Marina Ruths

Surface Characterization and Protein Interactions of Segmented Polyisobutylene-Based Thermoplastic Polyurethanes

The surface properties and biocompatibility of a class of thermoplastic polyurethanes (TPUs) with applications in blood-contacting medical devices have been studied. Thin films of commercial TPUs and novel polyisobutylene (PIB)-poly(tetramethylene oxide) (PTMO) TPUs were characterized by contact angle measurements, X-ray photoelectron spectroscopy, and atomic force microscopy (AFM) imaging. PIB-PTMO TPU surfaces have significantly higher C/N ratios and lower amounts of oxygen than the theoretical bulk composition, which is attributed to surface enrichment of PIB. Greater differences in the C/N ratios were observed with the softer compositions due to their higher relative amounts of PIB. The contact angles were higher on PIB-PTMO TPUs than on commercial polyether TPUs, indicating lower surface energy. AFM imaging showed phase separation and increasing domain sizes with increasing hard segment content. The biocompatibility was investigated by quantifying the adsorption of fouling and passivating proteins, fibrinogen (Fg) and human serum albumin (HSA) respectively, onto thin TPU films spin coated onto the electrode of a quartz crystal microbalance with dissipation monitoring (QCM-D). Competitive adsorption experiments were performed with a mixture of Fg and albumin in physiological ratio followed by binding of GPIIb-IIIa, the platelet receptor ligand that selectively binds to Fg. The QCM-D results indicate similar adsorbed amounts of both Fg and HSA on PIB-PTMO TPUs and commercial TPUs. The strength of the protein interactions with the various TPU surfaces measured with AFM (colloidal probe) was similar among the various TPUs. These results suggest excellent biocompatibility of these novel PIB-PTMO TPUs, similar to that of polyether TPUs.

Odd–Even Effects in the Friction of Self-Assembled Monolayers of Phenyl-Terminated Alkanethiols in Contacts of Different Adhesion Strengths

We have studied the frictional properties of self-assembled monolayers (SAMs) of phenyl-terminated alkanethiols, C6H5(CH2) n SH (n = 13–16) on template-stripped gold. The friction force was measured with atomic force microscopy (AFM), and the magnitude of the adhesion was controlled by immersing the sliding contact in ethanol (giving low adhesion) or dry N2 gas (giving enhanced adhesion relative to ethanol). We observed a linear friction force as a function of load (F = μL) in the systems with low adhesion and a non-linear friction force when the adhesion was higher. The non-linear behavior in the adhesive systems appeared to be area-dependent (F = S c A) and was compared to contact areas calculated using the extended Thin-Coating Contact Mechanics (TCCM) model. In ethanol, the coefficient of friction μ was found to be systematically higher for odd values of n (i.e., for the monolayers in which the terminal phenyl group was oriented closer to the surface normal).

Friction of Polyaromatic Thiol Monolayers in Adhesive and Nonadhesive Contacts

We have used friction force microscopy to study the effects of adhesion on the boundary friction of self-assembled monolayers of the aromatic compounds thiophenol, p-phenylthiophenol, p-terphenyl thiol, 2-naphthalenethiol, and benzyl mercaptan on gold. To control the adhesion between the monolayer-covered tip and substrate, the friction measurements were made in dry N(2) gas or in ethanol. At low loads, low adhesion (in ethanol) resulted in a linear dependence of the friction force on load (i.e., F = muL) whereas higher adhesion between the same monolayers (in N(2)) gave an apparent area-dependent friction. The friction in the adhesive systems was well described by F = S(c)A with the contact area, A, calculated for a thin, linearly elastic film confined between rigid substrates using the thin-coating contact mechanics (TCCM) model in a transition regime between its DMT- and JKR-like limits. With increasing packing density of the monolayers, a systematic decrease was found in the friction coefficient (mu) obtained in ethanol and the critical shear stress (S(c)) obtained in N(2). To describe these aromatic monolayers with the extended TCCM model, a higher Youngs modulus was neeeded than for fatty acid monolayers of similar packing density.

Frequency response of quartz crystal shear-resonator during an adhesive, elastic contact in a surface forces apparatus

Contact mechanics experiments on a single asperity contact between two dry mica surfaces have been performed with a surface forces apparatus where one mica surface was excited to oscillatory shear movements by a quartz-crystal resonator. We directly obtain the resonance parameters of the quartz and the radius of the adhesive contact (measured by optical interferometry) as a function of the external load. The frequency shift was found to increase linearly with increasing contact radius as predicted by the elastic point contact model by Laschitsch and Johannsmann [J. Appl. Phys. 85, 3759 (1999)]. The bandwidth increased more strongly than linearly with the contact radius, but not quadratically as predicted by the model. We attribute the differences to dissipative processes in the glue layers supporting the contacting surfaces.

Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes

Polymer chain bridging by multivalent ions and solvophobic attractions drives structure formation in charged polymer brushes. Subtle details about a polyelectrolyte’s surrounding environment can dictate its structural features and potential applications. Atomic force microscopy (AFM), surface forces apparatus (SFA) measurements, and coarse-grained molecular dynamics simulations are combined to study the structure of planar polyelectrolyte brushes [poly(styrenesulfonate), PSS] in a variety of solvent conditions. More specifically, AFM images provide a first direct visualization of lateral inhomogeneities on the surface of polyelectrolyte brushes collapsed in solutions containing trivalent counterions. These images are interpreted in the context of a coarse-grained molecular model and are corroborated by accompanying interaction force measurements with the SFA. Our findings indicate that lateral inhomogeneities are absent from PSS brush layers collapsed in a poor solvent without multivalent ions. Together, AFM, SFA, and our molecular model present a detailed picture in which solvophobic and multivalent ion–induced effects work in concert to drive strong phase separation, with electrostatic bridging of polyelectrolyte chains playing an essential role in the collapsed structure formation.

