Surface Forces Apparatus Research Articles

Interactions and visualization of bio-mimetic membrane detachment at smooth and nano-rough gold electrode surfaces

Non-specific physical and specific chemical interactions of cells, bacteria, and biomembranes with non-biological target surfaces (e.g., metallic and metal oxides) are crucial in determining the interfacial behavior (interaction forces, adhesion, local deformations and structuring) of many bio- and nano-inspired materials. Knowledge of the governing interactions provides physicochemical understanding of biological systems, and enables engineering of new nano-systems for biomaterials or biomedical benefit. We have directly measured and visualized membrane adhesion and detachment at nanoscopic and extended rough gold electrode surfaces through a multi-scale approach: interactions and contact mechanics measured by surface forces apparatus (SFA) are in quantitative agreement with atomic force microscopy (AFM) measurements, both of which show that membranes can strongly adhere to rough gold surfaces and asperities via specific amine–gold binding and non-specific hydrophobic interactions. The results give insights into membrane interactions at smooth and rough metallic surfaces, and provide a basis for improved design of nanoparticle and extended surface biomaterials.

Superresolution Inter-Surface Interaction Energy Mapping using Particle Tracking Microscopy (PTE)

In biology, binding reactions taking place between apposing surfaces, in contrast to reactions in solution, are controlling a plethora of critical processes including cell adhesion and motility, immunological signaling, neurotransmission etc. However he techniques developed to quantitatively characterize interfacial reactions (e.g. the surface force apparatus, surface plasmon resonance and quartz crystal microbalance) are either not at all amenable to imaging or have at best a resolution of tens of micrometers. Here, we monitored the transient interaction of diffusing particles with a surface to measure quantitatively and under equilibrium conditions, inter-surface on-rates, off-rates and energies for binding reactions (1, 2). These interactions could then be laterally resolved to produce an energy map with sub-diffraction-limited resolution. This novel method was termed Particle Tracking Microscopy.

Friction and Wear of Porcine Articular Joint and Effects of Selective Digestions

In this work, we explored the possible existence of a wear mechanism developing under mild conditions using surface force apparatus (SFA). By selectively digesting different components (type II collagen, Hyaluronic acid (HA), glycosaminoglycans (GAGs)) of the cartilage, we also establish correlation between the structural properties of cartilage surface and the tribological properties.We observed stick-slip friction in articular cartilage for the first time under mild conditions. To visualize load and speed regimes of stick-slip friction occurrence we introduced ‘Dynamic (friction) phase diagram'. Prolonged exposure of the cartilage surfaces to stick-slip sliding results in an increase of surface roughness similar to HA and GAGs digested cartilage suggesting that stick-slip motion is able to induce severe morphological changes of cartilage superficial zone. We also found that digestion of the different components of cartilage alters the morphology of the superficial zone in very different ways. HA and GAGs digestions increased surface roughness while collagen digestion decreased the surface roughness compared to normal cartilage. Friction forces increased up to 2, 5 and 10 times after HA, collagen and GAGs digestion, respectively, indicating no direct correlation between surface roughness and friction forces.

Normal and shear interactions between high grafting density polymer brushes grown by atom transfer radical polymerization

The normal and shear interactions in toluene of polystyrene polymer brushes with ultra-high surface coverage ranging from 15 to 70 mg m−2 formed by atom transfer radical polymerization were measured with a surface force apparatus. Significant hysteresis was observed between compression and separation cycles over the experiment time scale for all surface coverages. The magnitude of the hysteresis increased with increasing film thickness. The experimental relaxation time of the thickest brush layer was at least four orders of magnitude longer than that predicted by the Rouse model. Remarkably, the shear performance of the thickest brushes still demonstrated very good lubricity under compressions down to 35% solvent content. These findings are consistent with a reduction in solvent quality with compression leading to a shrinkage or collapse of the brush under high compression, while still maintaining a region of well solvated chains in the overlap region between the brushes. The results suggest the hysteresis in compression is primarily due to intra-brush entanglements and collapse of the brush layer rather than inter-brush entanglements and brush–brush interpenetration.

