Kinetics of exchange of alkanethiol monolayers self-assembled on polycrystalline gold

We report on the exchange between a hydrophilic thiol (11-mercapto-1-undecanol) in a liquid or gas phase and a hydrophobic thiol (dodecanethiol) of similar length self-assembled on a polycrystalline gold surface for a wide range of temperatures and times. The molecular composition of the mixed monolayers is determined by the static water contact angle and X-ray photoelectron spectroscopy measurements. Atomic force microscopy in lateral force mode is used to characterize the molecular domains at the nanometer level. The exchange first occurs rapidly at the gold grain boundaries, with an activation energy of about 66 +/- 4 kJ/mol. Then, boundaries of ordered thiol domains are progressively replaced, and the exchange is slowed because only regions of increasing perfection are left untouched. Higher temperatures lead to faster kinetics of replacement and the removal of larger amounts of the original thiol. No significant difference could be detected between exchange occurring in an ethanol solution or in the gas phase, and the initial rate of exchange was found to be similar for the displacement of dodecanethiol by 11-mercapto-1-undecanol molecules and for the converse displacement.     

Electroactive self-assembled biferrocenyl alkanethiol monolayers on Au(111) surface and on gold nanoclusters

The spectroscopic and electrochemical characterizations of electrochemically stable biferrocene-modified Au clusters and chemisorbed biferrocenylalkanethiols on Au(111) surface were studied. The characterizations of biferrocene-modified Au cluster using TEM, UV-vis, and NMR techniques are also reported. Two successive reversible one-electron redox waves were observed for the biferrocenylalkanethiol Au nanoclusters and biferrocenylalkanethiol monolayers on Au(111) surface in the cyclic voltammetry. Furthermore, the positive and negative current peaks for each redox wave occur at almost the same potential, and the peak current increases almost linearly with the sweep rate. Repeat scanning does not change the voltammograms, demonstrating that these monolayers are stable to electrochemical cycling. The coverages of electroactive biferrocene in the monolayers were calculated from the cyclic voltammograms. The standard electron-transfer rate constant was calculated from the splitting between the oxidation and reduction peaks.     

Adsorption kinetics of p-nitrobenzenethiol self-assembled monolayers on a gold surface

The adsorption kinetics of octadecanethiol (ODT) and p-nitrobenzenethiol (NBT) from ethanol solutions has been studied by means of contact angle, optical ellipsometry, angle-resolved X-ray photoelectron spectroscopy (ARXPS), and grazing angle attenuated total reflection Fourier transform infrared (FTIR) measurements. ODT data were used as a reference for the kinetics studies of film growth. The growth of self-assembled monolayers from dilute solutions follows Langmuir isotherm adsorption kinetics. A saturated film is formed within 5 h after immersion in solutions of concentrations ranging from 0.0005 to 0.01 mM. The density of the monolayer depends on the concentration of the solution.     

Frictional dynamics of fluorine-terminated alkanethiol self-assembled monolayers

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

Large-scale molecular dynamics simulations of alkanethiol self-assembled monolayers

Large-scale molecular dynamics simulations of self-assembled alkanethiol monolayer systems have been carried out using an all-atom model involving a million atoms to investigate their structural properties as a function of temperature, lattice spacing, and molecular chain length. Our simulations show that the alkanethiol chains of 13-carbons tilt from the surface normal by a collective angle of 25 degrees along next-nearest-neighbor direction at 300 K. The tilt structure of 13-carbon alkanethiol system is found to depend strongly on temperature and exhibits hysteresis. At 350 K the 13-carbon alkanethiol system transforms to a disordered phase characterized by small collective tilt angle, flexible tilt direction, and random distribution of backbone planes. The tilt structure also depends on lattice spacing: With increasing lattice spacing a the tilt angle increases rapidly from a nearly zero value at a=4.7 A to as high as 34 degrees at a=5.3 A at 300 K for 13-carbon alkanethiol system. Finally, the effects of the molecular chain length on the tilt structure are significant at high temperatures.     

