Self-assembled Alkanethiol Research Articles

Self-Assembly of Alkanethiols on an Oxide-Free Surface of a Copper Electrode from Alkaline Solutions under Electrochemical Control

Self-Assembly of Alkanethiols on an Oxide-Free Surface of a Copper Electrode from Alkaline Solutions under Electrochemical Control

Self-Assembly of Alkanethiols on an Oxide-Free Surface of a Copper Electrode from Alkaline Solutions under Electrochemical Control

Using voltammetry and chronoamperometry, the formation process and properties of insulating nanofilms of alkanethiols with different chain lengths (butane-, octane-, dodecanethiol) obtained on an oxide-free copper surface were studied. The electrochemical method for modifying the copper surface includes the removal of the oxide layer by its cathodic reduction, the adsorption of a thiol under electrochemical control, followed by studying the properties of the resulting nanofilm by voltammetry in one solution. It is shown that, with this approach, a dense thiol film is formed, with its blocking properties depending on the adsorption potential, the time of contact of the electrode with the thiol-containing solution, the thiol concentration, and the presence of dissolved oxygen in the solution. The introduction of ethanol into an aqueous alkali solution leads to a significant acceleration of the process of self-assembly of dodecanethiol, but greatly inhibits the process of self-assembly of butanethiol. The approach proposed in this work makes it possible to use aerated low-concentration thiol-containing solutions to obtain alkanethiol films on the Cu surface with good blocking properties.

Study ofn-Alkanethiol Self-Assembly Behavior on Iron Particles: Effect of Alkyl Chain Length and Adsorption Solvent on Resulting Iron-Based Magnetorheological Fluids

Self-assembled monolayers (SAMs) of organic molecules on metal surfaces are a type of inexpensive surface coating often used to improve metal substrate properties for sensors, electrochemistry, and nanofabrication applications. Iron, specifically, is one of the most commonly used metals, both as a pure metal and as an alloy due to its high conductivity, strong ferromagnetism, and low cost. However, magnetorheological fluids, which have shown impressive energy dampening in fields from civil infrastructure to biomedical devices utilizing iron dispersions, have suffered from low reliability and efficiency due to iron particle oxidation, corrosion, and settling. To understand the effect of self-assembled monolayers on iron and both the adsorbed particle's resistance against aggregation and performance impact, this work performs an in-depth study on alkanethiol-based self-assembled monolayers on iron particles. Adsorption of alkanethiols and the generation of SAMs on micron-sized iron particles were evaluated as a function of adsorption solvent polarity and alkanethiol chain length. Maximum alkanethiol loading, determined from appropriate isotherms, was found to strongly be a function of both parameters. Alkanethiol adsorption increased with increasing alkyl chain length and increasing solvent log P values in polar solvents. With respect to magnetorheologically relevant parameters, alkanethiol adsorption did not show any significant effect on both the magnetic properties of iron (as particles) and fluid on-state yield stress. The colloidal stability of n-alkanethiol adsorbed iron-based magnetorheological fluids (MRFs) was a function of both n-alkanethiol chain length and the iron particle adsorption solvent. MRFs composed of hexadecanethiol adsorbed iron prepared in polar solvents like methanol and ethanol showed excellent sedimentation stability compared to all other MRFs prepared in this study.

Study of surface modification strategies to create glassy carbon-supported, aptamer-based sensors for continuous molecular monitoring

Electrochemical, aptamer-based (E-AB) sensors uniquely enable reagentless, reversible, and continuous molecular monitoring in biological fluids. Because of this ability, E-AB sensors have been proposed for therapeutic drug monitoring. However, to achieve translation from the bench to the clinic, E-AB sensors should ideally operate reliably and continuously for periods of days. Instead, because these sensors are typically fabricated on gold surfaces via self-assembly of alkanethiols that are prone to desorption from electrode surfaces, they undergo significant signal losses in just hours. To overcome this problem, our group is attempting to migrate E-AB sensor interfaces away from thiol-on-gold assembly towards stronger covalent bonds. Here, we explore the modification of carbon electrodes as an alternative substrate for E-AB sensors. We investigated three strategies to functionalize carbon surfaces: (I) anodization to generate surface carboxylic groups, (II) electrografting of arenediazonium ions, and (III) electrografting of primary aliphatic amines. Our results indicate that electrografting of primary aliphatic amines is the only strategy achieving monolayer organization and packing densities closely comparable to those obtained by alkanethiols on gold. In addition, the resulting monolayers enable covalent tethering of DNA aptamers and support electrochemical sensing of small molecule targets or complimentary DNA strands. These monolayers also achieve superior stability under continuous voltammetric interrogation in biological fluids relative to benchmark thiol-on-gold monolayers when a positive voltage scan window is used. Based on these results, we postulate the electrografting of primary aliphatic amines as a path forward to develop carbon-supported E-AB sensors with increased operational stability.Graphical abstract

