction to solution phase synthesis techniques as well as the magnetic properties and aspects of the self-assembly process of nanoparticles will be given with the emphasis placed on selected applications, before recent developments of particles in sensor devices are outlined. Here, the paper focuses on the fabrication of granular magnetoresistive sensors by the employment of particles themselves as sensing layers. The role of interparticle interactions is discussed. PMID:21977397

  6. Epitaxial transfer through end-group coordination modulates the odd-even effect in an alkanethiol monolayer assembly.

    PubMed

    Yimer, Yeneneh Y; Jha, Kshitij C; Tsige, Mesfin

    2014-04-01

    Short spacer length and high end-group coordination lead to the top network acting as a template for the buried sulfur-gold interface of n-alkanethiols (SH-(CH2)n-OH or SH-(CH2)n-CH3) on gold {111}. Annealing and templating both drive toward a higher sampling of the spatially favorable bridge adsorption sites. The hydrogen-bonded network increases in strength by increasing the number of hydrogens participating per oxygen, from 1.75 to 1.98 for n = 14-30. Higher n leads to better packing (five times for hydroxyl-terminated and seven times for methyl-terminated for n = 14-30) and stability of monolayers, while lower n results in better epitaxial transfer (transfer coefficient ratio = 13.5 for {SH-(CH2)14-OH}/{SH-(CH2)30-CH3}) and actuation. Odd values of n for the hydroxyl-terminated n-alkanethiols lead to lattice spacing of an average of 0.04 ± 0.01 Å higher than even values. There is a structural transition in properties around spacer length n = 24-27. Characterization of monolayer assembly through correlation between adatom and network layers provides recursive design principles for actuation and sensing applications. PMID:24553572

  7. Self-Assembly of Hydrofluorinated Janus Graphene Monolayer: A Versatile Route for Designing Novel Janus Nanoscrolls

    PubMed Central

    Jin, Yakang; Xue, Qingzhong; Zhu, Lei; Li, Xiaofang; Pan, Xinglong; Zhang, Jianqiang; Xing, Wei; Wu, Tiantian; Liu, Zilong

    2016-01-01

    With remarkably interesting surface activities, two-dimensional Janus materials arouse intensive interests recently in many fields. We demonstrate by molecular dynamic simulations that hydrofluorinated Janus graphene (J-GN) can self-assemble into Janus nanoscroll (J-NS) at room temperature. The van der Waals (vdW) interaction and the coupling of C-H/π/C-F interaction and π/π interaction are proven to offer the continuous driving force of self-assembly of J-GN. The results show that J-GN can self-assemble into various J-NSs structures, including arcs, multi-wall J-NS and arm-chair-like J-NS by manipulating its original geometry (size and aspect ratio). Moreover, we also investigated self-assembly of hydrofluorinated J-GN and Fe nanowires (NWs), suggesting that Fe NW is a good alternative to activate J-GN to form J-NS. Differently, the strong vdW interaction between J-GN and Fe NW provides the main driving force of the self-assembly. Finally, we studied the hydrogen sorption over the formed J-NS with a considerable interlayer spacing, which reaches the US DOE target, indicating that J-NS is a promising candidate for hydrogen storage by controlling the temperature of system. Our theoretical results firstly provide a versatile route for designing novel J-NS from 2D Janus nanomaterials, which has a great potential application in the realm of hydrogen storage/separation. PMID:27243752

  8. Self-Assembly of Hydrofluorinated Janus Graphene Monolayer: A Versatile Route for Designing Novel Janus Nanoscrolls

    NASA Astrophysics Data System (ADS)

    Jin, Yakang; Xue, Qingzhong; Zhu, Lei; Li, Xiaofang; Pan, Xinglong; Zhang, Jianqiang; Xing, Wei; Wu, Tiantian; Liu, Zilong

    2016-05-01

    With remarkably interesting surface activities, two-dimensional Janus materials arouse intensive interests recently in many fields. We demonstrate by molecular dynamic simulations that hydrofluorinated Janus graphene (J-GN) can self-assemble into Janus nanoscroll (J-NS) at room temperature. The van der Waals (vdW) interaction and the coupling of C-H/π/C-F interaction and π/π interaction are proven to offer the continuous driving force of self-assembly of J-GN. The results show that J-GN can self-assemble into various J-NSs structures, including arcs, multi-wall J-NS and arm-chair-like J-NS by manipulating its original geometry (size and aspect ratio). Moreover, we also investigated self-assembly of hydrofluorinated J-GN and Fe nanowires (NWs), suggesting that Fe NW is a good alternative to activate J-GN to form J-NS. Differently, the strong vdW interaction between J-GN and Fe NW provides the main driving force of the self-assembly. Finally, we studied the hydrogen sorption over the formed J-NS with a considerable interlayer spacing, which reaches the US DOE target, indicating that J-NS is a promising candidate for hydrogen storage by controlling the temperature of system. Our theoretical results firstly provide a versatile route for designing novel J-NS from 2D Janus nanomaterials, which has a great potential application in the realm of hydrogen storage/separation.

  9. Self-Assembly of Hydrofluorinated Janus Graphene Monolayer: A Versatile Route for Designing Novel Janus Nanoscrolls.

    PubMed

    Jin, Yakang; Xue, Qingzhong; Zhu, Lei; Li, Xiaofang; Pan, Xinglong; Zhang, Jianqiang; Xing, Wei; Wu, Tiantian; Liu, Zilong

    2016-01-01

    With remarkably interesting surface activities, two-dimensional Janus materials arouse intensive interests recently in many fields. We demonstrate by molecular dynamic simulations that hydrofluorinated Janus graphene (J-GN) can self-assemble into Janus nanoscroll (J-NS) at room temperature. The van der Waals (vdW) interaction and the coupling of C-H/π/C-F interaction and π/π interaction are proven to offer the continuous driving force of self-assembly of J-GN. The results show that J-GN can self-assemble into various J-NSs structures, including arcs, multi-wall J-NS and arm-chair-like J-NS by manipulating its original geometry (size and aspect ratio). Moreover, we also investigated self-assembly of hydrofluorinated J-GN and Fe nanowires (NWs), suggesting that Fe NW is a good alternative to activate J-GN to form J-NS. Differently, the strong vdW interaction between J-GN and Fe NW provides the main driving force of the self-assembly. Finally, we studied the hydrogen sorption over the formed J-NS with a considerable interlayer spacing, which reaches the US DOE target, indicating that J-NS is a promising candidate for hydrogen storage by controlling the temperature of system. Our theoretical results firstly provide a versatile route for designing novel J-NS from 2D Janus nanomaterials, which has a great potential application in the realm of hydrogen storage/separation. PMID:27243752

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

    PubMed

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

    2016-01-01

    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. PMID:27045012

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

    PubMed

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

    2016-06-01

    Scattering matrix theory is used to describe resonant optical properties of molecular monolayers. Three types of coupling are included: exciton-exciton, exciton-photon, and exciton-phonon coupling. We use the K-matrix formalism, developed originally to describe neutron scattering spectra in nuclear physics to compute the scattering of polaritons by phonons. This perturbation approach takes into account the three couplings and allows one to go beyond molecular exciton theory without the need of introducing additional boundary conditions for the polariton. We demonstrate that reflection, absorption, and extinction of light by 2D self-assembled monolayers of molecules containing quinque-thiophene chromophoric groups can be calculated. The extracted coherence length of the Frenkel exciton is discussed. PMID:27276952

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    PubMed

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

    2016-08-01

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

  14. A pH-Sensitive Supramolecular Switch Based on Mixed Carboxylic Acid Terminated Self-Assembled Monolayers on Au(111).

    PubMed

    Jacquelín, Daniela K; Pérez, Manuel A; Euti, Esteban M; Arisnabarreta, Nicolás; Cometto, Fernando P; Paredes-Olivera, Patricia; Patrito, E Martín

    2016-02-01

    We show that homogeneously mixed self-assembled monolayers (SAMs) of mercaptoalkanoic acids of different chain lengths can be used to build up a pH-sensitive supramolecular switch. The acids with short and long alkyl chains interact via the strong hydrogen bond between carboxylic acid groups. The pH acts as a trigger by breaking or restoring the hydrogen bond interaction in basic or acidic solutions, respectively. The corresponding changes in the monolayer structure were determined by ellipsometry, surface-enhanced Raman spectroscopy, and contact angle measurements. Density functional theory (DFT) calculations were performed to elucidate the structures of interacting molecules compatible with the surface coverage obtained from electrochemical reductive desorption experiments. The simplicity of the preparation procedure assures a high reproducibility whereas the stability of the homogeneous mixed SAM guarantees the reversibility of the switching process. PMID:26799556

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

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

    2016-01-01

    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. PMID:27045012

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

    PubMed Central

    2016-01-01

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

  18. Ion transport and electron transfer at self-assembled alkylthiol/gold monolayers

    NASA Astrophysics Data System (ADS)

    Boubour, Emmanuelle

    The electrical and electrochemical properties of self-assembled n-alkylthiol monolayers (SAMs) on gold are important if SAMs are to be used as molecular building blocks in biomimetic membranes and in micro- or nano-electronics. Ion transport and electron transfer at SAM/electrolyte interfaces are two important processes which have been characterized by cyclic voltammetry and a.c. impedance spectroscopy. Ion transport from an aqueous phase to the hydrophobic SAM region has been addressed by investigating the insulating properties of a wide variety of X(CH2)nS/Au SAMs (X = CH3, OH, CO2H and CF 3, and n = 7, 9, 11, 15). It was established that when the phase angle at a frequency characteristic of ion diffusion processes ( i.e. 1 Hz) is ≥88°, the SAM is defect-free and obeys the Helmholtz ideal capacitor model. However, when ϕ1HZ < 88°, the SAM is no longer an ionic insulator and ion/water penetration from the electrolyte into the SAM hydrophobic region is observed. The behavior of the phase angle with frequency was used to characterize the permeability of SAMs to electrolyte ions (K+, H2PO4 -, and HPO42-) as a function of the applied d.c. potential. A critical potential, Vc, was identified for each type of SAM corresponding to a transition from an insulating state to a more permeable state. When X = CH3, V c becomes more cathodic with increasing chainlength, i.e. Vc = -0.15 V (vs. Ag/AgCl) for n = 7, -0.25 V for n = 9, 11, and -0.35 V for n = 15. The SAM ionic permeability can also be modulated by maintaining n constant (15) and by varying the terminal group X. Vc is considerably more anodic for hydrophilic SAM/electrolyte interfaces (+0.25 V vs . Ag/AgCl for X = OH and + 0.15 V for X = CO2H) than for hydrophobic interfaces (-0.35 V for X = CH3). The kinetics of electron transfer at CH3(CH2)15CH3 SAMs have been investigated by a.c. impedance spectroscopy at various d.c. overpotentials with three redox couples, Ru(NH3)63+/2+, Fe(CN)63-/4-, and Co(bpy)3 3+/2+. Fits

  19. Characteristics of localized surface plasmons excited on mixed monolayers composed of self-assembled Ag and Au nanoparticles.

    PubMed

    Tanaka, Daisuke; Imazu, Keisuke; Sung, Jinwoo; Park, Cheolmin; Okamoto, Koichi; Tamada, Kaoru

    2015-10-01

    The fundamental characteristics of localized surface plasmon resonance (LSPR) excited on mixed monolayers composed of self-assembled Ag and Au nanoparticles (AgNPs and AuNPs, respectively) were investigated. Mixed monolayered films were fabricated at the air-water interface at different mixing ratios. The films retained their phase-segregated morphologies in which AuNPs formed several 10 to 100 nm island domains in a homogeneous AgNP matrix phase. The LSPR bands originating from the self-assembled domains shifted to longer wavelengths as the domain size increased, as predicted by a finite-difference time-domain (FDTD) simulation. The FDTD simulation also revealed that even an alternating-lattice-structured two-dimensional (2D) AgNP/AuNP film retained two isolated LSPR bands, revealing that the plasmon resonances excited on each particle did not couple even in a continuous 2D sheet, unlike in the homologous NP system. The fluorescence quenching test of Cy3 and Cy5 dyes confirmed that the independent functions of AuNPs and AgNPs remained in the mixed films, whereas the AuNPs exhibited significantly higher quenching efficiency for the Cy3 dye compared with AgNPs due to the overlap of the excitation/emission bands of the dyes with the AuNP LSPR band. Various applications can be considered using this nanoheterostructured plasmonic assembly to excite spatially designed, high-density LSPR on macroscopic surfaces. PMID:26332039

  20. EPR studies on the organization of self-assembled spin-labeled organic monolayers adsorbed on GaAs.

    PubMed

    Ruthstein, Sharon; Artzi, Reit; Goldfarb, Daniella; Naaman, Ron

    2005-02-01

    Characterizing the structure and dynamic properties of a single monolayer is a challenge due to the minute amount of material that is probed. Here, EPR spectroscopy is used for investigating the spatial and temporal organization of self-assembled monolayers of 5- and 16-doxyl stearic acid (5 DSA and 16 DSA, respectively) adsorbed on a GaAs substrate. The results are complemented with FTIR and ellipsometery measurements, which provide the evidence for the formation of monolayers. Moreover, a comparison with the FTIR spectrum of a monolayer of stearic acid shows that the monolayers of the spin labeled molecules are less packed due to the hindrance introduced by the labeling group. The EPR spectra provide a new insight on the ordering in the layer and more interestingly, it reveals the time dependence of the organization. For 5DSA, with the spin-label group situated close to the substrate, the EPR spectrum immediately after adsorption is poorly resolved and dominated by the spin-exchange interaction between neighboring molecules. As time increases (up to 1 week) the resolution of the 14N hyperfine coupling increases, revealing a better organized monolayer where the molecules are more homogenously spaced. Moreover, the spectrum of the layer, after reaching equilibrium, shows that there is no motional freedom near the GaAs surface. Orientation dependence measurements on the equilibrated sample show the presence of a preferred orientation of the molecules, although with a wide distribution. The spectrum of the 16DSA monolayer, where the nitroxide spin label is situated at the end of the chain, far from the surface, also showed a poorly resolved spectrum at short times, but unlike 5DSA, it did not exhibit any time dependence. Through EPR line-shape simulations and by comparison with FTIR results, the differences between 5DSA and 16DSA were attributed to difference in coverage caused by the bulky spin label near the surface in the case of 5DSA. PMID:19785139

  1. Experimental setup for the coating of chlorosilane based self assembling monolayers to reduce stiction in MEMS devices

    NASA Astrophysics Data System (ADS)

    Steiner, H.; Sachse, M.; Schalko, J.; Hortschitz, W.; Kohl, F.; Jachimowicz, A.

    2011-06-01

    An often reported problem during production and operation of silicon MEMS is stiction. It describes the sticking of movable MEMS parts to surrounding structures. The probability of the occurrence of stiction is linked to the surface energy of the MEMS. Self assembling monolayers can be used to reduce the surface energy and therefore the probability of stiction. These monolayers have to resist high temperatures up to 400°C to be compatible with various micro-production processes, e.g., eutectic bonding. Several groups tried to coat such monolayers with different success and results. One problem is the instability of the coating method due to water contaminations of the coating solution. To circumvent this error source, an experimental setup was designed and built up to minimize the water content of the monolayer solvent and ensures reproducible conditions during the coating process. The required set of liquids is piped through a system of valves and tubes to rinse a trench with a silicon die. To avoid contamination of the liquids with water, the setup is partly placed in a box flushed with nitrogen. With this experimental setup, the surface energy γs of the MEMS structures had been reduced from 18.1 mJ/m2 to 33.1 μJ/m2 and 36.6 μJ/m2 for FDTS and DDMS, respectively.

  2. When do defectless alkanethiol SAMs in ionic liquids become penetrable? A molecular dynamics study.

    PubMed

    Kislenko, Sergey A; Nikitina, Victoria A; Nazmutdinov, Renat R

    2015-12-21

    Molecular dynamics simulations were performed to address the permeability of defectless alkanethiol self-assembled monolayers (SAMs) on charged and uncharged Au(111) surfaces in 1-butyl-3-methylimidazolium ([bmim][BF4]) room-temperature ionic liquid (IL). We demonstrate that ionic permeation into the monolayer does not start until a critical surface charge density value is attained (both for positive and negative surface charges). The free energy barrier for the permeation of IL components is shown to include nearly equal contributions from ion desolvation and the channel formation in the dense monolayer. Long chain alkanethiols (hexadecanethiol SC16H33) exhibit superior barrier properties as compared with short chain alkanethiols (hexanethiol SC6H13) due to the dense packing of alkanethiol chains in highly ordered zigzag conformation oriented at the same tilt angle. Computed critical charge densities correspond to the electrode potential values beyond the limits of the monolayer stability, which might indicate the impermeability of the defectless monolayer towards the IL components. Experimental findings on increased interfacial capacitance are interpreted, therefore as some manifestation of the monolayer defectiveness occurring in real electrochemical systems. The potential of the mean force is constructed for a typical redox probe ferrocene/ferrocenium (Fc/Fc(+)) as well, to investigate a possible permeation of the solute from the IL into the SC6H13 monolayer. PMID:26568158

  3. Biological passivation of porous silicon by a self-assembled nanometric biofilm of proteins

    NASA Astrophysics Data System (ADS)

    de Stefano, Luca; Rea, Ilaria; de Tommasi, Eduardo; Giardina, Paola; Armenante, Annunziata; Longobardi, Sara; Giocondo, Michele; Rendina, Ivo

    2009-10-01

    Self-assembled monolayers are surfaces consisting of a single layer of molecules on a substrate: widespread examples of chemical and biological nature are alkylsiloxane, fatty acids, and alkanethiolate which can be deposited by different techniques on a large variety of substrates ranging from metals to oxides. We have found that a self-assembled biofilm of proteins can passivate porous silicon (PSi) based optical structures without affecting the transducing properties. Moreover, the protein coated PSi layer can also be used as a functionalized surface for proteomic applications.

  4. Effects of different self-assembled monolayers on thin-film morphology: a combined DFT/MD simulation protocol.

    PubMed

    Alberga, Domenico; Mangiatordi, Giuseppe Felice; Motta, Alessandro; Nicolotti, Orazio; Lattanzi, Gianluca

    2015-10-01

    Organic thin film transistors (OTFTs) are multilayer field-effect transistors that employ an organic conjugated material as semiconductor. Several experimental groups have recently demonstrated that the insertion of an organic self-assembled monolayer (SAM) between the dielectric and the semiconductive layer is responsible for a sensible improvement of the OTFT performances in terms of an increased charge carrier mobility caused by a higher degree of order in the organic semiconductor layer. Here, we describe a combined periodic density functional theory (DFT) and classical molecular dynamics (MD) protocol applied to four different SAMs and a pentacene monolayer deposited onto their surfaces. In particular, we investigate the morphology and the surface of the four SAMs and the translational, orientational, and nematic order of the monolayer through the calculation of several distribution functions and order parameters pointing out the differences among the systems and relating them to known experimental results. Our calculations also suggest that small differences in the SAM molecular design will produce remarkable differences in the SAM surface and monolayer order. In particular, our simulations explain how a SAM with a bulky terminal group results in an irregular and rough surface that determines the deposition of a disordered semiconductive monolayer. On the contrary, SAMs with a small terminal group generate smooth surfaces with uninterrupted periodicity, thus favoring the formation of an ordered pentacene monolayer that increases the mobility of charge carriers and improves the overall performances of the OTFT devices. Our results clearly point out that the in silico procedure presented here might be of help in tuning the design of SAMs in order to improve the quality of OTFT devices. PMID:26367250

  5. Photoactivated electronic activities of Photosystem I (PS I) immobilized on self-assembled monolayer/gold substrates

    NASA Astrophysics Data System (ADS)

    Mukherjee, Dibyendu; Ivanov, Ilia; Khomami, Bamin

    2012-02-01

    Photosynthetic protein complex, Photosystem I (PS I) activates a light-induced (λ=680 nm) directional electron transfer chain that initiates at the lumenal side (mid-point potential, Em(P700/ P700+)˜+0.4 V) and terminates at the stromal side (Em(FA; FB; FX)˜-0.7 V) of PS I. In an effort to harness this photo-electrochemical activity of PS I in future bio-hybrid photovoltaic devices, precise electrochemical measurements have been used to investigate the photo-activated properties of PS I monolayers assembled on C9-alkanethiolate SAM/Au substrates. These measurements demonstrate, for the first time, a light-induced energetic electron transfer from the Au donor facilitated by photoexcitation of the reaction center P700 in PS I complexes. Furthermore, electrochemical impedance spectroscopy measurements, when fitted with equivalent electrical circuit models, reveal a light-induced reduction in the charge transfer resistance at the PS I/SAM-electrolyte interface. These observations, in conjunction with measurements for the transient electronic behavior, reveal the underlying mechanistic picture for the photo-excited electronic activities in PS I monolayer assembly on SAM/Au substrates.

  6. Directly Grafting Alkanethiol on Bare Si (111) by UV-assisted Photochemical Reaction

    NASA Astrophysics Data System (ADS)

    Chang, Lo-Yueh; Shiu, Hung-Wei; Gwo, Shangjr; Chen, Chia-Hao

    2014-03-01

    Self-assembled monolayers (SAMs) are organic molecules that self-assembled and closely packed on substrate surface. The surface physic and chemical properties are dependent on the controllable tail of SAMs. Therefore, SAMs is attracting a lot of attention in bio-sensing, nano-manipulating, and microfluidic field. The alkanethiol on noble metal surface, such as gold and silver, is a well-known SAM system to understand the fundamental properties. However, alkanethiols grown on semiconductor surfaces was less systematically studied, especially on bare silicon surface, despite their prospective applications. To have in-depth understanding of such system, we tried to grow alkanethiol SAMs on hydrogen-terminated Si surface by UV-assisted photochemical reaction. The resulting monolayer was studied by means of water contact angle measurement, synchrotron radiation based X-ray photoemission spectroscopy, and polarization dependent near-edge X-ray absorption fine structure. The combined characterization probes revealed a hydrophobic ambient surface, and the n-alkanethiols were directly attached on Si through Si-S bond that formed a highly order monolayer to prevent the air oxidation and contamination.

