Improved blocking properties of short-chain alkanethiol monolayers self-assembled on gold

Blocking of gold surfaces by self-assembled monolayers (SAMs) of n-octanethiol (OT) was investigated. Short-chain alkanethiols such as OT are known to form loosely-packed SAMs with abundant defects and pinholes, exhibiting poor blocking of the gold surface. Hence, gold substrates subjected to 20 h OT adsorption manifested excessive electrochemical penetrability, low contact angles with a large hysteresis, and extensive exchange of functional disulfide molecules into the OT SAM. It is shown that a single electrochemical cycle in H₂SO₄ solution after 1 h OT adsorption, followed by another 20 h adsorption, results in a dramatic improvement of the coverage and blocking properties of the SAM, showing considerably lower electrochemical penetrability, improved contact angles, and sluggish exchange of the functional molecules into the OT SAM. Insertion of the latter molecules into the monolayer was monitored by their ability to coordinatively attach ligand-substituted gold nanoparticles.     

Self-assembled monolayers (SAMs) of alkoxycyanobiphenyl thiols on gold surface using a lyotropic liquid crystalline medium

We have studied the self-assembled monolayers (SAMs) of alkoxycyanobiphenyl thiols on gold prepared in a lyotropic liquid crystalline medium using electrochemical techniques. We have used thiols of different alkyl chain lengths viz., C₅, C₈ and C₁₀ which exhibit nematic liquid crystalline order in bulk. They are dispersed in a hexagonal lyotropic liquid crystalline phase, consisting of a non-ionic surfactant, Triton X-100 and water. This medium provides a highly hydrophobic environment to solubilize the thiols and later facilitate their delivery to the gold surface to form a monolayer. The electrochemical techniques such as cyclic voltammetry and electrochemical impedance spectroscopy were used to evaluate the barrier property and ionic permeability of these monolayers on gold surface. We have compared our results with that of the corresponding monolayers prepared using dichloromethane as a solvent. We find from our studies that the monolayers prepared using the hexagonal liquid crystalline phase show a better electrochemical blocking ability towards the redox reactions and exhibit very low ionic permeability. From the impedance studies, we have determined a surface coverage value of >99.9% for the monolayer on Au surface for all the thiol molecules studied in this work. We have also proposed a model for the likely processes involved in the formation of monolayer from the liquid crystalline medium. This is the first example in literature of self-assembled monolayer formation on Au by a compound exhibiting bulk nematic phase that is dispersed in a lyotropic liquid crystalline medium.     

Self-assembled monolayers of metallosalophenes on gold

Salophene complexes of transition metals exhibit a reversible electrochemistry. We have synthesized salophene complexes with sulfur-containing sub-stituents aimed at the formation of self-assembled monolayers on a gold surface. Such monolayers have interesting cation complexating properties. The monolayers were fully characterized by wettability studies, grazing-angle Fourier transform infrared spectroscopy (FT-IRS), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary-ion mass spectrometry (TOF-SIMS), and electrochemical capacitance measurements. These measurements indicate liquid-like monolayers. Cation complexation could be monitored indirectly by electrochemical impedance spectroscopy measurements, showing responses for Na⁺ and K⁺. This complexation behavior of the metallosalophene monolayers could not be studied directly by electrochemistry of the metallosalophene either due to electrochemical instability of the monolayer or a smeared redox response.     

Ab initio electronic properties of dual phosphorus monolayers in silicon

In the midst of the epitaxial circuitry revolution in silicon technology, we look ahead to the next paradigm shift: effective use of the third dimension - in particular, its combination with epitaxial technology. We perform ab initio calculations of atomically thin epitaxial bilayers in silicon, investigating the fundamental electronic properties of monolayer pairs. Quantitative band splittings and the electronic density are presented, along with effects of the layers’ relative alignment and comments on disordered systems, and for the first time, the effective electronic widths of such device components are calculated.     

