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.     

A method for removing self-assembled monolayers on gold

Self-assembled monolayers (SAMs) have been widely used in studying interfacial phenomena, biological processes, electrochemistry, photoelectrochemistry, photoactivity and molecular interaction. Much research has been carried out in fabricating and removing SAMs on different substrates. In this work, we report for the first time, to our knowledge, that SAMs of thiolates on gold can be removed by immersing SAMs in 0.5 M NaBH 4 solution for 10 min. The procedure of removing thiolates was very convenient. Cyclic voltammetry, surface-enhanced Raman spectroscopy, and X-ray photoelectron spectroscopy were used to characterize this process. The results indicated that the SAMs of thiolates on gold can be removed efficiently by NaBH 4.     

Adsorption of self-assembled monolayers of mercaptan on gold

XPS and AES are suitable techniques for studying organic monolayers on metals if radiation doses are kept low. The adsorption of self-assembled (SA) mercaptan monolayers on gold is a process in two stages. The adsorption to near completeness is very rapid. However, the process of orientation of the carbon chains, which is responsible for the blocking of electrochemical reactions takes much longer, as could be shown by ARXPS (angle resolved X-ray photo electron spectroscopy). Adsorption under potential control allows electrochemical experiments during the adsorption process as e.g. the measurement of the capacity of the electric double layer. Furthermore the control of the potential guarantees sure that the metal/liquid interface is well defined during the adsorption process.     

FTIR-ATR study of self-assembled thiol monolayers on gold

Self-assembled monolayers of 1-teradecanethiol on gold were characterized by means of FTIR-ATR measurements, XPS and contact angle measurements. Linear dichroism measurements using FTIR-ATR are used to estimate the orientation of the alkyl chains. An equation for calculating the orientation angles of the alkyls chains was deduced.     

Blocking behavior of self-assembled monolayers on gold electrodes

Self-assembled monolayers (SAMs) with metal electrodes, especially thiols on gold, are the subject of this investigation because of the unique properties of SAM-modified surfaces. Normal alkanethiols are used to modify the surface of a conventional gold electrode to block certain ions such as Pb(II) and Cu(II) from the surface of the electrode. Normal alkanethiols are also used to study the SAM-gold interfacial adsorption-desorption behavior of the self-assembled monolayer. The effects of varying chain length of SAMs, varying concentration of the alkanethiol solutions, immersion time of the pure gold electrode in the SAM solution, and the stability of a SAM-modified gold electrode in fresh chloroform are investigated using the oxidation-reduction peaks of gold. Conditions that optimize the surface coverage and the uniformity of the SAMs have been determined. Normal alkanethiols proved to be a good insulator on the electrode surface. Received: 16 January 1997 / Accepted: 4 March 1997     

Adsorption of self-assembled monolayers of mercaptan on gold

XPS and AES are suitable techniques for studying organic monolayers on metals if radiation doses are kept low. The adsorption of self-assembled (SA) mercaptan monolayers on gold is a process in two stages. The adsorption to near completeness is very rapid. However, the process of orientation of the carbon chains, which is responsible for the blocking of electrochemical reactions takes much longer, as could be shown by ARXPS (angle resolved X-ray photo electron spectroscopy). Adsorption under potential control allows electrochemical experiments during the adsorption process as e.g. the measurement of the capacity of the electric double layer. Furthermore the control of the potential guarantees sure that the metal/liquid interface is well defined during the adsorption process.     

