Adhesion forces between functionalized latex microspheres and protein-coated surfaces evaluated using colloid probe atomic force microscopy

Proteins are important in bacterial adhesion, but interactions at molecular-scales between proteins and specific functional groups are not well understood. The adhesion forces between four proteins [bovine serum albumin (BSA), protein A, lysozyme, and poly-d-lysine] and COOH, NH2 and OH-functionalized (latex) colloids were examined using colloid probe atomic force microscopy (AFM) as the function of colloid residence time (T) and solution ionic strength (IS). For three of the proteins, OH-functionalized colloids produced higher adhesion forces to proteins (2.6-30.5 nN; IS=1 mM, T=10s) than COOH- and NH2-functionalized colloids (1.6-6.8 nN). However, protein A produced the largest adhesion force (8.1+/-1.0 nN, T=10 s) with the COOH-functionalized colloid, demonstrating the importance of specific and unanticipated protein-functional group interactions. The NH2-functionalized colloid typically produced the lowest adhesion forces with all proteins, likely due to repulsive electrostatic forces and weak bonds for NH2-NH2 interactions. The adhesion force (F) between functionalized colloids and proteins consistently increased with residence time (T), and data was well fitted by F=ATn. The constant value of n=0.21+/-0.07 for all combinations of proteins and functionalized colloids indicated that water exclusion and protein rearrangement were the primary factors affecting adhesion over time. Adhesion forces decreased inversely with IS for all functional groups interacting with surface proteins, consistent with previous findings. These results demonstrate the importance of specific molecular-scale interactions between functional groups and proteins that will help us to better understand factors colloidal adhesion to surfaces.     

Interaction forces measured using AFM between colloids and surfaces coated with both dextran and protein

Both proteins and polysaccharides are biopolymers present on a bacterial surface that can simultaneously affect bacterial adhesion. To better understand how the combined presence of proteins and polysaccharides might influence bacterial attachment, adhesion forces were examined using atomic force microscopy (AFM) between colloids (COOH- or protein-coated) and polymer-coated surfaces (BSA, lysozyme, dextran, BSA+dextran and lysozyme+dextran) as a function of residence time and ionic strength. Protein and dextran were competitively covalently bonded onto glass surfaces, forming a coating that was 22-33% protein and 68-77% dextran. Topographic and phase images of polymer-coated surfaces obtained with tapping mode AFM indicated that proteins at short residence times (<1 s) were shielded by dextran. Adhesion forces measured between colloid and polymer-coated surfaces at short residence times increased in the order protein+dextran < or = protein < dextran. However, the adhesion forces for protein+dextran-coated surface substantially increased with longer residence times, producing the largest adhesion forces between polymer coated surfaces and the colloid over the longest residence times (50-100 s). It was speculated that with longer interaction times the proteins extended out from beneath the dextran and interacted with the colloid, leading to a molecular rearrangement that increased the overall adhesion force. These results show the importance of examining the effect of the combined adhesion force with two different types of biopolymers present and how the time of interaction affects the magnitude of the force obtained with two-polymer-coated surfaces.     

Parameters affecting the adhesion strength between a living cell and a colloid probe when measured by the atomic force microscope

In this study, we used the colloid probe atomic force microscopy (AFM) technique to investigate the adhesion force between a living cell and a silica colloid particle in a Leibovitz's L-15 medium (L-15). The L-15 liquid maintained the pharmaceutical conditions necessary to keep the cells alive in the outside environment during the AFM experiment. The force curves in such a system showed a steric repulsion in the compression force curve, due to the compression of the cells by the colloid probe, and an adhesion force in the decompression force curve, due to binding events between the cell and the probe. We also investigated for the first time how the position on the cell surface, the strength of the pushing force, and the residence time of the probe at the cell surface individually affected the adhesion force between a living cell and a 6.84 μm diameter silica colloid particle in L-15. The position of measuring the force on the cell surface was seen not to affect the value of the maximum adhesion force. The loading force was also seen not to notably affect the value of the maximum adhesion force, if it was small enough not to pierce and damage the cell. The residence time of the probe at the cell surface, however, clearly affected the adhesion force, where a longer residence time gave a larger maximum force. From these results, we could conclude that the AFM force measurements should be made using a loading force small enough not to damage the cell and a fixed residence time, when comparing results of different systems.     

