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Sample records for alkanethiolate self-assembled monolayers

  1. Coadsorption of ferrocene-terminated and unsubstituted alkanethiols on gold: Electroactive self-assembled monolayers

    SciTech Connect

    Chidsey, C.E.D.; Bertozzi, C.R.; Putvinski, T.M.; Mujsce, A.M. )

    1990-05-23

    Self-assembled monolayers provide an ideal system for disentangling the fundamental events in interfacial electron transfer. Coadsorption of ferrocene-terminated alkanethiols with unsubstituted n-alkanethiols on evaporated gold films yields stable, electroactive self-assembled monolayers. Monolayers containing low concentrations of alkanethiols linked to ferrocene by a polar ester group (FcCO{sub 2}(CH{sub 2}){sub n}SH, Fc = ({eta}{sup 5}-C{sub 5}H{sub 5})Fe({eta}{sup 5}-C{sub 5}H{sub 4})) show thermodynamically ideal surface electrochemistry in 1 M HClO{sub 4}, indicating the ferrocene groups to be homogeneous and noninteracting. Higher surface concentrations or use of alkanethiols linked directly to the nonpolar ferrocene group (Fc(CH{sub 2}){sub n}SH) lead to broadened electrochemical features, indicating interactions among ferrocene groups or inhomogeneous sites. Longer chain lengths and lower ferrocene surface concentrations result in slower electron-transfer kinetics with the ferrocene groups. A fraction of the thiols in a monolayer exchange with thiols in an ethanol solution, but much of the monolayer remains unequilibrated after 10 days.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

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

    PubMed

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

    2013-10-22

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

  4. Dielectric properties and frequency response of self-assembled monolayers of alkanethiols.

    PubMed

    Wang, Bing; Luo, Jianglong; Wang, Xiaoping; Wang, Haiqian; Hou, J G

    2004-06-08

    This paper presents dielectric properties of alkanethiol self-assembled monolayers (SAMs) under an ac electric field. Using a Hg-SAM/SAM-Hg junction, we measured the ac impedance of alkanethiol SAMs using a sinusoidal perturbation of 30 mV (peak-to-peak) with frequency ranging from 1 Hz to 1 MHz at zero bias. Semicircles at higher frequencies and at middle frequencies along with Warburg lines at lower frequencies were observed in complex plane impedance plots, that is, Nyquist plots. The frequency response of SAMs was analyzed by modeling the junction using an equivalent circuit and fitting the Nyquist plots. The semicircles at higher frequencies are attributed to the effect of the SAM/SAM interfaces, and the ones at middle frequencies are attributed to the effect of alkanethiol SAMs. The comparison in the plots of the imaginary part of the impedance Z against frequency for the bare Hg electrodes (in pure ethanal) and the SAM-covered Hg electrodes (in alkanethiol solution) supports the analysis. The Warburg lines are attributed to a certain ionic impurity. The dielectric loss spectra are further analyzed. Chain-length-dependent peaks, which correspond to different relaxation mechanisms, at higher frequencies and middle frequencies were observed in the spectra of the dissipation factor (tan delta vs frequency). The peaks move to small frequency with the increase of chain length of alkanethiols. Using a correlation of peak position with the chain length, we then derived active energies of 39-99 meV for alkanethiol SAMs of C7-C18 under an ac electric field.

  5. Model of self assembled monolayer based molecular diodes made of ferrocenyl-alkanethiols

    NASA Astrophysics Data System (ADS)

    Duche, David; Planchoke, Ujwol; Dang, Florian-Xuan; Le Rouzo, Judikael; Bescond, Marc; Simon, Jean-Jacques; Balaban, Teodor Silviu; Escoubas, Ludovic

    2017-03-01

    There has been significant work investigating the use of self assembled monolayers (SAMs) made of ferrocenyl terminated alkanethiols for realizing molecular diodes, leading to remarkably large forward-to-reverse current rectification ratios. In this study, we use a multiband barrier tunneling model to examine the electrical properties of SAM-based molecular diodes made of HSC9Fc, HSC11Fc, and HSCiFcC13-i (0 ≤ i ≤ 13). Using our simple physical model, we reproduce the experimental data of charge transport across various ferrocenyl substituted alkanethiols performed by Nijhuis, Reus, and Whitesides [J. Am. Chem. Soc. 132, 18386-184016 (2010)] and Yuan et al. [Nat. Commun. 6, 6324 (2015)]. Especially, the model allows predicting the rectification direction in HSCiFcC13-i (0 ≤ i ≤ 13) based molecular diodes depending on the position of the ferrocenyl (Fc) moiety within the molecules. We show that the asymmetry of the barrier length at both sides of the Highest Occupied Molecular Orbital of the ferrocenyl moiety strongly contributes to the rectifying properties of ferrocenyl-alkanethiol based molecular junctions. Furthermore, our results reveal that bound and quasi-bound states play an important role in the charge transport.

  6. 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.

  7. 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

  8. Influence of Self-Assembled Alkanethiol Monolayers on Stochastic Amperometric On-Chip Detection of Silver Nanoparticles.

    PubMed

    Krause, Kay J; Adly, Nouran; Yakushenko, Alexey; Schnitker, Jan; Mayer, Dirk; Offenhäusser, Andreas; Wolfrum, Bernhard

    2016-04-05

    We investigate the influence of self-assembled alkanethiol monolayers at the surface of platinum microelectrode arrays on the stochastic amperometric detection of citrate-stabilized silver nanoparticles in aqueous solutions. The measurements were performed using a microelectrode array featuring 64 individually addressable electrodes that are recorded in parallel with a sampling rate of 10 kHz for each channel. We show that both the functional end group and the total length of the alkanethiol influence the charge transfer. Three different terminal groups, an amino, a hydroxyl, and a carboxyl, were investigated using two different molecule lengths of 6 and 11 carbon atoms. Finally, we show that a monolayer of alkanethiols with a length of 11 carbon atoms and a carboxyl terminal group can efficiently block the charge transfer of free nanoparticles in an aqueous solution.

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

    NASA Astrophysics Data System (ADS)

    Heinz, Bertram; Morgner, Harald

    1997-02-01

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

  10. 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.

  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. Mechanical and charge transport properties of alkanethiol self-assembled monolayers on Au (111) surface: The Role of Molecular Tilt

    SciTech Connect

    Mulleregan, Alice; Qi, Yabing; Ratera, Imma; Park, Jeong Y.; Ashby, Paul D.; Quek, Su Ying; Neaton, J. B.; Salmeron, Miquel

    2007-11-12

    The relationship between charge transport and mechanical properties of alkanethiol self-assembled monolayers (SAM) on Au(111) films has been investigated using an atomic force microscope with a conductive tip. Molecular tilts induced by the pressure applied by the tip cause stepwise increases in film conductivity. A decay constant {beta} = 0.57 {+-} 0.03 {angstrom}{sup -1} was found for the current passing through the film as a function of tip-substrate separation due to this molecular tilt. This is significantly smaller than the value of {approx} 1 {angstrom}{sup -1} found when the separation is changed by changing the length of the alkanethiol molecules. Calculations indicate that for isolated dithiol molecules S-bonded to hollow sites, the junction conductance does not vary significantly as a function of molecular tilt. The impact of S-Au bonding on SAM conductance is discussed.

  13. Improvements in the characterization of the crystalline structure of acid-terminated alkanethiol self-assembled monolayers on Au(111).

    PubMed

    Mendoza, Sandra M; Arfaoui, Imad; Zanarini, Simone; Paolucci, Francesco; Rudolf, Petra

    2007-01-16

    We report a study of acid-terminated self-assembled monolayers of alkanethiols of different length, 11-mercaptoundecanoic acid (11-MUA) and 16-mercaptohexadecanoic acid (16-MHDA), on Au(111). Scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and contact angle techniques were used for characterization, and the results were compared with those obtained from n-alkanethiols of similar chain length, providing a detailed description of the two-dimensional crystalline structure. Molecular resolution STM images show that 11-MUA forms a dense-packed monolayer arranged in a (square root 3 x square root 3)R30 degrees structure with a c(2 x 4) superlattice, where the simple hexagonal phase, the c(2 x 4) superlattice, and nonordered areas coexist. 16-MHDA assembles in a uniform monolayer with similar morphology to that of 11-MUA, but molecular resolution could not be reached in STM due to both the hydrophilicity of the acid groups and the poor conductivity of the thick monolayer. Nevertheless, the monolayer thicknesses estimated by XPS and electrochemistry and the highly blocking character of the film observed by electrochemistry as well as the low water contact angle are consistent with 16-MHDA molecules forming a compact monolayer on the Au(111) substrate with fully extended alkyl chains and acid groups pointing away from the surface. The results obtained for 16-MHDA were reproducible under different preparation conditions such as the addition or omission of acetic acid to the ethanolic solution. Contrary to other reports, we demonstrate that ordered acid-terminated self-assembled monolayers are obtained with the same preparation conditions as those of the methyl-terminated ones, without any additional treatment.

  14. Image Potential States of Electrons Interacting with Roughened Metal Surfaces Coated with Self-Assembled Alkanethiol Monolayers

    NASA Astrophysics Data System (ADS)

    Clark, B. K.; Standard, J. M.; Gregory, Brian W.

    2000-03-01

    Electrons in image potential states (IPS) [1] have been a topic of great interest at smooth dielectric/metal interfaces [2]. IPSs at roughened dielectric/metal interfaces have recently been reported [3]. The IPS model is extended to the case of a charge interacting with two intersecting metal planes. We discuss the role of the angle between intersecting metal planes (characteristic of roughened surfaces) on the IPS binding energies for electrons interacting with these structures. Our results are applied to roughened gold surfaces coated with self-assembled alkanethiol monolayers. [1] T. Fauster, Applied Phys. A 59, 479, 1994. [2] N.-H. Ge, C. M. Wong, R. L. Lingle, Jr., J. D. McNeill, K. J. Gaffney, and C. B. Harris, Science 279, 202, 1998, for example. [3] B. K. Clark, B. W. Gregory, A. Avila, T. M. Cotton, and J. M. Standard, J. Phys. Chem. B 103, 8201, 1999.

  15. 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.

  16. Microwave-Accelerated Surface Modification of Plasmonic Gold Thin Films with Self-Assembled Monolayers of Alkanethiols

    PubMed Central

    Grell, Tsehai A.J.; Alabanza, Anginelle M.; Gaskell, Karen; Aslan, Kadir

    2013-01-01

    A rapid surface modification technique for the formation of self-assembled monolayers (SAMs) of alkanethiols on gold thin films using microwave heating in less than 10 min is reported. In this regard, SAMs of two model alkanethiols, 11-mercaptoundecanoic acid (11-MUDA, to generate a hydrophilic surface) and undecanethiol (UDET, a hydrophobic surface), were successfully formed on gold thin films using selective microwave heating in 1) a semi-continuous and 2) a continuous fashion and at room temperature (24 hours, control experiment, no microwave heating). The formation of SAMs of 11-MUDA and UDET were confirmed by contact angle measurements, Fourier–transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The contact angles for water on SAMs formed by the selective microwave heating and conventional room temperature incubation technique (24 hours) were measured to be similar for 11-MUDA and UDET. FT-IR spectroscopy results confirmed that the internal structure of SAMs prepared using both microwave heating and at room temperature were similar. XPS results revealed that the organic and sulfate contaminants found on bare gold thin films were replaced by SAMs after the surface modification process was carried out using both microwave heating and at room temperature. PMID:24083414

  17. Microwave-accelerated surface modification of plasmonic gold thin films with self-assembled monolayers of alkanethiols.

    PubMed

    Grell, Tsehai A J; Alabanza, Anginelle M; Gaskell, Karen; Aslan, Kadir

    2013-10-29

    A rapid surface modification technique for the formation of self-assembled monolayers (SAMs) of alkanethiols on gold thin films using microwave heating in <10 min is reported. In this regard, SAMs of two model alkanethiols, 11-mercaptoundecanoic acid (11-MUDA, to generate a hydrophilic surface) and undecanethiol (UDET, a hydrophobic surface), were successfully formed on gold thin films using selective microwave heating in (1) a semicontinuous fashion and (2) a continuous fashion at room temperature (24 h, control experiment, no microwave heating). The formation of SAMs of 11-MUDA and UDET was confirmed by contact angle measurements, Fourier transform infrared (FT-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The contact angles for water on SAMs formed by the selective microwave heating and conventional room temperature incubation technique (24 h) were measured to be similar for 11-MUDA and UDET. FT-IR spectroscopy results confirmed that the internal structures of SAMs prepared using both microwave heating and room temperature were similar. XPS results revealed that the organic and sulfate contaminants found on bare gold thin films were replaced by SAMs after the surface modification process had been conducted using both microwave heating and room temperature.

  18. Inflammatory responses and cell adhesion to self-assembled monolayers of alkanethiolates on gold.

    PubMed

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

    2004-06-01

    The acute inflammatory response and the adhesion of cells to self-assembled monolayers (SAMs) of well-defined surface chemistry was studied in vivo using a rodent air-pouch model of inflammation. SAMs with three different terminal functional groups (OH, COOH and CH3) were implanted in subcutaneous air pouches induced in BALB/c mice. After 24 h, inflammatory cells were recovered from the air pouches and the implants were removed and prepared for observation by scanning electron microscopy (SEM). The implants coated with OH and CH3, were found to cause the highest recruitment of inflammatory cells into the subcutaneous pouches. Polymorphonuclear neutrophils (PMNs) leukocytes predominated over mononuclear cells in inflammatory exudates of SAMs-coated implants, the opposite being found in uncoated implants (controls). CH3-coated implants induced the highest number of inflammatory cells and also the largest percentage of PMNs seen in the subcutaneous pouches. Control and OH-covered implants presented the higher densities of attached inflammatory cells detected by SEM. In contrast, the CH3-coated implants showed a very low density of cells adherent to the implant surface. We conclude that the chemical nature and the degree of hydrophobicity of the surface of implants modulate both the local acute inflammatory reaction and the adhesion of leukocytes.

  19. Inhibition of Escherichia coli Biofilm Formation by Self-Assembled Monolayers of Functional Alkanethiols on Gold▿ †

    PubMed Central

    Hou, Shuyu; Burton, Erik A.; Simon, Karen A.; Blodgett, Dustin; Luk, Yan-Yeung; Ren, Dacheng

    2007-01-01

    Bacterial biofilms cause serious problems, such as antibiotic resistance and medical device-related infections. To further understand bacterium-surface interactions and to develop efficient control strategies, self-assembled monolayers (SAMs) of alkanethiols presenting different functional groups on gold films were analyzed to determine their resistance to biofilm formation. Escherichia coli was labeled with green florescence protein, and its biofilm formation on SAM-modified surfaces was monitored by confocal laser scanning microscopy. The three-dimensional structures of biofilms were analyzed with the COMSTAT software to obtain information about biofilm thickness and surface coverage. SAMs presenting methyl, l-gulonamide (a sugar alcohol tethered with an amide bond), and tri(ethylene glycol) (TEG) groups were tested. Among these, the TEG-terminated SAM was the most resistant to E. coli biofilm formation; e.g., it repressed biofilm formation by E. coli DH5α by 99.5% ± 0.1% for 1 day compared to the biofilm formation on a bare gold surface. When surfaces were patterned with regions consisting of methyl-terminated SAMs surrounded by TEG-terminated SAMs, E. coli formed biofilms only on methyl-terminated patterns. Addition of TEG as a free molecule to growth medium at concentrations of 0.1 and 1.0% also inhibited biofilm formation, while TEG at concentrations up to 1.5% did not have any noticeable effects on cell growth. The results of this study suggest that the reduction in biofilm formation on surfaces modified with TEG-terminated SAMs is a result of multiple factors, including the solvent structure at the interface, the chemorepellent nature of TEG, and the inhibitory effect of TEG on cell motility. PMID:17483274

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

    PubMed

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

    2014-09-16

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

  1. Molecular Dynamics Study of Alkanethiolate Self-Assembled Monolayer Coated Gold Nanoparticle

    DTIC Science & Technology

    2007-06-01

    component of function results for the uncoated gold nanoparticle to the the Irving -Kirkwood (IK) pressure tensor. [321 The normal results for an...pp. 24-34, 1983. Studies." Langmuir , 4, pp. 546-558, 1988. 23. Shevade, A. V., J. Zhou, M. T. Zin, and S. Jiang. Phase 8. Rosenbaum, A.W, M.A. Freedman...Au(l 11): A Configurational-Bias Monte Carlo Assembled Monolayers of Varying Chain Length." Journal of Simulation Study. Langmuir 17, pp. 7566-7572

  2. Identification of Surface Debye Temperature of an Alkanethiol Self Assembled Monolayer on Au(111) by Low Energy Helium Diffraction

    NASA Astrophysics Data System (ADS)

    West, Joshua; Camillone, Nicholas, III; Schwartz, Peter

    2005-03-01

    Using Low Energy Atomic Diffraction (LEAD), a nonperturbative and totally unpenetrating surface characterization technique, we have conducted measurements on the surface of self assembling monolayers (SAMs) of decanethiol on a Au(111) surface. Debye-Waller attenuation measurements were taken for substrate temperatures from 14.5 K to 110 K. For the lowest substrate temperatures, thermal Debye-Waller attenuation decreased consistent with a surface Debye temperature of about 100 K. The excellent order demonstrated by these particular data provided high resolution to six orders of the hexagonal peak (corresponding to the rt3 x rt3 thiol mesh). These data from higher order diffraction peaks allows us to more precisely measure the lateral thermal vibration of the terminal methyl groups, which is considerably less than previously reported

  3. Characterization of hydroxyphenol-terminated alkanethiol self-assembled monolayers: interactions with phosphates by chemical force spectrometry.

    PubMed

    Azmi, Alyza A; Ebralidze, Iraklii I; Dickson, Steven E; Horton, J Hugh

    2013-03-01

    Tannins and humic substances, commonly referred to as natural organic matter (NOM), constitute an important component of natural water and soil systems. These species contain numerous hydroxyl and carboxyl functional groups whose reactivity is strongly dependent on both the quantity and location of these moieties on the aromatic ring. In the present study, self-assembled monolayers (SAMs) of 4-(12-mercaptododecyl)benzene-1,2-diol (o-hydroxyphenol-terminated); 5-(12-mercaptododecyl)benzene-1,3-diol (m-hydroxyphenol-terminated); bis(11-thioundecyl) hydrogen phosphate (monoprotic phosphate); and 11-thioundecyl dihydrogen phosphate (diprotic phosphate) were prepared and characterized using X-ray photoelectron spectroscopy (XPS), attenuated total reflectance infrared spectroscopy (ATR-IR), and water contact angle measurements. The interactions between phenolic groups with phosphates were examined as a function of pH using the chemical force spectrometry (CFS) technique. The observations are discussed in the context of hydrogen bonding and electrostatic repulsion interaction between corresponding species. Adhesion force profiles of hydroxyphenol isomers interacting with monoprotic phosphate are dominated by ionic H-bonding; however the strength of o-hydroxyphenol interactions is significantly higher. The difference in location of hydroxyl groups on the interface also results in significantly different force-distance profiles for the isomeric hydroxyphenols when interacting with diprotic phosphate.

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

    PubMed

    Lu, Peng; Walker, Amy V

    2007-12-04

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

  5. Controlling noncovalent interactions between a lysine-rich α-helical peptide and self-assembled monolayers of alkanethiols on Au through functional group diversity

    NASA Astrophysics Data System (ADS)

    Raigoza, Annette F.; Onyirioha, Kristeen; Webb, Lauren J.

    2017-02-01

    Reliably attaching a structured biomolecule to an inorganic substrate would enable the preparation of surfaces that incorporate both biological and inorganic functions and structures. To this end, we have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to well-ordered alkanethiol self-assembled monolayers (SAM) on a Au(111) surface, in which the SAM is composed of a mixture of methyl and azide termination. Proteins, however, are composed of many diverse functional groups, and this composition directly effects protein structure, interactions, and reactivity. Here, we explore the utility of mixed SAMs with alternative terminating functional groups to tune and direct the reactivity of the surface through noncovalent peptide-surface interactions. We study both polar surfaces (OH-terminated) and charged surfaces (COOH- and NH3-terminated, which are negatively and positively charged, respectively, under our reaction conditions). Surfaces were functionalized with a bipolar peptide composed of Lys and Leu residues that could express different interactions through either hydrophilic and/or charge (Lys) or hydrophobic (Leu) influences. X-ray photoelectron spectroscopy (XPS) and surface infrared spectroscopy were used to characterize surfaces at all stages of the peptide functionalization procedure. This strategy resulted in a high density of surface-bound α-helices without aggregation. Mixed SAMs that included a positively charged alkanethiol along with the azide-terminated thiol resulted in a more efficient reaction and better alignment of the peptide with the azide on the surface. Negatively charged surfaces increased physisorption of the peptide, which was then removed during sample rinsing. This work demonstrates that varying easily controlled chemical inputs during the functionalization steps allows the reaction conditions to be balanced for the chemical needs of a

  6. Mixed self-assembled monolayers of alkanethiolates on ultrasmooth gold do not exhibit contact-angle hysteresis.

    PubMed

    Gupta, Pooja; Ulman, Abraham; Fanfan, Stephanie; Korniakov, Alexander; Loos, Katja

    2005-01-12

    We present the first study of mixed alkanethiolate SAMs on ultrasmooth gold surfaces. By eliminating surface roughness, it became possible, for the first time, to investigate wetting properties as a function of surface chemical composition. In three different surface compositions, it was found that contact-angle hysteresis apparently vanished. This suggests that surface chemical heterogeneity does not contribute to contact-angle hysteresis in mixed SAMs on ultrasmooth gold surfaces.

  7. 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.

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

    PubMed

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

    2006-09-01

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

  9. Molecular and electronic structure of electroactive self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Méndez De Leo, Lucila P.; de la Llave, Ezequiel; Scherlis, Damián; Williams, Federico J.

    2013-03-01

    Self-assembled monolayers (SAMs) containing electroactive functional groups are excellent model systems for the formation of electronic devices by self-assembly. In particular ferrocene-terminated alkanethiol SAMs have been extensively studied in the past. However, there are still open questions related with their electronic structure including the influence of the ferrocene group in the SAM-induced work function changes of the underlying metal. We have thus carried out a thorough experimental and theoretical investigation in order to determine the molecular and electronic structure of ferrocene-terminated alkanethiol SAMs on Au surfaces. In agreement with previous studies we found that the Fc-containing alkanethiol molecules adsorb forming a thiolate bond with the Au surface with a molecular geometry 30° tilted with respect to the surface normal. Measured surface coverages indicate the formation of a compact monolayer. We found for the first time that the ferrocene group has little influence on the observed work function decrease which is largely determined by the alkanethiol. Furthermore, the ferrocene moiety lies 14 Å above the metal surface covalently bonded to the alkanethiol SAM and its HOMO is located at -1.6 eV below the Fermi level. Our results provide new valuable insight into the molecular and electronic structure of electroactive SAMs which are of fundamental importance in the field of molecular electronics.

  10. Molecular and electronic structure of electroactive self-assembled monolayers.

    PubMed

    Méndez De Leo, Lucila P; de la Llave, Ezequiel; Scherlis, Damián; Williams, Federico J

    2013-03-21

    Self-assembled monolayers (SAMs) containing electroactive functional groups are excellent model systems for the formation of electronic devices by self-assembly. In particular ferrocene-terminated alkanethiol SAMs have been extensively studied in the past. However, there are still open questions related with their electronic structure including the influence of the ferrocene group in the SAM-induced work function changes of the underlying metal. We have thus carried out a thorough experimental and theoretical investigation in order to determine the molecular and electronic structure of ferrocene-terminated alkanethiol SAMs on Au surfaces. In agreement with previous studies we found that the Fc-containing alkanethiol molecules adsorb forming a thiolate bond with the Au surface with a molecular geometry 30° tilted with respect to the surface normal. Measured surface coverages indicate the formation of a compact monolayer. We found for the first time that the ferrocene group has little influence on the observed work function decrease which is largely determined by the alkanethiol. Furthermore, the ferrocene moiety lies 14 Å above the metal surface covalently bonded to the alkanethiol SAM and its HOMO is located at -1.6 eV below the Fermi level. Our results provide new valuable insight into the molecular and electronic structure of electroactive SAMs which are of fundamental importance in the field of molecular electronics.

  11. 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.

  12. Self-assembly of alkanethiolates directs sulfur bonding with GaAs(100)

    NASA Astrophysics Data System (ADS)

    Mancheno-Posso, Pablo; Muscat, Anthony J.

    2017-03-01

    Molecules that contain linear alkane chains self-assemble on a variety of surfaces changing the degree of wetting, lubricity, and reactivity. We report on the reoxidation of GaAs(100) in air after adsorbing five alkanethiols (CnH2n+1-SH where n = 3, 6, 12, 18, 20) and one alkanedithiol (HS-(CH2)8-SH) deposited from the liquid phase. The alignment of the alkane chains forms a self-assembled layer, however, air diffuses readily through the carbon layer and reaches the surface. The impact of alignment is to improve the bonding of sulfur with the surface atoms which reduces the oxidation rate based on fitting the data to a reaction-diffusion model. The layer thickness and molecular density scale linearly with the number of carbon atoms in the alkane chain. The thickness of the alkanethiolate (RS-) layer grows by 0.87 ± 0.06 Å for each C atom in the chain and the surface density by 0.13 ± 0.03 molecule per nm2 per C atom up to a coverage of 5.0 molecules/nm2 for n = 20 or 0.8 monolayer. The surface coverage increases with length because interactions between methylene (CH2) groups in neighboring chains reduce the tilt angle of the molecules with the surface normal. The tight packing yields areas per alkanethiolate as low as 20 Å2 for n = 20. The amount of C in the layer divided by the chain length is approximately constant up to n = 12 but increases sharply by a factor of 2-4× for n = 18 and 20 based on the C 1s X-ray photoelectron spectroscopy (XPS) peak. Fourier transform infrared (FTIR) spectroscopy shows that the asymmetric methylene stretch shifts continuously to lower wavenumber and the relative peak area increases sharply with the length of the alkane chain. Fitting the data to a reaction-diffusion model shows that for times less than 30 min the surface oxide coverage does not depend on the thickness of the self-assembled layer nor the diffusivity of oxygen through the layer. Instead increasing the layer thickness makes more S available for bonding with the

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

    PubMed

    Mrksich, Milan

    2009-03-01

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

  14. Ordering and defects in self-assembled monolayers on nanoporous gold

    NASA Astrophysics Data System (ADS)

    Patel, Dipna A.; Weller, Andrew M.; Chevalier, Robert B.; Karos, Constantine A.; Landis, Elizabeth C.

    2016-11-01

    Self-assembled monolayers are commonly used to tailor nanoporous structures for applications, and they also provide a model system for determining the effects of nanoscale structure on self-assembly. We have investigated the ordering and defects in alkanethiol self-assembled monolayers on nanoporous gold, a high surface area mesoporous material. Infrared reflection absorption spectroscopy was used to characterize the effects of alkyl chain length and nanoporous gold pore size on molecular layer ordering. Cyclic voltammetry was used to characterize the monolayer density and ordering, with ferrocenylalkylthiolates used to quantify and characterize defect sites. We find that dense and well-ordered molecular layers form quickly with low defect levels. However, we do not observe differences in molecular layer ordering or defects with changes in pore size.

  15. Recognition tunneling measurement of the conductance of DNA bases embedded in self-assembled monolayers.

    PubMed

    Huang, Shuo; Chang, Shuai; He, Jin; Zhang, Peiming; Liang, Feng; Tuchband, Michael; Li, Shengqing; Lindsay, Stuart

    2010-12-09

    The DNA bases interact strongly with gold electrodes, complicating efforts to measure the tunneling conductance through hydrogen-bonded Watson Crick base pairs. When bases are embedded in a self-assembled alkane-thiol monolayer to minimize these interactions, new features appear in the tunneling data. These new features track the predictions of density-functional calculations quite well, suggesting that they reflect tunnel conductance through hydrogen-bonded base pairs.

  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. Communication: Scanning tunneling microscopy study of the reaction of octanethiolate self-assembled monolayers with atomic chlorine

    NASA Astrophysics Data System (ADS)

    Jobbins, Matthew M.; Lee, David Y.; Kandel, S. Alex

    2012-04-01

    Scanning tunneling microscopy was used to investigate the reaction of octanethiolate self-assembled monolayers (SAMs) with atomic chlorine. We have found that exposing a SAM to low fluxes of radical Cl results primarily in the formation of new defects in areas with close-packed alkanethiolates, but has little to no effect on the domain boundaries of the SAM. Dosing high quantities of atomic chlorine results in the near-complete loss of surface order at room temperature, but not the complete removal of the thiolate monolayer. These observations are in stark contrast to the results of previous measurements of the reaction of atomic hydrogen with alkanethiolate SAMs.

  18. Optimized modification of gold nanoparticles with a self-assembled monolayer for suppression of nonspecific binding in DNA assays

    NASA Astrophysics Data System (ADS)

    Esashika, Keiko; Saiki, Toshiharu

    2016-10-01

    Homogeneous DNA assays using gold nanoparticles (AuNPs) require the reduction of nonspecific binding between AuNPs to improve sensitivity in detecting the target molecule. In this study, we employed alkanethiol self-assembled monolayers (SAMs) for modifying the AuNP surface to attain both good dispersability and high hybridization efficiency. The alkanethiol SAMs enhance the repulsive interaction between AuNPs, reducing nonspecific binding and promoting the extension of surface-immobilized ssDNA into the solvent, thus enhancing the hybridization process. Introduction of oligoethylene glycol into the alkanethiol prevented nonspecific binding caused by the entanglement of alkane chains. Finally, the conditions were optimized by controlling the surface charge density through the introduction of a COOH group at the alkanethiol terminus, resulting in the complete blocking of nonspecific binding and the maintenance of high hybridization efficiency.

  19. Contact-line friction of liquid drops on self-assembled monolayers: chain-length effects.

    PubMed

    Voué, M; Rioboo, R; Adao, M H; Conti, J; Bondar, A I; Ivanov, D A; Blake, T D; De Coninck, J

    2007-04-24

    The static and dynamic wetting properties of self-assembled alkanethiol monolayers of increasing chain length were studied. The molecular-kinetic theory of wetting was used to interpret the dynamic contact angle data and evaluate the contact-line friction on the microscopic scale. Although the surfaces had a similar static wettability, the coefficient of contact-line friction zeta0 increased linearly with alkyl chain length. This result supports the hypothesis of energy dissipation due to a local deformation of the nanometer-thick layer at the contact line.

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

    PubMed

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

    2009-09-01

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

  1. 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.

  2. 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.

  3. Method for measuring the self-assembly of alkanethiols on gold at femtomolar concentrations.

    PubMed

    Rijal, Kishan; Mutharasan, Raj

    2007-06-05

    We describe a cantilever-based method for measuring the self-assembly of alkanethiols on a gold surface in a flow system that permits easy step changes in concentration and acquire a continuous in situ measure of the resulting chemisorption through the change in resonance frequency. A gold-coated (2.2 mm2), piezoelectric-excited, millimeter-sized cantilever (PEMC) sensor was exposed to 1-hexadecanethiol (HDT) in ethanol at concentrations ranging from 1 fM to 1 mM, sequentially and separately. A high-order flexural mode at approximately 850 kHz was monitored during the self-assembly. The resonance frequency decreases as a result of increased mass as chemisorption occurs on the surface. We show for the first time that the chemisorption of HDT at 1 fM is readily measurable and gave a response of 220 +/- 13 Hz (n = 4). At higher concentrations (10 and 100 fM; 1, 10, and 100 pM; 1, 10, and 100 nM; 1 microM; and 1 mM), the responses were proportionately, but nonlinearly, higher. At high concentrations (1 mM), the responses to C4, C8, C11, C16, and C18 alkanethiols were linearly proportional and were complete in approximately 25 min. We report for the first time that, once the Au surface is equilibrated at 1 pM, further chemisorption at a lower HDT concentration does not take place, even though over 99% of surface adsorption sites are available. At 1 fM, the overall chemisorption rate did not increase with a 2-fold increase in the HDT flow rate, suggesting that chemisorption at 1 fM is not transport-limited. The measured overall chemisorption rate constant at 1 fM was more rapid than 0.1 min-1.

  4. Well-ordered self-assembled monolayers created via vapor-phase reactions on a monolayer template.

    PubMed

    Ferguson, Melinda K; Low, Emily R; Morris, John R

    2004-04-13

    The reaction of vapor-phase alkyl isocyanates (O=C=N-(CH2)n-1CH3) with OH-terminated alkanethiol template monolayers on Au produces well-organized self-assembled monolayers, containing intrachain carbamate linkages (Au/S(CH2)16O(C=O)NH(CH2)n-1CH3, where n = 1-8, 11, and 12). X-ray photoelectron spectroscopy, contact angle goniometry, and reflection absorption infrared spectroscopy suggest that the template surface completely reacts with the isocyanates yielding a monolayer that contains an interchain hydrogen-bonded carbamate network. Spectroscopic data indicates that the alkyl underlayer remains well ordered following reaction with the isocyanates. The order of the overlayer and the hydrogen-bonding interactions between adjacent chains increase as a function of the alkyl isocyanate chain length, n. The overlayer appears to be well ordered for n > or = 5.

  5. 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.

  6. Electroactive self-assembled monolayers of unique geometric structures by using rigid norbornylogous bridges.

    PubMed

    Darwish, Nadim; Eggers, Paul K; Da Silva, Paulo; Zhang, Yi; Tong, Yujin; Ye, Shen; Gooding, J Justin; Paddon-Row, Michael N

    2012-01-02

    Herein, we describe the synthesis of straight (S) and L-shaped (L) norbornylogous bridges (NBs) with an anthraquinone moiety at the distal end as the redox-active head group and two thiol feet at the proximal end, by which the molecules assemble on gold surfaces. The NB molecules were shown to form self-assembled monolayers (SAMs) with a well-behaved surface redox process. The SAMs were characterized by using in situ IR spectroscopy, cyclic voltammetry, scanning tunnelling microscopy and electrochemical impedance spectroscopy. The surface selection rules associated with the IR band intensities allowed the estimation of the position of the anthraquinone moiety with respect to the surface and the tilt of the bridge with respect to the surface normal, both in pure and diluted monolayers. It is shown that the S- and L-NBs hold the plane of the anthraquinone moiety close to the surface normal or the surface tangent, respectively. Neither NB molecule changes its orientation if spaced by diluents on the surface. The difference in the structure of the S- and L-NB SAMs provides a suitable framework for the investigation of factors that govern electron transfer of anthraquinone moieties across self-assembled monolayers with limited structural ambiguity, as compared with the commonly used structurally flexible alkanethiol monolayers.

  7. 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.

  8. 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.

  9. Kinetics of alkanethiol monolayer desorption from gold in air.

    PubMed

    Shadnam, Mohammad Reza; Amirfazli, A

    2005-10-14

    Thermal desorption of an alkanethiol monolayer from a gold substrate into a gaseous medium under ambient pressure was investigated using XPS and it was found that there exist 2 consecutive 1st order kinetics mechanisms with activation energies of 29.9 and 32.7 kcal mol(-1), respectively, i.e. on average approximately 15% higher than reports for liquid media desorption.

  10. Hyperthermal Carbon Dioxide Interactions with Self-Assembled Monolayer Surfaces

    DTIC Science & Technology

    2013-09-08

    time as well as density measurements of the thermosphere. The sensor under current development is based on the charge conversion of hyperthermal...oxygen atoms (O) to their anionic form (O−) upon collision with an organosilane/silicon self-assembled monolayer (SAM). The measured current of O− can...efficiency at charge conversion. The original goals of this project were to (1) measure the lifetimes of AFRL-provided SAMs under hyperthermal O

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

    NASA Technical Reports Server (NTRS)

    Hintze, Paul E.; Calle, Luz Marina

    2004-01-01

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

  12. One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

    NASA Astrophysics Data System (ADS)

    Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J.

    2017-02-01

    The Huisgen cycloaddition reaction ("click" chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

  13. Degradation of octanethiol self-assembled monolayers from hydrogen-atom exposure: A molecular-scale study using scanning tunneling microscopy

    NASA Astrophysics Data System (ADS)

    Kautz, Natalie A.; Fogarty, Daniel P.; Kandel, S. Alex

    2007-08-01

    Octanethiol self-assembled monolayers were exposed to gas-phase hydrogen atoms, and the resulting changes in the order and chemical structure of the surface were monitored using scanning tunneling microscopy (STM). Extensive damage to the monolayer was observed in the form of both dark and bright features in STM images. These changes began along domain boundaries and moved into close-packed regions of the monolayer as hydrogen-atom exposure time increased. Increasing exposure also results in an accelerated rate of observed surface changes, indicating that the reactivity of the surface increases as a result of initial gas-surface reactions. Complex restructuring of the alkanethiol monolayer is observed, including defect formation and the disordering of the alkanethiol monolayer. However, in some cases the monolayer demonstrates the capability of self-healing, with local annealing and reordering of close-packed domains. This annealing and reordering likely results from increased mobility of surface-bound alkanethiolates in the vicinity of monolayer defects, or from diffusion and readsorption of transiently formed alkanethiol molecules.