Interaction of adsorbed polymers with supported cationic bilayers

The interaction forces between bilayers of the cationic surfactant di(tallow ethyl ester)dimethyl ammonium chloride (DEEDMAC) were measured using a Surface Forces Apparatus (SFA) with and without an adsorbing polymer, polyacrylamide (PAM). In the absence of PAM, the forces measured between the bilayer surfaces were purely repulsive on approach and separation and is charge regulated. Addition of PAM induced structural changes to the bilayer interfaces, and resulted in the formation of bilayer-like patches of DEEDMAC decorated PAM (hydrated) on the mica surface. The interaction potential between these surfaces showed a modified DLVO interaction with an additional monotonic steric hydration repulsion on approach with an exponential force decay length of Dsteric ∼ 1 nm consistent with the measurements of hydration forces. On separating the surfaces, interdigitated polymers bridge between the two surfaces, resulting in a weak adhesion (adhesion energy, W0 ∼ 0.1 mJ m−2). Our results provide a picture of the complex molecular structure and interactions between uncharged adsorbing water soluble polymers and supported charged bilayers, and highlight the effects of adsorbing polymers on the structure of bilayers. Implications for the stability of vesicles in dispersions have been also discussed.

Dynamics of force generation by confined actin filaments

Forces generated by polymerizing/de-polymerizing actin filaments confined between two mica surfaces were measured using the Surface Forces Apparatus. The measurements show that confined actin filaments exhibit complex force-generation dynamics involving multiple “modes”, the predominance of which is determined by the confinement gap and the applied force (confining pressure).

Construction of ‘smart’ surfaces with polymer functionalized silica nanoparticles

Silica nanoparticles (SiNPs) coated with the pH responsive poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) shells have been synthesized in different sizes using surface-initiated atom transfer radical polymerization (ATRP). A mixture of the PDEAEMA functionalized SiNPs (20 and 128 nm) was found to efficiently change the surface property of a substrate. The surface properties were investigated at different ratios of functionalized SiNPs. Moreover, fluorescent-doped SiNPs with PDEAEMA were also prepared to study the adsorption/desorption behavior of the SiNPs on the substrates at different pHs. A Surface Forces Apparatus (SFA) was used to measure the interactions between PDEAEMA surfaces in aqueous solutions of different pHs, and the force–distance profiles directly indicate that the intermolecular interactions of PDEAEMA are pH sensitive. At pH < pKa (∼7.3) steric repulsion dominates while at pH ≥ pKa the hydrophobic attraction between PDEAEMA molecules plays a critical role in their molecular behaviors in solutions and on surfaces. Our results provide a new insight into the fundamental understanding and development of environmentally responsive and multifunctional surfaces and nanomaterials.

Computer simulations of ionic liquids at electrochemical interfaces

Ionic liquids are widely used as electrolytes in electrochemical devices. In this context, many experimental and theoretical approaches have been recently developed for characterizing their interface with electrodes. In this perspective article, we review the most recent advances in the field of computer simulations (mainly molecular dynamics). A methodology for simulating electrodes at constant electrical potential is presented. Several types of electrode geometries have been investigated by many groups in order to model planar, corrugated and porous materials and we summarize the results obtained in terms of the structure of the liquids. This structure governs the quantity of charge which can be stored at the surface of the electrode for a given applied potential, which is the relevant quantity for the highly topical use of ionic liquids in supercapacitors (also known as electrochemical double-layer capacitors). A key feature, which was also shown by atomic force microscopy and surface force apparatus experiments, is the formation of a layered structure for all ionic liquids at the surface of planar electrodes. This organization cannot take place inside nanoporous electrodes, which results in a much better performance for the latter in supercapacitors. The agreement between simulations and electrochemical experiments remains qualitative only though, and we outline future directions which should enhance the predictive power of computer simulations. In the longer term, atomistic simulations will also be applied to the case of electron transfer reactions at the interface, enabling the application to a broader area of problems in electrochemistry, and the few recent works in this field are also commented upon.

