Alkanethiol Molecules Research Articles

Synergistic effect of 1‐dodecanethiol upon inhibition of Schiff bases on carbon steel corrosion in sulphuric acid media

PurposeIn this paper, the main aim is to study the synergistic effects of alkanethiols upon inhibition of Schiff bases, N,N′‐ethylen‐bis and N,N′‐ortho‐phenylen‐bis in 0.5 M sulphuric acid solutions.Design/methodology/approachMeasurements were carried out in a three‐electrode cell assembly connected to the corrosion measurement system using software for Tafel polarization. Impedance measurements were carried out at open circuit potential using an electrochemical interface and frequency response analyzer at frequencies from 100 kHz to 10 MHz.FindingsResults obtained revealed that at high concentrations, each of the investigated Schiff bases and 1‐dodecanethiol (DT) were good inhibitors when added separately to the corrosive media. The decrease in corrosion rate was associated with an increase in their concentrations. It was found that the presence of DT together with Schiff bases in corrosive medium increased inhibition effect, especially at low concentrations. Synergistic effect is discussed from viewpoint of their co‐adsorption. The adsorption of combined inhibitors was found to follow Langmuir isotherm. Thermodynamic calculations revealed that adsorption of combined inhibitors had a physical nature.Research limitations/implicationsIn order to improve further the performance of Schiff bases and identifying their synergistic effects with other additives it is suggested that some more researches on other Schiff bases with other alkanethiol molecules must be done.Practical implicationsThe results of this paper can be used for acid cleaning of carbon steel in which suitable inhibitor systems with the highest efficiency is required.Originality/valueThis paper reveals that the presence of DT molecules in solution encourage the adsorption of Schiff bases by facilitating the electrostatic co‐adsorption of Schiff base molecules through a synergistic effect.

Simultaneous Nanoindentation and Electron Tunneling through Alkanethiol Self-Assembled Monolayers

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

Electronic interactions between gold nanoclusters in constrained geometries

The interactions between gold nanoclusters dispersed in decane $({\mathrm{C}}_{10}{\mathrm{H}}_{22})$ when confined in narrow gaps of a few nanometers were investigated. The diameter of the gold core was $1.8\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$. The clusters were capped off with alkanethiol molecules of different lengths (${\mathrm{C}}_{6}\mathrm{S}$ and ${\mathrm{C}}_{15}\mathrm{S}$) to prevent metallic contact with each other. By applying force to the gap walls, the cluster suspension was squeezed out of the gap in a nearly continuous way. In the case of the shorter ligand ${\mathrm{C}}_{6}\mathrm{S}$, the width of the minimum gap at the highest applied force was $7\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$ ($\ensuremath{\sim}3$ cluster diameters). In contrast with the continuous decrease in thickness, the gap capacitance exhibited stepwise increases, which are interpreted as Mott type insulator-to-metal transition of aggregates of clusters under pressure when the average distance between the metallic cores becomes less than $\ensuremath{\sim}1\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$. With longer ligands, ${\mathrm{C}}_{15}\mathrm{S}$, the thickness of the minimum gap was $12--15\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$. In that case, no discontinuous steps in thickness or capacitance were observed, showing that the longer ligand effectively prevents exchange interactions between the metallic cores of the nanoclusters.

Investigation into pH-Responsive Self-Assembled Monolayers of Acylated Anthranilate-Terminated Alkanethiol on a Gold Surface

This article describes the preparation of pH-responsive self-assembled monolayers (SAMs) of acylated anthranilate-terminated alkanethiol. These monolayers are formed by chemisorption of the alkanethiol molecules onto a gold surface, resulting in different wetting properties of the surfaces depending upon the pH. By using various characterization techniques (e.g., infrared spectroscopy, cyclic voltammetry, contact angle measurements, and surface energy analysis), we have found that the changes in the wetting properties originate from the different surface structures of the monolayers in different pH environments. From surface energy analysis, we found that the disperse components of the surface energy on such SAMs predominate after treatment with pH 1 water, whereas the polar components of the surface energy on such SAMs predominate after treatment with pH 13 water. It is greatly anticipated that this line of research will provide new insight into the mechanism behind pH-responsive properties, facilitating the design and synthesis of new surface-active molecules for the fabrication of pH-responsive functional surfaces.