Bacteria attachment to surfaces--AFM force spectroscopy and physicochemical analyses

Understanding bacterial adhesion to surfaces requires knowledge of the forces that govern bacterial-surface interactions. Biofilm formation on stainless steel 316 (SS316) by three bacterial species was investigated by examining surface force interaction between the cells and metal surface using atomic force microscopy (AFM). Bacterial-metal adhesion force was quantified at different surface delay time from 0 to 60s using AFM tip coated with three different bacterial species: Gram-negative Massilia timonae and Pseudomonas aeruginosa, and Gram-positive Bacillus subtilis. The results revealed that bacterial adhesion forces on SS316 surface by Gram-negative bacteria is higher (8.53±1.40 nN and 7.88±0.94 nN) when compared to Gram-positive bacteria (1.44±0.21 nN). Physicochemical analysis on bacterial surface properties also revealed that M. timonae and P. aeruginosa showed higher hydrophobicity and surface charges than B. subtilis along with the capability of producing extracellular polymeric substances (EPS). The higher hydrophobicity, surface charges, and greater propensity to form EPS by M. timonae and P. aeruginosa led to high adhesive force on the metal surface.     

Interaction forces between salivary proteins and Streptococcus mutans with and without antigen I/II

The antigen I/II family of surface proteins is expressed by oral streptococci, including Streptococcus mutans, and mediates specific binding to, among others, salivary films. The aim of this study was to investigate the interaction forces between salivary proteins and S. mutans with (LT11) and without (IB03987) antigen I/II through atomic force microscopy (AFM) and to relate these interaction forces with the adhesion of the strains to saliva-coated glass in a parallel plate flow chamber. Upon approach of the bacteria toward a saliva-coated AFM tip, both strains experienced a similar repulsive force that was significantly smaller at pH 6.8 (median 3.0 and 3.1 nN for LT11 and IB03987, respectively) than at pH 5.8 (median 4.6 and 4.7 nN). The decay length of these repulsive forces was between 19 and 37 nm. Upon retraction at pH 6.8, the combined specific and nonspecific adhesion forces were significantly stronger for the parent strain LT11 (median -0.4 nN) than for the mutant strain IB03987 (median 0.0 nN), whereas at pH 5.8 the median of the adhesion forces measured was 0.0 nN for both strains. Moreover, at pH 6.8, the parent strain LT11 adhered in significantly higher numbers (9.6 x 106 cm-2) to a salivary coating than the mutant strain IB03987 (2.5 x 106 cm-2). Similar to the difference in adhesion forces between both strains at pH 5.8, the difference in adhesion between both strains also disappeared at pH 5.8, which suggests the involvement of attractive electrostatic forces in the interaction between antigen I/II and salivary coatings. In summary, this study shows that antigen I/II at the surface of S. mutans LT11 is responsible for its increased adhesion to salivary coatings under flow through an additional attractive electrostatic force.     

Specific and nonspecific interaction forces between Escherichia coli and silicon nitride, determined by poisson statistical analysis