Impact of solvation on equilibrium conformation of polymer brushes in solvent mixtures

We have investigated the response of dextran brushes in aqueous dimethyl sulfoxide (DMSO) mixtures under normal compression using the extended surface forces apparatus. The hydrophilic, tethered polymer chains extend significantly in the studied aqueous mixtures and two brush-covered surfaces exhibit repulsive forces upon compression against each other; these attributes are relevant for both anti-biofouling and lubrication properties. An estimation of the height of the dextran brushes with varying solvent quality is made from measurements of the onset of the repulsion: the brush swells significantly in pure water, a decrease in swelling being observed with an increase in DMSO concentration (up to ∼50 vol%), followed by a more pronounced swelling at higher DMSO concentrations. This behavior is in qualitative agreement with the solubility of bulk dextran polymer in aqueous DMSO solutions. Besides the conformational changes, an increase in the compressibility of the dextran brushes upon increasing the DMSO concentration was observed and explained by the change in the solvation structure of the polymer brush. We describe the equilibrium configuration of the polymer brush under marginal/good solvent conditions with the help of a mean-field approach, considering both solvent quality and a solvation-structure-dependent bond length. This work shows that an appropriate selection of polymer brush and solvent mixture can be used to tune the conformational properties of the polymer brushes at the interface, as well as the consequent repulsive and frictional forces.

Hydrophobic Enhancement of Dopa-Mediated Adhesion in a Mussel Foot Protein

Dopa (3,4-dihydroxyphenylalanine) is recognized as a key chemical signature of mussel adhesion and has been adopted into diverse synthetic polymer systems. Dopa's notorious susceptibility to oxidation, however, poses significant challenges to the practical translation of mussel adhesion. Using a surface forces apparatus to investigate the adhesion of mussel foot protein 3 (Mfp3) "slow", a hydrophobic protein variant of the Mfp3 family in the plaque, we have discovered a subtle molecular strategy correlated with hydrophobicity that appears to compensate for Dopa instability. At pH 3, where Dopa is stable, Mfp3 slow, like Mfp3 "fast" adhesion to mica, is directly proportional to the mol % of Dopa present in the protein. At pH of 5.5 and 7.5, however, loss of adhesion in Mfp3 slow was less than half that occurring in Mfp3 fast, purportedly because Dopa in Mfp3 slow is less prone to oxidation. Indeed, cyclic voltammetry showed that the oxidation potential of Dopa in Mfp3 slow is significantly higher than in Mfp3 fast at pH of 7.5. A much greater difference between the two variants was revealed in the interaction energy of two symmetric Mfp3 slow films (E(ad) = -3 mJ/m(2)). This energy corresponds to the energy of protein cohesion which is notable for its reversibility and pH independence. Exploitation of aromatic hydrophobic sequences to protect Dopa against oxidation as well as to mediate hydrophobic and H-bonding interactions between proteins provides new insights for developing effective artificial underwater adhesives.

Interaction forces between DPPC bilayers on glass.

The surface force apparatus (SFA) was utilized to obtain force-distance profiles between silica-supported membranes formed by Langmuir-Blodgett deposition of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). In the absence of a membrane, a long-range electrostatic repulsion and short-range steric repulsion are measured as a result of the deprotonation of silica in water and the roughness of the silica film. The electrostatic repulsion is partially screened by the lipid membrane, and a van der Waals adhesion comparable to that measured with well-packed DPPC membranes on mica is measured. This finding suggest that electrostatic interactions due to the underlying negatively charged silica are likely present in other systems of glass-supported membranes. In contrast, the charge of an underlying mica substrate is almost completely screened when a lipid membrane is deposited on the mica. The difference in the two systems is attributed to the stronger physisorption of zwitterionic lipids to molecularly smooth mica compared to physisorption to rougher silica.

Hydrodynamics in nanoscale confinement: SFA and colloid probe AFM liquid drainage experiments

Flow and drainage of very thin liquid films play an important role in mineral recovery, drop coalescence and emulsion stability, as well as lubrication of micromechanical devices. Studies of liquid flow under strong confinement (i.e., film thickness below a few hundred of nanometers and down to a few nanometers) can reveal the limits of applicability of a classical hydrodynamics description, but are very challenging. The Surface Force Apparatus (SFA) technique has enabled studies of drainage at nanoscale separation between atomically smooth mica sheets. The development of the colloid probe Atomic Force Microscope (AFM) as an alternative technique has allowed a significantly wider variety of confining solid surfaces to be studied. Both the SFA and the colloid probe AFM have been adapted to permit the surfaces confining the film to be soft, e.g., the surface of a drop or bubble, and therefore deformable. We present a succinct review of the experimental and theoretical modeling challenges for such studies and critically discuss the outcomes of recent experiments.