Room-Temperature Kinetics of Short-Chain Alkanethiol Film Growth on Ag(111) from the Vapor Phase

We have used time-of-flight (TOF) direct recoiling spectroscopy (DRS) to follow propanethiol adsorption at 300 K from the vapor phase on an Ag(111) surface, for exposures ranging from 10(-1) to 10(5) L. Results show that the adsorption proceeds with changes in the sticking coefficient, consistent with at least three phases. At low exposures, the alkanethiol molecules adsorb with high probability at defect sites, followed by a slower growth mode that essentially covers the whole surface. A third change in the sticking coefficient is associated with the final saturation stage, corresponding to a thicker layer related to molecules in a more upright orientation. The adsorption kinetics for hexanethiol is similar to that of propanethiol but taking place at higher rates, stressing the importance of the hydrocarbon chain length in the growth process. ISS-TOF measurements during thermal desorption show that most of the C, H, and S go away together, suggesting that the molecules adsorb and desorb from flat regions without S-C bond cleavage. Fitting the desorption maximum at 450 K with a first-order desorption curve gives a desorption energy of 1.43 eV. A small final S content that is correlated with the initial Ag(111) surface roughness is observed after desorption.

Two-Site Adsorption Model for the (√3 × √3)-R30° Dodecanethiolate Lattice on Au(111) Surfaces

The surface structure of dodecanethiolate self-assembled monolayers (SAMs) on Au(111) surfaces, formed from the liquid phase, have been studied by grazing incidence X-ray diffraction (GIXRD), scanning tunneling microscopy (STM), and electrochemical techniques. STM images show that the surface structure consists of (square root 3 x square root 3)-R30 degrees domains with only a few domains of the c(4 x 2) lattice. The best fitting of GIXRD data for the (square root 3 x square root 3)-R30 degrees lattice is obtained with alkanethiolate adsorption at the top sites, although good fittings are also obtained for the fcc and hcp hollow sites. On the basis of this observation, STM data, electrochemical measurements, and previously reported data, we propose a two-site model that implies the formation of incoherent domains of alkanethiolate molecules at top and fcc hollow sites. This model largely improves the fitting of the GIXRD data with respect to those observed for single adsorption sites and, also, for the other possible two-site combinations. The presence of alkanethiolate molecules adsorbed at the less favorable top sites could result from the adsorption pathway that involves an initial physisorption step which, for steric reasons, takes place at on top sites. Once the molecules are chemisorbed, the presence of energy barriers for alkanethiolate surface diffusion, arising mostly from chain-chain interactions, "freezes" some of them at the on top sites, hindering their movement toward fcc hollow sites. By considering the length of the hydrocarbon chain and the adsorption time, the two-site model could be a tool to explain most of the controversial results on this matter reported in the literature.

Study of the transport properties of self-assembled alkanethiol monolayer by conduction atomic force microscopy

Self-assembled alkanethiol monolayers (SAMs) were prepared on the Au(111) substr ate. The behavior of the transport properties of SAMs under external load was in vestigated by the conduction atomic force microscopy. The current of SAM was fou nd to increase with the external load, and this property can be well characteriz ed by the Hertz model. It was also found that the conductance of SAM decreases e xponentially with the chain length of the alkanethiol molecules. The correspondi ng current decay constant β is demonstrated to decrease with the external load at first, and then becomes independent of the external load. Furthermore, the cu rrent of SAM with long chain molecules increases more apparently than that with short ones. These features all originate from the tunneling effect via nearby mo lecular chains for the charges.