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

    PubMed

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

    2015-06-30

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

  8. Fabrication of molecular nanopatterns at aluminium oxide surfaces by nanoshaving of self-assembled monolayers of alkylphosphonates

    NASA Astrophysics Data System (ADS)

    El Zubir, Osama; Barlow, Iain; Leggett, Graham J.; Williams, Nicholas H.

    2013-10-01

    Nanoshaving, by tracing an atomic force microscope probe across a surface at elevated load, has been used to fabricate nanostructures in self-assembled monolayers of alkylphosphonates adsorbed at aluminium oxide surfaces. The simple process is implemented under ambient conditions. Because of the strong bond between the alkylphosphonates and the oxide surface, loads in excess of 400 nN are required to pattern the monolayer. Following patterning of octadecylphosphonate SAMs, adsorption of aminobutyl phosphonate yielded features as small as 39 nm. Shaving of monolayers of aryl azide-terminated alkylphosphonates, followed by attachment of polyethylene glycol to unmodified regions in a photochemical coupling reaction, yielded 102 nm trenches into which NeutrAvidin coated, dye-labelled, polymer nanospheres could be deposited, yielding bright fluorescence with little evidence of non-specific adsorption to other regions of the surface. Structures formed in alkylphosphonate films by nanoshaving were used to etch structures into the underlying metal. Because of the isotropic nature of the etch process, and the large grain size, some broadening was observed, but features 25-35 nm deep and 180 nm wide were fabricated.

  9. Reversible work function changes induced by photoisomerization of asymmetric azobenzene dithiol self-assembled monolayers on gold

    SciTech Connect

    Ah Qune, Lloyd F. N.; Wee, Andrew T. S.; Akiyama, H.; Nagahiro, T.; Tamada, K.

    2008-08-25

    We measured reversible changes in the work function ({delta}{phi}{sub Au}) of gold substrates modified by asymmetric azobenzene dithiol self-assembled monolayers (SAMs) following photoisomerization and thermal recovery of the azo unit. The azobenzene derivative SAMs were photoisomerized to cis form by UV irradiation. {delta}{phi}{sub Au} was monitored in real time during thermal recovery to trans form by ultraviolet photoelectron spectroscopy using a synchrotron light source. Changing the substituted functional group in the p{sup '} position of the azobenzene from electron donating to electron withdrawing resulted in opposite responses of {delta}{phi}{sub Au} against photoisomerization. Hence, a direct correlation between {delta}{phi}{sub Au} and changes in molecular dipole moments was obtained.

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

    PubMed

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

    2016-01-26

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

  11. Structure and dynamics of water near the interface with oligo(ethylene oxide) self-assembled monolayers.

    PubMed

    Ismail, Ahmed E; Grest, Gary S; Stevens, Mark J

    2007-07-31

    We performed molecular dynamics simulations of the oligo(ethylene oxide) (OEO) self-assembled monolayers in water to determine the nature of the systems' interfacial structure and dynamics. The density profiles, hydrogen bonding, and water dynamics are calculated as a function of the area per molecule A of OEO. At the highest coverages, the interface is hydrophobic, and a density drop is found at the interface. The interfacial region becomes more like bulk water as A increases. The OEO and water become progressively more mixed, and hydrogen bonding increases within the interfacial region. Water mobility is slower within the interfacial region, but not substantially. The implications of our results on the resistance of OEO SAMs to protein adsorption are discussed. Our principal result is that as A increases the increasingly waterlike interfacial region provides a more protein-resistant surface. This finding supports recent experimental measurements that protein resistance is maximal for less than full coverage on Au. PMID:17622160

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    PubMed

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

    2008-11-18

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

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

    PubMed Central

    2015-01-01

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

  15. Self-assembled monolayers of methylselenolate on the Au(111) surface: A combined STM and DFT study

    NASA Astrophysics Data System (ADS)

    El-Kareh, L.; Mehring, P.; Caciuc, V.; Atodiresei, N.; Beimborn, A.; Blügel, S.; Westphal, C.

    2014-01-01

    In this study scanning tunneling microscopy (STM) and density functional theory (DFT) were used to investigate the structural formation of methylselenolate (CH3Se) self-assembled monolayers (SAMs) on the Au(111) surface. SAMs were prepared by two different methods, from solution and by exposing the Au(111) surface to gaseous dimethyldiselenide (DMDSe). For methylselenolate (MSe) on the Au(111) surface, our STM measurements revealed the presence of (4 × √3) and (3 × 2√3) rectangular striped phases. These structures were verified by DFT calculations. For both phases, the DFT calculations clearly found a bridge adsorption geometry for MSe on Au(111). Furthermore, they provide information about the electronic structure of the MSe-SAMs.

  16. Effect of Reactive Self-Assembled Monolayer at the Anode Interface of Organic Light-Emitting Diode.

    PubMed

    Ono, Sotaro; Usui, Satoshi; Kim, Seong-Ho; Tanaka, Kuniaki; Advincula, Rigoberto C; Usuil, Hiroaki

    2016-04-01

    Organic light-emitting diodes (OLEDs) were prepared on-indium-tin oxide (ITO) substrates that were modified with various self-assembled monolayers (SAMs) including those which have reactive terminal units. The OLED performance was analyzed in terms of molecular length, dipole moment and HOMO level of SAM molecules estimated by the density functional theory calculation. It was suggested that the current efficiency of OLED is partly improved by controlling the carrier balance, interfacial dipole moment, and electron energy level by SAM modification. More importantly, remarkable improvement in OLED efficiency was achieved by chemically tethering the inorganic/organic interface via benzophenone-terminated SAM. The reactive SAM having benzophenone terminal group can be a promising tool to control the inorganic/organic interface for organic devices. PMID:27451642

  17. Dithienylcyclopentene-functionalised subphthalocyaninatoboron complexes: photochromism, fluorescence modulation and formation of self-assembled monolayers on gold

    PubMed Central

    Weidner, Tobias; Baio, Joe E.; Seibel, Johannes

    2012-01-01

    Subphthalocyaninatoboron (SubPc) complexes bearing six peripheral n-dodecylthio substituents and an apical photochromic dithienylperfluorocyclopentene unit were prepared. The photoinduced isomerisation of the apical substitutent from the open to the ring-closed form significantly influences the photoluminescence of the covalently attached SubPc unit, which is more efficiently quenched by the ring-closed form. Films on gold were fabricated from these multifunctional conjugates and characterised by near-edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS). The results are in accord with the formation of self-assembled monolayers based on dome-shaped SubPc-based anchor groups. Their chemisorption is primarily due to the peripheral n-dodecylthio substituents, giving rise to covalently attached thiolate as well as coordinatively bound thioether units, whose alkyl chains are in an almost parallel orientation to the surface. PMID:22138955

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

    NASA Astrophysics Data System (ADS)

    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.

  19. Evaluation of Crystalline Silicotitanate and Self-Assembled Monolayers on Mesoporous Support for Cesium and Mercury Removal from DWPF Recycle

    SciTech Connect

    Oji, L.N.

    1999-11-05

    The affinities for cesium and mercury ions contained in DWPF recycle simulants and Tank-22H waste have been evaluated using Crystalline Silicotitanate (CST) and Self-Assembled Monolayers on Mesoporous Support (SAMMS) ion-exchange materials, respectively. Results of the performance evaluations of CST on the uptake of cesium with simulants and actual DWPF recycle samples (Tank 22H) indicate that, in practice, this inorganic ion-exchange material can be used to remove radioactive cesium from the DWPF recycle. SAMMS material showed little or no affinity for mercury from highly alkaline DWPF waste. However, at near neutral conditions (DWPF simulant solution pH adjusted to 7), SAMMS was found to have a significant affinity for mercury. Conventional Duolite/256 ion exchange material showed an increase in affinity for mercury with increase in DWPF recycle simulant pH. Duolite/256 GT-73 also had a high batch distribution coefficient for mercury uptake from actual Tank 22H waste.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  1. Angular Resolved X-Ray Absorption Near Edge Structure Investigation of Adsorbed Alkanethiol Monolayers on III-V(110) Surfaces

    NASA Astrophysics Data System (ADS)

    Chassé, T.; Zerulla, D.; Hallmeier, K. H.

    The structure of alkanethiol monolayers on III-V(110) surfaces was studied by analyzing the X-ray absorption near edge structure (XANES) of the carbon K edge. Pronounced absorption maxima were observed for special orientations of the polarization vector of the radiation as revealed from angular-dependent measurements, suggesting a rather well-defined molecular axis of the alkyl chains. From quantitative evaluations of these angular dependences the chains were found to be tilted from the normal towards the [001] direction of the (110) surfaces by 34° and 15° in the case of hexadecanethiol (HDT) adsorption on InP and GaP, respectively. The similarities as well as the differences in tilt angles between the substrates are dicussed in terms of constraints imposed by the surface structure and lattice constants as well as the space requirements of the van der Waals spheres of the adsorbed thiols. A unique feature observed on these monolayers is the nearly complete alignment of the alkyl chains with respect to the azimuthal orientation. We suggest that this adsorbate system represents the case of a single domain orientation within the organic monolayer.

  2. Quantifying Thiol Ligand Density of Self-Assembled Monolayers on Gold Nanoparticles by Inductively Coupled Plasma–Mass Spectrometry

    PubMed Central

    2013-01-01

    Gold nanoparticles (GNPs) are often used as colloidal carriers in numerous applications owing to their low-cost and size-controlled preparation as well as their straightforward surface functionalization with thiol containing molecules forming self-assembling monolayers (SAM). The quantification of the ligand density of such modified GNPs is technically challenging, yet of utmost importance for quality control in many applications. In this contribution, a new method for the determination of the surface coverage of GNPs with thiol containing ligands is proposed. It makes use of the measurement of the gold-to-sulfur (Au/S) ratio by inductively coupled plasma mass spectrometry (ICP–MS) and its dependence on the nanoparticle diameter. The simultaneous ICP–MS measurement of gold and sulfur was carefully validated and found to be a robust method with a relative standard uncertainty of lower than 10%. A major advantage of this method is the independence from sample preparation; for example, sample loss during the washing steps is not affecting the results. To demonstrate the utility of the straightforward method, GNPs of different diameters were synthesized and derivatized on the surface with bifunctional (lipophilic) ω-mercapto-alkanoic acids and (hydrophilic) mercapto-poly(ethylene glycol) (PEG)n-carboxylic acids, respectively, by self-assembling monolayer (SAM) formation. Thereby, a size-independent but ligand-chain length-dependent ligand density was found. The surface coverage increases from 4.3 to 6.3 molecules nm–2 with a decrease of ligand chain length from 3.52 to 0.68 nm. Furthermore, no significant difference between the surface coverage of hydrophilic and lipophilic ligands with approximately the same ligand length was found, indicating that sterical hindrance is of more importance than, for example, intermolecular strand interactions of Van der Waals forces as claimed in other studies. PMID:23331002

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

    PubMed

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

    2011-06-28

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

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

    ERIC Educational Resources Information Center

    Gerber, Ralph W.; Oliver-Hoyo, Maria

    2007-01-01

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

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

    EPA Science Inventory

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

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

    SciTech Connect

    Schalnat, Matthew C.; Pemberton, Jeanne E.

    2010-07-20

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

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  10. Formation and dissolution processes of the 6-thioguanine (6TG) self-assembled monolayer. A kinetic study.

    PubMed

    Madueño, Rafael; Pineda, Teresa; Sevilla, José Manuel; Blázquez, Manuel

    2005-02-01

    This is a report on the kinetics of the destruction and formation processes of the 6-thioguanine self-assembled monolayer (6TG SAM) on a mercury electrode from acid solutions by chronoamperometry. The destruction of the 6TG SAM that has been previously formed under open circuit potential conditions is carried out by stepping the potential from an initial value where the chemisorbed layer is stable up to potentials where the molecules are no longer chemisorbed. The destruction of the SAM has been described by a model that involves three types of contributions: (i) a Langmuir-type adsorption process, (ii) a 2D nucleation mechanism followed by a growth controlled by surface diffusion, and (iii) a 2D nucleation mechanism followed by a growth at a constant rate. The nonlinear fit of the experimental transients by using this procedure allows the quantitative determination of the individual contributions to the overall process. The kinetics of the formation process is studied under electrochemical conditions. The chronoamperometric experiment allows us to monitor the early stages of 6TG SAM formation. The implications of the physisorbed state at low potentials in the type of monolayer formation and destruction processes as well as the influence of temperature are also discussed. PMID:16851120

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

    NASA Astrophysics Data System (ADS)

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

    2011-04-01

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

  12. Indentation and self-healing mechanisms of a self-assembled monolayer--a combined experimental and modeling study.

    PubMed

    Meltzer, Christian; Paul, Jonas; Dietrich, Hanno; Jäger, Christof M; Clark, Timothy; Zahn, Dirk; Braunschweig, Björn; Peukert, Wolfgang

    2014-07-30

    A combination of in situ vibrational sum-frequency generation (SFG) spectroscopy and molecular-dynamics (MD) simulations has allowed us to study the effects of indentation of self-assembled octadecylphosphonic acid (ODPA) monolayers on α-Al2O3(0001). Stress-induced changes in the vibrational signatures of C-H stretching vibrations in SFG spectra and the results of MD simulations provide clear evidence for an increase in gauche-defect density in the monolayer as a response to indentation. A stress-dependent analysis indicates that the defect density reaches saturation at approximately 155 MPa. After stress is released, the MD simulations show an almost instantaneous healing of pressure-induced defects in good agreement with experimental results. The lateral extent of the contact areas was studied with colocalized SFG spectroscopy and compared to theoretical predictions for pressure gradients from Hertzian contact theory. SFG experiments reveal a gradual increase in gauche-defect density with pressure before saturation close to the contact center. Furthermore, our MD simulations show a spatial anisotropy of pressure-induced effects within ODPA domains: molecules tilted in the direction of the pressure gradient increase in tilt angle while those on the opposite side form gauche-defects. PMID:25054614

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

    PubMed

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

    2014-09-01

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

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

    NASA Astrophysics Data System (ADS)

    Ishida, Takao; Terada, Kei-ichi; Hasegawa, Kiichi; Kuwahata, Hironao; Kusama, Kazunori; Sato, Ryo; Nakano, Miki; Naitoh, Yasuhisa; Haga, Masa-aki

    2009-08-01

    The formation of self-assembled monolayer and multilayer using redox-active Ru complex molecules with phosphonic acids on SiO 2 surface has been examined using X-ray photoelectron spectroscopy (XPS), ellipsometry, and time of flight secondary mass-ion spectroscopy (TOF-SIMS). We found that an introduction of a Zr adlayer leads to higher surface molecular density of Ru complex SAMs on the SiO 2 surface, compared to that of obtained from the direct adsorption of Ru complex monolayer on the SiO 2 surface. We further tried to fabricate a multilayer film using this molecule with Zr(IV) ion acting as a chemical glue by a successive immersion process. The XPS data revealed that the molecular densities of the multilayers were also higher for the immobilization with Zr adlayer between Ru complex and SiO 2 surface than those without the Zr adlayer, suggesting that Zr adlayer is effective in forming highly packed molecular layer of phosphonic acids on SiO 2 surface. We found the film growth reached a saturation point after 6 layers on the SiO 2 surface. The film growth saturation can be explained by a molecular domain boundary effect encountered due to the large tilt angle of the molecular layer.

  15. Effect of molecular structure and packing density of an azo self-assembled monolayer on liquid crystal alignment.

    PubMed

    Vengatesan, M R; Lee, Seung-Ho; Son, Jong-Ho; Lim, Jeong-Ku; Song, Jang Kun

    2013-10-01

    We studied the alignment of liquid crystals (LCs) on a photo-switchable azo-containing self-assembled monolayer (azo-SAM) with different packing densities and molecular structures. The packing density of the azo-SAM substrates was varied by changing the dipping time of the substrate in azosilane monomers solution (2mM in toluene). The thickness of the monolayer on the silicon substrate increased as the dipping time was increased. The relative surface packing density on the glass substrates was estimated from the surface energies of the azo-SAM. The photo-induced dynamics of liquid crystal alignment on the azo-SAM significantly varied according to the packing density of the azo-SAM and the structure of the azo-SAM molecules. The azo-SAM from long octyloxy chain-terminated azosilane (azo-S1) possessed stable homeotropic alignment even after photobuffing, while the azo-SAM from short methyl group-terminated azosilane monomer (azo-S2) showed photo-switchable homeotropic and planar alignments. However, when the packing density was increased to an excessive degree, even the azo-SAM from azo-S2 exhibited stable homeotropic alignment regardless of photobuffing. PMID:23871311

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

    PubMed

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

    2011-09-20

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

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

    Platzman, Ilia; Haick, Hossam; Tannenbaum, Rina

    2010-09-01

    In this work, we present a novel surface-mount placement process that could potentially overcome the inadequacies of the currently used stencil-printing technology, when applied to devices in which either their lateral and/or their horizontal dimensions approach the nanometric scale. Our novel process is based on the "bottom-up" design of an adhesive layer, operative in the molecular/nanoscale level, through the use of self-assembled monolayers (SAMs) that could form protective and conductive bridges between pads and components. On the basis of previous results, 1,4-phenylene diisocyanide (PDI) and terephthalic acid (TPA) were chosen to serve as the best candidates for the achievement of this goal. The quality and stability of these SAMs on annealed Cu surfaces (Rrms=0.15-1.1 nm) were examined in detail. Measurements showed that the SAMs of TPA and PDI molecules formed on top of Cu substrates created thermally stable organic monolayers with high surface coverage (∼90%), in which the molecules were closely packed and well-ordered. Moreover, the molecules assumed a standing-up phase conformation, in which the molecules bonded to the Cu substrate through one terminal functional group, with the other terminal group residing away from the substrate. To examine the ability of these monolayers to serve as "molecular wires," i.e., the capability to provide electrical conductivity, we developed a novel fabrication method of a parallel plate junction (PPJ) in order to create symmetric Cu-SAM-Cu electrical junctions. The current-bias measurements of these junctions indicated high tunneling efficiency. These achievements imply that the SAMs used in this study can serve as conductive molecular bridges that can potentially bind circuital pads/components. PMID:20804143

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

    SciTech Connect

    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).

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

    PubMed

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

    2006-04-11

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

  1. Adhesion, Deformation and Friction for Self-Assembled Monolayers on Au and Si Surfaces

    SciTech Connect

    Houston, J.E.; Hsung, R.P.; Kiely, J.D.; Mulder, J.A.; Zhu, X.Y.

    1999-07-07

    Using Interracial Force Microscopy (IFM), we investigated the tribological behavior of hexadecanethiol monolayer on Au and films of octadecyltrichlorosilane (ODTS), perfluorodecyltrichlorosilane (PFTS) and dodecane on Si. We observe a strong correlation between hysteresis in a compression cycle (measured via nanoindentation) and friction. Additionally, we suggest that the amount of hysteresis and friction in each film is related to its detailed molecular structure, especially the degree of molecular packing.

  2. Reduced graphene oxide directed self-assembly of phospholipid monolayers in liquid and gel phases.

    PubMed

    Rui, Longfei; Liu, Jiaojiao; Li, Jingliang; Weng, Yuyan; Dou, Yujiang; Yuan, Bing; Yang, Kai; Ma, Yuqiang

    2015-05-01

    The response of cell membranes to the local physical environment significantly determines many biological processes and the practical applications of biomaterials. A better understanding of the dynamic assembly and environmental response of lipid membranes can help understand these processes and design novel nanomaterials for biomedical applications. The present work demonstrates the directed assembly of lipid monolayers, in both liquid and gel phases, on the surface of a monolayered reduced graphene oxide (rGO). The results from atomic force microscopy indicate that the hydrophobic aromatic plane and the defect holes due to reduction of GO sheets, along with the phase state and planar surface pressure of lipids, corporately determine the morphology and lateral structure of the assembled lipid monolayers. The DOPC molecules, in liquid phase, probably spread over the rGO surface with their tails associating closely with the hydrophobic aromatic plane, and accumulate to form circles of high area surrounding the defect holes on rGO sheets. However, the DPPC molecules, in gel phase, prefer to form a layer of continuous membrane covering the whole rGO sheet including defect holes. The strong association between rGO sheets and lipid tails further influences the melting behavior of lipids. This work reveals a dramatic effect of the local structure and surface property of rGO sheets on the substrate-directed assembly and subsequent phase behavior of the supported lipid membranes. PMID:25724816

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

    PubMed Central

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  5. Molecular dynamics simulations of ferrocene-terminated self-assembled monolayers.