Investigation of the interactions between alkanethiol self-assembled monolayers and a liquid overlayer using impedance spectroscopy

We report on changes in the complex impedance response of a quartz crystal microbalance (QCM) that result from the growth of an alkanethiol monolayer on the electrodes of the device. The purpose of this work is to understand the evolution of the interactions between alkanethiol-gold monolayers and a liquid overlayer as a function of time after initial deposition by evaluating the position, shape, and linewidth of the impedance spectra associated with the monolayer formation. We relate the complex impedance response of the QCM to the mass and viscosity of the monolayer through an established equivalent circuit model. The data show the organization of alkanethiol SAMs occurs at approximately the same rate for aliphatic chain lengths in the range of C(9)-C(16), as long as the thiol is readily soluble in the solvent system used. Our data are consistent with SAM annealing being mediated by the sulfur-gold adsorption and desorption equilibrium. Additionally, we have found that examination of a C(18) SAM is limited by the deposition conditions and thiol solubility. Bulk deposition was confirmed visually and related to the evolution of the peak position and shape changes with deposition time.     

Tetraferrocenylporphyrins as active components of self-assembled monolayers on gold surface

Novel tetraferrocenylporphyrins-containing self-assembled monolayers were prepared employing two different approaches. Self-assembled monolayers were characterized using UV-Vis spectroscopy and cyclic voltammetry (CV) whereas their photoelectrochemical properties were investigated by photocurrent generation (PG) experiments.     

Second-harmonic spectroscopy of surface immobilized gold nanospheres above a gold surface supported by self-assembled monolayers

We have investigated linear and nonlinear optical properties of surface immobilized gold nanospheres (SIGNs) above a gold surface with a gap distance of a few nanometers. The nanogap was supported by amine or merocyanine terminated self-assembled monolayers (SAMs) of alkanethiolates. A large second-harmonic generation (SHG) was observed from the SIGN systems at localized surface plasmon resonance condition. The maximum enhancement factor of SHG intensity was found to be 3 x 10(5) for the SIGN system of nanospheres 100 nm in diameter with a gap distance of 0.8 nm. The corresponding susceptibility was estimated to be chi((2))=750 pmV (1.8 x 10(-6) esu). In the SIGN system supported with the merocyanine terminated SAMs, the SHG response was also resonant to the merocyanine in the nanogap. It was found that the SHG response of the SIGN systems is strongly frequency dependent. This leads us to conclude that the large chi((2)) is caused by enhanced electric fields at the localized surface plasmon resonance condition and is not due to an increase of the surface susceptibility following from the presence of the gold nanospheres. The observed SHG was consistent with the theoretical calculations involving Fresnel correction factors, based on the quasistatic approximation.     

Mixed alkanethiol self-assembled monolayers as substrates for microarraying applications

In current microarraying experiments, data quality is in large part determined by the quality of the spots that compose the microarray. Since many microarrays are made with contact printing techniques, microarray spot quality is fundamentally linked to the surface characteristics of the microarray substrate. In this work, surface coatings, consisting of self-assembled monolayers (SAMs) of mixed alkanethiol molecules, were used to control the surface properties of the microarray substrate. X-ray photoelectron spectroscopy and equilibrium contact angle measurements were performed in order to confirm the chemical content and wettability of these surface coatings. To test their performance in microarraying applications, sample microarrays were printed on these mixed alkanethiol films and then characterized with a noncontact visual metrology system and a fluorescence scanner. This work demonstrates that utilizing mixed alkanethiol SAMs as a surface coating provides spatially homogeneous surface characteristics that are reproducible across multiple microarray substrates as well as within a substrate. In addition, this paper demonstrates that these films are stable and robust as they can maintain their surface characteristics over time. Overall, it is demonstrated that SAMs of mixed alkanethiols serve as a useful surface coating, which enhances spot and therefore data quality in microarraying applications.     

Effect of load on structural and frictional properties of alkanethiol self-assembled monolayers on gold: some odd-even effects

We have conducted molecular dynamics simulations to study the frictional properties of alkanethiols CH(3)(CH(2))(n-1)SH (Cn, 12 ≤ n ≤ 15) self-assembled monolayers (SAMs) on Au(111) surfaces, under various loading and shearing conditions. For the examined alkanethiols, we found some evidence of the friction coefficient being dependent on the number of carbon atoms in the molecule being odd or even. Alkanethiols with n = odd show consistently higher friction coefficients than those with n = even. Such odd-even effect seems to be independent of the sliding velocity. However, the effect is significant only at lower loads (<700 MPa). The structural origin of this odd-even effect has been discussed. The effect of loading on the structure is also studied. For dodecanethiol (n = 12) we find the film responds to increased loading initially by increasing the tilt and then by deformation of individual molecules. SAM-Au contacts under shear show periodic storage and release of energy and a clear stick-slip pattern in the shear stress, film thickness, and the tilt and tilt orientation angles.     