Experimental Investigation and Molecular Dynamics Simulation on the Anti-Adhesion Behavior of Alkanethiols on Nickel Insert in Micro Injection Molding

Due to the adhesion between the polymer melt and nickel (Ni) mold insert in the micro injection molding process, deformation defects frequently occur when the microstructures are demolded from the insert. In this study, self-assembled alkanethiols were applied to modify the surface of Ni mold insert to reduce its surface energy. Experimental trials were undertaken to explore the effect of alkanethiols coating on the replication quality. After that, molecular dynamics (MD) simulation was then used to investigate the adhesion behavior between the self-assembled coating and polypropylene (PP) by establishing three different types of alkanethiol material. The interaction energy, the potential energy change and radial distribution function were calculated to study the anti-adhesion mechanism. Experimental results show that all the three coatings can effectively decrease the adhesion and therefore promote the replication fidelity. It is demonstrated in MD simulation that the adhesion mainly comes from the van der Waals (vdW) force at the interface. The arrangement of sulfur atom on the Ni surface results in different absorbing behaviors. Compared with that of the PP–Ni interface, the interfacial energy and adhesion work after surface treatment is significantly reduced.

Self-assembly of octanethiol on oxide-free cobalt electrode from aqueous solution under electrochemical control

Self-assembly of alkanethiols on Co surface from organic solution has met with limited success due to the presence of the native oxides. A way needs to be found to remove any oxide and form perfect self-assembled monolayers (SAMs). We report the development of electrochemical approach for formation of alkanethiol self-assembled monolayers on base metals in aqueous solutions. For formation of octanethiol (OT) SAMs on oxide-free cobalt surfaces, we combine the surface renewal technique with in situ electrochemical procedure of removing the native oxide, thiol adsorption, and electrochemical control of SAMs properties in one aqueous solution. The use of aqueous thiol-containing media results in removing any oxide by electrochemical reduction, accelerated monolayer formation under electrochemical control, and investigating SAMs surface coverage and monolayer integrity by voltammetry. In this work, we study the influence of different factors on self-assembly process such as the surface pretreatment, adsorption time, the presence of dissolved oxygen, solution pH, and potential cycling on polycrystalline cobalt microelectrode from aqueous 0.1 M NaClO4 solutions of 0.1 mM OT. We obtain the high-quality self-assembled monolayers which are stable in wide range of potentials and show blocking characteristics toward the following Faradaic processes: Co surface oxidation and O2 and H+ reduction.

Scalable Fabrication of Quasi-One-Dimensional Gold Nanoribbons for Plasmonic Sensing.

Plasmonic nanostructures have a wide range of applications, including chemical and biological sensing. However, the development of techniques to fabricate submicrometer-sized plasmonic structures over large scales remains challenging. We demonstrate a high-throughput, cost-effective approach to fabricate Au nanoribbons via chemical lift-off lithography (CLL). Commercial HD-DVDs were used as large-area templates for CLL. Transparent glass slides were coated with Au/Ti films and functionalized with self-assembled alkanethiolate monolayers. Monolayers were patterned with lines via CLL. The lifted-off, exposed regions of underlying Au were selectively etched into large-area grating-like patterns (200 nm line width; 400 nm pitch; 60 nm height). After removal of the remaining monolayers, a thin In2O3 layer was deposited and the resulting gratings were used as plasmonic sensors. Distinct features in the extinction spectra varied in their responses to refractive index changes in the solution environment with a maximum bulk sensitivity of ∼510 nm/refractive index unit. Sensitivity to local refractive index changes in the near-field was also achieved, as evidenced by real-time tracking of lipid vesicle or protein adsorption. These findings show how CLL provides a simple and economical means to pattern large-area plasmonic nanostructures for applications in optoelectronics and sensing.