    PubMed

    Goujon, F; Bonal, C; Limoges, B; Malfreyt, P

    2010-05-20

    The present work describes our studies of the Fc(CH(2))(12)S-/C(10)S-Au monolayers to provide a more detailed molecular description. Molecular dynamics simulations of these mixed monolayers are carried out in conditions close to the electrochemical ones. For this purpose, a supporting electrolyte is added (NaClO(4) 1 M) and the electron transfer process is modeled through molecular simulations of ferrocene both in its neutral (initial state) and oxidized form (final state). The heterogeneity of the surface, that is, "clustered " or "isolated" ferrocene moieties, has been considered for the ferrocenylalkylthiolates using the same grafting densities. The structural properties (density profiles and angular distributions) are described in terms of redox induced orientation changes by comparison between the initial and final states. It is established that this orientation change due to the oxidation of the ferrocene to the ferrocenium is mainly observed in the random system, and it is less pronounced in the cluster system. Finally, the energy contributions underline the role played by the supporting electrolyte. PMID:20411913

  6. Optical absorption signature of a self-assembled dye monolayer on graphene

    PubMed Central

    Sghaier, Tessnim; Le Liepvre, Sylvain; Fiorini, Céline; Douillard, Ludovic

    2016-01-01

    Summary A well-organized monolayer of alkylated perylene-3,4,9,10-tetracarboxylic-3,4,9,10-diimide (PTCDI) has been formed onto CVD graphene transferred on a transparent substrate. Its structure has been probed by scanning tunnelling microscopy and its optical properties by polarized transmission spectroscopy at varying incidence. The results show that the transition dipoles of adsorbed PTCDI are all oriented parallel to the substrate. The maximum absorption is consistent with the measured surface density of molecules and their absorption cross section. The spectrum presents mainly a large red-shift of the absorption line compared with the free molecules dispersed in solution, whereas the relative strengths of the vibronic structures are preserved. These changes are attributed to non-resonant interactions with the graphene layer and the neighbouring molecules. PMID:27547603

  7. Diffusion and self-assembly of C60 molecules on monolayer graphyne sheets

    PubMed Central

    Ozmaian, Masoumeh; Fathizadeh, Arman; Jalalvand, Morteza; Ejtehadi, Mohammad Reza; Allaei, S. Mehdi Vaez

    2016-01-01

    The motion of a fullerene (C60) on 5 different types of graphyne is studied by all-atom molecular dynamics simulations and compared with former studies on the motion of C60 on graphene. The motion shows a diffusive behavior which consists of either a continuous motion or discrete movements between trapping sites depending on the type of the graphyne sheet. For graphyne-4 and graphyne-5, fullerenes could detach from the surface of the graphyne sheet at room temperature which was not reported for similar cases on graphene sheets. Collective motion of a group of fullerenes interacting with a graphyne studied and it is shown that fullerenes exhibit stable assemblies. Depending on the type of graphyne, these assemblies can have either single or double layers. The mobility of the assembled structures is also dependent on the type of the graphyne sheet. The observed properties of the motion suggests novel applications for the complexes of fullerene and monolayer graphynes. PMID:26912386

  8. Striped Phase of 3-Hexylthiophene Self-Assembled Monolayers on Au(1 11) Formed by Vapor Phase Deposition.

    PubMed

    Kim, Youngwoo; Kang, Hungu; Tsunoi, Azuho; Hayashi, Tomohiro; Hara, Masahiko; Noh, Jaegeun

    2016-03-01

    The formation and surface structure of 3-hexylthiophene (HTP) self-assembled monolayers (SAMs) on Au(111) prepared by solution and ambient-pressure vapor deposition at room temperature (RT) for 24 h were examined by means of scanning tunneling microscopy (STM) and cyclic voltammetry (CV). STM imaging revealed that HTP SAMs formed by solution deposition have a disordered phase, whereas those formed by vapor deposition exhibit a striped phase with a unidirectional orientation. The distance between the rows in the striped phase was measured to be 1.3 ± 0.1 nm, and the hexyl molecular backbones of HTP in the SAMs on Au(111) are oriented parallel to the Au(111) surface with the head-to-head orientation. From this STM observation, we suggest that the formation of this striped phase in HTP SAMs prepared by vapor deposition were mainly driven by the optimization of van der Waals interactions between the hexyl chains on the surface. CV measurements also demonstrated that HTP SAMs show a high blocking efficiency for electron transfer reactions between electrolytes and the gold electrode, suggesting the formation of SAMs on Au(111) from the vapor phase. Our results obtained here will be very useful for understanding the formation and structure of HTP SAMs on Au(111) surfaces and how they are influenced by deposition method. PMID:27455710

  9. Immobilisation of a thrombopoietin peptidic mimic by self-assembled monolayers for culture of CD34+ cells.

    PubMed

    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. PMID:25453940

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  11. Near-field photochemical and radiation-induced chemical fabrication of nanopatterns of a self-assembled silane monolayer.

    PubMed

    Fischer, Ulrich Christian; Hentschel, Carsten; Fontein, Florian; Stegemann, Linda; Hoeppener, Christiane; Fuchs, Harald; Hoeppener, Stefanie

    2014-01-01

    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-aminopropyl)triethoxysilane (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. PMID:25247126

  12. Dynamic pattern formation of liquid crystals using binary self-assembled monolayers on an ITO surface under DC voltage.

    PubMed

    Ishida, Takao; Oyama, Makiko; Terada, Kei-ichi; Haga, Masa-aki

    2014-12-01

    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. PMID:25327940

  13. Protein density profile at the interface of water with oligo(ethylene glycol) self-assembled monolayers.

    PubMed

    Skoda, M W A; Schreiber, F; Jacobs, R M J; Webster, J R P; Wolff, M; Dahint, R; Schwendel, D; Grunze, M

    2009-04-01

    We determined the density profile of a high-molecular-weight globular protein (bovine serum albumin, BSA) solution at the methoxy tri(ethylene glycol)-terminated undecanethiol SAM/protein solution interface by neutron reflectivity measurements. Information about the interactions between oligo(ethylene glycol) (OEG)-terminated self-assembled monolayers (SAMs) and proteins is derived from the analysis of the structure of the solid-liquid interface. The fitting results reveal oscillations of the protein density around the bulk value with decaying amplitude on a length scale of 4 to 5 nm. The amplitude, phase, period, and decay length are found to vary only slightly with temperature and the ionic strength of the protein solution. Adsorption is reversible within the limits of detection, which suggests that the hydrated ethylene glycol surface inhibits the protein from unfolding and irreversible bonding. The insensitivity of BSA adsorption toward the ionic strength of the solution contrasts with observations in surface force experiments with a fibrinogen-coated AFM tip, where electrostatic repulsion dominates theprotein/OEG SAM interaction. As reported previously, irreversible BSA adsorption takes place below 283 K, which we interpret as indicative of the presence of dynamic effects in the protein resistance of short-chain OEG-terminated surfaces. PMID:19714891

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

    PubMed

    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. PMID:26097165

  15. Full membrane spanning self-assembled monolayers as model systems for UHV-based studies of cell-penetrating peptides

    SciTech Connect

    Franz, Johannes; Graham, Daniel J.; Baio, Joe E.; Lelle, Marco; Peneva, Kalina; Müllen, Klaus; Castner, David G.; Weidner, Tobias

    2015-03-01

    Biophysical studies of the interaction of peptides with model membranes provide a simple yet effective approach to understand the transport of peptides and peptide based drug carriers across the cell membrane. Therein, the authors discuss the use of self-assembled monolayers fabricated from the full membrane-spanning thiol (FMST) 3-((14-((4'-((5-methyl-1-phenyl-35-(phytanyl)oxy-6,9,12,15,18,21,24,27,30,33,37-undecaoxa-2,3-dithiahenpentacontan-51-yl)oxy)-[1,1'-biphenyl]-4-yl)oxy)tetradecyl)oxy)-2-(phytanyl)oxy glycerol for ultrahigh vacuum (UHV) based experiments. UHV-based methods such as electron spectroscopy and mass spectrometry can provide important information about how peptides bind and interact with membranes, especially with the hydrophobic core of a lipid bilayer. Moreover, near-edge x-ray absorption fine structure spectra and x-ray photoelectron spectroscopy (XPS) data showed that FMST forms UHV-stable and ordered films on gold. XPS and time of flight secondary ion mass spectrometry depth profiles indicated that a proline-rich amphipathic cell-penetrating peptide, known as sweet arrow peptide is located at the outer perimeter of the model membrane.

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

    PubMed Central

    2013-01-01

    Self-assembled monolayers (SAMs) of pyridylthio-functionalized multiwalled carbon nanotubes (pythio-MWNTs) have been constructed on the gold substrate surface, which were used as a support to immobilize cytochrome c (Cyt c). The assembly processes of the SAMs and adsorption of Cyt c were monitored by using quartz crystal microbalance (QCM). Based on the frequency change of the QCM resonator, the surface coverage for the SAMs of pythio-MWNTs was estimated to be about 5.2 μg/cm2, and that of the Cyt c adsorbed was about 0.29 μg/cm2. For the gold electrode modified by the SAMs of pythio-MWNTs-Cyt c, a quasi-reversible redox wave was recorded with the cathodic and anodic potentials at about −0.55 and −0.28 V vs Ag/AgCl, respectively. Compositions and morphologies of the SAMs before and after immobilization of Cyt c were characterized by X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, and atomic force microscopy. PMID:23391460

  17. Nanosecond imaging of microboiling behavior on pulsed-heated au films modified with hydrophilic and hydrophobic self-assembled monolayers.

    PubMed

    Balss, Karin M; Avedisian, C Thomas; Cavicchi, Richard E; Tarlov, Michael J

    2005-11-01

    Fast transient microboiling has been characterized on modified gold microheaters using a novel laser strobe microscopy technique. Microheater surfaces of different hydrophobicity were prepared using self-assembled monolayers of hexadecane thiol (hydrophobic) and 16-mercaptohexadecanol (hydrophilic) as well as the naturally hydrophilic bare gold surface. The microheater was immersed in a pool of water, and a 5-micros voltage pulse to the heater was applied, causing superheating of the water and nucleation of a vapor bubble on the heater surface. Light from a pulsed Nd:Yag laser was configured to illuminate and image the sample through a microscope assembly. The timing of the short duration (7.5 ns) laser flash was varied with respect to the voltage pulse applied to the heater to create a series of images illuminated by the flash of the laser. These images were correlated with the transient resistance change of the heater both during and after the voltage pulse. It was found that hydrophobic surfaces produced a bubble that nucleated at an earlier time, grew more slowly to a smaller maximum size, and collapsed more rapidly than bubbles formed on hydrophilic surfaces. PMID:16262306

  18. A yeast glycolipid biosurfactant, mannosylerythritol lipid, shows high binding affinity towards lectins on a self-assembled monolayer system.

    PubMed

    Konishi, Masaaki; Imura, Tomohiro; Fukuoka, Tokuma; Morita, Tomotake; Kitamoto, Dai

    2007-03-01

    Mannosylerythritol lipids (MEL), which are glycolipid biosurfactants secreted by the Pseudozyma yeasts, show not only excellent surface-active properties but also versatile biochemical actions including antitumor and cell-differentiation activities. In order to address the biochemical actions, interactions between MEL-A, the major component of MEL, and different lectins were investigated using the surface plasmon resonance spectroscopy. The monolayer of MEL-A showed high binding affinity to concanavalin A (ConA) and Maackia amurensis lectin-I (MAL-I). The observed affinity constants for ConA and MAL-I were estimated to be 9.48 +/- 1.31 x 10(6) and 3.13 +/- 0.274 x 10(6) M(-1), respectively; the value was comparable to that of Manalpha1-6(Manalpha1-3)Man, which is one of the most specific probe to ConA. Significantly, alpha-methyl-D-mannopyranoside (1 mM) exhibited no binding inhibition between MEL-A and ConA. MEL-A is thus likely to self-assemble to give a high affinity surface, where ConA binds to the hydrophilic headgroup in a different manner from that generally observed in lectin-saccharide interactions. The binding manner should be related with the biochemical actions of MEL toward mammalian cells via protein-carbohydrate interactions. PMID:17205206

  19. Determination of thiodicarb using a biosensor based on alfalfa sprout peroxidase immobilized in self-assembled monolayers.

    PubMed

    Moccelini, Sally K; Vieira, Iolanda C; de Lima, Fábio; Lucca, Bruno G; Barbosa, Antônio M J; Ferreira, Valdir S

    2010-06-30

    A biosensor based on alfalfa sprout (Medicago sativa) homogenate as a source of peroxidase is proposed for the determination of thiodicarb by square-wave voltammetry. This enzyme was immobilized in self-assembled monolayers of l-cysteine on a gold electrode. Several parameters were investigated to evaluate the optimum conditions for operation of the biosensor. The analytical curve was linear for thiodicarb concentrations of 2.27 x 10(-6) to 4.40 x 10(-5) mol L(-1) with a detection limit of 5.75 x 10(-7) mol L(-1). The lifetime of the Au-alfalfa sprout-SAMs was 20 days (at least 220 determinations). The average recovery of thiodicarb from samples of vegetable extracts ranged from 99.02 to 101.04%. The results obtained for thiodicarb in vegetable extracts using the proposed method are in close agreement with those using a high performance liquid chromatography procedure at the 95% confidence level. PMID:20685452

  20. Molecular simulation studies of nanoscale friction between phosphorylcholine self-assembled monolayer surfaces: Correlation between surface hydration and friction

    NASA Astrophysics Data System (ADS)

    He, Yi; Chen, Shengfu; Hower, Jason C.; Bernards, Matthew T.; Jiang, Shaoyi

    2007-08-01

    We performed all-atom molecular dynamics simulations to study the friction between surfaces covered with two phosphorylcholine self-assembled monolayers (PC-SAM) under shear. PC-SAM surfaces with a √7×√7R19° lattice structure and a parallel arrangement of the head groups were used as model zwitterionic surfaces. They provide a full representation of the zwitterionic nature of phospholipid surfaces, which are believed to play an important role in the lubrication of biological joints such as knees and hips. The surfaces were immersed in aqueous solutions and kept in contact with two regions of bulk water. Sodium chloride and potassium chloride solutions at various concentrations were employed to study the effects of the presence of ions on friction. The results show a strong relationship between surface hydration and friction. Higher ionic concentrations or ions with shorter Debye lengths cause a larger disruption to the hydration around the zwitterionic surfaces, leading to larger friction forces. In addition, the results show that under nanoscale confinement, the friction coefficients of PC-SAM surfaces in pure water are directly proportional to both shear velocity and surface separation distance. These results are comparable to previously published experimental studies.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  2. Preparation and photolithography of self-assembled monolayers of 10-mercaptodecanylphosphonic acid on glass mediated by zirconium for protein patterning.

    PubMed

    Han, Xuemingyue; Sun, Shuqing; He, Tao

    2013-08-01

    Self-assembled monolayers (SAMs) formed by adsorption of octadecylphosphonic acid (ODPA) on zirconium mediated glass substrates were prepared. In this sandwich structure, Zr(4+) was used as a bi-linker to bind phosphonic acid head group in ODPA to glass substrates. The contact angle of the as-prepared SAMs was measured to be around 104°. X-ray photoelectron spectroscopy (XPS) characterization indicated the modification of Zr(4+) on glass substrates was critical for the formation of reasonably dense, well-ordered SAMs similar in quality to those typically formed on other metal oxide surfaces. Bifunctional molecule, 10-mercaptodecanylphosphonic acid (MDPA), bearing thiol terminal groups for various chemical reactions, was synthesized and formed SAMs on glass using the same approach, which allowed us to control the surface chemistry and functionality through photooxidation of the thiol terminal group. Photopatterning of proteins was performed first by exposing the SAMs to UV light through a mask, followed by protein immobilization to the masked regions through a heterobifunctional linker, while the exposed areas prohibit nonspecific protein absorption. The present strategy, which combined the SAMs assembly and photolithography, offered a facile approach for the fabrication of biomolecule patterning and could be applied to construction of biochips and other applications. PMID:23524079

  3. A priori calculations of the free energy of formation from solution of polymorphic self-assembled monolayers

    PubMed Central

    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.

    2015-01-01

    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. PMID:26512115

  4. Site-selective assembly of quantum dots on patterned self-assembled monolayers fabricated by laser direct-writing.

    PubMed

    Wu, Chong; Wang, Yongsheng; Han, Xuemingyue; Hu, Xinming; Cheng, Qianyi; Han, Baohang; Liu, Qian; Ren, Tianling; He, Yonghong; Sun, Shuqing; Ma, Hui

    2012-06-15

    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. PMID:22595703

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

    SciTech Connect

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

    2007-12-13

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

  6. Molecular dynamics simulations of water confined between matched pairs of hydrophobic and hydrophilic self-assembled monolayers.

    SciTech Connect

    Chandross, Michael Evan; Grest, Gary Stephen; Lane, J. Matthew D.; Lorenz, Christian Douglas; 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.

  7. Low density lipoprotein detection based on antibody immobilized self-assembled monolayer: investigations of kinetic and thermodynamic properties.

    PubMed

    Matharu, Zimple; Bandodkar, Amay Jairaj; Sumana, G; Solanki, Pratima R; Ekanayake, E M I Mala; Kaneto, Keiichi; Gupta, Vinay; Malhotra, B D

    2009-10-29

    Human plasma low density lipoprotein (LDL) immunosensor based on surface plasmon resonance (SPR) and quartz crystal microbalance (QCM) was fabricated by immobilizing antiapolipoprotein B (AAB) onto self-assembled monolayer (SAM) of 4-aminothiophenol (ATP). The AAB/ATP/Au immunosensor can detect LDL up to 0.252 microM (84 mg/dL) and 0.360 microM (120 mg/dL) with QCM and SPR, respectively. The SPR and QCM measurements were further utilized to study the reaction kinetics of the AAB-LDL interaction. The adsorption process involved was explored using Langmuir adsorption isotherm and Freundlich adsorption models. The thermodynamic parameters such as change in Gibb's free energy (DeltaG(ads)), change in enthalpy (DeltaH(ads)), and change in entropy (DeltaS(ads)) determined at 283, 298, and 308 K revealed that the AAB-LDL interaction is endothermic in nature and is governed by entropy. Kinetic, thermodynamic, and sticking probability studies disclosed that desorption of the water molecules from the active sites of AAB and LDL plays a key role in the interaction process and increase in temperature favors binding of LDL with the AAB/ATP/Au immunosensor. Thus, the studies were utilized to unravel the most important subprocess involved in the adsorption of LDL onto AAB-modified ATP/Au surface that may help in the fabrication of LDL immunosensors with better efficiency. PMID:19810739

  8. Dynamic information for cardiotoxin protein desorption from a methyl-terminated self-assembled monolayer using steered molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Hung, Shih-Wei; Hsiao, Pai-Yi; Chieng, Ching-Chang

    2011-05-01

    Dynamic information, such as force, structural change, interaction energy, and potential of mean force (PMF), about the desorption of a single cardiotoxin (CTX) protein from a methyl-terminated self-assembled monolayer (SAM) surface was investigated by means of steered molecular dynamics (SMD) simulations. The simulation results indicated that Loop I is the first loop to depart from the SAM surface, which is in good agreement with the results of the nuclear magnetic resonance spectroscopy experiment. The free energy landscape and the thermodynamic force of the CTX desorption process was represented by the PMF and by the derivative of PMF with respect to distance, respectively. By applying Jarzynski's equality, the PMF can be reconstructed from the SMD simulation. The PMFs, calculated by different estimators based upon Jarzynski's equality, were compared with the conventional umbrella sampling method. The best estimation was obtained by using the fluctuation-dissipation estimator with a pulling velocity of v = 0.25 nm/ns for the present study.

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

    PubMed

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

    2016-01-01

    Phosphonates have emerged as an alternative for functionalization of titanium surfaces by the formation of homogeneous self-assembled monolayers (SAMs) via Ti-O-P linkages. This study presents results from an investigation of the modification of Ti6Al4V alloy by chemisorption of osseoinductive alendronate using a simple, effective and clean methodology. The modified surfaces showed a tailored topography and surface chemistry as determined by SEM microscopy and RAMAN spectroscopy. X-ray photoelectron spectroscopy revealed that an effective mode of bonding is created between the metal oxide surface and the phosphate residue of alendronate, leading to formation of homogenous drug distribution along the surface. In-vitro studies showed that alendronate SAMs induce differentiation of hMSC to a bone cell phenotype and promote bone formation on modified surfaces. Here we show that this novel method for the preparation of functional coatings on titanium-based medical devices provides osseoinductive bioactive molecules to promote enhanced integration at the site of implantation. PMID:27468811

  10. Electrokinetic Stringency Control in Self-Assembled Monolayer-based Biosensors for Multiplex Urinary Tract Infection Diagnosis

    PubMed Central

    Liu, Tingting; Sin, Mandy L. Y.; Pyne, Jeff D.; Gau, Vincent; Liao, Joseph C.; Wong, Pak Kin

    2013-01-01

    Rapid detection of bacterial pathogens is critical toward judicious management of infectious diseases. Herein, we demonstrate an in situ electrokinetic stringency control approach for a self-assembled monolayer-based electrochemical biosensor toward urinary tract infection diagnosis. The in situ electrokinetic stringency control technique generates Joule heating induced temperature rise and electrothermal fluid motion directly on the sensor to improve its performance for detecting bacterial 16S rRNA, a phylogenetic biomarker. The dependence of the hybridization efficiency reveals that in situ electrokinetic stringency control is capable of discriminating single-base mismatches. With electrokinetic stringency control, the background noise due to the matrix effects of clinical urine samples can be reduced by 60%. The applicability of the system is demonstrated by multiplex detection of three uropathogenic clinical isolates with similar 16S rRNA sequences. The results demonstrate that electrokinetic stringency control can significantly improve the signal-to-noise ratio of the biosensor for multiplex urinary tract infection diagnosis. PMID:23891989

  11. A priori calculations of the free energy of formation from solution of polymorphic self-assembled monolayers.

    PubMed

    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. PMID:26512115

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

    PubMed Central

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

    2016-01-01

    Phosphonates have emerged as an alternative for functionalization of titanium surfaces by the formation of homogeneous self-assembled monolayers (SAMs) via Ti-O-P linkages. This study presents results from an investigation of the modification of Ti6Al4V alloy by chemisorption of osseoinductive alendronate using a simple, effective and clean methodology. The modified surfaces showed a tailored topography and surface chemistry as determined by SEM microscopy and RAMAN spectroscopy. X-ray photoelectron spectroscopy revealed that an effective mode of bonding is created between the metal oxide surface and the phosphate residue of alendronate, leading to formation of homogenous drug distribution along the surface. In-vitro studies showed that alendronate SAMs induce differentiation of hMSC to a bone cell phenotype and promote bone formation on modified surfaces. Here we show that this novel method for the preparation of functional coatings on titanium-based medical devices provides osseoinductive bioactive molecules to promote enhanced integration at the site of implantation. PMID:27468811

  13. Electron Processing at 50 eV of Terphenylthiol Self-Assembled Monolayers: Contributions of Primary and Secondary Electrons.

    PubMed

    Houplin, Justine; Dablemont, Céline; Sala, Leo; Lafosse, Anne; Amiaud, Lionel

    2015-12-22

    Aromatic self-assembled monolayers (SAMs) can serve as platforms for development of supramolecular assemblies driven by surface templates. For many applications, electron processing is used to locally reinforce the layer. To achieve better control of the irradiation step, chemical transformations induced by electron impact at 50 eV of terphenylthiol SAMs are studied, with these SAMs serving as model aromatic SAMs. High-resolution electron energy loss spectroscopy (HREELS) and electron-stimulated desorption (ESD) of neutral fragment measurements are combined to investigate electron-induced chemical transformation of the layer. The decrease of the CH stretching HREELS signature is mainly attributed to dehydrogenation, without a noticeable hybridization change of the hydrogenated carbon centers. Its evolution as a function of the irradiation dose gives an estimate of the effective hydrogen content loss cross-section, σ = 2.7-4.7 × 10(-17) cm(2). Electron impact ionization is the major primary mechanism involved, with the impact electronic excitation contributing only marginally. Therefore, special attention is given to the contribution of the low-energy secondary electrons to the induced chemistry. The effective cross-section related to dissociative secondary electron attachment at 6 eV is estimated to be 1 order of magnitude smaller. The 1 eV electrons do not induce significant chemical modification for a 2.5 mC cm(-2) dose, excluding their contribution. PMID:26606369

  14. Application of Self-Assembled Monolayers to the Electroless Metallization of High Aspect Ratio Vias for Microelectronics

    NASA Astrophysics Data System (ADS)

    Bernasconi, R.; Molazemhosseini, A.; Cervati, M.; Armini, S.; Magagnin, L.