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.     

Immobilization of amine-modified oligonucleotides on aldehyde-terminated alkanethiol monolayers on gold

Chemistry is described for the fabrication of DNA arrays on gold surfaces. Alkanethiols modified with terminal aldehyde groups are used to prepare a self-assembled monolayer (SAM). The aldehyde groups of the monolayer may be reacted with amine-modified oligonucleotides or other amine-bearing biomolecules to form a Schiff base, which may then be reduced to a stable secondary amine by treatment with sodium cyanoborohydride. The surface modifications and reactions are characterized by polarization modulation Fourier transform infrared reflection absorption spectroscopy (PM-FTIRRAS), and the accessibility, binding specificity, and stability of the DNA-modified surfaces are demonstrated in hybridization experiments.     

Surface vibrations in alkanethiol self-assembled monolayers of varying chain length

The effect of chain length on the low-energy vibrations of alkanethiol striped phase self-assembled monolayers on Au(111) was studied. We have examined the low-energy vibrational structure of well-ordered, low-density 1-decanethiol (C10), 1-octanethiol (C8), and 1-hexanethiol (C6) to further understand the interaction between adsorbate and substrate. Dispersionless Einstein mode phonons, polarized perpendicularly to the surface, were observed for the striped phases of C10, C8, and C6 at 8.0, 7.3, and 7.3 meV, respectively. An overtone at 12.3 meV was also observed for C6/Au(111). These results, in concert with molecular dynamics simulations, indicate that the forces between the adsorbate and substrate can be described using simple van der Waals forces between the hydrocarbon chains and the Au substrate with the sulfur chemisorbed in the threefold hollow site.     

Effects of omega-functional groups on pH-dependent reductive desorption of alkanethiol self-assembled monolayers

Self-assembled monolayers (SAMs) of alkanethiols having various terminal groups on their omega-positions were formed on a Au111 electrode, and their reductive desorption was studied by linear sweep voltammetry, focusing on effects of solution pH on the desorption behavior. The peak potentials (Ep) of cathodic waves representing reductive desorption were found to be reflected by the pKa value of the thiol group and were negatively shifted with an increase in pH of the electrolyte solution. The magnitude of the pH dependency of Ep was greatly influenced by the hydrophobicity of the terminal groups. In the cases of alkanethiol SAMs having pH-sensitive terminal groups such as carboxyl and amino groups, their basicity was estimated from bending points appearing in the pH titration profile of Ep. This method allows direct determination of not only the pKa value of the arrayed groups but also that of the groups dissolved in solution simultaneously. The pKa values of the arrayed carboxyl groups in SAMs were larger by ca. 3 pH units than their original ones, while those for amino groups were smaller by ca. 2 pH units.     

Electroformation of peptide self-assembled monolayers on gold

The application of a potential to deposit a monolayer of 3-mercaptopropionic acid-histidinyl-histidinyl-histidinyl-aspartyl-aspartyl (3-MPA-HHHDD-OH) controls the density and molecular structure of the peptide monolayer, which results in different wettabilities of the surface, surface density, orientation of the molecule (extended or bent), and nonspecific adsorption of serum proteins. 3-MPA-HHHDD-OH must be deposited at 200 mV to maintain an extended configuration, which promoted low biofouling properties.     

Surface plasmon microscopy of biotin-streptavidin binding reactions on UV-photopatterned alkanethiol self-assembled monolayers

We report surface plasmon imaging of streptavidin binding to photopatterned biotinylated alkanethiol self-assembled monolayers (SAMs) on gold. Micrometer-scale patterns of a mixed biotin- and hydroxyl-terminated monolayer were formed in an inert, hydroxy-terminated alkanethiol monolayer using a UV-photopatterning procedure. Using surface plasmon microscopy, contrast is readily observed between the mixed biotin- and hydroxy-terminated SAM region after specific binding of streptavidin has occurred and the pure hydroxy-terminated region where nonspecific binding of streptavidin is negligible. Surface plasmon microscopy was also able to monitor in situ and in real time the binding of streptavidin to the patterned SAMs. The ability of surface plasmon microscopy to detect and spatially resolve 2-dimensional monolayer binding events may prove useful in diagnostic applications involving the parallel interrogation at surface biomolecular arrays.     