  14. Direct patterning of self-assembled monolayers on gold using a laser beam.

    PubMed

    Shadnam, Mohammad R; Kirkwood, Sean E; Fedosejevs, Robert; Amirfazli, A

    2004-03-30

    The development of a methodology to manipulate surface properties of a self-assembled monolayer (SAM) of alkanethiol on a gold film using direct laser patterning is the objective of this paper. The present study demonstrates proof of the concept for the feasibility of laser patterning monolayers and outlines theoretical modeling of the process to predict the resulting feature size. This approach is unique in that it eliminates the need for photolithography, is noncontact, and can be extended to other systems such as SAMs on silicon wafers or potentially polymeric substrates. A homogeneous SAM made of 1-hexadecanethiol is formed on a 300-A sputtered film of gold (supported by a soda lime glass substrate). Localized regions are then desorbed by scanning the focal spot of a 488-nm continuous-wave argon ion laser beam under a nitrogen atmosphere. The desorption occurs as a result of a high substrate temperature produced by the moving laser beam with a Gaussian spatial profile at a constant speed of 200 microm/s. After completing the scans, the sample is dipped into a dilute solution of 16-mercaptohexadecanoic acid and a hydrophilic monolayer self-assembles along the previously irradiated regions. The resultant lines are viewed, and line widths are measured using both wetting with tridecane under a light microscope and scanning electron microscopy. Using the direct laser patterning method, we have produced straight line patterns with widths of 28-170 microm. A thermal model was constructed to predict the line width of the desorbed monolayer. The effect of the laser power, beam waist, and temperature dependence of the substrate conductivity on the theoretical predictions is considered. It is shown that the theoretical predictions are in good agreement with the experimental results, and, thus, the model can effectively be used to predict experimental results.

  15. Effect of Self-Assembled Monolayer Film Order on Nanofriction

    SciTech Connect

    Sambasivan,S.; Shieh, S.; Fischer, D.; Hsu, S.

    2006-01-01

    Self-assembled monolayers have increasingly been explored as potential protective films in devices against friction and adhesion. However, detailed characterization of the monolayer film structure is difficult. This article utilizes a combination of near edge x-ray absorption fine structure (NEXAFS) spectroscopy and Fourier transform infrared (FTIR) spectroscopy to determine the film structure in order to explain the observed nanofriction measurement results. A series of n-alkyltrichlorosilane self-assembled monolayer films with various chain lengths (C5-C30) was prepared on silicon (100) surfaces. Nanofriction measurements were conducted using an atomic force microscope. Results showed that the lowest friction was obtained with a C12 film with higher friction values observed for C5 and C30 films. To explain these observations, the x-ray absorption technique NEXAFS was used to quantitatively measure the surface molecular orientation (order) of these films. It was observed that C12, C16, and C18 films were highly ordered with a molecular orientation of the carbon backbone nearly perpendicular to the surface. C5 and C30 films were less oriented and C10 film showed partial orientation. FTIR spectra suggested that these films possessed different degrees of order. This combination of molecular orientation and order supports and confirms that nanofriction results were heavily influenced by the order and structure of these films.

  16. Propagating waves of self-assembly in organosilane monolayers

    PubMed Central

    Douglas, Jack F.; Efimenko, Kirill; Fischer, Daniel A.; Phelan, Fredrick R.; Genzer, Jan

    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) ≈ tβ, 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. PMID:17566108

  17. Two-laser mass spectrometry of thiolate, disulfide, and sulfide self-assembled monolayers.

    SciTech Connect

    Trevor, J. L.; Lykke, K. R.; Chemistry; Univ. of Illinois at Chicago

    1998-03-31

    Self-assembled monolayers (SAMs) of thiolates, disulfides (RSSR+), and sulfides were studied on Au by N2 laser desorption followed by vacuum ultraviolet (VUV) (118-nm) photoionization of secondary neutrals in a time-of-flight mass spectrometer. Dimers (RSSR+) dominated the photoionization mass spectrum from all chain lengths of alkanethiolates and disulfides studied. Nonmethyl-terminated alkanethiolates with X = (OH and COOH) were detected as dimers without loss of the terminal group. Phenyl-SAMs with X = (H, OH, OCH3, Cl, and NO2) were detected as both monomers and dimers. Thiocholesterol SAMs were detected solely as monomers. The data suggest that dimerization occurs as a result of the recombination of surface thiolates during desorption. The alkane sulfides were detected intact, but with additional monomer and dimer species present in the spectra. The appearance of dimers is not a strong function of adsorbate structure or ordering and therefore cannot be taken as evidence for or against the recently proposed model of thiolate dimers on Au surfaces. Two receptor adsorbates, resorcin[4]arene tetrasulfide and {beta}-cyclodextrin sulfide were examined by two-laser mass spectrometry (L2MS), but only the former gave identifiable high mass peaks. Mixed thiolate and disulfide monolayers generated both pure and mixed dimers, providing information on nearest neighbor interactions. The mixed disulfide results indicate there is a common adsorption state for thiolates and disulfides. The laser desorption and VUV photoionization cross sections for these various organosulfur SAMs were found to be similar. L2MS with VUV photoionization was nonselective in its detection of these organosulfur species and produced mass spectra with little fragmentation.

  18. 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.

  19. 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.

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

    NASA Astrophysics Data System (ADS)

    Dhirani, Al-Amin

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

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

    PubMed Central

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

    2016-01-01

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

    PubMed

    Noyhouzer, Tomer; Mandler, Daniel

    2011-01-17

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

  3. Patterning of conducting polymers using charged self-assembled monolayers.

    PubMed

    Jung, Mi-Hee; Lee, Hyoyoung

    2008-09-02

    We introduce a new approach to pattern conducting polymers by combining oppositely charged conducting polymers on charged self-assembled monolayers (SAMs). The polymer resist pattern behaves as a physical barrier, preventing the formation of SAMs. The patterning processes were carried out using commercially available conducting polymers: a negatively charged PEDOT/PSS (poly(3,4-ethylene-dioxythiophene)/poly(4-stylenesulphonic acid)) and a positively charged polypyrrole (PPy). A bifunctional NH 2 (positively charged) or COOH (negatively charged) terminated alkane thiol or silane was directly self-assembled on a substrate (Au or SiO 2). A suspension of the conducting polymers (PEDOT/PSS and PPy) was then spin-coated on the top surface of the SAMs and allowed to adsorb on the oppositely charged SAMs via an electrostatic driving force. After lift-off of the polymer resist, i.e., poly(methyl methacrylate, PMMA), using acetone, the conducting polymers remained on the charged SAMs surface. Optical microscopy, Auger electron spectroscopy, and atomic force microscopy reveal that the prepared nanolines have low line edge roughness and high line width resolution. Thus, conducting polymer patterns with high resolution could be produced by simply employing charged bifunctional SAMs. It is anticipated that this versatile new method can be applied to device fabrication processes of various nano- and microelectronics.

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

    PubMed Central

    Cheng, Fang; Ratner, Daniel M.

    2013-01-01

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

  5. Electrochemistry of redox-active self-assembled monolayers

    PubMed Central

    Eckermann, Amanda L.; Feld, Daniel J.; Shaw, Justine A.; Meade, Thomas J.

    2010-01-01

    Redox-active self-assembled monolayers (SAMs) provide an excellent platform for investigating electron transfer kinetics. Using a well-defined bridge, a redox center can be positioned at a fixed distance from the electrode and electron transfer kinetics probed using a variety of electrochemical techniques. Cyclic voltammetry, AC voltammetry, electrochemical impedance spectroscopy, and chronoamperometry are most commonly used to determine the rate of electron transfer of redox-activated SAMs. A variety of redox species have been attached to SAMs, and include transition metal complexes (e.g., ferrocene, ruthenium pentaammine, osmium bisbipyridine, metal clusters) and organic molecules (e.g., galvinol, C60). SAMs offer an ideal environment to study the outer-sphere interactions of redox species. The composition and integrity of the monolayer and the electrode material influence the electron transfer kinetics and can be investigated using electrochemical methods. Theoretical models have been developed for investigating SAM structure. This review discusses methods and monolayer compositions for electrochemical measurements of redox-active SAMs. PMID:20563297

  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. 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.

  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. 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

    2015-07-31

    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.

  10. Poly(ethylene glycol) self-assembled monolayer island growth.

    PubMed

    Rundqvist, Jonas; Hoh, Jan H; Haviland, David B

    2005-03-29

    Here, we report a study of the morphology and growth dynamics of a self-assembled monolayer (SAM) of the amide containing poly(ethylene glycol) (PEG) thiol (CH3O(CH2CH2O)17NHCO(CH2)2SH) on atomically flat Au(111) surfaces. SAM growth from a 20 muM ethanolic solution reveals island growth through three distinct steps: island nucleation, island growth, and coalescence. The coalescence-step, filling voids in the SAM, is by far slowest. The fine structure study reveals dendritic island formation, an observation which can be explained by attractive intermolecular interactions and surface diffusion-limited aggregation. We have also observed a change in the island height, which peaks during the island growth phase. This height change can be associated with a molecular conformational transition.

  11. Magnetism induced by the organization of self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Carmeli, I.; Leitus, G.; Naaman, R.; Reich, S.; Vager, Z.

    2003-06-01

    Unique occurrence of magnetism is shown, in which magnetism appears ex nihilo, when organic molecules are self-assembled as monolayers on gold substrate. The molecules as well as the substrate, when they stand alone, are diamagnetic. Using a superconducting quantum interference device type magnetometer we obtained direct evidence that close-packed organized thio-organic films adsorbed on gold substrates possess magnetic properties at room temperature. The films studied show very high specific magnetization, up to many tens Bohr magnetons per adsorbed molecule, with a very small hysteresis. It is highly anisotropic and shows almost no temperature dependence. The magnetism observed is related to charge transfer between the organic layer and the metal substrate. Yet, the uniqueness here is that many spins are polarized per adsorbed molecules. The magnetic effect is related to the two dimensional organization of the organic molecules on the metal substrate which might explain the high anisotropy.

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

    PubMed

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

    2014-12-10

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

  13. Fabrication of surface energy/chemical gradients using self-assembled monolayer surfaces.

    PubMed

    Meyyappan, S; Shadnam, M R; Amirfazli, A

    2008-03-18

    Direct laser patterning of surface energy gradients for alkanethiols on gold has been demonstrated. A homogeneous 1-hexadecanethiol self-assembled monolayer (SAM) on gold (supported by a glass substrate) was selectively desorbed using a focused laser beam. By continually varying the incident laser intensity along a straight line scan, a gradient in desorption was produced. This desorption gradient was then backfilled with the second SAM (16-mercaptohexadecanoic acid), to produce a wettability gradient. The gradient in wettability was characterized by condensation imaging. Secondary ion mass spectroscopy was also used to show variation of the second SAM population from maximum to zero along the length, representative of the chemical gradient. The hexadecanethiol desorption was found to be the most sensitive in a laser intensity range of 29.15-6.5 kW/cm2. By considering the functional behavior of the governing equations, the theoretical trend for desorption as a function of laser intensity (represented by the out-of-focus distance) was determined. It was found to conform to the experimental data. The proposed method is fast, simple, noncontact, and flexible in terms of producing different types of gradients.

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

    PubMed

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

    2004-01-21

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

  15. Communication: Site-dependent reactivity between chlorine atoms and mixed-chain-length alkanethiolate monolayers

    NASA Astrophysics Data System (ADS)

    Lee, David Y.; Kandel, S. Alex

    2013-10-01

    The chemical reaction of atomic chlorine with mixed monolayers of alkanethiolates having different chain lengths was investigated. In situ scanning tunneling microscopy was used to acquire time-lapsed series of images, allowing the measurement of the effect of monolayer structure and composition on reactivity. The rate of chemical reaction is strongly site-dependent. In particular, the boundary between two different-length alkanethiolates greatly promotes the reactivity of nearby molecules, much more so than any other native defect typical of single-component alkanethiolate monolayers.

  16. Intrinsic Electronic Transport through Alkanedithiol Self-Assembled Monolayer

    NASA Astrophysics Data System (ADS)

    Lee, Takhee; Wang, Wenyong; Reed, Mark A.

    2005-01-01

    Electronic transport through an alkanedithiol self-assembled monolayer (SAM) is investigated using a nanometer scale device. Temperature-independent current-voltage characteristics are observed, indicating tunneling is the main conduction mechanism. The measured current-voltage characteristics are analyzed with a metal-insulator-metal tunneling model. The inelastic electron tunneling spectroscopy (IETS) study on the octanedithiol device clearly shows the vibrational signatures of molecules. The pronounced IETS peaks correspond to vibrational modes perpendicular to the junction interface, which include the stretching modes of Au-S (at 33 mV) and C-C (at 133 mV), and wagging mode of CH2 (at 158 mV). Intrinsic linewidths are determined as 1.69 (upper limit), 3.73± 0.98, and 13.5± 2.4 meV for Au-S, C-C streching modes, and CH2 wagging mode, respectively. The observed peak intensities and peak widths are in good agreement with theoretical predictions.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Self-assembled monolayers of phosphorylcholine alkylthiols on gold

    NASA Astrophysics Data System (ADS)

    Tegoulia, Vassiliki; Rao, Weisun; Cooper, Stuart

    2000-03-01

    One of the most intriguing developments in biomaterials science in the past decade has been the observation that membrane-mimetic systems based on the phosphorylcholine head group limit the adsorption of proteins and cells on surfaces. This phenomenon may be related to the zwitterionic nature of the phosphorylcholine moiety and the tendency for a large amount of bound water to be associated with this structure. In this work, we have prepared and studied single and mixed self-assembled monolayers (SAMs) of phoshorylcholine (PC) and hydroxyl (OH) or methyl (CH3) terminated thiols on gold-coated substrates in order to create surfaces that resist protein adsorption and cell adhesion. The direct organization of monomolecular assemblies on solid surfaces provided a convenient method for fabricating substrates with well-defined compositions and structures. The surfaces have been characterized by means of contact angle measurements, ellipsometry, X-ray photoelectron spectroscopy and grazing angle-FTIR. The resulting surfaces exhibited good resistance to the adsorption of a variety of proteins such as fibrinogen, fibronectin and albumin. Results evaluating bacterial and leukocyte adhesion under flow on these surfaces will be discussed.

  3. Self-Assembled Monolayer Aging in Humid Environments

    NASA Astrophysics Data System (ADS)

    Kim, Byung-Il; Mayer, Thomas M.; Hankins, Matthew G.; Deboer, Maarten P.; Bunker, Bruce C.

    2003-03-01

    Self-assembled monolayers (SAMS) are used extensively to control friction and stiction in micromachines. While as-prepared coatings are effective at minimizing adhesion, coating performance can deteriorate in humid environments. We are using the interfacial force microscope (IFM) to monitor the aging behavior of SAMS as a function of temperature, humidity, time, SAM composition, and fabrication procedures. The IFM provides force-distance curves between functionalized scanning probe tips and substrate surfaces while avoiding the "snap-to-contact" problems associated with conventional atomic force microscopy. With the IFM, we can detect the adsorption of water on SAM surfaces as a function of relative humidity and monitor the extent to which humid environments promote interfacial adhesion. Our results indicate that adsorbed water can disrupt hydrogen bonds at the SAM-substrate interface, reorganizing the coating to create bare patches that promote adhesion. Processing strategies aimed at minimizing aging by replacing vulnerable interfacial hydrogen bonds with water-resistant covalent linkages will be discussed.

  4. Tribological properties of self-assembled monolayers in humid environments

    NASA Astrophysics Data System (ADS)

    Lorenz, Christian D.

    2005-03-01

    Microelectromechanical systems (MEMS) are a rapidly growing area of technology. Due to the large surface area to volume ratio in MEMS, surface forces including friction and adhesion are tribological limitations that affect their performance. Self-assembled monolayer (SAM) coatings, which have high hydrophobicity, low surface energies and compact packing structures, are good canditates for MEMS lubrication. Large scale molecular dynamics simulations are used to study the frictional and adhesive behavior of hydrocarbon and fluorocarbon SAMs coatings on amorphous silica in the presence of water. The systems consist of SAMS with a chain length of 11 carbons physisorbed to the amorphous silica substrate with the water placed between the SAMs and the substrate. Humidity has no observed effect on the maximum adhesion of either of the SAMs. The coefficient of friction decreases with increasing water, which is in agreement with what is observed experimentally. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

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

    PubMed

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

    2010-05-01

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

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

    NASA Astrophysics Data System (ADS)

    Fang, Guanjiu

    2007-12-01

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

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

    PubMed

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

    2003-06-15

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

  8. 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.

  9. 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.

  10. Electroactive Self-Assembled Monolayers Detect Micelle Formation.

    PubMed

    Dionne, Eric R; Badia, Antonella

    2017-02-15

    The interfacial electrochemistry of self-assembled monolayers (SAMs) of ferrocenyldodecanethiolate on gold (FcC12SAu) electrodes is applied to detect the micellization of some common anionic surfactants, sodium n-alkyl sulfates, sodium n-alkyl sulfonates, sodium diamyl sulfosuccinate, and sodium dodecanoate, in aqueous solution by cyclic voltammetry. The apparent formal redox potential (E°'SAM) of the FcC12SAu SAM is used to track changes in the concentration of the unaggregated surfactant anions and determine the critical micelle concentration (cmc). The effect of added salt (NaF) on the sodium alkyl sulfate concentration dependence of E°'SAM is also investigated. Weakly hydrated anions, such as ClO4(-), pair with the electrogenerated SAM-bound ferroceniums to neutralize the excess positive charge created at the SAM/electrolyte solution interface and stabilize the oxidized cations. E°'SAM exhibits a Nernstian-type dependence on the anion activity in solution. Aggregation of the surfactant anions into micelles above the cmc causes the free surfactant anion activity to deviate from the molar concentration of added surfactant, resulting in a break in the plot of E°'SAM versus the logarithm of the concentration of anionic surfactant. The concentration at which this deviation occurs is in good agreement with literature or experimentally determined values of the cmc. The effects of Ohmic potential drop, liquid junction potential, and surfactant adsorption behavior on E°'SAM are addressed. Ultimately, the E°'SAM response as a function of the anionic surfactant concentration exhibits the same features reported using potentiometry and surfactant ion-selective electrodes, which provide a direct measure of the free surfactant anion activity, thus making FcC12SAu SAM electrodes useful for the detection of surfactant aggregation and micelle formation.

  11. 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.

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

    PubMed

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

    2008-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  18. Electrocatalytic oxidation of dihydronicotineamide adenine dinucleotide on gold electrode modified with catechol-terminated alkanethiol self-assembly.

    PubMed

    Nakano, Koji; Ohkubo, Kimihiko; Taira, Hiroaki; Takagi, Makoto; Imato, Toshihiko

    2008-06-30

    Synthesis of a mercaptoundecaneamide derivative having a terminus of catechol is described. FT-IR spectroscopic characterization showed that the new molecular entry simply undergoes molecular self-assembly on Au substrate surfaces promoting intra- and intermolecular hydrogen bonds to form well-packed monolayers. Cyclic voltammetric (CV) measurements on the monolayer-modified Au electrode revealed that the surface adlayer possesses specific electrochemical activity due to the reversible catechol/o-quinone redox reaction having characteristics of a surface process and also pH-dependence in its formal potential (59 mV per pH). Detailed analysis of CVs gave fundamental electrochemical parameters including the electroactive surface coverage (0.20-0.24 nmol cm(-2)), the transfer coefficients (0.24 in oxidation and 0.81 in reduction), and also the electron transfer rate constant (1.10-2.76 s(-1)). These data were almost consistent to those seen in literature. We have also found that the catechol monolayer modified electrode exhibits an electrocatalytic function in NADH oxidation. That is, the faradaic current appeared reinforcingly at around the same potential where catechol function is oxidized in the monolayer and increased with an increase in the NADH concentration from 1 to 5 mM, and then reached to a plateau indicating a catalyzed reaction pathway. Detailed analyses revealed that the present system could be characterized by its weak stability of the intermediate compound formed and prompt reaction rate compared with the previously reported chemically modified electrode (CME) systems. We think this type of achievement should be important for the basics of biosensors that rely on dehydrogenase enzymes.

  19. Electrochemical stability of self-assembled monolayers of biphenyl based thiols studied by cyclic voltammetry and second harmonic generation

    NASA Astrophysics Data System (ADS)

    Thom, Ian; Buck, Manfred

    2005-04-01

    The reductive desorption of self-assembled monolayers (SAMs) of ω-(4'-methyl-biphenyl-4-yl)-alkanethiols (CH 3-C 6H 4-C 6H 4-(CH 2) n-SH, BP n) on Au(1 1 1) on mica was studied in 0.5 M KOH solution as a function of the length of the aliphatic spacer chain ( n = 1-6 and 12) and for two different preparations temperatures (295 K and 343 K). Second harmonic generation (SHG) was applied in situ parallel to cyclic voltammetry (CV). Odd-even differences in the structure of the BP n monolayers are clearly reflected in the electrochemical stability, as well as by the charge and shape of the desorption peak. For n = 1-5 a single desorption peak is detected whereas multiple peaks occur for BP6 similar to hexadecane thiol which was also studied for comparison. An increased preparation temperature affects the shape and width of the desorption peak but not the position. BP1 exhibits a temperature dependence different from the other homologues. The relationship between coverage monitored by SHG and desorption charge determined from the CVs is found to be linear and surprisingly independent from the details of the SAMs. The combined SHG and CV experiments suggest that capacitive and faradaic current are always closely coupled even for BP6 and hexadecane thiol which exhibit multiple desorption peaks.

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

    SciTech Connect

    Chinkap, Chung.

    1991-03-12

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

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

    PubMed

    Baldelli, Steven

    2008-11-10

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

  2. Nanometer-scale organic thin film transistors from self-assembled monolayers.

    PubMed

    Vuillaume, Dominique

    2002-01-01

    A survey of the most interesting results on nanometer-scale organic thin film transistors (nano-OTFT) is presented. Additionally, we discuss our recent results on the properties of end-group functionalized organic self-assembled monolayers and on their use in the fabrication of nanometer-scale field-effect transistors. Nanometer-scale organic transistors (channel length 30 nm) were fabricated, with a self-assembled monolayer as gate insulator. The carrier transport in these transistors, as a function of the channel length, was investigated, and a transition from a dispersive to a ballistic transport at a channel length of 200 nm was observed. On a molecular scale, alkyl monolayers functionalized at their omega-ends by aromatic moieties were prepared. A high anisotropic conductivity in molecular insulator/semiconductor heterostructures of monolayer thickness was observed. These molecular architectures provide a basis for the building blocks of molecular transistors.

  3. 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

  4. 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.

  5. Comparison of Self-Assembled Monolayers on Gold: Coadsorption of Thiols and Disulfides

    DTIC Science & Technology

    1989-02-15

    self-assembled monolayers of thiols and disulfides. Previous studies by Dubois et alt t of the adsorption of dimethyl disulfide and methanethiol on...with an activation energy of desorption of 28 kcal/mol of disulfide, but the methanethiol was only physisorbed on the gold surface and desorbed intact

  6. Cyclic Voltammetric Analysis of Ferrocene Alkanethiol Monolayer Electrode Kinetics Based on Marcus Theory

    DTIC Science & Technology

    1994-07-01

    Analysis of Ferrocene Alkanethiol Monolayer Electrode Kinectics Based on Marcus Theory & AUTHOR(S) N00014-90-J-1230 L. Tender, M. T. Carter, and R. W. Murray...immobilized monolayers in cyclic voltammetry is developed based on the Marcus free energy -rate relation. Numerical calculations show that when the...applied over-potential exceeds ca. 30% of the reorganizational energy of the electrode reaction, voltammetry predicted from Marcus theory differs from

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  8. Inflammatory cell recruitment and adhesion to methyl-terminated self-assembled monolayers: effect of implantation time.

    PubMed

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

    2005-01-01

    The contribution of methyl groups in implant-triggered inflammation was investigated in vivo using self-assembled monolayers (SAMs) of alkanethiols on gold. The CH(3)-coated implants were inserted in an air-pouch cavity induced in BALB/c mice. The in situ inflammatory response was monitored 24, 48, and 72 hours later. Inflammatory cells recovered from the air pouches were counted and observed by light microscopy. The cellularity of the implant surfaces was defined by scanning electron microscopy (SEM). In comparison with gold implants, the CH(3)-coated SAMs recruited a significantly higher number of inflammatory cells. Polymorphonuclear leukocytes (PMN) were more numerous than mononuclear cells (Mo) in the exudates recovered from the air pouches with CH(3)-coated SAMs. The opposite PMN/Mo proportion was observed in air pouches of the two control groups (mice receiving gold implants or sham-operated animals). A low density of adherent cells was seen on CH(3)-coated implants, with no significant quantitative differences during the time course of the study. In contrast, the gold-coated surfaces were covered with numerous cells during all of the 3 days of the inflammation. In conclusion, implants with CH(3) surfaces are likely to induce PMN-dominated local acute inflammation but these surfaces are not associated with a significant adherence of leukocytes to the implant.

  9. The influence of functional groups of self-assembled monolayers on fibrous capsule formation and cell recruitment.

    PubMed

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

    2006-03-15

    The contribution of the surface chemistry of an implant to the thickness of the fibrous capsule formed after implantation was herein investigated. For that, self-assembled monolayers (SAMs) of alkanethiols on gold with different terminal functional groups (COOH, OH, and CH(3)) were used. These surfaces were implanted in subcutaneous air pouches of BALB/c mice and the ensuing fibrous capsules were evaluated and compared with the initial inflammatory response caused by the implant. The thickness of the fibrous capsules that are under organization around the implant was measured 1 week after implantation by histology. Inflammatory exudates were collected from the air pouches 24 h after the implantation of SAMs and were analyzed by flow cytometry. A significant increase in the thickness of fibrous capsules was seen around implanted CH(3)-terminated SAMs, and also in gold surfaces, in comparison with the air pouch wall of sham-operated mice and of COOH- and OH-covered SAMs. The CH(3)-coated implants also recruited higher numbers of inflammatory cells; this enhancement involved a significant number of Mac-1(+) cells. Our data indicate that implant surfaces coated with CH(3) induce thick fibrous capsules and this may be the result of the stronger inflammatory effect of CH(3) in comparison with COOH or OH chemical groups.

  10. The attraction of Mac-1+ phagocytes during acute inflammation by methyl-coated self-assembled monolayers.

    PubMed

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

    2005-06-01

    We have used self-assembled monolayers (SAMs) of alkanethiolates on gold to study the contribution of methyl terminal functional groups in implant-triggered inflammation. The CH3-coated biomaterials were inserted in an air-pouch cavity of the BALB/c mouse and the in situ inflammatory response was monitored 4, 24, 48 and 72 h later. Flow cytometry was applied to define surface expression of the adhesion receptor Mac-1 (CD11b/CD18), a marker of activated leukocytes, and also of CD3 and B220 antigens (T and B lymphocytes). The CH3-coated surfaces caused a significant enhancement in the number of Mac-1+ cells in the implant. The only significant change in T and B lymphocytes was a transient increase in T cells detected 48 h after the implantation. Peak numbers of Mac-1+ phagocytes were observed 24 h after implantation. We conclude that if CH3 is present at the surface of implants, this chemical group will trigger a significant enhancement of activated phagocytes involved in the inflammatory reaction, and this phenomenon may extend the local phlogistic event.

  11. Thermo-kinetics study of laser-induced desorption of self-assembled monolayers from gold: case of laser micropatterning.

    PubMed

    Shadnam, Mohammad R; Kirkwood, Sean E; Fedosejevs, Robert; Amirfazli, A

    2005-06-23

    Laser-induced desorption of self-assembled monolayers (SAMs) from gold surfaces within context of the direct laser patterning methodology was investigated through combining results of a heat diffusion thermal model with desorption kinetics of alkanethiol SAMs. It was found that contrast plots of experimental scanning electron microscopy (SEM) images, which are correlated to surface coverage of SAMs desorbed after laser irradiation, agreed with the theoretically predicted surface composition of SAMs. The surface composition of SAM was then interpreted in terms of the wetting property of the resulting surface. The effect of incident laser beam power and size on the final spatial coverage of SAMs on the surface and feature sizes was investigated both experimentally and by modeling. Theoretical modeling and experimental evidence showed that the resulting feature sizes are wider when the surface is heated by a laser of higher power. Increasing the laser beam size results in broadening of feature sizes. Considering the correlation of the theoretical and experimental results, we concluded that the feature sizes are controllable in a predictable way (using the presented thermal-kinetics model) through varying laser beam power and beam size.

  12. Experimental and theoretical study of CO collisions with CH3- and CF3-terminated self-assembled monolayers

    NASA Astrophysics Data System (ADS)

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

    2009-02-01

    We present an experimental and theoretical study of the dynamics of collisions of the CO molecule with organic surfaces. Experimentally, we scatter CO at 60 kJ mol-1 and 30° incident angle from regular (CH3-terminated) and ω-fluorinated (CF3-terminated) alkanethiol self-assembled monolayers (SAMs) and measure the time-of-flight distributions at the specular angle after collision. At a theoretical level, we carry out classical-trajectory simulations of the same scattering process using CO/SAM potential-energy surfaces derived from ab initio calculations. Agreement between measured and calculated final translational energy distributions justifies use of the calculations to examine dynamical behavior of the gas/surface system not available directly from the experiment. Calculated state-to-state energy-transfer properties indicate that the collisions are notably vibrationally adiabatic. Similarly, translational energy transfer from and to CO rotation is relatively weak. These trends are examined as a function of collision energy and incident angle to provide a deeper understanding of the factors governing state-to-state energy transfer in gas/organic-surface collisions.

  13. 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.

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

    PubMed

    Romashov, Leonid V; Ananikov, Valentine P

    2013-12-23

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

  15. Self-Assembled, Perforated Monolayers for Enhanced Permselectivity in Membranes

    DTIC Science & Technology

    2006-11-01

    Selective Membranes. In the 1930s, Irving Langmuir and Katherine Blodgett introduced a method for fabricating monolayer and multilayer arrays of... Langmuir -Blodgett (LB) films. Here, we show how ionic cross-linking of multiply-charged surfactants (a process that we have termed, “gluing”) can yield...LB films on the order of 6 nm thick having extraordinary barrier properties, high flux, and stability. 2. Langmuir -Blodgett Films as Permeation

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

    PubMed

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

    2014-07-22

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

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

    NASA Astrophysics Data System (ADS)

    Rabara, L.; Aranyosiova, M.; Velic, D.

    2011-01-01

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

  18. 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

  19. 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.

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

    SciTech Connect

    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.

    2016-06-15

    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 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. 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.

  1. 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

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

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

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

  3. 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.

  4. Passivation of Black Phosphorus via Self-Assembled Organic Monolayers by van der Waals Epitaxy.

    PubMed

    Zhao, Yinghe; Zhou, Qionghua; Li, Qiang; Yao, Xiaojing; Wang, Jinlan

    2017-02-01

    An effective passivation approach to protect black phosphorus (BP) from degradation based on multi-scale simulations is proposed. The self-assembly of perylene-3,4,9,10-tetracarboxylic dianhydride monolayers via van der Waals epitaxy on BP does not break the original electronic properties of BP. The passivation layer thickness is only 2 nm. This study opens up a new pathway toward fine passivation of BP.

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

    PubMed

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

    2015-04-10

    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.

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

    PubMed

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

    2012-12-18

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

  7. Self-assembled monolayers improve protein distribution on holey carbon cryo-EM supports

    PubMed Central

    Meyerson, Joel R.; Rao, Prashant; Kumar, Janesh; Chittori, Sagar; Banerjee, Soojay; Pierson, Jason; Mayer, Mark L.; Subramaniam, Sriram

    2014-01-01

    Poor partitioning of macromolecules into the holes of holey carbon support grids frequently limits structural determination by single particle cryo-electron microscopy (cryo-EM). Here, we present a method to deposit, on gold-coated carbon grids, a self-assembled monolayer whose surface properties can be controlled by chemical modification. We demonstrate the utility of this approach to drive partitioning of ionotropic glutamate receptors into the holes, thereby enabling 3D structural analysis using cryo-EM methods. PMID:25403871

  8. A new organofunctional ethoxysilane self-assembly monolayer for promoting adhesion of rubber to aluminum.

    PubMed

    Wang, Fang; Xu, Juan; Luo, Heyi; Wang, Jinggang; Wang, Qian

    2009-10-12

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

  9. 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.

  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, 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

  11. 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.

  12. Ferrocene-based monolayers: Self-assembly via rigid bidentate anchor groups

    NASA Astrophysics Data System (ADS)

    Weidner, Tobias; Krohn, Bianca; Trojtza, Marta; Bruhn, Clemens; Rother, Dag; Siemeling, Ulrich; Träger, Frank

    2006-02-01

    Self-assembled monolayers of the bidentate ferrocene containing ligands diisocyanoferrocene (1), bis(diphenylphosphanyl) ferrocene (2), and diisothiocyanatoferrocene (3) have been prepared and their adsorption kinetics on gold films were characterized with optical second-harmonic generation and ellipsometry. As opposed to ferrocenylfunctionalized ligands used in earlier studies, the redox-active moieties discussed here carry two anchor groups to "pin" them to the substrate in a well-defined orientation and distance to the surface. 1 and 3 show monolayer film formation that follows first order, while film assembly of 2 is best described by a second order Langmuir kinetics.

  13. Omega-Terminated Alkanethiolate Monolayers on Surfaces of Copper, Silver and Gold Have Similar Wettabilities

    DTIC Science & Technology

    1991-12-01

    metal cxides and form oriented, oleophobic monolayers,25 0-hydroxy- and W-amino-alkanoic acids adsorb and form poorly organized films that are not wet...gold. Experinental Materials . 1l-Bromo-undecyl t-butyldimethylsilyl ether and most alkanethiols were available from pcrevious studies;6, 2 1, 4 8 ctn...er materials were obtained from Aldrich and used as received unless Specified. Octadecanethiol was distilled under reduced pressure prior to use

  14. 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.

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

    DOE PAGES

    Steinrück, H. -G.; Magerl, A.; Deutsch, 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

  16. 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.

  17. 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).

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

    NASA Astrophysics Data System (ADS)

    Zamborini, Francis Patrick

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

  19. Guided self-assembly of electrostatic binary monolayers via isothermal-isobaric control

    NASA Astrophysics Data System (ADS)

    Shestopalov, Nickolay V.; Henkelman, Graeme; Rodin, Gregory J.

    2011-10-01

    Self-assembly of a binary monolayer of charged particles is modeled using molecular dynamics and statistical mechanics. The equilibrium phase diagram for the system has three distinct phases: an ionic crystal; a geometrically ordered crystal with disordered charges; and a fluid. We show that self-assembly occurs near the phase transition between the ionic crystal and the fluid, and that the rate of ordering is sensitive to the applied pressure. By assuming an Arrhenius form for the rate of ordering, an optimality condition for the temperature and pressure is derived that maximizes the rate. Using the Clausius-Clapeyron equation, the optimal point on the phase boundary is expressed in terms of the thermodynamic changes in state variables across the boundary. The predicted optimal temperature and pressure conditions are in good agreement with numerical simulations and result in self-organization rates five times that of a simulation without applied pressure.

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  1. Structure and self-assembly of sequentially adsorbed coronene/octanethiol monolayers

    NASA Astrophysics Data System (ADS)

    Raigoza, Annette F.; Villalba, D. Andres; Kautz, Natalie A.; Kandel, S. Alex

    2010-09-01

    Scanning tunneling microscopy is used to investigate the structure of sequentially adsorbed coronene/octanethiol monolayers on Au(111). In these experiments, coronene-covered gold surfaces are exposed to octanethiol vapor. The resulting mixed monolayers are covered by close-packed octanethiol domains with clusters of coronene located within octanethiol domain boundaries. For these systems, the positions of coronene on the surface are determined by the kinetics of octanethiol monolayer formation and the local structure of the gold. The initial coverage and order of the coronene-covered surface influence the final structure of the mixed coronene/alkanethiol monolayer: deposition of coronene from the vapor phase, which creates a relatively lower coverage and higher degree of order than solution-based deposition, results in smaller coronene clusters. Statistical analysis of the locations of clusters of coronene shows that depending on the deposition parameters, coronene clusters are repelled in varying degree by upward-going and downward-going steps or are attracted to the top edges of surface step defects. In contrast to clusters, isolated coronene molecules are observed in the middle of close-packed octanethiol domains, but also appear to have an affinity for the edge of downward-going steps. We compare these results to mixed monolayers composed of C 70 and octanethiol.