    2016-07-01

    All-wet electroless metallization of through-silicon vias (TSVs) with a width of 5 μm and a 1:10 aspect ratio was carried out. Immersion in a n-(2-aminoethyl) 3-aminopropyl-trimethoxysilane (AEAPTMS) self-assembled monolayer (SAM) was used to enhance the adhesion between the metal film and substrate. Contact angle variation and atomic force microscopy were used to verify the formation of a SAM layer. A PdCl2 solution was later used to activate the silanized substrates, exploiting the affinity of the -NH3 functional group of AEAPTMS to palladium. A nickel-phosphorus-boron electroless bath was employed to deposit the first barrier layer onto silicon. The NiPB growth rate was evaluated on flat silicon wafers, while the structure of the coating obtained was investigated via glow discharge optical emission spectroscopy. Cross-sectional scanning electron microscope observations were carried out on metallized TSVs to characterize the NiPB seed, the Cu seed layer deposited with a second electroless step, and the Cu superfilling obtained with a commercial solution. Complete filling of TSV was achieved.

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

    PubMed

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

    2016-06-01

    A simple fabrication method for preparation of surfaces able to switch from superhydrophobic to superhydrophilic state in a reversible and fast way is described. A self-assembled monolayer (SAM) consisting of quaternary ammonium group with aliphatic tail bearing terminal thiol functionality was created on gold nano/microstructured and gold planar surfaces, respectively. A rough nano/microstructured surface was prepared by galvanic reaction on a silicon wafer. The reversible counterion exchange on the rough surface resulted in a switchable contact angle between <5° and 151°. The prewetted rough surface with Cl(-) as a counterion possesses a superoleophobic underwater character. The kinetics of counterion exchanges suggests a long hydration process and strong electron ion pairing between quaternary ammonium group and perfluorooctanoate counterion. Moreover, a wettability gradient from superhydrophobic to superhydrophilic can be formed on the modified rough gold surface in a robust and simple way by passive incubation of the substrate in a counterion solution and controlled by ionic strength. Furthermore, adsorption of gold nanoparticles to modified plain gold surface can be controlled to a high extent by counterions present on the SAM layer. PMID:27181793

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

    PubMed Central

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

    2014-01-01

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

  17. Photoluminescence studies on energy migration in multilayer organic photovoltaic devices based on ionically self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Schroeder, Raoul; Soman, C.; Brands, Charles; Heflin, James R.; Graupner, Wilhelm; Wang, Hong; Gibson, Harry W.; Marciu, Daniela; Miller, Michael B.

    2001-02-01

    We report the fabrication of thin organic layers and photovoltaic devices made from them. Building thin layers of organic materials via the method of ionically self-assembled monolayers provides control over the layer thickness and composition of multilayer structures on a nanometer scale. This allows to accurately dope a photoluminescent host material with energy or charge accepting guests, changing the emissive character of the pure photoluminescent host film to a predominantly non-emissive, charge generating structure. We show that by varying the concentration of the guest Copper phthalocyanine and C60(OH)2 in poly- (para-phenylene-vinylene) we can measure the energy migration as well as dissociation of the exciton and can determine the lifetime and the diffusion radius of the exciton. Increasing the number of dopands in the host material, the photoluminescence emission spectra shift and decrease in intensity reflecting a decrease in the number of excitons transferring to neighboring chains or conjugation segments. For high dopand concentrations the recombination of excitons only happens on the same chain as the generation. Building a device to achieve the optimal guest/host ratio for optimal exciton dissociation is one important step in the design of high efficiency photovoltaic devices.

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

    PubMed

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

    2010-01-01

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

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

    PubMed

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

    2011-02-21

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

  20. Monolayers of the lipid derivatives of isoniazid at the air/water interface and the formation of self-assembled nanostructures in water.

    PubMed

    Jin, Yiguang; Chen, Shufeng; Xin, Rui; Zhou, Yisheng

    2008-07-15

    Isoniazid (INH, isonicotinic acid hydrazide) is one of the most commonly used anti-tubercular drugs. However, resistance of Mycobacterium tuberculosis strains to anti-mycobacterial agents including INH is an increasing problem worldwide. Development of new anti-mycobacterial agents thus has attracted attention. Five lipid derivatives of INH were prepared in this study. They formed monolayers at the air/water interface, and some nanostructures with different morphologies were obtained through molecular self-assembly in water. The derivatives included one fatty acyl derivative containing a 12-C hydrocarbon-long chain (1), three fatty alcohol derivatives with a succinyl as spacer and an 8, 12 or 16-C hydrocarbon-long chain (2, 3 and 4), and one tetrahydro-2H-1,3,5-thiadiazine-2-thione (THTT) derivative containing a 12-C hydrocarbon-long chain (5). The surface pressure-area isotherms depended on the volume and configuration of heads and the length of tails of derivatives. Compound 2 had a relatively large head and a short tail, easily standing uprightly at the interface. Under a certain surface pressure, the linear polar head groups of 3 could be partly squeezed out and insert into subphase because the length of heads were comparable to the one of tails. The very long tails of 4 always maintained above the interface and led to a high collapse pressure. Compound 5 possessed an extended and large head consisting of the THTT and INH groups so that the relatively short tails tilted at the interface and difficultly contact with each other. The THTT rings might be partly squeezed out and enter into air under a certain surface pressure. The self-assembly behaviours of derivatives in water depended on the molecular configuration and agreed with the corresponding monolayer behaviours. The flexible and medium-long tails (1 and 3) led to the derivatives to form nanoscale vesicles, though the short or very long tails did not (2 and 4). Interestingly, intermolecular hydrogen

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

    PubMed

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

    2016-03-01

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

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

    PubMed

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

    2015-12-22

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

  3. Solid phase synthesis of functionalised SAM-forming alkanethiol-oligoethyleneglycols.

    PubMed

    Murray, James; Nowak, Dominika; Pukenas, Laurynas; Azhar, Rizuan; Guillorit, Mathieu; Wälti, Christoph; Critchley, Kevin; Johnson, Steven; Bon, Robin S

    2014-06-28

    We present an efficient solid phase synthesis methodology that provides easy access to a range of functionalised long-chain alkanethiol-oligoethyleneglycols that form well-defined self-assembled monolayers on gold and are compatible with pre- or post-assembly conjugation of (bio)molecules. We demonstrate the versatility of our synthetic route by synthesising LCAT-OEGs with a range of functional moieties, including peptides, electro-active redox groups, chemical handles for post-assembly conjugation of (bio)molecules, and demonstrate the application of our LCAT-OEG monolayers in immunosensing, where they show good biocompatibility with minimal biofouling. PMID:25400934

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

    SciTech Connect

    Gao, Fan; Zhang, Dakuan; Wang, Jianyu; Sheng, Yun; Wang, Xinran; Chen, Kunji; Zhou, Minmin; Yan, Shancheng; Shen, Jiancang; Pan, Lijia; Shi, Yi

    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.

  5. AFM investigation of effect of absorbed water layer structure on growth mechanism of octadecyltrichlorosilane self-assembled monolayer on oxidized silicon

    NASA Astrophysics Data System (ADS)

    Li, Shaowei; Zheng, Yanjun; Chen, Changfeng

    2016-06-01

    The growth mechanism of an octadecyltrichlorosilane (OTS) self-assembled monolayer on a silicon oxide surface at various relative humidities has been investigated. Atomic force microscopy images show that excess water may actually hinder the nucleation and growth of OTS islands. A moderate amount of water is favorable for the nucleation and growth of OTS islands in the initial stage; however, the completion of the monolayer is very slow in the final stage. The growth of OTS islands on a low-water-content surface maintains a relatively constant speed and requires the least amount of time. The mobility of water molecules is thought to play an important role in the OTS monolayers, and a low-mobility water layer provides a steady condition for OTS monolayer growth.

  6. AFM investigation of effect of absorbed water layer structure on growth mechanism of octadecyltrichlorosilane self-assembled monolayer on oxidized silicon.

    PubMed

    Li, Shaowei; Zheng, Yanjun; Chen, Changfeng

    2016-06-28

    The growth mechanism of an octadecyltrichlorosilane (OTS) self-assembled monolayer on a silicon oxide surface at various relative humidities has been investigated. Atomic force microscopy images show that excess water may actually hinder the nucleation and growth of OTS islands. A moderate amount of water is favorable for the nucleation and growth of OTS islands in the initial stage; however, the completion of the monolayer is very slow in the final stage. The growth of OTS islands on a low-water-content surface maintains a relatively constant speed and requires the least amount of time. The mobility of water molecules is thought to play an important role in the OTS monolayers, and a low-mobility water layer provides a steady condition for OTS monolayer growth. PMID:27369535

  7. Dynamics of Energy Transfer and Soft-Landing in Collisions of Protonated Dialanine with Perfluorinated Self-Assembled Monolayer Surfaces

    SciTech Connect

    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.

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

    PubMed

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

    2015-05-26

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

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

    SciTech Connect

    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.

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

    SciTech Connect

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

    2011-03-07

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

  11. Experimental and theoretical examination of surface energy and adhesion of nitrifying and heterotrophic bacteria using self-assembled monolayers.

    PubMed

    Khan, Mohiuddin Md Taimur; Ista, Linnea K; Lopez, Gabriel P; Schuler, Andrew J

    2011-02-01

    Biofilm-based systems, including integrated fixed-film activated sludge and moving bed bioreactors, are becoming increasingly popular for wastewater treatment, often with the goal of improving nitrification through the enrichment of ammonia and nitrite oxidizing bacteria. We have previously demonstrated the utility of self-assembled monolayers (SAMs) as tools for studying the initial attachment of bacteria to substrata systematically varying in physicochemical properties. In this work, we expanded these studies to bacteria of importance in wastewater treatment systems and we demonstrated attachment rates were better correlated with surface energy than with wettability (water contact angle). Toward the long-term goal of improving wastewater treatment performance through the strategic design of attachment substrata, the attachment rates of two autotrophic ammonia-oxidizing bacteria (Nitrosomonas europaea and Nitrosospira multiformis) and a heterotroph (Escherichia coli) were evaluated using SAMs with a range of wettabilities, surface energies, and functional properties (methyl, hydroxyl, carboxyl, trimethylamine, and amine terminated). Cell attachment rates were somewhat correlated with the water contact angles of the SAMs with polar terminal groups (hydroxyl, carboxyl, trimethylamine, and amine). Including all SAM surfaces, a better correlation was found for all bacteria between attachment rates and surface free energy, as determined using the Lewis Acid-Base approach. The ammonia-oxidizers had higher adhesion rates on the SAMs with higher surface energies than did the heterotroph. This work demonstrated the successful application of SAMs to determine the attachment surface preferences of bacteria important to wastewater treatment, and it provides guidance for a new area of research aimed at improving treatment performance through rational attachment surface design. PMID:21189005

  12. Adamantane-Based Tripodal Thioether Ligands Functionalized with a Redox-Active Ferrocenyl Moiety for Self-Assembled Monolayers

    PubMed Central

    Weidner, Tobias; Zharnikov, Michael; Hoβbach, Jens; Castner, David G.; Siemeling, Ulrich

    2010-01-01

    Self-assembled monolayers (SAMs) can decorate surfaces with `smart´ functional units possessing reversible stimulus–response behavior for optical, thermal, magnetic or redox-chemical stimuli. An independent performance of individual functional groups in such a film is desirable, which can be, in particular, ensured by fairly large lateral separations between tailgroups in the SAM. Adsorbate molecules with multiple attachment points are very promising in this context owing to their large surface footprint, which covers a surface area exceeding the lateral dimensions of the functional groups. To address these design constraints, novel tridentate long-chain tripodal thioether ligands with central adamantine units and a redox-active ferrocenyl tailgroup, 1-[4-(ferrocenylethynyl)phenyl]-3,5,7-tri[(4-n-octylsulfanyl)phenyl]adamantine (T8) and 1-[4-(ferrocenylethynyl)phenyl]-3,5,7-tri[(4-n-dodecylsulfanyl)phenyl]adamantine (T12), were synthesized and used as tripodal adsorbate molecules for the fabrication of redox-active ferrocenyl-terminated SAMs on Au(111). These SAMs were characterized by X-ray photoelectron spectroscopy, near edge X-ray absorption fine structure spectroscopy and sum frequency generation spectroscopy. The data suggest that T8 and T12 form almost contamination-free, well-aligned and fairly densely-packed SAMs on Au(111) with laterally separated ferrocenyl units. The SAMs show a homogeneous binding chemistry, an important requirement for high fidelity SAMs. SFG results indicate lateral interactions between neighboring molecules via the long-chain binding units. PMID:21399702

  13. Characterization of Self-Assembled Monolayers of Peptide Mimotopes of CD20 Antigen and Their Binding with Rituximab.

    PubMed

    Leo, Norman; Shang, Yuqin; Yu, Jing-jiang; Zeng, Xiangqun

    2015-12-29

    CD20, expressed in greater than 90% of B-lymphocytic lymphomas, is a target for antibody therapy. Rituximab is a chimeric therapeutic monoclonal antibody (mAb) against the protein CD20, allowing it to destroy B cells and to treat lymphoma, leukemia, transplant rejection, and autoimmune disorder. In this work, the binding of rituximab to self-assembled monolayers (SAMs) of peptide mimotopes of CD20 antigen was systematically characterized. Four peptide mimotopes of CD 20 antigen were selected from the literature and redesigned to allow their SAM immobilizations on gold electrodes through a peptide linker with cysteine. The bindings of these peptides with rituximab and control mAbs (trastuzumab and bevacizumab) were characterized by quartz crystal microbalance (QCM). Among the four peptide mimotopes initially selected, the peptide designated as CN-14 (CGSGSGSWPRWLEN) was the most selective and sensitive for rituximab binding. The CN-14 SAM was further characterized by ellipsometry and atomic force microscopy. The thickness of the CN-14 SAM film was approximately 32 Å, and the CN-14 SAM is suggested to be stabilized by a salt bridge of Arg-10 and Glu-13 between CN-14 peptides. The CN-14 salt bridge was evaluated by a series of modifications to the CN-14 peptide sequence and characterized by QCM. The CN-14 amide variant produced a better affinity to rituximab than CN-14 without a significant impact on selectivity. As the pKa of the Glu residue of CN-14 increased, the affinity of the SAM to rituximab increased, whereas the selectivity decreased. This was attributed to the weakening of the salt bridge between the CN-14 Arg-10 and Glu-13 at higher pKa values for Glu-13. Our study shows that peptide mimotopes have potential benefits in sensor applications, as the peptide-peptide interactions in the SAMs can be manipulated by the addition of functional groups to the peptide to influence the binding of target proteins. PMID:26609837

  14. Investigating organic multilayers by spectroscopic ellipsometry: specific and non-specific interactions of polyhistidine with NTA self-assembled monolayers

    PubMed Central

    Solano, Ilaria; Parisse, Pietro; Gramazio, Federico; Casalis, Loredana; Canepa, Maurizio

    2016-01-01

    Summary Background: A versatile strategy for protein–surface coupling in biochips exploits the affinity for polyhistidine of the nitrilotriacetic acid (NTA) group loaded with Ni(II). Methods based on optical reflectivity measurements such as spectroscopic ellipsometry (SE) allow for label-free, non-invasive monitoring of molecule adsorption/desorption at surfaces. Results: This paper describes a SE study about the interaction of hexahistidine (His6) on gold substrates functionalized with a thiolate self-assembled monolayer bearing the NTA end group. By systematically applying the difference spectra method, which emphasizes the small changes of the ellipsometry spectral response upon the nanoscale thickening/thinning of the molecular film, we characterized different steps of the process such as the NTA-functionalization of Au, the adsorption of the His6 layer and its eventual displacement after reaction with competitive ligands. The films were investigated in liquid, and ex situ in ambient air. The SE investigation has been complemented by AFM measurements based on nanolithography methods (nanografting mode). Conclusion: Our approach to the SE data, exploiting the full spectroscopic potential of the method and basic optical models, was able to provide a picture of the variation of the film thickness along the process. The combination of δΔi +1 ,i(λ), δΨi +1 ,i(λ) (layer-addition mode) and δΔ† i ', i +1(λ), δΨ† i ', i +1(λ) (layer-removal mode) difference spectra allowed us to clearly disentangle the adsorption of His6 on the Ni-free NTA layer, due to non specific interactions, from the formation of a neatly thicker His6 film induced by the Ni(II)-loading of the NTA SAM. PMID:27335745

  15. Insertion shuttle with carboxyl terminated self-assembled monolayer coatings for implanting flexible polymer neural probes in the brain

    PubMed Central

    Yoshida Kozai, Takashi D.; Kipke, Daryl R.

    2011-01-01

    Penetrating microscale microelectrodes made from flexible polymers tend to bend or deflect and may fail to reach their target location. The development of flexible neural probes requires methods for reliable and controlled insertion into the brain. Previous approaches for implanting flexible probes into the cortex required modifications that negate the flexibility, limit the functionality, or restrict the design of the probe. This study investigated the use of an electronegative self-assembled monolayer (SAM) as a coating on a stiff insertion shuttle to carry a polymer probe into the cerebral cortex, and then the detachment of the shuttle from the probe by altering the shuttle’s hydrophobicity. Polydimethylsiloxane (PDMS) and polyimide probes were inserted into an agarose in vitro brain model using silicon insertion shuttles. The silicon shuttles were coated with a carboxyl terminal SAM. The precision of insertion using the shuttle was measured by the percentage displacement of the probe upon shuttle removal after the probe was fully inserted. The average relative displacement of polyimide probes inserted with SAM-coated shuttles was (1.0 ± 0.66)% of the total insertion depth compared to (26.5 ± 3.7)% for uncoated silicon shuttles. The average relative displacement of PDMS probes was (2.1 ± 1.1)% of the insertion depth compared to 100% (complete removal) for uncoated silicon shuttles. SAM-coated shuttles were further validated through their use to reliably insert PDMS probes in the cerebral cortex of rodents. This study found that SAM-coated silicon shuttles are a viable method for accurately and precisely inserting flexible neural probes in the brain. PMID:19666051

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

    PubMed

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

    2014-02-14

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

  17. Interactions of Gaseous HNO3 with Self-Assembled Monolayers at Various Relative Humidities at Room Temperature

    NASA Astrophysics Data System (ADS)

    Nishino, N.; Finlayson-Pitts, B. J.

    2012-12-01

    Deposition of gaseous nitric acid (HNO3) to surfaces is an important loss process in the tropospheric boundary layer, and is generally considered as a sink for oxides of nitrogen (NOx). It is known that adsorbed HNO3 reacts on inorganic surfaces such as silica and aluminum oxide, forming surface nitrate ions and releasing gaseous species that include NO, NO2, and HONO. However, surfaces found in the boundary layer (e.g., airborne particles, building materials, vegetation etc. ) often hold organic compounds as well but there are few studies of the interaction of gas phase HNO3 with such surface-adsorbed organics. We report here the results of studies of the interaction of gaseous HNO3 with self-assembled monolayers (SAMs) used as a model for the surface of hydrophobic organic films in the boundary layer. SAMs were prepared on a germanium attenuated total reflectance (ATR) crystal that had been previously coated with a 20 nm silicon oxide (SiOx) layer. Individual SAMs of various lengths and structures, as well as mixtures of SAMS, were selected to study effects of the surface structure and order/disorder on the interaction with HNO3. SAMs were exposed to a flow of gaseous HNO3 in N2 in the absence and presence of water vapor (20-90% relative humidity), and surface species monitored in real time using Fourier Transform Infrared (FTIR) spectroscopy. The nature of the interaction of HNO3 with these surfaces will be presented and the implications for heterogeneous chemistry and photochemistry in the boundary layer discussed.

  18. Insertion shuttle with carboxyl terminated self-assembled monolayer coatings for implanting flexible polymer neural probes in the brain.

    PubMed

    Kozai, Takashi D Yoshida; Kipke, Daryl R

    2009-11-15

    Penetrating microscale microelectrodes made from flexible polymers tend to bend or deflect and may fail to reach their target location. The development of flexible neural probes requires methods for reliable and controlled insertion into the brain. Previous approaches for implanting flexible probes into the cortex required modifications that negate the flexibility, limit the functionality, or restrict the design of the probe. This study investigated the use of an electronegative self-assembled monolayer (SAM) as a coating on a stiff insertion shuttle to carry a polymer probe into the cerebral cortex, and then the detachment of the shuttle from the probe by altering the shuttle's hydrophobicity. Polydimethylsiloxane (PDMS) and polyimide probes were inserted into an agarose in vitro brain model using silicon insertion shuttles. The silicon shuttles were coated with a carboxyl terminal SAM. The precision of insertion using the shuttle was measured by the percentage displacement of the probe upon shuttle removal after the probe was fully inserted. The average relative displacement of polyimide probes inserted with SAM-coated shuttles was (1.0+/-0.66)% of the total insertion depth compared to (26.5+/-3.7)% for uncoated silicon shuttles. The average relative displacement of PDMS probes was (2.1+/-1.1)% of the insertion depth compared to 100% (complete removal) for uncoated silicon shuttles. SAM-coated shuttles were further validated through their use to reliably insert PDMS probes in the cerebral cortex of rodents. This study found that SAM-coated silicon shuttles are a viable method for accurately and precisely inserting flexible neural probes in the brain. PMID:19666051

  19. Gradients of Rectification: Tuning Molecular Electronic Devices by the Controlled Use of Different-Sized Diluents in Heterogeneous Self-Assembled Monolayers.