Electrochemical assessment of electrochemical oxidation stability of self-assembled monolayers on gold and preparation of binary self-assembled monolayers on gold

Binary thiolates self-assembled monolayers (SAMs) on gold have been prepared efficiently by using an electrochemical oxidation combining with replacement reaction method. The electrochemical results show that both the SAMs of mercaptoacetic acid (MAA) and 1-dodecanethiol (DT) on gold surface are oxidized at certain anodic potentials (noting: it is not oxidative redeposition of alkanethiolate monolayers on gold surface), and the degree of electrochemical oxidation of single thiolates-SAMs is function of the polarization potential and polarization time. Therefore, formation of binary MAA-DT thiolates-SAMs can be achieved if MAA or DT is present in solution after the electrochemical oxidation of DT or MAA SAMs on gold electrode. In this case, the ratio of MAA to DT on the binary thiolates-SAMs can be easily controlled by controlling polarization potential and/or polarization time. The present approach enables us to prepare homogeneously binary SAMs with different composition, and assess the electrochemical oxidation stability of single thiolates-SAMs by means of cyclic voltammetry measurements of redox probe.     

Theoretical studies on the structure and electronic properties of cubic gold nanoclusters

A multi‐scale approach involving molecular mechanics, semi‐empirical and density functional techniques have been carried out on the cubic gold nanoclusters (Au_n, n = 63, 126, 252, 504, 756, 1008, 1260, 1512, 1764 and 2016) to monitor their structural and electronic properties. Definite correlations have been found to connect the ionisation potentials, conductance and absorption properties of such clusters with their shapes and sizes. Analytical equations are developed based on three‐dimensional particle in a box model to explain the validity of such correlations. © 2012 Canadian Society for Chemical Engineering     

Self-assembled monolayers of a disulphide-derivatised cobalt-porphyrin on gold

A self-assembled monolayer (SAM) of a novel cobalt(II)porphyrin disulphide derivative was prepared on flat gold(1 1 1) electrode. Evidence for surface modification was provided by electrochemical reductive desorption of the monolayer and ellipsometry, consistent with a coverage of 2.5 × 10⁻¹⁰ mol cm⁻² and a thickness of 13 Å, respectively. Both results support the presence of SAMs where the molecules share an intermediate position between perpendicular and flat orientation. Scanning tunnelling microscopy have also proven the formation of CoPSS SAMs, however high-resolution images could only be obtained when the CoPSS molecules were diluted in an hexanethiol SAM. The electrocatalytic activity of the surface confined Co-porphyrin was evaluated for the oxygen reduction. Voltammetric data indicate that reaction involves two electrons consistent with the formation of hydrogen peroxide. Under similar experimental conditions the data obtained for an iron-porphyrin analogue points for a full reduction of dioxygen to water.     

Self-assembled monolayers of alkanethiols on gold: the adsorption and wetting properties of monolayers derived from two components with alkane chains of different lengths

This paper describes the preparation and wetting properties of two-component self-assembled monolayers (SAMs) obtained by the competitive adsorption of one short-chain (HS(CH₂)₁₀Sh) and one long-chain (HS(CH₂)₂₁Lg) alkanethiol onto gold from dilute ethanolic solutions. The four possible combinations of the tail groups CH₃ and CH₂OH were investigated: Sh = CH₃/Lg = CH₂OH, Sh = CH₂OH/Lg = CH₃, Sh = CH₂OH/Lg = CH₂OH, and Sh = CH₃/Lg = CH,. The compositions of these SAMs are not the same as the compositions of the solutions from which they were formed. Although the relationship between the composition of the SAM and the composition of the solution suggests that some phase separation may be occurring within the SAM, contact angles with water and hexadecane show that significant disorder still remains in the interfacial region.     

Vacancy- and doping-dependent electronic and magnetic properties of monolayer SnS2