Sum Frequency Generation Imaging Microscopy of Self-Assembled Monolayers on Metal Surfaces: Factor Analysis of Mixed Monolayers

Sum frequency generation (SFG) images of microcontact patterned self-assembled alkanethiol monolayers on metal surfaces were analyzed by factor analysis (FA) to determine the spatial distribution of the patterned monolayers over the images. Additionally, each significant abstract factor produced by FA was assessed to determine the information contained within it. These results indicate that FA of the SFG spectra is a promising method to determine the composition and identities of mixed alkanethiol systems that show different vibrational spectra and image contrast. Factor analysis has successfully been applied to SFG images obtained with low signals, which reduces the time required for full spectral SFG imaging.

Low detection limits using sandwich and inhibition assays on long-range surface plasmon waveguide biosensors

A long-range surface plasmon polariton waveguide composed of a gold stripe embedded in CYTOP with an etched microfluidic channel has been used as a label-free real-time biosensor to demonstrate enhanced assay formats capable of very low detection limits. Specifically, sandwich and inhibition (competitive) assays were developed and demonstrated using Bovine Serum Albumin (BSA) and anti-BSA produced in rabbit as a model bio-specific pair. Carbodiimide coupling to a self-assembled COOH-terminated alkanethiol monolayer on the gold stripe was used to immobilize biomaterial to its surface. The optical output power from the biosensor was measured continuously over time and converted into surface mass density. Titration curves were extracted for both immunoassays. We demonstrate that protein concentrations in solution of 10 pg/ml can be detected with a signal-to-noise ratio of 20 using this new optical biosensor technology.

The Effect of an Antigalvanic Reduction of Silver on Gold for the Stability of a Self-Assembled Alkanethiol Monolayer and Chemical Lift-Off Lithography

The effects of silver antigalvanic reduction (Ag AGR) on the structure of alkanethiol self-assembled monolayers (SAMs) on gold with regard to the ordered structure and surface coverage were studied using electrochemical methods. In this paper, we report the structure changes as well as the chemical lift-off lithography (CLL) performance of SAMs dependent on chain lengths, namely, 1-butanethiol, 6-mercapto-1-hexanol, and 11-mercapto-1-undecanol. Cyclic voltammetry of the redox probe and linear sweep voltammetry of the reductive desorption demonstrated that the structure of SAMs with Ag AGR pretreatment are more ordered, resulting from higher surface coverage and stronger molecular interaction. Meanwhile, the influence of Ag AGR on the CLL efficiency behaved differently depending on the SAM chain lengths in both electrochemistry and AFM imaging. In general, the formation of alkanethiol SAMs on Ag AGR/Au has enabled a facile method, which possesses a great potential on the quality control of the SAMs system.

Toward understanding weak matrix effects in TOF SIMS

Chemical imaging methods, including imaging mass spectrometry, are increasingly used for the analysis of samples ranging from biological tissues to electronic devices. A barrier to wider adoption of imaging mass spectrometry is the presence of matrix effects which complicate quantitative analysis. Interactions between an analyte molecule and its surroundings (the “matrix”) can substantially alter both the yield and type of ions observed. Furthermore, such “intrinsic” effects can be confused with nonlinear response due to detector saturation and other instrument-related complications. As a result, quantitative analyses of time-of-flight secondary ion mass spectrometry (TOF SIMS) data that attempt to account for matrix effects are rare. The authors discuss analysis of such data using maximum a posteriori reconstruction based on physically motivated models, and present progress toward the quantitative extraction of chemical concentration profiles and component spectra in the presence of matrix effects, using mixed self-assembled alkanethiolate monolayers as a test system. The authors demonstrate that the incorporation of matrix effects to lowest order using a series-expansion approach is an effective strategy and that doing so provides improved quantitative performance in measuring surface compositions and can also yield information about interactions between species during the SIMS process.

Adsorption and Fibrillization of Islet Amyloid Polypeptide at Self-Assembled Monolayers Studied by QCM-D, AFM, and PM-IRRAS.