    PubMed

    Kong, Gyu Don; Kim, Miso; Cho, Soo Jin; Yoon, Hyo Jae

    2016-08-22

    Molecular electronics has received significant attention in the last decades. To hone performance of devices, eliminating structural defects in molecular components inside devices is usually needed. We herein demonstrate this problem can be turned into a strength for modulating the performance of devices. We show the systematic dilution of a monolayer of an organic rectifier (2,2'-bipyridine-terminated n-undecanethiolate) with electronically inactive diluents (n-alkanethiolates of different lengths), gives remarkable gradients of rectification. Rectification is finely tunable in a range of approximately two orders of magnitude, retaining its polarity. Trends of rectification against the length of the diluent indicate the gradient of rectification is extremely sensitive to the molecular structure of the diluent. Further studies reveal that noncovalent intermolecular interactions within monolayers likely leads to gradients of structural defect and rectification. PMID:27443577

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

    NASA Astrophysics Data System (ADS)

    Frasconi, Marco; Mazzei, Franco

    2009-07-01

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

  1. Quantum-dot-sensitized solar cells: Assembly of CdS-quantum-dots coupling techniques of self-assembled monolayer and chemical bath deposition

    NASA Astrophysics Data System (ADS)

    Lin, Sheng-Chih; Lee, Yuh-Lang; Chang, Chi-Hsiu; Shen, Yu-Jen; Yang, Yu-Min

    2007-04-01

    Two methods, coupling self-assembled monolayer and chemical bath deposition (CBD), were utilized to assemble cadmium sulfide (CdS) quantum dots (QDs) onto mesoporous TiO2 films for dye-sensitized solar cell (DSSC) applications. Colloidal CdS QDs were first self-assembled on the TiO2 surface. CBD was then introduced to replenish the incorporated amount and increase the coverage ratio of CdS QDs on the TiO2 surface. The preassembled CdS QDs act as nucleation sites in the CBD process, forming a CdS nanofilm with an interfacial structure capable of inhibiting the recombination of injected electrons. An efficiency as high as 1.35% for the QD-sensitized DSSC was achieved using the present strategy.

  2. Formation and structure of self-assembled monolayers of N-octadecyltrichlorosilane on fumed and colloidal silicas

    NASA Astrophysics Data System (ADS)

    Wang, Rongwei

    2000-10-01

    The investigation of hydration states of fumed silicas [Aerosil OX50 (OX50) and 380 (A380) with nominal surface areas of 50 and 380 m2/g, respectively] by FTIR spectroscopy and thermogravimetric analysis (TGA) showed that the surface water content was related to the inherent surface properties of the silicas. It was confirmed that OX50 has less affinity to water molecules than A380. It was also clarified that the density of surface silanols varied with storage and pretreatment conditions. In turn, the amount of surface water was affected by the density and distribution of surface silanols. It has been found that the factors that mainly contribute to the formation and organization of octadecyltrichlorosilane (OTS) self-assembled monolayers (SAMs) are the (1) effective surface area of fumed silica; (2) density and distribution of surface silanols; (3) amount and type of surface water. Well-organized OTS SAMs formed on "suprehydrated" fumed and colloidal silicas. Raman spectral data revealed that the octadecyl chains in polyoctadecyl siloxane (POS) had higher conformational and intermolecular order than that on 106-nm "hydrated" silica beads. The latter were identical to the structures observed for OTS SAMs on "suprehydrated" fumed silicas, which is indicative that curvature did not affect the chain packing. The interactions of the head groups and octadecyl chain tails are two determinants that affect the structure of OTS SAMs at high or full coverage. The study of thermal stability of OTS SAMs by Raman spectroscopy indicated that below 150°C the change in the chain conformation in either POS or OTS SAMs on the silicas is reversible. The 200°C thermal treatment caused the permanent conformation change in case of "suprehydrated" A380 sample, which was attributed to both water in the interfacial region and surface curvature that make more free volume available for long alkyl chain reorganization and sequentially further cross-linking occur. Comparison of in-situ 120

  3. Synthesis and Evaluation of Self-Assembled Azido Monolayer as a Novel Dielectric Layer for Fabricating Pentacene-Based Organic Thin Film Transistors.

    PubMed

    Yeh, Je-Yuan; Tsai, Tzung-Da; Kuo, An Tsung; Chou, Ying-Shiun; Liou, Ying-Shian; Chang, Zhao-You; Tsiang, Raymond Chien-Chao; Guo, Tzung-Fang; Chang, Chien-Hsiang

    2015-05-01

    Self-assembled 3-azidopropyltriethoxysilane monolayer (SAM) is used as a dielectric layer to modify the interface between the silicon dioxide wafer and the pentacene semiconductor layer in an organic thin film transistor (OTFT), Au/pentacene/3-azidopropyltriethoxysilane/SiO2/Si. Compared to the commonly used alkyl siliane C18 dielectric, 3-azidopropyltriethoxysilane which possesses stable formal charges is far more effective in increasing the ON/OFF ratio of OTFT device with an improvement of nearly three orders of magnitude. Analysis and measurements reported in this paper have illustrated for the first time the improvement of OTFT performance by a SAM compound with stable formal charges. PMID:26504992

  4. Nonlinear optical property of hemicyanine self-assembled monolayers on gold and its adsorption kinetics probed by optical second-harmonic generation and surface plasmon resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Naraoka, Ryo; Kaise, Go; Kajikawa, Kotaro; Okawa, Haruki; Ikezawa, Hiroki; Hashimoto, Kazuhiko

    2002-08-01

    We have prepared the organosulfur self-assembled monolayer (SAM) containing hemicyanine on gold. It shows a large second-order nonlinear optical susceptibility χzzz=58 pm/V. The adsorption kinetics of the SAM on gold was also probed by the in situ real time measurements of second-harmonic generation (SHG) and surface plasmon resonance (SPR) spectroscopy. While the SHG kinetics was saturated immediately after the immersion of the gold substrate in the solution, the SPR kinetics showed additional slow adsorption for more than 20 000 s. This means that rapid formation of the well-ordered hemicyanine SAM is followed by gradual physisorption where the molecules are disordered.

  5. Beam Damage of HS (CH2)15 COOH Terminated Self Assembled Monolayer (SAM) as Observed by X-Ray Photoelectron Spectroscopy

    SciTech Connect

    Engelhard, Mark H.; Tarasevich, Barbara J.; Baer, Donald R.

    2011-10-25

    XPS spectra of HS(CH{sub 2}){sub 15} COOH terminated a self assembled monolayer (SAM)sample was collected over a period of 242 minutes to determine specimen damage during long exposures to monochromatic Al Ka x-rays. For this COOH terminated SAM we measured the loss of oxygen as a function of time by rastering a focused 100 W, 100 um diameter x-ray beam over a 1.4 mm x 0.2 mm area of the sample.

  6. Molecular Arrangement in Self-Assembled Azobenzene-Containing Thiol Monolayers at the Individual Domain Level Studied through Polarized Near-Field Raman Spectroscopy

    PubMed Central

    Chaigneau, Marc; Picardi, Gennaro; Ossikovski, Razvigor

    2011-01-01

    6-[4-(phenylazo)phenoxy]hexane-1-thiol self-assembled monolayers deposited on a gold surface form domain-like structures possessing a high degree of order with virtually all the molecules being identically oriented with respect to the surface plane. We show that, by using polarized near-field Raman spectroscopy, it is possible to derive the Raman scattering tensor of the ordered layer and consequently, the in-plane molecular orientation at the individual domain level. More generally, this study extends the application domain of the near-field Raman scattering selection rules from crystals to ordered organic structures. PMID:21541056

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

    PubMed

    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. PMID:25205623

  8. Self-Assembled Large-Scale Monolayer of Au Nanoparticles at the Air/Water Interface Used as a SERS Substrate.

    PubMed

    Guo, Qinghua; Xu, Minmin; Yuan, Yaxian; Gu, Renao; Yao, Jianlin

    2016-05-10

    Self-assembly of metal nanoparticles has attracted considerable attention because of its unique applications in technologies such as plasmonics, surface-enhanced optics, sensors, and catalysts. However, fabrication of ordered nanoparticle structures remains a significant challenge. Thus, developing an efficient approach for the assembly of large-scale Au nanoparticles films for theoretical studies and for various applications is highly desired. In this paper, a facial approach for fabricating a monolayer film of Au nanoparticles was developed successfully. Using the surfactant polyvinylpyrrolidone (PVP), a large-scale monolayer film of well-ordered, uniform-sized Au nanoparticles was fabricated at the air/water interface. The film exhibited a two-dimensional (2D) hexagonal close-packed (HCP) structure having interparticle gaps smaller than 2 nm. These gaps generated numerous uniform "hot spots" for surface-enhanced Raman scattering (SERS) activity. The as-prepared monolayer film could be transferred to a solid substrate for use as a suitable SERS substrate with high activity, high uniformity, and high stability. The low spot-to-spot and substrate-to-substrate variations of intensity (<10%), the large surface enhancement factor (∼10(6)), and the high stability (∼45 days) make the substrate suitable for SERS measurements. Transfer of the monolayer film onto a glassy carbon electrode produced an Au electrode with clean, well-defined nanostructure suitable for electrochemical SERS measurements. The adsorption process of ionic liquids on the electrode with the monolayer film is similar to that on bulk metal electrodes. The present strategy provides an effective way for self-assembly of Au nanoparticles into well-defined nanostructures that may form optimal reproducible SERS substrates for quantitative analysis. It also provides an electrode with clean, well-defined nanostructure for electrochemical investigations. PMID:27101361

  9. Nucleation and island growth of alkanethiolate ligand domains on gold nanoparticles.

    PubMed

    Wang, Yifeng; Zeiri, Offer; Neyman, Alevtina; Stellacci, Francesco; Weinstock, Ira A

    2012-01-24

    The metal oxide cluster α-AlW(11)O(39)(9-) (1), readily imaged by cryogenic transmission electron microscopy (cryo-TEM), is used as a diagnostic protecting anion to investigate the self-assembly of alkanethiolate monolayers on electrostatically stabilized gold nanoparticles in water. Monolayers of 1 on 13.8 ± 0.9 nm diameter gold nanoparticles are displaced from the gold surface by mercaptoundecacarboxylate, HS(CH(2))(10)CO(2)(-) (11-MU). During this process, no aggregation is observed by UV-vis spectroscopy, and the intermediate ligand-shell organizations of 1 in cryo-TEM images indicate the presence of growing hydrophobic domains, or "islands", of alkanethiolates. UV-vis spectroscopic "titrations", based on changes in the surface plasmon resonance upon exchange of 1 by thiol, reveal that the 330 ± 30 molecules of 1 initially present on each gold nanoparticle are eventually replaced by 2800 ± 30 molecules of 11-MU. UV-vis kinetic data for 11-MU-monolayer formation reveal a slow phase, followed by rapid self-assembly. The Johnson, Mehl, Avrami, and Kolmogorov model gives an Avrami parameter of 2.9, indicating continuous nucleation and two-dimensional island growth. During nucleation, incoming 11-MU ligands irreversibly displace 1 from the Au-NP surface via an associative mechanism, with k(nucleation) = (6.1 ± 0.4) × 10(2) M(-1) s(-1), and 19 ± 8 nuclei, each comprised of ca. 8 alkanethiolates, appear on the gold-nanoparticle surface before rapid growth becomes kinetically dominant. Island growth is also first-order in [11-MU], and its larger rate constant, k(growth), (2.3 ± 0.2) × 10(4) M(-1) s(-1), is consistent with destabilization of molecules of 1 at the boundaries between the hydrophobic (alkanethiolate) and the electrostatically stabilized (inorganic) domains. PMID:22136457

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

    PubMed

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

    2016-04-28

    In recent years organic field-effect transistors have received extensive attention, however, it is still a great challenge to fabricate monolayer-based devices of conjugated polymers. In this study, one single layer of poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) is directly dip-coated, and its self-assembly is precisely tuned from nanofibers to granular aggregates by controlling the dielectric roughness on a sub-nanometer scale. The charge carrier transport of the monolayer transistor exhibits a strong dependence on the dielectric roughness, which is attributed to the roughness-induced effects of higher densities of grain boundaries and charge trapping sites as well as surface scattering. These results mark a great advance in the bottom-up fabrication of organic electronics. PMID:27080325

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

    PubMed

    Asav, Engin; Akyilmaz, Erol

    2010-01-15

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

  12. Lubrication of Individual Microcontacts by a Self-Assembled Alkyl Phosphonic Acid Monolayer on α-Al2O3(0001).

    PubMed

    Paul, Jonas; Meltzer, Christian; Braunschweig, Björn; Peukert, Wolfgang

    2016-08-23

    We report on the tribological behavior of a self-assembled alkyl phosphonic acid monolayer on the microscale using the colloidal probe technique. Friction-load data and adhesion forces were measured with borosilicate glass particles on uncoated and octadecylphosphonic acid (ODPA) coated α-Al2O3(0001) surfaces. A significant decrease in friction force was observed after surface coating, while the adhesion force was only moderately reduced. We assume the lubrication effect of the ODPA self-assembled monolayer (SAM) to be close to the maximum obtainable of alkyl phosphonic acids in the studied system due to the high molecular order which was confirmed by vibrational sum-frequency generation. At small loads, a nonlinear dependence of friction force to load was maintained after surface coating. However, a shift from a contact behavior well described by the DMT model toward the JKR model occurred that is possibly related to the altered elastic properties of the coated surface. With increasing load, a linear friction-load behavior was observed on the coated samples. Molecular plowing and adhesive interactions were identified as responsible mechanisms. In all friction experiments, we could not detect any wear neither of the colloidal probes nor at the surfaces of uncoated and coated samples. This proves the high wear resistivity of the studied ODPA SAM. PMID:27478898

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

    PubMed Central

    Ladnorg, Tatjana; Welle, Alexander; Heißler, Stefan; Wöll, Christof

    2013-01-01

    Summary 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. PMID:24205458

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  15. DNA self-assembly-driven positioning of molecular components on nanopatterned surfaces.

    PubMed

    Szymonik, M; Davies, A G; Wälti, C

    2016-09-30

    We present a method for the specific, spatially targeted attachment of DNA molecules to lithographically patterned gold surfaces-demonstrated by bridging DNA strands across nanogap electrode structures. An alkanethiol self-assembled monolayer was employed as a molecular resist, which could be selectively removed via electrochemical desorption, allowing the binding of thiolated DNA anchoring oligonucleotides to each electrode. After introducing a bridging DNA molecule with single-stranded ends complementary to the electrode-tethered anchoring oligonucleotides, the positioning of the DNA molecule across the electrode gap, driven by self-assembly, occurred autonomously. This demonstrates control of molecule positioning with resolution limited only by the underlying patterned structure, does not require any alignment, is carried out entirely under biologically compatible conditions, and is scalable. PMID:27559837

  16. Self-assembled monolayers and chemical derivatization of Ba 0.5Sr 0.5TiO 3 thin films: Applications in phase shifter devices

    NASA Astrophysics Data System (ADS)

    Morales-Cruz, Angel L.; Keuls, Fred W. Van; Miranda, Félix A.; Cabrera, Carlos R.

    2005-11-01

    Thin films of barium strontium titanate (Ba 1- xSr x TiO 3 (BSTO)) have been used in coupled microstrip phase shifters (CMPS) for possible insertion in satellite and wireless communication platforms primarily because of their high dielectric constant, low loss, large tunability, and good structural stability. In an attempt to improve the figure of merit K (phase shift °/dB of loss) of phase shifters, modification of the metal/BSTO interface of these devices has been done through surface modification of the BSTO layer using a self-assembled monolayer approach. The impact of this nanotechnology promises to reduce RF losses by improving the quality of the metal/BSTO interface. In this study, compounds such as 3-mercaptopropyltrimethoxysilane (MPS), 16-mercaptohexadecanois acid (MHDA) and 3-mercaptopropionic acid (MPA) were used to form the self-assembled monolayers on the BSTO surface. As a result of the previous modification, chemical derivatization of the self-assembled monolayers was done in order to increase the chain length. Chemical derivatization was done using 3-aminopropyltrimethoxysilane (APS) and 16-mercaptohexadecanoic acid. Surface chemical analysis was done to reveal the composition of the derivatization via X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared (FT-IR). Low and high frequencies measurements of phase shifters were done in order measure the performance of these devices for insertion in antennas. X-ray photoelectron spectroscopy characterization of modified BSTO thin films with MPS showed a binding energy peak at 162.9 eV, indicative of a possible S sbnd O interaction: sulfur of the mercapto compound, MPS, used to modify the surface with the oxygen site of the BSTO thin film. This interaction is at higher binding energies compared with the thiolate interaction. This behavior is observed with the other mercapto compounds such as: MHDA and MPA. An FT-IR analysis present a band at 780 cm -1, which is characteristic of an O

  17. Surface sealing using self-assembled monolayers and its effect on metal diffusion in porous low-k dielectrics studied using monoenergetic positron beams

    NASA Astrophysics Data System (ADS)

    Uedono, Akira; Armini, Silvia; Zhang, Yu; Kakizaki, Takeaki; Krause-Rehberg, Reinhard; Anwand, Wolfgang; Wagner, Andreas

    2016-04-01

    Surface sealing effects on the diffusion of metal atoms in porous organosilicate glass (OSG) films were studied by monoenergetic positron beams. For a Cu(5 nm)/MnN(3 nm)/OSG(130 nm) sample fabricated with pore stuffing, C4F8 plasma etch, unstuffing, and a self-assembled monolayer (SAM) sealing process, it was found that pores with cubic pore side lengths of 1.1 and 3.1 nm coexisted in the OSG film. For the sample without the SAM sealing process, metal (Cu and Mn) atoms diffused from the top Cu/MnN layer into the OSG film and were trapped by the pores. As a result, almost all pore interiors were covered with those metals. For the sample damaged by an Ar/C4F8 plasma etch treatment before the SAM sealing process, SAMs diffused into the OSG film, and they were preferentially trapped by larger pores. The cubic pore side length in these pores containing self-assembled molecules was estimated to be 0.7 nm. Through this work, we have demonstrated that monoenergetic positron beams are a powerful tool for characterizing capped porous films and the trapping of atoms and molecules by pores.

  18. Study of the Packing Density and Molecular Orientation of Bimolecular Self-Assembled Monolayers of Aromatic and Aliphatic Organosilanes on Silica

    SciTech Connect

    Smith,M.; Efimenko, K.; Fischer, D.; Lappi, S.; Kilpatrick, P.; Genzer, J.

    2007-01-01

    Bimolecular self-assembled monolayers (SAMs) of aromatic and aliphatic chlorosilanes were self-assembled onto silica, and their characteristics were established by contact angle measurement, near-edge X-ray absorption fine structure spectroscopy, and Fourier transform infrared spectroscopy. Three aromatic constituents (phenyltrichlorosilane, benzyltrichlorosilane, and phenethyltrichlorosilane) were studied in combination with four aliphatic coadsorbates (butyltrichlorosilane, butyldimethylchlorosilane, octadecyltrichlorosilane, and octadecyldimethylchlorosilane). Our results demonstrate that whereas SAMs made of trichlorinated organosilanes are densely packed, SAMs prepared from monochlorinated species are less dense and poorly ordered. In mixed systems, trichlorinated aromatics and trichlorinated aliphatics formed SAMs with highly tunable compositions; their surfaces were compositionally homogeneous with no large-scale domain separation. The homogeneous nature of the resulting SAM was a consequence of the formation of in-plane siloxane linkages among neighboring molecules. In contrast, when mixing monochlorinated aliphatics with trichlorinated aromatics, molecular segregation occurred. Although the two shortest aromatic species did not display significant changes in orientation upon mixing with aliphatics, the aromatic species with the longest polymethylene spacer, phenethyltrichlorosilane, displayed markedly different orientation behavior in mixtures of short- and long-chain aliphatics.

  19. The self-assembly of 5,6,7-trithiapentacene-13-one molecules on gold: from low-coverage molecular chains to monolayer coverage

    NASA Astrophysics Data System (ADS)

    Larson, Amanda; Tang, Jian-Ming; Pohl, Karsten

    2015-03-01

    Understanding electronic devices down to the atomic scale is essential for the development of novel organic molecule based nanotechnologies. 5,6,7-trithiapentacene-13-one (TTPO) is a promising organic semiconductor with potential applications in high temperature photovoltaic devices. Scanning tunneling microscopy (STM) of TTPO on the close-packed stepped Au (788) surface reveals interesting nanoscale surface structures ranging from molecular chains at low coverage to an ordered self-assembled monolayer. Density functional theory (DFT) calculations have been used to further probe this unique 3-D angular assembly, where the long-axis of TTPO is parallel to the gold surface, distinctive from previously observed pentacene and pentacene derivative assemblies on surfaces. It is the lateral arrangement of the underlying pentacene backbone of the molecule that is unique, causing the thiol substituent side of the molecule to be angled down towards the gold surface, with the oxygen angled away. Combining imaging with density functional theory calculations allows for classification of these self-assembled structures with particular interest being directed toward the interaction between TTPO and gold at this organic-metallic interface. Understanding of the structure of such interfaces can potentially guide nanoscale modifications for improved electrical transport and energy-conversion efficiency in future devices.

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

    SciTech Connect

    Delafosse, G.; Patrone, L.; Merlen, A.; Clair, S.