The nature of the physical interactions between Escherichia coli JM109 and a model surface (silicon nitride) was investigated in water via atomic force microscopy (AFM). AFM force measurements on bacteria can represent the combined effects of van der Waals and electrostatic forces, hydrogen bonding, steric interactions, and perhaps ligand-receptor type bonds. It can be difficult to decouple these forces into their individual components since both specific (chemical or short-range forces such as hydrogen bonding) and nonspecific (long-range colloidal) forces may be present in the overall profiles. An analysis is presented based on the application of Poisson statistics to AFM adhesion data, to decouple the specific and nonspecific interactions. Comparisons with classical DLVO theory and a modified form of a van der Waals expression for rough surfaces were made in order to help explain the nature of the interactions. The only specific forces in the system were due to hydrogen bonding, which from the Poisson analysis were found to be -0.125 nN. The nonspecific forces of 0.155 nN represent an overall repulsive interaction. These nonspecific forces are comparable to the forces calculated from DLVO theory, in which electrostatic-double layer interactions are added to van der Waals attractions calculated at the distance of closest approach, as long as the van der Waals model for "rough" spherical surfaces is used. Calculated electrostatic-double layer and van der Waals interactions summed to 0.116 nN. In contrast, if the classic (i.e., smooth) sphere-sphere model was used to predict the van der Waals forces, the sum of electrostatic and van der Waals forces was -7.11 nN, which appears to be a large overprediction. The Poisson statistical analysis of adhesion forces may be very useful in applications of bacterial adhesion, because it represents an easy way to determine the magnitude of hydrogen bonding in a given system and it allows the fundamental forces to be easily broken into their components.     

Adhesion characteristics of two Burkholderia cepacia strains examined using colloid probe microscopy and gradient force analysis

Colloid probe atomic force microscopy (CP-AFM) was used to investigate two strains of Burkholderia cepacia in order to determine what molecular scale characteristics of strain Env435 make it less adhesive to surfaces than the parent strain, G4. CP-AFM approach curves analyzed using a gradient force method showed that in a high ionic strength solution (IS=100 mM, Debye length=1 nm), the colloid probe was attracted to the surface of strain G4 at a distance of approximately 30 nm, but it was repelled over a distance of 25 nm when approaching strain Env435. Adhesion forces measured under the same solution conditions during colloid retraction showed that 1.38 nN of force was required to remove the colloid placed in contact with the surface of strain G4, whereas only 0.58 nN was required using strain Env435. At IS=1mM (Debye length=10nm), the attractive force observed with G4 was no longer present, and the repulsive force seen with Env435 was extended to approximately 250 nm. The adhesion of the bacteria to the probe was much less at low IS solution (1 mM) than at high IS (100 mM). The greater adhesion characteristics of strain G4 compared to Env435 were confirmed in column tests. Strain G4 had a collision efficiency of alpha=0.68, while strain Env435 had a much lower collision efficiency of alpha=0.01 (IS=100 mM). These results suggest that the reduced adhesion of strain Env435 measured in column tests is due to the presence of high molecular weight extracellular polymeric substances that extend out from the cell surface, creating long-range steric repulsion between the cell and a surface. Adhesion is reduced as these polymers do not appear to be "sticky" when placed in contact with a surface in AFM tests.     

Surface thermodynamics and adhesion forces governing bacterial transmission in contact lens related microbial keratitis

Contact lens induced microbial keratitis results from bacterial transmission from one surface to another. We investigated the adhesion forces of Pseudomonas aeruginosa, Staphylococci and Serratia to different contact lenses, lens cases and corneal surfaces using AFM, and applied a Weibull analysis on these adhesion forces to calculate bacterial transmission probabilities from lens case to corneas with a contact lens as an intermediate. Also a new surface thermodynamic parameter was introduced, the interfacial free energy of transmission, which in essence compares the interfacial free energies of bacterial adhesion, calculated from measured contact angles with liquids on the donating and receiving surfaces in the transmission process. Bacterial adhesion forces were generally strongest among all eight strains for the lens case (-6.5 to -12.0 nN) and corneas (-3.5 to -11.5 nN), while contact lenses (-0.6 to -13.1 nN) exerted slightly smaller adhesion forces. Consequently, bacterial transmission from lens case to contact lens yielded a smaller contribution in the final transmission than from contact lens to cornea. Bacterial transmission probabilities as derived from force analyses were higher when the interfacial free energies of transmission were more negative, which is in line with surface thermodynamic principles. Therewith this parameter could provide useful in analyzing other bacterial transmission phenomena between donating and receiving surfaces as well.     