Stability of self-assembled monolayers on titanium and gold

Methyl- and hydroxyl-terminated phosphonic acid self-assembled monolayers (SAMs) were coated on Ti from aqueous solution. Dodecyl phosphate and dodecyltrichlorosilane SAMs were also coated on Ti using solution-phase deposition. The stability of SAMs on Ti was investigated in Tris-buffered saline (TBS) at 37 degrees C using X-ray photoelectron spectroscopy, contact angle goniometry, and atomic force microscopy. For comparison purposes, a hydroxyl-terminated thiol SAM was coated on Au, and its stability was also investigated under similar conditions. In TBS, a significant proportion of phosphonic acid or phosphate molecules were desorbed from the Ti surface within 1 day, while the trichlorosilane SAM on Ti or thiol SAM on Au was stable for up to 7 days under similar conditions. The stability of hydroxyl-terminated phosphonic acid SAM coated Ti and thiol SAM coated Au was investigated in ambient air and ultraviolet (UV) light. In ambient air, the phosphonic acid SAM on Ti was stable for up to 14 days, while the thiol SAM on Au was not stable for 1 day. Under UV-radiation exposure, the alkyl chains of the phosphonic acid SAM were decomposed, leaving only the phosphonate groups on the Ti surface after 12 h. Under similar conditions, decomposition of alkyl chains of the thiol SAM was observed on the Au surface accompanied by oxidation of thiolates.     

Reactivity of acid fluoride-terminated self-assembled monolayers on gold

This report describes the reactivity of acid fluoride (AF)-terminated self-assembled monolayers (SAMs) on gold toward amine and alcohol compounds and the potentiality of AF as a reactive intermediate for surface functionalizations. The AF group was generated in situ on a gold surface by reacting the terminal carboxylic acid group in the SAM of 16-mercaptohexadecanoic acid with cyanuric fluoride and pyridine under the optimized conditions. AF was found to be highly reactive toward various amine groups, such as primary and secondary amines, but it did not react effectively with alcohol. In addition, the amide coupling reaction by microcontact printing (microCP) was compared with the solution-based reaction: when amine-derivatized ferrocene compound was used for 1-min microCP on the AF-activated surface, the surface coverage of the reaction product was about 83% of 3.45 x 1014 cm-2, the coverage obtained in the solution-based reaction. On the basis of the high reaction efficiency of microCP, the AF-activated surface was also used as a platform for patterning a biological ligand, biotin.     

Dipodal ferrocene-based adsorbate molecules for self-assembled monolayers on gold

1,1'-Difunctionalised ferrocene derivatives have been studied, which contain groups suitable for chemisorption on gold substrates, namely -NC, -PR(2) as well as a range of sulfur-containing units like -NCS, -SR, and thienyl. Thin films on gold have been fabricated from solution with most of these adsorbate species. Film thickness, composition and structure were investigated primarily by X-ray photoelectron and near-edge X-ray absorption fine-structure spectroscopy. The quality of self-assembled monolayers fabricated from 1,1'-diisocyanoferrocene (1) and 1,1'-diisothiocyanatoferrocene (2) turned out to be superior to that of films based on the other adsorbate species investigated. In addition to the surface coordination behaviour of 1 towards gold substrates, relevant aspects of the molecular coordination chemistry of 1 have also been addressed, including the synthesis and characterisation of [(mu-1){Cr(CO)(5)}(2)], [Ag(2)(mu-1)(2)](NO(3))(2) x H(2)O and [(mu-1)(AuCl)(2)]. The crystal structure of the gold complex is governed by aurophilic interactions and can be taken as a model for the arrangement of 1 in self-assembled monolayers on gold.     

