Globotriose- and oligo(ethylene glycol)-terminated self-assembled monolayers: surface forces, wetting, and surfactant adsorption

A set of oligo(ethylene glycol)-terminated and globotriose-terminated self-assembled monolayers (SAMs) has been prepared on gold substrates. Such model surfaces are well defined and have good stability due to the strong binding of thiols and disulfides to the gold substrate. They are thus very suitable for addressing questions related to effects of surface composition on wetting properties, surface interactions, and surfactant adsorption. These issues are addressed in this report. Accurate wetting tension measurements have been performed as a function of temperature using the Wilhelmy plate technique. The results show that the nonpolar character of oligo(ethylene glycol)-terminated SAMs increases slightly but significantly with temperature in the range 20-55 degrees C. On the other hand, globotriose-terminated SAMs are fully wetted by water at room temperature. Surface forces measurements have been performed and demonstrated that the interactions between oligo(ethylene glycol)-terminated SAMs are purely repulsive and similar to those determined between adsorbed surfactant layers with the same terminal headgroup. On the other hand, the interactions between globotriose-terminated SAMs include a short-range attractive force component that is strongly affected by the packing density in the layer. In some cases it is found that the attractive force component increases with contact time. Both these observations are rationalized by an orientation- and conformation-dependent interaction between globotriose headgroups, and it is suggested that hydrogen-bond formation, directly or via bridging water molecules, is the molecular origin of these effects.     

Hydration of oligo(ethylene glycol) self-assembled monolayers studied using polarization modulation infrared spectroscopy

The interaction with water of protein-resistant monolayers (SAMs), self-assembled from (triethylene glycol) terminated thiol HS(CH2)11(OCH2CH2)3OMe solutions, was studied using in and ex situ polarization-modulated Fourier transform infrared spectroscopy. In particular, shifts in the position of the characteristic C-O-C stretching vibration were observed after the monolayers had been exposed to water. The shift in frequency increased when the SAM was observed in direct contact with a thin layer of water. It was found that the magnitude of the shift also depended on the surface coverage of the SAM. These findings suggest a rather strong interaction of oligo(ethylene glycol) SAMs with water and indicate the penetration of water into the upper region of the monolayer.     

Molecular simulation study of water interactions with oligo (ethylene glycol)-terminated alkanethiol self-assembled monolayers

Molecular simulations were performed to study a system consisting of protein (e.g., lysozyme) and self-assembled monolayers (SAMs) terminating with different chemical groups in the presence of explicit water molecules and ions. Mixed SAMs of oligo (ethylene glycol) [S(CH2)4(OCH2CH2)4OH, (OEG)] and hydroxyl-terminated SAMs [S(CH2)4OH] with a mole fraction of OEG at chiOEG = 0.2, 0.5, 0.8, and 1.0 were used in this study. In addition, methyl-terminated SAMs [S(CH2)11CH3] were also studied for comparison. The structural and dynamic behavior of hydration water, the flexibility and conformation state of SAMs, and the orientation and conformation of protein were examined. Simulation results were compared with those of experiments. It appears that there is a correlation between OEG surface resistance to protein adsorption and the surface density of OEG chains, which leads to a large number of tightly bound water molecules around OEG chains and the rapid mobility of hydrated SAM chains.     

One-step photochemical introduction of nanopatterned protein-binding functionalities to oligo(ethylene glycol)-terminated self-assembled monolayers

Exposure of oligo(ethylene glycol) (OEG)-terminated self-assembled monolayers (SAMs) to UV light leads to the formation of aldehyde groups, leading to a simple one-step method for the introduction of reactive functional groups to protein-resistant surfaces. X-ray photoelectron spectroscopy has been used to demonstrate binding of amines to the modified surfaces, while surface plasmon resonance has shown that proteins are covalently bound. Modified OEG monolayers bind streptavidin at least as well as N-hydroxysuccinimidyl ester functionalized monolayers. Micrometer and nanometer-scale patterns are conveniently fabricated by exposing the monolayers using, respectively, a mask and a scanning near-field optical microscope.     