  2. Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts.

    PubMed

    Hunt, Sean T; Milina, Maria; Alba-Rubio, Ana C; Hendon, Christopher H; Dumesic, James A; Román-Leshkov, Yuriy

    2016-05-20

    We demonstrated the self-assembly of transition metal carbide nanoparticles coated with atomically thin noble metal monolayers by carburizing mixtures of noble metal salts and transition metal oxides encapsulated in removable silica templates. This approach allows for control of the final core-shell architecture, including particle size, monolayer coverage, and heterometallic composition. Carbon-supported Ti(0.1)W(0.9)C nanoparticles coated with Pt or bimetallic PtRu monolayers exhibited enhanced resistance to sintering and CO poisoning, achieving an order of magnitude increase in specific activity over commercial catalysts for methanol electrooxidation after 10,000 cycles. These core-shell materials provide a new direction to reduce the loading, enhance the activity, and increase the stability of noble metal catalysts.

  3. Solvent Effect on Formation of Cysteamine Self-Assembled Monolayers on Au(111)

    NASA Astrophysics Data System (ADS)

    Lee, Sang Yun; Noh, Jaegeun; Ito, Eisuke; Lee, Haiwon; Hara, Masahiko

    2003-01-01

    Cysteamine (CA) self-assembled monolayers (SAMs) formed in various solutions on Au(111) were examined by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) to understand the solvent effect on the SAM structure. The STM study revealed that the surface structure of CA SAMs prepared in polar protic solutions was strongly influenced by immersion time, while there were no significant structural changes in the SAMs prepared in nonpolar and polar aprotic solutions. This result implies that the proticity of the solvent and the immersion time play important roles in determining the surface structures of the amino-terminated CA SAMs due to the coadsorptoin of solvent molecules onto the clean monolayers, which are stabilized by hydrogen bonding between polar protic solvents and the clean monolayers. In addition, our STM and XPS results for CA SAMs on Au(111) suggest the existence of two different structural conformations, i.e., trans and gauche conformers.

  4. Spontaneous waveguide Raman spectroscopy of self-assembled monolayers in silica micropores.

    PubMed

    Calkins, Jacob A; Peacock, Anna C; Sazio, Pier J A; Allara, David L; Badding, John V

    2011-01-18

    Advances in nanoscience are critically dependent on the ability to control and probe chemical and physical phenomena in confined geometries. A key challenge is to identify confinement structures with high surface area to volume ratios and controlled surface boundaries that can be probed quantitatively at the molecular level. Herein we report an approach for probing molecular structures within nano- to microscale pores by the application of spontaneous Raman spectroscopy. We demonstrate the method by characterization of the structural features of picomole quantities of well-organized octadecyltrichlorosilane (OTS) monolayers self-assembled on the interior pore surfaces of high aspect ratio (1 μm diameter × 1-10 cm length), near-atomically smooth silica microstructured optical fibers (MOFs). The simple Raman backscattering collection geometry employed is well suited for a wide variety of diagnostic applications as demonstrated by tracking the combustion of the hydrocarbon chains of the OTS self-assembled monolayer (SAM) and spectral confirmation of the formation of an adsorbed monolayer of human serum albumin (HSA) protein. Using this MOF Raman approach, molecular processes in precisely defined, highly confined geometries can be probed at high pressures and temperatures, with a wide range of excitation wavelengths from the visible to the near-IR, and under other external perturbations such as electric and magnetic fields.

  5. Self-Assembled Morphologies of Linear and Miktoarm Star Triblock Copolymer Monolayers.

    PubMed

    Deng, Hanlin; Li, Weihua; Qiu, Feng; Shi, An-Chang

    2017-04-12

    Monolayers of linear and miktoarm star ABC triblock copolymers with equal A and C blocks are investigated using the self-consistent field theory. The monolayers of ABC triblock copolymers are formed between two parallel surfaces that are attractive to the A and C blocks. The repulsive interaction parameter $\\chi_{AC}N$ between the A and C blocks is chosen to be weaker than the A/B and B/C interactions, quantified by $\\chi_{AB}N$ and $\\chi_{BC}N$, such that the B blocks are confined at the A/C interface, resulting in various B-domains with different geometries and arrangements. It is observed that two variables, the strength of the surface fields and the film thickness, are dominant factors controlling the self-assembly of the B blocks into various morphologies. For the linear triblock copolymers, the morphologies of B domains include disks, stripes (parallel cylinders), and hexagonal network (inverse disks). For the miktoarm star triblock copolymers, the competition between the tendency to align the junction points along a straight line and the constraint on their arrangement from the surface interactions leads to richer ordered morphologies. As a result of packing the junction points of the ABC miktoarm star copolymers, a counterintuitive phase sequence from low curvature phases to high curvature phases with increasing the length of B block is predicted. The study indicates that the self-assembly of monolayers of ABC triblock copolymers provides an interesting platform to engineer novel morphologies.

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

    PubMed

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

    2007-04-10

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

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

    DOEpatents

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

    2011-11-29

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

  8. 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.

  9. Tailoring of self-assembled monolayer for polymer light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Choi, Beomrak; Rhee, Jungsoo; Lee, Hong H.

    2001-09-01

    The choice of a self-assembled monolayer (SAM) is tailored to specifically remove water on an indium-tin oxide electrode and to reduce barrier height for long-term stability of polymer light-emitting diodes. Water, which is a major cause of long-term degradation, is shown to have entirely reversible effects on the power efficiency of the device. It is shown that the use of a SAM for the specific purposes results in a more than an order of magnitude increase in the half lifetime of the device based on poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene].

  10. 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.

  11. Mechanism for femtosecond laser pulse patterning of self-assembled monolayers on gold-coated substrates

    NASA Astrophysics Data System (ADS)

    Kirkwood, S. E.; Shadnam, M. R.; Amirfazli, A.; Fedosejevs, R.

    2007-04-01

    Self-assembled monolayer (SAM) patterning on gold thin films was performed using 800 nm, 118 fs laser pulses. SAM removal was ablative and was observed at fluences near the multishot ablation threshold for the thin gold film. Line widths six times smaller than the 2 e-folding intensity beam diameter were observed demonstrating sub-diffraction limited patterning with femtosecond lasers. Similar experimental results in air and N2 indicated that the removal process does not involve oxidation of the gold-sulfur bond as was claimed in the literature.

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

    DTIC Science & Technology

    2006-05-16

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

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

    PubMed

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

    2016-06-17

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

  14. Preparing metal-complex surfaces based on self-assembled monolayers of thiols and disulfides on gold

    NASA Astrophysics Data System (ADS)

    Dolzhikova, V. D.; Bogdanova, Yu. G.; Majouga, A. G.; Beloglazkina, E. K.; Kudrinsky, A. A.

    2017-02-01

    The complexation of monolayers of sulfur-containing ligands self-assembled on surface of gold with Co(II) and Cu(II) ions is studied using quartz crystal microbalance (QCM) and wetting measurements. The optimum conditions for obtaining metal-complex surfaces and the compositions of the resulting monolayers are determined.

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

    PubMed

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

    2014-09-07

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

  16. Effect of water-DNA interactions on elastic properties of DNA self-assembled monolayers.

    PubMed

    Domínguez, Carmen M; Ramos, Daniel; Mendieta-Moreno, Jesús I; Fierro, José L G; Mendieta, Jesús; Tamayo, Javier; Calleja, Montserrat

    2017-04-03

    DNA-water interactions have revealed as very important actor in DNA mechanics, from the molecular to the macroscopic scale. Given the particularly useful properties of DNA molecules to engineer novel materials through self-assembly and by bridging organic and inorganic materials, the interest in understanding DNA elasticity has crossed the boundaries of life science to reach also materials science and engineering. Here we show that thin films of DNA constructed through the self-assembly of sulfur tethered ssDNA strands demonstrate a Young's modulus tuning range of about 10 GPa by simply varying the environment relative humidity from 0% up to 70%. We observe that the highest tuning range occurs for ssDNA grafting densities of about 3.5 × 10(13) molecules/cm (2), where the distance between the molecules maximizes the water mediated interactions between the strands. Upon hybridization with the complementary strand, the DNA self-assembled monolayers significantly soften by one order of magnitude and their Young's modulus dependency on the hydration state drastically decreases. The experimental observations are in agreement with molecular dynamics simulations.

  17. Molecular Simulations of Gold Nanoparticles Coated With Self-Assembled Alkanethiolate Monolayers

    DTIC Science & Technology

    2006-11-01

    computed us- ing the Irving -Kirkwood pressure tensor [26]. The Irving - Kirkwood pressure tensor, equation 8, has contributions from two terms, namely the...surface tension. 6 S1 ri rj rA rB rij A B O Figure 8. Illustration of forces and posi- tion vectors used to calculate configurational term in Irving ...1000 K Surface Pressure Figure 9. Radial distribution of the normal component of the Irving -Kirkwood pressure tensor for bare 5nm gold nanoparticles at

  18. Novel Behavior in Self-Assembled Superparamagnetic Nanoparticle Monolayers at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Stanley, Jacob; Boucheron, Leandra; Dai, Yeling; Lin, Binhua; Meron, Mati; Shpyrko, Oleg

    2013-03-01

    Iron oxide nanoparticles, coated with an oleic acid ligand, have been found to form self-assembled monolayers when deposited at the air-water interface. Even for low particle densities these particles aggregate into hexagonally close-packed islands which merge into a uniform layer at higher densities. Using Grazing Incidence Small Angle X-Ray Scattering (GISAXS) we were able to measure the first through fifth order diffraction peaks. By analyzing the positions and shapes of these peaks we investigated the in-plane structure of these monolayers and characterized how the structure changes as a function of compression in a Langmuir-Blodgett trough. Since iron oxide nanoparticles are known to be super-paramagnetic, we sought to investigate the role magnetic effects may have on the interparticle interactions and ordering within the film. We performed Grazing Incidence Diffraction (GID) measurements on the film while varying an external magnetic field. We will discuss the results of our findings.

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

  1. Highly oriented, self-assembled alkanephosphate monolayers on tantalum(V) oxide surfaces

    SciTech Connect

    Brovelli, D.; Haehner, G.; Ruiz, L.

    1999-06-22

    Octadecyl phosphoric acid ester has been found to produce oriented, well-ordered monolayers on a flat tantalum(V) oxide surface, via self-assembly from a heptane/propan-2-ol solution. By means of contact angle, optical waveguide lightmode spectroscopy (OWLS), near-edge X-ray absorption fine structure spectroscopy (NEXASFS), and X-ray photoelectron spectroscopy (XPS) measurements, it has been shown that these layers closely resemble those formed by the corresponding thiol-gold system, with respect to packing density, inclination, and order. The system shows promise as an approach to functionalizing oxide surfaces with well-ordered organic monolayers, with potential applications in the fields of biochemical analysis and sensors.

  2. Smooth, aggregate-free self-assembled monolayer deposition of silane coupling agents on silicon dioxide.

    PubMed

    Diebold, Roger M; Clarke, David R

    2012-11-06

    Silane coupling agents (SCAs) are notorious for aggregating during deposition on oxide substrates, leading to nonuniform surface morphologies. To ameliorate this problem, we describe a vapor-phase deposition technique for silane coupling agents employing a spin-coated perfluoropolyether (PFPE) diffusion barrier that facilitates the formation of smooth, aggregate-free self-assembled monolayers (SAMs). Samples fabricated using PFPE barrier layers yielded SAMs exhibiting similar water contact angles, reduced water contact angle hysteresis, and a 2-fold reduction in rms roughness relative to those without a barrier. X-ray photoelectron spectroscopy confirms that the barrier layer can be completely removed after deposition, leaving behind a smooth monolayer. A basic analysis of the agglomerate separation ability of the barrier layers is discussed to understand the critical parameters involved. Generalized guidelines for selecting barrier materials are presented.

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

  4. 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.

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

    PubMed

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

    2012-10-23

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

  6. 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

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

    PubMed

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

    2013-01-28

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

  8. 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.

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

    DOE PAGES

    Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; ...

    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

  10. Nano-Engineered Electrochemical Sensors for Monitoring of Toxic Metals in Groundwater: Development of Novel Square Wave Anodic Stripping Voltammetry Electrodes Using Self Assembled Monolayers on Mesoporous Supports

    DTIC Science & Technology

    2007-03-15

    in Groundwater Development Of Novel Square Wave Anodic Stripping Voltammetry Electrodes Using Self Assembled Monolayers On Mesoporous Supports...Sensors for Monitoring of Toxic Metals in Groundwater Development Of Novel Square Wave Anodic Stripping Voltammetry Electrodes Using Self Assembled... Square Wave Anodic Stripping Voltammetry Electrodes Using Self Assembled onolayers On Mesoporous Supports SI-1267 95440Zemanian, Thomas S., and Lin

  11. 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

  12. Born-Haber cycle for monolayer self-assembly at the liquid-solid interface: assessing the enthalpic driving force.

    PubMed

    Song, Wentao; Martsinovich, Natalia; Heckl, Wolfgang M; Lackinger, Markus

    2013-10-02

    The driving force for self-assembly is the associated gain in free energy with decisive contributions from both enthalpy and entropy differences between final and initial state. For monolayer self-assembly at the liquid-solid interface, solute molecules are initially dissolved in the liquid phase and then become incorporated into an adsorbed monolayer. In this work, we present an adapted Born-Haber cycle for obtaining precise enthalpy values for self-assembly at the liquid-solid interface, a key ingredient for a profound thermodynamic understanding of this process. By choosing terephthalic acid as a model system, it is demonstrated that all required enthalpy differences between well-defined reference states can be independently and consistently assessed by both experimental and theoretical methods, giving in the end a reliable value of the overall enthalpy gain for self-assembly of interfacial monolayers. A quantitative comparison of enthalpy gain and entropy cost reveals essential contributions from solvation and dewetting, which lower the entropic cost and render monolayer self-assembly a thermodynamically favored process.

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

    SciTech Connect

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

    1993-08-01

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

  14. Positioning of CNTs over the gold substrate via self-assembled monolayer functionalization using dip-pen nanowriting

    NASA Astrophysics Data System (ADS)

    Agarwal, Pankaj B.; Sahu, Smriti; Kapse, Pooja; Gupta, Sanjeev K.

    2012-10-01

    The most important aspect of fabrication of Carbon Nanotubes (CNTs) based devices/sensors is the selective and controlled positioning of CNTs, which is a challenging issue for the researchers now a days. Here, we have presented a simple and efficient methodology for positioning of CNTs using 16-MHA self-assembled monolayers (SAMs), written over the gold substrate using Dip-pen Nanowriting (DPN). The analysis of the obtained AFM images clearly shows significant height increment of nanopatterns, which corresponds to the attachment of carbonaceous material over the written nanopatterns. Carbon Nanotubes (CNTs), Dip-pen Nanowriting (DPN), 16-MHA, 1-ODT and Self-assembled Monolayer (SAM).

  15. Comparative electrochemical and impedance studies of self-assembled rigid-rod molecular wires and alkanethiols on gold substrates.

    PubMed

    Aguiar, Francisco A; Campos, Rui; Wang, Changsheng; Jitchati, Rukkiat; Batsanov, Andrei S; Bryce, Martin R; Kataky, Ritu

    2010-11-28

    A study of the charge transfer and self-assembly characteristics of two new rigid-rod molecular wires 1 and 2 assembled on polycrystalline gold electrodes was carried out using electrochemical impedance spectroscopy and cyclic voltammetry. This class of wires have precisely controlled (ca. 1.5-2.5 nm) lengths of π-conjugation, with extended HOMO and LUMO wavefunctions. While rotations can occur around the C-C single bonds, the molecules cannot isomerise or fold due to their rigid backbone structures. The behaviour of these wires was compared with SAMs of heptanethiol (HPT) and dodecanethiol (DDT). It was found that SAMs of 1, which bears flexible hexyloxy sidechains, had randomly distributed pinholes which show microelectrode behaviour even when diluted with DDT. SAMs of 2, which do not have any sidechains, were well-organised at open-circuit potentials enabling evaluation of electron transfer kinetics assuming an average film thickness. However, impedance studies show that deviations from open circuit potentials resulted in an exponential decrease in charge transfer resistance, whereas capacitance remained constant, possibly attributable to conformational changes of the SAM. The syntheses and characterisation of the molecules is described.

  16. Self-assembled monolayers of ferrocene-substituted biphenyl ethynyl thiols on gold.

    PubMed

    Shaporenko, Andrey; Rössler, Katrin; Lang, Heinrich; Zharnikov, Michael

    2006-12-07

    Homogeneous and mixed [with biphenylthiol (BPT)] self-assembled monolayers (SAMs) of ferrocene-substituted biphenyl ethynyl thiols (Fc) were prepared on Au(111) substrates and characterized by several complementary spectroscopic techniques. The mixed films were fabricated either by subsequent immersion of the substrates into the BPT and Fc solutions or by immersion of the substrate into a mixed solution of BPT and Fc. The first procedure resulted in the preparation of high-quality mixed SAMs, in which the Fc molecules were stochastically distributed in the BPT matrix and well-separated from each other. The portion of these molecules in such films could be precisely varied from ca. 7 to 42% by selection of the immersion time in the BPT solution. The films prepared from the mixed solution exhibited a phase separation between the Fc and BPT constituents. These films contained mostly the Fc molecules ( approximately 80-90%), showing, thus, a significant deviation from the relative content of the target molecules in the primary solution (a 1:1 ratio). This finding shows that the Fc molecules, when competing with BPT, preferably adsorb onto Au(111) substrate, suggesting a significant impact of the ferrocene groups onto the structure-building interactions responsible for molecular self-assembly.

  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. 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.

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

    SciTech Connect

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

    1996-09-11

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

  20. 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.

  1. 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

  2. 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.

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

    NASA Astrophysics Data System (ADS)

    Hakamada, Masataka; Kato, Naoki; Mabuchi, Mamoru

    2016-11-01

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

  4. Effects of self-assembled monolayer and PFPE lubricant on wear characteristics of flat silicon tips.

    SciTech Connect

    Kim, H. J.; Jang, C. E.; Kim, D. E.; Kim, Y. K.; Choa, S. H.; Hong, S.; Materials Science Division; Yonsei Univ.; Samsung Adv. Inst. Science and Technology; Seoul National Univ. of Technology

    2009-01-01

    The effects of self-assembled monolayer (SAM) and perfluoropolyether (PFPE) lubricant on the wear characteristics of flat silicon tips were investigated. The wear test consisted of sliding the silicon tips fabricated on a flat silicon specimen against SAM and PFPE (Z-tetraol) coated silicon (100) wafer. The tips were slid at a low speed for about 15 km under an applied load of 39.2 {micro}N. The wear volume of the tip was obtained by measuring the tip profile using an Atomic Force Microscope (AFM). It was found that the coatings were effective in reducing the wear of the tips by an order of magnitude from 10{sup -6} to 10{sup -7}.

  5. 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.

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

    PubMed

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

    2016-11-17

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

  7. 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.

  8. 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.

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

    PubMed

    Yorganci, Emine; Akyilmaz, Erol

    2011-10-01

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

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

    PubMed

    Lederer; Godt; Howes; Kjaer; Als-Nielsen; Lahav; Wegner; Leiserowitz; Weissbuch

    2000-06-16

    Insertion of the 1,3-bis(ethynylene)benzene unit as a rigid spacer into a linear alkyl chain, thus separating the two resulting stems by 9 A. induces chain folding at the air-water interface. These folded molecules self-assemble into crystalline monolayers at this interface, with the plane of the folding unit almost perpendicular to the water surface, as determined by synchrotron grazing-incidence X-ray diffraction. Three distinct molecular shapes, of the types U, inverted U, and M, were obtained in the two-dimensional crystalline state, depending upon the number of spacer units, and the number and position of the hydrophilic groups in the molecule. The molecules form ribbons with a higher crystal coherence in the direction of stacking between the molecular ribbons, and a lower coherence along the ribbon direction. A similar molecule, but with a spacer unit that imposes a 5 A separation between alkyl chains, yields the conventional herringbone arrangement.

  11. Synthesis of Cu nanoparticles with self-assembled monolayers via inert-gas condensation.

    PubMed

    Kang, Min-Kyu; Kim, Jong-Woong; Kwak, Min-Gi; Yoon, Ho-Gyu; Kim, Young-Seok

    2011-07-01

    Cu nanoparticles with vaporized self-assembled monolayers (SAMs) for the prevention of oxidation were synthesized via inert-gas condensation (IGC). When processing the nanoparticles, the convection in the vacuum chamber was controlled using carrier gases such as Ar and He. Cu shots (2-8 mm) were used as raw materials and were evaporated via resistance heating. Octanethiol (CH3(CH2)7SH) was used for the SAMs and was introduced with the carrier gases during the process. The prepared samples were examined via scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to determine the particle sizes, the coating thicknesses of the SAMs, and the particle distribution states. The ingredients were confirmed via X-ray photoelectron spectroscopy (XPS) and energy-dispersive spectroscopy (EDS). The particle size and morphology were controlled by introducing various combinations of carrier gases, such as He, Ar and H2. Finally, stabilized Cu nanoparticles stably coated with octanethiol were successfully fabricated.

  12. 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.

  13. 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.

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

    PubMed

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

    2008-11-15

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

  15. 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.

  16. Affinity purification of proteins binding to kinase inhibitors immobilized on self-assembling monolayers.

    PubMed

    Bantscheff, Marcus; Hobson, Scott; Kuster, Bernhard

    2012-01-01

    Kinase inhibitors represent a relatively new class of drugs that offer novel therapies targeting specific -malfunctioning kinase-mediated signaling pathways in oncology and potentially inflammation. As the ATP binding sites of the ∼500 human kinases are structurally conserved and because most current drugs target the ATP binding site, there is a need to profile all the kinases that a drug may bind and/or inhibit. We have developed a chemical proteomics method that affinity purifies kinases from cell or tissue lysates using kinase inhibitors immobilized on self-assembling monolayers. The method can be applied to assess the selectivity of a given kinase inhibitor and thus to guide its preclinical or clinical development.

  17. Nanotribological properties and mechanisms of alkylthiol and biphenyl thiol self-assembled monolayers studied by AFM

    NASA Astrophysics Data System (ADS)

    Bhushan, Bharat; Liu, Huiwen

    2001-06-01

    Five kinds of alkylthiol and biphenyl thiol monolayers with different surface terminals, spacer chains, and head groups were prepared using a self-assembly method. The adhesion, friction, and wear properties were measured using atomic force microscopy (AFM). It is found that hexadecane thiol (HDT) with a-CH3 terminal exhibits the smallest adhesive force and friction force because of the terminal group with its low work of adhesion and high-compliance long carbon chain. Experimental results and a meniscus analysis indicate that the adhesive force varies linearly with work of adhesion of self-assembled monolayers (SAMs). A molecular spring model is presented to clarify the lubrication mechanisms of SAMs. The molecular spring constant, as well as the inter molecular forces, dictates the magnitude of the coefficients of friction of SAMs. 4,4'-dihydroxybiphenyl (DHBp) on Si(111), due to its rigid biphenyl spacer chains, stronger interface bonds, and a hard substrate, has the best wear resistance. For all of the SAMs, the wear depth with normal load curves show critical normal loads. Below the critical normal load, SAMs undergo orientation, while at the critical normal load SAMs undergo severe wear at the interface due to the weak interfacial bond strengths. The influence of relative humidity on adhesive and frictional forces of SAMs can be mainly understood by comparing their terminal polarization properties and work of adhesion. At higher humidity, water capillary condensation can either increase friction through increased adhesion in the contact zone or reduce friction through an enhanced water-lubricating effect.

  18. 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

    2009-12-02

    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

  19. 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…

  20. 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.

  1. m-Terphenyl thiols: rigid and bulky molecules for the formation of bioactive self-assembled monolayers on gold.

    PubMed

    Dickie, Diane A; Chan, Andy Y C; Jalali, Hanifa; Jenkins, Hilary A; Yu, Hua-Zhong; Clyburne, Jason A C

    2004-11-07

    The m-terphenyl 4-mercaptomethyl-2,6-diphenylbenzoic acid (3), was prepared and shown to form omega-carboxyl terminated self-assembled monolayers (SAMs) on gold with high surface pKa(10.1 +/- 0.2) and low density favourable for the binding of biological macromolecules.

  2. 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…

  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. 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.

  5. Self-assembled copt nanoparticles monolayer film and its IR optical properties.

    PubMed

    Zhou, Xin-Wen; Zhang, Rong-Hua; Jiang, Yan-Xia; Sun, Shi-Gang

    2010-12-01

    CoPt nanoparticles were prepared by galvanic displacement reaction, followed by a chemical reduction. The CoPt nanoparticles were spherical and the average diameter was about 33 nm obtained from the results of transmission electron microscopy (TEM), high resolution TEM and scanning electron microscopy (SEM). The results of powder X-ray diffration (XRD), energy dispersed X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) demonstrated that the surface of the product was mostly consist of Pt nanoparticles. An ordered monolayer film of CoPt nanoparticles on Si wafer was obtained by a Liquid/Liquid interface technique. In situ FTIR transmission spectral study indicates that the ordered self-assembled monolayer film of the CoPt nanoparticles shows Fano-like infrared effects, while the deposited CoPt nanoparticles exhibit normal enhanced IR adsorption. The results of the present paper demonstrated that the IR optical properties are closely related to the interactions and thickness of the nanomaterials and significant to understand the anomalous IR properties of nanometer materials.

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

    PubMed

    Ishikawa, Atsushi; Tanaka, Takuo

    2015-07-31

    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.

  7. 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

  8. Quartz crystal microbalance study of bovine serum albumin adsorption onto self-assembled monolayer-functionalized gold with subsequent ligand binding.

    PubMed

    Thourson, Scott B; Marsh, Caitlin A; Doyle, Brian J; Timpe, Shannon J

    2013-11-01

    Adsorption characteristics of the model protein bovine serum albumin (BSA) onto gold surfaces were examined using a 5 MHz quartz crystal microbalance. Protein immobilization was executed in the presence and absence of a homogenous self-assembled monolayer (SAM) of NHS-terminated alkanethiols. BSA concentrations in the range of 3.2 × 10(-6) to 1.0 × 10(-3)mol/L were found to saturate both SAM-functionalized and non-functionalized surfaces with similar densities of 450 ± 26 ng/cm(2). The lack of functionalization dependence is attributed to the large protein size relative to the density of available binding sites in either surface condition. The BSA ligand 8-anilino-1-naphthalenesulfonic acid (ANS) was subsequently introduced to the immobilized BSA to determine any effects of the protein immobilization conditions on ligand binding. The rate of ANS binding to BSA was found to increase with increasing BSA concentration used in the immobilization step. This suggests that protein concentration affects morphology and ligand binding affinity without significantly altering adsorption quantity.

  9. Structural investigation of 1,1'-biphenyl-4-thiol self-assembled monolayers on Au(111) by scanning tunneling microscopy and low-energy electron diffraction.

    PubMed

    Matei, D G; Muzik, H; Gölzhäuser, A; Turchanin, A

    2012-10-02

    Self-assembled monolayers (SAMs) of 1,1'-biphenyl-4-thiol (H-(C(6)H(4))(2)-SH) on Au(111) were prepared from solution or via vapor deposition in ultrahigh vacuum and characterized by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and X-ray photoelectron spectroscopy (XPS). In contrast to the typically observed for densely packed alkane-thiol SAMs on Au(111) (√3 × √3)R30° structure, the densely packed aromatic biphenylthiol SAMs prepared by both methods exhibit an unusual hexagonal (2 × 2) structure. Upon annealing at 100 °C, this structure evolves into the (2 × 7√3) structure resulting in the formation of highly ordered pinstripes oriented along the [1 -1 0] directions. Lower density SAMs, prepared by vapor deposition in vacuum, show mixed structures comprising the hexagonal (2 × 2) structure and two rectangular arrangements with the unit cells of (3√3 × 9) and (2√3 × 8). An extinction of the (3√3 × 9) structure in the favor of the (2√3 × 8) structure is observed upon annealing at temperatures of ~100 °C.

  10. Molecular Anchors for Self-Assembled Monolayers on ZnO: A Direct Comparison of the Thiol and Phosphic Acid Moieties

    SciTech Connect

    Perkins, C. L.

    2009-01-01

    Two of the most promising schemes for attaching organic molecules to metal oxides are based on the chemistry of the thiol and phosphonic acid moieties. We have made a direct comparison of the efficacy of these two molecular anchors on zinc oxide by comparing the chemical and physical properties of n-hexane derivatives of both. The surface properties of polycrystalline ZnO thin films and ZnO(000)-O crystals modified with 1-hexanethiol and 1-hexanephosphonic acid were examined with a novel quartz crystal microbalance (QCM)-based flow cell reactor, angle-resolved and temperature-dependent photoelectron spectroscopy, and contact angle measurements. A means of using ammonium chloride as a probe of molecule-ZnO interactions is introduced and used to ascertain the relative quality of self-assembled monolayers (SAMs) based on thiols and phosphonic acids. QCM data shows that a phosphonic acid-anchored alkyl chain only six carbons long can provide significant corrosion protection for ZnO against Bronsted acids, reducing the etch rate relative to the bare ZnO surface by a factor of more than nine. In contrast, we find that monolayers from the analogous molecule hexanethiol are more defective as revealed by their higher ionic permeability and lower hydrophobicity. Substrate attenuation X-ray photoelectron spectroscopy (XPS) experiments were used to determine the thickness of SAMs formed by the two hexane derivatives and it was found that SAMs from phosphonic acids were approximately twice as thick as those formed by hexanethiol. The thermal stability of the two linking groups was also explored and we find that previous claims of highly stable alkanethiolate monolayers on ZnO are suspect. Taken as a whole, our results indicate that the phosphonic acid moiety is preferred over thiols for the attachment of short alkyl groups to ZnO.

  11. STM imaging ortho- and para-fluorothiophenol self-assembled monolayers on Au(111).

    PubMed

    Jiang, Peng; Deng, Ke; Fichou, Denis; Xie, Si-Shen; Nion, Aymeric; Wang, Chen

    2009-05-05

    Self-assembled monolayers (SAMs) of para- and ortho-fluorothiophenol (p- and o-FTP) spontaneously formed on Au(111) substrate have been contrasted through investigation by a scanning tunneling microscope (STM) at room temperature. High-resolution STM imaging reveals that p-FTP adopts a 6 x radical3R30 degrees molecule arrangement containing six molecules. Two different kinds of p-FTP molecule dimer line structures have been formed on Au(111) by intermolecular pi-pi stacking along 112 substrate directions, besides a single p-FTP molecule line. In contrast, o-FTP molecules self-assemble into a much looser wave-like SAM, which can be described as a 5 x 3 radical3R30 degrees structure containing two molecules. Periodic density functional theory (DFT) calculations for the two systems suggest that these kinds of FTP molecules preferentially take the asymmetrical positions between 3-fold face-centered cubic (fcc) hollow and bridge sites on Au(111), tilting from the substrate surface. Theoretical simulation gives apparent average tilted angles of 58 degrees and 68 degrees for p-FTP and o-FTP with respect to the surface normal, respectively. This simulation shows that o-FTP is more inclined to lie down toward the Au(111) surface compared to p-FTP. The difference between p-FTP and o-FTP SAM structures can be qualitatively understood in terms of the variation of intermolecular dipole-dipole orientation. This suggests that, besides well-known Au-S and pi-pi interactions, electrostatic interactions including dipole-dipole, quadrupole-quadrupole, and dipole-quadrupole interactions might also play an important role in influencing the SAM structures formed by aromatic thiols with a permanent dipole moment.

  12. Scanning tunneling and atomic force microscopy probes of self-assembled, physisorbed monolayers: peeking at the peaks.

    PubMed

    Giancarlo, L C; Flynn, G W

    1998-01-01

    The imaging and control of self-assembled, physisorbed monolayers have been the subject of numerous scanning tunneling microscopy and atomic force microscopy investigations. The successful interpretation of the structures observed in scanning probe images of molecules self-assembled at liquid-solid and gas-solid interfaces has benefited greatly from recent experimental and theoretical work. These studies are converging on a general tunneling mechanism that accounts for the images of weakly bound, insulating adsorbates. Experiments in which the dynamical behavior of these monolayers has been monitored as a function of time both statically and after the introduction of an external perturbation are described, and novel studies of the selective control of monolayer structure that make use of internal and external electric fields, photons, and solvent coadsorption are reviewed.

  13. Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

    PubMed

    Harris; Baker; Van Stipdonk MJ; Crooks; Schweikert

    1999-01-01

    A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.

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

    PubMed

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

    2013-04-02

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

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

    PubMed Central

    Huang, Cheng; Moosmann, Markus; Jin, Jiehong; Heiler, Tobias; Schimmel, Thomas

    2012-01-01

    Summary A rapid and cost-effective lithographic method, polymer blend lithography (PBL), is reported to produce patterned self-assembled monolayers (SAM) on solid substrates featuring two or three different chemical functionalities. For the pattern generation we use the phase separation of two immiscible polymers in a blend solution during a spin-coating process. By controlling the spin-coating parameters and conditions, including the ambient atmosphere (humidity), the molar mass of the polystyrene (PS) and poly(methyl methacrylate) (PMMA), and the mass ratio between the two polymers in the blend solution, the formation of a purely lateral morphology (PS islands standing on the substrate while isolated in the PMMA matrix) can be reproducibly induced. Either of the formed phases (PS or PMMA) can be selectively dissolved afterwards, and the remaining phase can be used as a lift-off mask for the formation of a nanopatterned functional silane monolayer. This “monolayer copy” of the polymer phase morphology has a topographic contrast of about 1.3 nm. A demonstration of tuning of the PS island diameter is given by changing the molar mass of PS. Moreover, polymer blend lithography can provide the possibility of fabricating a surface with three different chemical components: This is demonstrated by inducing breath figures (evaporated condensed entity) at higher humidity during the spin-coating process. Here we demonstrate the formation of a lateral pattern consisting of regions covered with 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS) and (3-aminopropyl)triethoxysilane (APTES), and at the same time featuring regions of bare SiOx. The patterning process could be applied even on meter-sized substrates with various functional SAM molecules, making this process suitable for the rapid preparation of quasi two-dimensional nanopatterned functional substrates, e.g., for the template-controlled growth of ZnO nanostructures [1]. PMID:23019558

  16. 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

  17. 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.

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

    PubMed Central

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

    2016-01-01

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

  19. 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.

  20. 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).

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

    PubMed

    Hudalla, Gregory A; Murphy, William L

    2011-10-21

    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.

  2. 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.

  3. Electrically Modulated Localized Surface Plasmon around Self-Assembled-Monolayer-Covered Nanoparticles.

    PubMed

    Ma, Liyuan; Xu, Shandong; Wang, Chaoming; Wang, Haining; Zou, Shengli; Su, Ming

    2017-02-14

    This article reports the observation of electrical modulation of localized surface plasmon around self-assembled monolayer (SAM)-modified gold nanoparticles and the establishment of a new spectroscopy technique, that is, dynamic electro-optical spectroscopy (DEOS). The gold nanoparticles are deposited onto a transparent conductive substrate, and an electrical bias applied on the conductive substrate can cause shift of resonance plasmon response, where the direction of peak shift is related to the polarity of applied bias. The peak shift observed at 2.4 V is approximately ten times larger than those reported in previous work. It is postulated that significant peak shift is the result of reorientation of adsorbed water on electrode, which can change local dielectric environment of nanoparticles. An energy barrier is identified when adsorbed water molecules are turned from oxygen-down to oxygen-up. Frequency-dependent peak shifts on surface-modified gold nanoparticles show that reorientation is a fast reversible process with rich dynamics.

  4. 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.

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

    PubMed

    Paz, Yaron

    2011-01-01

    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 TiO(2) or, in a complementary manner, as TiO(2) grown on SAMs. Accordingly, the current status of knowledge regarding SAMs on TiO(2) 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.