Aggregation and fibrillization of human islet amyloid polypeptide (hIAPP) plays an important role in the development of type 2 diabetes mellitus. Understanding the interaction of hIAPP with interfaces such as cell membranes at a molecular level therefore represents an important step toward new therapies. Here, we investigate the fibrillization of hIAPP at different self-assembled alkanethiol monolayers (SAMs) by quartz crystal microbalance with dissipation monitoring (QCM-D), atomic force microscopy (AFM), and polarization-modulated infrared reflectionabsorption spectroscopy (PM-IRRAS). We find that hydrophobic interactions with the CH3-terminated SAM tend to retard hIAPP fibrillization compared to the carboxylic acid-terminated SAM where attractive electrostatic interactions lead to the formation of a three-dimensional network of interwoven fibrils. At the hydroxyl- and amino-terminated SAMs, fibrillization appears to be governed by hydrogen bonding between the peptide and the terminating groups which may even overcome electrostatic repulsion. These results thus provide fundamental insights into the molecular mechanisms governing amyloid assembly at interfaces.

Hydrophilic surfaces via the self-assembly of nitrile-terminated alkanethiols on gold

A series of CN-terminated alkanethiols were synthesized and used to generate self-assembled monolayers (SAMs) on gold. The SAMs were characterized using ellipsometry, contact angle goniometry, polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). The SAMs were compared to those derived from a series of analogous CH 3 -terminated alkanethiols. The CN-terminated SAMs exhibited lower film thicknesses than the CH 3 -terminated SAMs, which was largely due to their greater tilt angle on the surface. Additionally, the CN-terminated SAMs form well-ordered films on flat gold surfaces with relative packing densities being indistinguishable from the CH 3 -terminated SAMs. The CN-terminated SAMs exhibited a less hydrophobic character than the SAMs derived from CH 3 -terminated adsorbates, which was attributed to the dipole moment of the terminal group as well as the lone pair of the nitrogen atom of the CN-terminal group.

Hydrophilic surfaces via the self-assembly of nitrile-terminated alkanethiols on gold

A series of CN-terminated alkanethiols were synthesized and used to generate self-assembled monolayers (SAMs) on gold. The SAMs were characterized using ellipsometry, contact angle goniometry, polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). The SAMs were compared to those derived from a series of analogous CH₃-terminated alkanethiols. The CN-terminated SAMs exhibited lower film thicknesses than the CH₃-terminated SAMs, which was largely due to their greater tilt angle on the surface. Additionally, the CN-terminated SAMs form well-ordered films on flat gold surfaces with relative packing densities being indistinguishable from the CH₃-terminated SAMs. The CN-terminated SAMs exhibited a less hydrophobic character than the SAMs derived from CH₃-terminated adsorbates, which was attributed to the dipole moment of the terminal group as well as the lone pair of the nitrogen atom of the CN-terminal group.

Integration of organic electrochemical transistors and immuno-affinity membranes for label-free detection of interleukin-6 in the physiological concentration range through antibody-antigen recognition.

We demonstrate the label-free and selective detection of interleukin-6 (IL-6), a key cell-signaling molecule in biology and medicine, by integrating an OECT with an immuno-affinity regenerated cellulose membrane. The objective of the membrane is to increase the local concentration of IL-6 at the sensing electrode and, thereby, enhance the device response for concentrations falling within the physiological concentration range of cytokines. The OECT gate electrode is functionalized with an oligo(ethylene glycol)-terminated self-assembled alkanethiolate monolayer (SAM) for both the immobilization of anti IL-6 antibodies and the inhibition of non-specific biomolecule binding. The OECT gate/electrolyte interface is exploited for the selective detection of IL-6 through the monitoring of antigen-antibody binding events occurring at the gate electrode.

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

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.

Structure and Phase Behavior of Mixed Self-Assembled Alkanethiolate Monolayers on Gold Nanoparticles: A Monte Carlo Study.