Aging and stiction dynamics in confined films of a star polymer melt

The stiction properties of a star polyisoprene (PIP) melt (having 22 arms and an arm molecular weight of around 5000, M(w) ≈ 110,000) confined between mica surfaces were investigated using the surface forces apparatus. Stop-start experiments were carried out and the stiction spike was measured as a function of surface stopping (aging) time t and applied pressure P; the time constants of the phase transitions in the stiction dynamics (freezing on stopping and melting on starting) were obtained from the force relaxation behaviors. The results were compared with those of a confined linear-PIP melt (M(w) ≈ 48,000) and other confined fluid systems; the effect of star architecture on the phase transitions in confinement during aging is discussed. Estimation of the molecular size gives that the confined star-PIP films consist of three molecular layers; a non-adsorbed layer sandwiched between two layers adsorbed on opposed mica surfaces. There are (at least) four time constants in the freezing transition of the confined star-PIP melt; fast (τ(1)) and slow (τ(2)) time constants for lateral force relaxation on stopping, critical aging time for freezing (τ(f)), and the logarithmic increase of the spike height against t. The three time constants on stopping, τ(1), τ(2), and τ(f), increase with the increase of P (decrease of the thickness D). As regards the melting transition on starting, spike force decay was fitted by a single exponential function and one time constant was obtained, which is insensitive to P (D). Comparison of the time constants between freezing and melting, and also with the results of linear-PIP reveals that the stiction dynamics of the star-PIP system involves the relaxation and rearrangement of segmental-level and whole molecular motions. Lateral force relaxation on stopping is governed by the individual and cooperative rearrangements of local PIP segments and chain ends of the star, which do not directly lead to the freezing of the system. Instead, geometrical rearrangements of the soft star-PIP spheres into dense packing between surfaces (analogous to the concept of a colloidal glass transition) are the major mechanism of the freezing transition (stiction) after aging. Interdigitation of PIP segments/chain ends between neighboring star molecules also contributes to the spike growth along with aging, and the melting transition on starting.

Evaluation of pH of Water between Solid Surfaces Using Surface Forces Apparatus Fluorescence Spectroscopy

Abstract Fluorescence spectrum measurement of fluorescein was performed for monitoring the pH of water between mica and silica surfaces by varying the surface separation (D) using a surface forces apparatus (SFA) fluorescence spectroscopy. The pH value of water between silica surfaces decreased drastically with a decrease in D to values below 1200 nm, which was longer than that in the case of mica (600 nm). This pH decrease was attributed to concentrated proton in electric double layer of negatively charged surfaces.

Measurement and Scaling of Hydrodynamic Interactions in the Presence of Draining Channels

Central to the adhesion and locomotion of tree frogs are their structured toe pads, which consist of an array of 10 μm hexagonal epithelial cells separated by interconnected channels that are 1 μm wide and 10 μm deep. It has been proposed that the channels facilitate the drainage of excess fluid trapped between the toe pads and the contacting surface, and thus reduce the hydrodynamic repulsion during approach. We performed direct force measurement of the normal hydrodynamic interactions during the drainage of fluid from the gap between a structured and a smooth surface using surface force apparatus. The structured surface consisted of a hexagonal array of cylindrical posts to represent the network of interconnected channels. The measured hydrodynamic drainage forces agree with the predictions from Reynolds' theory for smooth surfaces at large separations. Deviations from theory, characterized by a reduction in the hydrodynamic repulsion, are observed below some critical separation (h(c)), which is independent of drive velocity. We employ a scaling analysis to establish the relationship between structural features (channel depth, width, and post diameter) and the critical separation for the onset of deviations. We find agreement between our experiments and the scaling analysis, which allows us to estimate a characteristic length scale that corresponds to the transition from the fluid being radially squeezed out of the nominal contact area to being squeezed out through the network of interconnected channels.