We have performed first-principles calculations to investigate the formation and migration of vacancies and doping with M (M = Ti, V, Co, Mo, W, Re) at the Sn sites and X (X = O, Se, Te) at the S sites in monolayer SnS₂. We find that the formation energies for S vacancy under both Sn- and S-rich environments are lower than those for Sn vacancy, indicating that the vacancies at the S sites are likely to be formed during the synthesis. Reducing the possibility of vacancy cluster formation, both the vacancies at the Sn and S sites remain robust due to high migration barrier. Additionally, SnS₂ with the vacancies at the Sn sites induces magnetic ground states with a magnetic moment of 4.00 μ_B. Both the Sn- and S-sites vacancies preserve the semiconducting nature of pristine SnS₂ with band gaps of 2.47 eV and 0.30 eV, respectively. Furthermore, we find that the dopants Ti, V, Mo, W, Re can be easily incorporated at the Sn sites in monolayer SnS₂ due to the low formation energies under the S-rich environment. However, Co may not be easily incorporated into SnS₂. The doping with M at the Sn sites induces magnetic ground states in non-magnetic SnS₂. Additionally, a long-range magnetic ordering is observed in SnS₂ doped with V, Co, and Mo. In contrast, easy incorporation of O, Se, and Te at the S sites under the Sn-rich environment has been observed while the semiconducting nature of SnS₂ preserves with small band gaps.     

Molecular-level design of binary self-assembled monolayers on polycrystalline gold electrodes

In this study, we followed up, by measuring the reductive desorption patterns, the time-dependent growth of the self-assembled monolayer (SAM) of a thiol compound (typically cysteine) formed on polycrystalline Au (poly-Au) electrode. Cysteine molecules appeared to adsorb preferentially and consecutively at the Au(1 1 0), Au(1 0 0) and then at the Au(1 1 1) surface domains of the poly-Au. A 95% surface coverage of cysteine (Γ_cysteine) was attained after 5 s, 120 s and more than 300 s for the Au(1 1 0), Au(1 0 0) and Au(1 1 1) domains, respectively, of the poly-Au electrode. The electrochemical reduction of molecular oxygen (O₂) in O₂-saturated 0.5 M KOH was utilized as a probing reaction for the extent of the compactness of the SAM. A binary SAM of two thiols (cysteine and cystamine) has been successfully designed over the poly-Au electrode at which a precise positioning of cysteine was achieved, i.e., cysteine was attached to the Au(1 1 1) domains, while cystamine to the Au(1 0 0) and Au(1 1 0) domains. SEM images for the electrodeposited Ag over the cysteine sub-SAM/Au electrode gave a possible mapping of the Au(1 1 1) domains of the poly-Au electrode.     

Structure of self-assembled monolayers of semifluorinated alkanethiols on gold and silver substrates

Self-assembled monolayers (SAMs) formed from semifluorinated alkanethiols (SFATs) CF₃(CF₂)₉(CH₂)_nSH (F10HnSH: n = 2, 11, and 17) on poly-crystalline Au and Ag were characterized by X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, and near edge X-ray absorption fine structure spectroscopy. SFATs were found to form highly ordered and densely packed SAMs on both substrates. The molecules are strongly bonded to the substrates via their sulfur head groups, in the same manner as conventional alkanethiol (AT) SAMs. The hydrocarbon (except for n = 2) and fluorocarbon parts of the adsorbed SFATs retain the expected planar zigzag and helical conformations of the respective bulk materials. The orientation of the fluorocarbon chains does not depend on the substrate. These entities are almost perpendicular to the substrate in F10H2S/Au and F10H2S/Ag and become slightly more tilted in SFAT SAMs with longer hydrocarbon moieties. However, the alkyl parts of the SFAT films exhibit tilt and twist angles that are similar to those of normal alkanethiol films on Ag and Au substrates despite the reduced packing density in the SFAT films as compared to normal AT SAMs. We suggest that the substrate-related differences in tilt and twist angles for both systems are associated with the different character of the head-group-substrate bonding on Au and Ag.     

Potential control characteristics of short-chain thiols of thioctic acid and mercaptohexanol self-assembled on gold

In this article we systematically investigated self-assembly of short-chain thiols of thioctic acid (TA) and mercaptohexanol (MCH) on gold under potential control, E_dc (−0.4, +0.4 and +0.7 V) and compared the results obtained with open circuit potential (E_OCP). Effect of E_dc on thiol self-asembly was inspected based on the changes in electrochemical parameters including interfacial capacitance (C), phase angle (Φ_1Hz), current density difference (Δi), charge transfer resistance (R_ct) through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Experimental results showed that E_dc could not obtain stable short-chain self-assembled monolayers (SAMs) (TA and MCH) in a short time. Both TA and MCH had slow self-assembly dynamics and needed a long time (> 24 h) to achieve adsorption equilibrium. Furthermore, the negative potential E_dc (−0.4 V) did not facilitate the ordering of SAMs. The ordering of TA-SAMs was found to be the best when assembled under E_dc (+0.4 V), whereas that of MCH-SAMs was almost the same when assembled under either E_OCP or E_dc (+0.4, +0.7 V). We considered that permeation of ions and water molecules perhaps dominated the slow self-assembly dynamics of short-chain thiols (TA and MCH) under E_dc and mutual interaction between adjacent chains of thiols played an important role in the ordering of SAMs.     