Host-guest interactions at self-assembled monolayers of cyclodextrins on gold

We have developed synthesis routes for the introduction of short and long dialkylsulfides onto the primary side of alpha-, beta-, and gamma-cyclodextrins. Monolayers of these cyclodextrin adsorbates were characterized by electrochemistry, wettability studies, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), and atomic force microscopy (AFM). The differences in thickness and polarity of the outerface of the monolayers were measured by electro-chemistry and wettability studies. On average about 70% of the sulfide moieties were used for binding to the gold, as measured by XPS. Tof-SIMS measurements showed that the cyclodextrin adsorbates adsorb without any bond breakage. AFM measurements revealed for beta-cyclodextrin monolayers a quasi-hexagonal lattice with a lattice constant of 20.6 A, which matches the geometrical size of the adsorbate. The alpha-cyclodextrin and gamma-cyclodextrin monolayers are less ordered. Interactions of the anionic guests 1-anilinonaphthalene-8-sulfonic acid (1,8-ANS) and 2-(p-toluidinyl)naphthalene-6-sulfonic acid (2,6-TNS) and the highly ordered monolayers of heptapodant beta-cyclodextrin adsorbates were studied by surface plasmon resonance (SPR) and electrochemical impedance spectroscopy. The SPR measurements clearly showed interactions between a beta-cyclodextrin monolayer and 1,8-ANS. Electrochemical impedance spectroscopy measurements gave high responses even at low guest concentrations (< or = 5 microM). The association constant for the binding of 1,8-ANS (K = 289,000 +/- 13,000M-1) is considerably higher than the corresponding value in solution. (Partial) methylation of the secondary side of the beta-cyclodextrin strongly decreases the binding.     

Organization-induced charge redistribution in self-assembled organic monolayers on gold

The charge redistribution that occurs within dipolar molecules as they self-assemble into organized organic monolayer films has been studied. The extent of charge transfer is probed by work function measurements, using low-energy photoelectron spectroscopy (LEPS), contact potential difference (CPD), and X-ray photoelectron spectroscopy (XPS), with the latter providing fine details about the internal charge distribution along the molecule. In addition, two-photon photoelectron spectroscopy is applied to investigate the electronic structure of the adsorbed layers. We show that charge transfer acts to reduce the dipole-dipole interaction between the molecules but may either decrease or increase the molecule-to-surface dipole moment.     

Micro-patterning of 3-aminopropyltrimethoxy- silane self-assembled monolayers with colloidal gold

This paper provides a new method to the micro-patterning of 3-aminopropyl-trimethoxysilane (ATS) self-assembled monolayers by colloidal Au. Photolithographing of ATS self-assembled monolayers on SiO₂-coated Si substrates and subsequent assembly of colloidal Au to the amino terminal groups in the unirradiated regions lead to the formation of Au microstructures. As revealed by scanning electron microscopy, the colloidal Au closely replicates the mask patterns on the unirradiated regions. The present approach may be applicable to fabrication of microelectronic circuits and microbiosensors.     

Stepwise synthesis of Gly-Gly-His on gold surfaces modified with mixed self-assembled monolayers

Peptide-modified electrode surfaces have been shown to have excellent recognition properties for metal ions. An efficient method of screening a potential peptide for its selectivity for a given metal would involve the synthesis of the peptide directly on the electrode surface. This paper outlines a procedure in which the tripeptide Gly-Gly-His was synthesized one amino acid at a time on a gold surface modified with a self-assembled monolayer of the mixed alkanethiolates 3-mercaptopropionic acid (MPA) and 3-mercaptopropane (MP). Electrochemistry and high-resolution mass spectrometry were used to elucidate the structure of the adsorbed species and follow the synthesis. The amino acids can be attached only to MPA, but the presence of a diluting unreactive molecule of MP reduces steric crowding about the reaction center. The maximum coverage of synthesized tripeptide occurs at a ratio of MPA/MP of 1:1.     

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.     

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

Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and digital simulation techniques were used to investigate quantitatively the mechanism of electron transfer (ET) through densely packed and well-ordered self-assembled monolayers (SAMs) of 11-mercaptoundecanoic acid on gold, either pristine or modified by physically adsorbed glucose oxidase (GOx). In the presence of ferrocenylmethanol (FcMeOH) as a redox mediator, ET kinetics involving either solution-phase hydrophilic redox probes such as [Fe(CN)6]3-/4- or surface-immobilized GOx is greatly accelerated: [Fe(CN)6]3-/4- undergoes diffusion-controlled ET, while the enzymatic electrochemical conversion of glucose to gluconolactone is efficiently sustained by FcMeOH. Analysis of the results, also including the digital simulation of CV and EIS data, showed the prevalence of an ET mechanism according to the so-called membrane model that comprises the permeation of the redox mediator within the SAM and the intermolecular ET to the redox probe located outside the monolayer. The analysis of the catalytic current generated at the GOx/SAM electrode in the presence of glucose and FcMeOH allowed the high surface protein coverage suggested by X-ray photoelectron spectroscopy (XPS) measurements to be confirmed.     