    2012-05-21

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

  1. Direct monitoring of opto-mechanical switching of self-assembled monolayer films containing the azobenzene group

    PubMed Central

    Tirosh, Einat; Benassi, Enrico; Pipolo, Silvio; Mayor, Marcel; Valášek, Michal; Frydman, Veronica

    2011-01-01

    Summary The potential for manipulation and control inherent in molecule-based motors holds great scientific and technological promise. Molecules containing the azobenzene group have been heavily studied in this context. While the effects of the cis–trans isomerization of the azo group in such molecules have been examined macroscopically by a number of techniques, modulations of the elastic modulus upon isomerization in self-assembled films were not yet measured directly. Here, we examine the mechanical response upon optical switching of bis[(1,1'-biphenyl)-4-yl]diazene organized in a self-assembled film on Au islands, using atomic force microscopy. Analysis of higher harmonics by means of a torsional harmonic cantilever allowed real-time extraction of mechanical data. Quantitative analysis of elastic modulus maps obtained simultaneously with topographic images show that the modulus of the cis-form is approximately twice that of the trans-isomer. Quantum mechanical and molecular dynamics studies show good agreement with this experimental result, and indicate that the stiffer response in the cis-form comprises contributions both from the individual molecular bonds and from intermolecular interactions in the film. These results demonstrate the power and insights gained from cutting-edge AFM technologies, and advanced computational methods. PMID:22259768

  2. Structural Development of Mercaptophenol Self-Assembled Monolayers And the Overlying Mineral Phase During Templated CaCo(3) Crystallization From a Transient Amorphous Film

    SciTech Connect

    Lee, J.R.I.; Han, T.Y.-J.; Willey, T.M.; Wang, D.; Meulenberg, R.W.; Nilsson, J.; Dove, P.M.; Terminello, L.J.; Buuren, T.van; Yoreo, J.J.De

    2009-06-01

    Formation of biomineral structures is increasingly attributed to directed growth of a mineral phase from an amorphous precursor on an organic matrix. While many in vitro studies have used calcite formation on organothiol self-assembled monolayers (SAMs) as a model system to investigate this process, they have generally focused on the stability of amorphous calcium carbonate (ACC) or maximizing control over the order of the final mineral phase. Little is known about the early stages of mineral formation, particularly the structural evolution of the SAM and mineral. Here we use near-edge X-ray absorption spectroscopy (NEXAFS), photoemission spectroscopy (PES), X-ray diffraction (XRD), and scanning electron microscopy (SEM) to address this gap in knowledge by examining the changes in order and bonding of mercaptophenol (MP) SAMs on Au(111) during the initial stages of mineral formation as well as the mechanism of ACC to calcite transformation during template-directed crystallization. We demonstrate that formation of ACC on the MP SAMs brings about a profound change in the morphology of the monolayers: although the as-prepared MP SAMs are composed of monomers with well-defined orientations, precipitation of the amorphous mineral phase results in substantial structural disorder within the monolayers. Significantly, a preferential face of nucleation is observed for crystallization of calcite from ACC on the SAM surfaces despite this static disorder.

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

    SciTech Connect

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

    2004-01-30

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

  4. Formation of a 1,8-octanedithiol self-assembled monolayer on Au(111) prepared in a lyotropic liquid-crystalline medium.

    PubMed

    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. PMID:20578682

  5. Enhancement of electron injection into a light-emitting polymer from an aluminum oxide cathode modified by a self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Vaynzof, Yana; Dennes, T. Joseph; Schwartz, Jeffrey; Kahn, Antoine

    2008-09-01

    A self-assembled monolayer (SAM) of octylphosphonate was deposited on an AlOx electrode using the tethering by aggregation and growth (T-BAG) procedure. Ultraviolet photoemission spectroscopy (UPS) measurements showed a decrease in the substrate work function from 3.8to3.3eV. Poly[9,9'-dioctylfluorene-co-bis-N ,N'-(4-butylphenyl)-diphenylamine] (TFB) films spin coated on the bare and the SAM-modified oxide surfaces were investigated by UPS. A shift in molecular levels, corresponding to a reduction in the electron injection barrier, was observed for the SAM-modified electrode. This barrier lowering was confirmed by current-voltage measurements showing a corresponding increase in electron current through the TFB/SAM/AlOx device.

  6. Water-COOH Composite Structure with Enhanced Hydrophobicity Formed by Water Molecules Embedded into Carboxyl-Terminated Self-Assembled Monolayers.

    PubMed

    Guo, Pan; Tu, Yusong; Yang, Jinrong; Wang, Chunlei; Sheng, Nan; Fang, Haiping

    2015-10-30

    By combining molecular dynamics simulations and quantum mechanics calculations, we show the formation of a composite structure composed of embedded water molecules and the COOH matrix on carboxyl-terminated self-assembled monolayers (COOH SAMs) with appropriate packing densities. This composite structure with an integrated hydrogen bond network inside reduces the hydrogen bonds with the water above. This explains the seeming contradiction on the stability of the surface water on COOH SAMs observed in experiments. The existence of the composite structure at appropriate packing densities results in the two-step distribution of contact angles of water droplets on COOH SAMs, around 0° and 35°, which compares favorably to the experimental measurements of contact angles collected from forty research articles over the past 25 years. These findings provide a molecular-level understanding of water on surfaces (including surfaces on biomolecules) with hydrophilic functional groups. PMID:26565476

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

    PubMed

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

    2015-07-01

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

  8. Improved microstructure and performance of PbS thin films via in-situ thermal decomposition of lead xanthate precursors using self-assembling monolayer

    NASA Astrophysics Data System (ADS)

    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.

  9. Water-COOH Composite Structure with Enhanced Hydrophobicity Formed by Water Molecules Embedded into Carboxyl-Terminated Self-Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    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.

  10. Estimated phase transition and melting temperature of APTES self-assembled monolayer using surface-enhanced anti-stokes and stokes Raman scattering

    NASA Astrophysics Data System (ADS)

    Sun, Yingying; Yanagisawa, Masahiro; Kunimoto, Masahiro; Nakamura, Masatoshi; Homma, Takayuki

    2016-02-01

    A structure's temperature can be determined from the Raman spectrum using the frequency and the ratio of the intensities of the anti-Stokes and Stokes signals (the Ias/Is ratio). In this study, we apply this approach and an equation relating the temperature, Raman frequency, and Ias/Is ratio to in-situ estimation of the phase change point of a (3-aminopropyl)triethoxysilane self-assembled monolayer (APTES SAM). Ag nanoparticles were deposited on APTES to enhance the Raman signals. A time-resolved measurement mode was used to monitor the variation in the Raman spectra in situ. Moreover, the structural change in APTES SAM (from ordered to disordered structure) under heating was discussed in detail, and the phase change point (around 118 °C) was calculated.

  11. Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries.

    PubMed

    Zettsu, Nobuyuki; Kida, Satoru; Uchida, Shuhei; Teshima, Katsuya

    2016-01-01

    We demonstrate herein that an ultra-thin fluoroalkylsilane self-assembled monolayer coating can be used as a modifying agent at LiNi0.5Mn1.5O4-δcathode/electrolyte interfaces in 5V-class lithium-ion batteries. Bare LiNi0.5Mn1.5O4-δ cathode showed substantial capacity fading, with capacity dropping to 79% of the original capacity after 100 cycles at a rate of 1C, which was entirely due to dissolution of Mn(3+) from the spinel lattice via oxidative decomposition of the organic electrolyte. Capacity retention was improved to 97% on coating ultra-thin FAS17-SAM onto the LiNi0.5Mn1.5O4 cathode surface. Such surface protection with highly ordered fluoroalkyl chains insulated the cathode from direct contact with the organic electrolyte and led to increased tolerance to HF. PMID:27553901

  12. Electrochemically Directed Self-Assembly and Conjugated Polymer Semiconductors for Organic Electronic Applications

    NASA Astrophysics Data System (ADS)

    Pillai, Rajesh Gopalakrishna

    2011-07-01

    The research work presented in this thesis investigates the mechanistic details of conventional as well as electrochemically directed self-assembly of alkylthiosulfates and explores the use of conjugated semiconducting polymers for organic electronic applications. Here, the significance of the use of conjugated polymers is twofold; first, to explore their applications in nanoelectronics and second, the possibility of using them as a top contact on the self-assembled monolayers (SAMs) for molecular electronic applications. Throughout this work, deposition of the organic materials was performed on prefabricated device structures that required no further lithographic or metal deposition steps after modification of the electrodes with the organic molecules. Self-assembly of alkylthiosulfates on gold are reported to form monolayers identical to those formed from the corresponding alkanethiols. However, these self-assembly processes follow more complex mechanisms of monolayer formation than originally recognized. Studies on the mechanism of alkylthiosulfate chemisorption on gold shows that the self-assembly process is influenced by electrolyte and solvent. Plausible mechanisms have been proposed for the role of trace water in the solvent on conventional as well as electrochemically assisted self-assembly of alkylthiosulfates on gold. Electroanalytical and spectroscopic techniques have been used to explore the mechanistic details of electrochemically directed self-assembly of alkylthiosulfates on gold. It has been found that the self-assembly process is dynamic under electrochemical conditions and the heterogeneous electron transfer process between the organosulfur compound and gold is mediated through gold surface oxide and accompanied by corrosion. Conducting polymers are serious candidates for organic electronic applications since their properties can be controlled by the manipulation of molecular architecture. Unique electronic properties of conjugated polypyrrole

  13. Single-molecule conductance measurement of self-assembled organic monolayers using scanning tunneling spectroscopy in combination with statistics analysis

    NASA Astrophysics Data System (ADS)

    Zhang, Yumei; Dou, Chengfu; Wang, Yin

    2011-05-01

    Based on ambient atmosphere scanning tunneling microscope (STM) technique, scanning tunneling spectroscopy (STS) combined with statistics analysis was developed to investigate the single-molecule conductance of various kinds of molecules which were self-assembled on the Au (1 1 1). Conductance histograms obtained from current-voltage curves revealed well-defined peaks at integer multiples of a fundamental conductance and were used to identify the conductance of a single molecule. The conductances of saturated molecules like 1,8-octanedithol and hexanethiocyanate were found to be 0.072 × 10 -4G 0 and 0.06 × 10 -4G 0 respectively and 0.23 × 10 -4G 0 and 0.13 × 10 -4G 0 for unsaturated molecules like 5,5'-dithiol- 2,2',5',2″-terthiophene and 4,4'-dithio-tert(phenylene ethylene).

  14. Determination of Parathion and Carbaryl Pesticides in Water and Food Samples Using a Self Assembled Monolayer/Acetylcholinesterase Electrochemical Biosensor

    PubMed Central

    Pedrosa, Valber A.; Caetano, Josiane; Machado, Sergio A. S.; Bertotti, Mauro

    2008-01-01

    An acetylcholinesterase (AchE) based amperometric biosensor was developed by immobilisation of the enzyme onto a self assembled modified gold electrode. Cyclic voltammetric experiments performed with the SAM-AchE biosensor in phosphate buffer solutions (pH = 7.2) containing acetylthiocholine confirmed the formation of thiocholine and its electrochemical oxidation at Ep = 0.28 V vs Ag/AgCl. An indirect methodology involving the inhibition effect of parathion and carbaryl on the enzymatic reaction was developed and employed to measure both pesticides in spiked natural water and food samples without pre-treatment or pre-concentration steps. Values higher than 91-98.0% in recovery experiments indicated the feasibility of the proposed electroanalytical methodology to quantify both pesticides in water or food samples. HPLC measurements were also performed for comparison and confirmed the values measured amperometrically.

  15. Bioreactive self-assembled monolayers on hydrogen-passivated Si(111) as a new class of atomically flat substrates for biological scanning probe microscopy.

    PubMed

    Wagner, P; Nock, S; Spudich, J A; Volkmuth, W D; Chu, S; Cicero, R L; Wade, C P; Linford, M R; Chidsey, C E

    1997-07-01

    This is the first report of bioreactive self-assembled monolayers, covalently bound to atomically flat silicon surfaces and capable of binding biomolecules for investigation by scanning probe microscopy and other surface-related assays and sensing devices. These monolayers are stable under a wide range of conditions and allow tailor-made functionalization for many purposes. We describe the substrate preparation and present an STM and SFM characterization, partly performed with multiwalled carbon nanotubes as tapping-mode supertips. Furthermore, we present two strategies of introducing in situ reactive headgroup functionalities. One method entails a free radical chlorosulfonation process with subsequent sulfonamide formation. A second method employs singlet carbenemediated hydrogen-carbon insertion of a heterobifunctional, amino-reactive trifluoromethyl-diazirinyl crosslinker. We believe that this new substrate is advantageous to others, because it (i) is atomically flat over large areas and can be prepared in a few hours with standard equipment, (ii) is stable under most conditions, (iii) can be modified to adjust a certain degree of reactivity and hydrophobicity, which allows physical adsorption or covalent crosslinking of the biological specimen, (iv) builds the bridge between semiconductor microfabrication and organic/biological molecular systems, and (v) is accessible to nanopatterning and applications requiring conductive substrates. PMID:9245759

  16. Effect of 3-Aminopropyltriethoxysilane Monolayer Self-Assembled Quartz Substrate on the Quality of Vapor Phase-Polymerized Poly(3,4-ethylenedioxythiophene) Nanofilm.

    PubMed

    Choi, Byoungbok; Choi, Sangil; Sohn, Honglae; Kim, Sungsoo

    2015-11-01

    Polymer thin film coated on the delay line section of a surface acoustic wave (SAW) sensor has been a main focus in sensor industry to improve its sensitivity. In this study, for an effort to build a highly sensitive SAW sensor, a versatile conducting polymer, Poly(3,4-ethylenedioxythiophene) (PEDOT), has been vapor phase polymerized on 3-aminopropyltriethoxysilane (APS) monolayer self-assembled quartz substrate, which is a representative piezoelectric materials for SAW sensor. And then, the quality and electrical properties of the thin film were evaluated by several thin film analyzing tools such as contact angle analyzer, FE-SEM, optical microscope, adhesion test and 4 point probe. From the evaluation, it was discovered that PEDOT nanofilm is highly smooth and dense, and it is strongly adhered to the substrate particularly when the quartz surface was coated with APS monolayer. Such good quality PEDOT thin film could be a potential candidate for a base platform of highly sensitive SAW sensor devices. PMID:26726531

  17. Influence of molecular ordering on electrical and friction properties of omega-(trans-4-stilbene)alkylthiol self-assembled monolayers on Au (111)

    SciTech Connect

    Qi, Yabing; Liu, Xiaosong; Hendriksen, B.L.M.; Navarro, V.; Park, Jeong Y.; Ratera, Imma; Klopp, J.M.; Edder, C.; Himpsel, Franz J.; Frechet, J.M.J.; Haller, Eugene E.; Salmeron, Miquel

    2010-04-21

    The electrical and friction properties of omega-(trans-4-stilbene)alkylthiol self-assembled monolayers (SAMs) on Au(111) were investigated using atomic force microscopy (AFM) and near edge x-ray absorption fine structure spectroscopy (NEXAFS). The sample surface was uniformly covered with a molecular film consisting of very small grains. Well-ordered and flat monolayer islands were formed after the sample was heated in nitrogen at 120 oC for 1 h. While lattice resolved AFM images revealed a crystalline phase in the islands, the area between islands showed no order. The islands exhibit substantial reduction (50percent) in friction, supporting the existence of good ordering. NEXAFS measurements revealed an average upright molecular orientation in the film, both before and after heating, with a narrower tilt-angle distribution for the heated fim. Conductance-AFM measurements revealed a two orders of magnitude higher conductivity on the ordered islands than on the disordered phase. We propose that the conductance enhancement is a result of a better pi-pi stacking between the trans-stilbene molecular units as a result of improved ordering in islands.

  18. Use of self assembled monolayers at variable coverage to control interface bonding in a model study of interfacial fracture: Pure shear loading

    SciTech Connect

    KENT,MICHAEL S.; YIM,HYUN; MATHESON,AARON J.; COGDILL,C.; NELSON,GERALD C.; REEDY JR.,EARL DAVID

    2000-05-16

    The relationships between fundamental interfacial interactions, energy dissipation mechanisms, and fracture stress or fracture toughness in a glassy thermoset/inorganic solid joint are not well understood. This subject is addressed with a model system involving an epoxy adhesive on a polished silicon wafer containing its native oxide. The proportions of physical and chemical interactions at the interface, and the in-plane distribution, are varied using self-assembling monolayers of octadecyltrichlorosilane (ODTS). The epoxy interacts strongly with the bare silicon oxide surface, but forms only a very weak interface with the methylated tails of the ODTS monolayer. The fracture stress is examined as a function of ODTS coverage in the napkin-ring (pure shear) loading geometry. The relationship between fracture stress and ODTS coverage is catastrophic, with a large change in fracture stress occurring over a narrow range of ODTS coverage. This transition in fracture stress does not correspond to a wetting transition of the epoxy. Rather, the transition in fracture stress corresponds to the onset of deformation in the epoxy, or the transition from brittle to ductile fracture. The authors postulate that the transition in fracture stress occurs when the local stress that the interface can support becomes comparable to the yield stress of the epoxy. The fracture results are independent of whether the ODTS deposition occurs by island growth (T{sub dep} = 10 C) or by homogeneous growth (T{sub dep} = 24 C).

  19. Self-assembled monolayer exchange reactions as a tool for channel interface engineering in low-voltage organic thin-film transistors.

    PubMed

    Lenz, Thomas; Schmaltz, Thomas; Novak, Michael; Halik, Marcus

    2012-10-01

    In this work, we compared the kinetics of monolayer self-assembly long-chained carboxylic acids and phosphonic acids on thin aluminum oxide surfaces and investigated their dielectric properties in capacitors and low-voltage organic thin-film transistors. Phosphonic acid anchor groups tend to substitute carboxylic acid molecules on aluminum oxide surfaces and thus allow the formation of mixed or fully exchanged monolayers. With different alkyl chain substituents (n-alkyl or fluorinated alkyl chains), the exchange reaction can be monitored as a function of time by static contact angle measurements. The threshold voltage in α,α'-dihexyl-sexithiophene thin-film transistors composed of such mixed layer dielectrics correlates with the exchange progress and can be tuned from negative to positive values or vice versa depending on the dipole moment of the alkyl chain substituents. The change in the dipole moment with increasing exchange time also shifts the capacitance of these devices. The rate constants for exchange reactions determined by the time-dependent shift of static contact angle, threshold voltage, and capacitance exhibit virtually the same value thus proving the exchange kinetics to be highly controllable. In general, the exchange approach is a powerful tool in interface engineering, displaying a great potential for tailoring of device characteristics. PMID:22963322

  20. Self assembling monolayers of dialkynyl bridged Pd(II) thiols obtained by thermally induced multilayer desorption: Thermal and chemical stability investigated by SR-XPS

    NASA Astrophysics Data System (ADS)

    Battocchio, C.; Fratoddi, I.; Bondino, F.; Malvestuto, M.; Russo, M. V.; Polzonetti, G.

    2012-02-01

    Self assembling monolayers (SAMs) of organometallic thiols trans-[HS-Pd(PBu3)2-SH], trans-[HS-Pd(PBu3)2(-Ctbnd C-C6H5)] and trans,trans-[HS-Pd(PBu3)2(-Ctbnd C-C6H4-C6H4-Ctbnd C-Pd(PBu3)2-SH] on gold were obtained from the corresponding multilayers through thermally induced desorption. Temperature-dependent synchrotron radiation-induced X-ray photoelectron spectroscopy (SR-XPS) measurements were carried out on the heated multilayers during the annealing process, in order to investigate the thermal and chemical stability of the systems. SAMs of the same organometallic thiols were also obtained by rinsing the thick films with appropriate solvents. SR-XPS was used to ascertain that the molecular and electronic structure of the two series of SAMs are not influenced by the rinsing or thermal desorption process, i.e. both strategies allow for obtaining well ordered monolayers of organometallic thiols.

  1. Etching of Crystalline ZnO Surfaces upon Phosphonic Acid Adsorption: Guidelines for the Realization of Well-Engineered Functional Self-Assembled Monolayers.

    PubMed

    Ostapenko, Alexandra; Klöffel, Tobias; Eußner, Jens; Harms, Klaus; Dehnen, Stefanie; Meyer, Bernd; Witte, Gregor

    2016-06-01

    Functionalization of metal oxides by means of covalently bound self-assembled monolayers (SAMs) offers a tailoring of surface electronic properties such as their work function and, in combination with its large charge carrier mobility, renders ZnO a promising conductive oxide for use as transparent electrode material in optoelectronic devices. In this study, we show that the formation of phosphonic acid-anchored SAMs on ZnO competes with an unwanted chemical side reaction, leading to the formation of surface precipitates and severe surface damage at prolonged immersion times of several days. Combining atomic force microscopy (AFM), X-ray diffraction (XRD), and thermal desorption spectroscopy (TDS), the stability and structure of the aggregates formed upon immersion of ZnO single crystal surfaces of different orientations [(0001̅), (0001), and (101̅0)] in phenylphosphonic acid (PPA) solution were studied. By intentionally increasing the immersion time to more than 1 week, large crystalline precipitates are formed, which are identified as zinc phosphonate. Moreover, the energetics and the reaction pathway of this transformation have been evaluated using density functional theory (DFT), showing that zinc phosphonate is thermodynamically more favorable than phosphonic acid SAMs on ZnO. Precipitation is also found for phosphonic acids with fluorinated aromatic backbones, while less precipitation occurs upon formation of SAMs with phenylphosphinic anchoring units. By contrast, no precipitates are formed when PPA monolayer films are prepared by sublimation under vacuum conditions, yielding smooth surfaces without noticeable etching. PMID:27159837

  2. Kinetic studies of attachment and re-orientation of octyltriethoxysilane for formation of self-assembled monolayer on a silica substrate.

    PubMed

    Hasan, Abshar; Pandey, Lalit M

    2016-11-01

    The present study deals with kinetic studies of the chemical modification for synthesizing a hydrophobic silica surface. Surface silanization (modification) via formation of Self-Assembled Monolayer (SAM) using a short chain triethoxyoctylsilane (TEOS) was carried out under inert atmosphere at room temperature. Fourier transmission infrared (FTIR) spectroscopy, water contact angle (WCA) and atomic force microscopy (AFM) were employed to investigate surface modification. FTIR analysis in the range from 900-1200cm(-1) and 2850-3000cm(-1) confirmed surface modification and re-orientation of the attached molecules. Kinetic studies of TEOS SAM formation were fitted by Exponential Association function. Kinetic fitting of FTIR data in the range from 900-1200cm(-1) revealed a very fast attachment of TEOS molecules resulting in total surface coverage within 16min whereas re-orientation rate was slow and continued till 512min. Further, change in orientation from lying-down to standing-up state was supported by contact angle analysis. AFM images initially showed small islands of ~20nm, which in-fill with time indicating formation of a smooth monolayer. Our findings indicate that formation of octyl SAM is fast process and completes within 8.5h in contrary to reported 24h in conventional SAM formation protocols. The kinetic fitting data can be explored to design a nanopatterned surface for a specific application. PMID:27524037

  3. Selective anion sensing by a tris-amide CTV derivative: 1H NMR titration, self-assembled monolayers, and impedance spectroscopy.