Molecular Structure Alters Apparent Height in nc-AFM Images of Alkanethiolate Embedded in Matrix

The non-contact atomic force microscopy (nc-AFM) images of the single alkanethiolate molecules embedded in the bicyclo[2,2,2]octylmethylthiolate (BCO) self-assembled monolayer (SAM) are simulated using the all-atom empirical force field model. The tip is modeled by the chemically inactive and unpolarized carbon nanocone apex. When the alkyl chain is longer than the BCO matrix, the protruded chain is observed to be lower than its actual height. Even if the alkyl chain has a similar height to the BCO, the former is observed to be slightly lower than the latter. These findings indicate that even when the chemical and electrostatic interactions are not relevant for imaging, the nc-AFM images do not always give true topographical information of the molecules under the tip. [DOI: 10.1380/ejssnt.2006.299]

Electrochemical Self-Assembly of Alkanethiolate Molecules on Ni(111) and Polycrystalline Ni Surfaces

In this work, the electrochemical formation of alkanethiolate self-assembled monolayers (SAMs) on Ni(111) and polycrystalline Ni surfaces from alkanethiol-containing aqueous 1 M NaOH solutions was studied by combining Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), electrochemical techniques, and density functional theory (DFT) calculations. Results show that alkanethiolates adsorb on Ni concurrent with NiO electroreduction. The resulting surface coverage depends on the applied potential and hydrocarbon chain length. Electrochemical and XPS data reveal that alkanethiolate electroadsorption at room temperature takes place without S-C bond scission, in contrast to previous results from gas-phase adsorption. A complete and dense monolayer, which is stable even at very high cathodic potentials (-1.5 V vs SCE), is formed for dodecanethiol. DFT calculations show that the greater stability against electrodesorption found for alkanethiolate SAMs on Ni, with respect to SAMs on Au, is somewhat related to the larger alkanethiolate adsorption energy but is mainly due to the larger barrier to interfacial electron transfer present in alkanethiolate-covered Ni. A direct consequence of this work is the possibility of using electrochemical self-assembly as a straightforward route to build stable SAMs of long-chained alkanethiolates on Ni surfaces at room temperature.

Relative Conductances of Alkaneselenolate and Alkanethiolate Monolayers on Au{111}

The electronic properties of alkanethiolate [CH3(CH2)nS-, n = 9 and 11] and alkaneselenolate [CH3(CH2)nSe-, n = 9 and 11] self-assembled monolayers on Au{111} have been quantitatively compared. Simultaneously acquired apparent tunneling barrier height (ATBH) and scanning tunneling microscopy (STM) images reveal that alkanethiolate molecules have a lower barrier to tunneling, and therefore a higher conductance than alkaneselenolates of the same alkyl chain length. Molecular and contact conductance differences were elucidated by using observed STM topographic tunneling height differences between the analogous species. This apparent topographic difference combined with comparative ATBH data indicate that the observed decrease in conductance for alkaneselenolates compared to alkanethiolates originates exclusively from the Au-chalcogenide physical, chemical, and electronic contact.

Adsorption behavior of binary mixed alkanethiol molecules on Au: Scanning tunneling microscope and linear-scan voltammetry investigation

Adsorption behavior of binary mixed alkanethiol molecules of octanethiol (OT) and dodecanethiol (DDT) on Au substrate has been investigated with a variation of molar fraction in solution at room temperature. Linear-scan voltammograms (LSV) taken from the binary mixed self-assembled monolayer (SAM) on Au/Si showed a single reductive desorption peak, continuously shifting with a variation of mixing ratio in solution. Molecule-resolved scanning tunneling microscope (STM) images obtained from the binary SAM on Au/mica showed the phase separation with a few nanometer sized domains. The difference in the chain length between OT and DDT was not large enough to induce the phase separation with much larger domains, which could be well detected by LSV. There was no preferential adsorption of DDT to OT.