Fabrication of biomolecular nanostructures by scanning near-field photolithography of oligo(ethylene glycol)-terminated self-assembled monolayers

The UV photo-oxidation of oligo(ethylene glycol) (OEG)-terminated self-assembled monolayers (SAMs) has been studied using static secondary ion mass spectrometry, X-ray photoelectron spectroscopy, contact angle measurement, and friction force microscopy. OEG-terminated SAMs are oxidized to yield sulfonates, but photodegradation of the OEG chain also occurs on a more rapid time scale, yielding degradation products that remain bound to the surface via gold-sulfur bonds. The oxidation of these degradation products is the rate-limiting step in the process. Photopatterning of OEG-terminated SAMs may be accomplished by using a mask and suitable light source or by using scanning near-field photolithography (SNP) in which the mask is replaced by a scanning near-field optical microscope coupled to a UV laser. Using SNP, it is possible to fabricate patterns in SAMs with a full width at half-maximum height (fwhm) as small as 9 nm, which is approximately 15 times smaller than the conventional diffraction limit. SNP-patterned OEG-terminated SAMs may be used to fabricate protein nanopatterns. By adsorbing carboxylic acid-terminated thiols into oxidized regions and converting these to active ester intermediates, it has been possible to fabricate lines of protein molecules with widths of only a few tens of nanometers.     

Ice nucleation and phase behavior on oligo(ethylene glycol) and hydroxyl self-assembled monolayers: simulations and experiments

The nucleation and phase behavior of ultrathin D2O-ice overlayers have been studied on oligo(ethylene glycol) (OEG)-terminated and hydroxyl self-assembled monolayers (SAMs) at low temperatures in ultrahigh vacuum. Infrared reflection-absorption spectroscopy (IRAS) is used to characterize the ice overlayers, the SAMs, and the interactions occurring between the ice and the SAM surfaces. Spectral simulations, based on optical models in conjunction with Maxwell Garnett effective medium theory, point out the importance of including voids in the modeling of the ice structures, with void fractions reaching 60% in some overlayers. The kinetics of the phase transition from amorphous-like to crystalline-like ice upon isothermal annealing at 140 K is found to depend on the conformational state of the supporting OEG SAM surface. The rate is fast on the helical OEG SAMs and slow on the corresponding all-trans SAMs. This difference in kinetics is most likely due to a pronounced D2O interpenetration and binding to the all-trans segments of the ethylene glycol portion of the SAM. No such penetration and binding was observed on the helical OEG SAM.     

Protein adsorption on oligo(ethylene glycol)-terminated alkanethiolate self-assembled monolayers: The molecular basis for nonfouling behavior

A study of protein resistance of oligo(ethylene glycol) (OEG), HS(CH2)11(OCH2CH2)nOH (n = 2, 4, and 6), self-assembled monolayers (SAMs) on Au(111) surfaces is presented here. Hydroxyl-terminated OEG-SAMs are chosen to avoid the hydrophobic effect observed with methyl-terminated OEG-SAMs, particularly at high packing densities. The structure of the OEG-SAM surfaces is controlled by adjusting the assembly solvent. These SAMs were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Protein adsorption on these surfaces was investigated by surface plasmon resonance (SPR). OEG-SAMs assembled from mixed ethanol and water solutions show higher packing density on gold than those from pure ethanol solution. For EG2OH- and EG4OH-SAMs, proteins (i.e., fibrinogen and lysozyme) adsorb more on the densely packed SAMs prepared from mixed ethanol and water solutions, while EG6OH-SAMs generally resist protein adsorption regardless of the assembly solvent used.     

In-situ characterization of self-assembled monolayers of water-soluble oligo(ethylene oxide) compounds

In-situ spectroscopic ellipsometry (SE) was utilized to examine the formation of the self-assembled monolayers (SAMs) of the water-soluble oligo(ethylene oxide) [OEO] disulfide [S(CH(2)CH(2)O)(6)CH(3)](2) {[S(EO)(6)](2)} and two analogous thiols - HS(CH(2)CH(2)O)(6)CH(3) {(EO)(6)} and HS(CH(2))(3)O(CH(2)CH(2)O)(5)CH(3) {C(3)(EO)(5)} - on Au from aqueous solutions. Kinetic data for all compounds follow simple Langmuirian models with the disulfide reaching a self-limiting final state (d=1.2nm) more rapidly than the full coverage final states of the thiol analogs (d=2.0nm). The in-situ ellipsometric thicknesses of all compounds were found to be nearly identical to earlier ex-situ ellipsometric measurements suggesting similar surface coverages and structural models in air and under water. Exposure to bovine serum albumin (BSA) shows the self-limiting (d=1.2nm) [S(EO)(6)](2) SAMs to be the most highly protein resistant surfaces relative to bare Au and completely-formed SAMs of the two analogous thiols and octadecanethiol (ODT). When challenged with up to near physiological levels of BSA (2.5mg/mL), protein adsorption on the final state [S(EO)(6)](2) SAM was only 3% of that which adsorbed to the bare Au and ODT SAMs.     