Ferrocenylalkylthiolate labeling of defects in alkylthiol self-assembled monolayers on gold

Coverage defects in alkylthiol self-assembled monolayers (SAMs) are critically important to function related to electron transfer from soluble redox probes. There is therefore a need for an accurate and direct measurement of the number and type of coverage defect in a range of SAMs. Ferrocenyldodecanethiol (FcC(12)SH) has been assessed as an electrochemically-addressable label of coverage defects. It is shown that short time exposure of a SAM to FcC(12)SH leads to a quantifiable Fc coverage (Gamma(Fc)), with Gamma(Fc) < 1% readily measurable. The voltammetric signature of FcC(12)SH label is also able to differentiate types of defect in a given SAM. A number of SAM preparation conditions are assessed for the density and type of coverage defect. This labeling method therefore will be a useful tool for research into SAM property-function relationships.     

Reactivity of acetylenyl-terminated self-assembled monolayers on gold: triazole formation

We report the reactivity of acetylenyl-terminated self-assembled monolayers (SAMs) on gold toward "click" chemistry, Huisgen 1,3-dipolar addition, leading to the formation of triazoles. After the formation of acetylenyl-terminated SAMs, the triazole formation was performed on the SAMs and the reaction was confirmed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ellipsometry, and contact angle goniometry. "Click" chemistry has offered a versatile strategy for the functionalization in solution chemistry with mild reaction conditions and a high compatibility in functional groups, and our result shows that the reaction could be applied to acetylenyl-terminated SAMs for the introduction of useful functional groups to the surfaces.     

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 monolayers on gold via bipodal dithiazepane anchoring groups

Novel dithiazepane-functionalized ferrocenyl-phenylethynyl oligomers 1 and 2 have been synthesized. Self-assembled monolayers (SAMs) of these ferrocene derivatives have been studied by X-ray photoelectron spectroscopy, ellipsometry, and cyclic voltammetry. It has been shown by XPS that monolayers of the dithiazepane-anchored molecules on gold electrodes contain gold-thiolate species. Cyclic voltammetry of the SAMs were characteristic of stable electroactive monolayers even for single-component SAMs of 1 and 2, with the more ideal responses recorded for the two-component SAMs diluted with undecanethiol. The small variation in peak splittings at progressively higher scan rates in these SAMs makes dithiazepane-bridged redox species promising candidates for further studies on molecular wires with bipodal anchoring.     

Fractional coverage of defects in self-assembled thiol monolayers on gold

Au electrodes are alkylated by self-assembled organic monolayers of octadecanethiol from alcohol solution. The electron tunnelling resistance of a monolayer-coated gold electrode has been investigated by ac impedance. The relation between the fractional coverage of different defects and the corresponding film thickness at these ‘collapsed’ sites has been deduced from electron tunnelling theory. By using the concepts of average film thickness at defect (d_a) and average fractional coverage of defect (θ_a), we have obtained the θ_ad_a plot. The influence of the apparent standard rate constant on the shape of the θ_ad_a plot has been discussed. In our experiments, Fe(CN)₆^3−/4− is used as a redox probe to study the θ_ad_a plot of an octadecanethiol monolayer. The θ_a versus d_a plot indicates that the defects with d_a<6 methylene groups and θ_a<0.1 can increase the apparent standard rate constant from 1.9×10⁻¹⁰ cm s⁻¹, which is the theoretical value calculated from electron tunnelling theory, to 2.9×10⁻⁷ cm s⁻¹. The average thickness of the whole monolayer (ATWM), which is obtained from the θ_a versus d_a plot and which can indicate the blocking property of the monolayer, is 11 methylene groups.