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

    PubMed

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

    2012-10-16

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

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

    PubMed Central

    Shen, Cai

    2014-01-01

    Summary The intercalation of Cu at the interface of a self-assembled monolayer (SAM) and a Au(111)/mica substrate by underpotential deposition (UPD) is studied as a means of high resolution patterning. A SAM of 2-(4'-methylbiphenyl-4-yl)ethanethiol (BP2) prepared in a structural phase that renders the Au substrate completely passive against Cu-UPD, is patterned by modification with the tip of a scanning tunneling microscope. The tip-induced defects act as nucleation sites for Cu-UPD. The lateral diffusion of the metal at the SAM–substrate interface and, thus, the pattern dimensions are controlled by the deposition time. Patterning down to the sub-20 nm range is demonstrated. The difference in strength between the S–Au and S–Cu bond is harnessed to develop the latent Cu-UPD image into a patterned binary SAM. Demonstrated by the exchange of BP2 by adamantanethiol (AdSH) this is accomplished by a sequence of reductive desorption of BP2 in Cu free areas followed by adsorption of AdSH. The appearance of Au adatom islands upon the thiol exchange suggests that the interfacial structures of BP2 and AdSH SAMs are different. PMID:24778947

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

    PubMed

    Shen, Cai; Buck, Manfred

    2014-01-01

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

  9. 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.

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

    SciTech Connect

    Kawanago, Takamasa Oda, Shunri

    2016-01-25

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

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

    NASA Astrophysics Data System (ADS)

    Cho, Woo Kyung; Park, Sangjin; Jon, Sangyong; Choi, Insung S.

    2007-10-01

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

  12. Formation of self-assembled monolayer of curcuminoid molecules on gold surfaces

    NASA Astrophysics Data System (ADS)

    Berlanga, Isadora; Etcheverry-Berríos, Álvaro; Mella, Andy; Jullian, Domingo; Gómez, Victoria Alejandra; Aliaga-Alcalde, Núria; Fuenzalida, Victor; Flores, Marcos; Soler, Monica

    2017-01-01

    We investigated the formation of self-assembled monolayers of two thiophene curcuminoid molecules, 2-thphCCM (1) and 3-thphCCM (2), on polycrystalline gold substrates prepared by immersion of the surfaces in a solution of the molecules during 24 h. The functionalized surfaces were studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Despite the fact that both molecules have the same composition and almost the same structure, these molecules exhibit different behavior on the gold surface, which can be explained by the different positions of the sulfur atoms in the terminal aromatic rings. In the case of molecule 1, the complete formation of a SAM can be observed after 24 h of immersion. In the case of molecule 2, the transition from flat-lying to upright configuration on the surface is still in process after 24 h of immersion. This is attributed to the fact that molecule 2 have the sulfur atoms more exposed than molecule 1.

  13. 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.

  14. 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

  15. Controlled crystallization of CaCO(3) on hyperbranched polyglycerol adsorbed to self-assembled monolayers.

    PubMed

    Balz, Mathias; Barriau, Emilie; Istratov, Vladislav; Frey, Holger; Tremel, Wolfgang

    2005-04-26

    The formation of biominerals by living organisms is governed by the cooperation of soluble and insoluble macromolecules with peculiar interfacial properties. To date, most of the studies on mineralization processes involve model systems that only account for the existence of one organic matrix and thus disregard the interaction between the soluble and insoluble organic components that is crucial for a better understanding of the processes taking place at the inorganic-organic interface. We have set up a model system composed of a matrix surface, namely, a self-assembled monolayer (SAM), and a soluble component, hyperbranched polyglycerol. The model mineral calcium carbonate displays diverse polymorphism. It could be demonstrated that the phase selection of calcium carbonate is controlled by the cooperative interaction of the SAM and hyperbranched polyglycerol of different molecular weights (M(n) = 500-6000 g/mol) adsorbed to the SAM. Our studies showed that hyperbranched polyglycerol is adsorbed to polar as well as to nonpolar SAMs. This effect can be related to its highly flexible structure and its amphiphilic character. The adsorption of hyperbranched polyglycerol to the SAMs with different surface polarities resulted in the formation of aragonite for alkyl-terminated SAMs and no phase selection for carboxylate-terminated SAMs.

  16. Asphaltene adsorption onto self-assembled monolayers of mixed aromatic and aliphatic trichlorosilanes.

    PubMed

    Turgman-Cohen, Salomon; Smith, Matthew B; Fischer, Daniel A; Kilpatrick, Peter K; Genzer, Jan

    2009-06-02

    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.

  17. Asphaltene adsorption onto self-assembled monolayers of alkyltrichlorosilanes of varying chain length.

    PubMed

    Turgman-Cohen, Salomon; Fischer, Daniel A; Kilpatrick, Peter K; Genzer, Jan

    2009-06-01

    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(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 N(C) and/or an increase in SAM grafting density, sigma(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.

  18. Investigation of the mechanism of nickel electroless deposition on functionalized self-assembled monolayers.

    PubMed

    Shi, Zhiwei; Walker, Amy V

    2011-06-07

    We have investigated the seedless electroless deposition (ELD) of Ni on functionalized self-assembled monolayers (SAMs) using scanning electron and optical microscopies, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry. For all SAMs studied, the Ni deposition rate is dependent on the bath pH, deposition temperature, and complexing agent. In contrast to the physical vapor deposition of Ni on SAMs, electrolessly deposited Ni does not penetrate through the SAM. This behavior indicates that ELD is a suitable technique for the deposition of low-to-moderate reactivity on organic thin films. We demonstrate that Ni can be selectively deposited on SAMs using two different methods. First, selectivity can be imparted by the formation of Ni(II)-surface complexes. As a demonstration, we selectively deposited Ni on the -COOH terminated SAM areas of patterned -COOH/-CH(3) or -COOH/-OH terminated SAMs. Here, Ni(2+) ions form Ni(2+)-carboxylate complexes with the -COOH terminal group, which comprise the nucleation sites for subsequent metal deposition. Second, we demonstrate that nickel is selectively deposited on the -CH(3) terminated SAM areas of a patterned -OH/-CH(3) terminated SAM. In this case, the Ni(2+) ion does not specifically interact with the -CH(3) terminal group. Rather, selectivity is imparted by the interaction of the reductant, dimethylamine borane (DMAB), with the -OH and -CH(3) terminal groups.

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

    NASA Astrophysics Data System (ADS)

    Peckys, Diana B.; Melechko, Anatoli V.; Simpson, Michael L.; McKnight, Timothy E.

    2009-04-01

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

  20. Tip-based simulations of nanotribology of self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Chandross, Michael

    2005-03-01

    Friction and adhesion simulations are generally performed with opposing flat-plate geometries, ignoring the effects of load-dependent contact areas arising from curved probe tips. While some previous tip/substrate simulations do exist, they tend to either use multi-timestep approximations or unrealistically sharp tips. We present the results of true dynamical nanotribological simulations of alkylsilane self-assembled monolayers (SAMs) with realistic tip/substrate geometries. Tips matching experimental dimensions (˜ 30 nm radius of curvature) were cut out of an amorphous silica substrate (a-SiO2) and either coated with SAMs or annealed for uncoated tips. The adhesion and friction of the tip in contact with a SAM-coated amorphous a-SiO2 substrate were studied with massively parallel molecular dynamics simulations. The effects of load-dependent contact areas are compared to previous simulations with flat plate geometries, and to atomic force microscopy measurments. Sandia is a multiprogram laboratory operated by Sandia Corp., a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  1. Interfacial Mechanical Properties of Graphene on Self-Assembled Monolayers: Experiments and Simulations.

    PubMed

    Tu, Qing; Kim, Ho Shin; Oweida, Thomas J; Parlak, Zehra; Yingling, Yaroslava G; Zauscher, Stefan

    2017-03-22

    Self-assembled monolayers (SAMs) have been widely used to engineer the electronic properties of substrate-supported graphene devices. However, little is known about how the surface chemistry of SAMs affects the interfacial mechanical properties of graphene supported on SAMs. Fluctuations and changes in these properties affect the stress transfer between substrate and the supported graphene and thus the performance of graphene-based devices. The changes in interfacial mechanical properties can be characterized by measuring the out-of-plane elastic properties. Combining contact resonance atomic force microcopy experiments with molecular dynamics simulations, we show that the head group chemistry of a SAM, which affects the interfacial interactions, can have a significant effect on the out-of-plane elastic modulus of the graphene-SAM heterostructure. Graphene supported on hydrophobic SAMs leads to heterostructures stiffer than those of graphene supported on hydrophilic SAMs, which is largely due to fewer water molecules present at the graphene-SAM interface. Our results provide an important, and often overlooked, insight into the mechanical properties of substrate-supported graphene electronics.

  2. Structural and Electronic Properties of Aromatic Isocyanide Self-Assembled Monolayers on Au(111) Surface

    NASA Astrophysics Data System (ADS)

    Li, Yan; Galli, Giulia

    2007-03-01

    The search for molecular assemblies with interesting transport properties for molecular electronic devices is an active field of research. Isocyanide self-assembled monolayers (SAMs) have received some attention lately, as they may provide a better π-network for electron transport than other molecular SAMs such as benzenethiols. We have studied the structural and electronic properties of the interface between a gold surface and an aromatic isocyanide SAM, using density-functional theory in the GGA-PBE approximation. Our calculations predict a herringbone arrangement at high coverage, instead of the conventional structure with (√3x√3)R30^o periodicity. The most favorable geometry is however found at low coverage, where the interaction between molecules is negligible and the barriers between differently tilted geometries are small compared to room temperature. These results explain the disordered patterns recently observed in room temperature STM measurements and point at possible difficulties in using isocyanide SAMs for molecular devices. Our calculations also give insight into the alignment of the molecular energy levels with respect to the Fermi energy of the metal substrate, and the charge redistribution at the interface, which provide essential guide for understanding and predicting transport properties of these SAMs, in case ordering can be achieved.

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

    PubMed

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

    2016-03-09

    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.

  5. 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.

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

    PubMed

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

    2017-02-21

    Molecular dynamics simulations are conducted to investigate the underwater oleophobicity of self-assembled monolayers (SAMs) with different head groups. Simulation results show that the order of underwater oleophobicity of SAMs is methyl < amide < oligo(ethylene glycol) (OEG) < ethanolamine (ETA) < hydroxyl < mixed-charged zwitterionic. The underwater-oil contact angles (OCAs) are <133° for all nonionic hydrophilic SAMs, while the mixed-charged zwitterionic SAMs are underwater superoleophobic (OCA can reach 180°). It appears that surfaces with stronger underwater oleophobicity have better antifouling performance. Further study on the effect of different alkyl ammonium ions on mixed-charged SAMs reveals that the underwater OCAs are >143.6° for all SAMs; mixed-charged SAMs containing primary alkyl ammonium ion are likely to possess the best underwater oleophobicity for its strong hydration capacity. It seems that alkyl sulfonate anion (SO3(-)) is more hydrophilic than alkyl trimethylammonium ion (NC3(+)) for the hydrophobic methyl groups on nitrogen atoms and that the hydration of SO3(-) in mixed-charged SAMs can be seriously blocked by NC3(+). The monomer of SO3(-) should be slightly longer than that of NC3(+) to obtain better underwater oleophobicity in NC3(+)-/SO3(-)-SAMs. In addition, the underwater oleophobicity of SAMs might become worse at low grafting densities. This work systematically proves that a zwitterionic surface is more underwater oleophobic than a nonionic surface. These results will help for the design and development of superoleophobic surfaces.

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

    PubMed

    J, Meena Devi

    2015-06-01

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

  8. 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.

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

    PubMed

    Peckys, Diana B; Melechko, Anatoli V; Simpson, Michael L; McKnight, Timothy E

    2009-04-08

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

  10. STM imaging, spectroscopy and manipulation of a self-assembled PTCDI monolayer on epitaxial graphene.

    PubMed

    Yang, H; Mayne, A J; Comtet, G; Dujardin, G; Kuk, Y; Sonnet, Ph; Stauffer, L; Nagarajan, S; Gourdon, A

    2013-04-14

    Scanning Tunneling Microscopy (STM), Scanning Tunneling Spectroscopy (STS), and manipulation studies were performed on an ordered self-assembled monolayer (SAM) of N,N'-bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide) molecules on epitaxial graphene on hexagonal silicon carbide - SiC(0001). Four novel aspects of the molecular SAM on graphene are presented. Molecules adsorb in both armchair and zig-zag configurations, giving rise to six orientations of the molecular layer with respect to the underlying substrate. The interaction between the molecules and the graphene surface shifts the LUMO towards the Fermi level, inducing a charge transfer and the opening of a band gap in the graphene, with the LUMO inside. This decouples the LUMO from the surface rendering it invisible in the dI/dV spectroscopy. The HOMO only becomes visible at short tip-surface distances, as its energy lies within the band gap of the SiC substrate. Finally, the observed molecular defects are very particular, being composed exclusively of molecular dimers. These molecular dimers have a stronger interaction with the graphene than other molecules.

  11. Orientated binding of photosynthetic reaction centers on gold using Ni-NTA self-assembled monolayers.

    PubMed

    Trammell, Scott A; Wang, Leyu; Zullo, Joseph M; Shashidhar, Ranganathan; Lebedev, Nikolai

    2004-07-15

    Coupling of photosynthetic reaction centers (RCs) with inorganic surfaces is attractive for the identification of the mechanisms of interprotein electron transfer (ET) and for possible applications in construction of photo- and chemosensors. Here we show that RCs from Rhodobacter sphaeroides can be immobilized on gold surfaces with the RC primary donor looking towards the substrate by using a genetically engineered poly-histidine tag (His(7)) at the C-terminal end of the M-subunit and a Ni-NTA terminated self-assembled monolayer (SAM). In the presence of an electron acceptor, ubiquinone-10, illumination of this RC electrode generates a cathodic photocurrent. The action spectrum of the photocurrent coincides with the absorption spectrum of RC and the photocurrent decreases in response to the herbicide, atrazine, confirming that the RC is the primary source of the photoresponse. Disruption of the Ni-NTA-RC bond by imidazole leads to about 80% reduction of the photocurrent indicating that most of the photoactive protein is specifically bound to the electrode through the linker.

  12. High-performance and high-sensitivity applications of graphene transistors with self-assembled monolayers.

    PubMed

    Yeh, Chao-Hui; Kumar, Vinod; Moyano, David Ricardo; Wen, Shao-Hsuan; Parashar, Vyom; Hsiao, She-Hsin; Srivastava, Anchal; Saxena, Preeti S; Huang, Kun-Ping; Chang, Chien-Chung; Chiu, Po-Wen

    2016-03-15

    Charge impurities and polar molecules on the surface of dielectric substrates has long been a critical obstacle to using graphene for its niche applications that involve graphene's high mobility and high sensitivity nature. Self-assembled monolayers (SAMs) have been found to effectively reduce the impact of long-range scatterings induced by the external charges. Yet, demonstrations of scalable device applications using the SAMs technique remains missing due to the difficulties in the device fabrication arising from the strong surface tension of the modified dielectric environment. Here, we use patterned SAM arrays to build graphene electronic devices with transport channels confined on the modified areas. For high-mobility applications, both rigid and flexible radio-frequency graphene field-effect transistors (G-FETs) were demonstrated, with extrinsic cutoff frequency and maximum oscillation frequency enhanced by a factor of ~2 on SiO2/Si substrates. For high sensitivity applications, G-FETs were functionalized by monoclonal antibodies specific to cancer biomarker chondroitin sulfate proteoglycan 4, enabling its detection at a concentration of 0.01 fM, five orders of magnitude lower than that detectable by a conventional colorimetric assay. These devices can be very useful in the early diagnosis and monitoring of a malignant disease.

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

    PubMed

    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 degrees 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 mJm2(nMm). 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 degrees 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 degrees C or 50 min at 80 degrees 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.

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

    PubMed

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

    2010-04-01

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

  15. 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.

  16. Self-assembled monolayers as a base for immunofunctionalisation: unequal performance for protein and bacteria detection.

    PubMed

    Baldrich, Eva; Laczka, Olivier; del Campo, F Javier; Muñoz, Francesc Xavier

    2008-03-01

    Biosensor development strongly depends on the optimisation of surface functionalisation strategies. When gold surfaces are considered, immunofunctionalisation by modification of self-assembled monolayers (SAMs) is one of the preferred approaches. In this respect, SAM-based antibody (Ab) incorporation has shown better performance than Ab physisorption for the detection of proteins and small targets. Reports on bacteria detection are less frequent. In this work, we assess the performance of various SAM-based gold immunofunctionalisation strategies, currently applied to protein detection, in the field of bacteria determination. We present the results for Ab chemical conjugation on mercaptopropanoic acid and mercaptoundecanoic acid SAMs, as well as on a dextranized cysteamine SAM. All the modified surfaces studied were shown to be appropriate for the direct detection of an enzyme-labelled protein, but none succeeded in detecting a bacterial target in a sandwich assay format. Conversely, gold functionalised by Ab physisorption allowed E. coli detection when a sandwich enzyme-linked assay was carried out. The implications of bacteria size and wall complexity are discussed. These results indicate that immunofunctionalisation strategies appropriate for protein detection are not necessarily transferable to work with more complex targets such as bacteria. In this respect, Ab physisorption appears to be a suitable alternative to SAM-based gold functionalisation for bacteria detection.

  17. 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.

  18. Bioinspired catechol-terminated self-assembled monolayers with enhanced adhesion properties.

    PubMed

    Guardingo, Mireia; Bellido, Elena; Miralles-Llumà, Rosa; Faraudo, Jordi; Sedó, Josep; Tatay, Sergio; Verdaguer, Albert; Busqué, Felix; Ruiz-Molina, Daniel

    2014-04-24

    The role of the catechol moiety in the adhesive properties of mussel proteins and related synthetic materials has been extensively studied in the last years but still remains elusive. Here, a simplified model approach is presented based on a self-assembled monolayer (SAM) of upward-facing catechols thiol-bound to epitaxial gold substrates. The orientation of the catechol moieties is confirmed by spectroscopy, which also showed lack of significant amounts of interfering o-quinones. Local force-distance curves on the SAM measured by atomic force microscopy (AFM) shows an average adhesion force of 45 nN, stronger than that of a reference polydopamine coating, along with higher reproducibility and less statistical dispersion. This is attributed to the superior chemical and topographical homogeneity of the SAM coating. Catechol-terminated SAMs are also obtained on high-roughness gold substrates that show the ability to assemble magnetic nanoparticles, despite their lack of enhanced adhesion at the molecular level. Finally, the influence of the catechol group on the formation and quality of the SAM is explored both theoretically (molecular dynamics simulations) and experimentally using direct-write AFM lithography.

  19. 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.

  20. Charge Retention by Peptide Ions Soft-Landed onto Self-Assembled Monolayer Surfaces

    SciTech Connect

    Laskin, Julia; Wang, Peng; Hadjar, Omar; Futrell, Jean H.; Alvarez, Jormarie; Cooks, Robert G.

    2007-08-01

    Soft-landing of singly and doubly protonated peptide ions onto three self-assembled monolayer surfaces (SAMs) was performed using a novel ion deposition instrument constructed in our laboratory and a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially designed for studying collisions of large ions with surfaces.. Modified surfaces were analyzed using in situ 2 keV Cs+ secondary ion mass spectrometry or ex situ 15 keV Ga+ time-of-flight secondary ion mass spectrometry (ToF-SIMS). The results demonstrate that a fraction of multiply protonated peptide ions retain more than one proton following soft-landing on the FSAM surface. [M+2H]2+ ions observed in FT-ICR SIMS spectra are produced by desorption of multiply charged ions from the surface, while re-ionization of singly protonated ions or neutral peptides is a source of [M+2H]2+ ions in Tof-SIMS spectra. Differences in neutralization efficiency of soft-landed ions following exposure of surfaces to laboratory air has a measurable effect on the results of ex situ ToF-SIMS analysis of soft-landed ions on SAM surfaces.

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

    PubMed

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

    2014-04-15

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

  2. 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.

  3. Evaporation dynamics of microdroplets on self-assembled monolayers of dialkyl disulfides.

    PubMed

    Li, Guangfen; Flores, Susana Moreno; Vavilala, Chandrasekhar; Schmittel, Michael; Graf, Karlheinz

    2009-12-01

    We present a study of the static wettability and evaporation dynamics of sessile microdroplets of water on self-assembled monolayers (SAMs) prepared with unsymmetric dialkyl disulfides CH(3)-(CH(2))(11+m)-S-S-(CH(2))(11)-OH (m = 0, +/- 2, +/- 4, +/- 6) on gold-covered mica. The advancing and receding contact angles decrease linearly with increasing hydrophilicity of the SAM. The latter was changed either via the molar ratio or via the chain length of the hydroxyl-terminated alkyl chains in the monolayer. In contrast to SAMs made of thiols, the contact angle hysteresis was 10 degrees for all disulfides, irrespective of their chain lengths. During evaporation of single droplets, a transition from pinning to constant contact angle mode was observed. The transition time between the modes increases with the surface hydrophilicity, leading to longer pinning. This way, the time for complete droplet evaporation decreases by approximately 30% owing to the fact that during pinning the overall droplet area stays large for a longer time. For single droplets the measured total evaporation times agree well with the calculated ones, showing the validity of the standard evaporation model for both evaporation modes. In contrast to the results for single droplets, many droplets with different initial volumes show a power-law dependence on the total evaporation time with an exponent different from 1.5 as expected from the standard model. For disulfides with m not equal 0, the exponent is in the range of 1.40-1.47 increasing with the surface hydrophilicity. For the SAMs with m = 0 the exponent increases up to 1.61 for the most hydrophilic surface. We explain this deviation from the standard evaporation model with the presence of a liquid precursor film around the droplet, which either enhances or decelerates evaporation. Our results suggest that SAMs of dialkyl disulfides offer the possibility to tune the wettability of gold surfaces in a more controlled way than thiols do.

  4. 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

  5. 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}.

  6. 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).

  7. 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.

  8. 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.

  9. Site-selective biofunctionalization of aluminum nitride surfaces using patterned organosilane self-assembled monolayers.

    PubMed

    Chiu, Chi-Shun; Lee, Hong-Mao; Gwo, Shangjr

    2010-02-16

    Surface biochemical functionalization of group-III nitride semiconductors has recently attracted much interest because of their biocompatibility, nontoxicity, and long-term chemical stability under demanding physiochemical conditions for chemical and biological sensing. Among III-nitrides, aluminum nitride (AlN) and aluminum gallium nitride (AlGaN) are particularly important because they are often used as the sensing surfaces for sensors based on field-effect transistor or surface acoustic wave (SAW) sensor structures. To demonstrate the possibility of site-selective biofunctionalization on AlN surfaces, we have fabricated two-dimensional antibody micropatterns on AlN surfaces by using patterned self-assembled monolayer (SAM) templates. Patterned SAM templates are composed of two types of organosilane molecules terminated with different functional groups (amino and methyl), which were fabricated on AlN/sapphire substrates by combining photolithography, lift-off process, and self-assembly technique. Because the patterned SAM templates have different surface properties on the same surface, clear imaging contrast of SAM micropatterns can be observed by field-emission scanning electron microscopy (FE-SEM) operating at a low accelerating voltage in the range of 0.5-1.5 kV. Furthermore, the contrast in surface potential of the binary SAM microstructures was confirmed by selective adsorption of negatively charged colloidal gold nanoparticles (AuNPs). The immobilization of AuNPs was limited on the positively charged amino-terminated regions, while they were scarcely found on the surface regions terminated by methyl groups. In this work, selective immobilization of green fluorescent protein (GFP) antibodies was demonstrated by the specific protein binding of enhanced GFP (EGFP) labeling. The observed strong fluorescent signal from antibody functionalized regions on the SAM-patterned AlN surface indicates the retained biological activity of specific molecular recognition

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

    PubMed

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

    2015-07-07

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

  11. Required Equipment for Photo-Switchable Donor-Acceptor (D-A) Dyad Interfacial Self-Assembled Monolayers for Organic Photovoltaic Cells

    DTIC Science & Technology

    2014-01-24

    Effects on interfacial morphology and charge injection in organic light-emitting diodes. Thin Solid Films 2007, 515 (5), 2833-2841. 3. Lee, J.; Jung...HBCU) - Required Equipment for Photo-switchable Donor- Acceptor (D-A) Dyad Interfacial Self-Assembled Monolayers for Organic Photovoltaic Cells...Equipment for Photo-switchable Donor-Acceptor (D-A) Dyad Interfacial Self-Assembled Monolayers for Organic Photovoltaic Cells" N/A FA9550-12-1-0468 CFDA

  12. Photochemical CVD of Ru on functionalized self-assembled monolayers from organometallic precursors.

    PubMed

    Johnson, Kelsea R; Arevalo Rodriguez, Paul; Brewer, Christopher R; Brannaka, Joseph A; Shi, Zhiwei; Yang, Jing; Salazar, Bryan; McElwee-White, Lisa; Walker, Amy V

    2017-02-07

    Chemical vapor deposition (CVD) is an attractive technique for the metallization of organic thin films because it is selective and the thickness of the deposited film can easily be controlled. However, thermal CVD processes often require high temperatures which are generally incompatible with organic films. In this paper, we perform proof-of-concept studies of photochemical CVD to metallize organic thin films. In this method, a precursor undergoes photolytic decomposition to generate thermally labile intermediates prior to adsorption on the sample. Three readily available Ru precursors, CpRu(CO)2Me, (η(3)-allyl)Ru(CO)3Br, and (COT)Ru(CO)3, were employed to investigate the role of precursor quantum yield, ligand chemistry, and the Ru oxidation state on the deposition. To investigate the role of the substrate chemistry on deposition, carboxylic acid-, hydroxyl-, and methyl-terminated self-assembled monolayers were used. The data indicate that moderate quantum yields for ligand loss (φ ≥ 0.4) are required for ruthenium deposition, and the deposition is wavelength dependent. Second, anionic polyhapto ligands such as cyclopentadienyl and allyl are more difficult to remove than carbonyls, halides, and alkyls. Third, in contrast to the atomic layer deposition, acid-base reactions between the precursor and the substrate are more effective for deposition than nucleophilic reactions. Finally, the data suggest that selective deposition can be achieved on organic thin films by judicious choice of precursor and functional groups present on the substrate. These studies thus provide guidelines for the rational design of new precursors specifically for selective photochemical CVD on organic substrates.

  13. A photo-aligned self-assembled monolayer for polymer transistors

    NASA Astrophysics Data System (ADS)

    Kawaguchi, Tatsuhiko; Okura, Takehiro; Suenaga, Yuusuke; Hanasaki, Tomonori; Fujieda, Ichiro

    2012-02-01

    There is a continuing interest in improving electrical characteristics of an organic thin-film transistor (OTFT). One can accomplish this by controlling molecular orientations of semiconductor materials in the vicinities of an insulating layer as well as an electrode material. First, it is widely known that a self-assembled monolayer (SAM) is effective for this purpose. Second, a thin structured layer underneath an organic semiconductor material is effective for aligning the organic molecules in a specific direction. Irradiating azobenzene compounds with ultraviolet light converts trans isomers into cis-forms. When exposed to linearly-polarized ultraviolet light, the difference in the absorbance between the two isomers leads to a state where the azobenzene molecules are aligned perpendicular to the polarization direction of the ultraviolet light. Such a photo-alignment layer results in anisotropic charge transport in an OTFT and the current flow along the channel direction is enhanced. In principle, we expect that combination of these two technologies (SAM and photo-alignment) would further improve the current flow in OTFTs. In experiment, we synthesized a compound 4-(3- (trichlorosilyl)propoxy)azobenzene (Azo-SAM) and used this material to align an organic semiconductor poly(3- hexylthiophene) (P3HT). We formed the Azo-SAM on a glass substrate, spin-coated a P3HT/1, 2, 4-trichlorobenzene solution, annealed in nitrogen atmosphere and exposed it to linearly-polarized ultraviolet light. Absorbance spectroscopy in the visible range revealed anisotropy in the two samples exposed to the two polarization directions orthogonal to each other. Fabrication of organic transistors with this photo-alignment SAM is under way.

  14. Unusual Aggregates from the Ozone Oxidation of Self-Assembled Monolayers

    NASA Astrophysics Data System (ADS)

    McIntire, T. M.; Lea, A.; Gaspar, D. J.; Jaitly, N.; Dubowski, Y.; Li, Q.; Finlayson-Pitts, B. J.

    2005-12-01

    Airborne particles are important in visibility, climate, human health and atmospheric reactions. Changes in the chemical and physical properties of organics associated with airborne dust particles, which are distributed globally, and which undergo oxidation to polar species during transport, are of considerable interest. In this work we report the first observation of large organic aggregates on surfaces generated by the ozone oxidation of terminal alkene self-assembled monolayers (SAMs) used as proxies for organics on airborne dust particles. SAMs with a terminal alkene group were generated on silicon substrates and reacted at room temperature with ~ 1 ppm gaseous ozone. A combination of experimental techniques including atomic force microscopy, scanning electron microscopy, Auger microprobe, time-of-flight secondary ion mass spectrometry, and transmission FTIR, were used to study the surface composition and morphology before and after oxidation. While the unreacted SAM was quite smooth, on the oxidized surface there were large (micron-size) organic aggregates and the surrounding substrate became depleted of carbon. This highly unusual result establishes that the mechanism of ozonolysis of alkene SAMs involves polymerization, likely induced by secondary reactions of the Criegee intermediate (CI). For that reason, formation of polymers under atmospheric conditions may be more common than previously recognized. The uptake of water was not increased upon oxidation of these films, in contrast to current expectations but consistent with the exposure of the substrate during reaction. The implications for SAM reactions and stability in air, ozonolysis of alkenes on surfaces, and for the oxidation of alkenes on airborne dust particles are discussed.

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

    PubMed

    Laskin, Julia; Hu, Qichi

    2017-03-13

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

  16. Thermal and photochemical oxidation of self-assembled monolayers on alumina particles exposed to nitrogen dioxide.

    PubMed

    Raff, Jonathan D; Szanyi, János; Finlayson-Pitts, Barbara J

    2011-01-14

    Alumina is an important component of airborne dust particles as well as of building materials and soils found in the tropospheric boundary layer. While the uptake and reactions of oxides of nitrogen and their photochemistry on alumina have been reported in the past, little is known about the chemistry when organics are also present. Fourier transform infrared (FTIR) spectroscopy at ∼23 °C was used to study reactions of NO(2) on γ-Al(2)O(3) particles that had been derivatized using 7-octenyltrichlorosilane to form a self-assembled monolayer (SAM). For comparison, the reactions with untreated γ-Al(2)O(3) were also studied. In both cases, the particles were exposed to water vapor prior to NO(2) to provide adsorbed water for reaction. As expected, surface-bound HONO, NO(2)(-), and NO(3)(-) were formed. Surprisingly, oxidation of the organic by surface-bound nitrogen oxides was observed in the dark, forming organo-nitrogen products identified as nitronates (R(2)C[double bond, length as m-dash]NO(2)(-)). Oxidation was more rapid under irradiation (λ > 290 nm) and formed organic nitrates and carbonyl compounds and/or peroxy nitrates in addition to the products observed in the dark. Mass spectrometry of the gas phase during irradiation revealed the production of NO, CO(2), and CO. These studies provide evidence for oxidation of organic compounds on particles and boundary layer surfaces that are exposed to air containing oxides of nitrogen, as well as new pathways for the formation of nitrogen-containing compounds on these surfaces.

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Laskin, Julia; Hu, Qichi

    2017-03-01

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

  19. Photochemical CVD of Ru on functionalized self-assembled monolayers from organometallic precursors

    NASA Astrophysics Data System (ADS)

    Johnson, Kelsea R.; Arevalo Rodriguez, Paul; Brewer, Christopher R.; Brannaka, Joseph A.; Shi, Zhiwei; Yang, Jing; Salazar, Bryan; McElwee-White, Lisa; Walker, Amy V.

    2017-02-01

    Chemical vapor deposition (CVD) is an attractive technique for the metallization of organic thin films because it is selective and the thickness of the deposited film can easily be controlled. However, thermal CVD processes often require high temperatures which are generally incompatible with organic films. In this paper, we perform proof-of-concept studies of photochemical CVD to metallize organic thin films. In this method, a precursor undergoes photolytic decomposition to generate thermally labile intermediates prior to adsorption on the sample. Three readily available Ru precursors, CpRu(CO)2Me, (η3-allyl)Ru(CO)3Br, and (COT)Ru(CO)3, were employed to investigate the role of precursor quantum yield, ligand chemistry, and the Ru oxidation state on the deposition. To investigate the role of the substrate chemistry on deposition, carboxylic acid-, hydroxyl-, and methyl-terminated self-assembled monolayers were used. The data indicate that moderate quantum yields for ligand loss (φ ≥ 0.4) are required for ruthenium deposition, and the deposition is wavelength dependent. Second, anionic polyhapto ligands such as cyclopentadienyl and allyl are more difficult to remove than carbonyls, halides, and alkyls. Third, in contrast to the atomic layer deposition, acid-base reactions between the precursor and the substrate are more effective for deposition than nucleophilic reactions. Finally, the data suggest that selective deposition can be achieved on organic thin films by judicious choice of precursor and functional groups present on the substrate. These studies thus provide guidelines for the rational design of new precursors specifically for selective photochemical CVD on organic substrates.

  20. Low adhesion, non-wetting phosphonate self-assembled monolayer films formed on copper oxide surfaces.

    PubMed

    Hoque, E; DeRose, J A; Bhushan, B; Hipps, K W

    2009-07-01

    Self-assembled monolayer (SAM) films have been formed on oxidized copper (Cu) substrates by reaction with 1H,1H,2H,2H-perfluorodecylphosphonic acid (PFDP), octadecylphosphonic acid (ODP), decylphosphonic acid (DP), and octylphosphonic acid (OP) and then investigated by X-ray photoelectron spectroscopy (XPS), contact angle measurement (CAM), and atomic force microscopy (AFM). The presence of alkyl phosphonate molecules, PFDP, ODP, DP, and OP, on Cu were confirmed by CAM and XPS analysis. No alkyl phosphonate molecules were seen by XPS on unmodified Cu as a control. The PFDP/Cu and ODP/Cu SAMs were found to be very hydrophobic having water sessile drop static contact angles of more than 140 degrees , while DP/Cu and OP/Cu have contact angles of 119 degrees and 76 degrees , respectively. PFDP/Cu, ODP/Cu, DP/Cu, and OP/Cu SAMs were studied by friction force microscopy, a derivative of AFM, to better understand their micro/nanotribological properties. PFDP/Cu, ODP/Cu, and DP/Cu had comparable adhesive force, which is much lower than that for unmodified Cu. ODP/Cu had the lowest friction coefficient followed by PFDP/Cu, DP/Cu, and OP/Cu while unmodified Cu had the highest. XPS data gives some indication that a bidentate bond forms between the alkyl phosphonate molecules and the oxidized Cu surface. Hydrophobic phosphonate SAMs could be useful as corrosion inhibitors in micro/nanoelectronic devices and/or as promoters for anti-wetting, low adhesion surfaces.

  1. Molecular simulation studies of the structure of phosphorylcholine self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Zheng, Jie; He, Yi; Chen, Shengfu; Li, Lingyan; Bernards, Matthew T.; Jiang, Shaoyi

    2006-11-01

    We report a study of the structure of phosphorylcholine self-assembled monolayers (PC-SAMs) on Au(111) surfaces using both molecular mechanics (MM) and molecular dynamics (MD) simulation techniques. The lattice structure (i.e., packing densities and patterns) of the PC chains was determined first, by examining the packing energies of different structures by MM simulations in an implicit solvent. The chain orientation (i.e., antiparallel and parallel arrangements of the PC head groups) was then evaluated. The initial azimuthal angles of the PC chains were also adjusted to ensure that the optimal lattice structure was found. Finally, the two most probable lattice structures were solvated with explicit water molecules and their energies were compared after 1.5ns of MD simulations to verify the optimal structures obtained from MM. We found that the optimal lattice structure of the PC-SAM corresponds to a √7×√7 R19° lattice structure (i.e., surface coverage of 50.4Å2/molecule) with a parallel arrangement of the head groups. The corresponding thickness of the optimal PC-SAM is 13.4Å which is in agreement with that from experiments. The head groups of the PC chains are aligned on the surface in such a way that their dipole components are minimized. The P →N vector of the head groups forms an angle of 82° with respect to the surface normal. The tilt direction of molecular chains was observed to be towards their next nearest neighbor.