Interaction of self-assembled monolayers of oligo(ethylene glycol)-terminated alkanethiols with water studied by vibrational sum-frequency generation

Vibrational sum-frequency generation (VSFG) was used to investigate the conformational changes in self-assembled monolayers (SAMs) of (1-mercaptoundec-11-yl) hexa(ethylene glycol) monomethylether (EG6-OMe) on gold when exposed to liquid water. VSFG spectra of the EG6-OMe SAMs were recorded before, during, and after exposure of the films to water and after a subsequent evacuation step. While in contact with water the entire ethylene glycol chains are found in a random, solvated state, after removal from the fluid water molecules remain absorbed only at the terminal groups of the film giving rise to distinct conformational changes. After evacuation, the structure of the EG6-OMe SAM reverts to its original state, indicating that water has been removed from the monolayer. Our findings support recent ab initio calculations and Monte Carlo simulations on the interaction of ethylene glycol-terminated monolayers with water.     

Using self-polymerized dopamine to modify the antifouling property of oligo(ethylene glycol) self-assembled monolayers and its application in cell patterning

We report a one-step, mild method to modify antifouling oligo(ethylene glycol)-terminated self-assembled monolayers. We demonstrate for the first time that self-polymerized dopamine, previously reported as an underwater adhesive, can be patterned on typical antifouling surfaces by microfluidic patterning or microcontact printing. The patterns can be applied in spatiotemporal cell patterning.     

Structure and dynamics of water near the interface with oligo(ethylene oxide) self-assembled monolayers

We performed molecular dynamics simulations of the oligo(ethylene oxide) (OEO) self-assembled monolayers in water to determine the nature of the systems' interfacial structure and dynamics. The density profiles, hydrogen bonding, and water dynamics are calculated as a function of the area per molecule A of OEO. At the highest coverages, the interface is hydrophobic, and a density drop is found at the interface. The interfacial region becomes more like bulk water as A increases. The OEO and water become progressively more mixed, and hydrogen bonding increases within the interfacial region. Water mobility is slower within the interfacial region, but not substantially. The implications of our results on the resistance of OEO SAMs to protein adsorption are discussed. Our principal result is that as A increases the increasingly waterlike interfacial region provides a more protein-resistant surface. This finding supports recent experimental measurements that protein resistance is maximal for less than full coverage on Au.     

Substrate effects in poly(ethylene glycol) self-assembled monolayers on granular and flame-annealed gold

Poly(ethylene glycol) (PEG) self-assembled monolayers (SAMs) are surface coatings that efficiently prevent nonspecific adhesion of biomolecules to surfaces. Here, we report on SAM formation of the PEG thiol CH3O(CH2CH2O)17NHCO(CH2)2SH (PEG(17)) on three types of Au films: thermally evaporated granular Au and two types of Au films from hydrogen flame annealing of granular Au, Au(111), and Au silicide. The different Au surfaces clearly affects the morphology and mechanical properties of the PEG(17) SAM, which is shown by AFM topographs and force distance curves. The two types of SAMs found on flame-annealed Au were denoted "soft" and "hard" due to their difference in stiffness and resistance to scratching by the AFM probe. With the aim of nanometer scale patterning of the PEG(17), the SAMs were exposed by low energy (1 kV) electron beam lithography (EBL). Two distinctly different types of behaviour were observed on the different types of SAM; the soft PEG(17) SAM was destroyed in a self-developing process while material deposition was dominant for the hard PEG(17) SAM.     