Quartz crystal resonators with atomically smooth surfaces for use in contact mechanics

A quartz crystal shear resonator was modified by gluing a thin piece of mica on one surface to obtain an acoustic sensor with a macroscopic atomically smooth area. Contact mechanics experiments with this resonator touching a half-spherical mica surface were performed at high shear rate by integrating it into a surface forces apparatus, which provides simultaneous load control and interferometric measurement of the real contact area and surface separation. The procedures for gluing mica on a quartz resonator without significant loss of its sensitivity and gluing a half-spherical mica surface are described in detail. Sensitivity issues and overtone order dependence are discussed. Although our work focuses on contact mechanics experiments, the technique is also relevant for quartz crystal microbalance applications.

The electric field effect on the sensitivity of tin oxide gas sensors on nanostructured substrates at low temperature

A novel low-temperature SnO2 gas sensor was prepared and studied on silicon nanostructures formed by femtosecond laser irradiation. By applying a bias voltage on the silicon substrate to alter the charge distribution on the surface of the SnO2, carbon monoxide (CO), and ammonia (NH3) gas can be distinguished by the same sensor at room temperature. The experimental results are explained with a mechanism that the sensor works at low temperature because of adsorption of gas molecules that trap electrons to the surface of the SnO2.

Detection of Liquid Penetration of a Micropillar Surface Using the Quartz Crystal Microbalance

A quantitative characterization of the wetting states of droplets on hydrophobic textured surfaces requires direct measurement of the liquid penetration into surface cavities, which is challenging. Here, the use of quartz crystal microbalance (QCM) technology is reported for the characterization of the liquid penetration depth on a micropillar-patterned surface. The actual liquid-air interface of the droplet was established by freezing the droplet and characterizing it using a cryogenically focused ion beam/scanning electron microscope (cryo FIB-SEM) technique. It was found that a direct correlation exists between the liquid penetration depth and the responses of the QCM. A very small frequency shift of the QCM (1.5%) was recorded when the droplet was in the Cassie state, whereas a significant frequency shift was observed when the wetting state changed to the Wenzel state (where full liquid penetration occurs). Furthermore, a transition from the Cassie to the Wenzel state can be captured by the QCM technique. An acoustic-structure-interaction based numerical model was developed to further understand the effect of penetration. The numerical model was validated by experimentally measured responses of micropillar-patterned QCMs. The results also show a nonlinear response of the QCM to the increasing liquid penetration depth. This research provides a solid foundation for utilizing QCM sensors for liquid penetration and surface wettability characterization.

Multivalent counterions diminish the lubricity of polyelectrolyte brushes

A brush with friction Polyelectrolyte brushes consist of charged polymer chains attached to a common backbone or surface. They provide excellent lubrication between two surfaces for both engineered and physiological materials. The packing of the brushes is sensitive to pH, temperature, or added salts. Yu et al. show that the presence of multivalent ions can cause brush collapse, similarly to monovalent ions (see the Perspective by Ballauff). Critically—and not observed with the addition of monovalent ions—very low concentrations of multivalent ions cause bridging between the brushes and increase friction between the surfaces to the extent that their value for biomedical devices is limited. Science, this issue p. 1434; see also p. 1399 Low concentrations of multivalent ions dramatically increase the friction between polymer brushes. Polyelectrolyte brushes provide wear protection and lubrication in many technical, medical, physiological, and biological applications. Wear resistance and low friction are attributed to counterion osmotic pressure and the hydration layer surrounding the charged polymer segments. However, the presence of multivalent counterions in solution can strongly affect the interchain interactions and structural properties of brush layers. We evaluated the lubrication properties of polystyrene sulfonate brush layers sliding against each other in aqueous solutions containing increasing concentrations of counterions. The presence of multivalent ions (Y3+, Ca2+, Ba2+), even at minute concentrations, markedly increases the friction forces between brush layers owing to electrostatic bridging and brush collapse. Our results suggest that the lubricating properties of polyelectrolyte brushes in multivalent solution are hindered relative to those in monovalent solution.

Structure and Functionality of Polyelectrolyte Brushes: A Surface Force Perspective

The unique functionality of polyelectrolyte brushes depends on several types of specific interactions, including solvent structure effects, hydrophobic forces, electrostatic interactions, and specific ion interactions. Subtle variations in the solution environment can lead to conformational and surface structural changes of the polyelectrolyte brushes, which are mainly discussed from a surface-interaction perspective in this Focus Review. A brief overview is given of recent theoretical and experimental progress in the structure of polyelectrolyte brushes in various environments. Two important techniques for surface-force measurements are described, the surface forces apparatus (SFA) and atomic force microscopy (AFM), and some recent results on polyelectrolyte brushes are shown. Lastly, this Focus Review highlights the use of these surface-grafted polyelectrolyte brushes in the creation of functional surfaces for various applications, including nonfouling surfaces, boundary lubricants, and stimuli-responsive surfaces.