Direct Measurement of Interaction Forces between Adsorbed Polymer Layers

Abstract The interaction forces between adsorbed layers of two graft copolymers were directly measured using surface force apparatus and atomic force microscopy. Two types of graft copolymers that were adsorbed on hydrophobic surfaces were used: (i) a graft copolymer consisting of poly(methyl methacrylate)/poly(methacrylic acid) backbone (the B chain) on which several poly(ethylene oxide) chains are grafted (to be referred to as PMMA/PEOn) and (ii) a graft copolymer consisting of inulin (linear polyfructose with degree of polymerization greater than 23) (the A chain) on which several C12 chains are grafted (INUTEC SP1). In the first case, adsorbed layers of the graft copolymer were obtained on mica sheets and the interaction forces were measured using the surface force apparatus. In the second case, the interaction forces were measured using atomic force microscopy (AFM). For this purpose, a hydrophobically modified glass sphere was attached to the tip of the cantilever of the AFM and the glass plate was also made hydrophobic. Both the sphere and the glass plate contained an adsorbed layer of INUTEC SP1. The curves of energy E(D) versus distance D for the graft copolymer of PMMA/PEOn between mica surfaces bearing the graft copolymer could be used to estimate the interaction energy between flat surfaces, by using Derjaguin approximation for cross cylinders. The results were compared with the theoretical calculations using de Gennes scaling theory. The agreement between experimental results and theoretical calculations was satisfactory. The same graft copolymer was used in latex dispersions, and the high frequency modulus G′∝ was measured as a function of the volume fraction φ of the dispersion. This high-frequency modulus could be related to the potential of mean force. In this way, one could compare the results obtained from rheology and those obtained from direct measurement of interaction forces. In the AFM method, the interaction forces are measured in the contact area between two surfaces, i.e., the surfaces of a spherical glass particle and a glass plate. The glass spheres and plates were hydrophobized using dichlorodimethylsilane. Results were obtained for adsorbed layers of INUTEC SP1 in water and in the presence of various concentrations of Na2SO4 (0.3, 0.8, 1.0, and 1.5 mol dm−3). All results showed a rapid increase in force with a decrease in the separation distance, and the forces were repulsive up to the highest Na2SO4 concentration. This explains the high stability of dispersions when using INUTEC SP1 as the stabilizer.

Molecular Interactions of a Polyaromatic Surfactant C5Pe in Aqueous Solutions Studied by a Surface Forces Apparatus

Studies on molecular mechanisms of polyaromatic surfactants in stabilizing water-in-oil (W/O) or oil-in-water (O/W) emulsions are of great scientific and practical importance. A polyaromatic surfactant N-(1-hexylheptyl)-N'-(5-carboxylicpentyl) perylene-3,4,9,10-tetracarboxylic bisimide (C5Pe) with well-defined molecular structure containing fused aromatic rings and heteroatoms similar to asphaltene molecules, was used in this study in an attempt to understand molecular interaction mechanisms of heavy oil components in aqueous solutions. A surface forces apparatus (SFA) was used to directly measure the molecular interactions of C5Pe. Solution pH, salt concentration and Ca(2+) addition showed a strong impact on molecular interactions between C5Pe adsorbed on mica surfaces. The repulsion observed between the two adsorbed C5Pe molecular layers was shown to have a steric and electrosteric origin. The force-distance profiles at short separation distances under high compression force were well fitted with the Alexander-de Gennes (AdG) model. At pH ≥ 4, the repulsive forces measured over a long separation distance under low compression force were shown to deviate from the AdG model but could be fitted with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, indicating an electrostatic origin of the observed repulsion due to ionization of -COOH groups. Adhesion between two C5Pe surfaces was shown to decrease sharply with increasing solution pH and salt concentration, being attributed to the decrease in surface hydrophobicity and hence hydrophobic attraction. Addition of Ca(2+) ions induced the formation of large C5Pe aggregates due to strong bonding of Ca(2+) with -COOH groups, leading to a longer range steric repulsion. Our results provide a new insight into the molecular interactions of polyaromatic surfactants at oil-water interfaces and in complex aqueous solutions.