Nanografting De Novo Proteins onto Gold Surfaces

The immobilization of novel proteins onto addressable locations on a flat surface has potential applications in a range of biotechnologies. Here we describe the nanopatterning of a de novo protein onto a gold surface. Patterning was achieved using a technique called nanografting, in which the tip of an atomic force microscope is used to disrupt a preexisting monolayer of alkanethiol molecules on a gold surface, thereby facilitating exchange with alternative thiol-linked molecules from the surrounding solution. The protein used for these studies was chosen from a designed combinatorial library of de novo sequences expressed in E. coli and was engineered to have a glycine-glycine-cysteine tag at its C-terminus, thereby enabling attachment to the gold surface through a single cysteine thiol. The average height of the grafted protein patterns was found to be somewhat higher than expected from the known NMR structure of the protein. Compression of the nanografted patches by an external force (below 10 nN) was reversible but showed some hysteresis. Interestingly, both the energy required to deform the immobilized protein patterns and the energy defined by the hysteresis loop were found to be of the same order as the energy required to unfold the monomeric protein in solution. These studies demonstrate the possibility of preparing nanometer scale protein arrays, lowering significantly the volume requirements of the protein samples necessary to fabricate protein-based biosensor arrays and thereby providing a base for increasing their sensitivity.

Investigation on gold corrosion by in situ quartz crystal microbalance and atomic force microscopy in self-assembled processes of alkanethiol monolayers

The corrosion behaviour on gold surface in air-exposed solution induced by alkanethiol molecules such as n-dodecanethiol in self-assembled process has been for the first time investigated in detail by in situ quartz crystal microbalance (QCM). The gold lost from the in situ QCM has been well explained by the observation of atomic force microscopy (AFM), which shows the evident image of corrosive defects or holes produced on the corresponding surface of gold grains. Both alkanethiol assembled monolayer and existing oxygen would be decisive factors for the gold corrosive dissolution on the substrate. The kinetic equation on the corrosion rate of gold dissolved in the air-exposed alkanethiol solution has been obtained. The initial corrosion rate on gold can be estimated to be 5.8×1010 Au atoms cm−2 s−1.

Molecular dynamics simulation study of the nano-wear characteristics of alkanethiol self-assembled monolayers

A molecular dynamics (MD) simulation study of the probe-based nano-lithography of an alkanethiol self-assembled monolayer (SAM) on a metal surface was performed. The motivation of this work was to understand the nano-tribological phenomena of the nano-metric scribing process of alkanethiol molecules and gain insight into the interaction between the probe tip and the SAM-coated surface during the scribing process. The simulation results revealed that the organothiol molecules were displaced and dragged by the probe tip during scribing due to the strong interchain interactions. It was also found that the scribed pattern width was largely dependent on the tip–surface interaction induced by the probe shape rather than the tip–surface contact size. Also, the minimum load for tip–substrate contact changed with the number of molecules that interact with the probe tip. Furthermore, from the investigation of the effect of the scribing speed on the surface-damage characteristics of the chain molecules, it was found that relatively high-speed scribing could induce excessive removal of the SAM molecules from the surface.

Controlled Texturing Modifies the Surface Topography and Plasmonic Properties of Au Nanoshells

We report a facile and controllable method for the postfabrication texturing of the surface topography of Au nanoshells based on site-selective chemical etching of the polycrystalline Au nanoshell surface by a bifunctional alkanethiol molecule, cysteamine. This nanoscale surface texturing process systematically introduces dramatic changes to the plasmonic properties of the Au nanoshells. The modification of the plasmon resonant properties of nanoshells as a function of increased surface roughness was examined experimentally and modeled theoretically using three-dimensional finite difference time domain (FDTD) simulations.

Potential Behavior of Biochemically Modified Gold Electrode for Extended-Gate Field-Effect Transistor

We propose potentiometric detection of biomolecules using an extended-gate field-effect transistor (EGFET). Using a gold film electrode as the extended gate, the stability of the interface potential was characterized for a shift and a drift, and found to depend on the surface roughness of the gold electrode. The surface of the gold film was coated with self-assembled monolayers (SAMs) of various types of alkanethiol molecules with functional sites such as amino groups, carboxyl groups, hydroxyl groups and oligonucleotides. In all the alkanethiol molecules, the interface potential decreased drastically just after the introduction of each molecule because of the negative charges of thiol groups in aqueous solutions. Moreover, the complementary target deoxyribonucleic acid (DNA) has been introduced to the gold electrode modified with oligonucleotide probes and hybridized with them. The interface potential shifted in the negative direction due to the negative charges of the target DNA. Thus, the charge density change due to DNA hybridization as well as the adsorption of alkanethiol molecules on the gold electrode could be successfully detected using the biochemically modified EGFET.