    PubMed

    Zhang, Sheng; Echegoyen, Luis

    2005-02-16

    A hydrogen-bond forming tris(amide) receptor based on cyclotriveratrylene (CTV) was prepared. Self-assembled monolayers (SAMs) of the receptor were formed on gold surfaces. Desorption experiments show a surface coverage of 2.26 x 10(-10) mol/cm(2). (1)H NMR and UV measurements confirm that the receptor exhibits the highest affinity for acetate ions among the anions studied. Electrochemical impedance was used to investigate anion sensing by the SAMs and proved to be an efficient and convenient technique for detecting anions in aqueous solutions. Upon binding acetate anions, the monolayer-modified gold electrodes show a drastic increase of the R(ct) values when Fe(CN)(6)(3-/4-) is used as the redox probe. When the probe was changed to a positively charged one, Ru(NH3)(6)(3+/2+), the R(ct) values decreased monotonically as the acetate concentration was increased, thus confirming the accumulation of negative surface charge upon anion binding. H(2)PO(4-) shows some interference when sensing AcO-. Other monovalent anions such as Cl-, Br-, NO3(-) and HSO4(-) do not bind to the CTV receptor either in solution or on the surfaces. PMID:15701037

  4. Electric bistability induced by incorporating self-assembled monolayers/aggregated clusters of azobenzene derivatives in pentacene-based thin-film transistors.

    PubMed

    Tseng, Chiao-Wei; Huang, Ding-Chi; Tao, Yu-Tai

    2012-10-24

    Composite films of pentacene and a series of azobenzene derivatives are prepared and used as the active channel material in top-contact, bottom-gate field-effect transistors. The transistors exhibit high field-effect mobility as well as large I-V hysteresis as a function of the gate bias history. The azobenzene moieties, incorporated either in the form of self-assembled monolayer or discrete multilayer clusters at the dielectric surface, result in electric bistability of the pentacene-based transistor either by photoexcitation or gate biasing. The direction of threshold voltage shifts, size of hysteresis, response time, and retention characteristics all strongly depend on the substituent on the benzene ring. The results show that introducing a monolayer of azobenzene moieties results in formation of charge carrier traps responsible for slower switching between the bistable states and longer retention time. With clusters of azobenzene moieties as the trap sites, the switching is faster but the retention is shorter. Detailed film structure analyses and correlation with the transistor/memory properties of these devices are provided. PMID:22974132

  5. Experimental investigation and molecular dynamics simulations of impact-mode wear mechanisms in silicon micromachines with alkylsilane self-assembled monolayer films

    NASA Astrophysics Data System (ADS)

    Douglas, C. M.; Rouse, W. A.; Driscoll, J. A.; Timpe, S. J.

    2015-10-01

    In the current work, polycrystalline silicon microdevices are treated with a 1H,1H,2H,2H-Perfluorodecyltrichlorosilane (FDTS) self-assembled monolayer (SAM) film. Using a microelectromechanical systems-based tribometer, the adhesion characteristics of the FDTS-treated surfaces are compared to those of untreated surfaces over a range of approximately 10 × 106 impact cycles. FDTS-treated surfaces showed a lower zero-hour adhesion force compared to untreated surfaces under identical environmental conditions. The presence of the monolayer did not have a discernible effect on the number of cycles to initiate the surface degradation that was manifested as an increase in the adhesion force. Based on trends in degradation, it is concluded that similar chemical and physical wear mechanisms dominate the evolution of adhesion in both treated and untreated devices. The qualitative results of the experiment are reinforced by molecular dynamics (MD) simulations of a single nanoasperity contact coated with an octadecyltrichlorosilane (ODTS) SAM. MD simulations show cleavage of bonds along the aliphatic chains of ODTS resulting in adhesion fluctuations. In agreement with experimental observations, the MD simulation shows a logarithmic increase in adhesion force with increasing number of cycles. MD simulations also predict a logarithmic decrease in adhesion energy with increasing cycles. These results provide insight into the physicohemical changes occurring during repetitive impact of surfaces coated with low surface energy films.

  6. Interactions between self-assembled monolayers and an organophosphonate: A detailed study using surface acoustic wave-based mass analysis, polarization modulation-FTIR spectroscopy, and ellipsometry

    SciTech Connect

    Crooks, R.M.; Yang, H.C.; McEllistrem, L.J.

    1997-06-24

    Self-assembled monolayers (SAMs) having surfaces terminated in the following functional groups: -CH{sub 3}, -OH, -COOH, and (COO{sup -}){sub 2}Cu{sup 2+} (MUA-Cu{sup 2+}) have been prepared and examined as potential chemically sensitive interfaces. Mass measurements made using surface acoustic wave (SAW) devices indicate that these surfaces display different degrees of selectivity and sensitivity to a range of analytes. The response of the MUA-Cu{sup 2+} SAM to the nerve-agent simulant diisopropyl methylphosphonate (DIMP) is particularly intriguing. Exposure of this surface to 50%-of-saturation DIMP yields a surface concentration equivalent to about 20 DIMP monolayers. Such a high surface concentration in equilibrium with a much lower-than-saturation vapor pressure has not previously been observed. Newly developed analytical tools have made it possible to measure the infrared spectrum of the chemically receptive surface during analyte dosing. Coupled with in-situ SAW/ellipsometry measurements, which permit simultaneous measurement of mass and thickness with nanogram and Angstrom resolution, respectively, it has been possibly to develop a model for the surface chemistry leading to the unusual behavior of this system. The results indicate that DIMP interacts strongly with surface-confined Cu{sup 2+} adduct that nucleates growth of semi-ordered crystallites having substantially lower vapor pressure than the liquid.

  7. Self-assembly of amphiphilic janus particles into monolayer capsules for enhanced enzyme catalysis in organic media.

    PubMed

    Cao, Wei; Huang, Renliang; Qi, Wei; Su, Rongxin; He, Zhimin

    2015-01-14

    Encapsulation of enzymes during the creation of an emulsion is a simple and efficient route for enhancing enzyme catalysis in organic media. Herein, we report a capsule with a shell comprising a monolayer of silica Janus particles (JPs) (referred to as a monolayer capsule) and a Pickering emulsion for the encapsulation of enzyme molecules for catalysis purposes in organic media using amphiphilic silica JPs as building blocks. We demonstrate that the JP capsules had a monolayer shell consisting of closely packed silica JPs (270 nm). The capsules were on average 5-50 μm in diameter. The stability of the JP capsules (Pickering emulsion) was investigated with the use of homogeneous silica nanoparticles as a control. The results show that the emulsion stabilized via amphiphilic silica JPs presented no obvious changes in physical appearance after 15 days, indicating the high stability of the emulsions and JP capsules. Furthermore, the lipase from Candida sp. was chosen as a model enzyme for encapsulation within the JP capsules during their formation. The catalytic performance of lipase was evaluated according to the esterification of 1-hexanol with hexanoic acid. It was found that the specific activity of the encapsulated enzymes (28.7 U mL(-1)) was more than 5.6 times higher than that of free enzymes in a biphasic system (5.1 U mL(-1)). The enzyme activity was further increased by varying the volume ratio of water to oil and the JPs loadings. The enzyme-loaded capsule also exhibited high stability during the reaction process and good recyclability. In particular, the jellification of agarose in the JP capsules further enhanced their operating stability. We believe that the monolayer structure of the JP capsules, together with their high stability, rendered the capsules to be ideal enzyme carriers and microreactors for enzyme catalysis in organic media because they created a large interfacial area and had low mass transfer resistance through the monolayer shell. PMID

  8. Direct Patterning of Organic Self-Assembled Monolayer (SAM) on GaAs Surfaces via Dip-Pen Nanolithography (DPN)

    NASA Astrophysics Data System (ADS)

    Xiong, Peng; Keiper, Timothy; Wang, Xiaolei; Zhao, Jianhua

    2015-03-01

    Hybrid structures of functional molecules and solid-state (SS) materials have attracted extensive interest in surface nanoscience and molecular electronics. The formation and micro/nano patterning of organic SAMs on SS surfaces are a key step in fabricating such devices. Here we report realization of high quality MHA SAMs on GaAs and direct formation of micro/nanoscale patterns of MHA SAM on the surface by micro-contact printing (μ CP) and DPN. The process begins with the preparation of an oxide-free surface of GaAs, for which we employed treatment by an ammonium polysulfide ((NH4)2 Sx) solution. The treatment strips native oxides from GaAs creating an atomic layer of sulfur covalently bonded to the fresh surface. Formation of high-quality SAMs of thiol molecules on GaAs then proceeds through exchange of the sulfur and the thiol terminal of the molecules. The effects of the sulfur-passivation and formation of MHA SAM on the treated surface were confirmed by XPS, HRTEM, and DPN. To the best of our knowledge, this is a first realization of direct DPN of nanoscale organic SAM on a semiconductor free of surface oxide. We further evidence the utility of the hybrid platform by demonstrating directed self-assembly of Au nanoparticles onto MHA/ODT SAM templates on GaAs.

  9. Influence of the solution pH in the 6-mercaptopurine self-assembled monolayer (6MP-SAM) on a Au(111) single-crystal electrode.

    PubMed

    Madueño, Rafael; García-Raya, Daniel; Viudez, Alfonso J; Sevilla, José M; Pineda, Teresa; Blázquez, Manuel

    2007-10-23

    Self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) have been prepared on a Au(111) single-crystal electrode by immersion of the metal surface in a 100 microM 6MP and 0.01 M HClO4 solution. The 6MP-SAM Au(111) single-crystal electrodes were transferred to the cell and allowed to equilibrate with the different aqueous working solutions before the electrochemical experiments. The influence of the solution pH was studied by cyclic voltammetry, double layer capacitance curves, and electrochemical impedance spectroscopy. The electrochemical behavior of the 6MP-SAM in acetic acid at pH 4 presents important differences in comparison to that obtained in 0.1 M KOH solutions. Cyclic voltammograms for the reductive desorption process in acid medium are broad and show some features that can be explained by a phase transition between a chemisorbed and a physisorbed state of the 6MP molecules. The low solubility of these molecules in acid medium could explain this phenomenon and the readsorption of the complete monolayer when the potential is scanned in the positive direction. The variation of the double-layer capacitance values in the potential range of monolayer stability with the pH suggests that the acid-base chemistry of the 6MP molecules is playing a role. This fact has been studied by following the variations of the electron-transfer rate constant of the highly charged redox probes as are Fe(CN)(6)-3/-4 and Ru(NH3)(6)+3/+2 as a function of solution pH. The apparent surface pKa value for the 6MP-SAM (pKa approximately 8) is explained by the total conversion of the different 6MP tautomers that exist in solution to the thiol species in the adsorbed state. PMID:17902711

  10. Microcontact printing of ultrahigh density gold nanoparticle monolayer for flexible flash memories.

    PubMed

    Han, Su-Ting; Zhou, Ye; Xu, Zong-Xiang; Huang, Long-Biao; Yang, Xiong-Bo; Roy, V A L

    2012-07-10

    A uniform monolayer of alkanethiol-protected gold nanoparticle arrays with ultrahigh density have been used as microcontact-printable charge-trapping layers for the application in flexible flash memories. The new devices are compared to two reference devices with a floating gate created by thermal evaporation and electrostatic self-assembly, and show a large memory window, long retention times and good endurance properties. PMID:22678769

  11. Tailoring the electrical properties of MoS2 field effect transistors by depositing Au nanoparticles and alkanethiol molecules.

    PubMed

    Cho, Kyungjune; Jeong, Hyunhak; Kim, Tae-Young; Pak, Jinsu; Kim, Jae-Keun; Choi, Barbara Yuri; Lee, Takhee

    2016-05-11

    We fabricated and characterized MoS2 field effect transistors. First, we measured the electrical properties of MoS2 field effect transistors (FETs) that were made with mechanically exfoliated MoS2 flakes. Then, we deposited Au nanoparticles on the MoS2 channel and measured the electrical properties. We observed whether the source-drain current increased or decreased after the Au particles were deposited. The deposited Au particles either formed an extra current path and increased the current or behaved as charge-withdrawing sites and decreased the current. Next, we deposited alkanethiol molecules on the Au particles to reduce the work function of the Au. Alkanethiol molecules are known to form a self-assembled monolayer on the Au surface, and the electric dipole moment of the molecules causes the work function of the Au to decrease. Au particles can capture electrons from the MoS2 channel due to their high work function. However, the decreased work function of the Au particles subjected to alkanethiol treatment could cause captured electrons to be released from the Au particles to MoS2. Therefore, the current increased after alkanethiol treatment. This study may provide useful methods to utilize surface treatments with particles and molecules to tailor the electrical properties of MoS2-based FETs. PMID:27057642

  12. Tailoring the electrical properties of MoS2 field effect transistors by depositing Au nanoparticles and alkanethiol molecules

    NASA Astrophysics Data System (ADS)

    Cho, Kyungjune; Jeong, Hyunhak; Kim, Tae-Young; Pak, Jinsu; Kim, Jae-Keun; Choi, Barbara Yuri; Lee, Takhee

    2016-05-01

    We fabricated and characterized MoS2 field effect transistors. First, we measured the electrical properties of MoS2 field effect transistors (FETs) that were made with mechanically exfoliated MoS2 flakes. Then, we deposited Au nanoparticles on the MoS2 channel and measured the electrical properties. We observed whether the source-drain current increased or decreased after the Au particles were deposited. The deposited Au particles either formed an extra current path and increased the current or behaved as charge-withdrawing sites and decreased the current. Next, we deposited alkanethiol molecules on the Au particles to reduce the work function of the Au. Alkanethiol molecules are known to form a self-assembled monolayer on the Au surface, and the electric dipole moment of the molecules causes the work function of the Au to decrease. Au particles can capture electrons from the MoS2 channel due to their high work function. However, the decreased work function of the Au particles subjected to alkanethiol treatment could cause captured electrons to be released from the Au particles to MoS2. Therefore, the current increased after alkanethiol treatment. This study may provide useful methods to utilize surface treatments with particles and molecules to tailor the electrical properties of MoS2-based FETs.

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

    SciTech Connect

    Willey, T; Willey, T

    2004-03-24

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

  14. Characterization of functionalized self-assembled monolayers and surface-attached interlocking molecules using near-edge X-ray absorption fine structure spectroscopy

    NASA Astrophysics Data System (ADS)

    Willey, Trevor Michael

    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 mechanically attached

  15. A Single-Level Tunnel Model to Account for Electrical Transport through Single Molecule- and Self-Assembled Monolayer-based Junctions

    PubMed Central

    Garrigues, Alvar R.; Yuan, Li; Wang, Lejia; Mucciolo, Eduardo R.; Thompon, Damien; del Barco, Enrique; Nijhuis, Christian A.

    2016-01-01

    We present a theoretical analysis aimed at understanding electrical conduction in molecular tunnel junctions. We focus on discussing the validity of coherent versus incoherent theoretical formulations for single-level tunneling to explain experimental results obtained under a wide range of experimental conditions, including measurements in individual molecules connecting the leads of electromigrated single-electron transistors and junctions of self-assembled monolayers (SAM) of molecules sandwiched between two macroscopic contacts. We show that the restriction of transport through a single level in solid state junctions (no solvent) makes coherent and incoherent tunneling formalisms indistinguishable when only one level participates in transport. Similar to Marcus relaxation processes in wet electrochemistry, the thermal broadening of the Fermi distribution describing the electronic occupation energies in the electrodes accounts for the exponential dependence of the tunneling current on temperature. We demonstrate that a single-level tunnel model satisfactorily explains experimental results obtained in three different molecular junctions (both single-molecule and SAM-based) formed by ferrocene-based molecules. Among other things, we use the model to map the electrostatic potential profile in EGaIn-based SAM junctions in which the ferrocene unit is placed at different positions within the molecule, and we find that electrical screening gives rise to a strongly non-linear profile across the junction. PMID:27216489

  16. 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)

    PubMed Central

    Phan, Hanh T. M.; Bartelt-Hunt, Shannon; Rodenhausen, Keith B.; Schubert, Mathias; Bartz, Jason C.

    2015-01-01

    Understanding protein adsorption kinetics to surfaces is of importance for various environmental and biomedical applications. Adsorption of bovine serum albumin to various self-assembled monolayer surfaces including neutral and charged hydrophilic and hydrophobic surfaces was investigated using in-situ combinatorial quartz crystal microbalance with dissipation and spectroscopic ellipsometry. Adsorption of bovine serum albumin varied as a function of surface properties, bovine serum albumin 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. PMID:26505481

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  18. Self-assembled monolayer of o-aminothiophenol on Fe(1 1 0) surface: a combined study by electrochemistry, in situ STM, and molecular simulations

    NASA Astrophysics Data System (ADS)

    Kong, De-Sheng; Yuan, Shi-Ling; Sun, Yu-Xi; Yu, Zhang-Yu

    2004-12-01

    Electrochemical measurements, in situ scanning tunneling microscopy (STM) observation, and molecular mechanics (MM) simulations were performed to study the physiochemical properties such as the corrosion-inhibition effect and the optimal packing structure of o-aminothiophenol (OATP) self-assembled monolayer (SAM) formed on Fe(1 1 0) surface in 0.1 M NaClO 4 solution. The formation of OATP SAMs drastically depressed the Faradaic processes at the Fe(1 1 0) surface and reduced the electrical double-layer capacitance at the electrode/electrolyte interface, revealing the anticorrosion property and the blocking behavior of OATP adlayers. Two-dimensional ordered molecular arrays of OATP on Fe(1 1 0) surface with a p(2 × 2) commensurate structure were observed by STM measurements. MM calculations showed that the p(2 × 2) packing pattern is indeed the preferable structure for OATP molecules adsorbed on Fe(1 1 0), in accordance with STM experiments. The OATP SAM on Fe(1 1 0) is ≈0.50 nm in thickness and with a dielectric constant of ˜7.0.

  19. Bioactive Co-Cr alloy for biomedical applications prepared by surface modification using self-assembled monolayers and poly-γ-glutamic acid.

    PubMed

    Liu, Chao; Matsunami, Chisato; Shirosaki, Yuki; Miyazaki, Toshiki

    2015-01-01

    Cobalt-chromium (Co-Cr) alloys are used in clinical practice for the hard tissue reconstruction because of their favorable biocompatibility and mechanical properties. However, their applications have been limited because of their poor bioactivity, making them poor at bone-bonding. In this study, the bioactivity of a Co-Cr alloy was evaluated following the immobilization of cross-linked poly-γ-glutamic acid (γ-PGA) onto its surface via the formation of 11-aminoundecylphosphonic acid self-assembled monolayers (SAMs). Results of X-ray photoelectron spectroscopy revealed the presence of a new P2p peak, which confirms SAMs formation. Furthermore, the surface became highly hydrophobic following the immobilization with γ-PGA. Subsequent treatment with CaCl2 at 0.5 M or more and soaking in a simulated body fluid led to the formation of a low crystalline apatite. The present results show that chemical modification can be used to induce the formation of an apatite layer on the surface of a Co-Cr alloy in simulated body fluid. PMID:26438996

  20. A facile method for construction of antifouling surfaces by self-assembled polymeric monolayers of PEG-silane copolymers formed in aqueous medium.

    PubMed

    Park, Sangjin; Chi, Young Shik; Choi, Insung S; Seong, Jiehyun; Jon, Sangyong

    2006-11-01

    Self-assembled polymeric monolayers (PMs) on Si/SiO2 wafers were prepared in water from a series of random copolymers of poly(ethylene glycol) methyl ether methacrylate (PEGMA) and 3-(trimethoxysilyl)propyl methacrylate (TMSMA), denoted as poly(TMSMA-r-PEGMA). Four polymers of poly(TMSMA-r-PEGMA) were synthesized by free radical polymerization with a systematic variation of co-monomer feed ratios. Regardless of PEG grafting density in the copolymers, all PMs formed approximately 1 nm-thick film as measured by ellipsometry. However, the PMs with a higher grafting density of PEG resulted in more hydrophilic surfaces in terms of water contact angle. The protein resistance of the PMs was evaluated using bovine serum albumin (BSA) as a model protein. Analyses by ellipsometry, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) showed that the PMs of the copolymers markedly reduced the nonspecific adsorption of proteins compared to the unmodified Si/SiO2 wafers. The study also revealed that the PMs prepared from the copolymers with a higher PEG grafting density were more effective in resisting the nonspecific protein adsorption. PMID:17252800

  1. A Single-Level Tunnel Model to Account for Electrical Transport through Single Molecule- and Self-Assembled Monolayer-based Junctions.

    PubMed

    Garrigues, Alvar R; Yuan, Li; Wang, Lejia; Mucciolo, Eduardo R; Thompon, Damien; Del Barco, Enrique; Nijhuis, Christian A

    2016-01-01

    We present a theoretical analysis aimed at understanding electrical conduction in molecular tunnel junctions. We focus on discussing the validity of coherent versus incoherent theoretical formulations for single-level tunneling to explain experimental results obtained under a wide range of experimental conditions, including measurements in individual molecules connecting the leads of electromigrated single-electron transistors and junctions of self-assembled monolayers (SAM) of molecules sandwiched between two macroscopic contacts. We show that the restriction of transport through a single level in solid state junctions (no solvent) makes coherent and incoherent tunneling formalisms indistinguishable when only one level participates in transport. Similar to Marcus relaxation processes in wet electrochemistry, the thermal broadening of the Fermi distribution describing the electronic occupation energies in the electrodes accounts for the exponential dependence of the tunneling current on temperature. We demonstrate that a single-level tunnel model satisfactorily explains experimental results obtained in three different molecular junctions (both single-molecule and SAM-based) formed by ferrocene-based molecules. Among other things, we use the model to map the electrostatic potential profile in EGaIn-based SAM junctions in which the ferrocene unit is placed at different positions within the molecule, and we find that electrical screening gives rise to a strongly non-linear profile across the junction. PMID:27216489

  2. Formation of Merocyanine Self-Assembled Monolayer and Its Nonlinear Optical Properties Probed by Second-Harmonic Generation and Surface Plasmon Resonance

    NASA Astrophysics Data System (ADS)

    Tsuboi, Kazuma; Seki, Kazuhiko; Ouchi, Yukio; Fujita, Katsuhiko; Kajikawa, Kotaro

    2003-02-01

    Nonlinear optical responses of a self-assembled monolayer (SAM) containing merocyanine chromophore, 1-alkyl-4-(4-hydroxystyryl) pyridinium bromide (HSP), on gold in water and in ethanol were studied by second-harmonic generation (SHG). The pH dependence of the SHG response clearly showed a solvatochromic characteristic of the merocyanine from a protonated form to a zwitterionic form. A large second-order susceptibility χzzz=5.0× 10-7 esu (2.1× 102 pm/V) was found in a basic solution of ethanol where the merocyanine is in the zwitterionic form. Combination of the SHG and surface plasmon resonance (SPR) spectroscopy measurements also provides us with details of the formation process of the merocyanine SAMs in the ethanol solution of the HSP-terminated-alkyldisulfide, ω,ω\\prime-dithiodi[1-undecyl-4-(4-hydroxystyryl)pyridinium bromide](HSPC11SS). A considerable difference was found in the kinetics between SPR and SHG, because SHG probes the molecules in a noncentrosymmetric fashion on the gold surface while SPR probes the optical thickness of the film. The difference enabled us to separate the chemisorption from the physisorption in the adsorption process. Interestingly, both probes showed slower kinetics in the solution of higher concentration, suggesting association of the disulfide molecules in the solution of high concentration.