Quantification of E. coli adhesion to polyamides and polystyrene with atomic force microscopy

Atomic force microscopy (AFM) was used to measure adhesion forces between E. coli bacteria and surfaces consisting of a series of polyamides and polystyrene, materials that are prominent in carpeting, upholstery, and other indoor surfaces. Bioparticle adhesion to such surfaces in air is poorly understood, yet these interactions are thought to play a key role in their accumulation and release as indoor air pollutants. The polymers employed were polyamide 6 (PA6), polyamide 6,6 (PA66), polyamide 12 (PA12) and polystyrene (PS). We report the interaction forces between immobilized E. coli and AFM tips coated with each polymer. The adhesion forces for the tip-bacterial interactions were in the range between 2.9 and 6.7 nN, which is of the same magnitude as the polymer-polymer interactions for the same series of polymers. Polystyrene had stronger adhesion with E. coli than any of the three polyamides, by an average factor of 1.4. The work of adhesion and Hamaker constants of the probe-surface interactions were calculated using a square-pyramid flat-surface model developed previously. A drag-force analysis suggests that model spheres with the same adhesion force as E. coli-poly(amide) (F approximately 4 nN) will remain adherent under normal foot traffic (F approximately 0.2 nN), but will release during vacuum cleaning (F>or=30 nN).     

Importance of LPS structure on protein interactions with Pseudomonas aeruginosa

Atomic force microscopy (AFM) was used to quantify the adhesion forces between Pseudomonas aeruginosa PAO1 and AK1401, and a representative model protein, bovine serum albumin (BSA). The two bacteria strains differ in terms of the structure of their lipopolysaccharide (LPS) layers. While PAO1 is the wild-type expressing a complete LPS and two types of saccharide units in the O-antigen (A(+) B(+)), the mutant AK1401 expresses only a single unit of the A-band saccharide (A(+) B(-)). The mean adhesion force (F(adh)) between BSA and AK1401 was 1.12 nN, compared to 0.40 nN for F(adh) between BSA and PAO1. In order to better understand the fundamental forces that would control bacterial-protein interactions at equilibrium conditions, we calculated interfacial free energies using the van Oss-Chaudhury-Good (VCG) thermodynamic modeling approach. The hydrogen bond strength was also calculated using a Poisson statistical analysis. AK1401 has a higher ability to participate in hydrogen bonding with BSA than does PAO1, which may be because the short A-band and absence of B-band polymer allowed the core oligosaccharides and lipid A regions to be more exposed and to participate in hydrogen and chemical bonding. Interactions between PAO1 and BSA were weak due to the dominance of neutral and hydrophilic sugars of the A-band polymer. These results show that bacterial interactions with protein-coated surfaces will depend on the types of bonds that can form between bacterial surface macromolecules and the protein. We suggest that strategies to prevent bacterial colonization of biomaterials can focus on inhibiting these bonds.     

Analysis of Contact Interactions between a Rough Deformable Colloid and a Smooth Substrate

A model was developed for the effect of van der Waals interactions between a rough, deformable, spherical colloid and a flat, smooth, hard surface in contact. The model demonstrates the significant effect of colloid roughness on removal force. Small changes in colloid roughness produce large changes in the predicted removal force. Several authors attribute discrepancies in the observed interaction force between particles and surfaces to colloid roughness, and our model supports their hypotheses. Experimental data documenting the force required to remove colloids of polystyrene latex from silica substrates in aqueous solution were collected during AFM studies of this system. When colloid roughness exists, as is the case in this work, our model bounds the observed removal force. The predicted range of removal forces is in better quantitative agreement with our removal force data than are forces predicted by classical DLVO theory. Copyright 2000 Academic Press.     

Bond-strengthening in staphylococcal adhesion to hydrophilic and hydrophobic surfaces using atomic force microscopy