  2. Surface modification of functional self-assembled monolayers on 316L stainless steel via lipase catalysis.

    PubMed

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

    2006-01-31

    Lipase catalyzed esterification of therapeutic drugs to functional self-assembled monolayers (SAMs) on 316L stainless steel (SS) after assembly has been demonstrated. SAMs of 16-mercaptohexadecanoic acid (-COOH SAM) and 11-mercapto-1-undecanol (-OH SAM) were formed on 316L SS, and lipase catalysis was used to attach therapeutic drugs, perphenazine and ibuprofen, respectively, on these SAMs. The reaction was carried out in toluene at 60 degrees C for 5 h using Novozyme-435 as the biocatalyst. The FTIR spectra after surface modification of -OH SAMs showed the presence of the C=O stretching bands at 1745 cm(-1), which was absent in the FTIR spectra of -OH SAMs. Similarly, the FTIR spectra after the reaction of the -COOH SAM with perphenazine showed two peaks in the carbonyl region, a peak at 1764 cm(-1), which is the representative peak for the C=O stretching for esters. The second peak at 1681 cm(-1) is assigned to the C=O stretching of the remaining unreacted terminal COOH. XPS spectra after lipase catalysis with ibuprofen showed a photoelectron peak evolving at 288.5 eV which arises from the carbon (C=O) of the carboxylic acid of the drug (ibuprofen). Similarly for -COOH SAMs, after esterifiation we see a small, photoelectron peak evolving at 286.5 eV which corresponds to the C in the methylene groups adjacent to the oxygen (C-O), which should evolve only after the esterification of perphenazine with the -COOH SAM. Thus, lipase catalysis provides an alternate synthetic methodology for surface modification of functional SAMs after assembly.

  3. Direct laser patterning of self-assembled monolayer using elliptical laser beams: A theoretical parametric study

    NASA Astrophysics Data System (ADS)

    Zhang, Martin Y.; Shadnam, Mohammad Reza; Amirfazli, A.

    2011-11-01

    A theoretical quantitative analysis of processing parameters for application of an elliptical laser beam to achieve maximum patterning area is the focus of this study. Direct laser patterning (DLP) of self-assembled monolayers (SAM) is achieved by localized heating of the sample above the SAM desorption temperature. Through use of elliptical laser beams in the present work, three goals are achieved by analyzing the heat diffusion model and related thermo-kinetics model: (1) optimal working conditions (combination of laser power, scanning velocity and aspect ratio) for DLP to produce maximum feature size, or highest processing velocity at a given power; (2) identification of conditions that reduces the potential thermal damage to the substrate; (3) shedding light on issues related to uniformity or homogeneity of heating a substrate using an elliptical laser beam. A heat diffusion model is employed to provide the resulting surface temperature caused by elliptical laser beams, and the coupled thermo-kinetics model is used to determine the final SAM coverage generated by DLP. Parametric analysis revealed that 70-150 mW can be used to pattern feature sizes in the range of 2-10 times of equivalent circular beam size. It is also found that each elliptical laser beam has a unique optimal aspect ratio to result in the widest feature size for a given laser power and scanning velocity. The edge transition width increases with an increase of the aspect ratio. Keeping the aspect ratio of elliptical laser beam small (i.e. β<20), a sharp edge definition could be obtained; if an aspect ratio larger than 30 is used, a surface with gradual edge definition could be obtained.

  4. 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.

  5. 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

    2016-04-07

    Soft landing of mass-selected ions onto surfaces often results in partial loss of charge that may affect the structure and reactivity of deposited species. In this study, Keggin phosphotungstate anions in two selected charge states, 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.

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

    SciTech Connect

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

    2016-01-01

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

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

    SciTech Connect

    Hu, Qichi; Laskin, Julia

    2016-06-09

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

  8. Catalytic self-assembled monolayers on Au nanoparticles: the source of catalysis of a transphosphorylation reaction.

    PubMed

    Zaupa, Giovanni; Mora, Claudia; Bonomi, Renato; Prins, Leonard J; Scrimin, Paolo

    2011-04-18

    The catalytic activity of a series of Au monolayer protected colloids (Au MPCs) containing different ratios of the catalytic unit triazacyclononane⋅Zn(II) (TACN⋅Zn(II) ) and an inert triethyleneglycol (TEG) unit was measured. The catalytic self-assembled monolayers (SAMs) are highly efficient in the transphosphorylation of 2-hydroxy propyl 4-nitrophenyl phosphate (HPNPP), an RNA model substrate, exhibiting maximum values for the Michaelis-Menten parameters k(cat) and K(M) of 6.7×10(-3) s(-1) and 3.1×10(-4) M, respectively, normalized per catalytic unit. Despite the structural simplicity of the catalytic units, this renders these nanoparticles among the most active catalysts known for this substrate. Both k(cat) and K(M) parameters were determined as a function of the mole fraction of catalytic unit (x(1)) in the SAM. Within this nanoparticle (NP) series, k(cat) increases up till x(1) ≈0.4, after which it remains constant and K(M) decreases exponentially over the range studied. A theoretical analysis demonstrated that these trends are an intrinsic property of catalytic SAMs, in which catalysis originates from the cooperative effect between two neighboring catalytic units. The multivalency of the system causes an increase of the number of potential dimeric catalytic sites composed of two catalytic units as a function of the x(1) , which causes an apparent increase in binding affinity (decrease in K(M)). Simultaneously, the k(cat) value is determined by the number of substrate molecules bound at saturation. For values of x(1) >0.4, isolated catalytic units are no longer present and all catalytic units are involved in catalysis at saturation. Importantly, the observed trends are indicative of a random distribution of the thiols in the SAM. As indicated by the theoretical analysis, and confirmed by a control experiment, in case of clustering both k(cat) and K(M) values remain constant over the entire range of x(1) .

  9. Mechanical properties of H2Pc self-assembled monolayers at the single molecule level by noncontact atomic force microscopy.

    PubMed

    Mao, Han-Qing; Li, Na; Chen, Xi; Xue, Qi-Kun

    2012-02-29

    The mechanical properties of molecular self-assembled monolayers (SAMs) play an important role in understanding the interactions between molecules in the self-assembly, the interactions between molecules and substrate, and thus the formation mechanism of SAMs. Using a high-resolution noncontact atomic force microscope (NC-AFM) combined with a scanning tunneling microscope (STM), we have successfully obtained the sub-molecular resolution of a H(2)Pc self-assembled monolayer grown on a Pb(111) surface. A 2 × 2 superstructure was observed in both AFM and STM topographic images. The lateral critical force of removing a H(2)Pcmolecule from its SAM and moving a single H(2)Pc molecule on Pb(111) were measured. An oscillation of the critical force along the edge of the H(2)Pc SAM with a period of two molecular sites was observed, which can be attributed to the 2 × 2 superstructure. The lateral critical force caused by intermolecular interaction was found to be 25 pN on average and is typically two times larger than the molecule-substrate interaction.

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

    NASA Astrophysics Data System (ADS)

    Lim, Taekyung; Han, Junebeom; Seo, Keumyoung; Joo, Min-Kyu; Kim, Jae-Sung; Kim, Wung-Yeon; Kim, Gyu-Tae; Ju, Sanghyun

    2015-04-01

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

  11. 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.

  12. Thermodynamic investigations using molecular dynamics simulations with potential of mean force calculations for cardiotoxin protein adsorption on mixed self-assembled monolayers.

    PubMed

    Hung, Shih-Wei; Hsiao, Pai-Yi; Lu, Ming-Chang; Chieng, Ching-Chang

    2012-10-25

    Understanding protein adsorption onto solid surfaces is of critical importance in the field of bioengineering, especially for applications such as medical implants, diagnostic biosensors, drug delivery systems, and tissue engineering. This study proposed the use of molecular dynamics simulations with potential of mean force (PMF) calculations to identify and characterize the mechanisms of adsorption of a protein molecule on a designed surface. A set of model systems consisting of a cardiotoxin (CTX) protein and mixed self-assembled monolayer (SAM) surfaces were used as examples. The set of mixed SAM surfaces with varying topographies were created by mixing alkanethiol chains of different lengths. The results revealed that CTX proteins underwent similar conformal changes upon adsorption onto the various mixed SAMs but showed distinctive characteristics in free energy profiles. Enhancement of the adsorption affinity, i.e., the change in free energy of adsorption, for mixed SAMs was demonstrated by using atomic force microscopic measurements. A component analysis conducted to quantify the physical mechanisms that promoted CTX adsorption revealed contributions from both SAMs and the solvent. Further component analyses of thermodynamic properties, such as the free energy, enthalpy, and entropy, indicated that the contribution from SAMs was driven by enthalpy, and the contribution from the solvent was driven by entropy. The results indicated that CTX adsorption was an entropy-driven process, and the entropic component from the solvent, i.e., the hydrophobic interaction, was the major driving force for CTX adsorption onto SAMs. The study also concluded that the surfaces composed of mixtures of SAMs with different chain lengths promoted the adsorption of CTX protein.

  13. Infrared spectroelectrochemical characterization of ferrocene-terminated alkanethiolate monolayers at gold

    SciTech Connect

    Popenoe, D.D.; Deinhammer, R.S.; Porter, M.D. Iowa State Univ., Ames, IA )

    1992-10-01

    Cyclic voltammetry and in situ infrared reflection-absorption spectroscopy with electrochemical modulation were applied to the study of monolayers self-assembled from 11-mercaptoundecyl ferrocene-carboxylate (FcCOOC[sub 11]SH) at gold. Voltammetry was used to assess both the reactivity and stability of the surface film in various aqueous electrolytes. The results of these studies indicated that the ferrocenyl monolayers are relatively unstable at pH > 2, except when perchlorate is the dominant anion present. A large change in double-layer capacitance observed upon oxidation of the ferrocenyl end group was attributed to the creation of cationic sites in the diffuse layer. Compositional and structural correlations between the monolayer and the redox chemistry of the ferrocenyl end group were probed using the in situ spectroscopic technique. The features observed in the differential spectra of the oxidized form of the film were ascribed to changes in the bond strengths of the adsorbate as a result of generation of a ferricinium ion. No detectable changes in orientation of the polymethylene chains as a function of applied voltage were observed. The spectral data also suggest that the redox chemistry leads to a reorientation of the water molecules in the region near the ferrocenyl end group. Vibrational mode assignments for FcCOOC[sub 11]SH, based on studies of several analogs with different alkoxy groups, are presented along with infrared spectra and band assignments for several isotopically labeled ferrocenyl esters (i.e., ethyl ferrocenecarboxylate, ethyl-d[sub 5] ferrocenecarboxylate, and 2-(dimethylamino)ethyl ferrocenecarboxylate). 55 refs., 7 figs., 2 tabs.

  14. Mimicking protein-protein electron transfer: voltammetry of Pseudomonas aeruginosa azurin and the Thermus thermophilus Cu(A) domain at omega-derivatized self-assembled-monolayer gold electrodes.

    PubMed

    Fujita, Kyoko; Nakamura, Nobufumi; Ohno, Hiroyuki; Leigh, Brian S; Niki, Katsumi; Gray, Harry B; Richards, John H

    2004-11-03

    Well-defined voltammetric responses of redox proteins with acidic-to-neutral pI values have been obtained on pure alkanethiol as well as on mixed self-assembled-monolayer (SAM) omega-derivatized alkanethiol/gold bead electrodes. Both azurin (P. aeruginosa) (pI = 5.6) and subunit II (Cu(A) domain) of ba(3)-type cytochrome c oxidase (T. thermophilus) (pI = 6.0) exhibit optimal voltammetric responses on 1:1 mixtures of [H(3)C(CH(2))(n)()SH + HO(CH(2))(n)()SH] SAMs. The electron transfer (ET) rate vs distance behavior of azurin and Cu(A) is independent of the omega-derivatized alkanethiol SAM headgroups. Strikingly, only wild-type azurin and mutants containing Trp48 give voltammetric responses: based on modeling, we suggest that electronic coupling with the SAM headgroup (H(3)C- and/or HO-) occurs at the Asn47 side chain carbonyl oxygen and that an Asn47-Cys112 hydrogen bond promotes intramolecular ET to the copper. Inspection of models also indicates that the Cu(A) domain of ba(3)-type cytochrome c oxidase is coupled to the SAM headgroup (H(3)C- and/or HO-) near the main chain carbonyl oxygen of Cys153 and that Phe88 (analogous to Trp143 in subunit II of cytochrome c oxidase from R. sphaeroides) is not involved in the dominant tunneling pathway. Our work suggests that hydrogen bonds from hydroxyl or other proton-donor groups to carbonyl oxygens potentially can facilitate intermolecular ET between physiological redox partners.

  15. Phase winding of a nematic liquid crystal by dynamic localized reorientation of an azo-based self-assembled monolayer.

    PubMed

    Shi, Yue; Fang, Guanjiu; Glaser, Matthew A; Maclennan, Joseph E; Korblova, Eva; Walba, David M; Clark, Noel A

    2014-08-12

    Azobenzene-based molecules forming a self-assembled monolayer (SAM) tethered to a glass surface are highly photosensitive and readily reorient liquid crystals in contact with them when illuminated with polarized actinic light. We probe the coupling of such monolayers to nematic liquid crystal in a hybrid cell by studying the dynamics of liquid crystal reorientation in response to local orientational changes of the monolayer induced by a focused actinic laser with a rotating polarization. The steady increase in the azimuth of the mean molecular orientation of the SAM around the laser beam locally reorients the nematic, winding up an extended set of nested rings of splay-bend nematic director reorientation until the cumulative elastic torque exceeds that of the surface coupling within the beam, after which the nematic director starts to slip. Quantitative analyses of the ring dynamics allow measurements of the anchoring strength of the azo-SAM and its interaction with the nematic liquid crystal.

  16. 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.

  17. Switching on/off the chemisorption of thioctic-based self-assembled monolayers on gold by applying a moderate cathodic/anodic potential.

    PubMed

    Sahli, Rihab; Fave, Claire; Raouafi, Noureddine; Boujlel, Khaled; Schöllhorn, Bernd; Limoges, Benoît

    2013-04-30

    An in situ and real-time electrochemical method has been devised for quantitatively monitoring the self-assembly of a ferrocene-labeled cyclic disulfide derivative (i.e., a thioctic acid derivative) on a polycrystalline gold electrode under electrode polarization. Taking advantage of the high sensitivity, specificity, accuracy, and temporal resolution of this method, we were able to demonstrate an unexpectedly facilitated formation of the redox-active SAM when the electrode was held at a moderate cathodic potential (-0.4 V vs SCE in CH3CN), affording a saturated monolayer from only micromolar solutions in less than 10 min, and a totally impeded SAM growth when the electrode was polarized at a slightly anodic potential (+0.5 V vs SCE in CH3CN). This method literally allows for switching on/off the formation of SAMs under "soft" conditions. Moreover the cyclic disulfide-based SAM was completely desorbed at this potential contrary to the facilitated deposition of a ferrocene-labeled alkanethiol. Such a strikingly contrasting behavior could be explained by an energetically favored release of the thioctic-based SAM through homolytic cleavage of the Au-S bond followed by intramolecular cyclization of the generated thiyl diradicals. Moreover, the absence of a discernible transient faradaic current response during the potential-assisted adsorption/desorption of the redox-labeled cyclic disulfide led us to conclude in a potential-dependent reversible surface reaction where no electron is released or consumed. These results provide new insights into the formation of disulfide-based SAMs on gold but also raise some fundamental questions about the intimate mechanism involved in the facilitated adsorption/desorption of SAMs under electrode polarization. Finally, the possibility to easily and selectively address the formation/removal of thioctic-based SAMs on gold by applying a moderate cathodic/anodic potential offers another degree of freedom in tailoring their properties and

  18. 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

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

    SciTech Connect

    Zhang, Wenyu; Engstrom, James R.

    2016-01-15

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

  20. 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

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

    PubMed

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

    2016-04-01

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

  2. Continuous ultrathin silver films deposited on SiO2 and SiNx using a self-assembled monolayer

    NASA Astrophysics Data System (ADS)

    Hafezian, Soroush; Maloney, Kate; Lefebvre, Josianne; Martinu, Ludvik; Kéna-Cohen, Stéphane

    2016-09-01

    In this letter, we study the deposition of ultrathin silver films on silicon oxide and nitride surfaces functionalized with self-assembled monolayers of (3-mercaptopropyl)-trimethoxysilane. First, we compare both solution and vapour-phase functionalization techniques and find the greatest improvement in electrical and optical properties using deposition from solution. Using X-ray photoelectron spectroscopy, we demonstrate that the formation of silver-sulfur covalent bonds is at the root of the improved wetting confirmed by ellipsometry, sheet resistance measurement, and atomic force microscopy. Second, we show that this technique can be extended to functionalize silicon nitride. Finally, we demonstrate a simple, but efficient, low-emissivity optical filter.

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

    PubMed

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

    2011-02-22

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

  4. In-situ guidance of individual neuronal processes by wet femtosecond-laser processing of self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Yamamoto, Hideaki; Okano, Kazunori; Demura, Takanori; Hosokawa, Yoichiroh; Masuhara, Hiroshi; Tanii, Takashi; Nakamura, Shun

    2011-10-01

    In-situ guidance of neuronal processes (neurites) is demonstrated by applying wet femtosecond-laser processing to an organosilane self-assembled monolayer (SAM) template. By scanning focused laser beam between cell adhesion sites, on which primary neurons adhered and extended their neurites, we succeeded in guiding the neurites along the laser-scanning line. This guidance was accomplished by multiphoton laser ablation of cytophobic SAM layer and subsequent adsorption of cell adhesion molecule, laminin, onto the ablated region. This technique allows us to arbitrarily design neuronal networks in vitro.

  5. Confirmation of heavy metal ions in used lubricating oil from a passenger car using chelating self-assembled monolayer.

    PubMed

    Ko, Young Gun; Kim, Choong Hyun

    2006-09-01

    In order to prevent engine failure, the oil must be changed before it loses its protective properties. It is necessary to monitor the actual physical and chemical condition of the oil to reliably determine the optimum oil-change interval. Our study focuses on the condition of the lubricating oil in an operated car engine. Shear stress curves and viscosity curves as a function of the shear rate for fresh and used lubricating oil were examined. Metal nitrate was detected in the lubricating oil from the operated car engine through the use of a chelating self-assembled monolayer.

  6. Characterization of the mixed self-assembled monolayer at the molecular scale.

    PubMed

    Ta, Van-Thao; Nimse, Satish Balasaheb; Song, Keum-Soo; Kim, Junghoon; Sayyed, Danishmalik Rafiq; Nguyen, Van-Thuan; Kim, Taisun

    2011-10-28

    The mixed SAM obtained by the self-assembly of the monothiolated calix[4]crown-5 receptor 1 and the subsequent addition of the thiolated alkylferrocene guest 3 was characterized at the molecular scale by the favorable receptor-guest interactions by using cyclic voltammetry (CV).

  7. 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.

  8. 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

  9. Assembly of self-assembled monolayer-coated Al2O3 on TiO2 thin films for the fabrication of renewable superhydrophobic-superhydrophilic structures.

    PubMed

    Nishimoto, Shunsuke; Sekine, Hitomi; Zhang, Xintong; Liu, Zhaoyue; Nakata, Kazuya; Murakami, Taketoshi; Koide, Yoshihiro; Fujishima, Akira

    2009-07-07

    A renewable superhydrophobic-superhydrophilic pattern with a minimum dimension of 50 microm is prepared from octadecyltrimethoxysilane self-assembled monolayer-covered superhydrophobic Al2O3 overlayers on a superhydrophilic TiO2 surface via self-assembly and calcination of boehmite (AlOOH.nH2O) particles. The resulting Al2O3 layer plays dual roles as a superhydrophobic layer and as a UV-blocking layer for the underlying TiO2.

  10. 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

  11. 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.

  12. 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.

  13. 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

    2016-02-02

    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.

  14. 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

    2016-06-07

    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.

  15. 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

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

    PubMed

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

    2016-08-04

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

  17. 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

  18. Dynamics of decanethiol self-assembled monolayers on Au(111) studied by time-resolved scanning tunneling microscopy.

    PubMed

    Wu, Hairong; Sotthewes, Kai; Kumar, Avijit; Vancso, G Julius; Schön, Peter M; Zandvliet, Harold J W

    2013-02-19

    We investigated the dynamics of decanethiol self-assembled monolayers on Au(111) surfaces using time-resolved scanning tunneling microscopy at room temperature. The expected ordered phases (β, δ, χ*, and φ) and a disordered phase (ε) were observed. Current-time traces with the feedback loop disabled were recorded at different locations on the surface. The sulfur end group of the decanethiolate molecule exhibits a stochastic two-level switching process when the molecule is adsorbed in a (local) β phase registry. This two-level process is attributed to the diffusion of the Au-thiolate complex between two adjacent adsorption sites. The irregular current jumps in the current-time traces recorded on the tails of decanethiolate molecules in the ordered β, δ, and χ* phases are ascribed to wagging of the alkyl tails. Finally, the disordered phase is characterized by even larger current jumps, which indicates that the tail of the decanethiolate flips up occasionally and makes contact with the tip. Our experiments reveal that the massive dynamics of the self-assembled monolayer is due to diffusion of decanethiol-Au complexes, rather than the diffusion of decanethiolate molecules.

  19. Fluorinated and Charged Hydrogenated Alkanethiolates Grafted on Gold: Expanding the Diversity of Mixed-Monolayer Nanoparticles for Biological Applications.

    PubMed

    Bidoggia, Silvia; Milocco, Francesca; Polizzi, Stefano; Canton, Patrizia; Saccani, Alessandra; Sanavio, Barbara; Krol, Silke; Stellacci, Francesco; Pengo, Paolo; Pasquato, Lucia

    2017-01-18

    Low intrinsic toxicity, high solubility, and stability are important and necessary features of gold nanoparticles to be used in the biomedical field. In this context, charged nanoparticles proved to be very versatile, and among them charged mixed-monolayer gold nanoparticles, displaying monolayers with well-defined morphologies, represent a paradigm. By using mixtures of hydrogenated and fluorinated thiols, the formation of monolayer domains may be brought to an extreme because of the immiscibility of fluorinated and hydrogenated chains. Following this rationale, mixed monolayer gold nanoparticles featuring ammonium, sulfonate, or carboxylic groups on their surface were prepared by using amphiphilic hydrogenated thiols and 1H,1H,2H,2H-perfluoro-alkanethiols. The toxicity of these systems was assessed in HeLa cells and was found to be, in general, low even for the cationic nanoparticles which usually show a high cytotoxicity and is comparable to that of homoligand gold nanoparticles displaying amphiphilic-charge neutral-hydrogenated or fluorinated thiolates in their monolayer. These properties make the mixed ligand monolayer gold nanoparticles an interesting new candidate for medical application.

  20. Kinetics of electron transfer through ferrocene-terminated alkanethiol monolayers on gold

    SciTech Connect

    Smalley, J.F.; Feldberg, S.W.; Newton, M.D.; Liu, Y.P.; Chidsey, C.E.D.; Linford, M.R.

    1995-08-31

    The kinetics of electron transfer between a substrate gold electrode and a self-assembled monolayer formed from CH{sub 3}(CH{sub 2}){sub n-1}SH and ({eta}{sup 5} C{sub 5}H{sub 5})Fe ({eta}{sup 5}-C{sub 5}H{sub 4})CO{sub 2}(CH{sub 2}){sub n}SH were studied as a function of n, the number of methylenes in the alkyl chain tethering the ferrocene moiety to the electrode, using the indirect laser-induced temperature jump method (ILIT). For 5 {<=} n {<=} 9 the standard electron-transfer rate constants vary according to {kappa}{sub {tau}a,n=0} exp[-{beta}{sub n}n] where {kappa}{sub {tau}a,n=0} is the (extrapolated) rate constant for the electron transfer at n = 0. At {Tau} = 25{degree}C, {kappa}{sub {tau}a,n} 0 {approx_equal} 6 x 10{sup 8} s{sup -1} and {beta}{sub n} = 1.21 x 0.05. The ILIT method allows rates to be measured that are too fast to be measured by conventional chronoamperometry at a macroelectrode, which is limited to rate constants of {<=} 10{sup 4} s{sup -1}. Using a Marcus formalism, the reorganization energy, {lambda}, for the electron-transfer process at a given n was determined from the slope of an Arrhenius plot over the temperature range 15-55{degree}C. Values of {lambda} determined from Arrhenius slopes for n = 8 and 9 using ILIT are in reasonable agreement with the value of {lambda} previously deduced from the potential dependence of the rate constant for n = 16. 39 refs., 13 figs., 3 tabs.

  1. Surface-enhanced Raman spectroscopy for detection of toxic amyloid β oligomers adsorbed on self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Voiciuk, Vladislava; Valincius, Gintaras; Budvytytė, Rima; Matijoška, Algirdas; Matulaitienė, Ieva; Niaura, Gediminas

    Surface-enhanced Raman spectroscopy (SERS) was used to detect different spectral features of small (1-2 nm) and large (5-10 nm) synthetic amyloid Aβ-42 oligomers, exhibiting high and no detectable neurotoxicities, respectively. Adsorption of peptides at self-assembled monolayers (SAM) terminated by methyl and pyridinium groups was employed to differentiate toxic and non-toxic oligomers. Three SAMs were analyzed: hydrophobic heptanethiol (HT) and octadecanethiol (ODT) as well as positively charged N-(6-mercapto)hexylpyridinium (MHP) chloride. SERS study revealed twofold adsorption effect, changes in the monolayer structure and appearance of new bands associated with the adsorbed peptides. A band at 1387 cm-1, observed as a result of the SAM and Aβ-42 interaction, is tentatively assigned to the peptide symmetric stretching vibration of carboxylate groups, and appears to be the most prominent spectral feature distinguishing toxic oligomers from the non-toxic Aβ-42 forms. This band was identified in the spectra of Aβ-42 adsorption on heptanethiol and MHP monolayers, while no clear perturbations were observed in the case of ODT monolayer.

  2. Electron transfer through a self-assembled monolayer of a double-helix peptide with linking the terminals by ferrocene.

    PubMed

    Okamoto, Shinpei; Morita, Tomoyuki; Kimura, Shunsaku

    2009-03-03

    A unique molecular structure, a double-helix peptide, was self-assembled on gold, and the electron transfer through the monolayer was studied. The double-helix peptide consists of two 9mer 3(10)-helical peptide chains having a disulfide group at each N terminal and being linked by a ferrocene dicarboxylic acid between the C terminals. Each helical peptide chain has three naphthyl groups in a linear arrangement along the helix. The monolayer properties and the electron transfer from the ferrocene unit to gold were studied with reference peptides with a similar double helix but without naphthyl groups, a single helix with a dicarboxylic ferrocene unit, and a single helix with a monocarboxylic ferrocene unit. It was demonstrated that the naphthyl groups on the side chains had no effect on electron transfer, and the electron-transfer rate in the double-helix monolayer was not promoted, despite the two electron pathways in the molecule. We propose that in the double-helix monolayer, molecular motions are suppressed, possibly by its rigid structure tethered by the two linkers on gold to cancel out acceleration effects of the 2-fold electron pathways and the ferrocene substitution number. The factors that affect the electron-transfer reaction across the helical peptide SAMs are discussed in depth.

  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. Sample Preconcentration Utilizing Nanofractures Generated by Junction Gap Breakdown Assisted by Self-Assembled Monolayer of Gold Nanoparticles

    PubMed Central

    Jen, Chun-Ping; Amstislavskaya, Tamara G.; Chen, Kuan-Fu; Chen, Yu-Hung

    2015-01-01

    The preconcentration of proteins with low concentrations can be used to increase the sensitivity and accuracy of detection. A nonlinear electrokinetic flow is induced in a nanofluidic channel due to the overlap of electrical double layers, resulting in the fast accumulation of proteins, referred to as the exclusion-enrichment effect. The proposed chip for protein preconcentration was fabricated using simple standard soft lithography with a polydimethylsiloxane replica. This study extends our previous paper, in which gold nanoparticles were manually deposited onto the surface of a protein preconcentrator. In the present work, nanofractures were formed by utilizing the self-assembly of gold-nanoparticle-assisted electric breakdown. This reliable method for nanofracture formation, involving self-assembled monolayers of nanoparticles at the junction gap between microchannels, also decreases the required electric breakdown voltage. The experimental results reveal that a high concentration factor of 1.5×104 for a protein sample with an extremely low concentration of 1 nM was achieved in 30 min by using the proposed chip, which is faster than our previously proposed chip at the same conditions. Moreover, an immunoassay of bovine serum albumin (BSA) and anti-BSA was carried out to demonstrate the applicability of the proposed chip. PMID:25970592

  5. Solvent polarity effect on quality of n-octadecanethiol self-assembled monolayers on copper and oxidized copper

    NASA Astrophysics Data System (ADS)

    Zhang, Yaozhong; Zhou, Jun; Zhang, Xiaoli; Hu, Jun; Gao, Han

    2014-11-01

    This article reports the effect of solvent polarity on the formation of n-octadecanethiol self-assembled monolayers (C18SH-SAMs) on pure copper surface and oxidized copper surface. The quality of SAMs prepared in different solvents (n-hexane, toluene, trichloroethylene, chloroform, acetone, acetonitrile, ethanol) was monitored by EIS, RAIRS and XPS. The results indicated that C18SH-SAMs formed in these solvents were in good barrier properties on pure copper surface and the structures of monolayers formed in high polarity solvents were more compact and orderly than that formed in low polarity solvents. For comparison, C18SH adsorbed on the surface of oxidized copper in these solvents were studied and the results indicated that C18SH could be adsorbed on oxidized copper surface after the reduction of copper oxide layer by thiols. Compared with high polarity solvents, a limited reduction process of oxidized copper by thiols led to the incompletely formation of monolayers in low polarity solvents. This can be interpreted that the generated water on solid-liquid interface and a smaller reaction force restrict the continuous reduction reaction in low polarity solvents

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

    PubMed

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

    2017-04-04

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

  7. Self-assembled monolayer of organic iodine on a Au surface for attachment of redox-active metal clusters.

    PubMed

    Yu, Ying; Dubey, Manish; Bernasek, Steven L; Dismukes, G Charles

    2007-07-17

    The attachment of a bifunctional iodo-organo-phosphinate compound to gold (Au) surfaces via chemisorption of the iodine atom is described and used to chelate a redox-active metal cluster via the phosphinate group. XPS, AFM, and electrochemical measurements show that (4-iodo-phenyl)phenyl phosphinic acid (IPPA) forms a tightly bound self-assembled monolayer (SAM) on Au surfaces. The surface coverage of an IPPA monolayer on Au was quantified by an electrochemical method and found to be 0.40 +/- 0.03 nmol/cm2, roughly corresponding to 0.4 monolayers. We show that the Au/IPPA SAM, but not the underivatized Au, adsorbs Mn4O4(Ph2PO2)6 from solution by a phosphinate exchange reaction to yield Au/IPPA/Mn4O4(Ph2PO2)5 SAM. The resulting SAM is firmly bound and not removed by sonication, as confirmed by manganese XPS (Mn 2p1/2) and by AFM. Electrochemistry confirms that Mn4O4(Ph2PO2)6 is anchored on the Au/IPPA surface and that redox chemistry can be mediated between the electrode and the surface-attached complex. Mn4O4(Ph2PO2)6 contains the reactive Mn4O46+ cubane core, a redox-active bioinspired catalyst.

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

    PubMed Central

    She, Zhe; DiFalco, Andrea; Hähner, Georg

    2012-01-01

    Summary Self-assembled monolayers (SAMs) of 4'-methylbiphenyl-4-thiol (MBP0) adsorbed on polycrystalline gold substrates served as templates to control electrochemical deposition of Cu structures from acidic solution, and enabled the subsequent lift-off of the metal structures by attachment to epoxy glue. By exploiting the negative-resist behaviour of MBP0, the SAM was patterned by means of electron-beam lithography. For high deposition contrast a two-step procedure was employed involving a nucleation phase around −0.7 V versus Cu2+/Cu and a growth phase at around −0.35 V versus Cu2+/Cu. Structures with features down to 100 nm were deposited and transferred with high fidelity. By using substrates with different surface morphologies, AFM measurements revealed that the roughness of the substrate is a crucial factor but not the only one determining the roughness of the copper surface that is exposed after lift-off. PMID:22428101

  9. 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.

  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.

  11. 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.

  12. Optical properties of azobenzene-functionalized self-assembled monolayers: Intermolecular coupling and many-body interactions

    NASA Astrophysics Data System (ADS)

    Cocchi, Caterina; Moldt, Thomas; Gahl, Cornelius; Weinelt, Martin; Draxl, Claudia

    2016-12-01

    In a joint theoretical and experimental work, the optical properties of azobenzene-functionalized self-assembled monolayers (SAMs) are studied at different molecular packing densities. Our results, based on density-functional and many-body perturbation theory, as well as on differential reflectance (DR) spectroscopy, shed light on the microscopic mechanisms ruling photo-absorption in these systems. While the optical excitations are intrinsically excitonic in nature, regardless of the molecular concentration, in densely packed SAMs intermolecular coupling and local-field effects are responsible for a sizable weakening of the exciton binding strength. Through a detailed analysis of the character of the electron-hole pairs, we show that distinct excitations involved in the photo-isomerization at low molecular concentrations are dramatically broadened by intermolecular interactions. Spectral shifts in the calculated DR spectra are in good agreement with the experimental results. Our findings represent an important step forward to rationalize the excited-state properties of these complex materials.

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

    PubMed

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

    2014-04-21

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

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

    PubMed

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

    2015-04-07

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

  15. 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

  16. 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.

  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. How nanoscience translates into technology: the case of self-assembled monolayers, electron-beam writing, and carbon nanomembranes.

    PubMed

    Palmer, R E; Robinson, A P G; Guo, Q

    2013-08-27

    One of the great quests in nanotechnology is to translate nanoprecision materials science into practical manufacturing processes. The paper by Angelova et al. in this issue of ACS Nano, which discusses the production of functional carbon-based membranes with a thickness of 0.5 to 3 nm, provides instructive insight into how researchers are pulling together complementary strands from a quarter century of nanoscience research to develop novel, hybrid processing schemes. In this Perspective, we reflect on the progress that is taking place in the two principal component technologies combined in this scheme, namely, (i) control of self-assembled monolayers, including their detailed atomic structures, and (ii) electron-induced manipulation and processing of molecular layers, as well as considering (iii) remaining challenges for thin membrane production in the future.

  19. Role of self-assembled monolayer passivation in electrical transport properties and flicker noise of nanowire transistors.

    PubMed

    Kim, Seongmin; Carpenter, Patrick D; Jean, Rand K; Chen, Haitian; Zhou, Chongwu; Ju, Sanghyun; Janes, David B

    2012-08-28

    Semiconductor nanowires have achieved great attention for integration in next-generation electronics. However, for nanowires with diameters comparable to the Debye length, which would generally be required for one-dimensional operation, surface states degrade the device performance and increase the low-frequency noise. In this study, single In(2)O(3) nanowire transistors were fabricated and characterized before and after surface passivation with a self-assembled monolayer of 1-octadecanethiol (ODT). Electrical characterization of the transistors shows that device performance can be enhanced upon ODT passivation, exhibiting steep subthreshold slope (~64 mV/dec), near zero threshold voltage (~0.6 V), high mobility (~624 cm(2)/V·s), and high on-currents (~40 μA). X-ray photoelectron spectroscopy studies of the ODT-passivated nanowires indicate that the molecules are bound to In(2)O(3) nanowires through the thiol linkages. Device simulations using a rectangular geometry to represent the nanowire indicate that the improvement in subthreshold slope and positive shift in threshold voltage can be explained in terms of reduced interface trap density and changes in fixed charge density. Flicker (low-frequency, 1/f) noise measurements show that the noise amplitude is reduced following passivation. The interface trap density before and after ODT passivation is profiled throughout the band gap energy using the subthreshold current-voltage characteristics and is compared to the values extracted from the low-frequency noise measurements. The results indicate that self-assembled monolayer passivation is a promising optimization technology for the realization of low-power, low-noise, and fast-switching applications such as logic, memory, and display circuitry.

  20. 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.

  1. 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...

  2. Solution-growth kinetics and thermodynamics of nanoporous self-assembled molecular monolayers

    NASA Astrophysics Data System (ADS)

    Bellec, Amandine; Arrigoni, Claire; Schull, Guillaume; Douillard, Ludovic; Fiorini-Debuisschert, Céline; Mathevet, Fabrice; Kreher, David; Attias, André-Jean; Charra, Fabrice

    2011-03-01

    The temperature and concentration dependences of the self-assembly onto graphite from solution of a series of molecular building blocks able to form nanoporous structures are analyzed experimentally by in situ scanning tunneling microscopy. It is shown that the commonly observed coexistence of dense and nanoporous domains results from kinetic blockades rather than a thermodynamic equilibrium. The ripening can be favored by high densities of domain boundaries, which can be obtained by cooling the substrate before the nucleation and growth. Then ripening at higher-temperature yields large defect-free domains of a single structure. This thermodynamically stable structure can be either the dense or the nanoporous one, depending on the tecton concentration in the supernatant solution. A sharp phase transition from dense to honeycomb structures is observed at a critical concentration. This collective phenomenon is explained by introducing interactions between adsorbed molecules in the thermodynamic description of the whole system.