The Electrochemical Surface Forces Apparatus: The Effect of Surface Roughness, Electrostatic Surface Potentials, and Anodic Oxide Growth on Interaction Forces, and Friction between Dissimilar Surfaces in Aqueous Solutions

We present a newly designed electrochemical surface forces apparatus (EC-SFA) that allows control and measurement of surface potentials and interfacial electrochemical reactions with simultaneous measurement of normal interaction forces (with nN resolution), friction forces (with μN resolution), and distances (with Å resolution) between apposing surfaces. We describe three applications of the developed EC-SFA and discuss the wide-range of potential other applications. In particular, we describe measurements of (1) force-distance profiles between smooth and rough gold surfaces and apposing self-assembled monolayer-covered smooth mica surfaces; (2) the effective changing thickness of anodically growing oxide layers with Å-accuracy on rough and smooth surfaces; and (3) friction forces evolving at a metal-ceramic contact, all as a function of the applied electrochemical potential. Interaction forces between atomically smooth surfaces are well-described using DLVO theory and the Hogg-Healy-Fuerstenau approximation for electric double layer interactions between dissimilar surfaces, which unintuitively predicts the possibility of attractive double layer forces between dissimilar surfaces whose surface potentials have similar sign, and repulsive forces between surfaces whose surface potentials have opposite sign. Surface roughness of the gold electrodes leads to an additional exponentially repulsive force in the force-distance profiles that is qualitatively well described by an extended DLVO model that includes repulsive hydration and steric forces. Comparing the measured thickness of the anodic gold oxide layer and the charge consumed for generating this layer allowed the identification of its chemical structure as a hydrated Au(OH)(3) phase formed at the gold surface at high positive potentials. The EC-SFA allows, for the first time, one to look at complex long-term transient effects of dynamic processes (e.g., relaxation times), which are also reflected in friction forces while tuning electrochemical surface potentials.

Supercritical Casimir effect in carbon dioxide

We present the first measurement of surface forces across supercritical carbon dioxide. An important finding is that long-range attractive surface forces are detected not just near the critical point, but along the supercritical extension of the coexistence line, which is commonly discussed as the supercritical ridge.Using a precisely adjustable model slit pore, our experiment can measure the change of thermodynamic potential together with changes in refractive index (mass density) in the confined CO2. The model slit pore is realized between two atomically smooth mica surfaces in a specially designed high-pressure surface forces apparatus. Our data suggest that thermal fluctuations of higher density are selectively depleted, which results in observation of a time- and space-averaged density reduction in the confined film. Direct observation of this confinement effect has consequences for theoretical understanding as well as technological applications of CO2 in porous materials.In the presence of small amounts of an acrylate solute (polyethyleneglycol-dimethacrylate), we found that multiple stable menisci of solute can be created between the surfaces and stretched out several micrometers. These liquid-liquid bridges are observed as an apparent birefringence effect. We demonstrate the critical character of the phenomena and discuss our findings in terms of a (super)critical Casimir effect.

Probing Molecular and Surface Interactions of Comb-Type Polymer Polystyrene-graft-poly(ethylene oxide) (PS-g-PEO) with an SFA

Using a surface forces apparatus (SFA), we have directly measured the molecular and surface interactions of well-defined comb-type polymer polystyrene-graft-poly(ethylene oxide) (PS-g-PEO). The interaction forces of PEO side chains end-functionalized with–OH were investigated in both symmetric (polymer vs polymer) and asymmetric (polymer vs mica) configurations. Long-range repulsive forces were measured between the swollen polymer brushes in aqueous solutions, which were shown to have a steric origin and could be well described using the Alexander–de Gennes model. Contact angle measurement showed the water contact angle on PS-g-PEO surface decreased by over 20° in about 1 min after the water droplet contacted with the polymer surface, which indicates that the PEO side chains are able to extend into water due to the strong van der Waals forces and hydrogen bonding between hydrophilic PEO side chains and water. The extended PEO side chains can act as a swollen brush, leading to the strong steric forces measured by SFA. Atomic force microscope (AFM) was also employed to provide complementary information regarding the surface morphology before and after the polymer was exposed to water. Solution ionic strength showed negligible impact on the molecular interactions of the comb-type polymer. The surface energy of PS-g-PEO film was determined to be γ ≈ 38.0 ± 1.0 mJ/m2 by both adhesion mechanics test and three-probe-liquid contact angle measurement. Our results provide important insights into the fundamental understanding of molecular interaction mechanisms of comb-type copolymers and the development of novel functional polymers/coatings with strong antifouling capabilities for engineering and biomedical applications.