Configurational-bias Monte Carlo (CBMC) simulations are carried out to investigate the structure and phase behavior of self-assembled monolayers consisting of equimolar alkanethiolate mixtures chemisorbed on the surface of gold nanoparticles. The simulations probe the effects of variations in the chain length, nanoparticle curvature, and exchange of alkanethiolates between nanoparticles. The TraPPE-UA force field is used for the alkanethiolates, whereas the nanoparticle is represented by gold atoms placed on the surface of a sphere. CBMC identity exchange moves are used to enhance sampling of the spatial distribution of the different ligands and to ensure that thermodynamic equilibrium is reached. At a temperature of 298 K, mixtures differing in length by four methylene units exhibit some degree of local segregation. In contrast, the hexanethiolate/tetradecanethiolate mixture yields Janus-like arrangement when the ligands are confined to a single nanoparticle but global demixing when the ligands are allowed to distribute between two nanoparticles.

Combining Nonadhesive Materials into Microstructured Composite Surfaces Induces Cell Adhesion and Spreading.

The synergistic effects between surface topography and chemical functionality were investigated in order to enhance the adhesion of cells to poorly adhesive materials. It has been established that many cell types are weakly adhesive to thin films of poly(N-isopropylacrylamide), or PNIPAAm, and self-assembled triethylene glycol-terminated alkanethiols (EG3SAM). To enhance adhesion, a topographical cue in the form of electrospun micron-width fibers of PNIPAAm was deposited to each coating. Both coatings, without fibers, supported less than 5% cell adhesion. With the deposition of the PNIPAAm fibers to the PNIPAAm coating, cell adhesion increased to 60% of the theoretical maximum at intermediate fiber coverage before decreasing again; however, cell spreading remained minimal. With the deposition of the PNIPAAm fibers onto the EG3SAM surface, cell adhesion increased to almost 100% at 60% fiber coverage, and unlike the PNIPAAm surface, cell spreading was significantly enhanced. This difference in spreading coincided with the assembly of fiber-associated focal adhesions when the underlying surface was EG3SAM, but not PNIPAAm. These findings indicate that the presence of a sparse topographical feature can stimulate cell adhesion on a typically nonadhesive material, but a chemical dissimilarity between the topographic features and the background is necessary for cell spreading. This work demonstrates for the first time that combining nonadhesive materials into microtextured composites can lead to cell adhesion and spreading on par with strongly adhesive surfaces.

Excitation and Relaxation Dynamics of Two-Dimensional Photoexcited Electrons on Alkanethiolate Self-Assembled Monolayers

The electron dynamics in alkanethiolate self-assembled monolayers (Cn-SAMs; n = 6–18, where n is the number of alkyl carbons) formed on Au(111) surfaces has been investigated by time- and angle-resolved two-photon photoemission spectroscopy. The time evolution of photoexcited electrons flowing down into image potential states (IPSs) formed on standing-up structure of SAMs is resolved two-dimensionally; the electron lifetime in the IPS increases with chain length, from sub-ps to 100 ps. The chain length dependence of the IPS lifetime is particularly marked at shorter chain lengths of n = 6–10, whereas it becomes milder at chain lengths above n = 10, whose alkyl layer thickness is ≈10 A. This thickness dependence can be explained by two competitive channels for the decay of IPS electrons: one is electronic coupling of IPS with unoccupied bulk Au states and an interfacial state localized at the Au–S linkage, and the other is IPS electron decay to the Au substrate through a tunneling barrier of insulating alk...

Unveiling the correlation between nanometer-thick molecular monolayer sensitivity and near-field enhancement and localization in coupled plasmonic oligomers.

Metal nanoclusters, sometimes called metamolecules or plasmonic oligomers, exhibit interesting optical properties such as Fano resonances and optical chirality. These properties promise a variety of practical applications, particularly in ultrasensitive biochemical sensing. Here we investigate experimentally the sensitivities of plasmonic pentamers and quadrumers to the adsorption of self-assembled nanometer-thick alkanethiol monolayers. The monolayer sensitivity of such oligomers is found to be significantly higher than that of single plasmonic nanoparticles and depends on the nanocluster arrangement, constituent nanoparticle shape, and the plasmon resonance wavelength. Together with full-wave numerical simulation results and the electromagnetic perturbation theory, we unveil a direct correlation between the sensitivity and the near-field intensity enhancement and spatial localization in the plasmonic "hot" spots generated in each nanocluster. Our observation is beyond conventional considerations (such as optimizing nanoparticle geometry or narrowing resonance line width) for improving the sensing performance of metal nanoclusters-based biosensors and opens the possibilities of using plasmonic nanoclusters for single-molecule detection and identification.