Time-dependent bacterial adhesion forces of four strains of Staphylococcus epidermidis to hydrophobic and hydrophilic surfaces were investigated. Initial adhesion forces differed significantly between the two surfaces and hovered around -0.4 nN. No unambiguous effect of substratum surface hydrophobicity on initial adhesion forces for the four different S. epidermidis strains was observed. Over time, strengthening of the adhesion forces was virtually absent on hydrophobic dimethyldichlorosilane (DDS)-coated glass, although in a few cases multiple adhesion peaks developed in the retract curves. Bond-strengthening on hydrophilic glass occurred within 5-35 s to maximum adhesion forces of -1.9 +/- 0.7 nN and was concurrent with the development of multiple adhesion peaks upon retract. Poisson analysis of the multiple adhesion peaks allowed separation of contributions of hydrogen bonding from other nonspecific interaction forces and revealed a force contribution of -0.8 nN for hydrogen bonding and +0.3 nN for other nonspecific interaction forces. Time-dependent bacterial adhesion forces were comparable for all four staphylococcal strains. It is concluded that, on DDS-coated glass, the hydrophobic effect causes instantaneous adhesion, while strengthening of the bonds on hydrophilic glass is dominated by noninstantaneous hydrogen bond formation.     

Probing surface adhesion forces of Enterococcus faecalis to medical-grade polymers using atomic force microscopy

The aim of this study was to compare the initial adhesion forces of the uropathogen Enterococcus faecalis with the medical-grade polymers polyurethane (PU), polyamide (PA), and poly(tetrafluoroethylene) (PTFE). To quantify the cell-substrate adhesion forces, a method was developed using atomic force microscopy (AFM) in liquid that allows for the detachment of individual live cells from a polymeric surface through the application of increasing force using unmodified cantilever tips. Results show that the lateral force required to detach E. faecalis cells from a substrate differed depending on the nature of the polymeric surface: a force of 19 +/- 4 nN was required to detach cells from PU, 6 +/- 4 nN from PA, and 0.7 +/- 0.3 nN from PTFE. Among the unfluorinated polymers (PU and PA), surface wettability was inversely proportional to the strength of adhesion. AFM images also demonstrated qualitative differences in bacterial adhesion; PU was covered by clusters of cells with few cell singlets present, whereas PA was predominantly covered by individual cells. Moreover, extracellular material could be observed on some clusters of PU-adhered cells as well as in the adjacent region surrounding cells adhered on PA. E. faecalis adhesion to the fluorinated polymer (PTFE) showed different characteristics; only a few individual cells were found, and bacteria were easily damaged, and thus detached, by the tip. This work demonstrates the utility of AFM for measurement of cell-substrate lateral adhesion forces and the contribution these forces make toward understanding the initial stages of bacterial adhesion. Further, it suggests that initial adhesion can be controlled, through appropriate biomaterial design, to prevent subsequent formation of aggregates and biofilms.     

Chemical force spectroscopy in heterogeneous systems: intermolecular interactions involving epoxy polymer,mixed monolayers,and polar solvents

We used chemical force microscopy (CFM) to study adhesive forces between surfaces of epoxy resin and self-assembled monolayers (SAMs) capable of hydrogen bonding to different extents. The influence of the liquid medium in which the experiments were carried out was also examined systematically. The molecular character of the tip, polymer, and liquid all influenced the adhesion. Complementary macroscopic contact angle measurements were used to assist in the quantitative interpretation of the CFM data. A direct correlation between surface free energy and adhesion forces was observed in mixed alcohol-water solvents. An increase in surface energy from 2 to 50 mJ/m(2) resulted in an increase in adhesion from 4-8 nN to 150-300 nN for tips with radii of 50-150 nm. The interfacial surface energy for identical nonpolar surface groups of SAMs was found not to exceed 2 mJ/m(2). An analysis of adhesion data suggests that the solvent was fully excluded from the zone of contact between functional groups on the tip and sample. With a nonpolar SAM, the force of adhesion increased monotonically in mixed solvents of higher water content; whereas, with a polar SAM (one having a hydrogen bonding component), higher water content led to decreased adhesion. The intermolecular force components theory was used for the interpretation of adhesion force measurements in polar solvents. Competition between hydrogen bonding within the solvent and hydrogen bonding of surface groups and the solvent was shown to provide the main contribution to adhesion forces. We demonstrate how the trends in the magnitude of the adhesion forces for chemically heterogeneous systems (solvents and surfaces) measured with CFM can be quantitatively rationalized using the surface tension components approach. For epoxy polymer, inelastic deformations also contributed heavily to measured adhesion forces.     