The electronic and magnetic properties of functionalized silicene: a first-principles study

ABSTRACT: Based on first-principles calculations, we study the structural, electronic, and magnetic properties of two-dimensional silicene saturated with hydrogen and bromine atoms. It is found that the fully saturated silicene exhibits nonmagnetic semiconducting behavior, while half-saturation on only one side with hydrogen or bromine results in the localized and unpaired electrons of the unsaturated Si atoms, showing ferromagnetic semiconducting or half-metallic properties, respectively. Total energy calculations show that the half-hydrogenated silicene exhibits a ferromagnetic order, while the half-brominated one exhibits an antiferromagnetic behavior.     

Supramolecular domains in mixed peptide self-assembled monolayers on gold nanoparticles

Self-organization in mixed self-assembled monolayers of small molecules provides a route towards nanoparticles with complex molecular structures. Inspired by structural biology, a strategy based on chemical cross-linking is introduced to probe proximity between functional peptides embedded in a mixed self-assembled monolayer at the surface of a nanoparticle. The physical basis of the proximity measurement is a transition from intramolecular to intermolecular cross-linking as the functional peptides get closer. Experimental investigations of a binary peptide self-assembled monolayer show that this transition happens at an extremely low molar ratio of the functional versus matrix peptide. Molecular dynamics simulations of the peptide self-assembled monolayer are used to calculate the volume explored by the reactive groups. Comparison of the experimental results with a probabilistic model demonstrates that the peptides are not randomly distributed at the surface of the nanoparticle, but rather self-organize into supramolecular domains.     

N-Hydroxysuccinimide-terminated self-assembled monolayers on gold for biomolecules immobilisation

Pure and mixed N-hydroxysuccinimide-terminated and butanethiol monolayers were prepared on flat gold (1 1 1) surfaces with the intent of developing suitable platforms for the direct biomolecules immobilisation. The self-assembled monolayers (SAMs) were characterised by electrochemical reductive desorption of the thiolate from the gold surface. The data have shown that certain solution proportions of the two compounds yield modified electrodes exhibiting intermediate electrochemical behaviour of the corresponding pure SAMs. The reactivity of the terminal N-hydroxysuccinimide (NHS) towards amine functionalities has been tested for the covalent attachment of Dopamine. The cyclic voltammetric responses of the investigated monolayers, after contacting with a Dopamine solution, have confirmed the chemical coupling of the amine as well as the formation of mixed SAMs. The Dopamine surface coverage increased with the amount of surface NHS. Laccase was also successfully immobilised onto this modified electrodes. The electrochemical behaviour of the modified SAMs with Laccase indicates direct electron transfer between the immobilised enzyme and the gold surface. Evidence for Laccase immobilisation was also provided by atomic force microscopic measurements.     

The electronic structure and optical properties of Mn and B,C, N co-doped MoS2 monolayers

The electronic structure and optical properties of Mn and B, C, N co-doped molybdenum disulfide (MoS₂) monolayers have been investigated through first-principles calculations. It is shown that the MoS₂ monolayer reflects magnetism with a magnetic moment of 0.87 μB when co-doped with Mn-C. However, the systems co-doped with Mn-B and Mn-N atoms exhibit semiconducting behavior and their energy bandgaps are 1.03 and 0.81 eV, respectively. The bandgaps of the co-doped systems are smaller than those of the corresponding pristine forms, due to effective charge compensation between Mn and B (N) atoms. The optical properties of Mn-B (C, N) co-doped systems all reflect the redshift phenomenon. The absorption edge of the pure molybdenum disulfide monolayer is 0.8 eV, while the absorption edges of the Mn-B, Mn-C, and Mn-N co-doped systems become 0.45, 0.5, and 0 eV, respectively. As a potential material, MoS₂ is widely used in many fields such as the production of optoelectronic devices, military devices, and civil devices.     