  3. Nanoscale wettability of self-assembled monolayers investigated by noncontact atomic force microscopy.

    PubMed

    Checco, Antonio; Schollmeyer, Hauke; Daillant, Jean; Guenoun, Patrick; Boukherroub, Rabah

    2006-01-03

    We report on a novel technique to nucleate nanometer-sized droplets on a solid substrate and to image them with minimal perturbation by noncontact atomic force microscopy (NC-AFM). The drop size can be accurately controlled, thus permitting hysteresis measurements. We have studied the nanoscale wettability of several methyl-terminated substrates prepared by the self-assembly of organic molecules. These substrates are alkyltrichlorosilanes on silica, alkylthiols on gold, alkyl chains on hydrogen-terminated silicon, and crystalline hexatriacontane chains on silica. For each of these systems, we report a deviation of the wetting contact angle from the macroscopic value, and we discuss this effect in term of mesoscale surface heterogeneity and long-range solid-liquid interactions.

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

    SciTech Connect

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

    2016-12-15

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

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

    NASA Astrophysics Data System (ADS)

    Cregger, Tricia Ann

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  7. Nanopattern formation in self-assembled monolayers of thiol-capped Au nanocrystals

    NASA Astrophysics Data System (ADS)

    Banerjee, R.; Hazra, S.; Banerjee, S.; Sanyal, M. K.

    2009-11-01

    The structure and the stability of the transferred monolayers of gold-thiol nanoparticles, formed at air-water interface at different surface pressure, on to silicon surface have been studied using two complementary techniques, x-ray reflectivity and atomic force microscopy (AFM). Networklike nanopatterns, observed through AFM, of the in-plane aggregated nanoparticles can be attributed to the late stage drying of the liquid trapped in the islands formed by nanoparticles. During drying process the trapped liquid leaves pinholes in the islands which by the process of nucleation and growth carry the mobile nanoparticles on their advancing fronts such that the nanoparticles are trapped at the boundaries of similar adjacent holes. This process continues bringing about in-plane as well as out-of-plane restructuring in the monolayer until the liquid evaporates completely rendering a patterned structure to the islands and instability in the monolayer is then stabilized.

  8. 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

  9. Molecular dynamics and energy landscape of decanethiolates in self-assembled monolayers on Au(111) studied by scanning tunneling microscopy.

    PubMed

    Sotthewes, Kai; Wu, Hairong; Kumar, Avijit; Vancso, G Julius; Schön, Peter M; Zandvliet, Harold J W

    2013-03-19

    The energetics and dynamics of the various phases of decanethiolate self-assembled monolayers on Au(111) surfaces were studied with scanning tunneling microscopy. We have observed five different phases of the decanethiolate monolayer on Au(111): four ordered phases (β, δ, χ*, and φ) and one disordered phase (ε). We have determined the boundary free energies between the disordered and order phases by analyzing the thermally induced meandering of the domain boundaries. On the basis of these results, we are able to accurately predict the two-dimensional phase diagram of the decanethiolate/Au(111) system. The order-disorder phase transition of the χ* phase occurs at 295 K, followed by the order-disorder phase transition of the β phase at 325 K. Above temperatures of 325 K, only the densely packed φ and disordered ε phases remain. Our findings are in good agreement with the phase diagram of the decanethiolate/Au(111) system that was put forward by Poirier et al. [Langmuir 2001, 17 (4), 1176-1183].

  10. An off-the-shelf integrated microfluidic device comprising self-assembled monolayers for protein array experiments

    PubMed Central

    Hen, Mirit; Ronen, Maria; Deitch, Alex; Barbiro-Michaely, Efrat; Oren, Ziv; Sukenik, Chaim N.; Gerber, Doron

    2015-01-01

    Microfluidic-based protein arrays are promising tools for life sciences, with increased sensitivity and specificity. One of the drawbacks of this technology is the need to create fresh surface chemistry for protein immobilization at the beginning of each experiment. In this work, we attempted to include the process of surface functionalization as part of the fabrication of the device, which would substitute the time consuming step of surface functionalization at the beginning of each protein array experiment. To this end, we employed a novel surface modification using self-assembled monolayers (SAMs) to immobilize biomolecules within the channels of a polydimethylsiloxane (PDMS) integrated microfluidic device. As a model, we present a general method for depositing siloxane-anchored SAMs, with 1-undecyl-thioacetate-trichlorosilane (C11TA) on the silica surfaces. The process involved developing PDMS-compatible conditions for both SAM deposition and functional group activation. We successfully demonstrated the ability to produce, within an integrated microfluidic channel, a C11TA monolayer with a covalently conjugated antibody. The antibody could then bind its antigen with a high signal to background ratio. We further demonstrated that the antibody was still active after storage of the device for a week. Integration of the surface chemistry into the device as part of its fabrication process has potential to significantly simplify and shorten many experimental procedures involving microfluidic–based protein arrays. In turn, this will allow for broader dissemination of this important technology. PMID:26421087

  11. 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

  12. Photoswitching of azobenzene-containing self-assembled monolayers as a tool for control over silicon surface electronic properties.

    PubMed

    Malyar, Ivan V; Titov, Evgenii; Lomadze, Nino; Saalfrank, Peter; Santer, Svetlana

    2017-03-14

    We report on photoinduced remote control of work function and surface potential of a silicon surface modified with a photosensitive self-assembled monolayer consisting of chemisorbed azobenzene molecules (4-nitroazobenzene). It was found that the attachment of the organic monolayer increases the work function by hundreds of meV due to the increase in the electron affinity of silicon substrates. The change in the work function on UV light illumination is more pronounced for the azobenzene jacketed silicon substrate (ca. 250 meV) in comparison to 50 meV for the unmodified surface. Moreover, the photoisomerization of azobenzene results in complex kinetics of the work function change: immediate decrease due to light-driven processes in the silicon surface followed by slower recovery to the initial state due to azobenzene isomerization. This behavior could be of interest for electronic devices where the reaction on irradiation should be more pronounced at small time scales but the overall surface potential should stay constant over time independent of the irradiation conditions.

  13. 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.

  14. Nanotribological properties of alkanephosphonic acid self-assembled monolayers on aluminum oxide: effects of fluorination and substrate crystallinity.

    PubMed

    Brukman, Matthew J; Oncins Marco, Gerard; Dunbar, Timothy D; Boardman, Larry D; Carpick, Robert W

    2006-04-25

    Two phosphonic acid (PA) self-assembled monolayers (SAMs) are studied on three aluminum oxide surfaces: the C and R crystallographic planes of single crystal alpha-alumina (sapphire) and an amorphous vapor-deposited alumina thin film. SAMs are either fully hydrogenated CH3(CH2)17PO3H2 or semifluorinated CF3(CF2)7(CH2)11PO3H2. Atomic force microscope (AFM) topographic imaging reveals that the deposited films are homogeneous, atomically smooth, and stable for months in the laboratory environment. Static and advancing contact angle measurements agree with previous work on identical or similar films, but receding measurements suggest reduced coverage here. To enable reproducible nanotribology measurements with the AFM, a scanning protocol is developed that leads to a stable configuration of the silicon tip. Adhesion for the semifluorinated films is either comparable to or lower than that for the hydrogenated films, with a dependence on contact history observed. Friction between each film and the tips depends strongly upon the type of molecule, with the fluorinated species exhibiting substantially higher friction. Subtle but reproducible differences in friction are observed for a given SAM depending on the substrate, revealing differences in packing density for the SAMs on the different substrates. Friction is seen to increase linearly with load, a consequence of the tip's penetration into the monolayer.

  15. 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

    2005-02-03

    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.

  16. Photoswitching of azobenzene-containing self-assembled monolayers as a tool for control over silicon surface electronic properties

    NASA Astrophysics Data System (ADS)

    Malyar, Ivan V.; Titov, Evgenii; Lomadze, Nino; Saalfrank, Peter; Santer, Svetlana

    2017-03-01

    We report on photoinduced remote control of work function and surface potential of a silicon surface modified with a photosensitive self-assembled monolayer consisting of chemisorbed azobenzene molecules (4-nitroazobenzene). It was found that the attachment of the organic monolayer increases the work function by hundreds of meV due to the increase in the electron affinity of silicon substrates. The change in the work function on UV light illumination is more pronounced for the azobenzene jacketed silicon substrate (ca. 250 meV) in comparison to 50 meV for the unmodified surface. Moreover, the photoisomerization of azobenzene results in complex kinetics of the work function change: immediate decrease due to light-driven processes in the silicon surface followed by slower recovery to the initial state due to azobenzene isomerization. This behavior could be of interest for electronic devices where the reaction on irradiation should be more pronounced at small time scales but the overall surface potential should stay constant over time independent of the irradiation conditions.

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

    PubMed

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

    2013-06-25

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

  18. Selective surface activation of a functional monolayer for the fabrication of nanometer scale thiol patterns and directed self-assembly of gold nanoparticles.

    PubMed

    Fresco, Zachary M; Fréchet, Jean M J

    2005-06-15

    Application of a voltage bias between the tip of an atomic force microscope (AFM) and a silicon substrate causes the localized modification of a specially designed self-assembled monolayer (SAM), transforming a surface-bound thiocarbonate into a surface-bound thiol. The resulting surface-bound thiols are used to direct the patternwise self-assembly of gold nanoparticles (AuNPs). This methodology is applied to deposit individual AuNPs onto a surface with nanometer precision and to produce 10 nm lines of closely spaced AuNPs that are a single nanoparticle in width.

  19. 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.

  20. Solvent and concentration effects on the surface characteristics and platelet compatibility of zwitterionic sulfobetaine-terminated self-assembled monolayers.

    PubMed

    Shen, Ching-Hsiung; Lin, Jui-Che

    2013-01-01

    The structural organization of a monolayer influences biological responses as the material makes contact with the bodily fluid. Zwitterionic materials containing the sulfobetaine functionalities have been shown to exhibit protein-repelling characteristics. In this study, the effect of solvent and thiol concentrations on the sulfobetaine-terminated SAM (self-assembled monolayer) is discussed. Four different types of solvents were selected: deionized water, PBS, methanol and ethanol. The total thiol concentration was set at either 2mM or 0.1 mM. X-ray photoelectron analyses indicated that all SAMs demonstrated similar chemical configurations. Reflection adsorption infrared spectroscopy showed that conformation of the SAMs was more organized when prepared from a 0.1 mM solution compared to a 2 mM solution. The contact angle of the SAMs prepared from 2 mM concentration was dependent upon the solvent utilized and was more hydrophobic than the SAMs prepared from 0.1 mM concentration. Moreover, all of these sulfobetaine-terminated SAMs showed a fairly negative zeta potential in PBS at pH 7.4. After contact with blood, these sulfobetaine-terminated SAMs demonstrated distinct platelet reactivity among each other. The highest platelet compatibility was shown on the SAMs prepared in 0.1 mM solution and the one formed in 2 mM ethanolic solution, where they exhibited a more organized conformation and enhanced hydrophilic properties. These properties might be caused by the different hydration layers, which are affected by the assembly conditions on the topmost monolayer. This study demonstrated that optimizing solvent and concentration conditions could control the structural organization of zwitterionic sulfobetaine-terminated SAMs and, consequently, modify biomedical properties.

  1. 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.

  2. 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

  3. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2009-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  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. Protein recognition by a self-assembled deep cavitand monolayer on a gold substrate.

    PubMed

    Liu, Ying; Taira, Toshiaki; Young, Michael C; Ajami, Dariush; Rebek, Julius; Cheng, Quan; Hooley, Richard J

    2012-01-17

    This paper details the first use of a self-folding deep cavitand on a gold surface. A sulfide-footed deep, self-folding cavitand has been synthesized, and its attachment to a cleaned gold surface studied by electrochemical and SPR methods. Complete monolayer formation is possible if the cavitand folding is templated by noncovalent binding of choline or by addition of space-filling thiols to cover any gaps in the cavitand adsorption layer. The cavitand is capable of binding trimethylammonium-tagged guests from an aqueous medium and can be deposited in 2 × 2 microarrays on the surface for characterization by SPR imaging techniques. When biotin-labeled guests are used, the cavitand:guest construct can recognize and immobilize streptavidin proteins from aqueous solution, acting as an effective supramolecular biosensor for monitoring protein recognition.

  9. Self-assembled monolayers from biphenyldithiol derivatives: optimization of the deprotection procedure and effect of the molecular conformation.

    PubMed

    Shaporenko, Andrey; Elbing, Mark; Błaszczyk, Alfred; von Hänisch, Carsten; Mayor, Marcel; Zharnikov, Michael

    2006-03-09

    A series of biphenyl-derived dithiol (BDDT) compounds with terminal acetyl-protected sulfur groups and different structural arrangements of both phenyl rings have been synthesized and fully characterized. The different arrangements were achieved by introducing hydrocarbon substituents in the 2 and 2' positions of the biphenyl backbone. The presented model compounds enable the investigation of the correlation between the intramolecular conformation and other physical properties of interest, like, e.g., molecular assembly or electronic transport properties. Here, the ability of these model compounds to form self-assembled monolayers (SAMs) on Au(111) and Ag(111) is investigated in details. The deprotection of the target molecules was performed in situ using either NH4OH or triethylamine (TEA) deprotection agent. The fabricated films were characterized by synchrotron-based high-resolution photoelectron spectroscopy and near-edge absorption fine structure spectroscopy. Whereas the deprotection by NH4OH was found to result in the formation of multilayer films, the deprotection by TEA allowed the preparation of densely packed BDDT SAMs with a noticeably higher orientational order and smaller molecular inclination on Ag than on Au. Introduction of the alkyl bridge between the individual rings of the biphenyl backbone did not lead to a noticeable change in the structure and packing density of the BDDT SAMs as long as the molecule had a planar conformation in the respective SAM. The deviation from this conformation resulted in the deterioration of the film quality and a decrease of the orientational order.

  10. Size-controlled electrochemical growth of PbS nanostructures into electrochemically patterned self-assembled monolayers.

    PubMed

    Nişancı, Fatma Bayrakçeken; Demir, Ümit

    2012-06-05

    1-Hexadecanethiol self-assembled monolayers (HDT SAMs) on Au(111) were used as a molecular resist to fabricate nanosized patterns by electrochemical reductive partial desorption for subsequent electrodeposition of PbS from the same solution simultaneously. The influences of potential steps of variable pulse width and amplitude on the size and the number of patterns were investigated. The kinetics of pattern formation by reductive desorption appears to be instantaneous according to chronoamperometric and morphological investigations. PbS structures were deposited electrochemically into the patterns on HDT SAMs by a combined electrochemical technique, based on the codeposition from the same saturated PbS solution at the underpotential deposition of Pb and S. Scanning tunneling microscopy measurements showed that all of the PbS deposits were disk shaped and uniformly distributed on Au(111) surfaces. Preliminary results indicated that the diameter and the density of PbS deposits can be controlled by controlling the pulse width and amplitude of potential applied at the reductive removal stage of HDT SAMs and the deposition time during the electrochemical deposition step.

  11. Site-selective assembly of quantum dots on patterned self-assembled monolayers fabricated by laser direct-writing

    NASA Astrophysics Data System (ADS)

    Wu, Chong; Wang, Yongsheng; Han, Xuemingyue; Hu, Xinming; Cheng, Qianyi; Han, Baohang; Liu, Qian; Ren, Tianling; He, Yonghong; Sun, Shuqing; Ma, Hui

    2012-06-01

    A simple and efficient route for quantum dot (QDs) patterning using self-assembled monolayers (SAMs) as templates is described. By means of a laser direct-writing (LDW) technique, SAMs of octadecylphosphonic acid formed by adsorption on native oxide layer of titanium film were patterned through laser-induced ablation of the SAM molecules. This technique allows the creation of chemical-specific patterns accompanied by slight change in the topography. Using atomic force microscopy and friction force microscopy, the dependence of feature size and characteristics on the irradiation dose was demonstrated. Upon immersion of a substrate with patterned SAMs bearing thiol as the terminal group into a dispersion of QDs resulted in the assembly of QDs on the specific thiol-terminated areas. Patterns of QDs with different photoluminescent wavelength were generated. The LDW technique, which is convenient and flexible due to its path-directed and maskless fabrication process, provided a new powerful approach for patterning materials on surfaces for various applications.

  12. The role of the crystalline face in the ordering of 6-mercaptopurine self-assembled monolayers on gold.

    PubMed

    Lobo Maza, Flavia; Grumelli, Doris; Carro, Pilar; Vericat, Carolina; Kern, Klaus; Salvarezza, Roberto C

    2016-10-06

    Well-ordered molecular films play an important role in nanotechnology, from device fabrication to surface patterning. Self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) on the Au(100)-(1 × 1) and Au(111)-(1 × 1) have been used to understand the interplay of molecule-substrate interactions for heterocyclic thiols capable of binding to the surface by two anchors, which spontaneously form a highly disordered film on Au(111). Our results reveal that for the same surface coverage the simple change of the substrate from Au(111)-(1 × 1) to Au(100)-(1 × 1) eliminates molecular disorder and yields well-ordered SAMs. We discuss these findings in terms of differences in the surface mobility of 6MP species on these surfaces, the energetics of the adsorption sites, and the number of degrees of freedom of these substrates for a molecule with reduced surface mobility resulting from its two surface anchors. These results reveal the presence of subtle molecule-substrate interactions involving the heteroatom that drastically alter SAM properties and therefore strongly impact on our ability to control physical properties and to build devices at the nanoscale.

  13. From single atoms to self-assembled quantum single-atomic nanowires: noble metal atoms on black phosphorene monolayers.

    PubMed

    Zhao, X J; Shan, Wen-Wen; He, Hao; Xue, Xinlian; Guo, Z X; Li, S F

    2017-03-15

    Transition metal (TM) nanostructures, such as one dimensional (1D) nanowires with/without substrates, usually possess drastically different properties from their bulk counterparts, due to their distinct stacking and electronic confinement. Correspondingly, it is of great importance to establish the dominant driving force in forming 1D single-metal-atom-wires (SMAWs). Here, with first-principles calculations, taking the black phosphorene (BP) monolayer as a prototype 2D substrate, we investigate the energetic and kinetic properties of all the 5d-TM atoms on the 2D substrate to reveal the mechanism of formation of SMAWs. In contrast to other 5d- and 4d-TMs, noble metal elements Pd and Pt are found to prefer to grow along the trough in an atom-by-atom manner, self-assembling into SMAWs with a significant magic growth behavior. This is due to distinct binding energies and diffusion barriers along the trough, i.e., zig-zag direction, as compared to other directions of the BP. The present findings are valuable in the fabrication and modulation of 1D nanostructures which can be anticipated to possess desirable functionalities for potential applications such as in nanocatalysis, nanosensors, and related areas.

  14. 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

  15. 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

  16. Structural Stability and Phase Transitions of Octanethiol Self-Assembled Monolayers on Au(111) in Ultrahigh Vacuum.

    PubMed

    Lee, Nam-Suk; Cho, Gyoujin; Shin, Hoon-Kyu; Noh, Jaegeun

    2016-06-01

    To understand the structural stability of as-prepared octanethiol (OT) self-assembled monolayers (SAMs) with a fully covered c(4 x 2) phase on Au(111) in ultrahigh vacuum (UHV) conditions of 3 x 10(-7) Pa at room temperature, we examined OT SAM samples obtained as a function of storage period using scanning tunneling microscopy (STM). STM imaging revealed that phase transition of OT SAMs after storage in UHV for 3 days occurs from the c(4 x 2) phase to the mixed phase containing ordered c(4 x 2) and disordered phases. It was also observed that the disordered phase was mainly located at around vacancy islands and near step edges of Au(111) terraces, implying that desorption of OT molecules chemisorbed on Au(111) in UHV occurs more quickly in these regions compared with in the closely packed and ordered domains. After a longer storage in UHV for 6 days, OT SAMs with the c(4 x 2) phase were changed to the disordered phase containing a partially ordered domain with a row structure. From this study, we clearly demonstrated that OT molecules in SAMs on Au(111) are desorbed spontaneously in UHV at room temperature, resulting in the formation of disordered and row phases.

  17. Toward metal-organic insulator-semiconductor solar cells, based on molecular monolayer self-assembly on n-Si

    NASA Astrophysics Data System (ADS)

    Har-Lavan, Rotem; Ron, Izhar; Thieblemont, Florent; Cahen, David

    2009-01-01

    Alkyl chain molecules on n-Si were used to test the concept of hybrid metal-organic insulator-semiconductor (MOIS) solar cells. Test structures were made by binding alkyl chain molecules via Si-O-C bonds to oxide-free n-Si surfaces, using self-assembly. With thiol groups at the terminals away from the Si, binding of Au nanoparticles, followed by electroless Au plating yields semitransparent top contacts. First cells give, under 25 mW/cm2 white light illumination, open-circuit voltage Voc=0.48 V and fill factor FF=0.58. Because with sulfur termination the molecules have a dipole that limits inversion of the Si, we also used methyl-terminated monolayers. Even though then we can work, at this point, only with a Hg top contact, without chemical bond to the molecules, we get, using only radiation (˜AM 1.5) collected around the contact, the expected higher Voc=0.54 V, and respectable 0.8 FF, justifying further MOIS cell development.

  18. 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.

  19. 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.

  20. Substrate effects in poly(ethylene glycol) self-assembled monolayers on granular and flame-annealed gold.

    PubMed

    Rundqvist, Jonas; Hoh, Jan H; Haviland, David B

    2006-09-01

    Poly(ethylene glycol) (PEG) self-assembled monolayers (SAMs) are surface coatings that efficiently prevent nonspecific adhesion of biomolecules to surfaces. Here, we report on SAM formation of the PEG thiol CH3O(CH2CH2O)17NHCO(CH2)2SH (PEG(17)) on three types of Au films: thermally evaporated granular Au and two types of Au films from hydrogen flame annealing of granular Au, Au(111), and Au silicide. The different Au surfaces clearly affects the morphology and mechanical properties of the PEG(17) SAM, which is shown by AFM topographs and force distance curves. The two types of SAMs found on flame-annealed Au were denoted "soft" and "hard" due to their difference in stiffness and resistance to scratching by the AFM probe. With the aim of nanometer scale patterning of the PEG(17), the SAMs were exposed by low energy (1 kV) electron beam lithography (EBL). Two distinctly different types of behaviour were observed on the different types of SAM; the soft PEG(17) SAM was destroyed in a self-developing process while material deposition was dominant for the hard PEG(17) SAM.

  1. 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.

  2. Covalent Immobilization of Peptides on Self-Assembled Monolayer Surfaces Using Soft-Landing of Mass-Selected Ions

    SciTech Connect

    Wang, Peng; Hadjar, Omar; Laskin, Julia

    2007-06-23

    Covalent immobilization of peptides on solid supports plays an important role in biochemistry with applications 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 improved cell adhesion. Self-assembled monolayer surfaces (SAMs) provide a simple and convenient platform for tailoring chemical properties of a variety of substrates. Existing techniques for linking peptides to SAMs are based on solution-phase synthetic strategies and require relatively large quantities of purified material. Here, we report a novel approach for highly selective covalent binding of peptides to SAMs using soft-landing (SL) of mass-selected ions. SL is defined as intact deposition of ions onto suitable substrates at hyperthermal (<100 eV) energies.Recent studies have demonstrated that SAMs are excellent deposition targets for SL due to their ability to dissipate kinetic energies of the projectiles and their efficiency in trapping captured species. It has been proposed that SL could be utilized for controlled preparation of protein arrays.

  3. 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.

  4. 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.

    2016-10-01

    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.

  5. Conformation-driven quantum interference effects mediated by through-space conjugation in self-assembled monolayers

    PubMed Central

    Carlotti, Marco; Kovalchuk, Andrii; Wächter, Tobias; Qiu, Xinkai; Zharnikov, Michael; Chiechi, Ryan C.

    2016-01-01

    Tunnelling currents through tunnelling junctions comprising molecules with cross-conjugation are markedly lower than for their linearly conjugated analogues. This effect has been shown experimentally and theoretically to arise from destructive quantum interference, which is understood to be an intrinsic, electronic property of molecules. Here we show experimental evidence of conformation-driven interference effects by examining through-space conjugation in which π-conjugated fragments are arranged face-on or edge-on in sufficiently close proximity to interact through space. Observing these effects in the latter requires trapping molecules in a non-equilibrium conformation closely resembling the X-ray crystal structure, which we accomplish using self-assembled monolayers to construct bottom-up, large-area tunnelling junctions. In contrast, interference effects are completely absent in zero-bias simulations on the equilibrium, gas-phase conformation, establishing through-space conjugation as both of fundamental interest and as a potential tool for tuning tunnelling charge-transport in large-area, solid-state molecular-electronic devices. PMID:27996036

  6. Development and characterization of a pressure-sensitive luminescent coating based on Pt(II)-porphyrin self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Sakamura, Y.; Suzuki, T.; Kawabata, S.

    2015-06-01

    A pressure-sensitive luminescent coating (PSLC) applicable to the visualization of pressure distributions in micro-scale flow devices was developed. Pt(II)-porphyrin was synthesized and covalently attached to the surface of indium tin oxide (ITO) glass plates by a self-assembled monolayer (SAM) process. The UV-visible absorption spectrum, pressure and temperature sensitivities and photostability of the PSLC were then measured to characterize the developed PSLC. It was found that (a) the chemisorption of the porphyrin did not greatly perturb the molecular orbitals of the porphyrin responsible for its photophysics, (b) the pressure dependency of the luminescent intensity of the PSLC obeyed a power function curve and the pressure sensitivities at 273, 293, 313 and 333 K were obtained in the pressure range from 5 to 120 kPa, (c) the luminescent intensity of the PSLC almost linearly decreased with temperature and the temperature sensitivities at 5, 40, 100 and 120 kPa evaluated in the temperature range from 273 to 333 K were -0.67, -0.72, -0.75 and -0.78%/K, respectively and (d) the decrease in the luminescent intensity of the PSLC after a 30 min exposure to an excitation light was 1.23% of its initial intensity and much smaller than that of Pt(II)-porphyrin absorbed on a TLC (thin-layer chromatography) sheet.

  7. 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.

  8. A scanning probe microscopy study of the physisorption and chemisorption of protein molecules onto carboxylate terminated self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Patel, N.; Davies, M. C.; Heaton, R. J.; Roberts, C. J.; Tendler, S. J. B.; Williams, P. M.

    Scanning probe microscopy offers the possibility of investigating biomolecular structure and function. However, successful imaging is technically limited by interactions between the probe and the sample. A strong attachment of the biomolecule to the substrate is often required. Here, we investigate the binding of the protein catalase to gold surfaces modified by self-assembled monolayers (SAMs). The chemical and physical adsorption of the protein molecules onto SAMs of 3-mercaptopropanoic acid (3-MPA), 11-mercaptoundecanoic acid (11-MUA) and a mixture of the two acid thiols (Mixed) was investigated utilizing tapping mode atomic force microscopy (AFM), scanning tunneling microscopy (STM) and surface plasmon resonance (SPR). The surface concentration of catalase adsorbed on the SAMs decreased in the order: Mixed>11-MUA>3-MPA. Utilizing the terminal carboxylic acid functionalities, catalase was immobilized with a water soluble carbodiimide and N-hydroxysuccinimide (NHS). Immobilization resulted in increased coverage of the protein. SPR studies on silver surfaces modified by these SAMs indicate immobilization of carbodiimide and NHS decreased in the order: Mixed>11-MUA>3-MPA.

  9. Conformation-driven quantum interference effects mediated by through-space conjugation in self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Carlotti, Marco; Kovalchuk, Andrii; Wächter, Tobias; Qiu, Xinkai; Zharnikov, Michael; Chiechi, Ryan C.

    2016-12-01

    Tunnelling currents through tunnelling junctions comprising molecules with cross-conjugation are markedly lower than for their linearly conjugated analogues. This effect has been shown experimentally and theoretically to arise from destructive quantum interference, which is understood to be an intrinsic, electronic property of molecules. Here we show experimental evidence of conformation-driven interference effects by examining through-space conjugation in which π-conjugated fragments are arranged face-on or edge-on in sufficiently close proximity to interact through space. Observing these effects in the latter requires trapping molecules in a non-equilibrium conformation closely resembling the X-ray crystal structure, which we accomplish using self-assembled monolayers to construct bottom-up, large-area tunnelling junctions. In contrast, interference effects are completely absent in zero-bias simulations on the equilibrium, gas-phase conformation, establishing through-space conjugation as both of fundamental interest and as a potential tool for tuning tunnelling charge-transport in large-area, solid-state molecular-electronic devices.

  10. 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.

  11. Conformation-driven quantum interference effects mediated by through-space conjugation in self-assembled monolayers.

    PubMed

    Carlotti, Marco; Kovalchuk, Andrii; Wächter, Tobias; Qiu, Xinkai; Zharnikov, Michael; Chiechi, Ryan C

    2016-12-20

    Tunnelling currents through tunnelling junctions comprising molecules with cross-conjugation are markedly lower than for their linearly conjugated analogues. This effect has been shown experimentally and theoretically to arise from destructive quantum interference, which is understood to be an intrinsic, electronic property of molecules. Here we show experimental evidence of conformation-driven interference effects by examining through-space conjugation in which π-conjugated fragments are arranged face-on or edge-on in sufficiently close proximity to interact through space. Observing these effects in the latter requires trapping molecules in a non-equilibrium conformation closely resembling the X-ray crystal structure, which we accomplish using self-assembled monolayers to construct bottom-up, large-area tunnelling junctions. In contrast, interference effects are completely absent in zero-bias simulations on the equilibrium, gas-phase conformation, establishing through-space conjugation as both of fundamental interest and as a potential tool for tuning tunnelling charge-transport in large-area, solid-state molecular-electronic devices.

  12. Study of the helium cross-section of unsymmetric disulfide self-assembled monolayers on Au(111)

    NASA Astrophysics Data System (ADS)

    Albayrak, Erol; Karabuga, Semistan; Bracco, Gianangelo; Danışman, M. Fatih

    2016-12-01

    We have investigated the formation of self-assembled monolayers (SAMs) of 11-hydroxyundecyl decyl disulfide (CH3-(CH2)9-S-S-(CH2)11-OH, HDD) and 11-hydroxyundecyl octadecyl disulfide (CH3-(CH2)17-S-S-(CH2)11-OH, HOD) produced by supersonic molecular beam deposition (SMBD). The study has been carried out by means of helium diffraction at very low film coverage. In this regime helium single molecule cross sections have been estimated in a temperature range between 100 K and 450 K. The results show a different behavior above 300 K that has been interpreted as the starting of mobility with the formation of two thiolate moieties either linked by a gold adatom or distant enough to prevent cross section overlapping. Finally, helium diffraction patterns measured at 80 K for the SAMs grown at 200 K are discussed and the results support the proposed hypothesis of molecular dissociation based on the cross section data.

  13. Interactions of leukocytes and platelets with poly(lysine/leucine) immobilized on tetraethylene glycol-terminated self-assembled monolayers.

    PubMed

    Martins, M Cristina L; Ochoa-Mendes, Vanessa; Ferreira, Gisela; Barbosa, Judite N; Curtin, Scott A; Ratner, Buddy D; Barbosa, Mário A

    2011-05-01

    Surfaces that bind heparin are important for biomaterials for blood deheparinization. In our recent work it was demonstrated that a polypeptide composed of L-lysine and L-leucine (pKL), after immobilization onto tetra(ethylene glycol) terminated self-assembled monolayers (EG4-SAMs), can bind heparin from blood plasma in a selective, concentration-dependent way. During this work the effect of this peptide on platelet adhesion and activation and leukocyte adhesion was studied. The surface charge of these nanostructured surfaces was evaluated in order to correlate the effect of positively charged amine groups and hydrophobic methyl groups on the behavior of platelets and leukocyte adhesion. The results demonstrated that the presence of pKL decreased leukocyte adhesion to EG4-SAMs at all concentrations used. This effect is even more pronounced when surfaces were pre-immersed in heparinized plasma. In contrast, there is an increase in platelet adhesion and activation with increased percentage immobilized pKL. This effect is enhanced when surfaces were pre-immersed in heparinized plasma. However, adsorbed pKL in very low amounts does not induce platelet adhesion and activation compared with EG4, even when pre-immersed in plasma. Since only low pKL amounts are necessary to induce heparin selectivity, these results are promising for the development of heparin-binding biomaterials for blood deheparinization.

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

    PubMed

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

    2007-04-30

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

  15. 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

    2016-07-29

    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.

  16. 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

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    Alkene-based self-assembled monolayers grafted on oxidized Pt surfaces were used as a scaffold to covalently immobilize oxidase enzymes, with the aim to develop an amperometric biosensor platform. NH2-terminated organic layers were functionalized with either aldehyde (CHO) or N-hydroxysuccinimide (NHS) ester-derived groups, to provide anchoring points for enzyme immobilization. The functionalized Pt surfaces were characterized by X-ray photoelectron spectroscopy (XPS), static water contact angle (CA), infrared reflection absorption spectroscopy (IRRAS) and atomic force microscopy (AFM). Glucose oxidase (GOX) was covalently attached to the functionalized Pt electrodes, either with or without additional glutaraldehyde crosslinking. The responses of the acquired sensors to glucose concentrations ranging from 0.5 to 100 mM were monitored by chronoamperometry. Furthermore, lactate oxidase (LOX) and human hydroxyacid oxidase (HAOX) were successfully immobilized onto the PtOx surface platform. The performance of the resulting lactate sensors was investigated for lactate concentrations ranging from 0.05 to 20 mM. The successful attachment of active enzymes (GOX, LOX and HAOX) on Pt electrodes demonstrates that covalently functionalized PtOx surfaces provide a universal platform for the development of oxidase enzyme-based sensors.

  20. 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.

  1. 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

    2010-01-05

    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.

  2. A modular molecular photovoltaic system based on phospholipid/alkanethiol hybrid bilayers: photocurrent generation and modulation.

    PubMed

    Xie, Hong; Jiang, Kai; Zhan, Wei

    2011-10-21

    Monolayer quantities of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), incorporated with either fullerenes or ruthenium tris(bipyridyl) (Ru(bpy)(3)(2+)) complexes, were formed on ferrocene-terminated C11-alkanethiol self-assembled monolayers (SAMs) through lipid fusion. Thus formed hybrid structures are characterized by quartz crystal microbalance, UV-vis spectroscopy, cyclic voltammetry and impedance analysis. In comparison to lipid monolayers deposited on C12-alkanethiol SAMs, photocurrent generation from these ferrocene-based structures is significantly modulated, displaying attenuated anodic photocurrents and enhanced cathodic photocurrents. While a similar trend was observed for the two photoagents studied, the degree of such modulations was always found to be greater in fullerene-incorporated bilayers. These findings are evaluated in the context of the film structure, energetics of the involved photo(electrochemical) species and cross-membrane electron-transfer processes.

  3. Predicting the Conditions for Homeotropic Anchoring of Liquid Crystals at a Soft Surface. 4-n-Pentyl-4'-cyanobiphenyl on Alkylsilane Self-Assembled Monolayers.

    PubMed

    Roscioni, Otello Maria; Muccioli, Luca; Zannoni, Claudio

    2017-04-05

    We have studied, using atomistic molecular dynamics simulations, the alignment of the nematic liquid-crystal 4-n-pentyl-4'-cyanobiphenyl (5CB) on self-assembled monolayers (SAMs) formed from octadecyl- and/or hexyltrichlorosilane (OTS and HTS) attached to glassy silica. We find a planar alignment on OTS at full coverage and an intermediate situation at partial OTS coverage because of the penetration of 5CB molecules into the monolayer, which also removes the tilt of the OTS SAM. Binary mixtures of HTS and OTS SAMs instead induce homeotropic (i.e., perpendicular) alignment. A comparison with the existing experimental literature is provided.

  4. Design and Synthesis of a New Class of Twin-Chain Amphiphiles for Self-Assembled Monolayer-based Electrochemical Biosensor Applications

    PubMed Central

    Fisher, Thomas J.; Cañete, Socrates Jose P.; Lai, Rebecca Y.; Dussault, Patrick H.