Evaluating protein attraction and adhesion to biomaterials with the atomic force microscope

Failure of implanted biomaterials is commonly due to nonspecific protein adsorption, which in turn causes adverse reactions such as the formation of fibrous capsules, blood clots, or bacterial biofilm infections. Current research efforts have focused on modifying the biomaterial interface to control protein reactions. Designing biomaterial interfaces at the molecular level, however, requires an experimental technique that provides detailed, dynamic information on the forces involved in protein adhesion. The goal of this study was to develop an atomic force microscope (AFM)-based technique to evaluate protein adhesion on biomaterial surfaces. In this study, the AFM was used to evaluate (i) protein-protein, (ii) protein-substrate, and (iii) protein-dextran interactions. The AFM was first used to measure the pull-off forces between bovine serum albumin (BSA) tips/BSA surfaces and BSA tips/anti-BSA surfaces. Results from these protein-protein studies were consistent with the literature. More importantly, the successful measurement of antibody-antigen binding interactions demonstrates that both the BSA and anti-BSA proteins retain their folded conformation and remain functional following our immobilization protocol. The AFM was also used to quantify the physiochemical interactions of proteins during adhesion to various self-assembled monolayers (SAMs) and dextran-coated substrates representative of potential biomaterial interface modifications. Dextran, which renders surfaces very hydrophilic, was the only surface coating that BSA protein did not adhere to. Hydrophobic interactions were not found to play a significant role in BSA adhesion. Therefore, the dextran molecules may resist protein adhesion by repulsive steric effects or hydration pressure. Moreover, the AFM-based methodology provides dynamic, quantitative information about protein adhesion at the nanoscale level.     

Measurement of polyamide and polystyrene adhesion with coated-tip atomic force microscopy

This work presents atomic force microscopy (AFM) measurements of adhesion forces between polyamides, polystyrene and AFM tips coated with the same materials. The polymers employed were polyamide 6 (PA6), PA66, PA12 and polystyrene (PS). All adhesion forces between the various unmodified or modified AFM tips and the polymer surfaces were in the range -1.5 to -8 nN. The weakest force was observed for an unmodified AFM tip with a PS surface and the strongest was between a PS-coated tip and PS surface. The results point to both the benefits and drawbacks of coated-tip AFM force-distance measurements. Adhesion forces between the two most dissimilar (PA6-PS and PA66-PS) materials were significantly asymmetric, e.g., the forces were different depending on the relative placement of each polymer on the AFM tip or substrate. Materials with similar chemistry and intermolecular interactions yielded forces in close agreement regardless of placement on tip or substrate. Using experimental forces, we calculated the contact radii via four models: Derjaguin, Muller, and Toporov; Johnson, Kendall, and Roberts; parametric tip-force-distance relation; and a square pyramid-flat surface (SPFS) model developed herein. The SPFS model gave the most reasonable contact tip radius estimate. Hamaker constants calculated from the SPFS model using this radius agreed in both magnitude and trends with experiment and Lifshitz theory.     

Interaction force measurement between E. coli cells and nanoparticles immobilized surfaces by using AFM

To better understand environmental behaviors of nanoparticles (NPs), we used the atomic force microscopy (AFM) to measure interaction forces between E. coli cells and NPs immobilized on surfaces in an aqueous environment. The results showed that adhesion force strength was significantly influenced by particle size for both hematite (α-Fe(2)O(3)) and corundum (α-Al(2)O(3)) NPs whereas the effect on the repulsive force was not observed. The adhesion force decreased from 6.3±0.7nN to 0.8±0.4nN as hematite NPs increased from 26nm to 98nm in diameter. Corundum NPs exhibited a similar dependence of adhesion force on particle size. The Johnson-Kendall-Roberts (JKR) model was employed to estimate the contact area between E. coli cells and NPs, and based on the JKR model a new model that considers local effective contact area was developed. The prediction of the new model matched the size dependence of adhesion force in experimental results. Size effects on adhesion forces may originate from the difference in local effective contact areas as supported by our model. These findings provide fundamental information for interpreting the environmental behaviors and biological interactions of NPs, which barely have been addressed.     