Surface stress, kinetics, and structure of alkanethiol self-assembled monolayers

The surface stress induced during the formation of alkanethiol self-assembled monolayers (SAMs) on gold from the vapor phase was measured using a micromechanical cantilever-based chemical sensor. Simultaneous in situ thickness measurements were carried out using ellipsometry. Ex situ scanning tunneling microscopy was performed in air to ascertain the final monolayer structure. The evolution of the surface stress induced during coverage-dependent structural phase transitions reveals features not apparent in average ellipsometric thickness measurements. These results show that both the kinetics of SAM formation and the resulting SAM structure are strongly influenced both by the surface structure of the underlying gold substrate and by the impingement rate of the alkanethiol onto the gold surface. In particular, the adsorption onto gold surfaces having large, flat grains produces high-quality self-assembled monolayers. An induced compressive surface stress of 15.9 +/- 0.6 N/m results when a c(4x2) dodecanethiol SAM forms on gold. However, the SAMs formed on small-grained gold are incomplete and an induced surface stress of only 0.51 +/- 0.02 N/m results. The progression to a fully formed SAM whose alkyl chains adopt a vertical (standing-up) orientation is clearly inhibited in the case of a small-grained gold substrate and is promoted in the case of a large-grained gold substrate.     

The nature of alkanethiol self-assembled monolayer adsorption on sputtered gold substrates

A detailed study of the self-assembly and coverage by 1-nonanethiol of sputtered Au surfaces using molecular resolution atomic force microscopy (AFM) and scanning tunneling microscopy (STM) is presented. The monolayer self-assembles on a smooth Au surface composed predominantly of [111] oriented grains. The domains of the alkanethiol monolayer are observed with sizes typically of 5-25 nm, and multiple molecular domains can exist within one Au grain. STM imaging shows that the (4 x 2) superlattice structure is observed as a (3 x 2) structure when imaged under noncontact AFM conditions. The 1-nonanethiol molecules reside in the threefold hollow sites of the Au[111] lattice and aligned along its [112] lattice vectors. The self-assembled monolayer (SAM) contains many nonuniformities such as pinholes, domain boundaries, and monatomic depressions which are present in the Au surface prior to SAM adsorption. The detailed observations demonstrate limitations to the application of 1-nonanethiol as a resist in atomic nanolithography experiments to feature sizes of approximately 20 nm.     

Investigations of tellurium-modified self-assembled monolayers of benzenedithiol on gold surface as molecular gate

In this paper, we report the obtention of tellurium modified with self-assembled monolayers of benzenedithiol on a gold surface as a molecular gate. The switching and electronic transport characteristics of the modified gold surface were investigated by cyclic voltammetry (CV). The CV results indicate that the switching of benzenedithiol gates is controlled by the oxidation state of tellurium, which is regulated by the applied potentials.     

Electron transfer of quinone self-assembled monolayers on a gold electrode

Dialkyl disulfide-linked naphthoquinone, (NQ-C_n-S)₂, and anthraquinone, (AQ-C_n-S)₂, derivatives with different spacer alkyl chains (C_n: n = 2, 6, 12) were synthesized and these quinone derivatives were self-assembled on a gold electrode. The formation of self-assembled monolayers (SAMs) of these derivatives on a gold electrode was confirmed by infrared reflection-absorption spectroscopy (IR-RAS). Electron transfer between the derivatives and the gold electrode was studied by cyclic voltammetry. On the cyclic voltammogram a reversible redox reaction between quinone (Q) and hydroquinone (QH₂) was clearly observed under an aqueous condition. The formal potentials for NQ and AQ derivatives were −0.48 and −0.58 V, respectively, that did not depend on the spacer length. The oxidation and reduction peak currents were strongly dependent on the spacer alkyl chain length. The redox behavior of quinone derivatives depended on the pH condition of the buffer solution. The pH dependence was in agreement with a theoretical value of E_1/2 (mV) = E′ − 59pH for 2H⁺/2e⁻ process in the pH range 3–11. In the range higher than pH 11, the value was estimated with E_1/2 (mV) = E′ − 30pH , which may correspond to H⁺/2e⁻ process. The tunneling barrier coefficients (β) for NQ and AQ SAMs were determined to be 0.12 and 0.73 per methylene group (CH₂), respectively. Comparison of the structures and the alkyl chain length of quinones derivatives on these electron transfers on the electrode is made.