Micropatterning of proteins on the surface of three-dimensional poly(ethylene glycol) hydrogel microstructures

This paper describes micropatterning of proteins on the surface of three-dimensional hydrogel microstructures. Poly(ethylene glycol) (PEG)-based hydrogel microstructures were fabricated on a glass substrate using a poly(dimethylsiloxane) (PDMS) replica as a molding insert and photolithography. The lateral dimension and height of the hydrogel microstructures were easily controlled by the feature size of the photomask and depth of the PDMS replica, respectively. Bovine serum albumin (BSA), a model protein, was covalently immobilized to the surface of the hydrogel microstructure via a 5-azidonitrobenzoyloxy N-hydroxysuccinimide bifunctional linker at a surface density of 1.48 mg cm⁻². The immobilization of BSA on the PEG hydrogel surface was demonstrated with XPS by confirming the formation of a new nitrogen peak, and the selective immobilization of fluorescent-labeled BSA on the outer region of the three-dimensional hydrogel micropattern was demonstrated by fluorescence. A hydrogel microstructure could immobilize two different enzymes separately, and sequential bienzymatic reaction was demonstrated by reacting glucose and Amplex Red with a hydrogel microstructure where glucose oxidase was immobilized on the surface and peroxidase was encapsulated. Activity of immobilized glucose oxidase was 16.5 U mg⁻¹, and different glucose concentration ranged from 0.1 to 20 mM could be successfully detected.     

Formation and structure of self-assembled monolayers of alkanethiolates on palladium

The adsorption of n-alkanethiols onto polycrystalline thin films of palladium containing a strong (111) texture produces well-organized, self-assembled monolayers. The organization of the alkane chains in the monolayer and the nature of the bonding between the palladium and the thiol were studied by contact angle measurements, optical ellipsometry, reflection absorption infrared spectroscopy (RAIRS), and X-ray photoelectron spectroscopy (XPS). The XPS data reveals that a compound palladium-sulfide interphase is present at the surface of the palladium film. The RAIR spectra, ellipsometry data, and wetting properties show that the palladium-sulfide phase is terminated with an organized, methyl-terminated monolayer of alkanethiolates. The local molecular environment of the alkane chains transitions from a conformationally disordered, liquidlike state to a mostly all-trans, crystalline-like structure with increasing chain length (n = 8-26). The intensities and dichroism of the methylene and methyl stretching modes support a model for the average orientation of an ensemble of all-trans-conformer chains with a tilt angle of approximately 14-18 degrees with respect to the surface normal and a twist angle of the CCC plane relative to the tilt plane of approximately 45 degrees. The SAMs are stable in air, although the sulfur present at the surface oxidizes in air over a period of 2-5 days at room temperature. The differences in chain organization between SAMs formed by microcontact printing and by solution deposition are also examined by RAIRS and XPS.     

Thermoresponsive oligo(ethylene glycol) methacrylate colloids with antifouling surface properties

Thermoresponsive polymeric colloids attract great attention in several biotechnological applications owing to their ability to manipulate drug release characteristics in a controlled manner. Majority of these applications utilized N‐isopropylacrylamide (NIPAM)‐based particles for controlled drug release. Despite its advantages, such as easy chemical modification and well‐documented literature, a potentially important bottleneck for NIPAM in biological applications is its tendency for nonspecific protein adsorption. Herein, we report a simple way to prepare novel thermoresponsive colloids composed of oligo(ethylene glycol) side chains via precipitation polymerization technique. In addition to displaying highly reversible thermal response, these particles also have considerably low nonspecific protein adsorption when compared with NIPAM counterparts. These crosslinked poly(ethylene glycol) ethyl ether methacrylate particles were characterized using dynamic light scattering and transmission electron microscopy. The effects of co‐monomer, crosslinker and initiator on particle characteristics were investigated. Finally, particle toxicity studies were carried out using 3T3 fibroblast cell lines in MTT cytotoxicity assay. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

pH-Dependent force spectroscopy of tri(ethylene glycol)- and methyl-terminated self-assembled monolayers adsorbed on gold

Self-assembled monolayers (SAMs) of methoxy-tri(ethylene glycol)- (EG(3)-OMe) and methyl-terminated alkanethiols (C(16)) adsorbed on polycrystalline gold were investigated by chemical force spectroscopy. Measurements were performed in aqueous electrolyte solutions depending on ionic strength and pH value. Charged and hydrophobic tips were employed as probes to mimic local patches of proteins and to study the interaction at the organic/liquid interface in detail. Force-distance curves reveal information about the origin of the observed interaction and the underlying mechanisms. The measurements confirm an effective negative surface charge to be present at the oligo(ethylene glycol) (OEG) and the methyl interface and suggest that the charges are due to the adsorption of hydroxyl ions from aqueous solution. pH-dependent measurements further support the robustness of the established charge associated with the OEG films. Its sign does not change over the whole range of investigated values between pH approximately 3.5 and approximately 10. In contrast, the hydrophobic self-assembled hexadecanethiol films on gold show an isoelectric point (IEP) around pH 4. While the mechanism of charge establishment appears to be similar for both SA films, the strength of hydrogen bonding to interfacial water, which acts as a template for hydroxyl ion adsorption, is likely to be responsible for the observed difference.     