Adhesion, stretching, and electrical charge assessment of dermatan sulfate molecules by colloidal probes

Electrical and mechanical properties of dermatan sulfate (DS) molecules are studied in an aqueous environment as a function of pH. DS molecules linked at various points distributed on the surface of mica previously silanizated along with a suitable functionalized microsphere, attached to the cantilever of an atomic force microscope (AFM), provided suitable surfaces for testing interactions through the colloidal probe methodology. The repulsive force between the surfaces indicated that the charge of DS increases with pH as a result of the gradual deprotonation of acidic groups. Pulling experiments revealed increasing adhesion of DS to the monolayer as a function of pH, presumably due both to the electrical nature of the interaction between these molecules and the progressive increase of the charge of DS with pH. Serrations exhibited by the force in pulling experiments indicate that more than a single DS molecule is stretched at the same time. In addition, pulling force remained significant even at extensions that went beyond the average contour length of a single DS molecule, which suggests the existence of a significant link between DS molecules.     

Interactions of benzoic acid and phosphates with iron oxide colloids using chemical force titration

Colloidal iron oxides are an important component in soil systems and in water treatment processes. Humic-based organic compounds, containing both phenol and benzoate functional groups, are often present in these systems and compete strongly with phosphate species for binding sites on the iron oxide surfaces. Here, we examine the interaction of benzoate and phenolic groups with various iron oxide colloids using atomic force microscopy (AFM) chemical force titration measurements. Self-assembled monolayers (SAMs) of 4-(12-mercaptododecyloxy)benzoic acid and 4-(12-mercaptododecyloxy)phenol were used to prepare chemically modified Au-coated AFM tips, and these were used to probe the surface chemistry of a series of iron oxide colloids. The SAMs formed were also characterized using scanning tunneling microscopy, reflection-absorption infrared spectroscopy, and X-ray photoelectron spectroscopy. The surface pK(a) of 4-(12- mercaptododecyloxy)benzoic acid has been determined to be 4.0 +/- 0.5, and the interaction between the tip and the sample coated with a SAM of this species is dominated by hydrogen bonding. The chemical force titraton profile for an AFM probe coated with 4-(12- mercaptododecyloxy)benzoic acid and a bare iron oxide colloid demonstrates that the benzoic acid function group interacts with all three types of iron oxide sites present on the colloid surface over a wide pH range. Similar experiments were carried out on colloids precipitated in the presence of phosphoric, gallic, and tannic acids. The results are discussed in the context of the competitive binding interactions of solution species present in soils or in water treatment processes.     

The deformation and adhesion of randomly rough and patterned surfaces

Using a surface forces apparatus (SFA) and an atomic force microscope (AFM) we have studied the effects of surface roughness (root-mean-square (RMS) roughness between 0.3 and 220 nm) on the "contact mechanics", which describes the deformations and loading and unloading adhesion forces, of various polymeric surfaces. For randomly rough, moderately stiff, elastomeric surfaces, the force-distance curves on approach and separation are nearly reversible and almost perfectly exponentially repulsive, with an adhesion on separation that decreases only slightly with increasing RMS. Additionally, the magnitude of the preload force is seen to play a large role in determining the measured adhesion. The exponential repulsion likely arises from the local compressions (fine-grained nano- or submicron-scale deformations) of the surface asperities. The resulting characteristic decay lengths of the repulsion scale with the RMS roughness and correlate very well with a simple finite element method (FEM) analysis based on actual AFM topographical images of the surfaces. For "patterned" surfaces, with a nonrandom terraced structure, no similar exponential repulsion is observed, suggesting that asperity height variability or random roughness is required for the exponential behavior. However, the adhesion force or energy between two "patterned" surfaces fell off dramatically and roughly exponentially as the RMS increased, likely owing to a significant decrease in the contact area which in turn determines their adhesion. For both types of rough surfaces, random and patterned, the coarse-grained (global, meso- or macroscopic) deformations of the initially curved surfaces appear to be Hertzian.