Electroreduction of laccase covalently bound to organothiol monolayers on gold electrodes

Cerrena unicolor laccase was immobilized on the gold electrode by covalent bonding to self-assembled monolayers of mercaptoundecanoic or mercaptopropionic acids. STM images of immobilized laccase proved high population of the laccase molecules on the monolayer modified electrode. The SERS experiments in concert with resonance Raman effect confirmed that the structure at the “blue” copper site of the immobilized protein remained intact. The accessibility of individual copper sites for electron exchange with the gold electrode surface was investigated by voltammetry. The electrode behavior of laccase is different in the presence and absence of oxygen, showing that the immobilized enzyme is reactive towards oxygen. Addition of two common mediators improved the electrical connectivity of the enzyme with the electrode, increased the catalytic efficiency of immobilized laccase and switched the onset of catalytic current to the potentials of the mediator. Immobilization of laccase on well-organized mercaptoundecanoic acid separates efficiently the enzyme from the electrode and does not allow easy access of mediators to the surface. Attachment of the enzyme at smaller distance from the electrode by means of significantly shorter spacer molecule—mercaptopropionic acid improved the efficiency of catalytic reduction of oxygen on the monolayer modified electrode.     

Surface modification of gold electrode with gold nanoparticles and mixed self-assembled monolayers for enzyme biosensors

This paper describes the development and evaluation of a generic method for the immobilization of enzymes onto a gold electrode and its application to amperometric biosensors. The surface of the gold electrode was modified with gold nano-particles (AuNP) and mixed self-assembled monolayers (SAMs) to form an enzyme biosensor matrix. Horseradish peroxidase (HRP) was immobilized on the modified surface to form a biosensor matrix on a gold electrode. After the deposition of gold nano-particles on a bare gold surface, the AuNP-deposited gold electrode and a bare electrode were compared for the surface area and electric current using AFM and cyclic voltammetry (CV). The AuNP strongly adhered to the surface of the gold electrode, had uniform distribution and was very stable. A mixed SAM, composed of two different monolayer molecules, dithiobis-N-succinimidyl propionate (DTSP) and inert tetradecane-1-thiol (TDT), was formed using reductive desorption technique and cyclic voltammetry was used to verify the formation of mixed deposition. First, 3-mercaptopropionic acid (MPA) and TDT were deposited with a specified deposition ratio between the two components. Then, MPA was desorbed by applying electric potential to the surface. Finally, DTSP was deposited where MPA was. The ratios of 20: 80 and 50: 50 between MPA and TDT were examined, and differences in the CV responses were discussed. HRP was immobilized on the mixed SAM surface. The investigated method is regarded as an effective way for stable enzyme attachment, while the presence of gold nanoparticles provides enhanced electrochemical activity; it needs very small amounts of samples and enzymes and the SAM matrix helps avoid enzyme leaking. It is interesting that the mixed SAM shows unique CV characteristics compared to the uni-molecular SAMs. The reaction kinetics of the SAM-immobilized enzyme is discussed with the CV results and is observed to obey the Michaelis-Menten equation.     

Probing the electronic properties and structural evolution of anionic gold clusters in the gas phase

Gold nanoparticles have been discovered to exhibit remarkable catalytic properties in contrast to the chemical inertness of bulk gold. A prerequisite to elucidate the molecular mechanisms of the catalytic effect of nanogold is a detailed understanding of the structural and electronic properties of gold clusters as a function of size. In this review, we describe joint experimental studies (mainly photoelectron spectroscopy) and theoretical calculations to probe the structural properties of anionic gold clusters. Electronic properties and structural evolutions of all known Au(n)(-) clusters as experimentally confirmed to date are summarized, covering the size ranges of n = 3-35 and 55-64. Recent experimental efforts in resolving the isomeric issues of small gold clusters using Ar-tagging, O(2)-titration and isoelectronic substitution are also discussed.