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

    PubMed

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

    2015-10-21

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

  4. Use of Self-Assembled Monolayers of Different Wettabilities To Study Surface Selection and Primary Adhesion Processes of Green Algal (Enteromorpha) Zoospores

    PubMed Central

    Callow, Maureen E.; Callow, J. A.; Ista, Linnea K.; Coleman, Sarah E.; Nolasco, Aleece C.; López, Gabriel P.

    2000-01-01

    We investigated surface selection and adhesion of motile zoospores of a green, macrofouling alga (Enteromorpha) to self-assembled monolayers (SAMs) having a range of wettabilities. The SAMs were formed from alkyl thiols terminated with methyl (CH3) or hydroxyl (OH) groups or mixtures of CH3- and OH-terminated alkyl thiols and were characterized by measuring the advancing contact angles and by X-ray photoelectron spectroscopy. There was a positive correlation between the number of spores that attached to the SAMs and increasing contact angle (hydrophobicity). Moreover, the sizes of the spore groups (adjacent spores touching) were larger on the hydrophobic SAMs. Video microscopy of a patterned arrangement of SAMs showed that more zoospores were engaged in swimming and “searching” above the hydrophobic sectors than above the hydrophilic sectors, suggesting that the cells were able to “sense” that the hydrophobic surfaces were more favorable for settlement. The results are discussed in relation to the attachment of microorganisms to substrata having different wettabilities. PMID:10919777

  5. A Single-Level Tunnel Model to Account for Electrical Transport through Single Molecule- and Self-Assembled Monolayer-based Junctions

    NASA Astrophysics Data System (ADS)

    Garrigues, Alvar R.; Yuan, Li; Wang, Lejia; Mucciolo, Eduardo R.; Thompon, Damien; Del Barco, Enrique; Nijhuis, Christian A.

    2016-05-01

    We present a theoretical analysis aimed at understanding electrical conduction in molecular tunnel junctions. We focus on discussing the validity of coherent versus incoherent theoretical formulations for single-level tunneling to explain experimental results obtained under a wide range of experimental conditions, including measurements in individual molecules connecting the leads of electromigrated single-electron transistors and junctions of self-assembled monolayers (SAM) of molecules sandwiched between two macroscopic contacts. We show that the restriction of transport through a single level in solid state junctions (no solvent) makes coherent and incoherent tunneling formalisms indistinguishable when only one level participates in transport. Similar to Marcus relaxation processes in wet electrochemistry, the thermal broadening of the Fermi distribution describing the electronic occupation energies in the electrodes accounts for the exponential dependence of the tunneling current on temperature. We demonstrate that a single-level tunnel model satisfactorily explains experimental results obtained in three different molecular junctions (both single-molecule and SAM-based) formed by ferrocene-based molecules. Among other things, we use the model to map the electrostatic potential profile in EGaIn-based SAM junctions in which the ferrocene unit is placed at different positions within the molecule, and we find that electrical screening gives rise to a strongly non-linear profile across the junction.

  6. Nanostructured materials based on the integration of ferrocenyl-tethered dendrimer and redox proteins on self-assembled monolayers: an efficient biosensor interface

    NASA Astrophysics Data System (ADS)

    Frasconi, Marco; Deriu, Daniela; D'Annibale, Andrea; Mazzei, Franco

    2009-12-01

    In this paper we report the use of ferrocenyl-tethered dendrimer (Fc-D) as an electrode modifier supported by a self-assembled monolayer coated gold surface. The pretreatment of electrodes with Fc-D allows the covalent immobilization of glucose oxidase. The resulting integrated hybrid system provides electrical contact between the redox center of the enzyme and the electrode, and improves the overall bioelectrocatalyzed oxidation of glucose. Cyclic voltammetry combined with surface plasmon resonance (SPR) is used to investigate the redox-induced orientation changes of ferrocene-tethered dendrimers and the optimal electrical wiring of the enzyme, depending on the length of the alkyl chain of the ferrocene-tethered groups. The amount of substrate controls the steady-state concentration ratio of Fc/Fc+ in the film composition. Therefore, the SPR spectrum of the film is controlled by the reversible change in the refractive index of the enzyme-integrated redox film. The proposed method demonstrates a new procedure for developing a stable amperometric redox enzyme-based sensor by designing a new nanostructured material that control the biosensing performance.

  7. Polar and azimuthal alignment of a nematic liquid crystal by alkylsilane self-assembled monolayers: effects of chain-length and mechanical rubbing.

    PubMed

    Malone, Stephanie M; Schwartz, Daniel K

    2008-09-01

    Alkylsilane self-assembled monolayers (SAMs) on oxide substrates are commonly used as liquid crystal (LC) alignment layers. We have studied the effects of alkyl chain length, photolytic degradation, and mechanical rubbing on polar and azimuthal LC anchoring. Both gradient surfaces (fabricated using photolytic degradation of C18 SAMs) and unirradiated SAMs composed of short alkyl chains show abrupt transitions from homeotropic to tilted alignment as a function of degradation or chain length. In both cases, the transition from homeotropic to tilted anchoring corresponds to increasing wettability of the SAM surfaces. However, there is an offset in the critical contact angle for the transition on gradient vs unirradiated SAMs, suggesting that layer thickness is more relevant than wettability for LC alignment. Mechanical rubbing can induce azimuthal alignment along the rubbing direction for alignment layers sufficiently near the homeotropic-to-planar transition. Notably, mechanical rubbing causes a small but significant shift in the homeotropic-to-tilted transition, e.g., unrubbed C5 SAMs induce homeotropic anchoring, but the same surface after rubbing induces LC pretilt. PMID:18686979

  8. Effect of Self-Assembled Monolayer Modification on Indium-Tin Oxide Surface for Surface-Initiated Vapor Deposition Polymerization of Carbazole Thin Films

    NASA Astrophysics Data System (ADS)

    Yuya Umemoto,; Seong-Ho Kim,; Rigoberto C. Advincula,; Kuniaki Tanaka,; Hiroaki Usui,

    2010-04-01

    With the aim of controlling the interface between an inorganic electrode and an organic layer, a surface-initiated vapor deposition polymerization method was employed to prepare carbazole polymer thin films that are chemically bound to an indium-tin oxide (ITO) surface. A self-assembled monolayer (SAM) that has an azo initiator as a terminal group was prepared on an ITO surface, on which carbazole acrylate monomers were evaporated under ultraviolet (UV) irradiation. The surface morphological characteristics of the films prepared with/without UV irradiation and with/without the SAM were compared. It was found that the UV irradiation leads to the polymerization of carbazole monomers irrespective of the type of substrate used. On the other hand, the surface morphological characteristics were largely dependent on the existence of the SAM. Uniform and smooth polymer thin films were obtained only when the monomers were evaporated on the SAM-modified surface under UV irradiation. A comparison of film growth characteristics on a UV-ozone-treated ITO surface suggested that the formation of uniform films was made possible not by the modification of surface energy but by the growth of the polymers chemically bound to the substrate surface.

  9. Corrosion resistant performances of alkanoic and phosphonic acids derived self-assembled monolayers on magnesium alloy AZ31 by vapor-phase method.

    PubMed

    Ishizaki, Takahiro; Okido, Masazumi; Masuda, Yoshitake; Saito, Naobumi; Sakamoto, Michiru

    2011-05-17

    Alkanoic and phosphonic acid derived self-assembled monolayers (SAMs) were formed on magnesium alloy by the vapor phase method. AFM and XPS studies showed that SAMs were formed on Mg alloy. The chemical and anticorrosive properties of the SAMs prepared on magnesium alloys were characterized using contact angle measurements, X-ray photoelectron spectroscopy (XPS), and electrochemical measurements. Water contact angle measurements revealed that, although SA and ISA have the same headgroup to anchor to the magnesium alloy surface, the packing density on the magnesium alloy surface could be considerably different. The contact angle hysteresis of SAMs with a carboxylate headgroup is much larger than that of SAMs with a phosphonic acid group. The XPS O 1s peaks indicated more likely a mix of mono-, bi-, or tridentate binding of phosphonic acid SAM to the oxide or hydroxide surface of the Mg alloy. The electrochemical measurements showed that the phosphonic acid derived SAM had better corrosion resistance compared to alkanoic acid derived SAM. The chemical stability of SAMs modified magnesium alloy was investigated using water contact angle and XPS measurements. The water contact angle and XPS measurements revealed that the molecular density of OP and PFEP on magnesium alloy would be higher than those of SA and ISA on magnesium alloy. PMID:21504153

  10. Devising Self-Assembled-Monolayers for Surface-Enhanced Infrared Spectroscopy of pH-Driven Poly-l-lysine Conformational Changes.

    PubMed

    Fallah, Mohammad A; Stanglmair, Christoph; Pacholski, Claudia; Hauser, Karin

    2016-07-26

    Surface-enhanced infrared absorption spectroscopy (SEIRA) is applied to study protein conformational changes. In general, the appropriate functionalization of metal surfaces with biomolecules remains a challenge if the conformation and activity of the biomolecule shall be preserved. Here we present a SEIRA study to monitor pH-induced conformational changes of poly-l-lysine (PLL) covalently bound to a thin gold layer via self-assembled monolayers (SAMs). We demonstrate that the composition of the SAM is crucial. A SAM of 11-mercaptoundecanonic acid (MUA) can link PLL to the gold layer, but pH-driven conformational transitions were hindered compared to poly-l-lysine in solution. To address this problem, we devised a variety of SAMs, i.e., mixed SAMs of MUA with either octanethiol (OT) or 11-mercapto-1-undecanol (MUoL) and furthermore SAMs of MT(PEG)4 and NHS-PEG10k-SH. These mixed SAMs modify the surface properties by changing the polarity and the morphology of the surface present to nearby PLL molecules. Our experiments reveal that mixed SAMs of MUA-MUoL and SAMs of NHS-PEG10k-SH-MT(PEG)4 are suitable to monitor pH-driven conformational changes of immobilized PLL. These SAMs might be applicable for chemoselective protein immobilization in general. PMID:27389421

  11. In Situ Analysis of the Growth and Dielectric Properties of Organic Self-Assembled Monolayers: A Way To Tailor Organic Layers for Electronic Applications.

    PubMed

    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 SAMs (εSAM = 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. PMID:27268402

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

    PubMed

    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. PMID:26506252

  13. Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries

    PubMed Central

    Zettsu, Nobuyuki; Kida, Satoru; Uchida, Shuhei; Teshima, Katsuya

    2016-01-01

    We demonstrate herein that an ultra-thin fluoroalkylsilane self-assembled monolayer coating can be used as a modifying agent at LiNi0.5Mn1.5O4−δcathode/electrolyte interfaces in 5V-class lithium-ion batteries. Bare LiNi0.5Mn1.5O4−δ cathode showed substantial capacity fading, with capacity dropping to 79% of the original capacity after 100 cycles at a rate of 1C, which was entirely due to dissolution of Mn3+ from the spinel lattice via oxidative decomposition of the organic electrolyte. Capacity retention was improved to 97% on coating ultra-thin FAS17-SAM onto the LiNi0.5Mn1.5O4 cathode surface. Such surface protection with highly ordered fluoroalkyl chains insulated the cathode from direct contact with the organic electrolyte and led to increased tolerance to HF. PMID:27553901

  14. 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

    SciTech Connect

    Albayrak, Erol; Karabuga, Semistan; Bracco, Gianangelo; Danışman, M. Fatih

    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.

  15. Measuring Drug Metabolism Kinetics and Drug-Drug Interactions Using Self-Assembled Monolayers for Matrix-Assisted Laser Desorption-Ionization Mass Spectrometry.

    PubMed

    Anderson, Lyndsey L; Berns, Eric J; Bugga, Pradeep; George, Alfred L; Mrksich, Milan

    2016-09-01

    The competition of two drugs for the same metabolizing enzyme is a common mechanism for drug-drug interactions that can lead to altered kinetics in drug metabolism and altered elimination rates in vivo. With the prevalence of multidrug therapy, there is great potential for serious drug-drug interactions and adverse drug reactions. In an effort to prevent adverse drug reactions, the FDA mandates the evaluation of the potential for metabolic inhibition by every new chemical entity. Conventional methods for assaying drug metabolism (e.g., those based on HPLC) have been established for measuring drug-drug interactions; however, they are low-throughput. Here we describe an approach to measure the catalytic activity of CYP2C9 using the high-throughput technique self-assembled monolayers for matrix-assisted laser desorption-ionization (SAMDI) mass spectrometry. We measured the kinetics of CYP450 metabolism of the substrate, screened a set of drugs for inhibition of CYP2C9 and determined the Ki values for inhibitors. The throughput of this platform may enable drug metabolism and drug-drug interactions to be interrogated at a scale that cannot be achieved with current methods. PMID:27467208

  16. Effect of fluorocarbon self-assembled monolayer films on sidewall adhesion and friction of surface micromachines with impacting and sliding contact interfaces

    SciTech Connect

    Xiang, H.; Komvopoulos, K.

    2013-06-14

    A self-assembled monolayer film consisting of fluoro-octyltrichlorosilane (FOTS) was vapor-phase deposited on Si(100) substrates and polycrystalline silicon (polysilicon) surface micromachines. The hydrophobic behavior and structural composition of the FOTS film deposited on Si(100) were investigated by goniometry and X-ray photoelectron spectroscopy, respectively. The effects of contact pressure, relative humidity, temperature, and impact/sliding cycles on the adhesive and friction behavior of uncoated and FOTS-coated polysilicon micromachines (referred to as the Si and FOTS/Si micromachines, respectively) were investigated under controlled loading and environmental conditions. FOTS/Si micromachines demonstrated much lower and stable adhesion than Si micromachines due to the highly hydrophobic and conformal FOTS film. Contrary to Si micromachines, sidewall adhesion of FOTS/Si micromachines demonstrated a weak dependence on relative humidity, temperature, and impact cycles. In addition, FOTS/Si micromachines showed low and stable adhesion and low static friction for significantly more sliding cycles than Si micromachines. The adhesive and static friction characteristics of Si and FOTS/Si micromachines are interpreted in the context of physicochemical surface changes, resulting in the increase of the real area of contact and a hydrophobic-to-hydrophilic transition of the surface chemical characteristics caused by nanoscale surface smoothening and the removal of the organic residue (Si micromachines) or the FOTS film (FOTS/Si micromachines) during repetitive impact and oscillatory sliding of the sidewall surfaces.

  17. Mixed Zwitterion-Based Self-Assembled Monolayer Interface for Impedimetric Glycomic Analyses of Human IgG Samples in an Array Format.

    PubMed

    Bertok, Tomas; Dosekova, Erika; Belicky, Stefan; Holazova, Alena; Lorencova, Lenka; Mislovicova, Danica; Paprckova, Darina; Vikartovska, Alica; Plicka, Robert; Krejci, Jan; Ilcikova, Marketa; Kasak, Peter; Tkac, Jan

    2016-07-19

    An impedimetric lectin biosensor for the detection of changes in the glycan structure of antibodies isolated from human serum is here correlated with the progression of rheumatoid arthritis (RA). The biosensor was built up from a mixed self-assembled monolayer (SAM) on gold consisting of two different thiolated zwitterionic derivatives, carboxybetaine and sulfobetaine, to resist nonspecific interactions. The carboxyl-terminated one was applied also for the covalent immobilization of lectin Ricinus communis agglutinin I (RCA-I). The process of building a bioreceptive layer was optimized and characterized using a diverse range of techniques. Impedimetric assays were integrated on a chip consisting of eight gold working electrodes, which is an important step toward the achievement of a moderate level of multiplexing for the analysis of human serum samples. At the end, the results obtained by the impedimetric analysis of immunoglobulins G (IgGs) isolated from serum samples were compared with those of two other standard bioanalytical methods employing lectins, that is, lectin microarrays (MAs) and enzyme-linked lectin binding assays (ELLBAs). The impedimetric results agreed very well with the DAS28 index (RA disease activity score 28), suggesting that impedimetric assays could be used for the development of a new diagnostic procedure sensitive to glycosylation changes in human IgGs and thus RA progression. PMID:27311591

  18. Spectroscopic ellipsometry meets AFM nanolithography: about hydration of bio-inert oligo(ethylene glycol)-terminated self assembled monolayers on gold.

    PubMed

    Solano, Ilaria; Parisse, Pietro; Gramazio, Federico; Cavalleri, Ornella; Bracco, Gianangelo; Castronovo, Matteo; Casalis, Loredana; Canepa, Maurizio

    2015-11-21

    For the first time, to our knowledge, spectroscopic ellipsometry (SE) has been combined with state-of-the-art AFM differential height measurements conducted after shaving nano-lithography of ultrathin, soft-matter films for thickness determination. We investigated self-assembled monolayers of SH-(CH2)11-EGn-OH molecules on gold, where EG is ethylene glycol units and n = 3 and 6, a prototypical non-fouling system. We performed SE measurements (245-1200 nm) focusing on the changes induced by the formation of the film (difference spectra). SE measurements, analysed by simple models, confirm the formation of the S-Au interface, transparency of the SAMs and provide a sharp picture of the ability of the EG functionality to protect the surface from unspecific adsorption of proteins. A quantitative assessment of the film thickness by SE was carried out ex situ, thanks to the optical contrast between the film and the ambient, and by AFM in liquid. The cross-check between SE and AFM height measurements combined with the comparison between in-liquid and ex situ SE measurements allowed obtaining non-perturbative information about the vertical density profile of the SAM. The in-liquid SE measurements indicate a refractive index matching between the aqueous medium and the outer part of the SAM, consistent with a disordered configuration of OEG and/or the penetration of water amid the OEG strands. A critical discussion provides a detailed insight into the subtle issues and pitfalls related to the thickness determination of soft-matter films to the monolayer limit. PMID:26445913

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

    PubMed Central

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

    2011-01-01

    The ordering of dodecyl-chain self-assembled monolayers (SAM) on different nanoscopic surfaces was investigated by FT-IR studies. As model systems plane-crystal-shaped ZrO2 nanoparticles and spherical SiO2 nanoparticles were examined. The type of capping agent was chosen dependent on the substrate, therefore dodecylphosphonic acid and octadecylphosphonic acid were used for ZrO2 and dodecyltrimethoxysilane for SiO2 samples. The plane ZrO2 nanocrystals yielded more ordered alkyl-chain structures whereas spherical SiO2 nanoparticles showed significantly lower alkyl-chain ordering. Submicron-sized silica spheres revealed a significantly higher alkyl chain ordering, comparable to an analogously prepared SAM on a non-curved plane oxidized Si-wafer. In the case of ZrO2 nanocrystals an intense alkyl-chain alignment could be disturbed by decreasing the grafting density from the maximum of 2.1 molecules/nm2 through the variation of coupling agent concentration to lower values. Furthermore, the co-adsorption of a different coupling agent, such as phenylphosphonic acid for ZrO2 and phenyltrimethoxysilane for SiO2, resulted in a significantly lower alkyl-chain ordering for ZrO2 plane crystals and for large SiO2 spherical particles at high grafting density. An increasing amount of order-disturbing molecules leads to a gradual decrease in alkyl-chain alignment on the surface of the inorganic nanoparticles. In the case of the ZrO2 nanoparticle system it is shown via dynamic light scattering (DLS) that the mixed monolayer formation on the particle surface impacts the dispersion quality in organic solvents such as n-hexane. PMID:21549385

  20. Two Cell Circuits of Oriented Adult Hippocampal Neurons on Self-Assembled Monolayers for Use in the Study of Neuronal Communication in a Defined System

    PubMed Central

    2013-01-01

    In this study, we demonstrate the directed formation of small circuits of electrically active, synaptically connected neurons derived from the hippocampus of adult rats through the use of engineered chemically modified culture surfaces that orient the polarity of the neuronal processes. Although synaptogenesis, synaptic communication, synaptic plasticity, and brain disease pathophysiology can be studied using brain slice or dissociated embryonic neuronal culture systems, the complex elements found in neuronal synapses makes specific studies difficult in these random cultures. The study of synaptic transmission in mature adult neurons and factors affecting synaptic transmission are generally studied in organotypic cultures, in brain slices, or in vivo. However, engineered neuronal networks would allow these studies to be performed instead on simple functional neuronal circuits derived from adult brain tissue. Photolithographic patterned self-assembled monolayers (SAMs) were used to create the two-cell “bidirectional polarity” circuit patterns. This pattern consisted of a cell permissive SAM, N-1[3-(trimethoxysilyl)propyl] diethylenetriamine (DETA), and was composed of two 25 μm somal adhesion sites connected with 5 μm lines acting as surface cues for guided axonal and dendritic regeneration. Surrounding the DETA pattern was a background of a non-cell-permissive poly(ethylene glycol) (PEG) SAM. Adult hippocampal neurons were first cultured on coverslips coated with DETA monolayers and were later passaged onto the PEG-DETA bidirectional polarity patterns in serum-free medium. These neurons followed surface cues, attaching and regenerating only along the DETA substrate to form small engineered neuronal circuits. These circuits were stable for more than 21 days in vitro (DIV), during which synaptic connectivity was evaluated using basic electrophysiological methods. PMID:23611164