    2013-01-01

    A new class of twin-chain hydroxyalkylthiols (mercaptoalkanols) featuring a nearly constant cross-section and the potential for modification of one or both termini are available with complete regioselectivity through Pd-mediated couplings of benzene diiododitriflate, including an example of a previously unreported coupling to generate an ortho-substituted arene bis acetic acid. Self-assembled monolayers (SAMs) prepared from the new amphiphiles demonstrate improved stability in an electrochemical sensor system compared with monolayers prepared from analogous single chain thiols. PMID:24431984

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

    NASA Astrophysics Data System (ADS)

    Gao, Fan; Zhang, Dakuan; Wang, Jianyu; Sheng, Yun; Yan, Shancheng; Wang, Xinran; Chen, Kunji; Shen, Jiancang; Pan, Lijia; Zhou, Minmin; Shi, Yi

    2015-01-01

    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.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. Increased detection of human cardiac troponin I by a decrease of nonspecific adsorption in diluted self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Ren, Jun; Ding, Xiuqing; Greer, John J.; Shankar, Karthik

    2012-04-01

    In this paper, we tested the hypothesis that there is an increased sensitivity for detecting and measuring disease biomarkers (such as human cardiac troponin I, cTnI) by a decrease of nonspecific adsorption in diluted self-assembled monolayers (SAMs) on planar sputtered gold films. Combining grazing angle Fourier-transform infrared spectroscopy (FT-IR) and antibody-antigen-antibody (sandwich) fluorescence-based immunoassay, we examined the relationship of sensitivity, specificity of detection of cTnI and the level of nonspecific protein adsorption in the following SAMs: pure MHA (16-mercaptohexadecanoic acid, 1 mM, with head COO-, x = 1.0), a mixed SAM comprising MHA (0.1 mM) and UDT (1-undecane thiol, 0.9 mM, with hydrophobic head CH3, x = 0.1UDT), and a mixed SAM comprising MHA (0.1 mM) and MUD (11-mercapto-1-undecanol, 0.9 mM, with hydrophilic head OH, x = 0.1MUD). Our data revealed that nonspecific binding to SAMs is favored in the following order: CH3 > COO- > OH, consistent with previous studies. Compared with pure SAMs, diluting MHA SAMs with MUD increases the sensitivity of cTnI, whereas diluted MHA SAMs with UDT has the same sensitivity of detection of cTnI, suggesting it is the nature of the second diluting thiol that plays an important role on the amount of adsorbed protein on the surface. We obtained a 10-fold increase in the limit of detection of cTnI to 10 ng/ml using x = 0.1MUD due to a decrease of nonspecific binding. Further, specific binding between the antigen cTnI and its antibody is unaltered on pure and diluted SAMs.

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

    PubMed

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

    2013-10-01

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

  12. 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.

  13. Simulation and modeling of self-assembled monolayers of carboxylic acid thiols on flat and nanoparticle gold surfaces.

    PubMed

    Techane, Sirnegeda; 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) software and X-ray photoelectron spectroscopy (XPS) experimental measurements. XPS measurements of C16 COOH-SAMs on flat gold surfaces were made at nine different photoelectron emission angles (5-85° in 10° 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. On the basis of 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 1.1 Å/CH(2) group, an RSA of 1.05, and a 1.5 Å CH(2)-contamination overlayer (total film thickness = 21.5 Å) 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 indicated a slightly thinner overlayer with parameters of 0.9 Å/CH(2) group in the SAM, an RSA of 1.06 RSA, and a 1.5 Å CH(2)-contamination overlayer (total film thickness = 18.5 Å). The 3 Å difference in SAM thickness between the flat Au and AuNP surfaces suggests that the alkyl chains of the SAM are slightly more tilted or disordered on the AuNP surfaces.

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

    PubMed

    Cheng, Hefa; Hu, Yuanan

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2000-04-01

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

  16. Phase diagram, design of monolayer binary colloidal crystals, and their fabrication based on ethanol-assisted self-assembly at the air/water interface.

    PubMed

    Dai, Zhengfei; Li, Yue; Duan, Guotao; Jia, Lichao; Cai, Weiping

    2012-08-28

    Flexible structural design and accurate controlled fabrication with structural tunability according to need for binary or multicomponent colloidal crystals have been expected. However, it is still a challenge. In this work, the phase diagram of monolayer binary colloidal crystals (bCCs) is established on the assumption that both large and small polystyrene (PS) colloidal spheres can stay at the air/water interface, and the range diagram for the size ratio and number ratio of small to large colloidal spheres is presented. From this phase diagram, combining the range diagram, we can design and relatively accurately control fabrication of the bCCs with specific structures (or patterns) according to need, including single or mixed patterns with the given relative content. Further, a simple and facile approach is presented to fabricate large-area (more than 10 cm(2)) monolayer bCCs without any surfactants, using differently sized PS spheres, based on ethanol-assisted self-assembly at the air/water interface. bCCs with different patterns and stoichiometries are thus designed from the established phase diagram and then successfully fabricated based on the volume ratios (V(S/L)) of the small to large PS suspensions using the presented colloidal self-assembling method. Interestingly, these monolayer bCCs can be transferred to any desired substrates using water as the medium. This study allows us to design desired patterns of monolayer bCCs and to more accurately control their structures with the used V(S/L).

  17. 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.

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

    PubMed

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

    2017-02-28

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

  19. Opto-electrical studies of self-assembled monolayer diodes and bulk hetero-junction organic photovoltaic devices

    NASA Astrophysics Data System (ADS)

    Ndobe, Alexandre

    The present dissertation is the result of our studies of the optical and electrical properties of self-assembled monolayer (SAM) diodes and bulk heterojunction organic photovoltaic(BOPV) devices. In our studies of SAM diodes, we fabricated solid-state mixtures of two different kinds of molecules; 1,4 benzene-dimethane-thiol (MeBDT) and 1-pentanethiol (PT). By varying the concentration r of MeBDT with respect to PT, we can go from a regime of isolated molecular wires (10--8 < r 10-3). For r = 0, we found that a potential barrier dominated the transport properties of the device. In the isolated molecules regime, the conductance of MeBDT dominates the transport. In this regime, because of the linearity of the conductance with respect to r, we were able to obtain a "single molecule resistance" at V = 0.1 V of RM = 6x 10--9 . In the aggregated molecules regime, an ohmic response in the current-voltage (I-V) characteristics was observed for bias voltages ≤ 0.5V with the appearance of a new band in the differential conductance around V = 0 along with a new double band in the optical gap at 2.4eV resulting in yellow/red photoluminescence emission. Opto-electrical studies of BOPV devices reveal that there are very few similarities between these types of solar cells and conventional solar cells. From simulations and experiemental measurements of the I-V characteristics, we found that while the open voltage circuit (Voc) is important for engineers, it carries no intrinsic information of the device. It cannot exceed the built-in potential of the device (Vbuilt--in ). The later origin was found to be dependent on electrode work function difference for a non-Ohmic contact configuration and on the active layer's blend in an Ohmic contact configuration. In a bid to improve BOPV device performance, we added to the blend spin 1/2 radical molecules. At concentration ( ≤2%), an increase in device performance was observed. The principal cause for this increase was the increase in

  20. Dual functional, polymeric self-assembled monolayers as a facile platform for construction of patterns of biomolecules.

    PubMed

    Park, Sangjin; Lee, Kyung-Bok; Choi, Insung S; Langer, Robert; Jon, Sangyong

    2007-10-23

    We report a facile approach to the construction of patterns of biomolecules based on polymeric self-assembled monolayers (pSAMs) that possess dual functions: "bio-reactive (post-functionalizable)" and "bio-inert (anti-biofouling)" properties. To prepare pSAMs on Si/SiO2 wafers were synthesized new random copolymers by radical polymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMA), 3-(trimethoxysilyl)propyl methacrylate (TMSMA), and N-acryloxysuccinimide (NAS), and referred to as poly(TMSMA-r-PEGMA-r-NAS). Poly(TMSMA-r-PEGMA-r-NAS) was designed to play triple roles: "surface-reactive", "bio-reactive", and "bio-inert" ones. The pSAMs of poly(TMSMA-r-PEGMA-r-NAS) were formed on Si/SiO2 wafers with 1 h incubation of the substrates in the polymer solution, which showed approximately a 1 nm-thick film as measured by ellipsometry. After the formation of the pSAMs, the feasibility of the pSAMs as a dual functional surface (bio-inert and bio-reactive properties) was examined. The ability of the pSAMs to block nonspecific adsorption of proteins was evaluated against bovine serum albumin as a model protein. High-resolution N(1s) X-ray photoelectron spectroscopy (XPS) analysis on the protein adsorption revealed that significant reduction up to approximately 97% was observed compared to the unmodified Si/SiO2 wafer. In addition, micropatterns of streptavidin with high signal-to-noise ratios were achieved using microcontact printing (microCP) of NH2-bearing biotin onto the pSAMs of poly(TMSMA-r-PEGMA-r-NAS) on glass slides, which suggests that other biomolecules could also be efficiently immobilized onto the pSAMs with high specificity while minimizing nonspecific adsorption. On the other hand, the surface density of both bio-reactive and anti-biofouling functionality could be tailored by simply changing initial feed ratios of each monomer in the polymer synthesis: different molar ratios of the bio-reactive group (NAS: 33%, 20%, and 10%, respectively) were

  1. Experimental and theoretical studies of the interaction of gas phase nitric acid and water with a self-assembled monolayer.

    PubMed

    Moussa, S G; Stern, A C; Raff, J D; Dilbeck, C W; Tobias, D J; Finlayson-Pitts, B J

    2013-01-14

    Nitric acid in air is formed by atmospheric reactions of oxides of nitrogen and is removed primarily through deposition to surfaces, either as the gas or after conversion to particulate nitrate. Many of the surfaces and particles have organic coatings, but relatively little is known about the interaction of nitric acid with organic films. We report here studies of the interaction of gaseous HNO(3) with a self-assembled monolayer (SAM) formed by reacting 7-octenyltrichlorosilane [H(2)C=CH(CH(2))(6)SiCl(3)] with the surface of a germanium infrared-transmitting attenuated total reflectance (ATR) crystal that was coated with a thin layer of silicon oxide (SiO(x)). The SAM was exposed at 298 ± 2 K to dry HNO(3) in a flow of N(2), followed by HNO(3) in humid N(2) at a controlled relative humidity (RH) between 20-90%. For comparison, similar studies were carried out using a similar crystal without the SAM coating. Changes in the surface were followed using Fourier transform infared spectroscopy (FTIR). In the case of the SAM-coated crystal, molecular HNO(3) and smaller amounts of NO(3)(-) ions were observed on the surface upon exposure to dry HNO(3). Addition of water vapor led to less molecular HNO(3) and more H(3)O(+) and NO(3)(-) complexed to water, but surprisingly, molecular HNO(3) was still evident in the spectra up to 70% RH. This suggests that part of the HNO(3) observed was initially trapped in pockets within the SAM and shielded from water vapor. After increasing the RH to 90% and then exposing the film to a flow of dry N(2), molecular nitric acid was regenerated, as expected from recombination of protons and nitrate ions as water evaporated. The nitric acid ultimately evaporated from the film. On the other hand, exposure of the SAM to HNO(3) and H(2)O simultaneously gave only hydronium and nitrate ions. Molecular dynamics simulations of defective SAMs in the presence of HNO(3) and water predict that nitric acid intercalates in defects as a complex with a

  2. Equilibrium and non-equilibrium kinetics of self-assembled surfactant monolayers: a vibrational sum-frequency study of dodecanoate at the fluorite-water interface.

    PubMed

    Schrödle, Simon; Richmond, Geraldine L

    2008-04-16

    The adsorption, desorption, and equilibrium monomer exchange processes of sodium dodecanoate at the fluorite(CaF 2)-water interface have been studied. For the first time, we use in situ vibrational sum-frequency spectroscopy (VSFS) to gain insights into the mechanism and kinetics of monolayer self-assembly at the mineral-water interface. By exploiting the nonlinear optical response of the adsorbate, the temporal correlation of headgroup adsorption and alignment of the surfactant's alkyl chain was monitored. Because of the unique surface-specificity of VSFS, changes in the interfacial water structure were also tracked experimentally. The spectra clearly reveal that the structure of interfacial water molecules is severely disturbed at the start of the adsorption process. With the formation of a well-ordered adsorbate layer, it is partially reestablished; however, the molecular orientation and state of coordination is significantly altered. Even at very low surfactant concentrations, overcharging of the mineral surface (i.e., the adsorption of adsorbates past the point of electrostatic equilibrium) was observed. This points out the importance of effects other than electrostatic interactions and it is proposed that cooperative effects of both water structure and surfactant hemimicelle formation at the interface are key factors. The present study also investigates desorption kinetics of partially and fully established monolayers and a statistical model for data analysis is proposed. Additional experiments were performed in the presence of electrolytes and showed that uni- and divalent anions affect the nonequilibrium kinetics of self-assembled monolayers in strikingly different ways.

  3. 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

  4. Bound excitons and many-body effects in x-ray absorption spectra of azobenzene-functionalized self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Cocchi, Caterina; Draxl, Claudia

    2015-11-01

    We study x-ray absorption spectra of azobenzene-functionalized self-assembled monolayers (SAMs), investigating excitations from the nitrogen K edge. Azobenzene with H-termination and functionalized with CF3 groups is considered. The Bethe-Salpeter equation is employed to compute the spectra, including excitonic effects, and to determine the character of the near-edge resonances. Our results indicate that core-edge excitations are intense and strongly bound: their binding energies range from about 6 to 4 eV, going from isolated molecules to densely-packed SAMs. Electron-hole correlation rules these excitations, while the exchange interaction plays a negligible role.

  5. Selective area atomic layer deposited ZnO nanodot on self-assembled monolayer pattern using a diblock copolymer nano-template.

    PubMed

    Kim, Doyoung; Yoon, Jaehong; Kim, Hyungjun

    2012-02-01

    ZnO nanodots were prepared by selective area atomic layer deposition (SA-ALD) on an octadecyltrichlorosilane (ODTS) self-assembly monolayers (SAMs) patterns formed using a diblock co-polymer (DBC) nanotemplate. In order to transfer well-ordered nanaotemplate in SAMs, SiO2 sacrificial layer was inserted between DBC and SAMs. Cylindrical nanoholes under 16 nm diameters were well-formed on SiO2 layer. SA-ALD of ZnO was successfully performed on by ODTS SAMs.

  6. Improved protein crystallization by vapor diffusion from drops in contact with transparent, self-assembled monolayers on gold-coated glass coverslips

    NASA Astrophysics Data System (ADS)

    Ji, David; Arnold, Christine M.; Graupe, Michael; Beadle, Eric; Dunn, Robert V.; Phan, My N.; Villazana, Ramon J.; Benson, Ronald; Colorado, Ramon, Jr.; Randall Lee, T.; Friedman, Jonathan M.

    2000-09-01

    The surfaces of glass coverslips of the type typically used for protein crystallization were modified with four types of transparent, chemically distinct self-assembled monolayers (SAMs). The SAM-functionalized surfaces exhibit a much higher degree of order and chemical uniformity than silanized glass, as judged by contact angle measurements. These characteristics lead to a marked increase in the range of solution conditions under which large crystals of lysozyme, α-lactalbumin, ribonuclease, hemoglobin, thaumatin, and catalase are observed to form. The results are rationalized in terms of a marked reduction in the rate of non-productive nucleation relative to the rate of crystal growth.

  7. 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.

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

    PubMed

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

    2015-10-21

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

  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.

  10. DNA self-assembly-driven positioning of molecular components on nanopatterned surfaces

    NASA Astrophysics Data System (ADS)

    Szymonik, M.; Davies, A. G.; Wälti, C.

    2016-09-01

    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.

  11. 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.

  12. Numerical simulations of electric field driven hierarchical self-assembly of monolayers of binary mixtures of particles

    NASA Astrophysics Data System (ADS)

    Amah, Edison; Musunuri, Naga; Hossain, Shahadat; Fischer, Ian; Singh, Pushpendra

    2016-11-01

    We numerically study the process of self-assembly of particle mixtures on fluid-liquid interfaces when an electric field is applied in the direction normal to the interface. Lateral forces cause particles to self-assemble into molecular-like hierarchical arrangements consisting of composite particles arranged in a pattern. As in experiments, if the particles sizes differ by a factor of two or more, the composite particle has a larger particle at its core with several smaller particles forming a ring around it. Approximately same sized particles form chains (analogous to polymeric molecules) in which positively and negatively polarized particles alternate when their concentrations are approximately equal, but when their concentrations differ substantially the particles whose concentration is larger form rings around the particles whose concentration is smaller. In some instances, particle chains with a positively polarized particle at one end and a negatively particle at the other folded to form circular chains. For submicron particles, only when the electric field intensity is larger than a critical value required for overcoming Brownian forces, a hierarchical pattern consisting of composite particles will form. The work was supported by National Science Foundation.

  13. Sensing Escherichia coli O157:H7 via frequency shift through a self-assembled monolayer based QCM immunosensor*

    PubMed Central

    Wang, Li-jiang; Wu, Chun-sheng; Hu, Zhao-ying; Zhang, Yuan-fan; Li, Rong; Wang, Ping

    2008-01-01

    By means of the specific immuno-recognition and ultra-sensitive mass detection, a quartz crystal microbalance (QCM) biosensor for Escherichia coli O157:H7 detection was developed in this work. As a suitable surfactant, 16-mercaptohexadecanoic acid (MHDA) was introduced onto the Au surface of QCM, and then self-assembled with N-hydroxysuccinimide (NHS) raster as a reactive intermediate to provide an active interface for the specific antibody immobilization. The binding of target bacteria with the immobilized antibodies decreased the sensor’s resonant frequency, and the frequency shift was correlated to the bacterial concentration. The stepwise assembly of the immunosensor was characterized by means of the electrochemical techniques. Using the immersion-dry-immersion procedure, this QCM biosensor could detect 2.0×102 colony forming units (CFU)/ml E. coli O157:H7. In order to reduce the fabrication time, a polyelectrolyte layer-by-layer self-assembly (LBL-SA) method was adopted for fast construction. Finally, the reproducibility of this biosensor was discussed. PMID:18257134

  14. Chemical and physical passivation of type II strained-layer superlattice devices by means of thiolated self-assembled monolayers and polymer encapsulates

    NASA Astrophysics Data System (ADS)

    Henry, Nathan C.; Knorr, Daniel B.; Williams, Kristen S.; Baril, Neil; Nallon, Eric; Lenhart, Joseph L.; Andzelm, Jan W.; Pellegrino, Joseph; Tidrow, Meimei; Cleveland, Erin; Bandara, Sumith

    2015-05-01

    The efficacy of solution deposition of thiolated self-assembled monolayers (SAMs) has been explored for the purpose of passivating III-V type II superlattice (T2SL) photodetectors, more specifically a p-type heterojunction device. Sulfur passivation has previously been achieved on T2SL devices. However, degradation over time, temperature sensitivity and inconsistent reproducibility necessitate a physical encapsulate that can chemically bond to the chemical passivant. Thus, this research investigates two passivation methods, surface passivation with a thiol monolayer and passivation with a polymer encapsulant with a view toward future combination of these techniques. Analysis of the physical and chemical condition of the surface prior to deposition assisted in the development of ideal processes for optimized film quality. Successful deposition was facilitated by in situ oxide removal. Various commercially available functional (cysteamine) and non-functional (alkane) thiolated monolayers were investigated. Dark current was reduced by 3 orders of magnitude and achieved negligible surface leakage at low bias levels. The lowest dark current result, 7.69 × 10-6 A/cm2 at 50 mV, was achieved through passivation with cysteamine.

  15. Study on the reversible changes of the surface properties of an L-cysteine self-assembled monolayer on gold as a function of pH.

    PubMed

    Filimon, Andrei-Daniel; Jacob, Peter; Hergenröder, Roland; Jürgensen, Astrid

    2012-06-12

    A stimuli-response biological surface of L-cysteine was prepared on a polycrystalline gold surface from aqueous solution. The effect of the pH value of the rinsing solution on the surface composition was studied with X-ray photoelectron spectroscopy (XPS). Qualitative and quantitative analysis of the amino, carboxyl, and thiol functional groups of these self-assembled monolayers indicate that L-cysteine molecules exist in the neutral and zwitterionic forms and that they are sensitive to the pH of the rinsing solution. In addition, the wetting properties of the functionalized surface were studied by contact angle (CA) analysis: they were also dependent on the pH of the rinsing solution. Furthermore, it was shown that this functionalization process was reversible.

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

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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

  17. Structure and homogeneity of pseudo-physiological phospholipid bilayers and their deposition characteristics on carboxylic acid terminated self-assembled monolayers.

    PubMed

    Mechler, Adam; Praporski, Slavica; Piantavigna, Stefania; Heaton, Steven M; Hall, Kristopher N; Aguilar, Marie-Isabel; Martin, Lisandra L

    2009-02-01

    Supported phospholipid bilayers are frequently used to establish a pseudo-physiological environment required for the study of protein function or the design of enzyme-based biosensors and biocatalytic reactors. These membranes are deposited from bilayer vesicles (liposomes) that rupture and fuse into a planar membrane upon adhesion to a surface. However, the morphology and homogeneity of the resulting layer is affected by the characteristics of the precursor liposome suspension and the substrate. Here we show that two distinct liposome populations contribute to membrane formation--equilibrium liposomes and small unilamellar vesicles. Liposome deposition onto carboxylic acid terminated self-assembled monolayers resulted in planar mono- and multilayer, vesicular and composite membranes, as a function of liposome size and composition. Quartz crystal microbalance data provided estimates for layer thicknesses and sheer moduli and were used for classification of the final structure. Finally, atomic force microscopy data illustrated the inherently inhomogeneous and dynamic nature of these membranes.

  18. Tuning the Rectification Ratio by Changing the Electronic Nature (Open-Shell and Closed-Shell) in Donor-Acceptor Self-Assembled Monolayers.

    PubMed

    Souto, Manuel; Yuan, Li; Morales, Dayana C; Jiang, Li; Ratera, Imma; Nijhuis, Christian A; Veciana, Jaume

    2017-03-16

    This Communication describes the mechanism of charge transport across self-assembled monolayers (SAMs) of two donor-acceptor systems consisting of a polychlorotriphenylmethyl (PTM) electron-acceptor moiety linked to an electron-donor ferrocene (Fc) unit supported by ultraflat template-stripped Au and contacted by a eutectic alloy of gallium and indium top contacts. The electronic and supramolecular structures of these SAMs were well characterized. The PTM unit can be switched between the nonradical and radical forms, which influences the rectification behavior of the junction. Junctions with nonradical units rectify currents via the highest occupied molecular orbital (HOMO) with a rectification ratio R = 99, but junctions with radical units have a new accessible state, a single-unoccupied molecular orbital (SUMO), which turns rectification off and drops R to 6.

  19. Immobilization of quantum dots via conjugated self-assembled monolayers and their application as a light-controlled sensor for the detection of hydrogen peroxide.

    PubMed

    Khalid, Waqas; El Helou, Mira; Murböck, Tobias; Yue, Zhao; Montenegro, Jose-Maria; Schubert, Kirsten; Göbel, Gero; Lisdat, Fred; Witte, Gregor; Parak, Wolfgang J

    2011-12-27

    A light-addressable gold electrode modified with CdS and FePt or with CdS@FePt nanoparticles via an interfacial dithiol linker layer is presented. XPS measurements reveal that trans-stilbenedithiol provides high-quality self-assembled monolayers compared to benzenedithiol and biphenyldithiol, in case they are formed at elevated temperatures. The CdS nanoparticles in good electrical contact with the electrode allow for current generation under illumination and appropriate polarization. FePt nanoparticles serve as catalytic sites for the reduction of hydrogen peroxide to water. Advantageously, both properties can be combined by the use of hybrid nanoparticles fixed on the electrode by means of the optimized stilbenedithiol layer. This allows a light-controlled analysis of different hydrogen peroxide concentrations.

  20. Conditioning of self-assembled monolayers at two static immersion test sites along the east coast of Florida and its effect on early fouling development.

    PubMed

    Thome, I; Bauer, S; Vater, S; Zargiel, K; Finlay, J A; Arpa-Sancet, M P; Alles, M; Callow, J A; Callow, M E; Swain, G W; Grunze, M; Rosenhahn, A

    2014-09-01

    Among the first events after immersion of surfaces in the ocean is surface 'conditioning'. Here, the accumulation and composition of the conditioning films formed after immersion in the ocean are analyzed. In order to account for different surface chemistries, five self-assembled monolayers that differ in resistance to microfouling and wettability were used. Water samples from two static immersion test sites along the east coast of Florida were collected at two different times of the year and used for experiments. Spectral ellipsometry revealed that conditioning films were formed within the first 24 h and contact angle goniometry showed that these films changed the wettability and rendered hydrophobic surfaces more hydrophilic and vice versa. Infrared reflection adsorption spectroscopy showed that the composition of the conditioning film depended on both the wettability and immersion site. Laboratory and field assays showed that the presence of a conditioning film did not markedly influence settlement of microorganisms.

  1. 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.

  2. 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.

  3. Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Zettsu, Nobuyuki; Kida, Satoru; Uchida, Shuhei; Teshima, Katsuya

    2016-08-01

    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.

  4. Electrical conduction behavior of organic light-emitting diodes using fluorinated self-assembled monolayer with molybdenum oxide-doped hole transporting layer.

    PubMed

    Park, Sang-Geon; Mori, Tatsuo

    2015-06-01

    The electrical conductivity behavior of a fluorinated self-assembled monolayer (FSAM) of a molybdenum oxide (MoOx)-doped α-naphthyl diamine derivative (α-NPD) in organic light-emitting diodes (OLEDs) was investigated. The current density of the MoOx-doped α-NPD/FSAM device was proportional to its voltage owing to smooth carrier injection through the FSAM and the high carrier density of its bulk. The temperature-dependent characteristics of this device were investigated. The current density-voltage characteristics at different temperatures were almost the same owing to its very low activation energy. The activation energy of the device was estimated to be 1.056 × 10(-2) [eV] and was very low due to the inelastic electron tunneling of FSAM molecules.

  5. True nature of an archetypal self-assembly system: mobile Au-thiolate species on Au(111).

    PubMed

    Yu, Miao; Bovet, N; Satterley, Christopher J; Bengió, S; Lovelock, Kevin R J; Milligan, P K; Jones, Robert G; Woodruff, D P; Dhanak, V

    2006-10-20

    Alkanethiol self-assembled monolayer (SAM) phases on Au(111) have been assumed to involve direct S head group bonding to the substrate. Using x-ray standing wave experiments, we show the thiolate actually bonds to gold adatoms; self-organization in these archetypal SAM systems must therefore be governed by the movement of these Au-S-R moieties on the surface between two distinct local hollow sites on the surface. The results of recent ab initio total energy calculations provide strong support for this description, and a rationale for the implied significant molecular mobility in these systems.

  6. True Nature of an Archetypal Self-Assembly System: Mobile Au-Thiolate Species on Au(111)

    NASA Astrophysics Data System (ADS)

    Yu, Miao; Bovet, N.; Satterley, Christopher J.; Bengió, S.; Lovelock, Kevin R. J.; Milligan, P. K.; Jones, Robert G.; Woodruff, D. P.; Dhanak, V.

    2006-10-01

    Alkanethiol self-assembled monolayer (SAM) phases on Au(111) have been assumed to involve direct S head group bonding to the substrate. Using x-ray standing wave experiments, we show the thiolate actually bonds to gold adatoms; self-organization in these archetypal SAM systems must therefore be governed by the movement of these Au-S-R moieties on the surface between two distinct local hollow sites on the surface. The results of recent ab initio total energy calculations provide strong support for this description, and a rationale for the implied significant molecular mobility in these systems.

  7. 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. PMID:27873775

  8. 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.

  9. 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.

  10. 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.

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

    PubMed

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

    2015-01-01

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

  12. 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).

  13. Metal overlayers on organic functional groups of self-assembled monolayers: VIII. X-ray photoelectron spectroscopy of the Ni/COOH interface

    SciTech Connect

    Herdt, G.C.; Czanderna, A.W.

    1999-11-01

    The interaction of vacuum deposited Ni with the COOH organic functional groups of mercaptoundecanoic acid [HS(CH{sub 2}){sub 10}COOH] self-assembled monolayers formed on an Au substrate has been characterized with {ital in situ} x-ray photoelectron spectroscopy. Steady loss and complete disappearance of the hydroxyl component of O&hthinsp;1s peak at 532.8 eV provides evidence for the formation of a Ni{endash}O bond at the Ni/COOH interface. Further evidence for interfacial compound formation is provided by a binding energy shift in the high binding energy component of the Ni&hthinsp;2p{sub 3/2} peak from 854.8 to 854.4 eV for Ni coverages below {approximately}0.2 nm. These results are consistent with the donation of electrons from the deposited Ni to the COOH oxygens at low Ni coverages. The absence of the characteristic satellite feature in the Ni&hthinsp;2p peak excludes the possibility that a full electron charge is donated to each COOH organic functional group as a bidentate complex. However, the data are consistent with a two step reaction mechanism in which Ni initially reacts weakly with the oxygens in COOH below one monolayer coverage and then forms a complex above this coverage. {copyright} {ital 1999 American Vacuum Society.}

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

    NASA Astrophysics Data System (ADS)

    Battocchio, C.; Fratoddi, I.; Venditti, I.; Yarzhemsky, V. G.; Norov, Yu. V.; Russo, M. V.; Polzonetti, G.

    2011-01-01

    The molecular structure and organization of self-assembled monolayers (SAMs) and multilayer films grafted onto Au/Si(1 1 1) surfaces of mononuclear transition metal dialkynyl bridged Pd(II) complexes trans-[HS-Pd(PBu 3) 2-SH] ( 1), trans-[HS-Pd(PBu 3) 2(-C tbnd C-C 6H 5)] ( 2) and of the binuclear complex trans, trans-[HS-Pd(PBu 3) 2(-C tbnd C-C 6H 4-C 6H 4-C tbnd C-Pd(PBu 3) 2-SH] ( 3), have been investigated by extended X-ray absorption fine structure spectroscopy in total reflection conditions (reflEXAFS). ReflEXAFS analysis of the data lead to determine the local structure around Pd atoms, assessing the square-planar geometry around the transition metal in the multilayers case, preserved in the monolayer regime. The investigation on the SAMs also provided the assessment of the S-Au bond length and Pd-S-Au bond angle and on the molecular orientation on the gold substrate of the complexes, confirmed by quantum chemical calculations.

  15. 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.

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  18. "Click" Patterning of Self-Assembled Monolayers on Hydrogen-Terminated Silicon Surfaces and Their Characterization Using Light-Addressable Potentiometric Sensors.

    PubMed

    Wang, Jian; Wu, Fan; Watkinson, Michael; Zhu, Jingyuan; Krause, Steffi

    2015-09-08

    Two potential strategies for chemically patterning alkyne-terminated self-assembled monolayers (SAMs) on oxide-free silicon or silicon-on-sapphire (SOS) substrates were investigated and compared. The patterned surfaces were validated using a light-addressable potentiometric sensor (LAPS) for the first time. The first strategy involved an integration of photolithography with "click" chemistry. Detailed surface characterization (i.e. water contact angle, ellipsometry, AFM, and XPS) and LAPS measurements showed that photoresist processing not only decreases the coverage of organic monolayers but also introduces chemically bonded contaminants on the surfaces, thus significantly reducing the quality of the SAMs and the utility of "click" surface modification. The formation of chemical contaminants in photolithography was also observed on carboxylic acid- and alkyl-terminated monolayers using LAPS. In contrast, a second approach combined microcontact printing (μCP) with "click" chemistry; that is azide (azido-oligo(ethylene glycol) (OEG)-NH2) inks were printed on alkyne-terminated SAMs on silicon or SOS through PDMS stamps. The surface characterization results for the sample printed with a flat featureless PDMS stamp demonstrated a nondestructive and efficient method of μCP to perform "click" reactions on alkyne-terminated, oxide-free silicon surfaces for the first time. For the sample printed with a featured PDMS stamp, LAPS imaging showed a good agreement with the pattern of the PDMS stamp, indicating the successful chemical patterning on non-oxidized silicon and SOS substrates and the capability of LAPS to image the molecular patterns with high sensitivity.

  19. 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.

  20. Self-assembled monolayer initiated electropolymerization: a route to thin-film materials with enhanced photovoltaic performance.

    PubMed

    Hwang, Euiyong; de Silva, K M Nalin; Seevers, Chad B; Li, Jie-Ren; Garno, Jayne C; Nesterov, Evgueni E

    2008-09-02

    Continuing progress in the field of organic polymer photovoltaic (PV) devices requires the development of new materials with better charge-transport efficiency. To improve this parameter, we have investigated surface-attached bilayer polymer PV thin films prepared starting from a covalently attached monolayer of an electroactive initiator using sequential electropolymerization of dithiophene and its derivatives. These systems were found to show significantly increased photocurrent generation quantum yields as compared to systems made through conventional approaches. In addition, the described PV thin films possess remarkable mechanical, air, and photostability. These properties likely arise from the more uniform and better ordered bulk layer morphologies as well as tighter covalently bonded contacts at the interfacial junctions, contributing to improved charge transport. While more studies on the fundamental reasons behind the discovered phenomenon are currently underway, this information can be readily applied to build more efficient organic polymer photovoltaics.

  1. Oriented immobilization of antibodies by a self-assembled monolayer of 2-(biotinamido)ethanethiol for immunoarray preparation.

    PubMed

    Jung, Se-Hui; Son, Ha-Young; Yuk, Jong Seol; Jung, Jae-Wan; Kim, Kyung Hwan; Lee, Chang-Hee; Hwang, Hoon; Ha, Kwon-Soo

    2006-01-15

    Orientation of antibodies is very important in the preparation of immunoarrays to keep the activity of antibodies on solid surfaces. Thus, we synthesized a new bifunctional compound, 2-(biotinamido)ethanethiol, and investigated whether the thiol compound is useful to analyze antibody-antigen interactions on immunoarrays with a spectral SPR biosensor. The synthesized organic thiol was characterized by nuclear magnetic resonance spectroscopy and mass spectrometry. 2-(Biotinamido)ethanethiol formed a monolayer on a gold surface and properly immobilized antibodies via streptavidin and biotinylated protein G. Optimal molar ratio of 2-(biotinamido)ethanethiol and mercaptohexanol for antigen-antibody interactions was 1:2. Thus, 2-(biotinamido)ethanethiol is an useful bifunctional linker in the preparation of immunoarrays on gold surfaces.

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

    SciTech Connect

    Willey, Trevor M.

    2004-04-01

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

  3. A molecular simulation study of methylated and hydroxyl sugar-based self-assembled monolayers: Surface hydration and resistance to protein adsorption

    NASA Astrophysics Data System (ADS)

    Hower, Jason C.; He, Yi; Jiang, Shaoyi

    2008-12-01

    In this work molecular simulations are performed to investigate protein interactions with hydroxylated and methylated mannitol and sorbitol terminated self-assembled monolayer (SAM) surfaces in the presence of explicit water molecules. The role of surface hydrogen bond donor versus acceptor groups is evaluated by comparing the hydration layer structure and resulting forces generated by the two classes of sugar SAM surfaces. Both hydroxyl and methyl-terminated sugar SAM surfaces interact with hydrating water molecules. Regardless of hydrogen bond donor or acceptor groups, both classes of sugar SAM surface groups interact strongly with hydrating water molecules to induce significant repulsive forces and resistance to protein adsorption. Our results indicate that the repulsive force generated on the probe protein is related to the ability of the surface to orient the hydration layer water. The repulsive force is also proportional to the number of hydrating water molecules interacting with the protein. The repulsive force and subsequent resistance to protein adsorption are dependent on the surface hydration, not the origin of that hydration.

  4. 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

  5. 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

  6. 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

    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.

  7. 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.

  8. 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

  9. Revealing and Resolving the Restrained Enzymatic Cleavage of DNA Self-Assembled Monolayers on Gold: Electrochemical Quantitation and ESI-MS Confirmation.

    PubMed

    Gao, Xiaoyi; Geng, Mingxi; Li, Yunchao; Wang, Xinglin; Yu, Hua-Zhong

    2017-02-21

    Herein, we report a combined electrochemical and ESI-MS study of the enzymatic hydrolysis efficiency of DNA self-assembled monolayers (SAMs) on gold, platform systems for understanding nucleic acid surface chemistry, and for constructing DNA-based biosensors. Our electrochemical approach is based on the comparison of the amounts of surface-tethered DNA nucleotides before and after exonuclease I (Exo I) incubation using electrostatically bound [Ru(NH3)6](3+) as redox indicators. It is surprising to reveal that the hydrolysis efficiency of ssDNA SAMs does not depend on the packing density and base sequence, and that the cleavage ends with surface-bound shorter strands (9-13 mers). The ex-situ ESI-MS observations confirmed that the hydrolysis products for ssDNA SAMs (from 24 to 56 mers) are dominated with 10-15 mer fragments, in contrast to the complete digestion in solution. Such surface-restrained hydrolysis behavior is due to the steric hindrance of the underneath electrode to the Exo I/DNA binding, which is essential for the occurrence of Exo I-catalyzed processive cleavage. More importantly, we have shown that the hydrolysis efficiency of ssDNA SAMs can be remarkably improved by adopting long alkyl linkers (locating DNA strands further away from the substrates).

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

    PubMed

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

    2015-06-17

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

  11. 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.

  12. Label-free impedimetric sensor for a ribonucleic acid oligomer specific to hepatitis C virus at a self-assembled monolayer-covered electrode.