Band Gap Engineering of CdTe Nanocrystals through Chemical Surface Modification

We demonstrate band gap control of CdTe nanocrystals by selective surface modification using alkanethiol molecules. Both absorption and emission wavelengths can be tuned simply by mixing a dispersion of the nanocrystals with alkanethiol at room temperature, resulting in blue shifts in the optical spectra during reaction. The degree of blue shift depends on both the concentration of alkanethiols and the reaction time, thereby providing kinetic control over the emission peak wavelength of the nanocrystals in mild conditions. The observed spectral changes are suggested to be caused by a decrease in the size of the CdTe core through formation of CdTe1-x(SC10)x shells because of specific exchange of Te with alkanethiolates. The results reported herein provide a new band gap engineering scheme for semiconductor nanocrystals and offer opportunities for the design of ligand-stabilized semiconductor nanocrystals with tunable composition and optical properties.

Theory of Nanoscale Atomic Lithography. An ab Initio Study of the Interaction of “cold” Cs Atoms with Organthiols Self-assembled Monolayers on Au(111)

This paper deals with the microscopic mechanism of nanolithography of self-assembled monolayers (SAM) of alkanethiol molecules on Au(111) induced by the exposure of the film to a beam of "cold" Cs atoms. Density functional theory calculations have been carried out to elucidate the mechanism of interaction of the Cs atoms with the SAM. We found that the film damage occurs in two steps: the Cs atom penetrates the SAM and at a distance of 10-12 Angstrom from the surface donates one electron to Au, forming a Cs(+) cation which binds strongly to the surface and interacts with the polar head of the SR molecule. The thermal energy released in this process largely exceeds the energy required to stimulate the desorption of RS-SR disulfide molecules from the Au surface with consequent damage of the film. No chemical interaction occurs between Cs or Cs(+) and the hydrocarbon chain of the thiol molecule.

Alkanethiol Mediated Release of Surface Bound Nanoparticles Fabricated by Nanosphere Lithography

ABSTRACTThis work presents an innovative approach to produce monodisperse solution-phase triangular silver nanoparticles with well-controlled geometry. Ag nanotriangles are fabricated by nanosphere lithography (NSL), functionalized with alkanethiol molecules and then released from the substrate into solution. The resulting single isolated nanoparticles are subsequently asymmetrically functionalized with alkanedithiol molecules to form dimer pairs. The optical properties of the Ag nanoparticles have been measured using UV-Vis spectroscopy while their structural properties have been characterized using atomic force microscopy (AFM) and transmission electron microscopy (TEM). Theoretical calculations based on Mie theory and the Discrete Dipole Approximation (DDA) method have been done to interpret the optical properties of the released Ag nanoparticles.

Edge-Spreading Lithography: Use of Patterned Photoresist Structures to Direct the Spreading of Alkanethiols on Gold

Edge-spreading lithography (ESL) has been extended to fabricate gold structures with different geometries and feature sizes on silicon substrates. In the present variant of ESL, we used photoresist structures patterned on a thin film of gold to transport alkanethiol molecules from an elastomeric stamp to the gold surface where they formed a self-assembled monolayer (SAM) along the edge of each resist feature. The emerging SAM could expand laterally on the gold via reactive spreading, during which the footprints of the resist structures were enlarged in the same fashion. Upon removal of the photoresist, selective etching of gold revealed those regions that were protected by the SAM, yielding accurate outlines of the resist features on the substrate. The width of resultant gold structures was determined by the distance over which the monolayer expanded during spreading, and could be conveniently controlled well below 200 nm by varying the contact time and/or the concentration of alkanethiol in the ink.