Reversible protein adsorption and bioadhesion on monolayers terminated with mixtures of oligo(ethylene glycol) and methyl groups

Surface-grafted, environmentally responsive polymers have shown great promise for controlling adsorption and desorption of macromolecules and cells on solid surfaces. In the paper, we demonstrate that certain mixed self-assembled monolayers (SAMs) of oligo(ethylene glycol) (OEG) and methyl-terminated alkanethiolates on gold form surfaces with switchable hydrophobicity and tendency for protein adsorption and cellular attachment. At temperatures above 32 degrees C, SAMs with a surface density of approximately 50% OEG adsorbed significant amounts of pyruvate kinase and lysozyme, whereas below this temperature, these same SAMs were resistant to the adsorption of these proteins. Furthermore, protein layers adsorbed to these SAMs above 32 degrees C were removed upon rinsing with water below this temperature. Similar results were seen for attachment and release of the marine bacterium, Cobetia marina. The change from nonresistance to adsorptive state of the SAMs was concomitant with a change in advancing water contact angle. Vibrational sum frequency generation spectroscopy suggests that the temperature-induced changes coincide with a disorder-to-partial order transition of the hydrated methylene chains of the OEG moieties within the SAMs. Mixed OEG-methyl SAMs represent both a convenient means of controlling macromolecular and cellular adsorption within the laboratory and a useful tool for relating adsorption properties to molecular structures within the SAMs.     

Micropatterning of lanthanum-based oxide thin film on self-assembled monolayers

We studied the direct micropatterning of a lanthanum-based thin film on a template of self-assembled monolayers in an aqueous solution at 80 degrees C. The template composed of silanol and octadecyl areas was prepared by UV-modified octadecyltrichlorosilane SAMs through a photomask. The amorphous La(2)O(CO(3))(2) x H(2)O thin films were selectively deposited in the silanol regions. Crystallized La(2)O(3) was obtained after heating at 800 degrees C in air.     

Measurement of the azimuthal anchoring energy of liquid crystals in contact with oligo(ethylene glycol)-terminated self-assembled monolayers supported on obliquely deposited gold films

We report measurements of the orientations and azimuthal anchoring energies of the nematic liquid crystal 4-cyano-4'-pentylbiphenyl (5CB) on polycrystalline gold films that are deposited from a vapor at an oblique angle of incidence and subsequently decorated with organized monolayers of oligomers of ethylene glycol. Whereas the gold films covered with monolayers presenting tetra(ethylene glycol) (EG4) lead to orientations of 5CB that are perpendicular to the plane of incidence of the gold, monolayers presenting tri(ethylene glycol) (EG3) direct 5CB to orient parallel to the plane of incidence of the gold during deposition of the gold film. We also measure the azimuthal anchoring energy of the 5CB to be smaller on the surfaces presenting EG3 (3.2 +/- 0.8 microJ/m2) as compared to EG4 (5.5 +/- 0.9 microJ/m2). These measurements, when combined with other results presented in this paper, are consistent with a physical model in which the orientation and anchoring energies of LCs on these surfaces are influenced by both (i) short-range interactions of 5CB with organized oligomers of ethylene glycol at these surfaces and (ii) long-range interactions of 5CB with the nanometer-scale topography of the obliquely deposited films. For surfaces presenting EG3, these short- and long-range interactions oppose each other, leading to small net values of anchoring energies that we predict are dependent on the level of order in the EG3 SAM. These measurements provide insights into the balance of interactions that control the orientational response of LCs to biological species (proteins, viruses, cells) on these surfaces.     

Synthesis of oligo(ethylene glycol) methacrylate polymer brushes

Here we report a study into controlling the polymerization of mono-hydroxy and mono-methoxy terminated oligo(ethylene glycol) methacrylates (HOEGMA and MeOEGMA, respectively) from functionalised, planar surfaces via atom transfer radical polymerization (ATRP). The effects of initiator structure, initiator density, temperature, and monomer ratios have been investigated for these polymerizations. The polymer brushes grown in this way were found to convey protein resistance to the underlying inorganic substrates, prone to facile protein adsorption in their native state.