    PubMed

    Park, Jin-Young; Lee, Yoon-suk; Chang, Byoung-Yong; Kim, Byeang Hyean; Jeon, Sangmin; Park, Su-Moon

    2010-10-01

    A ribonucleic acid (RNA) sensor based on hybridization of its peptide nucleic acid (PNA) molecule with a target RNA oligomer of the internal ribosome entry site sequence specific to the hepatitis C virus (HCV) and the electrochemical impedance detection is described. This RNA is one of the most conservative molecules of the whole HCV RNA genome. The ammonium ion terminated PNA molecule was immobilized via its host-guest interactions with the diaza crown ring of 3-thiophene-acetamide-diaza-18-crown-6 synthesized by a simple two-step method, which forms a well-defined self-assembled monolayer (SAM) on gold. Hybridization events of the probe PNA with the target RNA were monitored by measuring charge-transfer resistances for the Fe(CN)(6)(3-/4-) redox probe using Fourier transform electrochemical impedance spectroscopy. The ratio of the resistances of the SAM-covered electrode measured before and after hybridization increased linearly with log[RNA] in the rat liver lysate with a detection limit of about 23 pM.

  13. Directed immobilization of protein-coated nanospheres to nanometer-scale patterns fabricated by electron beam lithography of poly(ethylene glycol) self-assembled monolayers.

    PubMed

    Rundqvist, Jonas; Hoh, Jan H; Haviland, David B

    2006-05-23

    Controlling the spatial organization of biomolecules on solid supports with high resolution is important for a wide range of scientific and technological problems. Here we report a study of electron beam lithography (EBL) patterning of a self-assembled monolayer (SAM) of the amide-containing poly(ethylene glycol) (PEG) thiol CH(3)O(CH(2)CH(2)O)(17)NHCO(CH(2))(2)SH on Au and demonstrate the patterning of biomolecular features with dimensions approaching 40 nm. The electron dose dependence of feature size and pattern resolution is studied in detail by atomic force microscopy (AFM), which reveals two distinct patterning mechanisms. At low doses, the pattern formation occurs by SAM ablation in a self-developing process where the feature size is directly dose-dependent. At higher doses, electron beam-induced deposition of material, so-called contamination writing, is seen in the ablated areas of the SAM. The balance between these two mechanisms is shown to depend on the geometry of the pattern. The patterned SAMs were backfilled with fluorescent 40-nm spheres coated with NeutrAvidin. These protein-coated spheres adhered to exposed areas in the SAM with high selectivity. This direct writing approach for patterning bioactive surfaces is a fast and efficient way to produce patterns with a resolution approaching that of single proteins.

  14. An Electrochemical Immunosensor for Detection of Staphylococcus aureus Bacteria Based on Immobilization of Antibodies on Self-Assembled Monolayers-Functionalized Gold Electrode

    PubMed Central

    Braiek, Mohamed; Rokbani, Karima Bekir; Chrouda, Amani; Mrabet, Béchir; Bakhrouf, Amina; Maaref, Abderrazak; Jaffrezic-Renault, Nicole

    2012-01-01

    The detection of pathogenic bacteria remains a challenge for the struggle against biological weapons, nosocomial diseases, and for food safety. In this research, our aim was to develop an easy-to-use electrochemical immunosensor for the detection of pathogenic Staphylococcus aureus ATCC25923. The biosensor was elaborated by the immobilization of anti-S. aureus antibodies using a self-assembled monolayer (SAMs) of 3-Mercaptopropionic acid (MPA). These molecular assemblies were spontaneously formed by the immersion of the substrate in an organic solvent containing the SAMs that can covalently bond to the gold surface. The functionalization of the immunosensor was characterized using two electrochemical techniques: cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Here, the analysis was performed in phosphate buffer with ferro/ferricyanide as the redox probe. The EIS technique was used for affinity assays: antibody-cell binding. A linear relationship between the increment in the electron transfer resistance (RCT) and the logarithmic value of S. aureus concentration was observed between 10 and 106 CFU/mL. The limit of detection (LOD) was observed at 10 CFU/mL, and the reproducibility was calculated to 8%. Finally, a good selectivity versus E. coli and S. epidermidis was obtained for our developed immunosensor demonstrating its specificity towards only S. aureus. PMID:25586032

  15. Successive coordination of palladium(II)-ions and terpyridine-ligands to a pyridyl-terminated self-assembled monolayer on gold

    NASA Astrophysics Data System (ADS)

    Poppenberg, Johannes; Richter, Sebastian; Darlatt, Erik; Traulsen, Christoph H.-H.; Min, Hyegeun; Unger, Wolfgang E. S.; Schalley, Christoph A.

    2012-02-01

    The deposition of palladium on a novel, reversibly protonatable, pyridyl-terminated self-assembled monolayer on gold substrates has been studied by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS spectroscopy) and time of flight-secondary ion mass spectrometry (ToF-SIMS). For this purpose, 12-(pyridin-4-yl)dodecane-1-thiol, consisting of a surface-active head group, an unfunctionalized hydrocarbon backbone and a terminal pyridyl group, has been synthesized and deposited on gold surfaces. Coordination of Pd(II) ions to the pyridyl group was examined. Furthermore, a reversible protonation/deprotonation cycle has been applied, and the relation between protonation and the amount of complexed palladium was studied. Investigation of the SAM by angle-resolved NEXAFS spectroscopy revealed the aliphatic backbone to be preferentially upright oriented with the aromatic head group being not preferentially oriented. The palladium layer was further coordinated with a CF3-labeled terpyridine ligand in order to prove the accessibility of the Pd(II) ions to further complexation and the platform useful for deposition of further layers toward a multi-layered system.

  16. 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.

  17. Improving the Stability and Sensing of Electrochemical Biosensors by Employing Trithiol-Anchoring Groups in a Six-carbon Self-assembled Monolayer

    PubMed Central

    Phares, Noelle; White, Ryan J.; Plaxco, Kevin W.

    2009-01-01

    Alkane thiol self-assembled monolayers (SAMs) have seen widespread utility in the fabrication of electrochemical biosensors. Their utility, however, reflects a potentially significant compromise. While shorter SAMs support efficient electron transfer, they pack poorly and are thus relatively unstable. Longer SAMs are more stable, but suffer from less efficient electron transfer, thus degrading sensor performance. Here we use the electrochemical DNA (E-DNA) sensor platform to compare the signaling and stability of biosensors fabricated using a short, six-carbon monothiol with those employing either of two commercially available, trihexylthiol anchors (a flexible Letsinger-type and a rigid adamantane type). We find that all three anchors support efficient electron transfer and E-DNA signaling, with the gain, specificity and selectivity of all three being effectively indistinguishable. The stabilities of the three anchors, however, vary significantly. Sensors anchored with the flexible trithiol exhibit enhanced stability, retaining 75% of their original signal and maintaining excellent signaling properties after 50 days storage in buffer. Likewise these sensors exhibit excellent temperature stability and robustness to electrochemical interrogation. The stability of sensors fabricated using the rigid trithiol anchor, by comparison, are similar to those of the monothiol. Both exhibit significant (>60%) loss of signal upon wet storage or thermocycling. Employing a flexible trithiol anchor in the fabrication of SAM-based electrochemical biosensors may provide a means of improving sensor robustness without sacrificing electron transfer efficiency or otherwise impeding sensor performance. PMID:19133790

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

    PubMed

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

    2011-02-01

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

  19. Laterally Mobile, Functionalized Self-Assembled Monolayers at the Fluorous−Aqueous Interface in a Plug-Based Microfluidic System: Characterization and Testing with Membrane Protein Crystallization

    SciTech Connect

    Kreutz, Jason E.; Li, Liang; Roach, L. Spencer; Hatakeyama, Takuji; Ismagilov, Rustem F.

    2009-11-04

    This paper describes a method to generate functionalizable, mobile self-assembled monolayers (SAMs) in plug-based microfluidics. Control of interfaces is advancing studies of biological interfaces, heterogeneous reactions, and nanotechnology. SAMs have been useful for such studies, but they are not laterally mobile. Lipid-based methods, though mobile, are not easily amenable to setting up the hundreds of experiments necessary for crystallization screening. Here we demonstrate a method, complementary to current SAM and lipid methods, for rapidly generating mobile, functionalized SAMs. This method relies on plugs, droplets surrounded by a fluorous carrier fluid, to rapidly explore chemical space. Specifically, we implemented his-tag binding chemistry to design a new fluorinated amphiphile, RfNTA, using an improved one-step synthesis of RfOEG under Mitsunobu conditions. RfNTA introduces specific binding of protein at the fluorous-aqueous interface, which concentrates and orients proteins at the interface, even in the presence of other surfactants. We then applied this approach to the crystallization of a his-tagged membrane protein, Reaction Center from Rhodobacter sphaeroides, performed 2400 crystallization trials, and showed that this approach can increase the range of crystal-producing conditions, the success rate at a given condition, the rate of nucleation, and the quality of the crystal formed.

  20. Using Self-Assembled Monolayers to Model Cell Adhesion to the 9th and 10th Type III Domains of Fibronectin†

    PubMed Central

    2009-01-01

    Most mammalian cells must adhere to the extracellular matrix (ECM) to maintain proper growth and development. Fibronectin is a predominant ECM protein that engages integrin cell receptors through its Arg-Gly-Asp (RGD) and Pro-His-Ser-Arg-Asn (PHSRN) peptide binding sites. To study the roles these motifs play in cell adhesion, proteins derived from the 9th (containing PHSRN) and 10th (containing RGD) type III fibronectin domains were engineered to be in frame with cutinase, a serine esterase that forms a site-specific, covalent adduct with phosphonate ligands. Self-assembled monolayers (SAMs) that present phosphonate ligands against an inert background of tri(ethylene glycol) groups were used as model substrates to immobilize the cutinase-fibronectin fusion proteins. Baby hamster kidney cells attached efficiently to all protein surfaces, but only spread efficiently on protein monolayers containing the RGD peptide. Cells on RGD-containing protein surfaces also displayed defined focal adhesions and organized cytoskeletal structures compared to cells on PHSRN-presenting surfaces. Cell attachment and spreading were shown to be unaffected by the presence of PHSRN when compared to RGD alone on SAMs presenting higher densities of protein, but PHSRN supported an increased efficiency in cell attachment when presented at low protein densities with RGD. Treatment of suspended cells with soluble RGD or PHSRN peptides revealed that both peptides were able to inhibit the attachment of FN10 surfaces. These results support a model wherein PHSRN and RGD bind competitively to integrins―rather than a two-point synergistic interaction―and the presence of PHSRN serves to increase the density of ligand on the substrate and therefore enhance the sticking probability of cells during attachment. PMID:20560553

  1. 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

  2. Immobilization of biomaterials to nano-assembled films (self-assembled monolayers, Langmuir-Blodgett films, and layer-by-layer assemblies) and their related functions.

    PubMed

    Ariga, Katsuhiko; Nakanishi, Takashi; Michinobu, Tsuyoshi

    2006-08-01

    For utilization of highly sophisticated functions of biomaterials in nano-scale functional systems, immobilization of biomaterials on artificial devices such as electrodes via thin film technology is one of the most powerful strategies. In this review, we focus on three major organic ultrathin films, self-assembled monolayers (SAM), Langmuir-Blodgett (LB) films, and layer-by-layer (LBL) assemblies, and from the viewpoints of biomaterial immobilization, typical examples and recent progresses in these film technologies are described. The SAM method allows facile contact between biomaterials and man-made devices, and well used for bio-related sensors. In addition, recent micro-fabrication techniques such as micro-contact printing and dip-pen nanolithography were successfully applied to preparation of biomaterial patterning. A monolayer at the air-water interface, which is a unit structure of LB films, provides a unique environment for recognition of aqueous biomaterials. Recognition and immobilization of various biomaterials including nucleotides, nucleic acid bases, amino acids, sugars, and peptides were widely investigated. The LB film can be also used for immobilization of enzymes in an ultrathin film on an electrode, resulting in sensor application. The LBL assembling method is available for wide range of biomaterials and provides great freedom in designs of layered structures. These advantages are reflected in preparation of thin-film bio-reactors where multiple kinds of enzymes sequentially operate. LBL assemblies were also utilized for sensors and drug delivery systems. This kind of assembling structures can be prepared on micro-size particle and very useful for preparation of hollow capsules with biological functions.

  3. Controlled hierarchical assembly of gold nanoparticles in macroscopic films: from densely packed monolayers to networks of micropores and nanobundles.

    PubMed

    Gravelsins, Steven; Hasham, Minhal; Lin, Yi; Yu, Kevin; Tie, Monique; Goh, Cynthia; Dhirani, Al-Amin

    2017-03-29

    The present study demonstrates the ability of excess, weakly amphiphilic n-alkanethiols (n = 4, 12, 18) and solvent composition to tune through a wide range of large-scale, macroscopic architectures formed by alkanethiol-capped Au nanoparticles (NPs). Both the alkanethiols and NPs are significantly hydrophobic species and compete for surface area at an air-water interface. When solutions of the two species are spread on a large (50 cm(2)) water surface in a Teflon well, a thin film forms and exhibits co-existing macroscopic regions with various distinct NP self-assembled architectures, namely a close packed monolayer, a network phase characterized by micron-sized pores (micropores) surrounded by quasi-linear bundles of nanoparticles, and finally aggregates. We hypothesize that the co-existence of various NP architectures results from fast, non-uniform evaporation across the large water surface. When solutions are instead deposited on a smaller (5 cm(2)) water surface contained within a Teflon ring to control the water surface curvature and the evaporation rate is slowed, we show for the first time that NPs form macroscopically uniform self-assemblies whose architectures can be tuned from monolayersmonolayers with micropores → extended micropore/NP bundle networks by varying excess alkanethiol concentration and solvent composition. We propose that competition between NPs and excess alkanethiols for water surface area, and alkanethiol self-assembly as well as solvent dewetting play important roles in the formation of the network phase, and discuss a potential mechanism for its formation.

  4. Molecular self-assembly for biological investigations and nanoscale lithography

    NASA Astrophysics Data System (ADS)

    Cheunkar, Sarawut

    Small, diffusible molecules when recognized by their binding partners, such as proteins and antibodies, trigger enzymatic activity, cell communication, and immune response. Progress in analytical methods enabling detection, characterization, and visualization of biological dynamics at the molecular level will advance our exploration of complex biological systems. In this dissertation, analytical platforms were fabricated to capture membrane-associated receptors, which are essential proteins in cell signaling pathways. The neurotransmitter serotonin and its biological precursor were immobilized on gold substrates coated with self-assembled monolayers (SAMs) of oligo(ethylene glycol)alkanethiols and their reactive derivatives. The SAM-coated substrates present the biologically selective affinity of immobilized molecules to target native membrane-associated receptors. These substrates were also tested for biospecificity using antibodies. In addition, small-molecule-functionalized platforms, expressing neurotransmitter pharmacophores, were employed to examine kinetic interactions between G-protein-coupled receptors and their associated neurotransmitters. The binding interactions were monitored using a quartz crystal microbalance equipped with liquid-flow injection. The interaction kinetics of G-protein-coupled serotonin 1A receptor and 5-hydroxytyptophan-functionalized surfaces were studied in a real-time, label-free environment. Key binding parameters, such as equilibrium dissociation constants, binding rate constants, and dissociative half-life, were extracted. These parameters are critical for understanding and comparing biomolecular interactions in modern biomedical research. By integrating self-assembly, surface functionalization, and nanofabrication, small-molecule microarrays were created for high-throughput screening. A hybrid soft-lithography, called microcontact insertion printing, was used to pattern small molecules at the dilute scales necessary for highly

  5. Self Assembly and Pyroelectric Poling for Organics

    DTIC Science & Technology

    2015-07-06

    molecular phosphonic acid (PA) self-assembled monolayers (SAMs) have been developed for applications in organic field-effect transistors (OFETs) and graphene...and semiconducting molecular phosphonic acid (PA) self-assembled monolayers (SAMs) have been developed for applications in organic field-effect...appeal for organic semiconductor applications due to their low-cost processing, reduced material quantity needed compared to traditional organic thin

  6. Triblock polyphiles through click chemistry: self-assembled thermotropic cubic phases formed by micellar and monolayer vesicular aggregates.

    PubMed

    Tan, Xiaoping; Kong, Leiyang; Dai, Heng; Cheng, Xiaohong; Liu, Feng; Tschierske, Carsten

    2013-11-25

    Three series of triblock polyphiles consisting of a rigid 4-phenyl-1,2,3-triazole or 1,4-diphenyl-1,2,3-triazole core with three lipophilic and flexible alkoxyl chains at one end and a polar glycerol group at the opposite end were synthesized by copper-catalyzed azide-alkyne click reactions. Their mesophase behavior was studied by polarizing optical microscopy, differential scanning calorimetry, and XRD. Depending on alkyl chain length and core length, a transition from hexagonal columnar to Pm3n-type cubic phases was observed. In the cubic phases, the molecules are organized as spherical objects. Remarkably, compounds with a longer core unit have a higher tendency to form these cubic phases, and their stability is strongly enhanced over those of the compounds with a shorter core, despite longer cores having a smaller cone angle and therefore being expected to disfavor the formation of spherical objects. There is a large difference in the number of molecules involved in the spherical aggregates formed by compounds with long and short cores. Whereas the aggregates in the cubic phases of the compounds with short rod units are small and could be regarded as micellar, the long-core compounds form much larger aggregates which are regarded as a kind of monolayer vesicular aggregate.

  7. Structure and stability characterization of anti-adhesion self-assembled monolayers formed by vapour deposition for NIL use

    NASA Astrophysics Data System (ADS)

    Garidel, Sophie; Zelsmann, Marc; Voisin, Pauline; Rochat, Nevine; Michallon, Philippe

    2007-03-01

    Anti-sticking efficiency remains a key issue in nanoimprint lithography. In order to address this problem, a selfassembled monolayer (SAM) of a fluorinated silane release agent is generally applied to the stamp surface, either in wet or in vapour phase. We present here the study on vapour deposition of (tridecafluoro-1,1,2,2-tetrahydrooctyl)TriChloroSilane (F 13-TCS) and wet and vapour deposition of a commercial product, OPTOOL DSX from Daikin. They are both fluorinated silanes used for the formation of anti-adhesive layers in nanoimprint lithography. Results will be compared in term of anti-adhesion properties and homogeneity for the obtained layers. Characterizations are made by means of contact angle measurements, Fourier Transform Infra-Red analysis and Atomic Force Microscopy observations. The vapour phase deposition of F 13-TCS allows us to reach surface energies as low as 11mN/m without increasing initial roughness. OPTOOL DSX TM deposition in wet phase presents comparable results, but with an increased roughness mainly due to the deposition procedure. The durability of the formed layers was investigated as a function of number of prints. For both materials, a significant degradation of the anti-adhesion properties occurs after few imprinted dies.

  8. Ultrasonic-assisted self-assembly of monolayer graphene oxide for rapid detection of Escherichia coli bacteria

    NASA Astrophysics Data System (ADS)

    Chang, Jingbo; Mao, Shun; Zhang, Yang; Cui, Shumao; Zhou, Guihua; Wu, Xiaogang; Yang, Ching-Hong; Chen, Junhong

    2013-04-01

    Due to potential risks to the environment and human health arising from pathogens/chemical contaminants, novel devices are being developed for rapid and precise detection of those contaminants. Here, we demonstrate highly sensitive and selective field-effect transistor (FET) sensor devices for detection of Escherichia coli (E. coli) bacteria using thermally reduced monolayer graphene oxide (TRMGO) sheets as semiconducting channels. The graphene oxide (GO) sheets are assembled on the aminoethanethiol (AET)-functionalized gold (Au) electrodes through electrostatic interactions with ultrasonic assistance. Anti-Escherichia coli (anti-E. coli) antibodies are used as receptors for selective detection of E. coli cells and integrated on the FET device through covalent bonding with Au nanoparticles on the GO surface. The TRMGO FET device shows great electronic stability and high sensitivity to E. coli cells with a concentration as low as 10 colony-forming units (cfu) per mL. The biosensing platform reported here is promising for large-scale, sensitive, selective, low-cost, and real-time detection of E. coli bacteria.

  9. Ultrasonic-assisted self-assembly of monolayer graphene oxide for rapid detection of Escherichia coli bacteria.

    PubMed

    Chang, Jingbo; Mao, Shun; Zhang, Yang; Cui, Shumao; Zhou, Guihua; Wu, Xiaogang; Yang, Ching-Hong; Chen, Junhong

    2013-05-07

    Due to potential risks to the environment and human health arising from pathogens/chemical contaminants, novel devices are being developed for rapid and precise detection of those contaminants. Here, we demonstrate highly sensitive and selective field-effect transistor (FET) sensor devices for detection of Escherichia coli (E. coli) bacteria using thermally reduced monolayer graphene oxide (TRMGO) sheets as semiconducting channels. The graphene oxide (GO) sheets are assembled on the aminoethanethiol (AET)-functionalized gold (Au) electrodes through electrostatic interactions with ultrasonic assistance. Anti-Escherichia coli (anti-E. coli) antibodies are used as receptors for selective detection of E. coli cells and integrated on the FET device through covalent bonding with Au nanoparticles on the GO surface. The TRMGO FET device shows great electronic stability and high sensitivity to E. coli cells with a concentration as low as 10 colony-forming units (cfu) per mL. The biosensing platform reported here is promising for large-scale, sensitive, selective, low-cost, and real-time detection of E. coli bacteria.

  10. Experimental Investigation of Microbially Induced Corrosion of Test Samples and Effect of Self-Assembled Hydrophobic Monolayers. Exposure of Test Samples to Continuous Microbial Cultures, Chemical Analysis, and Biochemical Studies

    SciTech Connect

    Laurinavichius, K.S.

    1998-09-30

    The study of biocorrosion of aluminum and beryllium samples were performed under conditions of continuous fermentation of thermophilic anaerobic microorganisms of different groups. This allowed us to examine the effect of various types of metabolic reactions of reduction-oxidation proceeding at different pH and temperatures under highly reduced conditions on aluminum and beryllium corrosion and effect of self-assembled hydrophobic monolayers.

  11. Interface effects and deposition process of ionically self-assembled monolayer films: In situ and ex situ second harmonic generation measurements

    NASA Astrophysics Data System (ADS)

    Brands, Charles

    2003-07-01

    In this thesis, detailed studies are presented into self-assembled, noncentrosymmetric, optically active films. Second harmonic generation (SHG) is used to measure the second order nonlinear optical susceptibility (chi(2)) of ionically self-assembled monolayer (ISAM) thin films. Conventional ISAM films are fabricated by alternately immersing a substrate into oppositely-charged polyelectrolyte solutions. The polyelectrolytes bind electrostatically to the oppositely-charged substrate, and thus reverse the charge of the substrate. The charge reversal limits the amount of adsorbed material and primes the substrate for the next layer. During the deposition of the nonlinear optical (NLO) active layer, the chromophores are attracted to the oppositely-charged surface, which results in net orientation of the chromophores. Some of the net orientation is lost during the deposition of the next NLO-inactive layer as this layer orients some of the chromophores away from the substrate. A disadvantage of the polymer ISAM deposition method is that although there is a net orientation toward the substrate, a large number of chromophores are randomly or oppositely oriented. This reduces the nonlinear optical response. To overcome this problem, two alternative methods with a better net orientation are discussed: hybrid covalent/ionic deposition and multivalent monomer deposition. In both deposition methods, the NLO-active material is a monomer instead of a polymer. In hybrid covalent/ionic deposition, the NLO-inactive polymer is deposited using electrostatic attraction while the NLO-active monomer is deposited covalently. This forces alignment of the chromophores. The multivalent method uses chromophores with multiple charges on one side of the molecule and one charge (same sign) on the other. The difference in electrostatic attraction causes a preferential orientation of the chromophores during deposition. Attempts have been made to further improve the net orientation by complexation

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

    PubMed

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

    2004-03-01

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

  13. Enhanced sensitivity of self-assembled-monolayer-based SPR immunosensor for detection of benzaldehyde using a single-step multi-sandwich immunoassay.

    PubMed

    Gobi, K Vengatajalabathy; Matsumoto, Kiyoshi; Toko, Kiyoshi; Ikezaki, Hidekazu; Miura, Norio

    2007-04-01

    This paper describes the fabrication and sensing characteristics of a self-assembled monolayer (SAM)-based surface plasmon resonance (SPR) immunosensor for detection of benzaldehyde (BZ). The functional sensing surface was fabricated by the immobilization of a benzaldehyde-ovalbumin conjugate (BZ-OVA) on Au-thiolate SAMs containing carboxyl end groups. Covalent binding of BZ-OVA on SAM was found to be dependent on the composition of the base SAM, and it is improved very much with the use of a mixed monolayer strategy. Based on SPR angle measurements, the functional sensor surface is established as a compact monolayer of BZ-OVA bound on the mixed SAM. The BZ-OVA-bound sensor surface undergoes immunoaffinity binding with anti-benzaldehyde antibody (BZ-Ab) selectively. An indirect inhibition immunoassay principle has been applied, in which analyte benzaldehyde solution was incubated with an optimal concentration of BZ-Ab for 5 min and injected over the sensor chip. Analyte benzaldehyde undergoes immunoreaction with BZ-Ab and makes it inactive for binding to BZ-OVA on the sensor chip. As a result, the SPR angle response decreases with an increase in the concentration of benzaldehyde. The fabricated immunosensor demonstrates a low detection limit (LDL) of 50 ppt (pg mL(-1)) with a response time of 5 min. Antibodies bound to the sensor chip during an immunoassay could be detached by a brief exposure to acidic pepsin. With this surface regeneration, reusability of the same sensor chip for as many as 30 determination cycles has been established. Sensitivity has been enhanced further with the application of an additional single-step multi-sandwich immunoassay step, in which the BZ-Ab bound to the sensor chip was treated with a mixture of biotin-labeled secondary antibody, streptavidin and biotin-bovine serum albumin (Bio-BSA) conjugate. With this approach, the SPR sensor signal increased by ca. 12 times and the low detection limit improved to 5 ppt with a total response

  14. Multiple step growth of single crystalline rutile nanorods with the assistance of self-assembled monolayer for dye sensitized solar cells.

    PubMed

    Yang, Mengjin; Neupane, Suman; Wang, Xuewen; He, Jin; Li, Wenzhi; Pala, Nezih

    2013-10-09

    A novel multiple step growth (MSG) process has been developed to synthesize rutile nanorods (NRs) on fluorine-doped tin oxide (FTO) glass with the assistance of a self-assembled monolayer (SAM) aiming to increase the internal surface area of the 1D materials for dye sensitized solar cell (DSSC) applications. The experimental result reveals that the SAM layer can be selectively decomposed at the tip of the nanorod, namely the rutile (001) surface, due to the anisotropic photocatalytic property of the rutile. The remaining SAM layer on the side-wall of the NRs remains intact and serves as water repellent which prevents the radial growth of the NRs during the next step hydrothermal synthesis; therefore, the spacing between the NRs and the porosity of the NR array can be retained after additional growth cycles. On the other hand, introduction of a middle layer formed via TiCl4 solution treatment before the next growth cycle is found to be an effective way to control the diameters of the newly grown NRs. The performance of DSSC made from the rutile NRs grown using the MSG technique has been examined, and it is significantly affected by the internal surfaces of the NRs. Furthermore, the MSG combined with NR etching treatment by acid at low temperature (150 °C) leads to a significant enhancement in the solar cell performance. The gigantic wettability difference of the NRs before and after the SAM treatment as well as the MSG method could be adapted to prepare superhydrophobic and superhydrophilic nanostructured patterns for other applications.

  15. Electron and ion transfer through multilayers of gold nanoclusters covered by self-assembled monolayers of alkylthiols with various functional groups.

    PubMed

    Uosaki, Kohei; Kondo, Toshihiro; Okamura, Masayuki; Song, Wenbo

    2002-01-01

    The electrochemical characteristics of various kinds of multilayers of gold nanoclusters (GNCs) were investigated. Two types of gold nanoclusters, one covered by self-assembled monolayers (SAMs) of mercaptoundecanoic acid (MUA), hexanethiol (C6SH), and ferrocenylhexanethiol (FcC6SH), MHF-GNC, and the other with MUA and C6SH, MH-GNC, were used. The multilayers were constructed on a Au(111) surface based on a carboxylate/metal cation (Cu++)/carboxylate or carboxylate/cationic polymer (poly(allylamine hydrochloride):PAH)/carboxylate electrostatic interaction. While the multilayers constructed by the former method were stable only in nonaqueous solutions, those constructed by the latter method were stable even in aqueous solutions. Electrochemical measurements of the multilayers of MHF-GNCs showed a pair of waves corresponding to the redox of the ferrocene group around 350-480 mV and the charge of these peaks, i.e., the amount of adsorbed GNC, increased linearly with the construction cycle up to 6 cycles in the former and to 18 cycles in the latter. A rather reversible redox response of the ferrocene moiety was observed even at the gold electrodes with five GNC layers of two different sequences in which MHF-GNC exists as the layer closest to the gold electrode, ie., the first layer, or as the outermost layer with MH-GNC in the other layers. These results show the facile transfer of electrons and ions through the multilayers of the SAM-covered GNCs and electron transfer between the ferrocene moiety and the Au(111) electrode takes place through the GNC cores by hopping.

  16. Detection of Tetrodotoxins in Puffer Fish by a Self-Assembled Monolayer-Based Immunoassay and Comparison with Surface Plasmon Resonance, LC-MS/MS, and Mouse Bioassay.

    PubMed

    Reverté, Laia; de la Iglesia, Pablo; del Río, Vanessa; Campbell, Katrina; Elliott, Christopher T; Kawatsu, Kentaro; Katikou, Panagiota; Diogène, Jorge; Campàs, Mònica

    2015-11-03

    The increasing occurrence of puffer fish containing tetrodotoxin (TTX) in the Mediterranean could represent a major food safety risk for European consumers and threaten the fishing industry. The work presented herein describes the development of a new enzyme linked immunosorbent assay (mELISA) based on the immobilization of TTX through dithiol monolayers self-assembled on maleimide plates, which provides an ordered and oriented antigen immobilization and favors the antigen-antibody affinity interaction. The mELISA was found to have a limit of detection (LOD) of TTX of 0.23 mg/kg of puffer fish matrix. The mELISA and a surface plasmon resonance (SPR) immunosensor previously developed were employed to establish the cross-reactivity factors (CRFs) of 5,6,11-trideoxy-TTX, 5,11-deoxy-TTX, 11-nor-TTX-6-ol, and 5,6,11-trideoxy-4-anhydro-TTX, as well as to determine TTX equivalent contents in puffer fish samples. Results obtained by both immunochemical tools were correlated (R(2) = 0.977). The puffer fish samples were also analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS), and the corresponding CRFs were applied to the individual TTX contents. Results provided by the immunochemical tools, when compared with those obtained by LC-MS/MS, showed a good degree of correlation (R(2) = 0.991 and 0.979 for mELISA and SPR, respectively). The mouse bioassay (MBA) slightly overestimated the CRF adjusted TTX content of samples when compared with the data obtained from the other techniques. The mELISA has been demonstrated to be fit for the purpose for screening samples in monitoring programs and in research activities.

  17. Fast, simple, combinatorial routes to the fabrication of reusable, plasmonically active gold nanostructures by interferometric lithography of self-assembled monolayers.

    PubMed

    Tsargorodska, Anna; El Zubir, Osama; Darroch, Brice; Cartron, Michaël L; Basova, Tamara; Hunter, C Neil; Nabok, Alexei V; Leggett, Graham J

    2014-08-26

    We describe a fast, simple method for the fabrication of reusable, robust gold nanostructures over macroscopic (cm(2)) areas. A wide range of nanostructure morphologies is accessible in a combinatorial fashion. Self-assembled monolayers of alkylthiolates on chromium-primed polycrystalline gold films are patterned using a Lloyd's mirror interferometer and etched using mercaptoethylamine in ethanol in a rapid process that does not require access to clean-room facilities. The use of a Cr adhesion layer facilitates the cleaning of specimens by immersion in piranha solution, enabling their repeated reuse without significant change in their absorbance spectra over two years. A library of 200 different nanostructures was prepared and found to exhibit a range of optical behavior. Annealing yielded structures with a uniformly high degree of crystallinity that exhibited strong plasmon bands. Using a combinatorial approach, correlations were established between the preannealing morphologies (determined by the fabrication conditions) and the postannealing optical properties that enabled specimens to be prepared "to order" with a selected localized surface plasmon resonance. The refractive index sensitivity of gold nanostructures formed in this way was found to correlate closely with measurements reported for structures fabricated by other methods. Strong enhancements were observed in the Raman spectra of tetra-tert-butyl-substituted phthalocyanine. The shift in the position of the plasmon band after site-specific attachment of histidine-tagged green fluorescent protein (His-GFP) and bacteriochlorophyll a was measured for a range of nanostructured films, enabling the rapid identification of the one that yielded the largest shift. This approach offers a simple route to the production of durable, reusable, macroscopic arrays of gold nanostructures with precisely controllable morphologies.

  18. Model non-equilibrium molecular dynamics simulations of heat transfer from a hot gold surface to an alkylthiolate self-assembled monolayer.

    PubMed

    Zhang, Yue; Barnes, George L; Yan, Tianying; Hase, William L

    2010-05-07

    Model non-equilibrium molecular dynamics (MD) simulations are presented of heat transfer from a hot Au {111} substrate to an alkylthiolate self-assembled monolayer (H-SAM) to assist in obtaining an atomic-level understanding of experiments by Wang et al. (Z. Wang, J. A. Carter, A. Lagutchev, Y. K. Koh, N.-H. Seong, D. G. Cahill, and D. D. Dlott, Science, 2007, 317, 787). Different models are considered to determine how they affect the heat transfer dynamics. They include temperature equilibrated (TE) and temperature gradient (TG) thermostat models for the Au(s) surface, and soft and stiff S/Au(s) models for bonding of the S-atoms to the Au(s) surface. A detailed analysis of the non-equilibrium heat transfer at the heterogeneous interface is presented. There is a short time temperature gradient within the top layers of the Au(s) surface. The S-atoms heat rapidly, much faster than do the C-atoms in the alkylthiolate chains. A high thermal conductivity in the H-SAM, perpendicular to the interface, results in nearly identical temperatures for the CH(2) and CH(3) groups versus time. Thermal-induced disorder is analyzed for the Au(s) substrate, the S/Au(s) interface and the H-SAM. Before heat transfer occurs from the hot Au(s) substrate to the H-SAM, there is disorder at the S/Au(s) interface and within the alkylthiolate chains arising from heat-induced disorder near the surface of hot Au(s). The short-time rapid heating of the S-atoms enhances this disorder. The increasing disorder of H-SAM chains with time results from both disorder at the Au/S interface and heat transfer to the H-SAM chains.

  19. AFM Study of Surface Nanobubbles on Binary Self-Assembled Monolayers on Ultraflat Gold with Identical Macroscopic Static Water Contact Angles and Different Terminal Functional Groups.

    PubMed

    Song, Bo; Chen, Kun; Schmittel, Michael; Schönherr, Holger

    2016-11-01

    All experimental findings related to surface nanobubbles, such as their pronounced stability and the striking differences of macroscopic and apparent nanoscopic contact angles, need to be addressed in any theory or model of surface nanobubbles. In this work we critically test a recent explanation of surface nanobubble stability and their consequences and contrast this with previously proposed models. In particular, we elucidated the effect of surface chemical composition of well-controlled solid-aqueous interfaces of identical roughness and defect density on the apparent nanoscopic contact angles. Expanding on a previous atomic force microscopy (AFM) study on the systematic variation of the macroscopic wettability using binary self-assembled monolayers (SAMs) on ultraflat template stripped gold (TSG), we assessed here the effect of different surface chemical composition for macroscopically identical static water contact angles. SAMs on TSG with a constant macroscopic water contact angle of 81 ± 2° were obtained by coadsorption of a methyl-terminated thiol and a second thiol with different terminal functional groups, including hydroxy, amino, and carboxylic acid groups. In addition, surface nanobubbles formed by entrainment of air on SAMs of a bromoisobutyrate-terminated thiol were analyzed by AFM. Despite the widely differing surface potentials and different functionality, such as hydrogen bond acceptor or donor, and different dipole moments and polarizability, the nanoscopic contact angles (measured through the condensed phase and corrected for AFM tip broadening effects) were found to be 145 ± 10° for all surfaces. Hence, different chemical functionalities at identical macroscopic static water contact angle do not noticeably influence the apparent nanoscopic contact angle of surface nanobubbles. This universal contact angle is in agreement with recent models that rely on contact line pinning and the equilibrium of gas outflux due to the Laplace pressure and

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

    NASA Astrophysics Data System (ADS)

    Youn, Jangdae

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